8 Advances in Environmental Research Vol 32 - Reyes & Kneeshaw 2014

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ADVANCES IN ENVIRONMENTAL RESEARCH
ADVANCES IN ENVIRONMENTAL
RESEARCH
VOLUME 32
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ADVANCES IN ENVIRONMENTAL
RESEARCH
VOLUME 32
JUSTIN A. DANIELS
EDITOR
New York
Copyright 2014 by Nova Science Publishers, Inc.

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CONTENTS
Preface
vii
Chapter 1
Improved Gas and Vapor Detection Using Denuder Technology

Amanda L. Jenkins
Chapter 2
Environmental Protection from Thermodynamic Properties,

the Performance of Refrigeration Cycles and Air Conditioning
Abdeen Mustafa Omer
23
Chapter 3
Some Aspects of Solar and Wind Energy Resources

Abdeen Mustafa Omer
Chapter 4
Rationalization of Salt-Related Processes in the

Leather Industry as a Tool for Minimization of Their
Environmental Impact
Karel Kolomaznk, Michaela Bainov, Ji Pecha
and Dagmar Janov
137
Defuzzification of Fuzzy Concepts to Support Vulnerability

Assessments of Climate Change Impacts in the Philippines
Lilibeth A. Acosta and Jemimah Mae A. Eugenio
165
Ecological Resilience: Is It Ready for Operationalisation

in Forest Management?
Gerardo Reyes and Daniel Kneeshaw
195
Chapter 5
Chapter 6
103
Chapter 7
Climate Change and an Australian Rainforest Conifer

Rohan Mellick
Chapter 8
A Novel Thermal Seawater Desalination Process

Based on Self-Heat Recuperation
Hiroyuki Mizuno, Yasuki Kansha and Atsushi Tsutsumi
267
Biochemical Gas Sensor Bio-Sniffer and Imaging System

for Medical and Health Care Science
Takahiro Arakawa and Kohji Mitsubayashi
279
Chapter 9
213
vi
Chapter 10
Chapter 11
Contents
Desalination of Brackish Water by Electrodialysis:
Effects of Operational Parameters and Water Composition
on Process Efficiency
Mourad Ben Sik Ali, Amor Hafiane, Mahmoud Dhahbi
and Bchir Hamrouni
295
Appropriate Time Scale for Aggregating Climatic Data

to Predict Flowering and Boll Setting Behavior of Cotton
Zakaria M. Sawan
331
Index
347
PREFACE
This series covers leading-edge research focusing on the environment, including current
research data on improved gas and vapor detection using denuder technology; environmental
protection from thermodynamic properties; solar and wind energy resources; salt-related
processes in the leather industry; climate change impacts in the Philippines; ecological
resilience; climate change and Australian rainforest; seawater desalination; biochemical gas
sensors; desalination of brackish water; and time scales for aggregating climatic data.
Chapter 1 - An improved method for accomplishing air/vapor sample collection and
transport has been achieved through the use of denuder technology. Denuders use gas
injection technology to continuously introduce a gas or aerosol into a solvent stream where
the analyte is taken into a trapping solution preselected for a specific analyte. This
extraction has been demonstrated to have greater than 96% efficiency. Unlike extraction or
bubbler methods denuder extraction takes place in real time and with less loss. Once the
materials are in solution they can be transported to many different types of analytical
detection platforms including LC-MS and ion selective electrodes. This chapter describes
several different applications of the denuder to enhance gas/aerosol detection as well as a
novel vapor generation system to provide a means to challenge the detection methods.
Chapter 2 - Over the years, all parts of a commercial refrigerator, such as the compressor,
heat exchangers, refrigerant, and packaging, have been improved considerably due to the
extensive research and development efforts carried out by academia and industry. However,
the achieved and anticipated improvement in conventional refrigeration technology are
incremental since this technology is already nearing its fundamentals limit of energy
efficiency is described is magnetic refrigeration which is an evolving cooling technology.
The word green designates more than a colour. It is a way of life, one that is becoming more
and more common throughout the world. An interesting topic on sustainable technologies for
a greener world details about what each technology is and how it achieves green goals.
Recently, conventional chillers using absorption technology consume energy for hot water
generator but absorption chillers carry no energy saving. With the aim of providing a single
point solution for this dual purpose application, a product is launched but can provide
simultaneous chilling and heating using its vapour absorption technology with 40% saving in
heating energy. Using energy efficiency and managing customer energy use has become an
integral and valuable exercise. The reason for this is green technology helps to sustain life on
earth. This not only applies to humans but to plants, animals and the rest of the ecosystem.
Energy prices and consumption will always be on an upward trajectory. In fact, energy costs
viii
Justin A. Daniels
have steadily risen over last decade and are expected to carry on doing so as consumption
grows. Refrigerants such as hydrochloroflurocarbons (HCFCs) are present in the ground
source heat pump (GSHP) systems and can pose a threat to the environment through being
toxic, flammable or having a high global warming potential.
However, new types and blends of refrigerant with minimal negative impacts are being
developed. A correctly fitted system will also greatly reduce the potential for leakage, which
is why using a professional installer is highly recommended. Significant CO2 savings can be
gained by displacing fossil fuels. Even compared to the most efficient gas or oil condensing
boilers, a well-designed heat pump with COP of 3-4 will reduce emissions by 30-35%.
Further carbon savings can be made if the electricity used to power the pump comes from a
renewable energy source such as photovoltaic or a renewable electricity tariff. Also, measures
can be taken to reduce the impact of pollution from using grid electricity generated through
fossil fuel. For example, one can purchase dual tariff green electricity from a number of
suppliers. However, even if ordinary grid electricity is used to run the compressor, the system
will still produce less CO2 emissions than even the most efficient condensing gas or oil boiler
with the same output. The term vapour compression refrigeration is somewhat of a
misnomer, it would be more accurately described as 'vapour suction refrigeration'. Vapour
compression is used to reclaim the refrigerant and is more aptly applied to heat pumps.
Vapour compression refrigeration exploits the fact that the boiling temperature of a liquid is
intimately tied to its pressure. Generally, when the pressure on a liquid is raised its boiling
(and condensing) temperature rises, and vice-versa. This is known as the saturation pressuretemperature relationship.
Chapter 3 - Renewable energy resources (solar, wind and biomass) is one of the most
fundamental of natural resources that Sudan must harness in its efforts for rapid economic
development. The role of renewable energy technologies in the development process cannot
be over emphasised. The demand for energy in Sudan has increased tremendously over the
years and will continue to increase in view of the accelerating pace of population growth,
urbanisation and industrialisation. Comprehensive renewable energy resources management
is a necessity. Human resource development should be based on education and training
programmes funded both by the private and public sector. Promotion research and
development, demonstration and adaptation of energy resources amongst national, regional,
and international organisations which seek clean, pure, safe, and abundant energy sources.
Results, suggest that, wind pumps, solar stills, and biogas energy must be encouraged,
invested, and implemented, but especially for remote rural areas of Sudan.
Chapter 4 - The main purpose of the authors contribution is reducing the existing
environmental burden related to the worldwide use of sodium chloride for raw hide curing.
The essential step is rationalization of the curing process itself, since it determines the amount
of salt to deal with in the subsequent operations such as pre-soaking, soaking, after-soaking
and desalting of animal fleshings during their complex processing into valuable products.
Leather industry has been known as major producer of total dissolved solids (TDS),
particularly sodium chloride. The salt often gets to water environment, or right to the soils
resulting in arid conditions in the spilling areas, from where it can be again washed away to
water sources. Despite intensive search for alternative methods, sodium chloride remains the
most common way of raw hide curing worldwide. This method not only represents
considerable environmental burden, but insufficient application of the theory of the related
transport phenomena also has economic impacts, such as high consumption of the
Preface
ix
preservation agent, of water and electric power. Rationalization of the curing process brings
considerable reduction in the time necessary for proper curing and thus reduction in the
amount of salt which in subsequent soaking operation would get to tannery effluents.
Understanding the related transport processes, particularly diffusion of sodium chloride into
or from the hide inner volume, gives ground for their optimization and thus to reduction of
their adverse environmental impact as well as minimization of the consumption of sodium
chloride, water and energies. The authors approach lies in application of theoretical tools of
chemical engineering, namely indirect modeling based on quantitative relations from the
theory of transport phenomena. This method is in particular cases supported by
experimentally measured data, mainly estimation of the value of the effective diffusion
coefficient of sodium chloride in animal fleshings and its application in calculation the
minimal time necessary for proper curing of raw hides. The acquired knowledge is applied in
newly emerging industrial field, complex processing of animal fleshings into valuable
products such as quality biodiesel and gelatin. The fleshings contain considerable amount of
preservation salt, therefore desalting represents the key operation in their processing and the
quality of the resulting products is highly dependent on the precise performance of the
desalting process. The essential step leading to the optimization was the determination of the
time dependence of sodium chloride concentration (from the hide surface towards its internal
volume), in other words, a non-stationary concentration field of sodium chloride in the hide
during the curing process. Subsequently, the solution of the model allowed the calculation of
the optimum time necessary for sufficient preservation.
Chapter 5 - Climate change is one of the most pressing global issues that require
innovative methods to address the complexity of human-environment interactions. Many
aspects of vulnerability to climate change and adaptation measures to address its adverse
impacts remain vague and unquantifiable. Vulnerability assessments require methods that can
reduce the vagueness and imprecision of interpretations of data and information in human and
environment systems. This chapter illustrates an empirical application of fuzzy logic analysis
and the utility of this analytical tool in integrated modeling assessments in the context of
climate change. Using the intervulnerability framework, fuzzy logic models can be used to
assess trade-offs of adaptive capacity and hotspots of vulnerable regions. In particular, the
authors used data on socio-economic and ecological indicators that are relevant for the
assessments of adaptive capacity and vulnerability in the different provinces and regions in
the Philippines. The empirical application in this country shows the advantages of fuzzy set
theory in terms of its (1) transparency, which allows explicit presentation of model
assumptions through inference rules; and (2) flexibility, which allows direct inclusion of
informal and expert knowledge in combining various indicator sets. The results of the fuzzy
models show that the types of indicators and determinants traded-off depend on the social and
economic conditions in the regions. Vulnerable provinces are mostly located in northern and
southern parts of the Philippines. Vulnerability in the former can be reduced through
improving water availability for agriculture, whilst in the latter through improving peace and
order condition that affects socio-economic development.
Chapter 6 - Given the physiographic variability, variation in socio-political landscapes,
and differences in connectedness of people and communities associated with boreal forest
ecosystems, approaches to forest management that are flexible enough to accommodate this
variation are needed. Moreover, to ensure sustainable forest resource use, we need to embrace
the inherent complexity of boreal forest ecosystems rather than eliminate it, and be prepared
Justin A. Daniels
to adapt and adjust as environmental conditions change. While ecological resilience may be a
useful forest management objective to this end, developing general guidelines to integrate it
into practice remains elusive. The authors address a number of questions often posed by
managers when attempting to include ecological resilience into forest management planning.
The authors goal is to determine if the theoretical foundation of ecological resilience is
sufficiently developed to provide a general framework that can be applied for boreal forest
management.
Chapter 7 - Revealing the evolutionary trends of the recent past (late Quaternary) will
allow climate change science to anticipate the demographic response of species to future
disturbance. The genetic disjunctions and distribution of a long-lived rainforest conifer
provide a valuable signature of past demographic response to climate change a biological
autograph of time, climatic cycles and the environment. This chapter reviews literature
pertaining to three case studies. Case study one determines the level of genetic diversity and
structure within naturally occurring populations of Podocarpus elatus and resolves the
influence of historic and contemporary drivers on divergence. Case study two explores the
impact of glacial cycle climatic changes on the palaeodistribution of the species: by
combining population genetic analysis, coalescent-based analysis, the observed fossil record
and environmental niche modeling. Case study three hypothesizes that future adaptive
potential is indicative of genetic/demographic change and range expansion/contraction trends
in Podocarpus elatus associated with the Clarence River Corridor. The final section of the
chapter concludes the case studies and suggests conservation strategies applicable to longlived species allied with threatened communities.
Chapter 8 - Thermal desalination processes, which separate pure water from seawater by
evaporation, have been used throughout the world. Thermal desalination typically comprises
either multi-stage flash or multi-effect desalination processes. These processes have the
following characteristics: the product water salinity is low enough for industrial use and
seawater quality does not seriously affect the operating conditions. However, heat is not
recovered perfectly by either process and is partly discarded to cooling water. Therefore,
energy consumption in conventional thermal processes is large.
A novel thermal desalination process based on self-heat recuperation, which is a
technology designed to save energy, has been proposed recently. In this process, all of the
heat is recirculated and energy is required only for producing a temperature difference in the
heat exchangers. As a result, the energy consumption can be dramatically reduced. At the
same time, it has been reported that the specific energy consumption, defined as the total
energy added divided by the product water flow rate, may be further decreased by increasing
the recovery ratio (the product water flow rate / the feed water flow rate).
In this chapter, the authors describe a novel desalination process based on self-heat
recuperation technology and explain its potential for saving energy compared with its
conventional counterparts. In addition, they summarize recent development of the process.
Chapter 9 - The authors introduce biochemical gas sensors bio-sniffer which leverage
biochemical reactions and characteristics of various enzymes. Volatile substances associated
with diseases and breath odors are released from human body. Hence, highly sensitive and
highly selective bio-sniffers have been developed and demonstrated in biomedical and health
care applications utilizing enzymes as biomarkers of related diseases. The authors present
three topics of bio-sniffer techniques for monitoring of gaseous components of methyl
mercaptan, formaldehyde and ethanol. A bio-sniffer for gaseous methyl mercaptan (MM) is
Preface
xi
applied to measure halitosis (oral odor) in breath. MM is known as one of the important
chemicals of halitosis in oral care. And then, a fiber-optic biochemical gas sensor for
assessment of indoor environment is fabricated and demonstrated in monitoring of
formaldehyde. Finally, two-dimensional visualization system of gaseous ethanol is
demonstrated in spatial and temporal imaging of gaseous components of exhaled breath. In
this chapter, the authors describe the details and future prospects of biochemical gas sensors
for environmental analysis, medical and health care.
Chapter 10 - Electrodialysis is an electro-membrane process for separation of ions across
charged membranes from one solution to another under the influence of an electrical potential
difference used as a driving force. The transfer of the charged species is carried out according
to a mechanism of exchanges of ions between the ions of the solution and the counter ions of
the membrane.
This chapter is dealing with the effectiveness of the desalination of brackish water by this
process. A laboratory scale electrodialysis cell was used for this purpose.
The desalination of brackish solutions containing only one salt according to the
continuous mode (single pass process) was carried out initially. This study revealed that the
effectiveness of the process is dependent on the operational parameters of the electrodialysis
cell. But the rate of desalination is relatively weak. This rate does not exceed 50% and
sometimes does not allow reaching the awaited results.
Study of another configuration was carried out. This configuration is the discontinuous
mode or total recirculation mode (batch process). In this mode, the solutions are recycled in
the cell until the desired concentration is reached. While working with this mode, the
desalination rates of various solutions reached quickly high values. Indeed, they exceeded the
75% rate in few minutes.
This study concluded also that the composition of the solution itself influences the
effectiveness of desalination process. Indeed, the transfer of the ions from one compartment
to another depends on the various ionic species present in solution.
The presence of the calcium ions largely decreases the transfer of the magnesium ions
and vice versa. This is explained by the competition effect between two ions of same valence
during their transfers through exchanging membranes.
Moreover, the rates of transfer of the cations and more precisely calcium and magnesium
ions undergo reductions in the presence of anions and in particular sulfate ions. The desired
rates of desalination are also obtained for longer handling times which have an immediate
effect on energy consumption. In fact, the consumption of energy is more important for more
complex solutions.
Chapter 11 - This study covers the predicted effects of climatic factors during convenient
intervals (in days) on cotton flower and boll production compared with daily observations.
Evaporation, sunshine duration, relative humidity, surface soil temperature at 1800 h, and
maximum air temperature, are the important climatic factors that significantly affect flower
and boll production. The least important variables were found to be surface soil temperature
at 0600 h and minimum temperature. The five-day interval was found to be more adequately
and sensibly related to yield parameters. There was a negative correlation between flower and
boll production and either evaporation or sunshine duration, while that correlation with
minimum relative humidity was positive. Higher minimum relative humidity, short period of
sunshine duration, and low temperatures enhanced flower and boll formation.
In: Advances in Environmental Research. Volume 32

Editor: Justin A. Daniels
ISBN: 978-1-63117-329-5
2014 Nova Science Publishers, Inc.
Chapter 1
IMPROVED GAS AND VAPOR DETECTION USING

DENUDER TECHNOLOGY
Amanda L. Jenkins, Ph.D.
ASK Inc., Hebron, MD, US
ABSTRACT
An improved method for accomplishing air/vapor sample collection and
transport has been achieved through the use of denuder technology. Denuders use gas
injection technology to continuously introduce a gas or aerosol into a solvent stream
where the analyte is taken into a trapping solution preselected for a specific
analyte. This extraction has been demonstrated to have greater than 96% efficiency.
Unlike extraction or bubbler methods denuder extraction takes place in real time and
with less loss. Once the materials are in solution they can be transported to many
different types of analytical detection platforms including LC-MS and ion selective
electrodes. This chapter describes several different applications of the denuder to
enhance gas/aerosol detection as well as a novel vapor generation system to provide
a means to challenge the detection methods.
INTRODUCTION
A large number of analytical methods require gas and aerosol concentrations to be
measured in real-time using validated procedures. Unfortunately, many of these methods have
only been developed for aqueous samples. Getting the air/vapor sample into a liquid vehicle
for detection is time consuming, highly problematic and often has significant loss. One way
of solving this problem is to use impingers, which are glass bubble tubes used to collect
chemicals such as acids and anhydrides. A known volume of air is actively pumped through
an impinger, which contains a liquid medium, causing the liquid to bubble. The liquid
chemically reacts with, or physically dissolves, the chemical being sampled. The liquid is
ASK Inc. 7447 Rockawalkin Rd, Hebron, MD 21830. Tel: 410-543-7642. E-mail: Amanda21801@yahoo.com.
Amanda L. Jenkins
then analyzed to determine the airborne concentration. However, there are many issues
associated with using impingers including the difficulty of use, the time required, and the lack
of reproducibility making them less than optimal [1-3]. Instrumentation like GC-MS does
have the capability of detecting gas samples directly without the need for introduction into a
liquid vehicle, but getting the sample to the instrument provides its own set of problems. For
example, sampling of many gases through tubing can lead to severe sample losses from the
material sticking to the walls of the tubing.
Typically, air samples are ported to the instrumentation via heated transfer lines and
special tubing to address this issue, but line losses can still be significant. If the line is too hot,
the analyte can break down, and if it is too cold, the material being sampled will tend to
adsorb to these regions. A novel method for accomplishing air/vapor sample collection and
transport has been achieved through the use of denuder technology. This technique was
adapted from a method developed by Steve Hoke and coworkers at the Aberdeen test Center
to detect acid gases in fire fighting applications [4- 6] Denuders are similar to continuous
impingers using gas injection analysis technology (similar to flow injection analysis) to
continuously introduce a gas or aerosol sample into a solvent stream where the analyte of
interest is taken up into a trapping solution. The trapping solution is delivered to the
denuder using a chemical pump, i.e., a solenoid, syringe, peristaltic, rotary or highperformance liquid chromatography (HPLC) pump. Airflow on the order of 1-10 L/min is
obtained using a mass flow controller (rotometers or critical orifice) and a vacuum source.
This vacuum source, located external to the analyzer, draws sample air into the denuder
where the chemical agent gases and aerosols are immediately extracted into the liquid phase
of the trapping solution to be detected. The solution can then be discarded or re-circulated to
continue collection and provide a cumulative detection scheme.
Another challenge in doing gas analysis and detection is how to generate standards to
evaluate the analytical methods. Traditional means of generating chemical vapors such as
standard saturator cells and aerosol generators (which could be combined with heat and air to
create vapors), are not always suitable for compounds that may be temperature-sensitive, have
a low volatility, or have a high cost of custom synthesis. This type of chemical is often costprohibitive and/or difficult to obtain in quantities large enough to operate standard saturator
cells or other aerosolvapor types of generators. Additionally, many of these materials can be
highly toxic, which makes working with them in large quantities undesirable.[7] A novel
approach was developed to address these issues and create a stable high- flow vapor generator
for low-volatility materials that require only a minimum amount of chemical consumption
(milligrams). The technique was based on the science of static-coating capillary columns. [8]
Like methods for column preparation, a packed bed of inert particles was filled with a
solution of the test chemical. As the volatile solvent was stripped away under vacuum, the test
chemical remained behind as a film, coating the contacted surfaces, and a generator was
created when a carrier gas flowed through the packed bed. In this manner, an operator can
predetermine the amount of chemical needed to conduct the required testing. With wellestablished engineering principles used in the packed-bed design, [9] the resulting generator
could be scaled to meet the flow-rate requirements of the test. When an inert carrier gas is
used, and the temperature of the bed is constant, the vaporchemical film-coating equilibrium
is not exceeded at the outlet end of the generator, and the vapor generator will produce stable
output-chemical concentrations based on the vapor pressure of the test chemical. The output
concentration will remain constant until the chemical is either consumed or the dynamic
factors change [10].
This chapter describes the preparation and evaluation of packed bed vapor generators for
validation of air detection methods. It also describes several diverse applications of the
denuder to demonstrate how it can help solve some important gas/aerosol detection problems.
In the first application, the denuder is coupled to an LC-MS for rapid high throughput
detection samples. In the second method, the denuders are coupled with ion selective
electrodes (ISEs) for acid gas detection. Lastly the use of denuders with molecularly
imprinted polymer sensors (MIPs) will be discussed. Detection limits in all the examples are
dependent on the sensitivity of the analytical platform.
VERIFICATION OF DENUDER COLLECTION EFFICIENCY

Extraction efficiency of the denuders was evaluated using a double-needle atomizer that
sprayed a solution of 25 mg/mL of sodium fluorescein in PEG200. Two aerosol filters were
installed on the upstream side of the denuder and one filter was installed on the downstream
side. Fluorescein aerosol samples were generated and collected for 15 min. Sample flow rates
were varied between 2-3 L/min. The filter pads were removed after each test and saved for
analysis. The fluorescein was extracted from the pads using 3 mL of phosphate buffered
saline solution (PBS). The samples were evaluated against a series of freshly prepared
standards using a Sequoia-Turner Model 450 fluorometer. (Sparks, NV) The extraction
efficiency of the denuder was determined by comparing the fluorescein captured on the
upstream and downstream aerosol pads. Particle size distribution was also determined for
each run. An example of this is given in Figure 1. The replicate data showed that a flow rate
between 2 and 2.5 was optimal for denuder extraction efficiency. Flows below 2 L/min were
too low to provide the necessary amount of air needed for extraction and flows at 3 and above
were too high. The extraction efficiencies using the denuder were determined to be between
92.5 and 96.8 % with the highest extraction efficiency at a flow rate of 2ml/min. [11].
Figure 1. The particle size distribution of the aerosols generated for the test.
Amanda L. Jenkins
VAPOR GENERATOR PREPARATION

The vapor-generation techniques were validated using VX. VX was chosen since its
vapor pressure is lower than many compounds, so if the method worked for VX it should
work even better for higher volatility materials. The high flow (liters per minute) generator
was constructed using a 40 cm length of 5.0 cm diameter 316 stainless steel pipe, packed with
an inert material, to serve as a structural support for the test chemical. The pipe was filled
with 4 mm borosilicate glass beads supported between two laminated, 100 mesh stainless
steel screens that were machined into the surface of the corresponding flanged O-ring end
caps. Each end cap was ported and equipped with 9.5 mm ball valves (Swagelok Co., Solon,
OH) and sealed with Viton O-rings. The exterior of the pipe was wrapped with a single layer
of 6.4 mm o.d. thin-walled copper refrigeration tubing (Cerro Flow Products, St. Louis, MO)
and insulated with 1.25 cm closed-cell foam pipe insulation. A Neslab RTE-111 temperature
bath (Thermo Neslab, Newington, NH) was connected to the copper tubing to maintain
temperature control of the generator.
Once the vapor generator was assembled, the inner walls of the pipe were rinsed several
times with dichloromethane to remove impurities. The filling solution was prepared by
dissolving milligram quantities of the analyte in approximately 50 mL of dichloromethane.
With all the ball valves open, the resulting solution was transferred into the generator, filling
it from the inlet endcap using a funnel fitted with a two-way, 6.4 mm ball valve and a vertical
length of 6.4 mm o.d. 3.2 mm i.d. polytetrafluoroethylene (PTFE) tubing that served as a
sight-glass during this process, as shown in Figure 2. Repeated solvent rinses were added
through the funnel to wash any residual filling solution into the generator. Solvent was added
until the solution level was within 2 cm of the top retaining screen.
To remove the solvent, the two-way ball valve was closed at the base of the funnel, and a
vacuum was slowly applied to the top outlet end cap using a suitable pressure controller rated
at approximately 1 Lpm flow rate at 100 torr. The gradual reduction from ambient pressure to
200 torr over 20 min allowed the chemical solution to be mixed during the solvent
outgassing. The evaporation was monitored using a surface-mounted thermocouple placed on
the bottom inlet end cap of the generator canister. As the leading quantity of the liquid solvent
evaporated past the thermocouple, that area of the canister cooled. Once the solvent was
completely removed, the end cap warmed to room temperature as shown in Figure 3. The
entire solvent-stripping process took approximately 5 h.
To prepare the vapor generator for use, the filling-tube and funnel assembly were
removed from the bottom inlet ball valve and replaced with the inert-carrier stream hardware
and corresponding MFC used for the ensuing filter test. The vapor generator bed temperature
was set to subambient temperature conditions, and the top outlet end cap was heated
(approximately 20 C higher than ambient) with a heating tape to avoid condensation of the
test chemical downstream of the generator. The generator was then conditioned for
approximately 24 h under airflow into a waste-scrubber filter to remove high-volatility
impurities and to purge residual test chemical from above the retaining screen. The generator
was integrated into the test system at this point. The airstream entered the base of the
generator and passed through the thin-film coating of the chemically wetted surfaces of the
glass beads, which produced chemical-vapor outlet concentrations equal to the vapor pressure
of the test chemical at the temperature of the bed. The chemical stream then exited the top of
the generator and entered a chemical-intake manifold. The stream was combined with a
premixed humidified airstream and a chemical-free diluent airstream through a static mixer to
produce the target feed concentration that was required for testing.
Figure 2. Schematic of the packed-bed vapor generator.
The output of the VX generator was monitored using a GC. Initial generator output
showed several peaks that corresponded to higher volatility impurities coming from the
sample. However, after 24 h, the only peak observed in the GC results was that of the VX
(Figure 4). This result provided verification that the sample being generated was pure VX.
Figure 5 shows the stable output of VX over several days. The success of the VX testing
provided validation of the concept. Since then, the procedure has been used for various other
materials including other chemical agents and toxic industrial chemicals (TICs). The time
between regeneration of the generator is dependent on the amount of loading on the column,
the flow rate used to deliver the chemical and the vapor pressure of the material.
Amanda L. Jenkins
Figure 3. Temperature response resulting from evaporative cooling of the solvent front as it moves past
the sensor. The minimum indicates completion of the solvent evaporation process.
Smaller scale versions of the vapor generator have also been developed for lower flow
applications, typically on the order of 10-100mL/min of flow. These vapor generators have
been prepared for VX, dimethyl methyl phosphonate (DMMP), tributyl phosphate (TBP) as
well as many other materials, using a custom designed plastic coated borosilicate glass
saturator cells filled with 4mm borosilicate beads as shown in Figure 6. (Glassblowers Inc.
Turnersville, NJ). Just like the larger version, once the vapor generators were filled with
beads, the inner walls of the cell were rinsed several times with dichloromethane to remove
any impurities.
Filling solutions were prepared by dissolving 50-100 mg of analyte to be generated (VX,
DMMP, etc) in approximately 60 mL of dichloromethane. The resulting solution was then
transferred into one arm of the saturator cell. Repeated solvent rinses were added to wash any
residual filling solution into the generator. Solvent was added until the solution level was
within 2 cm of the top of the beads [11].
For the smaller version, the solvent was removed by slowly applying a vacuum to the exit
arm of the saturator using a pressure controller rated at approximately 1 Lpm flow rate at 100
torr. The gradual reduction from ambient pressure to 100 torr over 20 min allowed the
chemical solution to be mixed during the solvent out gassing. The evaporation was monitored
visually to ensure the bubble rate in the beads was not violent enough to cause splashing on
the walls.
Figure 4. GC-MS from VX during generation demonstrating purity of the sample.
The entire solvent-stripping process took 4-5 h per cell. Solvents other than
dichloromethane such as methanol have been used when necessary for solubility. The time
required for the stripping process varied based on the solvent.
Figure 5. Output of the VX generator at 16 C.
Amanda L. Jenkins
Figure 6. Schematic of the packed-bed vapor generator.
Once filled, the generators were prepared for use, by placing Swagelok parts over the
inlet and outlet ports. Inert-carrier stream gas (nitrogen) was flowed into the bed using a mass
flow controller (MFC) (Brooks Inst., Hatfield, PA). The vapor generator bed temperature was
set to sub-ambient temperature conditions, and the top outlet end cap was heated
(approximately 20 C higher than ambient) with a heating tape to avoid condensation of the
test chemical downstream of the generator. The generator was then conditioned for 24-48 h
under airflow into a waste-scrubber filter to remove high-volatility impurities and to purge
residual test chemical from the arm of the generator.
Once conditioned, these smaller generators were placed in a water bath (Thermo Neslab,
Newington, NH) so the temperature could be carefully controlled for testing. Then the
generator was integrated into the test system. The airstream entered the side arm of the
generator and passed through the thin-film coating of the chemically wetted surfaces of the
glass beads, which produced chemical-vapor outlet concentrations equal to the vapor pressure
of the test chemical at the temperature of the bed. The chemical stream then exited the center
arm of the generator and was delivered to the denuder for analysis. Once the generator was
placed in the water bath and connected to the denuder system, the arm carrying the vapor
stream was wrapped in heat tape. Then the entire system was wrapped again in aluminum
foil. These precautions were taken to prevent any of the sample from condensing out in a
cold spot before it reached the denuder. The temperature of the water bath was controlled
through the same Labview software that controlled the timings of the collection. Temperature
of the water bath at every set point was verified by an external mercury thermometer. The
nitrogen flow rate through the generator was 100 sccm/min (standard cubic centimeters/min)
for temperatures 30C and above, and 10 sccm/min for temperatures below 30C.
DENUDER-LCMS SYSTEM
The denuder-LCMS system was used to analyze concentrations of an analyte from air
samples. [7, 11] The limits of detection and range of compounds depended entirely upon the
LC-MS. The data presented here describes the use of the system to determine vapor pressure
of low volatility materials, but it has also been successfully used to monitor breakthrough of
filter bed systems and as a method for chamber analysis. Vapor sampling (shown in Figures
7-8) was conducted using A-7 denuders (St. Johns Associates, Beltsville, MD) with 1.25 cm
diameter bodies and 6.4 mm tapered pipe threads. The denuders were fabricated of
chemically resistant Kel-F material. Except where noted, all tubing used to connect this
sampling system was 3.2 mm o.d. 1.6 mm i.d. PTFE. The trapping solution used was either
HPLC grade acetonitrile (Aldrich) or deionized water depending on analyte solubility. Any
aqueous or organic solvent can be used depending on the analyte. The trapping solution was
transported to the denuder via a Lab Alliance 1500 Series HPLC pump (Thomas Scientific,
Swedesboro, NJ) set to a flow rate of 2.0 mL/min.
Figure 7. The denuder system flow schematic.
10
Amanda L. Jenkins
Figure 8. The denuder sampling apparatus.
Figure 9. Sample transfer schematic.
The pump delivered the solution to the denuder through an inline 500 psi back-pressure
check valve to maintain pumping efficiency via 1.6 mm PTFE tubing that was connected
directly to the base of the denuder. The vacuum return line of the denuder was connected to
the top of a specially designed U-tube bottle (Glassblowers Inc., Turnersville, NJ) fitted with
a three-hole GL45 vacuum cap (Diba Industries, Danbury, CT) to coalesce the returning
trapping solution. Vacuum tubing connected to the opposite top end of the U-tube was used to
siphon off the excess trapping solution, once the U-tube was filled, and to direct it to a glass
waste container that was fitted with a similar two-hole vacuum cap (Diba Industries). The
sample vacuum through each of the denuders (2.0 sLpm) was controlled by a suitable MFC
11
protected by an in-line filter. The in-line filter was useful in creating a slight pressure drop
between the waste container and MFC to prevent vapor condensation inside of the controller.
A 3.2 mm, two-position, six-port 316 SS switching valve (Valco Instruments Company,
Inc.; Houston, TX), shown in Figure 9, allowed for convenient sampling during testing.
Solenoid pumps with 50 L displacement (model 130SP2450-1TP, Bio-Chem Fluidics,
Boonton, NJ), operating on a 3 s cycle, were used to pump a portion of the trapping solution
from their respective U-tubes to the stream-selector valve SV1. The selected denuder stream
(output form from SV1) was connected to a similar six-port valve, SV2, and configured as
shown in Figures 9-10.
Figure 10. Second stage of the denuder sample-collection system.
Table 1. LC-MS Instrument Settings

Parameter
Test Conditions
Mobile phase 0.1% formic acid in acetonitrile, run at 400 L/min
Run time
4 min
zoom scan; range 2 u, centered on the parent ion of the test
Tune type
chemical
Due to the high pressure of the LC-MS injection system, a separate HPLC pump was
used to transfer the sample loop (0.5 mL) contents from the selected denuder sample to the
(25 L) LC-MS injection loop. The same trapping solution that was used in the denuder
sample collection was used as the mobile phase (0.40 mL/min) for the HPLC pump to fill the
injection loop of the LCQ Advantage Max LC-MS (Thermo Finnegan, San Jose, CA) for
analysis. The LC-MS mobile phase was 0.1% formic acid of 98+% purity (Sigma Aldrich, St.
Louis, MO) in the same solvent as the trapping solution (water, acetonitrile, etc). All valveswitching, temperature controls on the water bath, and start signals were provided through an
automated LabView (National Instruments, Austin, TX) process-control program that was
12
Amanda L. Jenkins
written in-house. The filling of the LC-MS analysis loop was timed to receive the center cut
of the denuder sampling loop of SV2. Data was calculated and collected using the Thermo
LC-MS software that was available with the instrument.
The denuder-LC-MS method was validated by performing vapor pressure measurements
and comparing those with vapor pressure measurements collected using the dynatherm
method. [12-13] VX was selected as the material for comparison as that material had been
well characterized in our lab. A small VX generator was prepared and placed in the water
bath. (Thermo Neslab, Newington, NH). The nitrogen flow rate through the generator was
100 sccm/min (standard cubic centimeters/min). Temperature was varied between -10C and
30C using the water bath. Temperature in the bath was verified with a mercury thermometer.
Concentration values at each temperature were collected every 5 minutes for 4 hours
(approximately 48 data points per temp). The last 15 points were averaged to give the value
for each temperature. Each experiment consisted of 6 temperatures, with a set of standards
run in between each experiment. This ensured that instrument reproducibility would not affect
the results. The entire process of temperature measurements and standards was repeated 4
times to get a statistical average. Five freshly prepared standards in trapping solution
(acetonitrile) were used for each analysis. The standards were made from stock solution in
trapping solution also prepared fresh daily. The fresh standards were used to prevent any bias
from degradation of the sample over time. Each standard was measured at least 24 times and
the last 12-15 measurements were averaged for each calibration point. Figure 11 shows an
example of the VX calibration curve.
Figure 11. Example of the VX calibration curve.
13
Figure 12. Comparison of the VX vapor pressure from several methods.
Using the concentration data at each temperature, the vapor pressure of VX at each
temperature was calculated. This data was then plotted and compared with existing data as
shown in Figure 12. [12-13] The denuder-LC-MS method gave values comparable to the
existing dynatherm method and was accepted as an alternate but equally acceptable method.
Since this validation, the vapor pressure of many more materials has been evaluated. Many of
the materials were unable to be measured using any other method due to thermal instability,
low vapor pressure or other factors. The addition of the denuder-LC-MS method has provided
a valuable tool in the measurement of vapor pressure for difficult materials.
THE DENUDER ION SELECTIVE ELECTRODE (ISE) SYSTEM

Vapor sampling for acid gases using ions selective electrodes (ISEs) was also conducted
using specially designed A-7 denuders (St. Johns Associates, Beltsville, MD) with tapered
pipe threads.[14-15] Except where noted, all tubing used to connect this sampling system was
3.2 mm o.d. 1.6 mm i.d. PTFE. The trapping solution used for in this study was a pH 7.6
ionic strength adjuster buffer (TISAB). The trapping solution was prepared fresh weekly by
dissolving 54.4 g of potassium hydrogen phosphate (KH2PO4)[0.2 M], 24 g of sodium
chloride (NaCl) [0.2 M] (ACS certified from Fisher Scientific Company, Fair Lawn, NJ
07410) in 1000 mL of distilled water. Once a clear solution was obtained, 22-23 g of
potassium hydroxide (KOH) (ACS certified from Fisher Scientific Company, Fair Lawn, NJ
07410) was added, and the pH adjusted to 7.6 by the slow addition of 1.0 M KOH. Twenty
four milliliters of a 20:1 Tween-20R solution (Fisher Scientific, Fair Lawn, NJ 07410) was
added as a nonionic surfactant wetting agent to suppress the electrical noise produced by the
electrode surfaces. To retard biological growth, 250 ppm chlorine (8 mL of 5% Bleach) was
also added. The volume was then diluted to the 2L mark of a volumetric flask. A schematic of
the denuder-ISE setup is shown in Figure 13.
14
Amanda L. Jenkins
The trapping solution was transported to the denuder via a Lab Alliance 1500 Series
HPLC pump (Thomas Scientific, Swedesboro, NJ) set to a flow rate of 2.0 mL/min. The
pump delivered the solution to the denuder through an inline 500 psi back-pressure check
valve to maintain pumping efficiency via 1.6 mm PTFE tubing that was connected directly to
the base of the denuder. A vacuum source connected to a mass flow controller (Brooks Inst.,
Hatfield, PA) was used to draw sample air into the denuder at a rate of 2 sLpm, where it
combined with the trapping solution, flowed through the flow cell (in the bottom and out the
top), and out into a vacuum bottle fitted with a two hole screw cap (Diba Industries, Danbury,
CT). The liquid portion was removed through tubing placed into one of the holes. The
sampled air then passed through a particulate filter to reduce the pressure of this saturated gas
stream to avoid condensation and protect the mass flow controller (MFC) before the vapor
stream was vented. Fluoride ion selective electrodes (ISEs) (Thermo-Orion, Beverly, MA)
were inserted into this flow stream by wetting the outer surface of the electrode barrel with
trapping solution to help the electrode slide through dual sealing o-rings of the flow cell until
it touched the rim at the bottom of the flow cell. Output from the ion selective electrodes was
collected into a LabView program and converted into concentration using the calibration
curve, an example of the data output is shown in Figure 14.
A complete calibration study to verify the performance of the denuderISE system was
conducted using six standards in the concentration range of 0.1 to 1000ppm. After this, a
three-point calibration was conducted at the start of each day. Standards were prepared fresh
daily by dilution of sodium fluoride in the trapping solution. Standards were analyzed by
pumping the calibration solution through the denuder in an effort to eliminate any bias.
Calibration was performed by turning on the gas analyzer and pumping trapping solution
through the flow cell for about 5 min. Then flow control valve was switched from the
trapping solution to the low level standard. Once 10-15 stable readings had been collected, the
process was repeated with the other standards. Once the data was collected, the electrode
response in millivolts (mV) at each concentration (an average over the stable readings) was
plotted against the log of the concentration in Molarity (M). At the end of the day the HPLC
pumps and the vacuum supply were turned off and the electrodes were removed from the
system and stored in a solution of 1x10-2 to 1x10-3M NaF. HF calibration curves for 3
different electrodes are shown in Figure 15. The HF denuder method demonstrated excellent
reproducibility and reliability for near real-time measurement of HF gas. Trapping solution
flow rates of 2 mL/min and an air flow rate of 2 L/min were determined to be optimal for this
setup and they also provided convenient calculation values. Initially, the trapping solution
was prepared without the bleach but significant bacterial growth was seen in the trapping
solution after a few days. The bleach proved to be successful in retarding the growth. Fresh
standards and trapping solutions were prepared on a weekly basis to eliminate concerns over
sample degradation. Subsequent studies have been performed using the denuder with
chlorine, chloride, and bromide ion selective electrodes. [14] The trapping solutions vary
somewhat depending on the electrode but all had similar performance characteristics to the
one presented here.
Figure 13. Scematic of the denuder-ISE setup.
Figure 14. Example of how the electrode responds to changes in concentration.
15
16
Amanda L. Jenkins
Figure 15. Typical Calibration curves for the HF electrodes.
DENUDER BASED IMPRINTED POLYMER SENSOR

Molecularly imprinted polymers (MIPs) are synthetic materials made using the molecular
imprinting technique. MIP cavity sites are produced so that they only recognize the
corresponding target molecule based on its size, shape, and chemical functionality. Molecular
imprinting is often called lock and key technology. In essence, the polymer matrix becomes
an artificial lock for a specific molecule that serves as the key. This process mimics many
basic biological functions from signaling between nerve and muscle cells to antibody-antigen
reactions. One of the greatest advantages of artificial receptors over naturally occurring ones
is freedom of molecular design. These artificial receptors are also much more chemically and
thermally stable than their biological counterparts. Functionality and responses can be
provided by using appropriate functional groups and/or counter ions like metals. These
polymers have an enhanced affinity for the original molecule and have been used in
applications such as chemical separations, catalysis, or molecular sensors.
The MIP-denuder work was initially undertaken to see if existing MIP sensors designed
for the detection of chemical agents in aqueous environments could be coupled with the
denuder to allow detection of gases and aerosols. Previous attempts to use the MIP sensors as
a standalone air detection method had been unsuccessful. Pinacolyl methylphosphonate,
(PMP), the hydrolysis product of the nerve agents sarin and soman was chosen as the target
since that MIP sensor has been well characterized in prior publications. [16-21] Initial tests
were conducted to verify that the PMP sensors prepared for this work were performing as
well as previously reported.
The PMP-MIP was synthesized by preparing complexes of the target using a
stoichiometric ratio of 1:1:3 europium, target (PMP) and monomer, vinyl benzoate. (The
number of binding species was chosen to accommodate the nine coordinate Eu (III).)
Europium nitrate (Eu (NO3)3) was prepared by dissolving europium oxide in water with just
enough nitric acid to produce a clear solution. The PMP was diluted and dissolved in a 50/50
17
water-methanol mixture to which the vinyl monomer was subsequently added. The resulting
solution was added to the Eu (NO3)3 and the pH adjusted with sodium hydroxide to a pH of 9
and 10 for complexation. The resulting solutions were stirred approximately 2 hours, then
covered with a watch glass and left to crystallize overnight. The crystals were then removed
and the spectra interpreted.
Once the complex was made, polymeric coatings were prepared by dissolving 3 mole
percent complex compound in styrene with approximately 0.1 mole percent
azobis(isobutyronitrile) (AIBN) added as an initiator, and 2 mole percent divinyl benzene
(DVB) added as a cross linking agent. The resulting solution was placed in a glass vial,
purged with nitrogen, and sealed using parafilm and screw-on tops. The solution was
sonicated at approx. 60C until it became viscous. The fiber optic sensors consisted of a
400micron multimode optical fiber (Thor Labs, Newton, NJ) with the polymeric sensing
element chemically bound on the distal end. The fibers were prepared by terminating one end
with an SMA connector. The end to be coated was tapered by heating it in an air/acetylene
flame and manually pulling the stripped end. (Tapered fibers are much more efficient at
coupling the evanescent field to the polymer.) The tapered fiber tips were dipped into the
chemically initiated viscous copolymer leaving a uniform layer on the fiber. The polymer
finished curing, under a small UV lamp, overnight.
Once cured, the polymers were swelled in water with gradually increasing amounts of
methanol to remove unreacted monomer and expand the polymer pores which produces
accessible sites and facilitates the removal of the imprinting molecules. The imprinted
molecules were removed by washing with 1.0M nitric acid which leaves a weakly
coordinated nitrate ion in the cavity. Template removal was verified spectroscopically.
Measurements for the calibration data and response time for all tests were performed
using the same fiber to demonstrate the reversibility of the sensors and maintain continuity.
For the first test, the large monochromator laser system was used. The MIP fiber was inserted
directly into each solution and spectra collected at one minute intervals. The response leveled
off after about 11 minutes and that was taken to be our response time. A calibration curve was
generated based on the 11minute data. Analytical figures of merit were calculated and the
sensor was determined to have a detection limit of about 1ppt (0.7ppt was the reported LOD
in the previous work). Detection limit is calculated as 3sigma or 3 times the standard
deviation of the blank. Standards were analyzed in the order of both increasing and
decreasing concentration in order to demonstrate the reversibility of the sensor. This response
was taken as the baseline measurement for the technology and used for comparison with the
denuder.
The detection platform was built on commercially available off the shelf (COTS)
technologies. Polymer luminescence was excited using a model 60X-argon ion laser (Melles
Griot, Carlsbad, CA). A 488 nm holographic filter (Kaiser Optical Systems, Ann Arbor,
Michigan) turned to pass the 465.8 nm line, was used to exclude all other laser lines. Spectra
were collected using an f/4, 0.5m monochromator (CVI, Albuquerque, NM) equipped with a
Model ST-6 CCD (Santa Barbara Instruments Group, Santa Barbara, CA) using Kestrel Spec
Software (K&M Co., Torrance, CA, USA). Spectra were also collected with a StellarNet Blue
Wave miniature fiber optic UV-vis Spectrometer (StellarNet Inc, Tampa, FL).
It has an integrated thermo electric cooler (TEC) to stabilize references and allow long
detector integration times. The spectral range is 500-850nm with a single element holographic
concave grating that produces a flat field image for uniform resolution. The grating is
18
Amanda L. Jenkins
aberration corrected for spectral imaging. The detector has a 25um slit for 1nm resolution,
and runs on Spectra Wiz software. A second StellarNet system identical to the one described
above but also containing an integrated 15 Watt Deuterium light source with 4000 hour
Hamamatsu L2D2 bulb, and 0.5inch diameter filter to allow only the 470-490nm light
through was also evaluated.
The MIP-Denuder system (Figure 16) combined the MIP setup (either the large bench top
version or the miniature StellarNet setup) with the denuder. [22] The trapping solution (water
adjusted to pH =9.5 with 1M NaOH) was delivered to the denuder at a flow rate ranging from
2 mL/min using an HPLC pump as previously described. Airflow on the order of 2 L/min was
obtained using a vacuum source that drew sample air with trapping solution into the denuder
where the target gases and aerosols were immediately extracted into the trapping solution.
The resulting mixture was then passed over the MIPs coated fiber that senses the captured
CWA/NTA. A series of 6 standards were incorporated into the system to provide an internal
calibration check.
Once the sensor and detector were determined to be working properly the denuder study
was undertaken. The MIP was placed into T connector so the effluent from the denuder
would pass over it. The standards were then pumped through the denuder and over the MIP
inline. The response from the MIP was collected at one minute. In this phase of the work,
maximum response was seen in 9 minutes (so the denuder decreases the response time).
Detection limits for the sensor were calculated based on the 9 minute data. (Figure 17) The
detection limit for the standards through the denuder was calculated to be 54ppt. This rise in
detection limit was believed to be a result of the fast flow rate over the MIP which possibly
decreased the contact time. Several different air and liquid flows were evaluated to see if the
detection limit was influenced by the flow. Lower flows did lower the detection limit of the
MIP sensor but were at a level that they decreased the efficiency of the denuder.
Figure 16. The MIP-Denuder system.
19
Figure 17. Results from the denuder calibration testing with Pinacolyl methylphosphonate.
Figure 18. Headspace analysis of empty PMP bottle. Spectra were collected every 2 minutes until it
reached steady state at 10 minutes.
In an attempt to the improve the contact time of the solution with the fiber without
compromising the denuder, a specially designed glass U shaped tube was developed to collect
and hold the solution near the MIP for a slightly longer time. (See Figures 8-9) This design
was then incorporated into the LC-MS system setup as well. Testing with this tube in the
system improved the detection limits of the system to make the MIP-denuder system as
20
Amanda L. Jenkins
sensitive as the MIP system alone is. In an effort to verify the ability to detect vapors, a
headspace study was conducted. The intake portion of the denuder system was placed over an
empty (but not cleaned) bottle of the PMP. Signals were collected every minute using the
large scale system. Positive detection of the PMP vapor was seen within the first minute of
analysis and the maximum signal was detected within 7 minutes. This represents the first time
that this type of MIP sensor previously used for liquid samples has ever detected a vapor.
(Figure 18) The amount of PMP in the headspace was calculated to be 0.9 ppm. Headspace
analysis measurements were also conducted on the same sample using the Stellarnet
miniature spectrometer. Using the miniature fiber optic system the headspace concentration
was determined to be 0.8 ppm.
The miniature spectrometer system works almost as well the large monochromator
system with approximately a 10-15% loss in sensitivity. In most cases, the convenience and
portability of the miniature spectrometer outweigh the slight loss in sensitivity.
CONCLUSION
This chapter presented three completely different applications of the denuder to improve
the process of getting a gas/aerosol sample into a liquid vehicle for sample transport and
detection as well as a new method for generating high and low flow calibration standards to
evaluate the methods. Coupling the denuder with the LC-MS allowed real time detection of
analytes for monitoring and breakthrough processes. It also provided a means of determining
vapor pressure for materials that had been previously difficult to work with due to
temperature instability and or low vapor pressure. In the hydrogen fluoride work, the denuder
ion selective electrode method was sensitive enough to provide detection of the breakthrough
in filter test systems as well as handle the high concentrations required for feed monitoring.
The methods have also been used with hydrogen chloride (HCl) and hydrogen bromide (HBr)
electrodes but should work well with any ion selective electrode.
The denuder in the molecularly imprinted polymer (MIP) system allowed the sensors to
detect air/vapor samples previously undetectable by the method. This represented the first
time a chemical agent has been able to be detected in liquid and gas/vapor using a single
molecularly imprinted polymer platform. These polymers have been demonstrated to have
unprecedented sensitivity for over 30 chemical agents and related compounds to date and
more are being added all the time. The applicability of this technique to air and vapor opened
up new, more sensitive methods for monitoring acid gases for a wide range of applications.
The addition of a small relatively inexpensive device, the denuder, has improved the
detection capabilities of methods. It reduces the time and difficulties in using traditional
sample extraction techniques and serves as a method of pre-concentration. Denuders are realtime, and can be used in a variety of applications and with a wide range of analytes since they
are chemically resistant and thermally stable. The technology could be modified and used
with almost any type of instrumentation requiring a liquid sample not just the ones described
in this chapter. Development of the denuder technique has led to an overall improvement in
the way we sample and detect gases and aerosols.
21
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
White, J,; Ann. Occup. Hyg. 2006, 50(1), p.15-27.

Richards, J.; Holder, T.; Goshaw, D.; Optimized Method 202 Sampling Train to
Minimize the Biases Associated with Method 202 Measurement of Condensable
Particulate Matter Emissions Proceedings from Hazardous Waste Combustion
Specialty Conference St. Louis, MO Nov. 2-3, 2005.
Linak, William P.; Ryan, Jeffrey V.; Ghorishi, Behrooz S.; Wendt, Jost O. L.; Issues
Related to Solution Chemistry in Mercury Sampling Impingers Journal of the Air &
Waste Management Association; 2001, Vol. 51(5), p.688.
Hoke, S.H.; Analytica Chimica Acta, 2002, 460, p.219-225.
Hoke, S.H.; Herud, C.; Proceedings of the Halon Alternatives Technical Working
Conference, 11-13 May 1993; Albuquerque, NM, 1993, p.185-190.
Hoke, S.H.; Arnold, M.F.; Holmes, T.D.; Proceedings of the Halon Options Technical
Working Conf., 14th, 4-6 May 2004; NIST SP-984-2; Albuquerque, NM, 2004; p. 1-7.
Jenkins, Amanda L., Ellzy, M.W.; Buettner, Leonard C.; Bruni, Eric J., New Approach
for Evaluating Military Filter Performance with Low Volatility Chemical Vapors Using
a Denuder-LC/MS Technique ECBC-TR-1094; U.S. Army Edgewood Chemical
Biological Center: Aberdeen Proving Ground, MD 2013.
Grob, K. Making and Manipulating Capillary Columns for Gas Chromatography,
Huethig: Heidelberg, 1986.
Geankoplis, C.J. Transport Processes and Unit Operation, 2nd ed.; Allyn and Bacon,
Inc.: Boston, 1983, p. 371414.
Buettner, L.C. Solid State Vapor Generator, U.S. Patent 6,722,182 B1, 2004.
Jenkins, A.L.; Buettner, L.C. Vapor and Aerosol Capture and Transport Using
Denuder Technology; ECBC-TR-866; U.S. Army Edgewood Chemical Biological
Center: Aberdeen Proving Ground, MD, 2011; UNCLASSIFIED Report.
Tevault, D.E.; Brozena, A.; Buchanan, J.H. Abercrombie-Thomas, P.E.; Buettner, L.C.
Thermophysical Properties of VX and RVX; J. Chem. Eng. Data 2012, 57, p.
19701977.
Buchanan, J. H..; Buettner, L. C.; Tevault, D. E. Vapor Pressure of VX; ECBC-TR068; U.S. Army Edgewood Chemical Biological Center: Aberdeen Proving Ground,
MD, 1999; UNCLASSIFIED Report.
Jenkins, Amanda L.; Buettner, Leonard C.; Maxwell, Amy H.; and Bruni, Eric J.,
Methodology Assessment for Chlorine and Hydrogen Chloride Gas Analysis ECBCTR-948; U.S. Army Edgewood Chemical Biological Center: Aberdeen Proving
Ground, MD 2012, UNCLASSIFIED Report.
Peterson, G.W.; Buettner, L.C.; Jenkins, A.L. Hydrogen Fluoride Removal
byImpregnated, Activated Carbons; ECBC-TR-837; U.S. Army Edgewood Chemical
Biological Center: Aberdeen Proving Ground, MD, 2011; UNCLASSIFIED Report.
Jenkins, A.L.; Murray, G.M. Anal. Chem.; 1996, 68(17), p. 2974-2980.
Jenkins, A.; Uy, M.; Murray, G. Anal. Chem. 1999, 71, p. 373-378.
Jenkins, A.; Yin, R.; Jensen, J. Analyst 2001, 126, p. 798802.
Murray, G.M.; Uy, O.M.; Jenkins, A.L. Polymer Based Lanthanide Luminescent
Sensors for the Detection of Organophosphorus Compounds. U.S. Patent 2008.
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[20] Jenkins, A.; Bae, S. Analytica Chimica Acta. 2005, 542(1), p. 32-37.
[21] Jenkins, A.L., Buettner, L.C., Ellzy, M.W. Molecularly Imprinted Polymer Sensors for
Detection in the Gas, Liquid and Vapor Phase J. Molec. Recog. Vol. 25 No. 6 p. 330335; 2012.
[22] Jenkins, A.L., Buettner, L.C. Molecularly Imprinted Polymer Sensors for the Near
Real-time Detection of Gases, Aerosols and Vapors, Patent accepted 2013.

ISBN: 978-1-63117-329-5
Chapter 2
ENVIRONMENTAL PROTECTION
FROM THERMODYNAMIC PROPERTIES,
THE PERFORMANCE OF REFRIGERATION
CYCLES AND AIR CONDITIONING
Abdeen Mustafa Omer
Energy Research Institute (ERI), Nottingham, UK
ABSTRACT
Over the years, all parts of a commercial refrigerator, such as the compressor, heat
exchangers, refrigerant, and packaging, have been improved considerably due to the
extensive research and development efforts carried out by academia and industry.
However, the achieved and anticipated improvement in conventional refrigeration
technology are incremental since this technology is already nearing its fundamentals limit
of energy efficiency is described is magnetic refrigeration which is an evolving cooling
technology. The word green designates more than a colour. It is a way of life, one that
is becoming more and more common throughout the world. An interesting topic on
sustainable technologies for a greener world details about what each technology is and
how it achieves green goals. Recently, conventional chillers using absorption technology
consume energy for hot water generator but absorption chillers carry no energy saving.
With the aim of providing a single point solution for this dual purpose application, a
product is launched but can provide simultaneous chilling and heating using its vapour
absorption technology with 40% saving in heating energy. Using energy efficiency and
managing customer energy use has become an integral and valuable exercise. The reason
for this is green technology helps to sustain life on earth. This not only applies to humans
but to plants, animals and the rest of the ecosystem. Energy prices and consumption will
always be on an upward trajectory. In fact, energy costs have steadily risen over last
decade and are expected to carry on doing so as consumption grows. Refrigerants such as
hydrochloroflurocarbons (HCFCs) are present in the ground source heat pump (GSHP)
systems and can pose a threat to the environment through being toxic, flammable or
having a high global warming potential.
However, new types and blends of refrigerant with minimal negative impacts are
being developed. A correctly fitted system will also greatly reduce the potential for
24
Abdeen Mustafa Omer

leakage, which is why using a professional installer is highly recommended. Significant
CO2 savings can be gained by displacing fossil fuels. Even compared to the most efficient
gas or oil condensing boilers, a well-designed heat pump with COP of 3-4 will reduce
emissions by 30-35%. Further carbon savings can be made if the electricity used to power
the pump comes from a renewable energy source such as photovoltaic or a renewable
electricity tariff. Also, measures can be taken to reduce the impact of pollution from
using grid electricity generated through fossil fuel. For example, one can purchase dual
tariff green electricity from a number of suppliers. However, even if ordinary grid
electricity is used to run the compressor, the system will still produce less CO 2 emissions
than even the most efficient condensing gas or oil boiler with the same output. The term
vapour compression refrigeration is somewhat of a misnomer, it would be more
accurately described as 'vapour suction refrigeration'. Vapour compression is used to
reclaim the refrigerant and is more aptly applied to heat pumps. Vapour compression
refrigeration exploits the fact that the boiling temperature of a liquid is intimately tied to
its pressure. Generally, when the pressure on a liquid is raised its boiling (and
condensing) temperature rises, and vice-versa. This is known as the saturation pressuretemperature relationship.
Keywords: Absorption
thermodynamic
cycles,
environment,
heat
pumps,
refrigeration
NOMENCLATURE
A
COP
Cp
Cp
E
g
h
I
m
Ns
NTU
P
R
Sgen
T
To
U
surface area (m2)

coefficient of performance
specific heat (J kg-1 k-1)
specific heat at constant pressure (kJ kg-1 k-1)
exergy rate (W)
local acceleration of gravity ((ms-2)
enthalpy (j kg-1)
irreversibility (W)
mass flow rate (kg s-1)
entropy generation number
number of heat transfer units
pressure (Pa)
gas constant (j kg-1 K-1)
entropy generation rate (W K-1)
temperature (K)
reference temperature (k)
overall heat transfer coefficient (W m-2 K-1)
Greek Symbols
effectiveness
rational efficiency
heat exchanger effectiveness
cycles,
Environmental Protection from Thermodynamic Properties
25
efficiency
density (kg/m3)
Subscripts
c
h
in
max
min
out
cold stream
hot stream
inlet
maximum
minimum
outlet
Superscripts
cond
abs
cg
evap
fg
gen
gh
p
p
R
rhx
shx
sol
t
condenser or cooling mode

absorber
condenser to generator
evaporator
fluid to vapour
generator
high-temperature generator
pressure energy component
pump
refrigerating or evaporator conditions
refrigerant heat exchanger
solution heat exchanger
solution
heat transfer energy component
1. INTRODUCTION
One of the most energy efficient methods of domestic heating is to use heat pumps. Heat
pumps use electrical energy to reverse the natural flow of environmental heat from cold to
hot. A typical heat pump requires only 100 kWh of electrical power to turn 200 kWh of freely
available environmental heat into 300 kWh of useful heat [1]. In every case, the useful heat
output will be greater than the energy required to operate the pump itself. Heat pumps also
have a relatively low carbon dioxide output, less than half that of oil, electric and gas heat
production.
Heat pumps for domestic heating are a relatively new concept in Britain; however the
technology is widely used in an industrial capacity. Across Europe, hundreds of thousands of
domestic heat pump units are in use, and the technology is tried, tested and reliable.
Ideally, a refrigerant will have the following characteristics.
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Abdeen Mustafa Omer
Non-toxic - for health and safety reasons.

Non-flammable - to avoid risks of fire or explosion.
Operate at modest positive pressures - to minimise pipe and component weights (for
strength) and avoid air leakage into the system.
Have a high vapour density to keep the compressor capacity to a minimum and
pipe diameters relatively small.
Easily transportable - because refrigerants are normally gases at SSL conditions they
are stored in pressurised containers.
Environmentally friendly - non-polluting and non-detrimental to the atmosphere,
water or ground.
Easily recycleable.
Relatively inexpensive to produce.
Compatible with the materials of the refrigeration system - non-corrosive, miscible
with oil, chemically benign.
In practice, the choice of a refrigerant is a compromise, e.g., Ammonia is good but toxic
and flammable. R12 is very good but detrimental to the Ozone layer [2]. An air-source heat
pump is convenient to use and so it is a better method for electric heating. The ambient
temperature in winter is comparatively high in most regions, so heat pumps with high
efficiency can satisfy their heating requirement. On the other hand, a conventional heat pump
is unable to meet the heating requirement in severely cold regions anyway, because its
heating capacity decreases rapidly when ambient temperature is below -10oC. According to
the weather data in cold regions, the air-source heat pump for heating applications must
operate for long times with high efficiency and reliability when ambient temperature is as low
as -15oC. Hence, much researches and developments have been conducted to enable heat
pumps to operate steadily with high efficiency and reliability in low temperature
environments [2]. For example, the burner of a room air conditioner, which uses kerosene,
was developed to improve the performance in low outside temperature [3]. Similarly, the
packaged heat pump with variable frequency scroll compressor was developed to realise high
temperature air supply and high capacity even under the low ambient temperature of 10 to
20oC [4]. Such a heat pump systems can be conveniently used for heating in cold regions.
However, the importance of targeting the low capacity range is clear if one has in mind that
the air conditioning units below 10 kW cooling account for more than 90% of the total
number of units installed in the EU [5].
2. ENERGY EFFICIENCY CONSIDERATIONS

IN HEAT EXCHANGERS DESIGNS
Heat exchangers are devices, designed to efficiently transfer heat, from one medium to
another, i.e., water-to-air, refrigerant-to-air, refrigerant-to-water, stream-to-water. Heat
exchangers are widely used in power engineering, chemical industries, petroleum refineries,
food industries and in HVAC technology. Therefore, heat transfer and the design of heat
transfer equipment continue to be a centrally important issue in energy conservation. With
increasing worldwide awareness of the serious environmental problems due to fossil fuel
27
consumption, efforts are being made to develop energy efficient and environmentally friendly
systems by utilisation of non-polluting renewable energy sources, such as solar energy,
industrial waste heat or geothermal water. The GSHPs are suitable for heating and cooling of
buildings and so could play a significant role in reducing CO2 emissions. Ground source or
geothermal heat pumps are a highly efficient, renewable energy technology for space heating
and cooling. This technology relies on the fact that, at depth, the Earth has a relatively
constant temperature, warmer than the air in winter and cooler than the air in summer.
2.1. Heat Transfer Mechanisms
Single-phase convection on both sides

Single-phase convection on one side
Two-phase convection on other side
Two-phase convection on both sides
Examples: condensers, boilers, evaporators and radiators (Figure 1).

Naturally, it would be preferred, for comfort reasons that this index would be small,
preferably nil. It may be seen that the variable is directly related to temperature discomfort:
the larger the value of the index, the farthest will inside conditions be from expected
wellbeing. Also, the use of electricity operated air conditioning systems will be more
expensive the higher this variable is. Hence, energy expenditure to offset discomfort will be
higher when comparing two index values; the ratio of them is proportional to the expected
energy savings.
When the external shade blocks the windowpane completely, the excessive heat gains
belong to the lowest values in the set, and the dimensionless index will be constant with
orientation. For the climate conditions of the locality, it can be seen that a naked window can
produce undesirable heat gains if the orientation is especially unfavourable, when the index
can have an increase of up to 0.3 with respect to the totally shaded window.
Figure 1. Diagram of a phase change heat pump: 1) condensator coil 2) expansion valve 3) evaporator
coil and 4) compressor.
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Abdeen Mustafa Omer
2.2. Brief Methodology of Heat Exchanger Design Based on the Log Mean
Temperature Difference (LMTD) and Effectiveness
A heat exchanger is usually referred to as a micro heat exchanger (HX) if the smallest
dimension of the channels is at the micrometer scale, for example from 10 m to 1 mm.
Beside the channel size, another important geometric characteristic is the surface area density
(m2/m3), which is defined as the ratio of heat exchange surface area to volume for one fluid.
It reflects the compactness of a heat exchanger and provides a criterion of classification. Note
that the two parameters, the channel size and surface area density, are interrelated, and the
surface area density increases when the channel size decreases. The exchangers that have
channels with characteristic dimensions of the order of 100 m are likely to get an area
density over 10 000 m 2/m 3 and usually referred to as HXs [6-10].
By introducing efficiency () in the specific heat exchanger performance equation, the
volumetric heat transfer power P/V (W/m 3) can be expressed as follows:
P= FUA Tm= FUA V Tm
(1)
P/V = FU Tm
(2)
Tm
[(Th,out Tc ,out ) (Th,in Tc,in )]
Ln(Th,out Tc,out ) (Th,in Tc ,in )
(3)
where, U, Tm and F refer to the overall heat transfer coefficient (W/m2 K), the mean
temperature difference (K) and the dimensionless mean temperature difference correction
factor for flow configuration respectively. A is the heat transfer surface area. Note that for a
specific heat exchanger performance, high values of lead to a corresponding high
volumetric heat transfer power, larger than that of the conventional equipment by several
orders of magnitude. As a result, heat exchanger design by miniaturisation technology has
become a common research focus for process intensification [11].
The main advantages of the HX design are compactness, effectiveness and dynamic.
These properties enable exact process control and intensification of heat and mass transfer
[12]:
Compactness: The high surface area density reduces the volume of the heat exchanger
needed for the same thermal power substantially. As a result, the space and costly material
associated with constructing and installing the heat exchanger could be reduced significantly.
Moreover, the fluid hold-up is small in a HX; this is important for security and economic
reasons when expensive, toxic, or explosive fluids are involved.
Effectiveness: The relatively enormous overall heat transfer coefficient of the HXs
makes the heat exchange procedure much more effective. In addition, the development of
microfabrication techniques [13] such as LIGA, stereolithography, laser beam machining, and
electroformation allows designing a HX with more effective configurations and high
pressure resistance.
Dynamic: The quick response time of a HX provides a better temperature control for
relatively small temperature differences between fluid flows. The quick response (small time
constant) is connected to the small inertia of the heat transfer interface (the small metal
29
thickness that separates the two fluids). On the other hand, the exchanger as a whole,
including the peripheric material, usually has a greater inertia than conventional
exchangers, entailing a large time-constant. Thus the response of one fluid to a temperature
change of the other fluid comprises two temperature-change waves, with very distinct timeconstants. In conventional exchangers, it is possible that the two responses are blurred into
one.
However, the HXs are not without shortcomings. On the one hand, the high
performance is counterbalanced by a high pressure drop, a rather weak temperature jump and
an extremely short residence time. On the other hand, those fine channels (~100 m) are
sensitive to corrosion, roughness and fouling of the surfaces. Moreover, the distinguishing
feature of the HXs is their enormous volumetric heat exchange capability accompanied with
some difficulties in realisation. The HXs design optimisation lies, on the one hand, in
maximising the heat transfer in a given volume taking place principally in microchannels,
while, on the other, minimising the total pressure drops, the dissipations, or the entropy
generation when they function as a whole system. Moreover, difficulties such as the
connection, assembly, and uniform fluid distribution always exist, all of which should be
taken into account at the design stage of the HXs. All these make the optimisation of the
HXs design a multi-objective problem, which calls for the introduction of multi-scale
optimisation method in order to bridge the microscopic world and the macroscopic world
[14]. In recent years, the fractal theory [15] and constructal theory [16] were introduced to
bridge the characteristics of heat and mass transfer that mainly takes place in micro-scale and
the global performance of the heat exchanger system in macro-scale [17].
The concept of multi-scale heat exchanger is expected to have the following
characteristics [18]:
A relatively significant specific heat exchange surface compared to that of traditional

exchangers;
A high heat transfer coefficient, as heat transfer is taking place at micro-scales and
meso-scales;
An optimised pressure drop equally distributed between the various scales;
A modular character, allowing assembly of a macro-scale exchanger from
microstructured modules.
Some difficulties still exist. On the one hand, the properties of flow distribution in such
an exchanger are still unknown [19]. A lot of research work still needs to be done for the
equidistribution optimisation. On the other hand, 3-D modelling of heat transfer for such an
exchanger requires a thorough knowledge of the hydrodynamics and profound studies on
elementary volume (smallest scale micro channels). Finally, maintenance problems for this
type of integrated structures may become unmanageable when fouling; corrosion, deposits or
other internal perturbations are to be expected. Figures 2-4 show the connections of the heat
exchanger, water pump, heat rejection fan expansion valve, and the power supply to heat
injection fan (Figure 5).
Renewable energy is the term to describe a wide range of naturally occurring, and
replenishing energy sources. The use of renewable energy sources and the rational use of
energy are the fundamental inputs for a responsible energy policy. The energy sector is
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Abdeen Mustafa Omer
encountering difficulties because increased production and consumption levels entail higher
levels of pollution and eventually climate changes, with possibly disastrous consequences.
Moreover, it is important to secure energy at acceptable cost to avoid negative impacts on
economic growth. On the technological side, renewables have an obvious role to play. In
general, there is no problem in terms of the technical potential of renewables to deliver energy
and there are very good opportunities for renewable energy technologies to play an important
role in reducing emissions of greenhouse gases into the atmosphere-certainly far more than
have been exploited so far. But there are still technical issues to be addressed to cope with the
intermittency of some renewables, particularly wind and solar. However, the biggest problem
with replying on renewables to deliver the necessary cuts in greenhouse gas emissions is more
to do with politics and policy issues than with technical ones.
Figure 2. Shows the heat exchanger.
Figure 3. Shows the connections of the heat exchanger, water pump, heat rejection fan and expansion
valve.
31
The single most important step governments could take to promote and increase the use
of renewables would be to improve access for renewables to the energy market. That access
to the market would need to be under favourable conditions and possibly under favourable
economic rates. One move that could help-or at least justify-better market access would be to
acknowledge that there are environmental costs associated with other energy supply options,
and that these costs are not currently internalised within the market price of electricity or
fuels. It could make significant difference, particularly if, appropriate subsidies were applied
to renewable energy in recognition of environmental benefits it offers. Cutting energy
consumption through end-use efficiency is absolutely essential. And this suggests that issues
of end-use consumption of energy will have to come onto the table in the foreseeable future.
Thermal comfort is an important aspect of human life. Buildings where people work
require more light than buildings where people live. In buildings where people live the energy
is used for maintaining both the temperature and lighting. Hence, natural ventilation is rapidly
becoming a significant part in the design strategy for non-domestic buildings because of its
potential to reduce the environmental impact of building operation, due to lower energy
demand for cooling. A traditional, naturally ventilated building can readily provide a high
ventilation rate. On the other hand, the mechanical ventilation systems are very expensive.
However, a comprehensive ecological concept can be developed to achieve a reduction of
electrical and heating energy consumption, optimise natural air condition and ventilation,
improve the use of daylight and choose environmentally adequate building materials. Energy
efficiency brings health, productivity, safety, comfort and savings to homeowner, as well as
local and global environmental benefits. The use of renewable energy resources could play an
important role in this context, especially with regard to responsible and sustainable
development. It represents an excellent opportunity to offer a higher standard of living to
local people and will save local and regional resources. Implementation of the ground source
heat pump systems offers a chance for maintenance and repair services. It is expected that the
pace of implementation will increase and the quality of work to improve in addition to
building the capacity of the private and district staff in contracting procedures. The financial
accountability is important and more transparent.
Figure 4. Shows the connections of the heat exchanger and expansion valve.
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Abdeen Mustafa Omer
Figure 5. Shows the power supply to heat injection fan.
Various passive techniques have been put in perspective, and energy saving passive
strategies can be seen to reduce interior temperature and increase thermal comfort, and
reducing air conditioning loads. The scheme can also be employed to analyse the marginal
contribution of each specific passive measure working under realistic conditions in
combination with the other housing elements. In regions where heating is important during
winter months, the use of top-light solar passive strategies for spaces without an equatorfacing faade can efficiently reduce energy consumption for heating, lighting and ventilation.
The use of renewable energy resources could play an important role in this context, especially
with regard to responsible and sustainable development. It represents an excellent opportunity
to offer a higher standard of living to local people and will save local and regional resources.
Implementation of the GSHPs offers a chance for maintenance and repair services.
An annual sinusoidal ambient temperature profile and an exponentially decaying
sinusoidal temperature profile as a function of depth are assumed. Temperature at any given
depth in a moment can be estimated on the basis of the following equation.
T ( x, t ) As e x
2
x 365
t to
cos
365
365
2
(4)
where:
T(x, t) is the soil temperature at the depth (x) and time (t) (oC), Tm is an average soil
temperature (oC), As is the thermal wave amplitude (oC), x is the depth (m), t is the day of
year (in days, where t=0 at midnight on 31 December), to is the phase constant (days), and
is the apparent thermal diffusivity (m3/day).
The heat exchanger effectiveness is defined as the ratio of actual heat transfer versus
maximum possible heat transfer. The actual heat transfer may be computed by calculating
either the energy lost by the hot fluid or the energy gained by cold fluid. For counter flow and
parallel flow heat exchangers it is given as:
Q = (mcp) h (Th, in-Th, out)
= (mcp) c (Tc, out-Tc, in)
(5)
33
The maximum possible heat transfer expressed as:

Q = (mcp) min (Th, in-Tc, in)
(6)
The minimum fluid may be either the hot or cold fluid, depending on the mass flow rates
and specific heats. For counter flow heat exchanger, the effectiveness is given as:
(mcp )c (Tc ,out Tc ,in )

(mcp ) min (Th,in Tc ,in )
(mcp )c (Tc ,in Tc ,out )

(mcp ) min (Th ,in Tc ,in )
(7)
For given effectiveness and maximum heat transfer rate, actual heat transfer rate be
obtained from:
Q (mcp) min (Tc,in Tc,in )
(8)
The number of heat transfer units designates the non dimensional heat transfer size of the
heat exchangers is defined as:
NTU = UA/Cmin
(9)
Defining capacity rate as the product of mass flow rate and specific heat as:
(mCp) c = Cc and (mCp) h = Ch
(10)
According, Cmin and Cmax will be minimum and maximum capacity rate respectively. The
relationship between effectiveness and number of heat transfer units, NTU is given for
counter flow heat exchanger configuration as follows:
( )
1 e NTU (1 C min/ C max)

1 (C min/ C max)e NTU (1 C min/ C max)
(11)
Compared to the LMTD method of analysis of heat exchanger, effectiveness- NTU

method provides a direct solution. LMTD method requires the outlet temperature of both the
streams which is not so in effectiveness- NTU method.
2.3. Thermodynamic Efficiency Analysis of Heat Exchanger

The maximum useful work that could be obtained from the system at a given state in a
specified environment is known as exergy also called available energy. The property exergy
serves as a valuable tool in determining the quality of energy and comparing work potential
34
Abdeen Mustafa Omer
of different energy sources or systems. From the second law point of view, a measurement
procedure is required to compare the performance of different processes or equipment.
The type of exergy efficiency called the rational efficiency is defined by Kotas, 1985 as
the ratio of desired exergy output to exergy used:
()
Edesiredoutput
Eused
(12)
is the sum of all exergy transfers from the system, which must regarded as constituting
the desired output, plus any by-product, which is produced by the system. The desired output
is determined by examining the function of the system. Eused is the required exergy input for
the process to be performed which can be expressed in terms of irreversibilities as:
Eused = Edesiredoutput + I
(13)
Alternative form of the rational efficiency can be obtained from:
()
Edesiredoutput
Eused I
(14)
From the consideration of the heat exchanger, Kotas considered that the desired exergy
output as the increase of the thermal component of exergy of the cold stream:
Edesiredoutput E c
(15)
where:
E E
T
c ,out
E c,in
T
(16)
with reference to equation (12), in which rational efficiency is formulated, the following
identify the required exergy input, Eused as:
E ht E c E h
T
used
(17)
By using equation (12) and equation (14), the rational efficiency of the heat exchanger is
obtained as:
T
( )
E
E E E
T
h
h
P
E
E I
c
(18)
T
c
The exergy change of the hot and cold streams can be written with the help of ideal gas
relations as follows:

Eout Ein = m [hout hin + To (sout Sin)]
= mCp (Tout Tin) To mCp Ln (Tout/Tin) + mToR Ln (Pout/Pin)
35
(19)
The desired exergy output which is the increase of the thermal component of exergy of
the cold stream is obtained by equation (19) as:
T
c
= (mCp )c[(Tc , out Tc , in) ToCpLn(
Tc, out
)]
Tc, in
(20)
Expressing the outlet temperature in terms of inlet temperature and effectiveness from
equation (7), the above equation becomes:
T
c
= Cc [ C min/ Cc(Tc , in Tc , out) TcLn[1 C min/ Cc(
Tc, out
1]]
Tc, in
(21)
The irreversibility, also called exergy destruction or exergy loss, is calculated by exergy
balance and taking the difference between all incoming and outgoing exergy flows given by
Kotas, 1985:
I = Ein-Eout
(22)
Another way of calculating the irreversibility can be done by the Gouy-Stodola formula,
in which the entropy generation rate is multiplied by the environmental temperature as:
I = To Sgen
(23)
which, in turn can be written in terms of summation of irreversibilities due to temperature

difference between the fluid streams and pressure drop respectively as:
Sgen = (mCp ) Ln(
Tc , out
Tc , out
) + (mCp)c Ln(
) - (mR) c Ln (Pc, out/Pc, in) - (mR) h
Tc , in
Tc , in
Ln (Ph, out/Ph, in)

(24)
The entropy generation rate in the heat exchanger is formulated using first and second
law statements:
I = IT + IP
(25)
Defining entropy generation number by dividing entropy generation by minimum heat

capacity, i.e., Cmin as given by:
Ns = Sgen/Cmin
(26)
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Abdeen Mustafa Omer
This number is second-law relative of the order concept of the NTU, which is used in
traditional first-law analyses of heat exchangers. Ns represent a high or a low entropy
generation rate depends on the following factors:
The size of heat exchanger Ns that can be economically tolerated;

On the magnitude of the remnant irreversibility, Ns, imbalance;
On the entropy generation levels shown by the other components that make up the
greater system.
Heat exchangers are generally inefficient from an energy conservation point of view
because they have been designed in the past on the basis of low cost that dictates a minimumsize unit. To achieve the small-size heat exchanger, the temperature difference between the
fluid streams is maximised.
However, the larger is the temperature difference in a heat exchanger, the greater will be
the loss during heat transfer. Also, capacity mismatch is used between the streams to increase
the performance.
3. SOURCES OF HEAVY METALS IN THE ENVIRONMENT

Various industries generate heavy metal containing wastewater includes tanning, battery,
glassware, ceramics, electroplating, fertiliser, mining, paints, photographic industries. The
waste contain heavy metals such as chromium, lead, cadmium, arsenic, copper, iron,
manganese, nickel, mercury, and cobalt among others. The amount and the number of metals
present in any wastewater are related directly to the operations carried out in an industry. For
example, tanneries discharge chromium in wastewater; copper, chromium, zinc, and cadmium
are widely generated form metal plating; the production of electrical equipment and mining,
smelting, and fossil fuel combustion contribute to mercury pollution; and lead is generated
from a number of industrial and mining sources. In most wastewater, the concentration of
heavy metals present is much larger than the safe permissible limits and therefore, they need
to be removed. Table 1 summarises the anthropogenic sources of heavy metal in the
environment.
Magnetic nanoparticles offer tremendous opportunity to treat wastewater containing toxic
metal ions because of their high surface area, high physicochemical stability, multi
functionality, ease in coating, and low-cost of synthesis. Equilibrium isotherm models are
usually classified into the empirical equation and the mechanistic model. The mechanistic
models are based on mechanism of metal ion adsorption, which are able not only to represent
but also to explain and predict the experimental behaviour. Some empirical models for single
solute systems are listed in Table 2.
Desorption is very much necessary when the material synthesis is costly. Regenerability
of loaded magnetic nanoparticles is a key factor for improving the economy of adsorption
process. The economic feasibility of using adsorbent based on magnetic nanoparticles to
remove heavy metals from aqueous solution relies on its regeneration ability during multiple
adsorption/desorption cycle. Elutant must be none damaging to the magnetic nanoparticles,
less costly, eco-friendly and effective. Figure 6 Effect of pH on the adsorption of metal ions.
37
Table 1. Significant anthropogenic sources of heavy metal in the environment

Industry
Electroplating
Metals
Cr, Ni, Zn, Cu
Pollution arising
liquid effluents from plating processes
Waste battery fluid, contamination of soil
Batteries
Ps, Sb, Zn, Cd, Ni, Hg
and groundwater
Aqueous waste from manufacture, old
Paints and pigments
Pb, Cr, As, Ti, Ba, Zn
paint deterioration and soil pollution
Landfill leachate, contamination of ground
Landfill leachate
Zn, Cu, Cd, Pb, Ni, Cr, Hg
and surface water
Aqueous and solid metallic waste from
Electronics
Pb, Cd, Hg, Pt, Au, Cr, As, Ni, Mn
manufacturing and recycling process
Metalliferous mining
Cd, Cu, Ni, Cr, Co, Zn, As
Acid mine drainage, tailings, slag heaps
Run-off, surface and groundwater
Fertilisers
Cd, Cr, Mo, Pb, U, V, Zn
contamination, plant bio-accumulation
Land spreading threat to ground and
Manures sewage sludge Zn, Cu, Ni, Pb, Cd, Cr, As, Hg
surface water
Specialist alloys and
Manufacture, disposal and recycling of
Pb, Mo, Ni, Cu, Cd, As, Te, U, Zn
steels
metals, tailings and slag heaps
Paper and pulp
Zn, Cu, Cd, Pb, Ni, Fe, Mn
Wastewater effluents
Table 2. Summary of widely used isotherms for systems with their advantages
and disadvantages
Isotherms
Functional
form
Linear form
Plot
Advantages
Langmuir
qe = Qm KL Ce (1 +
KL Ce)
Ce/qe = 1/(Kl qm) +
1/qm Ce
Ce/qe VS.Ce
has Henry law and
finite saturation limit
so valid over a wide
range of
concentration
Freudlich
Temkin
qe = (RT/b) In (KT
qe = KF (Ce)
Ce)
In qe = In KF + 1/n In qe = RT/b In KT +
Ce
RT/b In Ce
In qe VS. In Ce
qe VS. In Ce
Redlich-Peterson
qe = KRP Ce (1+aRP
(Ce)B
In [(KRPCe/qe)-1] = In
aRP + b In Ce
In [(KRP Ce)-1] VS. In Ce
Simple expression
and has parameter
for surface
heterogeneity
Approaches Freudlich at
high concentration
1/n
Does not have Henry

law and no
saturation limit, not
Based on monolayer
Disadvantages
structured, not
assumption
applicable over wide
range of
concentration
Simple expression
Same as Freudlich.
It does not have
correct Henry law
limit and finite
No special advantages
saturation limit,
not applicable over
wide range of
concentration
The following are the more remarkable ones:
National decisions must be based on scientific knowledge such that the measures are
designed to consider the potential sources of accidental admixture and the likelihood
of contamination from each source.
38
Abdeen Mustafa Omer
The measures must be effective, financially feasible and proportional to the labelling
parameters established.
The balance among producers interests must be guaranteed.
The civil liability regulations have to ensure that legal frameworks offer equal and
adequate compensation for economic damages to farmers.
Regarding the latter point, farmers who introduce genetically modified (GM) crops are
responsible for any damages and the implementation of the necessary agricultural
management practices to limit genetic contamination. The recommendation identifies the
primary potential accidental admixture sources including seed impurities, natural regeneration
or seed remaining in the soil after a harvest, cross-pollination, harvest and post-harvest
processes, transport and storage, and the final processing of the products. Similarly, it
complies a catalogue of coexistence measures related with the above-mentioned accidental
admixture sources (Table 3).
Removal efficiency (%)
120
100
80
Zn
60
Cu
40
Pb
20
Cd
0
1
Inital pH
Figure 6. Effect of pH on the adsorption of metal ions; adsorbent 0.05 g, concentration ions 100 mg L-1,
volume of metal ions solution 50 ml, time 2 hr, at 298 K.
Table 3. Classification of the main coexistence measures according to the sources

accidental admixture
Source of admixture
Coexistence measures at the farm-level
Coexistence measures
at the region-level
Impurities in the
Certification and registration of GM * seeds
propagation material
Isolation distances
Buffer zones
Voluntary agreements
Cross pollination
Coordination between neighbours to stagger flowering
among producers
periods
Conditions that enable
Production segregation
Sowing, harvest and
Training in good agricultural practices: cleaning machinery, installations, means
post-harvest activities
of transport, etc.
Notifications to public administrations and neighbours
* GM Genetically modified.
39
Table 4. Traffic related lead concentration levels in selected African countries

Country
Egypt
Kenya
Nigeria
Senegal
South Africa
Uganda
Zambia
Air (g/m3)
0.6-4.8 (1.9)
0.4-1.3
0.5-45
N.A.
0.36-2.1 (0.76)
N.A.
0.15
Soil (g/g)
N.A.
26.73-4000 (105)
N.A.
N.A.
76.7-80
2.5-703 (25.5)
16-1000050 (1830)
Food (g/g)
N.A.
0.45-85.5 (10.15)
0.01-1.6 (0.1)
N.A.
N.A.
N.A.
0.4-66
Water (g/l)
N.A.
0.11-19.1 (5.65)
0.9-9.8 (4.05)
N.A.
N.A.
N.A.
N.A.
Blood (g/dl)
11-36 (19)
N.A.
8.7-60 (30.1)
6.1-10.67 (8.4)
3.8-12 (9.7)
N.A.
N.A.
Source: (UNEP, 2006) [20].
gCO2/km
450
400
350
2000
2020
2050
300
250
200
150
100
50
0
W Europe
E Europe
Pacific
Africa
World
Average
Re gions
Figure 7. The GHG emissions intensity of automobile stock by regions.
The growth in vehicle emissions has, to a large extent, diminished Africas carrying
capacity, posing a significant threat to human health, ecosystems on which livelihoods
depend, materials and infrastructure, climate change and biodiversity (Table 4) [20].
Figures in the parentheses are median concentrations.
The reported values are from available literature published in the period 1982-2005.
The total emissions emanating from the regions are projected to surpass those of their
industrialised counterparts, i.e., Western Europe, North America, and Japan (Figure 7)
(WBCSD, 2004) [21].
3.1. Co-Precipitation
Co-precipitation is very facile and convenient way to synthesise iron oxide nanoparticles
(either Fe3O4 or -Fe2O3) from aqueous Fe2+/Fe3+ salt solutions by addition of a base under
inert atmosphere at room temperature or at elevated temperature. The chemical reaction of
Fe3O4 formation may be written as:
40
Abdeen Mustafa Omer

Fe2+ + 2Fe3+ + 8OH- Fe3O4 + H2O
(27)
According to the thermodynamics of this reaction, complete precipitation of Fe3O4 should

be expected at a pH between 8 and 14, with a stoichiometric ratio of 2:1 (Fe3+/ Fe2+) in nonoxidising oxygen environment. The size, shape and composition of magnetic nanoparticles
very much depends on the type of salt used (e.g., chlorides, sulphates, nitrates), the Fe2+/Fe3+
ratio, the reaction temperature, the pH value and ionic strength of the media. With this
synthesis, one the synthetic conditions are fixed, the quality of the magnetite nanoparticles is
fully reproducible.
However, magnetite nanoparticles are not very stable under ambient conditions and are
easily oxidised to maghemite or dissolved in an acidic medium.
Fe3O4+ 2H+ -Fe2O4 + Fe2+ + H2O
(28)
3.2. Hydrothermal Syntheses

Several scientists have reported the hydrothermal synthesis of magnetic nanoparticles for
wide range of applications. The reaction between Fe(NO3)3 solution and NH3.H2O is shown
in equation:
Fe(NO3)3 + 3NH3.H2O Fe(OH)3 + 3NH4.NO3
(29)
and -Fe2O3 particles will form through a two-step phase transformation, according to the
following equation:
Fe(OH)3 + FeOOH Fe2O3
(30)
Ethylene glycol will have an effect on preventing Fe(OH)3 the nanoparticles from
agglomeration. Therefore, uniform Fe2O3 nanocrystals were obtained after being heated at
200-289oC to complete the phase transformation.
4. THERMODYNAMICS
Thermodynamics is the study of energy, its transformations and its relation to states of
matter. Thermodynamic system is a region in space or a quantity of matter bounded by a
closed surface.
The surroundings include everything external to the system and the system is separated
from the surroundings by the system boundaries. These boundaries can be movable or fixed,
real or imaginary.
41
4.1. The Pseudo-First Order Kinetic

The Lagergreens first-order rate expression based on solid capacity is generally
expressed as follows:
dq
qe q
dt k 1
(31)
where q and qe are amounts of adsorbate adsorbed (mg/g) at time t and at equilibrium
respectively, k1 is the rate constant of adsorption (l/min). Integration of the above equation
with the boundary conditions: t=0, q=0 and t=t, q=q gives:
q q 1 exp(k 1t )
e
(32)
Kinetic adsorptions by numerous magnetic nanomaterials have been studied using the
pseudo-first-order kinetic model.
dq
dt k 2
qe q
(33)
Integration of above equation with the boundary conditions t=0, q=0 and t=t, q=q result
in:
qe q
)(
qe
) k 2t
(34)
This equation can be stated in the linear form as:
t
t
1
( ) ( )
2
q
qe
k 2 qe
(35)
where k2 is the equilibrium rate constant of pseudo-first-order adsorption (g/mg/min).

Pseudo-first-order model is derived on the basis of the sorption capacity of the solid
phase expressed as in equation (33).
4.2. The Weber and Morris Sorption Kinetic Model

The Weber and Morris sorption kinetic model was initially employed by Pavasant to
describe their biosorption experimental data. This model has the following form:
q KWM
(36)
42
Abdeen Mustafa Omer

The intraparticle diffusion can be estimated with:
D=
dpKWM
(
)
8640 qe
(37)
The external mass transfer process was determined by:

dq
i
dt k 2
c Cis
(38)
4.3. Freundlich Isotherm

Freundlich isotherm is an empirical equation. This equation is one among the most
widely used isotherms for the explanation of adsorption equilibrium. This equation has the
following form:
qe K F Ce
1/ n
(39)
It can also be expressed in the linearised logarithmic form:
log qe log
1
log Ce
n
(40)
By applying these assumptions and a kinetic principle (rate of adsorption and desorption
from the surface is equal), the Langmuir equation can be written in the following form:
qe q
max
KLCe
)
1 KLCe
(41)
The linear form of this equation is often written as:

Ce
qe
1
q
Ce (
1
)
KL.q max
(42)
max
Langmuir isotherm constant can be used in biosorption to estimate the thermodynamic

parameters Gibbs free energy (G), change in enthalpy (H) and change in entropy (S). The
negative (G) indicates the spontaneity of the adsorption process. The free energy of
adsorption (G) can be related with the Langmuir equilibrium constant by the following
expression:
G RTLnKL
(43)
43
Enthalpy and entropy changes are also related to the Langmuir equilibrium constant by
the following expression:
ln KL
s H
R RT
(44)
Thus, a plot of Ln KL versus 1/T should be a straight line. H and S values could be
obtained from the slope and intercept of this plot. Magnetic nanoparticles offer tremendous
opportunity to treat wastewater containing toxic metal ions because of their high surface area,
high physiochemical stability, multi functionality, ease in coating and low-cost of synthesis.
5. STORED ENERGY
Thermal (internal) energy is caused by the motion of molecules and/or intermolecular
forces. Potential energy (PE) is caused by attractive forces existing between molecules, or the
elevation of the system.
PE = mgz
(45)
where: m is the mass; g is the local acceleration of gravity; and z is the elevation above
horizontal reference plane.
Kinetic energy (KE) is the energy caused by the velocity of molecules and is expressed
as:
KE = mV2
(46)
where: V is the velocity of a fluid stream crossing the system boundary.

Flow work is energy carried into or transmitted across the system boundary because a
pumping process occurs somewhere outside the system, causing fluid to enter the system.
Flow work also occurs as fluid leaves the system (Figure 8).
Flow work (per unit mass) = pv
(47)
Enthalpy h is an important property that includes internal energy and flow work and is
defined as:
h u pv
(48)
5.1. First Law of Thermodynamics

The first law of thermodynamics is often called the law of conservation of energy. The
following form of the first-law equation is valid only in the absence of a nuclear or chemical
reaction.
44
Abdeen Mustafa Omer
Figure 8. Energy flows in general thermodynamic system.
Based on the first law or the law of conservation of energy for any system, open or
closed, there is an energy balance as:
[Net amount of energy added to system] = [Net increase of stored energy in system] (49)
or
[Energy in] [Energy out] = [Increase of stored energy in system]
(50)
For the general case of multiple mass flows with uniform properties in and out of the
system, the energy balance can be written:
m (u pv V2
in
(u pv V
gz )in mout
gz )out Q W
(51)
[ mf (u pv V gz ) f mi (u pv V gz )i ]system
2
2
where subscripts i and f refer to the initial and final states respectively.
Nearly all important engineering processes are commonly modelled as steady-flow
processes. Steady flow signifies that all quantities associated with the system do not vary with
time. Consequently:
2
min (h pv V gz )in mou min(h V gz )in Q W 0
allstreamsleaving
2
2
allstreamsentering
(52)
where: h = u +pv as described in equation (48).

A second common application is the closed stationary system for which the first law
equation reduces to:
Q W = [m (uf ui] system
(53)
45
5.2. Second Law of Thermodynamics

The second law of thermodynamics differentiates and quantifies processes that only
processed in a certain direction (irreversible) from those that are reversible. Reducing total
irreversibility in a cycle improves cycle performance. In the limit of no irreversibilities a
cycle attains its maximum ideal efficiency. In open system, the second law of
thermodynamics can be described in terms of entropy as:
dS
system
Q
T
misi mese dI
(54)
where: dSsystem is the total change within system in time dt during process; misi is the entropy
increase caused by mass entering (increasing); mese is the entropy decrease caused by mass
leaving (exiting); Q/T is the entropy change caused by reversible heat transfer between
system and surroundings at temperature T; dI is the entropy change caused by irreversibilities
(always positive).
Equation (54) accounts for all entropy changes in the system, Rearranged, this equation
becomes:
Q T [(mese misi) dSsystem dI ]
(55)
5.3. Thermodynamics and Refrigeration Cycles

In integration form, if inlet and outlet properties, mass flow and interactions with the
surroundings do not vary with time, the general equation for the second law is:
( Sf Si) system
rev
Q
T
(ms)in (ms)out I
(56)
In many applications, the process can be considered to operate steadily with no change in
time. The change in entropy of the system is therefore zero. The irreversibility rate, which is
the rate of entropy production caused by irreversibilities in the process, can be determined by
rearranging equation (56):
I (ms)out (ms)in
Q
Tsurr
(57)
Equation (57) is commonly applied to a system with one mass flow in, the same mass
flow out, no work and negligible kinetic or potential energy flows, combining equation (52)
and (57) yields:
46
Abdeen Mustafa Omer
I m( sout sin)
hout hin
Tsurr
(58)
In a cycle, the reduction of work producing by a power cycle (or the increase in work
required by a refrigeration cycle) equals the absolute ambient temperature multiplied by the
sum of irreversibilities in all processes in the cycle. Thus, the difference in reversible and
actual work for any refrigeration cycle, theoretical or real, operating under the same
conditions, becomes:
Wcatual Wreversible To I
(59)
5.4. Thermodynamic Analysis of Refrigeration Cycles

Refrigeration cycles transfer thermal energy from a region of low temperature TR to one
of higher temperature.
Usually the higher temperature heat sink is ambient air or cooling water, at temperature
To, the temperature of the surroundings. The first and second laws of thermodynamics can be
applied to individual components to determine mass and energy balances and the
irreversibility of components.
Performance of a refrigeration cycle is usually described by a coefficient of performance
(COP), defined as the benefit of the cycle (amount of heat removed) divided by the required
energy input to operate the cycle:
Ue
COP
(60)
Ne
where: Ue is the useful refrigeration effect, and Ne is the net energy supplied from external
sources.
COP
Q
W
evap
(61)
net
In an absorption refrigeration cycle, the net energy supplied is usually in the form of heat
into the generator and work into the pump and fans, or:
COP
evap
W net Q
(62)
gen
47
In many cases, work supplied to an absorption system is very small compared to the
amount of heat supplied to the generator, so the work term is often neglected. Applying the
second law to an entire refrigeration cycle shows that a completely reversible cycle operating
under the same conditions has the maximum possible COP. Departure of the actual cycle
from an ideal reversible cycle is given by the refrigerating efficiency:
COP
COP
(63)
rev
The Carnot cycle usually serves as the ideal reversible refrigeration cycle. For multistage
cycles, each stage is described by a reversible cycle.
5.5. Equation of State

The equation of state of a pure substance is a mathematical relation between pressure,
specific volume and temperature. When the system is in thermodynamic equilibrium:
f ( p, v, T ) 0
(64)
The principles of statistical mechanics are used to (1) explore the fundamental properties
of matter, (2) predict an equation of state based on the statistical nature of a particular system,
or (3) propose a functional form for an equation of state with unknown parameters of a
substance.
A fundamental equation with this basis is the virial equation, which is expressed as an
expression in pressure p or in reciprocal values of volume per unit mass v as:
pv
1 B' p C '
RT
D'
...
(65)
pv
2
3
1 B / v C / v D / v ...
RT
(66)
where coefficients B, C, D, etc., and B, C, D, etc., are the virial coefficients. B and B are
the second virial coefficients; C and C are the third virial coefficients, etc. The virial
coefficients are functions of temperature only and values of the respective coefficients in
equation (65) and (66) are related. For example, B=B/RT and C=(C-B2)/ (RT)2. The
universal gas constant R is defined as:
R' lim p 0
( pv' )T
T
(67)
48
Abdeen Mustafa Omer
where (pv)T is the product of the pressure and the molar specific volume along an isotherm
with absolute temperature T. The current best value of R is 8314.41 J/(kg mol-1 K). The gas
constant R is equal to the universal gas constant R divided by the molecular mass M of the
gas or gas mixture.
The quantity pv/RT is also called the compressibility factor Z, or:
Z 1 B / v C / v D / v ...
2
(68)
The Benedict-Webb-Rubin (B-W-R) equation has been extensively for hydrocarbons:
P ( RT / v) ( BoRT Ao Co / T ) / v (bRT a) / v
2
( /
(a / v [c(1 / v ) e
6
v )] /
vT
T C e
A B T C e
A B
(v b)
(v b)
T C e
T C e
A B
A B
(v b)
(v b)
(A B T)e
RT
P
vb
( kT / Tc )
( kT / Tc )
2
2
( kT / Tc )
3
3
( kT / Tc )
4
4
(69)
5
5
(70)
( av)
where the constant coefficients are A1, B1, C1, k, b and a.

The Strobridge equation is accurate within the uncertainty of the measured p-v-T data:
P RT p [ Rn1T n 2 nT 3 Tn24
( Rn 6T n 7) n8T
3
n5 ]
T4
[ n92 nT 130 nT 141 ] exp ( n1 6 )

T
5
2
6
[ n122 nT 133 nT 144 ] exp ( n1 6 ) n1 5
T
3
(71)
The 15 coefficients of this equations linear terms are determined by a least-square fit to
experimental data.
5.6. Calculating Thermodynamic Properties

Entropy may be considered a function of T and p and from calculus an infinitesimal
change in entropy can be written as:
ds (
s
s
) pdT ( )Tdp
T
p
49
(72)
Likewise, a change in enthalpy can be written as:
dh (
h
h
) pdT ( )Tdp
T
p
(73)
At least two intensive properties (properties independent of the quantity of substance,

such as temperature, pressure, specific volume and specific enthalpy) must be known to
determine the remaining properties. If two known properties are (p, v, or T) (these are
relatively easy to measure and are commonly used in simulations), the third can be
determined throughout the range of interest using an equation of state.
Using the Gibbs relation Tds = dh = vdp and the definition of specific heat at constant
pressure, Cp = (h/T)p, Equation (73) can be rearranged to yield:
ds (
Cp
dp
h
)dT [( ) p v]
T
T
p
(74)
Equation (72) and (74) combine to yield (s/T)p = cp/T. Then using the Maxwell
relation (s/p)T = -(v/T)p, Equation (72) may be written as:
ds (
Cp
v
)dT [( ) pdp
T
T
(75)
This is an expression for an exact derivative, so it follows that:
Cp
(
)T T ( v2 ) pdp
p
T
2
(76)
Table 5. Thermodynamic property values

State Temperature
(oC)
1
-20.0
2
2.8
3
0.0
4
33.6
5
30.0
6
0.0
7
0.0
8
-20.0
Pressure
(kPa)
132.73
292.80
292.80
770.20
770.20
292.80
292.80
132.73
Specific volume
(m3/kg)
0.14739
0.07097
0.06931
0.02726
0.00084
0.01517
0.000772
0.01889
Specific enthalpy
(kJ/kg)
386.55
401.51
398.60
418.68
241.72
241.72
200.00
200.00
Specific entropy
(kJ/(kg K)
1.7413
1.7413
1.7282
1.7282
1.1435
1.15297
1.0000
1.00434
50
Abdeen Mustafa Omer

Table 6. Measured and computed thermodynamic properties of R-22
Measured
Computed
State Temperature
(oC)
Pressure
(kPa)
Specific
Specific enthalpy (kJ/kg) Specific entropy
volume (m3/kg)
(kJ/(kg K)
1
2
3
4
5
6
7
310.0
304.0
1450.0
1435.0
1410.0
1405.0
320.0
0.07558
0.07946
0.02057
0.01970
0.00086
0.00086
0.019010
-10.0
-4.0
82.0
70.0
34.0
33.0
-12.8
402.08
406.25
454.20
444.31
241.40
240.13
240.13
1.7810
1.7984
1.8165
1.7891
1.1400
1.1359
1.1561
Table 7. Thermodynamic property data

t, (oC)
-20.0
37.8
30.0
-20.0
State
1
2
3
4
v, (m3/kg)
0.14739
0.02798
0.000842
0.047636
p, (kPa)
132.73
770.20
770.20
132.73
h, (kJ/kg)
386.55
423.07
241.72
241.72
s, (kJ/(kg K)
1.7413
1.7413
1.1435
1.1692
Table 8. Energy transfers and irreversibility rates for refrigeration system

Component
Evaporator
Suction line
Compressor
Discharge line
Condenser
Liquid line
Expansion device
Total
q, kW
7.000
0.1802
-0.4276
-0.4274
-8.7698
-0.0549
0
-2.4995
W, kW
0
0
2.5
0
0
0
0
2.5
I, W/K
0.4074
0.1575
2.1928
0.2258
0.8747
0.0039
0.8730
4.7351
I/Itotal (%)
9
3
46
5
18
0
18
Table 9. EU criteria pollutant standards in the ambient air environment

Pollutant
CO
NO2
O3
SO2
PM10
SO2 + PM10
Pb
Total suspended particulate (TSP)
HC
EU limit
30 mg/m2; 1h
200 g/m2; 1h
235 g/m2; 1h
250-350 g/m2; 24 h
80-120 g/m2; annual
250 g/m2; 24 h
80 g/m2; annual
100-150 g/m2; 24 h
40-60 g/m2; annual
2 g/m2; annual
260 g/m2; 24 h
160 g/m2; 3 h
51
Table 10. Significant EU environmental directives in water, air

and land environments
Environment
Water
Air
Land
Directive name
Surface water for drinking
Sampling surface water for drinking
Drinking water quality
Quality of freshwater supporting fish
Shellfish waters
Bathing waters
Dangerous substances in water
Groundwater
Urban wastewater
Nitrates from agricultural sources
Smokes in air
Sulphur dioxide in air
Lead in air
Large combustion plants
Existing municipal incineration plants
New municipal incineration plants
Asbestos in air
Sulphur content of gas oil
Lead in petrol
Emissions from petrol engines
Air quality standards for NO2
Emissions from diesel engines
Protection of soil when sludge is applied
Thermodynamic property data are summarised in Table 5. Table 6 lists the measured and
computed thermodynamic properties of the refrigerant, neglecting the dissolved oil. The
property data are tabulated in Table 7.
This result is within computational error of the measured power input to the compressor
of 2.5 kW. The analysis demonstrated in Table 8 can be applied to any actual Vapour
compression refrigeration system. The only required information for second law analysis is
the refrigerant thermodynamic state points and mass flow rates and the temperatures in which
the system is exchanging heat.
Technological progress has dramatically changed the world in a variety of ways. It has,
however, also led to developments of environmental problems, which threaten man and
nature. During the past two decades the risk and reality of environmental degradation have
become more apparent. Growing evidence of environmental problems is due to a combination
of several factors since the environmental impact of human activities has grown dramatically
because of the sheer increase of world population, consumption, industrial activity, etc.
throughout the 1970s most environmental analysis and legal control instruments concentrated
on conventional effluent gas pollutants such as SO2, NOx, CO2, particulates, and CO (Table
9). Recently, environmental concerns has extended to the control of micro or hazardous air
pollutants, which are usually toxic chemical substances and harmful in small doses, as well to
that of globally significant pollutants such as CO2. Aside from advances in environmental
science, developments in industrial processes and structures have led to new environmental
problems. For example, in the energy sector, major shifts to the road transport of industrial
goods and to individual travel by cars has led to an increase in road traffic and hence a shift in
attention paid to the effects and sources of NOx and volatile organic compound (VOC)
52
Abdeen Mustafa Omer
emissions. Environmental problems span a continuously growing range of pollutants, hazards

and ecosystem degradation over wider areas.
The main areas of environmental problems are: major environmental accidents, water
pollution, maritime pollution, land use and sitting impact, radiation and radioactivity, solid
waste disposal, hazardous air pollutants, ambient air quality, acid rain, stratospheric ozone
depletion and global warming (greenhouse effect, global climatic change) (Table 10). The
four more important types of harm from mans activities are global warming gases, ozone
destroying gases, gaseous pollutants and microbiological hazards (Table 11).
Table 11. The external environment
Damage
Manifestation
Design
NOx, SOx
Irritant
Acid rain land damage
Acid rain fish damage
Global warming
Rising sea level
Drought, storms
Increased ultra violet
Skin cancer
Crop damage
Pontiac fever
Legionnaires
Low NOx burners

Low sulphur fuel
Sulphur removal
Thermal insulation
Heat recovery
Heat pumps
No CFCs or HCFCs
Minimum air conditioning
Refrigerant collection
Careful maintenance
Dry cooling towers
CO2
O3 destruction
Legionnellosis
Table 12. Refrigerant/absorbent pairs

Refrigerant
H2O
NH3
TFE (organic)
SO2
Absorbents
Salts
Alkali halides
(LiBr, LiClO3, CaCl2, ZnCl2, ZnBr)
Alkali nitrates
Alkali thiocyanates
Bases
Alkali hydroxides
Acids (H2SO4, H3PO4)
H2O
Alkali thiocyanates
NMP
E181
DMF
Organic solvents
5.7. Thermodynamics and Refrigeration Cycles

However, one advantage of absorption cycles is they can maximise benefit from lowtemperature, high-glide heat sources. That ability derives from the fact that the desorption
process inherently embodies temperature glide, and hence can be tailored to match the heat
source glide. Similarly, absorption also embodies glide, which can be made to match the glide
of the heat rejection medium.
53
Table 12 lists refrigerant/absorbent pairs. Several appear suitable for certain cycles and
may solve some problems associated with tradition pairs. However, information on
properties, stability and corrosion is limited. Also, some of the fluids are somewhat
hazardous.
Integrating this expression at a fixed temperature yields:
Cpo
T ( v2 )dpT
Cp
T
o
(77)
where Cpo is the known zero-pressure specific heat and DpT is used to indicate that
integration is performed at a fixed temperature. The second partial derivative of specific
volume with respect to temperature can be used determined from the equation of state. Thus,
equation (77) can be used to determine the specific heat at any pressure.
Using Tds = dh-vdp, and equation (76) can be written as:
dh CpdT [ v T (
v
) pdp
T
(78)
Equations (74) and (78) may be integrated at constant pressure to obtain:

T1
s (T 1, Po) s (To, Po)
To
Cp
)dTp
T
(79)
and
T1
h(T 1, Po) h(To, Po) CpdT
(80)
To
Integrating the Maxwell relation (s/p)T = - (v/T)p gives an equation for entropy
changes at a constant temperature as:
p1
s (T 0, P1) s (To, Po) (

po
v
)dpT
T
(81)
Likewise, integrating equation (78) along an isotherm yields the following equation for
enthalpy changes at a constant temperature:
p1
h(T 0, P1) h(To, Po) [ v T (

po
v
) p ]dp
T
(82)
Therefore, the Clapeyron equation is of particular value; for equation evaporation or

condensation, it gives:
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Abdeen Mustafa Omer
dp
sfg
hfg
) ( ) sat (
)
dT
vfg
Tvfg
(83)
where: Sfg is the entropy of vaporisation; hfg is the enthalpy of vaporisation; and vfg is the
specific volume difference between vapour and liquid phases.
5.7.1. Phase Equilibria for Multi-Component Systems

To understand phase equilibria, consider a container full of a liquid made of two
components; the more volatile component is designated i and the less volatile component j
(Figure 9A). Heat added at a constant pressure raises the mixtures temperature and a
sufficient increase causes vapour to form, as shown in Figure 2B. If heat at constant pressure
continues to be added, eventually the temperature becomes so high that only vapour remains
in the container (Figure 9C).
Figure 10 is a typical T-x diagram valid at a fixed pressure. The case shown in Figure 9A,
a container full of liquid mixture with mole fraction xi,o at temperature To, is point 0 on the Tx diagram. Most mixtures have T-x diagrams that behave in this fashion, but some have a
markedly different feature. If the dew-point and bubble-point curves intersect at any point
other than at their ends, the mixture exhibits azeotropic behaviour at that composition. This
case is shown as position a in the T-x diagram of Figure 11.
Figure 9. Mixture of i and j component in constant pressure container.
5.7.2. Carnot Cycle

The Carnot cycle, which is completely reversible, is a perfect model for a refrigeration
cycle operating between two fixed temperatures, or between two fluids at different
temperatures and each with infinite heat capacity. Reversible cycles have two important
properties: (1) no refrigerating cycle may have a coefficient of performance higher than that
for a reversible cycle operated between the same temperature limits and (2) all reversible
cycles, when operated between the same temperature limits, have the same coefficient of
performance. Figure 12 shows the Carnot cycle on temperature-entropy coordinates. Heat is
withdrawn at constant temperature TR from the region to be refrigerated.
Figure 10. Temperature concentration (T-x) diagram zerotropic mixture.
Figure 11. Azerotropic behaviour shown on T-x diagram.
55
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Abdeen Mustafa Omer
Figure 12. Carnot refrigeration cycle.
Qo = To (S2-S3)
Qi = TR (s1-S4) = TR (S2-S3)
Wnet = Qo-Qi
Thus, by equation (62):
COP
(84)
T R
o
Flow of energy and its area representation in Figure 13 are:

Energy
Qi
Qa
W
kJ
125
150
25
Area
a
a+b
a
The Carnot cycle in Figure 14 shows a process in which heat is added and rejected at
constant pressure in the two-phase region of a refrigerant. Saturated liquid at state 3 expands
isentropically to the low temperature and pressure of the cycle at state d. heat is added
isothermally and isobarically by evaporating the liquid-phase refrigerant from state d to
state 1.
The cold saturated vapour at state 1 is compressed isentropically to the high temperature
in the cycle at state b.
However, the pressure at state b is below the saturation pressure corresponding to the
high temperature in the cycle. The compression process is completed by an isothermal
compression process from state b to state c. the cycle is completed by an isothermal and
isobaric heat rejection or condensing process from state c to state 3. Applying the energy
equation for a mass of refrigeration m yields (all work and heat transfer are positive.
57
Figure 13. Temperature-entropy diagram for Carnot refrigeration cycle.

3Wd
= m (h3-hd)
(85a)
1Wb
= m (hb-h1)
(85b)
bWc
= To (sb-sc) m (hb-hc)
(85c)
dQ 1
= m (h1-hd) = Area def1d
(85d)
The net work for the cycle is:

Wnet = 1Wb + bWc 3Wd = Area d1bc3d
(85e)
and
COP
Q1
TR
Wnet T o T R
d
(85f)
5.7.3. Theoretical Single-Stage Cycle Using a Pure Refrigerant or Azeotropic Mixture

A system designed to approach the ideal model shown in Figure 14 is desirable.
A pure refrigerant or azeotropic mixture can be used to maintain constant temperature
during phase changes by maintaining constant pressure. Because of concerns such as high
initial cost and increased maintenance requirements, a practical machine has one compressor
instead of two and the expander (engine or turbine) is replaced by a simple expansion valve,
which throttles refrigerant from high to low pressure.
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Abdeen Mustafa Omer
Figure 14. Carnot vapours compression cycle.
Figure 15 shows the theoretical single-stage cycle used as a model for actual systems.
Applying the energy equation for a mass m of refrigerant yields:
= m (h1-h4)
(86a)
1W2
= m (h2-h1)
(86b)
2Q3
= m (h2-h3)
(86c)
4Q1
h3 = h4
(86d)
Constant-enthalpy throttling assumes no heat transfer or change in potential or kinetic

energy through the expansion valve.
The coefficient of performance is:
COP
Q1
1W 2
4
h h
h h
1
(87)
The theoretical compressor displacement (CD) (at 100% volumetric efficiency) is:
CD = mv1
(88)
Table 13. Thermodynamic property data for figure 17
state
1
2
3
4
t, oC
-20.0
37.8
30.0
-20.0
p, kPa
132.73
770.20
770.20
132.73
v, m3/kg
0.14739
0.02798
0.000842
0.047636
h, kJ/kg
386.55
423.07
241.72
241.72
s, kJ(kg.K)
1.7413
1.7413
1.1435
1.16918
59
Figure 15. Theoretical single-stage vapours compression refrigeration cycle.
Figure 16 shows a schematic p-h diagram for the problem with numerical property data.
The property data are tabulated in Table 13. The saturation temperatures of the single-stage
cycle strongly influence the magnitude of the coefficient of performance (Figure 17).
5.7.4. Lorenz Refrigeration Cycle

The Carnot refrigeration cycle includes two assumptions that make it impractical. Figure
18 is a schematic of a Lorenz cycle.
Qo = (To + T/2) (S2-S3)
(89a)
Q1 = (TR T/2) (S1-S4) = (TR-T/2) (S2-S3)
(89b)
Wnet = Qo QR
(89c)
COP
T (T / 2)
T T T
R
(89d)
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Abdeen Mustafa Omer
Figure 16. Schematic p-h diagrams for the problem with numerical property data.
Figure 17. Areas on T-s diagrams representing refrigerating effect and work supplied for theoretical
single-stage cycle.
A practical method to approximate the Lorenz refrigeration cycle is to use a fluid mixture
as the refrigerant and the four system components. When the mixture is not azeotropic and
phase change occurs at constant pressure, the temperatures change during evaporation and
condensation and the theoretical single-stage cycle can be shown on T-s coordinates as
Figure 19.
61
Figure 18. Processes of Lorenz refrigeration cycle.
Figure 19. Areas on T-s diagrams representing refrigerating effect and work supplied for theoretical
single-stage cycle using Zerotropic mixture as refrigerant.
5.7.5. Multistage Vapour Compression Refrigeration Cycles

Multistage or multipressure vapour compression refrigeration is used when several
evaporators are needed at various temperatures, such as in a supermarket, or when evaporator
temperature becomes very low.
Thermodynamic analysis of multistage cycles is similar to analysis of single-stage cycles,
except that mass flow differs through various components of the system. For multistage
cycles, the expression for the coefficient of performance should be written as:
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Abdeen Mustafa Omer
COP
Qf
Wnet
(90)
When compressors are connected in series, the vapour between stages should be cooled
to bring the vapour to saturated conditions before proceeding to the next stage of
compression. Intercooling usually minimises the displacement of the compressors, reduces
the work requirement, and increases the COP of the cycle. If the temperature is below
ambient, which is the usual case, the refrigerant itself must be used to cool the vapour. This is
accomplished with a flash intercooler. Figure 20 shows a cycle with a flash intercooler
installed.
Figure 20. Schematic and pressure-enthalpy diagram for dual-compression, dual-expansion cycles.
63
5.7.6. Actual Refrigeration Systems

Actual systems operating steadily differ from the ideal cycles considered. Refrigerant
pressures and temperatures are measured at seven locations shown in Figure 21. An aircooled, direct-expansion, single-stage mechanical vapour-compression refrigerator uses R-22
and operates under steady condition.
A pressure-enthalpy diagram of cycle is shown in Figure 22. The following performance
data are obtained:
Ambient air temperature

Refrigerated space temperature
Refrigeration load
Compressor power input
Condenser fan input
Evaporator fan input
to = 30oC
tg = -10oC
Qevap = 7.0 kW
Wcomp = 2.5 kW
WCF + 0.15 kW
WEV = 0.11 kW
Figure 21. Schematic of real, direct-expansion, single-stage mechanical vapour-compression

refrigeration system.
6. THERMODYNAMICS AND REFRIGERATION CYCLES

The following cycles are summarised:
6.1. Absorption Refrigeration Cycles

An absorption cycle is a heat activated thermal cycle. It exchanges only thermal energy
with its surroundings; no appreciate mechanical energy is changed. Absorption cycles are
used in applications where one or more of the exchanges of heat with the surroundings is the
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Abdeen Mustafa Omer
useful product (e.g., refrigeration, air conditioning and heat pump). The two great advantages
of this type of cycle in comparison to other cycles with similar product are:
Figure 22. A pressure-enthalpy diagram of cycle.
No large, rotating mechanical equipment is required.

Any source of heat can be used, including low-temperature sources (e.g., waste heat).
6.2. Ideal Thermal Cycle

All absorption cycle include at least three thermal energy exchanges with their
surroundings (i.e., energy exchanger at three different temperatures). The highest and lowesttemperature heat flows are in one direction and the mid-temperature one (or two) is in the
opposite direction. In the forward cycle, the extreme (hottest and coldest) heat flows are into
the cycle. Figure 23 illustrated both types of thermal cycles.
This fundamental constraint of heat flow into or out of the cycle at three or more different
temperatures established the first limitation on cycle performance. By the first law of
thermodynamics (at steady state):
heat
cold
mid
(91)
(Positive heat quantities are into the cycle)

The second law requires that:
Q
T
hot
hot
Q
T
cold
cold
Q
T
mis
mist
with equality holding in the ideal case.
(92)
65
Figure 23. Thermal cycles.
From these two laws alone (i.e., without invoking any further assumptions) it follows
that, for the ideal forward cycle:
COPideal
Q
Q
cold
The heat ratio
(T hot Tmid )
hot
Q
Q
cold
hot
T cold
(T
mid
T cold )
(93)
is commonly called the coefficient of performance (COP), which is
hot
the cooling realised divided by the driving heat supplied.

Heat rejected to ambient may be at two different temperatures, creating a fourtemperature cycle. The ideal COP of the four-temperature cycle is also expressed by equation
(93), with Tmid signifying the entropic mean heat rejection temperature. In that case, Tmid is
calculated as follows:
Q
Tmid
Q
T
midhot
midhot
midhot
midcold
midcold
midcold
This expression results from assigning all the entropy flow to the single Tmid.
(94)
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Abdeen Mustafa Omer
The ideal COP for the four-temperature cycle requires additional assumptions, such as
the relationship between the various heat quantities. Under the assumptions that
and Q hot Q
the following expression results:
Q cold Q
midcold
mihot
(T hot Tmidhot)
COPiideal
x T cold x T cold
hot
midcold
(95)
midcold
Working fluid phase change constraints

Absorption cycles require at least two working substances: a sorbent and a fluid
refrigerant, these substances undergo phase changes. As illustrated in Figure 24, the
refrigerant phase changes occur in an evaporator and a condenser and the sorbent phase
changes in an absorber and desorber (generator). For the forward absorption cycle, the
highest-temperature heat is always supplied to the generator.
heat
gen
(96)
and the coldest heat is supplied to the evaporator:
cold
evap
(97)
The second result of the phase change constraint is that, for all known refrigerants and
sorbents over pressure ranges of interest.
cond
evap
(98)
and
gen
abs
(99)
The ideal single-effect forward-cycle COP expression is:
COPiideal
(T gen Tabs)
gen
T evap
(T
midcold
T evap)
x T cond
(100)
abs
Practical liquid absorbents for absorption cycles have a significant negative deviation
from behaviour predicted by Raoults law. This has the beneficial effect of reducing the
required amount of absorbent recirculation, at the expense of reduced lift (Tcond-Tevap) and
increased sorption duty. In practical terms, most absorbents:
67
Figure 24. Single-effect absorption cycle.
Q
Q
(101)
1.2to1.3
abs
condt
and
gen
T abs 1.2(T
cond
T evap)
(102)
The net result of applying these approximations and constraints to the ideal-cycle COP
for the single-effect forward cycle is:
COPideal 1.2
(T evap Tcond)
T gen Tabs
Q
(Q
cond
0.8
(103)
abs
In practical terms, the temperature constraint reduces the ideal COP to 0.9 and the heat
quantity constraint further reduces it to 0.8. Another useful result is:
gen min
T cond T abs T evap
(104)
Alternative approaches are available that lead to nearly the same upper limit on idealcycle COP. This leads to the expression:
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Abdeen Mustafa Omer
COPideal
(T evap)
abs
T
(T
cond
(105)
gen
6.3. Working Fluids

Working fluids for absorption cycles fall into four categories, each requiring a different
approach to cycle modelling and thermodynamic analysis. Liquid absorbents can be nonvolatile (i.e., vapour phase is always pure refrigerant, neglecting condensables) or volatile
(i.e., vapour concentration varies, so cycle and component modelling must track both vapour
and liquid concentration). Solid sorbents can be grouped by whether they are physisorbents
(also known as absorbents), for which, as for liquid absorbents, sorbent temperature depends
on both pressure and refrigerant loading (bivariance) or chemisorbents, for which sorbent
temperature does not vary with loading at least over small ranges. Beyond these distinctions,
various other characteristics are either necessary or desirable for suitable liquid
absorbent/refrigerant pairs as follows:
6.3.1. Absence of Solid Phase (Solubility Field)

The refrigerant/absorbent pair should not solidify over the expected range of composition
and temperature. If a solid forms, it will stop flow and shut down equipment. Controls must
prevent operation beyond the acceptable solubility range.
6.3.2. Relative Volatility
The refrigerant should be much more volatile than the absorbent so the two can be
separated easily. Otherwise, cost and heat requirements may be excessive. Many absorbents
are effectively non-volatile.
6.3.3. Affinity
The absorbent should have a strong affinity for the refrigerant under conditions in which
absorption takes place.
Strong affinity allows less absorbent to be circulated for the same refrigeration effect,
reducing sensible heat losses, and allows a smaller liquid heat exchanger to transfer heat from
the absorbent to the pressurised refrigerant/absorption solution. On the other hand, as affinity
increases, extra heat is required in the generators to separate refrigerant from the absorbent
and the COP suffers.
6.3.4. Pressure
Operating pressures established by the refrigerants thermodynamic properties should be
moderate.
High pressure requires heavy-walled equipment and significant electrical power may be
needed to pump fluids from the low-pressure side to the high-pressure side. Vacuum requires
large-volume equipment and special means of reducing pressure drop in the refrigerant
vapour paths.
69
6.3.5. Corrosion
Most absorption fluids corrode materials used in construction. Therefore, corrosion
inhibitors are used.
6.3.6. Stability
High chemical stability is required because fluids are subjects to severe conditions over
many years of services. Instability can cause undesirable formation of gases, solids or
corrosive substances. Purity of all components charged into the system is critical for high
performance and corrosion prevention.
6.3.7. Safety
Precautions as dictated by code are followed when fluids are toxic, inflammable or at
high pressure. Codes vary according to country and region.
6.3.8. Transport Properties
Viscosity, surface tension, thermal diffusivity and mass diffusivity are important
characteristics of the refrigerant/absorbent pair. For example, low viscosity promotes heat and
mass transfer and reduces pumping power.
6.3.9. Latent Heat
The refrigerant latent heat should be high so the circulation rate of the refrigerant and
absorbent can be minimised.
6.4. Eco-Friendly Natural Refrigerants

Over the years, all parts of a commercial refrigerator, such as the compressor, heat
exchangers, refrigerant, and packaging, have been improved considerably due to the extensive
research and development efforts carried out by academia and industry. However, the
achieved and anticipated improvement in conventional refrigeration technology are
The word green designates more than a colour. It is a way of life, one that is becoming more
and more common throughout the world. An interesting topic on sustainable technologies for
a greener world details about what each technology is and how it achieves green goals.
grows.
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Abdeen Mustafa Omer
The word green designates more than a colour. It is a way of life, one that is becoming
more and more common throughout the world. An interesting topic on sustainable
technologies for a greener world details about what each technology is and how it achieves
green goals. Over the years, all parts of a commercial refrigerator, such as the compressor,
heat exchangers, refrigerant, and packaging, have been improved considerably due to the
extensive research and development efforts carried out by academia and industry. However,
the achieved and anticipated improvement in conventional refrigeration technology are
grows. On hot summer days in particular, many of us appreciate a refreshing drinks. The
word green designates more than a colour. It is a way of life that is becoming more and
more common throughout the world.
6.4.1. Ozone Depletion Potential (ODP)

The ozone layer is damaged by the catalytic action of chlorine, fluorine and bromine in
compounds, which reduce ozone to oxygen and thus destroy the ozone layer (Table 14). The
ozone depletion potential (ODP) of a compound is shown as chlorine equivalent (ODP of a
chlorine molecule = 1).
6.4.2. Global Warming Potential (GWP)
The greenhouse effect arises from the capacity of materials in the atmosphere to reflect
the heat emitted by the earth back onto the earth. The direct global warming potential (GWP)
of a compound is shown as a CO2 equivalent (GWP of a CO2 molecule = 1)
The reason for this is green technology helps to sustain life on earth. This not only
applies to humans but to plants, animals and the rest of the ecosystem. Energy prices and
consumption will always be on an upward trajectory. In fact, energy costs have steadily risen
over last decade and are expected to carry on doing so as consumption grows (Tables 15-17).
Today, buildings are largest consumers of energy. Air conditioning and heating consume
about 40% of the power in the buildings. Demand to conserve energy has become necessity as
there has been rising costs of energy consistently and this make us to think to go green and
innovate the greener concept for buildings. A green building uses less water, optimises energy
efficiency, conserves natural resources, generates less waste and provides healthier spaces for
occupants. And, a green home can have benefits, such as reduction in water and operating
energy costs of the building.
71
Table 14. Global warming potential (GWP)

Subject
Ammonia (NH3)
Carbon dioxide (CO2)
Hydrocarbons (propane C3H8, propene C3H6, isobutene C4H10)
Water (H2O)
Chlorofluoro-hydrocarbons (CFCs)
Partially halogenated Chlorofluoro-hydrocarbons (HCFCs)
Per-fluorocarbons (PFCs)
Partially halogenated fluororinated-hydrocarbons (HFCs)
Ozone depletion
potential (ODP)
0
0
0
0
1
0.02-0.06
0
0
Global warming
potential (GWP)
0
1
<3
0
4680-10720
76-12100
5820-12010
122-14310
Table 15. Energy saving in terms of MW/h and economic saving % for annual operation
between an intelligent free-cooling system and traditional free-cooling
City
Frankfurt
Rome
Milan
Manchester
Paris
Amsterdam
Stockholm
Madrid
Berlin
London
Copenhagen
Energy saving (kWh)

34560
31587
29132
46008
36954
42558
28167
36743
31525
46018
38077
Energy saving (%)

5%
3%
4%
6%
4%
7%
5%
4%
4%
6%
6%
Table 16. Comparison between the energy consumption of standard chillers, freecooling chillers and intelligent free-cooling (Absorbed power (MWh))
City
Frankfurt
Rome
Milan
Manchester
Paris
Amsterdam
Stockholm
Madrid
Berlin
London
Copenhagen
Standard chillers
1107
1245
1144
1116
1178
1062
1001
1204
1088
1103
1061
Free-cooling chillers
747
1056
815
789
910
651
541
938
707
154
638
Intelligent free-cooling
712
1025
786
743
873
609
513
902
676
708
599
This may also mean refrigerant-based chillers and compressors to be shut off or to be
operated at reduced capacity. With the environmental protection posing as the number one
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Abdeen Mustafa Omer
global problem, man has no choice but reducing his energy consumption, one way to
accomplish this is to resort to passive and low-energy systems to maintain thermal comfort in
buildings.
Traditionally hot water generators have been used to generate hot water, which are either
fossil fuel fired like gas, oil, etc., or steam fired (Tables 18-21).
Table 17. Comparison between the energy consumption of standard chillers and
intelligent free-cooling
City
Frankfurt
Rome
Milan
Manchester
Paris
Amsterdam
Stockholm
Madrid
Berlin
London
Copenhagen
Standard chillers (MWh)

394
220
357
373
304
452
487
301
411
394
462
Intelligent free-cooling (%)

36%
18%
31%
33%
26%
43%
49%
25%
38%
36%
44%
Table 18. Energy consumption and corresponding expenses occurred

Per day
Water cooler system Energy
(W)
Conventional water
cooler with air
4.6
cooled condenser
Modified water
cooler with water
3.94
cooled condenser
Per day
Expenditure
($)
Per month Per month

Per year
Per year
Energy
Expenditure
Expenditure
Energy (W)
(W)
($)
($)
19.32
138
743.4
1656
8920.8
16.55
118.2
658.26
1418.4
7899.12
The conventional and modern designs of wind towers can successfully be used in the hot
arid regions to maintain thermal comfort (with or without the use of ceiling fans) during all
hours of the cooling season, or a fraction of it. Climatic design is one of the best approaches
to reduce the energy cost in buildings. Proper design is the first step of defence against stress
of climate. Buildings should be designed according to climate of the site for reducing the need
of mechanical heating or cooling hence maximum natural energy can be used for creating
pleasant environment inside the built envelope. Technology and industry progress of the last
decade diffused electronic and informatics devices in many human activities and now appear
also in building construction. The utilisation and operating opportunities components,
increase the reduction of heat losses by varying the thermal insulation, optimise the lighting
distribution with louver screens and operate mechanical ventilation for coolness in indoor
spaces. In addiction to these parameters the intelligent envelope can act for security control
73
and became an important part of the building demotic revolution. Application of simple
passive cooling measure is effective in reducing the cooling load of buildings in hot and
humid climates. 43% reductions can be achieved using a combination of well-established
technologies such as glazing, shading, insulation, and natural ventilation. More advanced
passive cooling techniques such as roof pond, dynamic insulation, and evaporative water
jacket need to be considered more closely.
The building sector is a major consumer of both energy and materials worldwide, and the
consumption is increasing. Most industrialised countries are in addition becoming more and
more dependent on external supplies of conventional energy carriers, i.e., fossil fuels. Energy
for heating and cooling can be replaced by new renewable energy sources. New renewable
energy sources, however, are usually not economically feasible compared with the traditional
carriers. In order to achieve the major changes needed to alleviate the environmental impacts
of the building sector, it is necessary to change and develop both the processes in the industry
itself, and to build a favourable framework to overcome the present economic, regulatory and
institutional barriers.
The greenhouse effect is one result of the differing properties of heat radiation when it is
generated at different temperatures. Objects inside the greenhouse, or any other building, such
as plants, re-radiate the heat or absorb it. Because the objects inside the greenhouse are at a
lower temperature than the sun, the re-radiated heat is of longer wavelengths, and cannot
penetrate the glass. This re-radiated heat is trapped and causes the temperature inside the
greenhouse to rise. Note that the atmosphere surrounding the earth, also, behaves as a large
greenhouse around the world.
Table 19. High efficiency chiller heater
Description
Units
Cooling capacity, i.e., Q1

Chilled water temperature profile
Chilled water flow rate
Heating capacity, i.e., Q3
Hot water temperature profile
Hot water flow rate
Fuel type
Steam pressure
Fuel consumption
For chilling
For heating
External heat input i.e., Q2
Cooling water inlet temperature
Cooling water flow
Cooling tower rejection i.e., Q4
Cooling COP considering no saving in
heating
Hot water generator or

High
conventional chiller heater efficiency
chiller heater
TR
100
100
kW
352
352
o
C
12/7
12/7
3
m /h
60.5
60.5
kW
260
260
o
C
80-90
80-90
m3/h
22.9
22.9
Steam
Steam
kg/cm2 g 8
8
kg/h
kg/h
kW
o
C
m3/h
kW
380
391
251
32
100
Q1+Q2
603
1.40
380
235
406
32
100
Q1+Q2-Q3
498
2.4
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Abdeen Mustafa Omer

Table 20. Gas based operation
Description
Units
Compression chiller
Chiller heater
Chilling capacity
TR
100
100
Heating capacity
kW
260
260
Energy source for chilling
Electricity
Natural gas
Energy source for heating
Natural gas
Natural gas
Natural gas consumption for chilling
Nm3/h
26.3
3
Natural gas consumption for heating
Nm /h
27.2
16.3
Total natural gas consumption
Nm3/h
27.2
42.6
Cooling tower duty
Electrical power requirement
Cooling tower fan
kW
3.0
3.7
Chiller power
kW
80.0
5.6
Total power
kW
83.0
9.3
Gas cost
$/Nm3
30.0
30.0
Electrical power rate
$/kWh
8.0
8.0
Hourly operational cost
Gas cost
$/h
816
1278
Electrical power cost
$/h
664
1278
Total hourly operational cost
$/h
1480
75
Hourly saving
$/h
127
127
Assumptions: natural gas calorific value 9650 kCal/Nm3, burner efficiency 85%, and higher power cost
because of commercial applications.
Table 21. Steam based operation

Description
Chilling capacity
Heating capacity
Energy source for chilling
Energy source for heating
Steam consumption for chilling
Steam consumption for heating
Total Steam consumption
Cooling tower duty
Electrical power requirement
Cooling tower fan
Chiller power
Total power
Steam cost
Electrical power rate
Hourly operational cost
Gas cost
Electrical power cost
Total hourly operational cost
Hourly saving
Units
TR
kW
kg/h
kg /h
Kg/h
Compression chiller
100
260
Electricity
Steam
391
432
Chiller heater
100
260
Steam
Steam
380
235
498
kW
kW
kW
$/Nm3
$/kWh
3.0
70.0
73.0
0.75
6.0
3.7
3.0
6.7
0.75
6.0
$/h
$/h
$/h
$/h
293.25
438
731.25
229.75
461.25
40.2
501.5
229.75
75
Changes to the gases in the atmosphere, such as increased carbon dioxide content from
the burning of fossil fuels, can act like a layer of glass and reduce the quantity of heat that the
planet earth would otherwise radiate back into space. This particular greenhouse effect,
therefore, contributes to global warming. The application of greenhouses for plants growth
can be considered one of the measures in the success of solving this problem. Maximising the
efficiency gained from a greenhouse can be achieved using various approaches, employing
different techniques that could be applied at the design, construction and operational stages.
The development of greenhouses could be a solution to farming industry and food security.
6.4.3. Vapour Absorption Chiller Heater

Three important indices of energy efficiency are:
Specific electric power (SP) (kW of electric power input per tone of refrigeration =
kW/TR).
Energy efficiency ratio (EER) = cooling load in W/electric input in W
Expressed in W/W it is generally in the range of 2.3 to 3.1.
The coefficient of performance (COP) is given by:

COP = 3.516/ (kW/TR)
Table 22 gives the energy efficiency performance of typical split and window ACs.
Table 22. Inherent energy efficiency
Particular
Nominal capacity (TR)
EER (W/W)
SP (kW/TR)
EER (W/W)
SP (kW/TR)
Window ACs
1.5
2.80
1.26
2.80
1.20
Split ACs
2.0
2.50
1.30
2.48
1.23
Advantages of water/lithium bromide include high (1) safety, (2) volatility ratio, (3)
affinity, (4) stability and (5) latent heat. However, this pair tends to form solids and operates
at deep vacuum. Because the refrigerant turns to ice at 0oC, it cannot be used for lowtemperature refrigeration.
6.5. Absorption Cycle Representations

The quantities of interest to absorption cycle designers are temperature, concentration,
pressure and enthalpy. The most useful plots use linear scales and plot the key properties as
straight lines. Some of the following plots are used:
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Abdeen Mustafa Omer
Absorption plots embody the vapour-liquid equilibrium of both the refrigerant and
the sorbent. Plots on linear pressure-temperature coordinates have a logarithmic
shape and hence are little used.
The Duhring (solution temperature versus reference temperature) retains the
linearity. The primary drawback is the need for a reference substance (Figure 25).
Temperature-entropy coordinates are occasionally used to relate absorption cycles to
their mechanical vapour compression counterparts.
Figure 25. Double-effect absorption cycle.
Table 23. Assumptions for single-effect water/lithium bromide model

Assumptions
Generator and condenser as well as evaporator and absorber are under same
pressure
Refrigerant vapour leaving the evaporator is saturated pure water
Liquid refrigerant leaving the condenser is saturated
Strong solution leaving the generator is boiling
Refrigerant vapour leaving the generator has the equilibrium temperature of the
weak solution at generator pressure
Weak solution leaving the absorber is saturated
No liquid carryover from evaporator
Flow restrictors are adiabatic
Pump is isentropic
No jacket heat losses
The LMTD (log mean temperature difference) expression adequately estimates the
latent changes
77
Figure 26. Generic triple-effect cycles.
Figure 26 shows a double-effect absorption cycle formed by coupling the absorbers and
evaporators of two single-effect cycles into an integrated, single hermetic cycle. Figure 27
shows twelve generic triple-effect cycles. Table 23 shows a simulation of the chiller starts by
specifying the assumptions and the design parameters and operating conditions at the design
point (Table 24).
Figure 27. Single-effect water/lithium bromide absorption cycle.
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Figure 28 shows double-effect water/lithium bromide absorption cycle with state points.
Figure 29 shows single-effect ammonia/water absorption cycle.
With the assumptions and the design parameters and operating conditions as specified in
Table 24, the cycle simulation can be conducted by solving the following set of equations
Figure 28. Double-effect water/lithium bromide absorption cycle with state points.
Figure 29. Single-effect ammonia/water absorption cycle.
79
Table 24. Design parameters and operating conditions for single-effect water/lithium
bromide absorption chiller
Item
Evaporator
Condenser
Absorber
Generator
Solution
General
Design parameters
USevap = 319.2 kW/K, countercurrent film
UScond = 180.6 kW/K, countercurrent film
USabs = 186.9 kW/K, countercurrent filmabsorber
USgen = 143.4 kW/K, countercurrent
USsol = 33.8 kW/K, pool-generator
mweak = 12 kg/s
Operating conditions
tchill in = 12oC
tchill out = 6oC
tcool out = 35oC
tcool in = 27oC
mhot = 74.4 kg/s
Qevap = 2148 kW
6.5.1. Mass Balances
refr
mstron mweak
strong
strong
(106)
mweak weak
(107)
6.5.2. Energy Balances
mrefr (hvapour,evap hliq,cond)
mchill (hchillin hchillout)
evap
evap
(108)
mrefr (hvapour, gen hliq,cond)
Q
Q
mcool (hcoolout hcoolmean)
mrefr hvapour,evap mstrong hstrong, gen mweak hweak,abs Q
mcool (hcoolout hcoolmean)
evap
evap
abs
(109)
sol
evap
(110)
gen
mrefr hvapour, gen mstrong hstrong, gen mweak hweak,abs Q
hot
mcool (hhotin hhotout)
mstrong (hstrong, gen hstrong,sol)
sol
sol
(111)
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Abdeen Mustafa Omer
sol
mweak (hweak,sol hweak,abs)
(112)
6.5.3. Heat Transfer Equations

(
)
Qevap UAevap ( t chillin t chillout )
t chillin t vapour,evap )
ln(
(t
cond
UAcond
abs
UAabs
(t liq,cond t coolmean)
(t
liq ,cond
gen
UAgen
sol
UAsol
coolout
(t strong,abs t coolmean)
(t
weak, abs
(t hotins t strong, gen)
(t
hotout
(116)
weak, gen
(t strong, gen t weak, sol) (t strong, sol t weak,abs)

ln(
(t strong, gen t weak, sol)
(t
strong, sol
(115)
coolin
(t hotin t strong, gen) (t hotout t weak, gen)

ln(
(114)
(t strong,abs t coolmean) (t weak,abs t coolin)

ln(
vapour,evap
(t coolout t coolmean)
ln(
chillout
(113)
(117)
weak, abs
Table 25. Simulation results for single-effect water/lithium bromide absorption chiller
Item
Evaporator
Condenser
Absorber
Generator
Solution
General
Internal parameters
t vapour evap = 1.8 oC
P out evap = 0.697 kPa
T liq cond = 46.2 oC
P sol cond = 10.2 kPa
weak = 59.6%
t weak = 40.7 oC
t strong abs = 49.9 oC
strong = 64.6%
t strong gen = 103.5 oC
t weak gen = 92.4 oC
t weak sol = 76.1 oC
t strong sol = 62.4 oC
t weak sol = 76.1 oC
m vapour = 0.93 kg/s
m strong = 11.06 kg/s
Performance parameters
Qevap = 2148 kW
m chill = 85.3 kg/s
Q cond = 2332 kW
m cool = 158.7 kg/s
Q abs = 2984 kW
t cool mean = 31.5 oC
Q gen = 3158 kW
t hot in = 125 oC
t hot cond = 115 oC
Q sol = 825 kW
= 65.4%
COP = 0.68
81
6.5.4. Fluid Property Equations at Each State Point

Thermal equations of state: h water (t, p), h sol (t, p, )
Two-phase equilibrium: t water out (p), t sol out (p, )
The results are listed in Table 25.
Table 26. Inputs and assumptions for double-effect water-lithium bromide model
Inputs
Capacity Q evap = 1760 kW
Evaporator temperature t10 = 5.1 oC
Desorber solution exit temperature t14 = 170.7 oC
Condenser/absorber low temperature t1, t8 = 42.4 oC
Solution heat exchanger effectiveness e = 0.6
Assumptions
steady state
refrigerant is pure water
no pressure changes except through flow restrictors and pump
state points at 1, 4, 8, 11, 14 and 18 are saturated
state point 10 is saturated vapour
temperature difference between high-temperature condenser and low-temperature generator is 5 K
parallel flow
both solution heat exchangers have same effectiveness
upper loop solution flow rate is selected such that upper condenser heat exactly matches lower generator heat
requirement
flow restrictors are adiabatic
pumps are isentropic
no liquid carryover from evaporator to absorber
vapour leaving both generators is at equilibrium temperature of entering solution stream
Table 27. State point data for double-effect lithium bromide/water cycle
Point
h (kJ/kg)
m (kg/s)
p (kPa)
Q Fraction
t (oC)
x (% LiBr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
117.7
117.7
182.3
247.3
177.2
177.2
2661.1
177.4
177.4
2510.8
201.8
201.8
301.2
378.8
270.9
270.9
2787.3
430.6
430.6
9.551
9.551
9.551
8.797
8.797
8.797
0.320
0.754
0.754
0.754
5.498
5.498
5.498
5.064
5.064
5.064
0.434
0.434
0.434
0.88
8.36
8.36
8.36
8.36
0.88
8.36
8.36
0.88
0.88
8.36
111.8
111.8
111.8
111.8
8.36
111.8
111.8
8.36
0.0
42.4
42.4
75.6
97.8
58.8
53.2
85.6
42.4
5.0
5.0
85.6
85.6
136.7
170.7
110.9
99.1
155.7
102.8
42.4
59.5
59.5
59.5
64.6
64.6
64.6
0.0
0.0
0.0
0.0
59.5
59.5
59.5
64.6
64.6
64.6
0.0
0.0
0.0
0.0
0.004
0.0
0.063
1.0
0.0
0.0
0.008
0.0
0.105
COP = 1.195 Q evap = 1760 kW

t = 5 K Q gen = 1472 kW
= 0.600 Q abs1 = 617 kW
Q abs = 2328 kW Q abs2 = 546 kW
Q gen = 1023 kW Wp1 = 0.043 kW
Q cond = 905 kW Wp2 = 0.346 kW
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Abdeen Mustafa Omer

Table 28. Inputs and assumptions for single-effect ammonia/water cycle
Inputs
Capacity Q evap = 1760 kW
High-side pressure p high = 1461 kPa
Low-side pressure p low = 515 kPa
Absorber exit temperature t1 = 40.6 oC
Generator exit temperature t4 = 59 oC
Rectifier vapour exit temperature t1 = 55 oC
Solution heat exchanger effectiveness shx = 0.692
Refrigerant heat exchanger effectiveness rhx = 0.629
Assumptions
steady state
no pressure changes except through flow restrictors and pump
state points at 1, 4, 8, 11 and 14 are saturated liquid
state point 12 and 13 are saturated vapour
flow restrictors are adiabatic
pumps are isentropic
no jacket heat losses
no liquid carryover from evaporator to absorber
vapour leaving both generators is at equilibrium temperature of entering solution stream
Table 29. State point data for single-effect ammonia/water cycle

Point
h (kJ/kg)
m (kg/s)
1
-57.2
10.65
2
-56.0
10.65
3
89.6
10.65
4
195.1
9.09
5
24.6
9.09
6
24.6
9.09
7
1349
1.55
8
178.3
1.55
9
82.1
1.55
10
82.1
1.55
11
1216
1.55
12
1313
1.55
13
1429
1.59
14
120.4
0.04
COP = 0.571 Q evap = 1760 kW
t rhx = 7.24 K Q gen = 3083 kW
t rhx = 16.68 K Q rhx = 149 kW
shx = 0.629 Q abs = 170 kW
rhx=0.692 Q shx = 1550 kW
Q abs = 2869 kW W = 12.4 kW
Wp1 = 0.043 kW
p (kPa)
515.0
1461
1461
1461
1461
515.0
1461
1461
1461
515.0
515.0
515.0
1461
1461
Q Fraction
0.0
0.006
1.000
0.0
0.049
0.953
1.000
1.000
0.0
t (oC)
40.56
40.84
78.21
95.00
57.52
55.55
55.00
37.82
17.80
5.06
6.00
30.57
79.15
79.15
x, fraction
NH3
0.50094
0.50094
0.50094
0.41612
0.41612
0.41612
0.99809
0.99809
0.99809
0.99809
0.99809
0.99809
0.99809
0.50094
83
Double-effect cycle calculations can be performed in a manner similar to that for the
single-effect cycle. Mass and energy balances of the model shown in Figure 28 were
calculated using the inputs and assumptions listed in Table 26. The results are shown in
Table 27.
Figure 29 shows the diagram of a typical single-effect ammonia/water absorption cycle.
The inputs and assumptions in Table 28 are used to calculate a single-cycle solution, which is
summarised in Table 29.
CONCLUSION
The building sector is a major consumer of both energy and materials worldwide, and the
consumption is increasing. Most industrialised countries are in addition becoming more and
more dependent on external supplies of conventional energy carriers, i.e., fossil fuels. Energy
for heating and cooling can be replaced by new renewable energy sources. New renewable
energy sources, however, are usually not economically feasible compared with the traditional
carriers. In order to achieve the major changes needed to alleviate the environmental impacts
of the building sector, it is necessary to change and develop both the processes in the industry
itself, and to build a favourable framework to overcome the present economic, regulatory and
institutional barriers. Today, buildings are largest consumers of energy. Air conditioning and
heating consume about 40% of the power in the buildings. Demand to conserve energy has
become necessity as there has been rising costs of energy consistently and this make us to
think to go green and innovate the greener concept for buildings. A green building uses less
water, optimises energy efficiency, conserves natural resources, generates less waste and
provides healthier spaces for occupants. And, a green home can have benefits, such as
reduction in water and operating energy costs of the building. This may also mean refrigerantbased chillers and compressors to be shut off or to be operated at reduced capacity. With the
environmental protection posing as the number one global problem, man has no choice but
reducing his energy consumption, one way to accomplish this is to resort to passive and lowenergy systems to maintain thermal comfort in buildings.
Naturally, it would be preferred, for comfort reasons that this index would be small,
preferably nil. It may be seen that the variable is directly related to temperature discomfort:
the larger the value of the index, the farthest will inside conditions be from expected
wellbeing. Also, the use of electricity operated air conditioning systems will be more
expensive the higher this variable is. Hence, energy expenditure to offset discomfort will be
higher when comparing two index values; the ratio of them is proportional to the expected
energy savings. When the external shade blocks the windowpane completely, the excessive
heat gains belong to the lowest values in the set, and the dimensionless index will be constant
with orientation. For the climate conditions of the locality, it can be seen that a naked window
can produce undesirable heat gains if the orientation is especially unfavourable, when the
index can have an increase of up to 0.3 with respect to the totally shaded window.
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Abdeen Mustafa Omer
TECHNICAL DEFINITION
Refrigeration
The achievement of a temperature below that of the immediate surroundings.
Latent Heat of Fusion

The quantity of heat (Btu/Ib) required changing 1 Ib of material from the solid phase into
the liquid phase.
Sensible Heat
Heat that is absorbed/rejected by a material, resulting in a change of temperature.
Latent Heat
Heat that is absorbed/rejected by a material resulting in a change of physical state
(occurring at constant temperature).
Saturation Temperature
That temperature at which a liquid starts to boil (or vapour starts to condense). The
saturation temperature (boiling temperature) is constant at a given pressure (except for
zoetrope refrigerant) and increase as the pressure increases. A liquid cannot be raised above
its saturation temperature. Whenever the refrigerant is present in two states (liquid and
vapour) the refrigerant mixture will be at the saturation temperature.
Subcooling
At a given pressure, the difference between a liquids temperature and its saturation
temperature.
Ton of Refrigeration
The amount of cooling required to change (freeze) 1 ton of water at 32oF into ice at 32oF,
in a 24 hour period.
85
Btu
British thermal unit: The amount of heat required to raise 1 Ib of water 1oF.
1 Ton
12,000 Btu/hr
Refrigeration Effect (RE)

This is the total heat transfer in Btu/Ib from the refrigeration space to the refrigerant.
Heat of Compression (HOC)

This is the amount of heat added to the refrigerant from the compression process.
Refrigerant Circulation Rate (RCR)

The amount of refrigerant in Ib/min, which must circulate in the system to meet the
demands of the load.
Compressor Horsepower Required

The horsepower/ton required to meet the load demand.
Heat of Rejection (HOR)

This is the amount of heat that has to be rejected at the condenser. The heat transferred to
the refrigerant from the refrigerated space (RE) and the heat transferred to the refrigerant
during compression (HOC).
Compressor Volume Required

The compressor cylinder volume required need to pump the RCR in cu ft/ton. The vapour
specific volume is read on the lines of constant volume.
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Abdeen Mustafa Omer
Compression Ratio
The ratio of absolute discharge pressure/absolute suction pressure. The compressor motor
amperage will increase as the compression ratio increases.
Discharge Temperature
A good measure of the relative health or sickness of the system.
Supplemental Heat Lockout

Outdoor thermostats sense the outdoor temperature and lock out the use of secondary
heating devices (supplemental heat) unless the temperature drops below a preset point (except
when the heat pump is not working and needs emergency heat). The advantage of this
strategy is that it is a positive lockout that will not be defeated by "thermostat fiddlers".
Smart Thermostats
Smart thermostats (microprocessor controlled) sense only the indoor temperature. They
will not turn on supplemental heat unless the heat pump is unable to keep the house at the
desired temperature. The advantage of this strategy is that it is tied to indoor comfort. There is
considerable debate about which is the better strategy. But either one is clearly better than no
lockout at all.
Staged Supplemental Heat

Most heat pumps have controls that cause all of the supplemental heat to be on at the
same time. However, there are important benefits to staging supplemental heat. Staging refers
to turning the supplemental heat on in two or more stages. The first stage comes on in mild
temperatures just below the heat pump balance point. If the temperature falls below a point
that the first stage is not enough, the second stage provides more heat. There are two
important benefits of staging supplemental heat. Firstly, is more comfortable and secondly, it
benefits utility ratepayers. One of the major costs of operating an electric utility is the cost of
"peak" power as defined by a high point of electrical customer demands. This peak occurs
during the winter when lots of heating systems need power. By staging the backup heat, the
utility's peak is likely to be lower, reducing utility operating costs. These savings are
particularly important when they can help to avoid the cost of expensive new electrical
generating facilities. Depending on the control system, staging supplemental heat may reduce
the on/off cycles of the heat pump. Reduced cycling can increase the longevity of the heat
pump.
87
Staging supplemental heat increases the comfort of a heat pump. As it gets colder outside
the refrigeration components produce less heat, so then, when the supplemental heat is not on,
the temperature of the air coming out of the registers gets lower as it gets colder outside. The
supplemental heat adds more heat to the air, making it more comfortable. If all supplemental
heat comes on at once, it may run only for a short time. The delivered air temperature drops
as soon as it goes off. When only one stage of supplemental heat comes on, it stays on longer.
Staged supplemental heat provides higher temperature air for longer periods of time, so the
house will be more comfortable during winter cold spells.
Defrost Control
There are many types of defrost controls. They can be grouped into two categories. First,
is the time and temperature and, second is the demand. Time and temperature controls turn on
the defrost cycle at specified intervals whenever the outdoor temperature reaches a
predetermined point. It is assumed that below a certain outdoor temperature there will be
frequent frost formation and defrost will be necessary. Unfortunately this can result in
unnecessary defrost cycles, which waste energy. There may not actually be frost during the
times specified. Demand controls actually detect the presence of frost on the outdoor coils.
When the controls sense frost, they initiate the defrost cycle. When the frost is melted, the
defrost cycle is terminated. Since the defrost cycle is only used when needed, this is much
more efficient and reduces heating costs.
Emergency Heat Indicator

"Emergency heat" comes on when the heat pump breaks down. Auxiliary heat proves all
the heat to the house. A break down could be caused by a mechanical failure or by the
operation of the safety switches. Since the house will still be warm when emergency heat is
on, occupants may not realise that the heat pump is not working. The emergency electric heat
is more expensive to operate than the heat pump. Many thermostats come with a light that
turns on when the emergency heat is on; indicating that the heat pumps is not working when it
should. This is a highly desirable feature as it serves as a reminder that the heat pump needs
repairs. The terms "emergency heat," "auxiliary heat" and "supplemental heat" are often used
interchangeably, since they all refer to the heating unit(s) that add to, or take over from, the
heat pump when needed. Manufacturers are understandably reluctant to put a light called
"emergency heat" on their equipment, so the emergency heat indicator may have a different
name. A thermostat with an emergency heat light should be specified, even if it goes by a
different name. A supplemental heat indicator, called "auxiliary heat" indicator on some
thermostats, tells when the supplemental heat is on. Unlike emergency heat, supplemental
heat is a normal occurrence. It comes on when the heat pump alone cannot keep the house
warm enough. The heat pump keeps working while the supplemental heat is on.
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Abdeen Mustafa Omer
Safety Switches
To prevent compressor damage, a heat pump should have pressure sensors that indicate
either excessively high or dangerously low refrigerant pressures. If either condition occurs,
the heat pump should automatically shut down, and switch on the emergency heat if needed.
These adverse conditions are often accompanied by high temperature. Accordingly, those in
the heat pump business often call these pressure/temperature switches.
Accumulator
Heat pump compressors are designed to compress gases, not liquids. Liquids are much
more difficult to compress than gases. If liquid refrigerant enters the compressor, it may
damage the compressor. Since compressors are very expensive to replace, heat pumps should
be protected with an accumulator. The accumulator traps liquid refrigerant to prevent it from
entering the compressor. However, scroll compressors are the exception to this rule as they
can handle some liquid refrigerant without damage, so they do not require an accumulator.
Filter/Drier
The filter/drier does two things: It filters the refrigerant to remove dirt and other
impurities that can cause damage to the compressor and other heat pump parts. Also, it
removes moisture from the refrigerant. Moisture can cause a variety of problems, so it is
important to remove it from the system quickly.
Crankcase Heater
When the heat pump is off during cold weather, liquid refrigerant can migrate to the
compressor crankcase, reducing lubrication effectiveness. When the heat pump comes on, the
refrigerant evaporates rapidly. Foam forms in the oil preventing adequate lubrication of the
compressor and shorten its life. The compressor should be equipped with a crankcase heater,
which prevents the refrigerant from liquefying in the oil. Most crankcase heaters are on at all
times. Some are designed to operate only when needed. Again, the scroll compressor is the
exception, as it does not require a crankcase heater to operate safely.
Salt Air Models

The outdoor unit may have a shorter life in coastal locations where salt air corrosion is a
problem. Consequently, some companies manufacture outdoor units designed and built to
resist salt air corrosion.
89
Types of Heat Pump Technologies

Characteristics of two types of heat pumps are summarised below:
Variable Speed Heat Pumps

A long awaited heat pump has just come on the market. It is called a "variable speed"
heat pump because it adjusts its output to match the heating or cooling requirement of the
home. This allows the heat pump to run continuously rather than starting and stopping
frequently during mild weather. This is more efficient and reduces wear. It can also improve
comfort since the fan speed is matched to the heat output, reducing drafts when the output is
low.
Scroll Compressor
Another recent development is a new type of compressor called a "scroll compressor". It
has a rotary motion that reduces noise more than any other rotary compressors, due to its
unique design. It has a higher efficiency at lower temperatures than reciprocating compressors
for better seasonal heating performance. It also tolerates small amounts of liquid refrigerant,
so it does not require an accumulator or crankcase heater.
Proper Sizing and Installation

It is difficult for the consumer to verify that the contractor properly sizes and installs the
system, and they should at least let the contractor know the expected criteria to be met. If it is
in a utility-sponsored heat pump programme, the utility may help ensure the system meets
these criteria.
Heat Pump Sizing

There are three reasons that a heat pump should be properly sized for the house, cost,
durability and efficiency.
Cost: Large equipment is more expensive. If the system is too large, too much money
will be spent on it. On the other hand, if the heat pump is undersized for heating,
supplemental heat will operate too often, increasing the electric bill.
Durability: Most wear and tear on a compressor occurs when it starts up. Oversized
equipment will cycle on and off more often than accurately sized systems.
Efficiency: Oversized systems have shorter "on" times, which means a greater portion of
"on" time is spent getting started, an inefficient part of the heat pump cycle.
Load Calculations
The only way to properly size a heat pump is to do heating and cooling load calculations
and then match the equipment to the calculated loads. These load calculations should take the
following into account:
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Abdeen Mustafa Omer
The dimensions of the floors, basement walls, above ground walls, windows, doors
and ceilings.
The energy efficiency of these components (insulation, window types, air tightness,
etc.).
Local weather: Loads should be calculated for a cold winter day (but not the coldest
on record) and a hot summer day (but not the hottest on record). The local electric
utility may be able to recommend appropriate design temperatures.
If the heat pump is for heating use only, then only heat load calculations are needed. If
the plan is to do both heating and cooling, both heating and cooling load calculations are
needed. It is important to properly calculate the heating and cooling loads and not to guess for
the reasons explained in the previous section (Heat pump sizing).
Load Calculation Methods

There are several widely accepted methods of calculating heating and cooling loads. The
most popular are based on methods and data developed by the American Society of Heating,
Cooling and Air- conditioning Engineers (ASHRAE). One of the best is called Manual
Journal: Load Calculation developed by the Air Conditioning Contractors of America
(ACCA). Manufacturers often simplify ASHRAE and ACCA methods so that the process can
be speeded up. Most major manufacturers provide forms that help contractors size their
heating equipment. If the forms are based on ASHRAE or Manual Journal, the contractor will
probably do a good job of estimating the sizing requirements.
Room-by-Room Load Calculations

Load calculations should be done for each "room" in the house, because each room has
its own heating and cooling requirement. It is the only way contractors know how much
heating or cooling to deliver to each room. Otherwise, they can only guess at duct sizes, and
deliver incorrect amounts of heating or cooling. Areas that are open to each other are treated
as one "room". For example, one "room" could include kitchen, family and dining areas.
Sizing for Heating and Cooling

In most homes, heat pumps provide both heating and cooling. Proper sizing requires
calculating both heating and cooling loads as explained above. A heat pump that matches
both loads as closely as possible should be chosen.
First, choose equipment that meets the cooling needs of the house. Then check the heat
output of the equipment against the heating requirement "Choosing the best size for heating".
If the heat output is too small, larger equipment can be chosen as long as it does not oversize
the cooling load by more than 25 percent (some utility financing programmes allow 50
percent over-sizing). When sizing for cooling, both sensible and latent cooling loads should
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be considered. Sensible cooling is most important, and its the types of cooling people are
familiar with - simply reducing the air temperature. Latent cooling is reducing the humidity
so that occupants can be comfortable at the temperature they choose for indoor living. Since
European summers are typically not humid, latent load is not as important. However, in
general, equipment should be chosen to meet sensible plus latent loads. If the equipment
matching the heating requirement is not available without over-sizing for cooling, then one of
the following strategies may need to be considered:
1. Upgrade the insulation and windows and reduce the air leakage from the house to
reduce the winter heating requirement; or
2. Choose a unit that is undersized for heating, realising that the supplemental heat will
operate more than optimal, hence, reducing the potential savings.
Choosing the Best Size

Appendix 1 shows the relationship between the heating requirement of the house and the
heat output of four hypothetical heat pumps.
Appendix 1. The relationship between the heating requirement of the house and the heat output of four
hypothetical heat pumps.
The four heat pumps are different sizes (they have different heat outputs), so the balance
point occurs at different outdoor temperatures for each. This graph can help to choose the best
heat pump for heating. Assume that the ideal heating unit in the climate has a typical balance
point near 30oF. There is a range of 3 to 5 degrees on either side. Two heat pumps in the
graph are close enough. The smaller heat pump has a balance point of 32oF, and the larger
one, 27oF. None of the units give the exact balance point and the cooling load should be
checked to see which one is acceptable. If the larger unit is outside the boundary of 125-150
percent of the cooling load, then the smaller unit would be chosen. If both were in the
acceptable range for cooling, the larger unit would be chosen for increased heating economy.
The Duct Systems

The issues relating to the duct systems are summarised below:
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Duct Sizing
One of the most important aspects of proper installation is to ensure that the ductwork
can deliver adequate airflows to maintain comfort in the house. But even more importantly,
the airflow needs to be adequate to prevent damage to the heat pump.
Airflow must meet the manufacturer's specifications otherwise the refrigerant will not be
able to get rid of excess heat. If the refrigerant gets too hot, refrigerant pressure may exceed
the limits of the compressor and cause it to fail. Replacing a compressor is expensive; it costs
more than the added cost of properly designing and installing the duct system.
A large volume of air moving through the ducts may be needed. It is important that it
does not move too fast. Air velocity in supply (warm air) ducts should not exceed 235 metres
per minute (mpm) for smooth metal ducts or 200 mpm for a flexible duct. Return duct air
(room temperature air returning to heat pump) velocities should not exceed 200 mpm,
regardless of duct type. As a consumer it is necessary to verify these criteria are met. If the
system exceeds these velocities, it will be noisy.
Return Air System
Most customers are aware of the warm air supply outlets because they deliver warm air to
the house. And it is easy to figure out that there are usually ducts that connect the heat pump
to those outlets. However, it is easy to overlook the return side of the system - the ducts and
grills that carry air back to the heat pump. In fact, the return airside is often installed as
though it is an afterthought. Ideally, there is a return grill and duct in each room where there
is a warm air supply. That is usually expensive, but it is worthwhile to get as many returns as
practical. At a minimum, there should be one for the main living areas and one for the
bedrooms. It is also worth considering separate returns for large living rooms and master
bedrooms. A good return air system can help reduce differences in pressure throughout the
house, reduce drafts and improve comfort.
Terminals
Terminals are the registers, vents and grills at the ends of the ducts that deliver air to
rooms or return air to the heat pump. Terminals should distribute conditioned air properly in
each room of the house. The room-by-room heat load calculations mentioned earlier tell the
contractor how much airflow each room needs.
An important consideration for selecting terminals is the air velocity going through them.
In general, larger terminals produce slower velocities. If the velocity is too high, terminals
will be noisy and cause drafts. Supply registers and vents should have a velocity of less than
250 mpm and the correct "throw" (distance the air is projected from the terminal-usually
about three metres). Return grills should have a velocity of 130 mpm or less. Again, recognise
that consumers probably will not be able to verify that these criteria are met.
Terminals should direct airflow away from sitting areas, work areas and other occupied
places. The best design is to deliver air from the floor parallel to an outside wall.
Dampers
Adjustable duct dampers must be installed so airflow can be set for each room, according
to the room-by-room heat load calculations. After the system is installed, the heating
contractor should "balance" the system by adjusting each damper for correct air flows. These
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dampers are usually found in branch ducts near where they take off from the main duct. Once
the dampers have been adjusted to balance the system, they are usually not moved unless the
system is modified.
Duct Air Sealing

Air leakage from ducts is typically one of the main sources of heat loss in the house.
Ducts should be sealed at joints between sections, along seams in individual duct sections,
and where ducts penetrate from unheated to heated areas. Ducts are typically sealed with duct
tape. Aluminum tape is more durable than cloth varieties.
The energy savings are worth the expense. Sealing is also important for comfort; one may
not be comfortable if warm air leaks out of the duct before it gets to the room. Also,
eliminating duct leaks is critical for heat pump system efficiency.
Duct Insulation
Ducts passing through unheated areas such as garages, crawl spaces and attics should be
insulated. Northwest regional conservation standards require sheet metal ducts to be insulated
with R-11 insulation and insulated flex duct with two layers of R-4 or one layer of R-11
insulation.
Flexible Duct
Some contractors use flexible ducts with insulation already built in. Because flexible
ducts can be installed by less experienced trades people than required by sheet metal ones,
there is some concern that flexible ducts encourage poor installation practices. Flexible ducts
should be installed according to the following guidelines.
1. Use R-11 or "double wrap" ducts (two layers of R-4).
2. Make all bends gradual so airflow is not restricted.
3. Make connections between sheet metal and flexible ducts with metal or nylon
clamps.
4. Seal connections (aluminium duct tape) between flexible and sheet metal ducts.
5. Support flexible ducts so they do not sag (restricting air flow) using supports at least
2.5 cm wide.
6. Stretch duct to its full length so air passages are as smooth as possible.
The Outdoor Unit

The outdoor units may require the followings.
Outdoor Unit Installation

The outdoor portion of the heat pump should be installed on a concrete pad (unless the
manufacturer specifies other support), separate from the house foundation. Some units are
elevated on legs so air can flow under the unit. In cold climates, the legs should be tall enough
so that snow will not block the airflow. The unit should be far enough out from the eaves so
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snow falling from the roof will not land on it. If possible, someone needs to place the unit so
that it is sheltered from prevailing winter winds, and the shrubs do not block airflow.
Outdoor Unit Location

The outdoor unit should be located where its noise will not bother the neighbours.
Likewise, make sure that it is not located under bedroom windows. If it is difficult to find a
good location, then one may need a heat pump with special sound reduction features. The
outdoor unit should be located to minimise the length of the copper refrigerant lines that
connect the indoor and outdoor units.
Refrigerant Lines
The lines should be reasonably straight. Any excess lines that need to be coiled should be
coiled horizontally so they do not form an oil trap. Vertical coils may prevent lubricant from
returning to the compressor. Both refrigerant lines should be insulated; to reduce unwanted
heat loss and heat gain in order to save energy.
Condensate Drain
When the heat pump is in its summer cooling mode, water from air inside the house often
condenses on the indoor coil. This water must be drained from the house (but not into the
crawl space). Locating the drain where it will work by gravity alone may be difficult or
impossible. Some systems require condensate pumps.
Heat Distribution System

The heat pump works by promoting the evaporation and condensation of a refrigerant to
move heat from one place to another. A heat exchanger transfers heat from the
water/antifreeze mixture in the ground loop to heat and evaporate refrigerants, changing them
to a gaseous state. A compressor is then used to increase the pressure and raise the
temperature at which the refrigerant condenses. This temperature is increased to
approximately 40oC. A condenser gives up heat to a hot water tank, which then feeds the
distribution system.
Lengths of plastic pipe are buried in the ground, either in a borehole or a horizontal
trench. The pipe is a closed loop, which is filled with a water/antifreeze mixture. This mixture
circulates in the pipe, absorbing heat from the ground. Horizontal trenches are dug to a depth
of 1-2 metres and can cost less than boreholes, but require a greater area of land. Placing
coiled piping in horizontal trenches will enhance the performance compared with straight
piping. A borehole is drilled to a depth of between 15-100 metres and will benefit from higher
ground temperatures than the horizontal trench, although installation costs will be greater.
Because the GSHPs raise the temperature to approximately 40oC, they are most suitable
for under-floor heating systems, which require temperatures of 30-35oC, as opposed to
conventional boiler systems, which require higher temperatures of 60-80oC. The GSHPs can
also be combined with radiator space heating systems and with domestic hot water systems.
However, top-up heating would be required in both cases in order to achieve temperatures
high enough for these systems. Some systems can also be used for cooling in the summer.
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Installation
The Installation of a GSHP should be carried out by a trained engineer. At present, the
UK market is small and there is currently no network of accredited installers as with other
technologies. Manufacturers and suppliers should also be able to provide trained engineers
but geographical limitations may increase installation costs.
The cost of a professionally installed GSHP is ranging from about 1,200-1,700 per kW
of peak heat output. This includes the cost of the distribution system. Vertical borehole
systems would be at the higher end of this scale, due to greater installation costs. A typical 8
kW system would therefore vary between 9,600-13,600. The costs will vary from property
to property.
Depending on the size of the system installed, the heat distribution system chosen and the
resulting coefficient of performance (COP), the GSHPs can be a cheaper form of space
heating than oil, LPG or electric storage heaters. It is, however, comparably more expensive
than natural gas. However, the GSHP technology is low in maintenance as systems have very
few moving parts. Systems can have an operating life of over 20 years.
Running Costs
COP is an indicator of the efficiency of a GSHP system. This is the ratio of the number of
units of heat output for each unit of electricity input used to drive the compressor and pump
for the ground loop.
Typical COPs range between 2.5-4. The higher end of this range is for underfloor
heating, because it works at a lower temperature (30-35oC) than radiators. If grid electricity is
used for the compressor and pump, then an economy 7 tariff usually gives the lowest running
costs.
Environmental Impacts
The main environmental impacts of a GSHP system can be summarised as follows:
(1) Emission of Green House Gases

Significant CO2 savings can be gained by displacing fossil fuels. Even compared to the
most efficient gas or oil condensing boilers, a well-designed heat pump with COP of 3-4 will
reduce emissions by 30-35%. Further carbon savings can be made if the electricity used to
power the pump comes from a renewable energy source such as photovoltaic or a renewable
electricity tariff.
Also, measures can be taken to reduce the impact of pollution from using grid electricity
generated through fossil fuel. For example, one can purchase dual tariff green electricity from
a number of suppliers. However, even if ordinary grid electricity is used to run the
compressor, the system will still produce less CO2 emissions than even the most efficient
condensing gas or oil boiler with the same output.
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(2) Use of Refrigerants in the System

Refrigerants such as hydrochloroflurocarbons (HCFCs) are present in the GSHP systems
and can pose a threat to the environment through being toxic, flammable or having a high
global warming potential. However, new types and blends of refrigerant with minimal
negative impacts are being developed. A correctly fitted system will also greatly reduce the
potential for leakage, which is why using a professional installer is highly recommended.
Heat Pump Operation

Using direct combustion (gas or oil) to generate heat is never the most efficient use of
fuel. Heat pumps are more efficient because they use renewable energy in the form of lowtemperature heat.
Geothermal heat pumps (GHPs) are a relatively new technology application that can save
homeowners money. These GHPs use the natural heat storage capacity of the earth or ground
water to provide energy efficient heating and cooling. The GHPs should not be confused with
air-source heat pumps that rely on heated air.
The GHPs use the relatively constant temperature of the ground or water several feet
below the earth's surface as source of heating and cooling. They are appropriate for retrofit or
new homes, where both heating and cooling are desired. In addition to heating and cooling,
geothermal heat pumps can provide domestic hot water. Furthermore, they can be used for
virtually any size home or lot in any region of the world.
A GHP system consists of indoor heat pump equipment, a ground loop, and a flow center
to connect the indoor and outdoor equipment. The heat pump equipment works like a
reversible refrigerator by removing heat from one location and depositing it in another
location. The ground loop, which is invisible after installation, allows the exchange of heat
between the earth and the heat pump.
The GHPs can be open or closed-loop. Open-loop systems draw well water for use as the
heat source or heat sink, and after use, return the well water to a drainage field or another
well. Closed-loop or earth-coupled systems use a water and antifreeze solution, circulated in a
ground loop of pipe to extract heat from the earth. Ground loops can be installed in a vertical
well or a horizontal loop. Vertical wells are usually more expensive and used where space is
limited. The length of loop pipe required will vary with soil type, loop configuration, and
system capacity. Loop length can range from 80-330 metres per ton of capacity.
Special heat pump features can include variable speed blowers and multiple-speed
compressors. These features can improve comfort and efficiency in areas where heating and
cooling loads are quite different. Additional features include the capability to produce hot
water. Desuperheaters can be added to supplement the production of domestic hot water when
there is a demand for space heating or cooling. These devices make use of excess heat during
the cooling cycle and use some of the heat during the heating cycle to supplement hot water
production. Dedicated water heaters can be added which operate whenever there is a demand
for hot water.
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Factors Affecting Heat Pump Performance

The performance of heat pumps is affected by a large number of factors. For heat pumps
in buildings these include:
The climate - annual heating and cooling demand and maximum peak loads.
The temperatures of the heat source and heat distribution system.
The auxiliary energy consumption, e.g., pumps, and controls.
The technical standard of the heat pump.
The sizing of the heat pump in relation to the heat demands and the operating
characteristics of the heat pump.
6. The heat pump control system.
1.
2.
3.
4.
5.
Heat Pump Characteristics

The following needs to be considered to enhance heat pump characteristics:
A Constant Heat
A heat pump delivers a lower supply air temperature than a furnace over a longer period
of time to provide a more constant heat. It may give the impression that the system "never
stops running", or "it feels like cold air". At times, the temperature of the air coming out of
the vents is less than the body temperature so it feels like cold air. But it is still providing heat
for the house. And when it can no longer keep-up with the heat loss of the structure, the
second stage or auxiliary heat will automatically energise, bringing on a much warmer heat.
Water Run-off
During the heating cycle, one may notice water running off the outdoor coil. Moisture
from the air is condensed on the outside surface of the coil where it gathers and runs off. This
is normal.
Outdoors Coil Defrosting
At certain conditions (low temperature, high humidity), frost, even ice, may build up on
the coil of the outdoor unit. In order to maintain heating efficiency, the system will
automatically defrost itself. Steam rising from the outdoor unit is normal and is an indication
of proper operation. The vapour cloud will only last for a few minutes. When the defrost
cycle is completed, the system will automatically switch back to heating. Supplemental heat
is automatically energised to maintain comfort during defrost.
Heat flows naturally from a higher to a lower temperature. Heat pumps, however, are
able to force the heat flow in the other direction, using a relatively small amount of high
quality drive energy (electricity, fuel, or high temperature waste heat). Thus heat pumps can
transfer heat from natural heat sources in the surroundings, such as the air, ground or water,
or man-made heat sources such as industrial or domestic waste, to a building or an industrial
application. Heat pumps can also be used for cooling. Heat is then transferred in the opposite
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direction, from the application that is cooled, to surroundings at a higher temperature.

Sometimes the excess heat from cooling is used to meet a simultaneous heat demand.
In order to transport heat from a heat source to a heat sink, external energy to drive the
heat pump is needed. Theoretically, the total heat delivered by the heat pump is equal to the
heat extracted from the heat source, plus the amount of drive energy supplied. Electrically
driven heat pumps for heating of buildings typically supply 100 kWh of heat with just 20-40
kWh of electricity. Many industrial heat pumps can achieve even higher performance, and
supply the same amount of heat with only 3-10 kWh of electricity. But simply, during the
cooling cycle, a heat pump will remove heat and humidity from the home and will transfer
this heat to the outdoor air. Likewise, during the heating cycle, a heat pump will remove heat
and humidity from the outdoor air and will transfer this heat to homes. This is possible
because, even at 32 degrees Centigrade, outdoors air contains a great deal of heat. The heat
pump does not generate much heat; it merely transfers it from one place to another.
Loops can be installed in three ways: horizontally, vertically or in a pond or lake
(Appendix 2). The type chosen depends on the available land area, soil and rock type at the
installation site. These factors help to determine the most economical choice for installation
of the ground loop. The GSHP delivers 3-4 times as much energy as it consumes when
heating, and cools and dehumidifies for a lower cost than conventional air conditioning. It can
cut homes or business heating and cooling costs by 50% and provide hot water free or with
substantial savings. The GSHPs can reduce the energy required for space heating, cooling and
service water heating in commercial/institutional buildings by as much as 50%.
Appendix 2. The GSHPs extract solar heat stored in the upper layers of the earth.
The GSHP is an electrically powered system that takes advantage of the earth's relatively
constant ground temperature to provide heating, cooling and hot water for homes or business.
The water-to-water system is especially designed for supplying the hot water for radiant floor
heating or for heating swimming pools. The water to air system is an excellent furnace
replacement or enhancer.
The GSHP is called such, because it pumps heat. Through the use of a simple, yet tried
and tested refrigeration system, it pumps heat from the warm earth in the winter and places it
in homes or businesses. In the summertime the process is reversed. Since it costs far less to
move heat than to make it, much less energy is consumed. This results in huge reductions in
energy costs and greatly reduces the environmental impact of space conditioning. For closed
loop systems, water or an antifreeze solution is circulated through plastic pipes buried beneath
the earth's surface. During the winter the fluid collects heat from the earth and carries it
99
through the system and into the building. During the summer the system reverses itself to
cool the building by pulling heat from the building, carrying it through the system and placing
it in the ground. Open systems operate on the same principle as closed loop systems and can
be installed where an adequate supply of suitable water is available and open discharge is
feasible. Benefits similar to the closed loop system are realised.
Benefits:
Requires less mechanical room space.

Requires less outdoor equipment.
Does not require roof penetrations, maintenance decks or architectural blends.
Quiet operation.
Reduces operation and maintenance costs.
Limitations:
Requires surface area for heat exchanger field.

Higher initial cost.
Requires additional site co-ordination/supervision.
Higher design cost.
The GSHPs replace the need for a boiler in winter by utilising heat stored in the ground;
this heat is upgraded by a vapour-compressor refrigeration cycle. In summer, heat from a
building is rejected to the ground. This eliminates the need for a cooling tower or heat
rejecter, and also lowers operating costs because the ground is cooler than the outdoor air.
Water-to-air heat pumps are typically installed throughout a building with ductwork serving
only the immediate zone; a two-pipe water distribution system conveys water to and from the
ground-source heat exchanger. The heat exchanger field consists of a grid of vertical
boreholes with plastic u-tube heat exchangers connected in parallel. Simultaneous heating and
cooling can occur throughout the building, as individual heat pumps, controlled by zone
thermostats, can operate in heating or cooling as required.
Unlike conventional boiler/cooling tower type water loop heat pumps, the heat pumps
used in the GSHP applications are generally designed to operate at lower inlet water
temperature. They are also more efficient than conventional heat pumps, with higher COPs.
Because there is lower water temperatures in the two-pipes loop, piping needs to be insulated
to prevent sweating. In addition, a larger circulation pump is needed because the units are
slightly larger in the perimeter zones requiring larger flows.
The GSHPs reduce energy use and hence atmospheric emissions. Conventional boilers
and their associated emissions are eliminated, since no supplementary form of energy is
usually required. Typically, single packaged heat pump units have no field refrigerant
connections and thus have significantly lower refrigerant leakage compared to central chiller
systems. The GSHP units have life spans of 20 years or more and the two-pipe water-loop
system typically used, allows for unit placement changes to accommodate new tenants or
changes in building use. The plastic piping used in the heat exchanger should last as long as
the building itself. When the system is disassembled, attention must be given to the removal
and recycling of the hydrochlorofluorocarbon (HCFC) or Higher heating value
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Abdeen Mustafa Omer
hydrofluorocarbon (HFC) refrigerants used in the heat pumps themselves and the anti-freeze
solution typically used in the ground heat exchanger.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
Luo, L.; Tondeur, D.; Le Gall, H.; and Corbel, S. (2007). Constructal approach and
multi- scale components. Applied Thermal Engineering, 27, 1708-1714.
Luo, L.; Fan, Y.; and Tondeur, D. (2007). Heat exchanger: from micro to multi- scale
design optimisation. International Journal of Energy Research, 31, 1266-1274.
Philappacopoulus, A.J.; and Berndt, M.L. (2001). Influence of de-bonding in ground
heat exchangers used with geothermal heat pumps. Geothermics, 30(5): 527-545.
Jo, H.Y.; Katsumi, T.; Benson, C.H.; and Edil, T.B. (2001). Hydraulic conductivity and
swelling of non-prehydrated GCLs permeated with singlespecies salt solutions.
Journal of Geotechnical and Geo-environmental Engineering, 127(7): 557-567.
Anandarajah, A. (2003). Mechanism controlling permeability changes in clays due to
changes in pore fluids. Journal of Geotechnical and Geo-environmental Engineering,
129(2): 163-172.
Fridleifsson, I. B. (2003). Status of geothermal energy amongst the worlds energy
sources. Geothermics, 30: 1-27.
ASHRAE. (1995). Commercial/Institutional Ground Source Heat Pump Engineering
Manual. American Society of heating, Refrigeration and Air conditioning Engineers,
Inc. Atlanta, GA: USA.
Kalbus, E.; Reinstrof, F.; and Schirmer, M. (2006). Measuring methods for
groundwater surface water interactions: a review. Hydrology and Earth System
Sciences, 10, pp. 873-887.
Shah, R. K. (1991). Compact Heat Exchanger Technology and Applications, in Heat
Exchange Engineering, Volume 2: Compact Heat Exchangers: Techniques of Size
Reduction, eds. Foumeny E. A.; and P. J. Heggs, pp. 123, Ellis Horwood Limited,
London.
Ramshaw, C. (1995). Process Intensification in the Chemical Industry, Mechanical
Engineering Publications Ltd, London.
Bergles A. E. (1988). Some perspectives on enhanced heat transfer - second generation
heat transfer technology. Journal of Heat Transfer, 110, 1082-1096.
Bowman, W. J.; and Maynes, D. (2001). A Review of Micro-Heat Exchangers Flow
Physics, Fabrication Methods and Application. Proc. ASME IMECE, New York, USA,
HTD-24280.
Li, J.; Zhang, J.; Ge, W.; and Liu, X. (2004). Multi-scale methodology for complex
systems. Chemical Engineering Science, 59, 1687-1700.
Mandelbrot, B. (1982). The Fractal Geometry of Nature, 2nd ed., W. H. Freeman, San
Francisco, California.
Bejan A. (2000). Shape and Structure, from Engineering to Nature. Cambridge
University Press: London. The many faces of protease-protein inhibitor interaction.
EMBO J. 7: 1303-1130.
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[16] Luo, L.; Tondeur, D. (2005). Multiscale optimisation of flow distribution by constructal
approach. Particuology, 3, 329-336.
[17] Omer, A. M. (2011). Principle of cooling and heating with ground source energy,
Cooling India, Vol. 7, No. 7, p. 64-77, India, October 2011.
[18] Omer, A. M. (2012). Cooling and heating with ground source energy, International
Journal of Energy Optimisation and Engineering, Vol. 1, No. 2, p. 41-58, Malaysia,
April-June 2012.
[19] Tozer, R.M; and James, R.W. (1997). Fundamental thermodynamics of ideal absorption
cycles. International Journal of Refrigeration 20 (2): 123-135.
[20] United Nations Environment Programme (UNEP). (2006). African regional
implementation review for the 14th session of the Commission on Sustainable
Development (CSD-14). Report on atmospheric and air pollution. New York: UNEP.
[21] World Business Council for Sustainable Development (WBCSD). (2004). Supporting
IEA/SMP transport model documentation and reference case projections. The
sustainable mobility project. World Business Council for Sustainable Development.

ISBN: 978-1-63117-329-5
Chapter 3
SOME ASPECTS OF SOLAR AND

WIND ENERGY RESOURCES
Abdeen Mustafa Omer
Energy Research Institute (ERI), Nottingham, UK
ABSTRACT
Renewable energy resources (solar, wind and biomass) is one of the most
fundamental of natural resources that Sudan must harness in its efforts for rapid
economic development. The role of renewable energy technologies in the development
process cannot be over emphasised. The demand for energy in Sudan has increased
tremendously over the years and will continue to increase in view of the accelerating pace
of population growth, urbanisation and industrialisation. Comprehensive renewable
energy resources management is a necessity. Human resource development should be
based on education and training programmes funded both by the private and public
sector. Promotion research and development, demonstration and adaptation of energy
resources amongst national, regional, and international organisations which seek clean,
pure, safe, and abundant energy sources. Results, suggest that, wind pumps, solar stills,
and biogas energy must be encouraged, invested, and implemented, but especially for
remote rural areas of Sudan.
Keywords: Renewable technologies, solar energy, wind energy, biomass energy, Sudan,
environment
1. INTRODUCTION
Sudan has a population of about 26 million with an annual growth rate of 2.8% with a
population density of less than 10 per square kilometres. In the last two decades, Sudan has
been suffering from an imbalance of trade. This has led to serious energy problems and
environmental destruction.
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Abdeen Mustafa Omer
Energy supply in Sudan is about 11.7 million tons of oil equivalents (TOE). Out of this
only 57% reached the end users due to conversion losses. About 87% of this energy supply is
biomass [1]. Petroleum energy supply represented only 12% of the total energy supply.
Electricity supply represented almost 1% of the total energy (hydropower supplies 58%, and
the rest is supplied by thermal and gas turbines). As Sudan is a tropical country with high
solar radiation and moderate wind; solar and wind energies seem to be attractive sources of
energy. In Sudan, great attention is given to renewable energy utilisation since the country has
potential for this.
This communication presents a review of three projects carried by national company for
manufacturing water equipment limited (NCMWE). Wind pumps (two are locally
manufactured, installed and tested), solar stills, and biogas technology. The future efforts
must be toward the use of renewable environmentally friendly, and appropriate technologies
in Sudan.
With increasing urbanisation in the world, cities are growing in number, population and
complexity. At present, 2% of the worlds land surface is covered by cities, yet the people
living in them consume 75% of the resources consumed by mankind [2]. Indeed, the
ecological footprint of cities is many times larger than the areas they physically occupy.
Economic and social imperatives often dictate that cities must become more concentrated,
making it necessary to increase the density to accommodate the people, to reduce the cost of
public services, and to achieve required social cohesiveness. The reality of modern
urbanisation inevitably leads to higher densities than in traditional settlements and this trend
is particularly notable in developing countries.
Today, the challenge before many cities is to support large numbers of people while
limiting their impact on the natural environment. Buildings are significant users of energy and
materials in a modern society and, hence, energy conservation in buildings plays an important
role in urban environmental sustainability. A challenging task of architects and other building
professionals, therefore, is to design and promote low energy buildings in a cost effective and
environmentally responsive way. Passive and low energy architecture has been proposed and
investigated in different locations of the world [3-4]; design guides and handbooks were
produced for promoting energy efficient buildings [5-8]. However, at present, little
information is available for studying low energy building design in densely populated areas.
Designing low energy buildings in high-density areas requires special treatment to the
planning of urban structure, co-ordination of energy systems, integration of architectural
elements, and utilisation of space. At the same time, the study of low energy buildings will
lead to a better understanding of the environmental conditions and improved design practices.
This may help people study and improve the quality of built environment and living
conditions.
However, the term low energy is often not uniquely defined in many demonstration
projects and studies [9]. It may mean achieving zero energy requirements for a house or
reduced energy consumption in an office building. A major goal of low energy building
projects and studies usually is to minimise the amount of external purchased energy such as
electricity and fuel gas. Yet, sometimes the target may focus on the energy costs or a
particular form of energy input to the building. As building design needs to consider
requirements and constraints, such as architectural functions, indoor environmental
conditions, and economic effectiveness, a pragmatic goal of low energy building is also to
achieve the highest energy efficiency, which requires the lowest possible need for energy
105
within the economic limits of reason. Since many complicated factors and phenomena
influence energy consumption in buildings, it is not easy to define low energy building
precisely and to measure and compare the levels of building energy performance. The loose
fit between form and performance in architectural design also makes quantitative analysis of
building energy use more difficult. Nevertheless, it is believed that super-efficient buildings,
which have significantly lower energy consumption, can be achieved through good design
practices and effective use of energy efficient technology [10].
In an ideal case, buildings can even act as producers rather than consumers of energy.
Besides the operational energy requirements of buildings, it is important to consider two
related energy issues. The first one is the transport energy requirements as a result of the
building and urban design patterns and the second one is the embodied energy or energy
content of the building materials, equipment or systems being used. Transport energy is
affected by the spatial planning of the built environment, transport policies and systems, and
other social and economic factors. It is not always possible to study the effect of urban and
building design on transport energy without considering the context of other influencing
factors. The general efficiency rules are to promote spatial planning and development, which
reduce the need to travel, and to devise and enforce land-use patterns that are conducive to
public transport [11]. Embodied energy, on the other hand, is the energy input required to
quarry, transport and manufacture building materials, plus the energy used in the construction
process. It represents the total life-cycle energy use of the building materials or systems and
can be used to help determine design decisions on system or materials selection [12]. At
present, the field of embodied energy analysis is generally still only of academic interest and
it is difficult to obtain reliable data for embodied energy. Research findings in some countries
indicate that the operating energy often represents the largest component of life-cycle energy
use. Therefore, most people, when studying low energy buildings, would prefer to focus on
operating energy, and perhaps carry out a general assessment of embodied energy only.
To handle population growth on a limited land basis, the word density is unavoidable.
Instead of expanding the boundary, cities often respond to development pressure by setting
targets for increased urban densities. This, however, results in the establishment of a high-rise
cityscape and compact urban settings. The effects of urban concentrated load centres and
compactness of land use patterns will bring benefits to energy distribution and transport
system design, but crowded conditions may create congestion and undesirable local
microclimate. Burchell and Listokin [13] have discussed the urban energy advantage and
believed that cities are more energy efficient for the following reasons:
1.
2.
3.
4.
The urban building stock, due its density and compactness, consumes less energy.
Cities benefit from advantageous transportation and commutation characteristics.
Cities can easily capitalise from emerging more efficient energy systems, and
High densities and mixing of land uses may contribute to better efficiency.
2. RENEWABLE ENERGY TECHNOLOGIES

The increased exploitation of renewable energy sources is central to any move towards
sustainable development. However, casting renewable energy thus carries with it an inherent
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Abdeen Mustafa Omer
commitment to other basic tenets of sustainability, openness, democraticisations, etc. Due to

increasing fossil fuel prices, the research in renewable energy technologies (RETs) utilisation
has picked up a considerable momentum in the world. The present day energy arises has
therefore resulted in the search for alternative energy resources in order to cope with the
drastically changing energy picture of the world. The environmental sustainability of the
current global energy systems is under serious question. A major transition away from fossil
fuels to one based on energy efficiency and renewable energy is required. Alternatively
energy sources can potentially help fulfill the acute energy demand and sustain economic
growth in many regions of the world. The mitigation strategy of the country should be based
primarily ongoing governmental programmes, which have originally been launched for other
purposes, but may contribute to a relevant reduction of greenhouse gas emissions (energysaving and afforestation programmes). Throughout the study several issues relating to
renewable energies, environment and sustainable development are examined from both
current and future perspectives. The exploitation of the energetic potential (solar and wind)
for the production of electricity proves to be an adequate solution in isolated regions where
the extension of the grid network would be a financial constraint.
The provision of good indoor environmental quality while achieving energy and cost
efficient operation of the heating, ventilating and air-conditioning (HVAC) plants in buildings
represents a multi variant problem. The comfort of building occupants is dependent on many
environmental parameters including air speed, temperature, relative humidity and quality in
addition to lighting and noise. The overall objective is to provide a high level of building
performance (BP), which can be defined as indoor environmental quality (IEQ), energy
efficiency (EE) and cost efficiency (CE).
Indoor environmental quality is the perceived condition of comfort that building

occupants experience due to the physical and psychological conditions to which they
are exposed by their surroundings. The main physical parameters affecting IEQ are
air speed, temperature, relative humidity and quality.
Energy efficiency is related to the provision of the desired environmental conditions
while consuming the minimal quantity of energy.
Cost efficiency is the financial expenditure on energy relative to the level of
environmental comfort and productivity that the building occupants attained. The
overall cost efficiency can be improved by improving the indoor environmental
quality and the energy efficiency of a building.
2.1. Wind Energy

Forty years ago, wind pumps were very common in central Sudan. Unfortunately, they
disappeared gradually due to scarce spare parts, lack of maintenance skills as well as stiff
competition from relatively cheap diesel pumps. The government reintroduced wind pumps to
counter the high prices of imported diesel fuel and the difficulties in transporting it to remote
areas.
In 1985, the energy research institute (ERI) in cooperation with a consultancy services
firm started a wind pumps project. The project was financed by the Netherlands ministry of
foreign affairs [14]. During the 14 months of the project life, ten imported wind pumps were
107
installed in Khartoum area, while one was locally manufactured for demonstration. Results
suggested that wind energy would be more profitably used for local applications in Sudan.
After the termination of the project, the ERI continued monitoring and testing the
performance of the installed pumps.
The consultancy firm set out to produce wind pumps for low head pumping applications
which could be built in developing countries. The wind pump produced consists of an eight
bladed rotor which is directly coupled to a specially designed piston pump. This pump is
fabricated with a small leak hole (to facilitate starting) and a continuous replenished air
chamber (served by a small air pump driven by a wind machine). The design is relatively
simple and is within the capabilities of the local manufacturers. So far, two wind pumps have
been manufactured locally at a cost of us $ 2500 each. The test results show that the design
has some deficiencies. The wind pumps performance is about 50% of that predicted by the
firm. This could be due to low pump efficiency and high start up wind speed (3 ms-1). The
frequency of maintenance required is high (at least once every two months).
For wind pumps to be effective, it is recommended that more research should be carried
out on adapting the design to the materials available in the local market, quality control
guidelines ought to be set up and users should be trained on how to utilise the pumps more
efficiently.
2.2. Solar Energy

Sudan enjoys bright sunshine and dry weather most of the year. It receives 10 to 12 hours
of sunshine per day with a high level of radiation. The solar radiation is abundant and can
contribute to the countrys energy use if suitable and appropriate technologies are introduced.
Solar energy can be utilised directly for water desalination or water heating. Due to the
rise in the prices of conventional fuels, solar desalination is more promising and cheaper to
use. It offers an attractive alternative as it is hygienic and helps to reduce the consumption of
fuel wood. Fortunately the areas which lack potable water supplies have abundant solar and
wind energies.
Solar desalination was initiated in Sudan as a possible answer for converting the
underground brackish water into potable water to contribute to the anti thirst campaign
especially at those isolated arid areas lacking both fresh water and power.
Solar stills are used for distilling the water. A solar still unit consists of a basin, insulating
bottom layer, black lining, transparent cover arranged in such a way that the surface slope
downwards and rests on a collecting trough at the sides. The design is simple in construction,
operation, and maintenance; rigid and firm enough to resist the worst prevailing
environmental conditions; and attempts to use locally available materials (essential foreign
materials are minimised to the least). The energy research institute (ERI) set up a bilateral
project in conjunction with the national company for manufacturing water equipment limited
(NCMWE) in February, 1995.
This project aims at solving the salinity problem in isolated areas. It has been under
taking research with a view to developing a solar still design that is economical and
technically suitable for use in Sudan. It has also carried out tests on the performance of
existing solar stills under varying prevailing operational conditions.
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Abdeen Mustafa Omer
The parameters that affect the average productivity of the solar stills include: solar
radiation, ambient temperature, wind velocity, depth of the brine in the basin, cover material
and its shape, and construction; and insulating materials used (the life span of a still is 5 10
years).
Tests were done in kilo eight area of Khartoum show that the average productivity of a
solar still is about one gallon per square meter per day. The daily productivity of solar stills is
only slightly affected by dust, clouds, and cold weather. Solar stills are suitable for use in
laboratories, medical purposes, charging and topping batteries, supplying drinking water to
small communities in isolated sunny areas as well as local markets.
2.3. Biogas Energy

Many countries with agriculturally based economics face the growing problem of human,
animal and plant waste. This waste is on one hand a very dangerous and continuous source of
pollution, but is on the other hand a very useful source of energy.
A very common technique that utilises such waste is anaerobic fermentation, also called
anaerobic digestion. The gas produced by the digestion of organic waste is known as biogas.
It is colourless, flammable, and generally contains 50 70% methane (CH4) and 30 40%
carbon dioxide (CO2), with small amounts of other gases such as Hydrogen (H2), Nitrogen
(N2), and Hydrogen Sulphide (H2S). Its energy is more than 20,000 kJm3.
Among the many uses of biogas are water heating, space heating, lighting and cooking.
Conversion of internal combustion engines to run on biogas can be relatively simple; thus the
gas can also be used for pumping water and small scale electric power generation. From the
point of view of better thermal energy utilisation, it is more economical and convenient to use
biogas to generate electricity for lighting, than to burn the biogas directly in biogas lamps.
In rural areas, it is very practical to change a small internal combustion engine with an
asynchronous generator. This has many advantages such as simple structure, ease of operation
and maintenance, less trouble, more safety and low installation cost. It is suitable for farms
whose inhabitants are not too widely scattered. But such an engine generator is usually
regarded as unsuitable to supply a wider area on account of its low efficiency. Moreover, the
digester can produce not only an excellent gas fuel but also a large quantity of digested sludge
which is an excellent pollution free organic fertiliser. Thus the promotion and development
of agricultural and animal husbandry in rural areas can be optimised by coordination of
biogas, fertiliser and pollution control.
3. EFFECTS OF URBAN DENSITY

As the quality of living and built environments has become a critical issue in many urban
areas, it is useful to investigate low energy design and evaluate it against the social and
environmental objectives. From psychological and sociological points of view, high
population density and the effect of crowding are interesting topics, which have attracted
much attention. A crowded and stressful urban environment may have unhealthy effects on
the occupants due to air pollution and noise problems. On the other hand, the level of mobility
109
and traffic speed will benefit the working and living of the people. Therefore, it should be
noted that density and crowding are not necessarily found together. People who live under
crowded conditions may not suffer from being crowded if the built environment has been
designed to provide enough personal space and functional open space.
Compact development patterns can reduce infrastructure demands and the need to travel
by car. As population density increases, transportation options multiply and dependence
areas, per capita fuel consumption is much lower in densely populated areas because people
drive so much less. Few roads and commercially viable public transport are the major merits.
On the other hand, urban density is a major factor that determines the urban ventilation
conditions, as well as the urban temperature [15]. Under given circumstances, an urban area
with a high density of buildings can experience poor ventilation and strong heat island effect.
In warm-humid regions these features would lead to a high level of thermal stress of the
inhabitants and increased use of energy in air-conditioned buildings.
However, it is also possible that a high-density urban area, obtained by a mixture of high
and low buildings, could have better ventilation conditions than an area with lower density
but with buildings of the same height. Closely spaced or high-rise buildings are also affected
by the use of natural lighting, natural ventilation and solar energy. If not properly planned,
energy for electric lighting and mechanical cooling/ventilation may be increased and
application of solar energy systems will be greatly limited.
Table 1. Effects of urban density on citys energy demand
Positive effects
Transport:
Promote public transport and reduce the need
for, and length of, trips by private cars.
Infrastructure:
Reduce street length needed to accommodate a
given number of inhabitants.
Shorten the length of infrastructure facilities
such as water supply and sewage lines, reducing
the energy needed for pumping.
Thermal performance:
Multi-story, multiunit buildings could reduce the
overall area of the buildings envelope and heat
loss from the buildings.
Shading among buildings could reduce solar
exposure of buildings during the summer period.
Natural lighting:
Energy systems:
District cooling and heating system, which is
usually more energy efficiency, is more feasible
as density is higher.
Ventilation:
A desirable in flow pattern around buildings may
be obtained by proper arrangement of high-rise
building blocks.
Negative effects
Transport:
Congestion in urban areas reduces fuel
efficiency of vehicles.
Vertical transportation:
High-rise buildings involve lifts, thus increasing
the need for electricity for the vertical
transportation.
Ventilation:
A concentration of high-rise and large buildings
may impede the urban ventilation conditions.
Urban heat island:
Heat released and trapped in the urban areas may
increase the need for air conditioning.
The potential for natural lighting is generally
reduced in high-density areas, increasing the
need for electric lighting and the load on air
conditioning to remove the heat resulting from
the electric lighting.
Use of solar energy:
Roof and exposed areas for collection of solar
energy are limited.
Table 1 gives a summary of the positive and negative effects of urban density. All in all,
denser city models require more careful design in order to maximise energy efficiency and
satisfy other social and development requirements. Low energy design should not be
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Abdeen Mustafa Omer
considered in isolation, and in fact, it is a measure, which should work in harmony with other
environmental objectives. Hence, building energy study provides opportunities not only for
identifying energy and cost savings, but also for examining indoor and outdoor environment.
3.1. Energy Saving in Buildings

The admission of daylight into buildings alone does not guarantee that the design will be
energy efficient in terms of lighting. In fact, the design for increased daylight can often raise
concerns relating to visual comfort (glare) and thermal comfort (increased solar gain in the
summer and heat losses in the winter from larger apertures). Such issues will clearly need to
be addressed in the design of the window openings, blinds, shading devices, heating system,
etc. In order for a building to benefit from daylight energy terms, it is a prerequisite that lights
are switched off when sufficient daylight is available. The nature of the switching regime;
manual or automated, centralised or local, switched, stepped or dimmed, will determine the
energy performance. Simple techniques can be implemented to increase the probability that
lights are switched off [16]. These include:
Making switches conspicuous.

Loading switches appropriately in relation to the lights.
Switching banks of lights independently.
Switching banks of lights parallel to the main window wall.
There are also a number of methods, which help reduce the lighting energy use, which, in
turn, relate to the type of occupancy pattern of the building [16]. The light switching options
include:
Centralised timed off (or stepped)/manual on.

Photoelectric off (or stepped)/manual on.
Photoelectric and on (or stepped), hotoelectric dimming.
Occupant sensor (stepped) on/off (movement or noise sensor).
Likewise, energy savings from the avoidance of air conditioning can be very substantial.
Whilst day-lighting strategies need to be integrated with artificial lighting systems in order to
become beneficial in terms of energy use, reductions in overall energy consumption levels by
employment of a sustained programme of energy consumption strategies and measures would
have considerable benefits within the buildings sector. The perception often given however is
that rigorous energy conservation as an end in itself imposes a style on building design
resulting in a restricted aesthetic solution. Better perhaps would be to support a climate
sensitive design approach which encompassed some elements of the pure conservation
strategy together with strategies which work with the local ambient conditions making use of
energy technology systems, such as solar energy, where feasible. In practice, low energy
environments are achieved through a combination of measures that include:
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The application of environmental regulations and policy.

The application of environmental science and best practice.
Mathematical modelling and simulation.
Environmental design and engineering.
Construction and commissioning.
Management and modifications of environments in use.
While the overriding intention of passive solar energy design is to achieve a reduction in
purchased energy consumption, the attainment of significant savings is in doubt. The nonrealisation of potential energy benefits is mainly due to the neglect of the consideration of
post-occupancy user and management behaviour by energy scientists and designers alike.
Buildings consume energy mainly for cooling, heating and lighting as shown in Table 2. The
energy consumption shown in the table was based on the assumption that the building
operates within ASHRAE-thermal comfort zone during the cooling and heating periods [17].
Most of the buildings incorporate energy efficient passive cooling, solar control, photovoltaic,
lighting and day lighting, and integrated energy systems. It is well known that thermal mass
with night ventilation can reduce the maximum indoor temperature in buildings in summer
[18]. Hence, comfort temperatures may be achieved by proper application of passive cooling
systems. However, energy can also be saved if an air conditioning unit is used [19]. The
reason for this is that in summer, heavy external walls delay the heat transfer from the outside
into the inside spaces.
Table 2. Energy-saving in buildings
Passive Comfort
Measures
Natural ventilation
Active Comfort
Measures
Mechanical
ventilation
Night ventilation
Artificial cooling
Evaporative cooling
Free cooling
Heavy-weight
construction
Light-weight
construction
Artificial heating
Solar heating
Free heating
Incidental heat
Insulation/permeability
Solar control/shading
Daytime
artificial lighting
Day lighting features
Mediterranean
6
4
Climatic zones
Subtropical
Tropical
7
7
5
6
Desert
7
6
6
3
3
5
6
7
5
2
6
2
7
5
2
6
2
7
6
7
7
6
4
6
5
4
5
6
3
0
0
0
0
0
6
3
0
0
0
0
0
6
3
1
0
0
0
4
7
2
* 0 = not important, 4 = important, and 7 = very important (importance is rated from 0 to 7).
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Moreover, if the building has a lot of internal mass the increase in the air temperature is
slow. This is because the penetrating heat raises the air temperature as well as the temperature
of the heavy thermal mass. The result is a slow heating of the building in summer as the
maximal inside temperature is reached only during the late hours when the outside air
temperature is already low. The heat flowing from the inside heavy walls can be removed
with good ventilation in the evening and night. The capacity to store energy also helps in
winter, since energy can be stored in walls from one sunny winter day to the next cloudy one.
One can define four levels of thermal mass as follows:
Light building: no thermal mass, e.g., a mobile home.

Medium-light building: light walls, but heavy floor, e.g., cement tiles on concrete
floor, and concrete ceiling.
Semi-heavy building: heavy floor, ceiling and external walls (20 cm concrete blocks)
but light internal partitions (Gypsums boards).
Heavy building: heavy floor, ceiling, external and internal walls (10 cm concrete
blocks, with plaster on both sides).
The exact reduction in the maximum indoor temperature depends on the amount of
thermal mass, the rate of night ventilation, and the temperature swing between day
and night.
3.2. Energy Efficiency and Architectural Expression

The focus of the worlds attention on environmental issues in recent years has stimulated
response in many countries, which have led to a closer examination of energy conservation
strategies for conventional fossil fuels. Buildings are important consumers of energy and thus
important contributors to emissions of greenhouse gases into the global atmosphere. The
development and adoption of suitable renewable energy technology in buildings has an
important role to play. A review of options indicates benefits and some problems [20-29].
There are two key elements to the fulfilling of renewable energy technology potential within
the field of building design; first the installation of appropriate skills and attitudes in building
design professionals and second the provision of the opportunity for such people to
demonstrate their skills. This second element may only be created when the population at
large and clients commissioning building design in particular, become more aware of what
can be achieved and what resources are required.
Terms like passive cooling or passive solar use mean that the cooling of a building or the
exploitation of the energy of the sun is achieved not by machines but by the buildings
particular morphological organisation. Hence, the passive approach to themes of energy
savings is essentially based on the morphological articulations of the constructions. Passive
solar design, in particular, can realise significant energy and cost savings. For a design to be
successful, it is crucial for the designer to have a good understanding of the use of the
building. Few of the buildings had performed as expected by their designers. To be more
precise, their performance had been compromised by a variety of influences related to their
design, construction and operation. However, there is no doubt that the passive energy
approach is certainly the one that, being supported by the material shape of the buildings has
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a direct influence on architectural language and most greatly influences architectural

expressiveness [30]. Furthermore, form is a main tool in architectural expression. To give
form to the material things that one produces is an ineluctable necessity. In architecture, form,
in fact, summarises and gives concreteness to its every value in terms of economy, aesthetics,
functionality and, consequently, energy efficiency [31]. The target is to enrich the expressive
message with forms producing an advantage energy-wise. Hence, form, in its geometric and
material sense, conditions the energy efficiency of a building in its interaction with the
environment. It is, then, very hard to extract and separate the parameters and the elements
relative to this efficiency from the expressive unit to which they belong. By analysing energy
issues and strategies by means of the designs, of which they are an integral part, one will,
more easily, focus the attention on the relationship between these themes, their specific
context and their architectural expressiveness. Many concrete examples and a whole literature
have recently grown up around these subjects and the wisdom of forms and expedients that
belong to millennia-old traditions has been rediscovered. Such a revisiting, however, is only,
or most especially, conceptual, since it must be filtered through todays technology and
needs; both being almost irreconcilable with those of the past. Two among the historical
concepts are of special importance. One is rooted in the effort to establish rational and
friendly strategic relations with the physical environment, while the other recognises the
interactions between the psyche and physical perceptions in the creation of the feeling of
comfort. The former, which may be defined as an alliance with the environment deals with
the physical parameters involving a mixture of natural and artificial ingredients such as soil
and vegetation, urban fabrics and pollution [32]. The most dominant outside parameter is, of
course, the suns irradiation, our planets primary energy source. All these elements can be
measured in physical terms and are therefore the subject of science. Within the second
concept, however, one considers the emotional and intellectual energies, which are the prime
inexhaustible source of renewable power [33]. In this case, cultural parameters, which are not
exactly measurable, are involved. However, they represent the very essence of the
architectural quality. Objective scientific measurement parameters tell us very little about the
emotional way of perceiving, which influences the messages of human are physical sensorial
organs. The perceptual reality arises from a multitude of sensorial components; visual,
thermal, acoustic, olfactory and kinaesthetics. It can, also, arise from the organisational
quality of the space in which different parameters come together, like the sense of order or of
serenity. Likewise, practical evaluations, such as usefulness, can be involved too. The
evaluation is a wholly subjective matter, but can be shared by a set of experiencing persons
[33]. Therefore, these cultural parameters could be different in different contexts in spite of
the inexorable levelling on a planet- wide scale. However, the parameters change in the
anthropological sense, not only with the cultural environment, but also in relation to function.
The scientifically measurable parameters can, thus, have their meanings very profoundly
altered by the non-measurable, but describable, cultural parameters.
However, the low energy target also means to eliminate any excess in the quantities of
material and in the manufacturing process necessary for the construction of our built
environment. This claims for a more sober, elegant and essential expression, which is not
jeopardising at all, but instead enhancing, the richness and preciousness of architecture, while
contributing to a better environment from an aesthetic viewpoint [34]. Arguably, the most
successful designs were in fact the simplest. Paying attention to orientation, plan and form
can have far greater impact on energy performance than opting for elaborate solutions [35].
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However, a design strategy can fail when those responsible for specifying materials for
example, do not implement the passive solar strategy correctly. Similarly, cost-cutting
exercises can seriously upset the effectiveness of a design strategy. Therefore, it is imperative
that a designer fully informs key personnel, such as the quantity surveyor and client, about
their design and be prepared to defend it. Therefore, the designer should have an adequate
understanding of how the occupants or processes, such as ventilation, would function within
the building. Thinking through such processes in isolation without reference to others can
lead to conflicting strategies, which can have a detrimental impact upon performance.
Likewise, if the design intent of the building is not communicated to its occupants, there is a
risk that they will use it inappropriately, thus, compromising its performance. Hence, the
designer should communicate in simple terms the actions expected of the occupant to control
the building. For example, occupants should be well informed about how to guard against
summer overheating. If the designer opted for a simple, seasonally adjusted control; say,
insulated sliding doors were to be used between the mass wall and the internal space. The
lesson here is that designers must be prepared to defend their design such that others
appreciate the importance and interrelationship of each component. A strategy will only work
if each individual component is considered as part of the bigger picture. Failure to implement
a component or incorrect installation, for example, can lead to failure of the strategy and
consequently, in some instances, the building may not liked by its occupants due to its poor
performance.
3.3. Sustainable Practices

Within the last decade sustainable development and building practices have acquired
great importance due to the negative impact of various development projects on the
environment. In line with a sustainable development approach, it is critical for practitioners to
create a healthy, sustainable built environment [36-37]. In Europe, 50% of material resources
taken from nature are building-related, over 50% of national waste production comes from the
building sector and 40% of energy consumption is building-related [38]. Therefore, more
attention should be directed towards establishing sustainable guidelines for practitioners.
Furthermore, the rapid growth in population has led to active construction that, in some
instances, neglected the impact on the environment and human activities. At the same time,
the impact on the traditional heritage, an often-neglected issue of sustainability, has not been
taken into consideration, despite representing a rich resource for sustainable building
practices.
Sustainability has been defined as the extent to which progress and development should
meet the need of the present without compromising the ability of the future generations to
meet their own needs [38]. This encompasses a variety of levels and scales ranging from
economic development and agriculture, to the management of human settlements and
building practices. This general definition was further developed to include sustainable
building practices and management of human settlements. The following issues were
addressed during the Rio Earth Summit in 1992 [39]:
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The use of local materials and indigenous building sources.

Incentive to promote the continuation of traditional techniques, with regional
resources and self-help strategies.
Regulation of energy-efficient design principles.
International information exchange on all aspects of construction related to the
environment, among architects and contractors, particularly non-conventional
resources.
Exploration of methods to encourage and facilitate the recycling and reuse of
building materials, especially those requiring intensive energy use during
manufacturing, and the use of clean technologies.
The objectives of the sustainable building practices aim to:
Develop a comprehensive definition of sustainability that includes socio-cultural,

bio-climate, and technological aspects.
Establish guidelines for future sustainable architecture.
Predict the CO2 emissions in buildings.
The proper architectural measure for sustainability is efficient, energy use, waste
control, population growth, carrying capacity, and resource efficiency.
Establish methods of design that conserve energy and natural resources.
A building inevitably consumes materials and energy resources. The technology is

available to use methods and materials that reduce the environmental impacts, increase
operating efficiency, and increase durability of buildings. Literature on green buildings
reveals a number of principles that can be synthesised in the creation of the built environment
that is sustainable. According to Lobo [40], these are: land development, building design and
construction, occupant considerations, life cycle assessment, volunteer incentives and
marketing programmes, facilitate reuse and remodelling, and final disposition of the structure.
These parameters and many more are essential for analysis, making them an important
element of the design decision-making process.
Today, architects should prepare for this as well as dealing with existing buildings with
many unfavourable urban environmental factors, such as many spaces have no choice of
orientation, and, often, set in noisy streets with their windows opening into dusty and polluted
air and surrounding buildings overshadowing them.
3.4. Buildings and CO2 Emission

To achieve carbon dioxide, CO2, emission targets, more fundamental changes to building
designs have been suggested [41]. The actual performance of buildings must also be
improved to meet the emission targets. To this end, it has been suggested that the
performance assessment should be introduced to ensure that the quality of construction,
installation and commissioning achieve the design intent. Air-tightness and the
commissioning of plant and controls are the main two elements of assessing CO2 emission.
Air-tightness is important as uncontrolled air leakage wastes energy. Uncertainties over
116
Abdeen Mustafa Omer
infiltration rates are often the reason for excessive design margins that result in oversized and
inefficient plants. On the other hand, commissioning to accept procedures would significantly
improve energy efficiency. The slow turnover in the building stock means that improved
performance of new buildings will only cut CO2 emissions significantly in the long term.
Consequently, the performance of existing buildings must be improved. For example,
improving 3% of existing buildings would be more effective in cutting emissions than, say,
improving the fabric standards for new non-domestic buildings and improving the efficiency
of new air conditioning and ventilation systems [42]. A reduction in emissions arising from
urban activities can, however, only be achieved by a combination of energy efficiency
measures and a move away from fossil fuels.
3.5. Low Energy Buildings

There is no single, simple formula for achieving low energy buildings. The basic
principle is to minimise energy demand and to optimise energy supply through a greater
reliance on local and renewable resources. Cities need to take a close look at how to make
more efficient use of resources while fulfilling the needs of the people. An energy dimension
should be included in the development process to measure the sustainability of urban and
building design and growth planning models. Previous experience in public transport systems
indicates that density is conductive to profitability and efficiency [43]. A compact urban form
with vertical zoning through multi-level and multi-functional urban clusters may be an
efficient option for high-density living. There are, however, opportunities for high-density
cities to explore and develop effective energy technologies, which can take full advantage of
the concentrated loads and high-rise context, such as using district energy systems and
vertical landscapes. Designing and constructing low energy buildings require the design team
to follow an energy design process that considers how the building envelope and systems
work together [44].
As low energy design is becoming more and more complicated, there is a need to develop
analytical methods and skills, such as simulation and modelling techniques, for the evaluation
of energy performance of buildings and the analysis of design options and approaches [45].
Kausch [46] pointed out that low energy building design is compatible with a wide range of
architectural styles. Studio Nicoletti [47] also illustrated the methods of architectural
expression for low energy buildings in their projects. For high-density conditions, some of
their methods are still valid but adaptation or modification may be needed to satisfy the local
requirements. Climate consideration is a key element and starting point for formulating
building and urban design principles that aim at minimising the use of energy for
environmental control. In densely populated areas, analysis of the climatic and solar
conditions is critical for the design optimisation. It should be noted that in urban areas, the
group of buildings would in fact modify the climatic conditions surrounding it.
Measures to maximise the use of high-efficiency generation plants and on-site renewable
energy resources are important for raising the overall level of energy efficiency. For
renewable energy systems, energy storage is still the major technical constraint to their
applications [48]. Loads concentration in high-density cities might provide opportunities for
better utilisation of renewable energy systems. At present, lack of incentives and shortage of
land and space are the key factors limiting the deployment of renewable energy systems.
117
High-rise buildings and high population density make it difficult to find suitable locations for
solar collectors and equipment. As the demand for heating energy is relatively low in many
buildings because of the warm climate throughout the year, the economic advantage of
directly using solar heat is weakened. To promote renewables, it is necessary to create new
development patterns and shift from a centralised view of energy sector to a regional
perspective [49]. One important aspect often being overlooked is the raising of awareness and
the education about low energy design. More efforts are needed to educate the people and
establish the culture so that more people would accept and consider low energy buildings an
important element of their living and working environment. It is important to recognise that
solutions to the energy problems are not simply a matter of applying technology and
enforcement through legislation [50]. It requires public awareness and participation as well.
Therefore, measures to promote public awareness and education are crucial for the
implementation of energy efficiency and renewable energy policies.
In summary, achieving low energy building requires comprehensive strategy that covers;
not only building designs, but also considers the environment around them in an integral
manner. Major elements for implementing such a strategy are as follows.
3.5.1. Efficiency use of energy

Climate responsiveness of buildings.
Good urban planning and architectural design.
Good house keeping and design practices.
Passive design and natural ventilation.
Use landscape as a means of thermal control.
Energy efficiency lighting.
Energy efficiency air conditioning.
Energy efficiency household and office appliances.
Heat pumps and energy recovery equipment.
Combined cooling systems.
Fuel cells development.
3.5.2. Utilise renewable energy
Photovoltaics.
Wind energy.
Small hydros (Table 3).
Waste-to-energy.
Landfill gas.
Biomass energy.
Biofuels.
3.5.3. Reduce transport energy
Reduce the need to travel.
Reduce the level of car reliance.
Promote walking and cycling.
Use efficient public mass transport.
Alternative sources of energy and fuels.
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Abdeen Mustafa Omer
3.5.4. Increase awareness

Promote awareness and education.
Encourage good practices and environmentally sound technologies.
Overcome institutional and economic barriers.
Stimulate energy efficiency and renewable energy markets.
4. DISCUSSIONS
A number of years of data on the solar radiation on horizontal surface, sunshine duration,
and wind speed in Sudan have been compiled, evaluated and presented in this study.
Measurements of global solar radiation on horizontal surface at 16 stations for couples of
years are compared with predictions made by several independent methods. In the first
method, Angstrom formula was used to correlate relative global solar irradiance to the
corresponding relative duration of bright sunshine. Regression coefficients are obtained and
used for prediction global solar irradiance. The predicted values were consistent with
measured values ( 8.01% variation). In the second method, by Barbaro et al., sunshine
duration, and minimum air mass were used to derive an empirical correlation for the global
radiation. The predicted values compared well with measured values ( 12% variation). The
diffuse solar irradiance is estimated using Pages, Lui and Jordans correlations. The results
of the two formulas have a close agreement. Radiation map of Sudan was prepared from the
estimated radiation values. The annual daily mean global radiation ranges from 3.05 to 7.62
kWhm-2 per day. Routine wind data from 70 stations were analysed. Monthly average wind
speeds, and average powers were determined for each station. The derived annual average
speeds range from 1.53 to 5.07 ms-1. Maximum extractable average wind powers were found
to vary between 1.35 and 49.5 wm-2. Wind map of Sudan was also prepared (Figure 1).
Figure 2 Yearly wind probability density (k = 1.99, c = 7.81ms-1. Figure 3 Schematic of
the construction of the wind pump.
4.1. Factors Determine Consumption

The following factors determine energy consumption in Sudan:
4.1.1. Urban and Rural

Substitution options for household energy in Sudan urban dwellings are electricity, LPG,
kerosene/gasoline and fuelwood. Rural towns and villages are the viable consumers of wood
and charcoal. Due to unavailability or un-affordability of fuelwood in these areas household
consumption was shifted towards agriculture residues.
Table 3. Recent assessments of comparative costs of turbine and diesel pump

Year
Water Current Turbine
Cost
Installation & training
3 yrs spares
Annual Maintenance
3 yrs maintenance
Annual cost
Accumulation Cost
10
11
12
6750
450
7200
7200
90
90
90
7470
972
90
90
1152
8622
90
8712
90
8802
1080
135
6
400
1621
6263
1207
1080
135
6
400
1621
7884
738
1080
135
6
400
1621
9505
-793
1080
135
6
400
1621
11126
-2324
90
90
90
90
7290
90
7380
972
90
90
1152
9954
90
90
90
10134
972
90
90
1152
11286
90
11376
90
11466
1080
135
6
400
1621
15389
-5255
1080
135
6
400
1621
17010
-5724
1080
135
6
400
1621
18631
-7255
1080
135
6
400
1621
20252
-8786
90
90
90
10044
1080
135
6
200
1421
13768
-3724
3 Diesel Pump
Cost
2000
Fuel
Oil
Grease
Spares & Maintenance
Annua1 cost
2000
Accumulation Cost
2000
WCT Diesel Pump
5200
Note: Figures shown in D.S * 100.
1080
135
6
1221
3221
4069
1080
135
6
200
1421
4642
2738
1080
135
6
1221
12347
-2393
120
Abdeen Mustafa Omer
Figure 1. Annual average wind speeds of Sudan (ms-1).
Figure 2. Yearly wind probability density (k = 1.99, c = 7.81ms-1.
121
Figure 3. Schematic of the construction of the wind pump.
4.1.2. Occupation
Occupation pattern are different in urban/rural areas. Housewives consider themselves
unemployed, through they are occupied by household management and children raising
(especially in rural area) are active in farms assisting their husband.
4.1.3. Income
Highest consumption of LPG and electricity is found in higher income households. For
wood and charcoal the situation is the reverse, highest consumption by low-income group and
lowest by high-income groups.
4.1.4. Education
It is quite evident that the share of illiteracy developed from 2.4% in high income
households up to 58.9% in rural low income in systematic matter which shows a direct
correlation between level of income, mode of living and education (result of household
survey 1994). In general illiteracy rates are higher among rural population compared to urban,
with levels around 4045% except for Khartoum rural with 21% illiterate.
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Abdeen Mustafa Omer
4.1.5. Family Size

The increase in energy supplies especially biomass was mainly observed due to
population growth which directly related to family size.
Figure 4 Performance of the CWD 5000. Figure 5 Locally-manufactured wind pump
installed at kilo 8 site.
4.2. Synthesis of the Renewable Energy

Although the overall impact of renewables has been necessarily low, the experience has
clearly demonstrated their potential as sustainable energy alternatives. There has been
substantial learning in disseminating and managing various technologies on account of:
Scale: with increasing numbers, teething problems have been overcome and better
knowledge has been gained in different aspects related to planning, implementation, operation
and maintenance.
Indigenisation: through joint ventures with international industry, the technology transfer
process has been facilitated, helping in developing local production capacities.
Infrastructure: a strong infrastructure has been created over the years to provide the
technical, operational and managerial support to intervention programmes. This includes
research institutions, training agencies, NGOs, financial intermediaries, etc.
Figure 4. Performance of the CWD 5000.
Diverse strategies: though the whole renewable energy programme started with the same
technology push approach, diversification occurred over a period of time in terms of
strategies and to promote different technologies according to market conditions.
123
Figure 5. Locally-manufactured wind pump installed at kilo 8 site.

50
20
18
40
Output (l/min)
16
14
30
12
10
20
8
6
Outp ut (l/min)
Efficiency (%)
10
2
0
0
1
10
Wind speed (m/s)
Figure 6. Wind pumps output and efficiency.
11
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Abdeen Mustafa Omer

Solar
Efficiency
6%
14%
30%
8%
Biofuels
Biomass
Wnd
8%
18%
16%
Other renewables
Low carbon
technologies
Figure 7. Renewable systems over the world.
4.2.1. Wind Power Calculation

The theoretical maximum power that can be extracted from the wind is:
P = * C p * a * A * V 3
(1)
Where:
P is the power available from wind Wm-2; Cp = 16/27 = 0.593; a is the average density of
air in Sudan, at the height of 10 m, taken as 1.15 kgm-3; A is the area swept by rotor,
projected in a plane perpendicular to the direction of wind m2 and V is the average wind
speed ms-1.
Annual mean wind speeds were derived from the original monthly mean wind speeds.
Annual mean wind powers were derived from monthly mean wind speeds, which were
calculated according to the following procedure: given a monthly mean wind speed V, the
maximum extractable monthly mean wind power per unit cross-sectional area, P is given by
[51]:
P = 0.3409 * V3
(2)
Where:
V is in ms-1 and P is in Wm-2.
Figure 6 Wind pump output and efficiency. Figure 7 Renewable systems over the world.
A note should be added on a distinction between wind pumps for different purposes:
(1) Low lift (<6 m), high volume applications (2 pumps are available).
(2) Medium lift application (<50 m) (10 pumps).
(3) Deep-well applications (>50 m) (more than 13 pumps).
125

1%
Germany
20%
Spain
3%
46%
1%
Europe
China
India
1%
Asia
10%
Aust ralia
18%
World
Figure 8. Wind distributions over the world.
In the beginning, priority has to be given to further industrial improvement of the

technology around Khartoum. Once the technology is sufficiently reliable, the focus has to
shift to applications in more remote areas for irrigation and for water supply purposes. The
overall specifications of modified CWD 5000 wind pump are as follows (modified by ERI):
Wind machine:
Rotor diameter
Number of blades
Tower height
Transmission
Safety mechanism
=5m
=8
=9m
= Crankshaft & connecting rod
= Furling system
Pump:
Diameter
Stroke
Static head
Cut-in wind seed
Rated wind speed
Cut-out wind speed
= 76 mm
= 20 cm
= 20 m
= 4 ms-1
= 9 ms-1
=12 ms-1
Figure 8 Wind distributions over the world.

The actual value that can be achieved practically is less than the above because of
mechanical losses and aerodynamic problems, which are not considered in collection the
0.593 value.
The most obvious region to start with seems to be the northern region because of a
combination of:
(1)
(2)
(3)
(4)
Good wind regime.

Shallow ground water level 5-10 m depth.
Need for additional rural water supply.
Existing institutional infrastructure: National Company for Manufacturing Water
Equipment Limited (NCMWE), Sahara Engineering Company, Sudanese
Agricultural Bank (SAB).
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Abdeen Mustafa Omer
4.2.2 Cost Comparison of Diesel and Wind Pumps

Two types of water lifting from ground water (40 m deep) are distinguished:
(1) A borehole of 35-40 m deep with 18 HP = 13.3 kW diesel engine-turbine pump.
(2) A borehole of 25-30 m deep with CWD 5000 wind pump.
A tentative cost comparison was made of a diesel engine pump and the CWD 5000 wind
pump as shown in Table 4, using the most common formula:
CT = (A + F x P + M)/v
(3)
Where CT is the total cost-based on initial capital cost, life, and discount rate; F is the
total fuel consumption; P is the fuel cost per litre; M is the maintenance cost; and v is the
volume of water pumped.
The annual cost is the function of the capital cost which is calculated by the interest rate
and the life of the system [52].
A = [C x I x (I+1)]T/[I+1]T-1
(4)
Where A is the annual cost; C is the capital cost; I is the interest rate or discount rate; and
T is the lifetime.
Figure 9 Conventional energies. Figure 10 Wind plants in Europe. Figure 11 Energy
conservation measures.
The comparison indicates that the necessary fuel and maintenance needed to run the
diesel pump unit long-term is the main factors, which govern the overall cost, and not the
capital cost of the diesel pump itself. Therefore, in the case of Sudan where the fuel is
expensive, the supply is uncertain, the infrastructure is poor, and areas are remote, the use of
wind machines is the ideal.
The following is concluded:
The initial investment cost of wind pumps is high; this may be a scale problem.
Maintenance costs in some areas are too high for the user.
The pumping costs are more or less the same.
Parallel and integrated projects could reduce costs.
Local production versus import: one of the perceptions is the installation of local
production.
(6) Utilities and water authorities should set up in and take over responsibilities
regarding technology and investment.
(7) There are substantial power production fluctuations due to variation in wind speed,
and using storage devices can smooth these out.
(1)
(2)
(3)
(4)
(5)
127

Table 4. Cost comparison of diesel and wind pumps in Sudanese Dinar (S.D)
Specification
Cost of borehole deep well
Cost of the system (purchased or fabricated in Sudan)
Cost of storage tank
Cost of annual fuel consumption
Cost of maintenance and repair
Total annual cost
Specific water pumping cost
Diesel pump
182400
93600
343700
120000
1582100
79.1 per m3
Wind pump
114000
440000
420000
110000
1084000
54.2 per m3
1 US $ = S.D 250 (Sudanese Dinar), in July 2000.

Annual output 15000-20000 m3 of water.
Annual fuel consumption: Average 491 gallons and price S.D 350-700 per gallons.
Interest rate 15%.
Ot her developing count ries

India
China and Hong Kong
Coal
Ot her developed count ries
Oil
Russia
Nat ural Gas
Japan
European Union
Unit ed St at es
0
0.2
0.4
0.6
0.8
Mi l l i on tons of oi l e qui val e nt
Figure 9. Conventional energies.
6000
5000
4000
Total plant capacity
3000
(1000 t)
Under construction
Operational
2000
1000
0
Ger
Ita
Spn
UK
Fra
Aus
Fin
Figure 10. Wind plants in Europe.
128
Abdeen Mustafa Omer
Gas
Oil
BU
Coal
Conservation measures
continued
Renewables
Maximum conservation
Hydro
Nuclear
0
0.2
0.4
0.6
0.8
Generation output (GWh)
Figure 11. Energy conservation measures.
80
Relative annual cost (%)
70
60
50
Maintenance
Charge controler
40
PV generator
30
Battery
20
10
0
1
Battery lifetime
Figure 12. Battery lifetime versus relative annual cost (%).
Figure 12 Battery lifetime versus relative annual cost (%). Figure 13 PV installed
capacity (MW). Figure 14 Landfill, recycled, composted and incineration in European
countries. Figure 15 PV generations in some leading countries.
The increased exploitation of renewable energy sources is central to any move towards
sustainable development. However, casting renewable energy thus carries with it an inherent
commitment to other basic tenets of sustainability, openness, democraticisations, etc. Due to
increasing fossil fuel prices, the research in renewable energy technologies (RETs) utilisation
has picked up a considerable momentum in the world. The present day energy arises has
therefore resulted in the search for alternative energy resources in order to cope with the
drastically changing energy picture of the world. The environmental sustainability of the
129
current global energy systems is under serious question. A major transition away from fossil
fuels to one based on energy efficiency and renewable energy is required. Alternatively
energy sources can potentially help fulfill the acute energy demand and sustain economic
growth in many regions of the world. The mitigation strategy of the country should be based
primarily ongoing governmental programmes, which have originally been launched for other
purposes, but may contribute to a relevant reduction of greenhouse gas emissions (energysaving and afforestation programmes). Throughout the study several issues relating to
renewable energies, environment and sustainable development are examined from both
current and future perspectives. The exploitation of the energetic potential (solar and wind)
for the production of electricity proves to be an adequate solution in isolated regions where
the extension of the grid network would be a financial constraint.
The provision of good indoor environmental quality while achieving energy and cost
efficient operation of the heating, ventilating and air-conditioning (HVAC) plants in buildings
represents a multi variant problem. The comfort of building occupants is dependent on many
environmental parameters including air speed, temperature, relative humidity and quality in
addition to lighting and noise. The overall objective is to provide a high level of building
performance (BP), which can be defined as indoor environmental quality (IEQ), energy
efficiency (EE) and cost efficiency (CE).
Indoor environmental quality is the perceived condition of comfort that building

occupants experience due to the physical and psychological conditions to which they
are exposed by their surroundings. The main physical parameters affecting IEQ are
air speed, temperature, relative humidity and quality.
Energy efficiency is related to the provision of the desired environmental conditions
while consuming the minimal quantity of energy.
Cost efficiency is the financial expenditure on energy relative to the level of
environmental comfort and productivity that the building occupants attained. The
overall cost efficiency can be improved by improving the indoor environmental
quality and the energy efficiency of a building.
10000
Base
1000
Int ermediat e
(%)
Reserve
P eak
100
10
1
1
9 10 11 12 13 14 15 16 17 18
In stal l e d capaci ty (MW )
Figure 13. PV installed capacity (MW).
130
Abdeen Mustafa Omer
Netherlands
Belgium
Germany
Austria
Landfill
Recycled/composeted
Spain
Incineration
Finland
UK
Greece
0%
20%
40%
60%
80%
100%
% of total waste
Figure 14. Landfill, recycled, composted and incineration in European countries.
Japan
Switzeralnd
Germany
Australia
Netherlands
EU-15
USA
0
0.5
1.5
2.5
Power (Wp)
Figure 15. PV generations in some leading countries.
3.5
An expression for the volume of airflow induced by wind is:

Qwind = K A V (1)
Qwind is the volume of airflow (m3/h)
A is the area of smaller opening (m2)
V is the outdoor wind speed (m/h)
K is the coefficient of effectiveness
131
132
Abdeen Mustafa Omer
CONCLUSION
Conclusion
Many cities around the world are facing the problem of increasing urban density and
energy demand. As cities represent a significant source of growth in global energy demand,
their energy use, associated environmental impacts, and demand for transport services create
great pressure to global energy resources. Low energy design of urban environment and
buildings in densely populated areas requires consideration of a wide range of factors,
including urban setting, transport planning, energy system design, and architectural and
engineering details. It is found that densification of towns could have both positive and
negative effects on the total energy demand. With suitable urban and building design details,
population should and could be accommodated with minimum worsening of the
environmental quality.
Wind Energy
Application of wind energy available in Sudan is a major issue in the future energy
strategic planning for the alternative to fossil conventional energy to provide part of the local
energy demand. This communication presents potential of wind regimes available in many
sites in Sudan; northern states (Dongola); eastern states (Port Sudan); and central states (Wad
Medani). The meteorological parameters must be reported, and can be considered as nucleus
information for executing research and development of wind energy projects; as the same
time, they could determine sites that are likely to have a better prospect, and will serve as a
good source of information for statistical analyses and correlation among various stations.
Also, it highlights future plans concerning optimum technical, economical, and environmental
utilisation of all wind energy available in Sudan. This theme presents a review of wind energy
activities, including research work, studies, and pilot projects in wind energy applications,
which are feasible technically and economically in Sudan. It highlights the promotion,
development and demonstration of wind energy resources amongst national, regional and
international organisations which involved; seek clean, safe, and abundant energy sources.
Sudan is rich in wind, about 50% of Sudan area is suitable for generating electricity
(annual average wind speed more than 5 ms-1), and 75% of Sudan area is suitable for
pumping water (annual average wind speed range between 3 5 ms-1).
In areas where there is wind energy potential, and not connected to the electric grid,
the challenge is the simplicity in the design, and higher efficiency.
The research and development in the field of wind pumps should be directed towards
utilising the local skills, and the local available materials.
Local production of wind pump should be encouraged on both public and private
organisations.
133
Solar Energy
Provide incentives to encourage the household sector to use solar energy.

Invest in research and development.
Assist in launching public awareness programmes with respect to solar energy.
Availing training opportunities to personnel at different levels.
Provide loans and / or grants to achieve the above objectives.
Biogas Energy
Biogas technology cannot only provide fuel, but also important for comprehensive
utilisation of biomass forestry, animal husbandry, fishery, evoluting the agricultural
economy, protecting the environment, realising agricultural recycling, as well as
improving the sanitary conditions, in rural areas.
The biomass energy, one of the important options, which might gradually replace the
oil in facing the increased demand for oil and may be an advanced period in the
coming century. Sudan can depend on the biomass energy to satisfy part of local
consumption.
Development of biogas technology is vital component of alternative rural energy
programme in Sudan, whose potential is yet to be exploited. A concerted effort is
required by all if this has to be realised. The technology will find ready use in
domestic, farming, and small scale industrial applications.
The diminishing agricultural land may hamper biogas energy development but
appropriate technological and resource management techniques will offset the
effects.
Support biomass research and exchange experiences with countries that are advanced
in this field. In the meantime, the biomass energy can help to save exhausting the oil
wealth.
REFERENCES
[1]
[2]
[3]
[4]
[5]
Eisa, E. I. (1981). A design study for wind pumps system for use in the Sudan, PhD
Thesis, University of Reading, Reading.
Hamid, Y. H. and Jansen, W. A. M. (1981). Wind energy in Sudan, CWD report 81,
2, The Netherlands.
Posoriski, et al. (1984). Case studies of the wind potential and its utilisation for water
pumping in Northern Sudan, Special Energy Programme (SEP), Khartoum, Sudan,
August.
Joop Van, Meel, Paul, H. and Abdeen Mustafa, Omer. (1987). Evaluation of Sudan
wind energy project, CWD ERI, October, 5 16.
Abu Bakr, E. H. (1988). The boundary layer wind regime at a representative tropical
Africa region, Central Sudan, PhD Thesis, Eindhoven, University of Technology, The
Netherlands, December.
134
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
Abdeen Mustafa Omer

Abdeen Mustafa, Omer. (1993). Wind speeds and wind power potential in Sudan, 4th
Arab International Solar Energy Conference, Amman, Jordan, November.
Hamid, E. B. (1995). Design and testing of a wind pump with pneumatically transmitted
power, M.Sc. Thesis, University of Khartoum, Sudan, December.
Abdeen Mustafa, Omer. (1997). Compilation and evaluation of solar and wind energy
resources in Sudan, Renewable Energy, Vol. 12, No. 1, 39 69.
Naga, A.M. and Amin, M. (1996). Towards a healthy urban environment in hot-humid
zones-information systems as an effective evaluation tool for urban conservation
techniques. In: Proceedings of XXIV IAHS World Congress: Ankara. Turkey.
Steele, J. (1997). Sustainable architecture: principles, paradigms, and case studies.
New York: McGraw-Hill Inc.
Sitarz, D. Editor. (1992). Agenda 21: The Earth Summit Strategy to save our planet.
Boulder (CO): Earth Press.
Omer, A.M. and Yemen, D. (2001). Biogas an appropriate technology. Proceedings of
the7th Arab International Solar Energy Conference, pp.417, Sharjah, UAE, 19-22
February.
Sarafiddis, Y., Diakoulaki, D., Papayannabis, L. and Zervos, A. (1999). A regional
planning approach for the promotion of renewable energies. Renewable Energy, 18(3),
317-30.
Tong, C.O. and Wong, S.C. (1997). Advantages of a high density, mixed land use,
linear urban development. Transportation, 24(3), 295-307.
Lam, J.C. (2000). Shading effects due to nearby buildings and energy implications.
Energy Conversion and Management, 47(7), 647-59.
Martin, W. (1996). Air quality control in commercial buildings. WREC.
Limb, M.J. (1995). Air intake positioning to avoid contamination of ventilation. AIVC.
Burge, P., Jones, P. and Robertson, A. (1993). Sick building syndrome. Proceedings
Indoor Air Quality. Finland.
Persily, A.K. (1989). Ventilation rates in office buildings. ASRAE, 128-136. Atlanta:
USA.
Givoni, B. (1976). Man climate and architecture. Applied Science Publishers Ltd, 289306. London, UK.
Koenigsberger, O., Ingersoll, T., Mayhew, A. and Szokolay, S. (1973). Manual of
tropical housing and building. Part 1: Climate design. Longmas, 119-130. London, UK.
Boulet, T. (1987). Controlling air movement: a manual for architects and builders.
McGraw-Hill, 85-138, New York: USA.
Szokolay, S. (1990). Design and research issues: passive control in the tropic.
Proceedings First World Renewable Energy Congress, 2337-2344, Reading: UK.
Borda-Daiz, N., Mosconi, P. and Vazquez, J. (1989). Passive cooling strategies for a
building prototype design in a warm-humid tropical climate. Solar and Wind
Technology, 6, 389-400.
Givoni, B. (1965). Laboratory study of the effect of window sizes and location on
indoor air motion. Architectural Science Review, 8, 42-46.
Fordham, M. (2000). Natural ventilation. Renewable Energy, 19, 17-37.
Hirunlabh, J. and Khedari, J. (1999). Study of natural ventilation of houses by a
metallic solar wall under tropical climate. Renewable Energy, 18, 109-119.
135
[28] Mats, S. and Barhram, M. (1998). Ventilated solar roof airflow and heat transfer
investigation. Renewable Energy, 15, 287-292.
[29] Campbell, J. (1988). Use of passive solar energy in office. In: OSullivan P, editor,
Passive Solar Energy in Buildings. The Watt Committee on Energy. New York:
Elsevier Applied Science.
[30] ASHRAE. (1993). Principle of the heating and ventilation and air conditioning.
Handbook-Fundamentals. American Society of Heat and Refrigerating and Air
Conditioning Engineers. USA.
[31] Molla, M. (1997). Air pollutants and its probable transmutation in the ionosphere.
Renewable Energy, 10 (2/3), 327-329.
[32] Jones, P.G. and Cheshire, D. (1996). Bulk data for marking non-domestic building
energy consumption. CIBSE/ASHRAE Joint National Conference. Harrogate, 29
September 1 October, 03-213.
[33] BRECSU. (1998). Energy use in offices. Energy Consumption Guide 19. Watford:
Building Research Energy Conservation Support Unit.
[34] Farm Energy Centre. (2000). Helping agriculture and horticulture through technology,
energy efficiency and environmental protection. Warwickshire.
[35] Randall, M. (1992). Environmental Science in Building. Third Edition.
[36] Tiwari, G.N. and Goyal, R.K. (1998). Greenhouse technology. New Delhi: Narosa
Publishing House.
[37] Santamouris, M., Balaras, C.A., Dascalaki, E. and Vallindras, M. (1994). Passive solar
agricultural greenhouse; a worldwide classification evaluation of technologies and
systems used for heating purpose. Solar Energy, 53(5), 411-26.
[38] Santamouris, M., Arigirious, A. and Vallindras, M. (1993). Design and operation of a
low energy consumption passive greenhouse. Solar Energy, 52(5), 371-8.
[39] Mercier, I. (1982). Design and operation of a solar passive greenhouse in the South
West France. In: Proceedings of the International Congress on Energy Conservation of
Agriculture and Fishculture. London.
[40] Grafiadellis, M. (1987). Greenhouse heating with solar energy. In: Von Zabettitz C
(Editor), FAO, Rome.
[41] Lobo, C. (1998). Defining a sustainable building. In: Proceedings of 23rd National
Passive Conference, ASES98. Albuquerque (USA): American Solar Energy Society.
[42] Pacheco, M., Marreivos, S. and Rosa, M. (1987). Energy conservation and renewable
energies for greenhouse heating. In: Von Zabettitz C (Editor), FAO, Rome.
[43] Santamouris, M., Mihalakakow, G., Belaras, C.A., Lewis, J.O., Vallindras, M. and
Argiriou, A. (1996). Energy conservation in greenhouses with buried pipes. Energy,
21(5), 353-60.
[44] Garzoli, K.V. and Blackwell, J. (1981). An analysis of the nocturnal heat loss from a
single skim plastic greenhouse. J. Agric. Engg. Res., 26, 203-14.
[45] Chandra, P. & Albright, L.D. (1980). Analytical determination of the effect on
greenhouse heating requirements of using night curtains. Trans ASAE, 23(4), 99941000.
[46] Blackwell, J. and Garzoli, K.V. (1981). Australian development of a low energy
greenhouse based on thermal storage rock piles. Acta Horticulture, 115, 113-23.
136
Abdeen Mustafa Omer
[47] Kausch A. (1998). Is low-energy building compatible with any architectural style? In:
Environmental friendly cities. Proceedings of PLEA 98, Lisbon: Portugal, June, 217220.
[48] Studio Nicoletti. (1998). Architectural expression and low energy design.
RenewableEnergy, 15, 32-41.
[49] Sutar, R.F. and Tiwari, G.N. (1995). Analytical and numerical study of a controlled
environment agricultural system for hot and dry climatic conditions. Energy and
Building, 23, 9-18.
[50] Carpenter G. (1986). Dust in livestock buildings- a review of some aspects. Journal of
Agricultural Engineering Research, 33, 227-241.
[51] Dawson J. (1990). Minimising dusts in livestock buildings: possible alternatives to
mechanical separation. Journal of Agricultural Engineering Research, 47, 235-248.

ISBN: 978-1-63117-329-5
Chapter 4
RATIONALIZATION OF SALT-RELATED PROCESSES

IN THE LEATHER INDUSTRY AS A TOOL FOR
MINIMIZATION OF THEIR ENVIRONMENTAL IMPACT
Karel Kolomaznk, Michaela Bainov, Ji Pecha
and Dagmar Janov
Faculty of Applied Informatics, Tomas Bata University in Zlin, nm.
T. G. Masaryka, Czech Republic
ABSTRACT
The main purpose of our contribution is reducing the existing environmental burden
related to the worldwide use of sodium chloride for raw hide curing. The essential step is
rationalization of the curing process itself, since it determines the amount of salt to deal
with in the subsequent operations such as pre-soaking, soaking, after-soaking and
desalting of animal fleshings during their complex processing into valuable products.
particularly sodium chloride. The salt often gets to water environment, or right to the
soils resulting in arid conditions in the spilling areas, from where it can be again washed
away to water sources. Despite intensive search for alternative methods, sodium chloride
remains the most common way of raw hide curing worldwide. This method not only
represents considerable environmental burden, but insufficient application of the theory
of the related transport phenomena also has economic impacts, such as high consumption
of the preservation agent, of water and electric power. Rationalization of the curing
process brings considerable reduction in the time necessary for proper curing and thus
reduction in the amount of salt which in subsequent soaking operation would get to
tannery effluents. Understanding the related transport processes, particularly diffusion of
sodium chloride into or from the hide inner volume, gives ground for their optimization
and thus to reduction of their adverse environmental impact as well as minimization of
the consumption of sodium chloride, water and energies. Our approach lies in application
of theoretical tools of chemical engineering, namely indirect modeling based on
quantitative relations from the theory of transport phenomena. This method is in
particular cases supported by experimentally measured data, mainly estimation of the
value of the effective diffusion coefficient of sodium chloride in animal fleshings and its
138
Karel Kolomaznk, Michaela Bainov, Ji Pecha et al.

application in calculation the minimal time necessary for proper curing of raw hides. The
acquired knowledge is applied in newly emerging industrial field, complex processing of
animal fleshings into valuable products such as quality biodiesel and gelatin. The
fleshings contain considerable amount of preservation salt, therefore desalting represents
the key operation in their processing and the quality of the resulting products is highly
dependent on the precise performance of the desalting process. The essential step leading
to the optimization was the determination of the time dependence of sodium chloride
concentration (from the hide surface towards its internal volume), in other words, a nonstationary concentration field of sodium chloride in the hide during the curing process.
Subsequently, the solution of the model allowed the calculation of the optimum time
necessary for sufficient preservation.
INTRODUCTION
As well as in medicine it is said that prevention is better than cure, the same applies for
industrial utilization of sodium chloride (common salt, NaCl). Examples of that utilization are
preservation of meat products, cheese manufacturing or processes in which raw hide is
transformed into leather.
Raw hides must be technologically processed by 12 hours after flaying [1] to prevent
microbiological and autolytical degradation which negatively affects the properties of the
final product leather. Since such quick processing is not possible in many areas, the hides
must be preserved before transportation to tanneries.
Since the authors have gained extensive experience in optimization and rationalization of
leather production from raw hides, this contribution will deal in particular with the processes
which involve sodium chloride namely raw hide curing and a specific operation called
pickling of white hide, which precedes the most important process tanning.
particularly sodium chloride. The salt often gets to water environment, or right to the soils
resulting in arid conditions in the spilling areas, from where it can be again washed away to
water sources. According to FAO [2], the worldwide leather production in 2010 was 6,214
ths. tons of bovine hides and 726 ths. tons of sheep and goatskins. For example in Kenya,
with yearly production of 2,8 mil. hides and 6 mil. skins, 85% of them are preserved with
sodium chloride, with an average of 11 ths. tons of salt spent every year [3]. Considering that
the amount of salt is about 300 kg of salt for one ton of hides, and by rough estimation more
than 60 % of world hides and skins are salt-cured, we get some million tons of sodium
chloride to deal with every year, most of it coming to waste waters.
Ozgunay et al. in their work [4] describe the main environmental impacts of salt coming
from leather industry, focusing mainly on the problem of limited water availability of saline
water for plants that are not salt-tolerant and soil degradation in the areas of storage of saltcured solid wastes. Due to concentration of leather industry within the last decades into
clusters limited to a relatively narrow geographical areas, the problem with increased salinity
applies especially to these areas and affects both soils and fresh waters (lakes, rivers, ground
water). It should be also considered that high salt content in rivers may temporarily or in long
time periods change the osmotic conditions especially when the river empties into water
reservoirs with higher evaporation rate than the influx.
Rationalization of Salt-Related Processes in the Leather Industry ...
139
There are various methods for optimization of salt consumption in raw hide curing. In our
contribution, we applied indirect modeling, which is based on mathematical analysis of
physical or physical-mechanical mechanisms of processes. On the contrary, direct modeling
is based only on experimental procedures without knowing the exact mechanisms and their
mathematical physical description, which is used so far in most of published tannery
research. The decision whether to apply direct or indirect modelling is a key step in a
proposal of a new technology or optimization of an existing one [5].
In direct modelling, we choose such an experimental laboratory (or pilot scale) procedure
that, without calculation and mathematical analysis of physical or physical-mechanical
processes, gives us direct answer to how the operating plant will behave. The experiment
therefore should be conducted in such a manner that the relationship between laboratory and
real operating process is as close as possible and the proposed design and operating mode of
the industrial apparatus do not require high abstraction. In conclusion, direct modelling builds
on long-time experience and comprises extensive and demanding experimental work.
Compared to this, the indirect modelling is based on mathematical models describing the
industrial processes or technological devices according to the nature of elementary actions,
that is physical-chemical processes, transport phenomena, sorption processes, etc. This
approach is based on highly abstracted data, i.e., data independent on the employed
experimental apparatus and its mode of operation. The experimental design in this way of
modelling can substantially differ from the real industrial setup as well as of laboratory
measuring potentially being quite different.
At present, the direct method is becoming hardly applicable in many industries including
leather manufacturing. The main reasons are high financial and time demands, and with
increasing production it is also getting difficult to approximate a laboratory experiment to real
industrial conditions, resulting in often unacceptable extent of intuitive extrapolation. On the
other hand, relying only on indirect modelling based exclusively on published data can also
be treacherous. This particularly applies to leather industry where well-conducted
experiments still play indispensable role because in most cases it represents the only way how
to obtain the elementary mechanism and properties of the studied process. For effective
combination of mathematical modelling and experimental work, it is necessary to perform
such experiments that allow precise evaluation and subsequent design of a technological
device on the basis of the experiment results.
An example of successful application of indirect modelling is given in [6]. The authors
use mathematical modeling of the soaking operation, i.e., the operation in which the
preservation salt has to be removed from cured hides for their further processing. In the series
of processes in which raw hide is transformed into leather, soaking is of great importance in
view of the quality of the final product, especially in the cases when the hides are cured with
solid rock salt. Incorrectly performed desalination may cause extensive damage to thinner
parts of cured hides and consequently lead to substantial economical losses. The damage can
be observed under scanning electron microscope as a collapse of the hide texture in the areas
close to the surface and is caused during rapid desalination due to the presence of great
osmotic (concentration) changes, so-called concentration shock. As a result, there are
considerable losses in the hide matter and also subsequent increase in the COD in the
effluents. In the said publication, mathematical models were worked out to define the
conditions under which the concentration shock occurs, and based on the models and
experimental verification, a technology of through-flow washing was proposed to preserve
140
the quality of fine fiber structure of the hides and eliminate the increase in COD in tannery
effluents.
OPTIMIZATION OF RAW HIDE PRESERVATION

Curing and soaking of raw hides are heterogeneous processes in which transport
phenomena often play crucial role. Description of the transport phenomena accompanying the
curing or desalting is closely related to the hide texture which predetermines not only the
properties of final leather, but also the demands on the hide curing and soaking [Bailey].
The hide texture is in close relation with the inner arrangement of collagen fibers. This
arrangement gives the hides their unique rheological properties [7] particularly their
substantial rigidity and tensile strength. On the other hand, the elasticity of hides results from
the presence of elastin, which unlike collagen shows relatively low rigidity. These properties
influence the mechanical action of the technological devices (tanning drums), which can
positively affect the operation times. The overall mechanical properties of hides are then
given mostly from the ratio of the said components and their spatial arrangement [8]. Other
important factor is the interfiber and intercellular space, the major part of which is liquid. The
presence of this free space filled with liquid ranks hides among porous materials
characterized by physical quantity called porosity, which is defined as a ratio of free volume
(pores) to the total volume of the solid material.
In addition to the free liquid (water) present in the pores, the hide also contains
considerable amount of water bound in the native structure of collagen. This water plays
important role in stabilization of the collagen macromolecule conformation by influencing the
chemical and physical properties of the hides as well as the value of the effective diffusion
coefficients. There are generally two ways of how water is bound in collagen structure
intramolecularly within the collagen triple helix, and intermolecularly between peptide chains
of different macromolecules [9]. Free water can be removed from hides by increased
pressure, resulting in the reduction in the hide volume. The reverse process is called
collagen/hide swelling. On the contrary, bound water remains in collagen structure even after
pressure increase over 70 MPa. In this stage, the hide contains about 45 % of water from the
original 60-70 %. This water shows some characteristic features different from common
water, such as losing the ability of electrolyte dissolving, freezing at -20C and change in
collagen structure (roentgenogram) after its removal [9]. About 2.5 % of this water is in
bound very firmly and can only be removed by drying at tempreratures above 100C, which
leads to structural changes in collagen macromolecules [9].
From the viewpoint of water distribution, cured hides can be classified as of good,
medium and poor consistence, which substantially affects the soaking (desalting) processes
[10]. The authors of this work observed slower removal of NaCl from hides of low moisture
content, the reason being supposedly the closure of the majority of pores due to conformation
changes in dehydrated collagen as a result of overdrying. Decelerated release of NaCl from
cured hides also occurs in the hides with higher content of fat on the flesh side.
One of indispensable functions of skin (hide) is preventing undesirable microorganisms
from getting into the body. As soon as the animal is slaughtered, microorganisms start to
penetrate through this protective barrier, reproduce and cause damage to the hide structure
141
[1]. For this reason it is crucial to protect fresh hides from microbial decay by preservation
(curing).
There are generally two ways of preservation short- and long-term. Short-term
preservation is effective within days up to few weeks and involves various methods of
cooling and/or antiseptics and biocides. Long-term preservation comprises drying, freezing
and salting. Wherever possible, fresh hides should be fleshed in order to dispose of fat and
excess subcutaneous tissue (so-called green fleshings). The fleshing operation results in
considerable reduction in the hide weight, facilitates preservation and the generated organic
waste does not contain additional chemicals, which makes it more valuable for its possible
processing.
If a beamhouse is located within reasonable distance from the abattoir, fresh hides are
cooled to preserve their natural, chemically untreated state. The cooling can be performed in
several ways such as chilling (cooling to 10-15C), refrigeration (deep cooling to the freezing
point) or freezing (at temperatures dropping from -10 to -30C) [11]. Chilled hides must be
processed by 3 days, refrigerated hides can be stored up to 3 weeks and frozen hides will last
for months. Disadvantages of the said preservation methods have rather practical aspect the
hides must be cooled individually immediately after flaying and cannot be exposed to higher
temperatures during transportation. Moreover, short-term chilling (when the chilled hides
must be delivered for further processing to tanneries within up to 24 hours) leads to
insufficient sorting of the hides by their weight and type. For this reason, advanced method of
cooling using dry ice was developed to preserve the hides for weeks (depending on
temperature) and allowing adequate sorting before their further processing [12]. Other longterm preservation is drying. This environmentally friendly method is still being used in the
countries with suitable climatic conditions. Drying can be applied on pelts and skins of
smaller animals (e.g., goatskins), but is not suitable for cattle hides which substantially limits
the general use of this method. There are also problems resulting from too fat or too slow
drying and last but not least, the drying skins can be attacked by insects [1].
Curing with common salt (sodium chloride, NaCl) is the most common way of long-term
preservation of raw hides [13]. At moderate temperatures, salt-cured hides can be stored up to
1 year, depending on the way of salting [1]. The use of crystalline NaCl is more common in
Europe, while in the United States the most prevalent method is brine curing with saturated
solution of NaCl [9]. In his comprehensive study [1] Bailey describes the dual effect of salt
curing for one thing, addition of salt removes water from the hide and thus reduces bacteriafriendly conditions inside the hide, and for another the presence of salt kills the organisms
adapted to normal osmotic conditions. Preservation with sodium chloride is advantageous
from several points of view it is relatively easy, cheap and suitable for transportation.
However, it also entails numerous disadvantages.
One of them is that hides cured with saturated brine solution are susceptible to attacks of
halophilic bacteria, it means bacteria adapted to habitats with increased salt concentrations.
There is a wide range of microorganisms capable of growing in saline environments. These
organisms can be generally classified as halotolerant, which are able to grow at moderate salt
concentrations although their optimal growth is in the absence of NaCl, and halophilic, the
growth of which is directly fixed on saline conditions. Halophilic organisms can be further
classified as mild, moderate and extreme halophils on the basis of the range of optimal salt
concentrations. Mild halophiles require 1-6% salt, moderate halophiles 6-15% salt and
extreme halophiles require 15-30% NaCl [14]. Some of these bacteria called haloarchaea can
142
be found even in saturated brine solutions used for raw hide curing. They contain high
amount of carotenoid compounds and cause red stains on brine cured hides, called the red
heat. While it was believed in the past that that the presence of halophils only indicates the
presence of other microorganisms which deteriorates the quality of final leather, more recent
publications imply otherwise. Bailey and Birbir [15] carried out detailed experimental study
on the action of halophilic bacteria and its correlation with the damage of hide structure. The
results of their research suggest that halophils themselves have an adverse effect on the
quality of leather made of attacked hides. This damage is mild or even negligible when cured
hides are stored at moderate temperatures and humidity, but with increased time of storage (as
early as 7 weeks and longer) and at higher temperatures the damage can be substantial.
The occurrence of red heat can be also influenced by the origin of salt used for curing.
Sea salt and salt from salt lakes generally contain higher numbers of halophilic bacteria
compared to rock salt. Birbir and Eryilmaz [16] found out that crude salt from salt lakes
contains up to 105-106 cfu/g of extremely halophilic bacteria (where cfu stands for colony
forming units and the authors of [17] describe about 82 strains of halophilic bacteria living in
natural sources of salt including salt lakes. High occurrence of these organisms substantially
limits direct utilization of this salt for raw hide preservation. On the contrary, sea salt dried in
drying oven contains practically no halophilic bacteria [18]. Other limitation of utilization of
salt from salt lake is higher concentration of particularly calcium and magnesium ions, which
in the case of calcium salts can lead to formation of salt stains and in the case of magnesium
salts to the formation of salt stippen (star-like elevations visible after de-hairing) [19].
Preservation method also plays a role in the occurrence of halophilic microorganisms.
Hides cured with solid salt are less susceptible to halophilic bacteria attack than those cured
in brine solution. It is said that rock salt cured hides generally contain 103-104 cfu/g, while
brine cured hides contain up to 106-107 cfu/g [20]. The difference comes from the fact that in
curing with dry salt only fresh and clean salt is used; on the contrary, in brine curing many
hides go through one brine solution, which makes it a bacteria reservoir that inoculates every
other hide put into the solution. The degree of bacterial contamination rapidly increases with
higher temperatures and the amount of hides going through one brine solution.
Red heat can be prevented by addition of specific substances aimed directly at halophilic
strains of bacteria. Orlita [21] proposes a combination of 2 % sodium carbonate and 2 %
naphthalene, or possibly 2 % zinc diethyldithiocarbamate (related to the weight of curing
salt). Vreeland et al. [22] inhibited halophilic microorganisms bile salts applied directly onto
cured hides, or as an additive in brine solution. Birbir and Eriylmaz [16] describe the
possibility of using natural antimicrobial substances called halocins which are produced by
some halophilic bacteria strains and serve as inhibitors of competitive halobacteria inhabiting
the same ecosystem.
Another disadvantage of salt curing is corrosion on transportation devices and generally
on all industrial equipment used in curing [1]. However, the most serious problem related to
salt curing is its adverse effect on the environment, especially on the amount of total
dissolved solids (TDS) in tannery effluents [23]. For this reason, alternatives to salt curing
have been sought intensively, based both on substantial reduction in the amount of salt used
or its complete substitution with other methods or chemicals.
According to the Leather International [24], the global trends in reduction in the amount
of salt in tannery effluents are the following:
143
low-salt pickling with polysulphonic acid

salt-free liquid chemicals
recycling of salt from waste waters (e.g., with membrane technologies)
Our approach lies in optimization of the brine curing process to reduce the total amount
of salt entering the hide-processing technological chain, keeping all the other advantages of
this method of preservation.
One of the alternatives is preservation with chemicals with antimicrobial and/or
fungicidal properties, which at the same time meet the required hygienic, economic and
environmental parameters. Antibacterial action is of major importance in raw hide curing,
because raw hides are susceptible to bacterial deterioration, while processed hides (for
example those tanned to the wet blue) are more likely attacked by mould [25]. An important
environmental parameter of mainly bactericidal substances is whether they show an adverse
effect on the activated sludge used in waste water treatment plants. Hides treated with
antibacterial chemicals last for weeks. Some of these chemicals were or have been used
commercially, although none of them have found global application. Examples can be
bacteriostatic substance Silostan developed in former Czechoslovakia [26] or Liricure
developed in South Africa, which was originally used for preservation of goatskins and later
on its application was extended to cattle hides [27]. Its wider application was limited by high
operation costs, though its environmental impact was considerably lower than that of sodium
chloride.
Mitchell [28] introduced a biocidal preparation Proxel X in combination with boric acid,
which according to Bailey [1] represents the best option for short-term raw hide preservation.
Other commercially used chemicals are for example didecyldimethylammonium chloride [25]
and products on the basis of dimethyldithiocarbamate [29] or 2-thiocyanomethylthiobenzothiazole [30], especially because of their minimal environmental impacts and low
health risks. These substances are usually used in the amount of 0.02-0.1 % related to the
weight of raw hides. At the said dosage and usual dilution in waste waters, the concentration
of these substances is generally below the levels which may negatively affect activated sludge
in waste water treatment plants and their residues in waste waters are usually eliminated
before biological treatment [25]. Hughes [31] describes raw hide preservation in a bath
containing concentrated solution of boric acid. Bailey and Hopkins [32] applied sodium
sulfite in combination with acetic acid and successfully tested this method on industrial scale
in a small abattoir in Illinois. Another promising alternative is according to Vankar and
Dwivedi [33] treatment of raw hides with sodium sulfate. Their study is supported by
successful experiments on both goatskins and buffalo hides, which represent one of the major
raw materials for Indian leather industry. The method with sodium sulfate is considered
prospectively sustainable also in more recent bibliographical sources [34].
Another chemical alternative to sodium chloride is its replacement with potassium
chloride (KCl) [35]. Hides cured with KCl have analogical properties as those cured with
NaCl and the excess KCl can be used as potassium fertilizer. Moreover, hides treated in this
way do not show signs of halophilic bacteria attacks. Its disadvantage is relatively high price
compared to NaCl and higher dependence of KCl solubility on temperature.
Radiation is another environmentally friendly alternative. It can be performed either in
the form of gamma [36] or electron beam irradiation [37]. While gamma irradiation has not
144
found wider application due to limited sources of gamma rays, electron beam irradiation has
been used commercially to a limited extent (its limitations come from high investment costs
and the need for additional biocidal treatment of irradiated hides). However, the latter method
is listed in the reference document of the European Commission [29] among BATs (best
available techniques).
Raw hides can also be preserved by pickling [1,9]. This operation leads to partial removal
of non-fibrous proteins which are most susceptible to bacterial degradation. Hides are
commonly pickled in 10 % solution of NaCl and 1% solution of sulfuric acid. Pickling can be
applied to light skins such as lambskins and goatskins. Relatively low pH (around 3.5)
protects the skins from bacterial degradation and the skins can be stored for several months.
The authors of the American patent [38] describe other non-salt method, namely
fatliquoring prior to tanning, which is subsequently followed by de-liming, bating and
pickling. This procedure leads to dry, flexible and preserved hides ready for the transportation
and tanning.
Quite common and efficient preservation method is chrome tanning to a product called
wet blue [1]. This method is suitable also for cattle hides and other heavy hides and reduces
the content of salt in waste water. The wet blue stock can be further treated with fungicides or
antibacterial preparations based on dimethyldithiocarbamate. In his comprehensive study [1]
Bailey also mentions the possibility of bio-preservation of raw hides with bacteria-produced
peptides (so-called bacitracins). Bacitracins were first isolated in 1945 from the bacteria
species Bacillus subtilis var Tracy [39]. Although their medicinal application is limited due to
high toxicity of these substances, they show biocidal effect even on bacteria species resistant
to most of the existing antibiotics including strains of exteremely halophilic bacteria (for
example in combination with novobiocin [17]). As far as the authors are concerned, this
research has not been brought to a commercial use so far, despite excellent preliminary results
mentioned by Bailey [1].
Other group of methods does not avoid utilization of NaCl completely, but works on the
basis of partial substitution of the salt load with other substances. Salt curing can be
combined with other preservation agents such as superabsorbent (co)polymers (SAP) [40], pchloro-meta-cresol after prior dehydration of the hides or sodium metabisulfite Na2S2O5 [41,
42]. The authors of the U. S. Patent [43] describe application of preservation additives such as
essential oils with antibacterial properties in combination with non-ionic surfactants that
enhance the diffusion of NaCl into the hides and thus make the preservation procedure more
efficient. Kanagaraj et al. [44] tested raw hide preservation with 5 % solution of boric acid, as
well as a preservation system composed of 2 % boric acid and 5% solution of NaCl. The
reference document of the European Commission [29] describes a method called flo-ice
which is commonly used in the fishing industry for fish preservation. Flo-ice is made in a
refrigerator device containing 3-5 % solution of NaCl to stay in the liquid state, at the
temperatures between 0 to -10C. Hides cured in this way can be stored in waterproof
containers for up to 3 days for which the temperature remains under 10C. This period can be
modified with the change of NaCl concentration. This method requires initial investment in
the flo-ice generating machinery.
Research in less-salt and salt-less alternatives is only one of the possible approaches how
to reduce the salt content in tannery effluents. Close attention is also paid to salt curing itself
since it still is the most commonly used and available way of preservation. Generally there are
two main research areas. We opened our contribution saying that the proverb prevention is
145
better than cure applies to many industrial areas and raw hide preservation is no exception.
Let us briefly start with the cure, in other words methods of salt regeneration once it is
dissolved in tannery effluents. The authors of [23, 45] describe methods for salt regeneration
from technological waters after soaking and its re-use in the preservation process. However,
the authors of [46] point out that generally this approach is not profitable from the economic
point of view. Re-use of such salt is limited due to organic contamination and fresh salt is
widely available at reasonable prices. Up to 10% of the spent salt can be mechanically shaken
out in suitable drums from hides cured with solid salt. After elimination of solid impurities,
this salt can be re-used in pickling, but cannot serve for curing due its contamination with
halophilic bacteria. The authors of [23] proposed a laboratory-tested procedure of NaCl
regeneration from brine solutions and its re-use in goatskin preservation; however, the
publication does not provide detailed analysis on the presence of halophilic bacteria. Reverse
osmosis and other membrane technologies have been discussed recently in relation to
reducing the salt content in tannery effluents. Basically, reverse osmosis (RO) has proved a
powerful tool in water desalination; for example, RO-based technologies are used in the
majority of sea water desalination plants [47]. Despite the fact that in principle RO also
significantly reduces the salt content in tannery effluents [48], the nature of tannery effluents
brings challenging tasks particularly from the viewpoint of optimization and economical
feasibility of RO applications. High organic content of tannery effluents leads to rapid fouling
of RO membranes with a consequent reduction of performance, which makes it necessary to
involve pre-treatment steps such as ultrafiltration or membrane bioreactors [48]. General
problem of pressure-driven membrane technologies including RO is the occurrence of
concentration polarization, which is an increase in concentration of salts dissolved in the feed
solution in the stagnant boundary layer at the membrane surface. The boundary concentration
thus exceeds the concentration of the bulk feed, leading to reduction of the feed flux rate
and/or formation of crystals that plug the membrane pores [49]. This undesirable
phenomenon cannot be eliminated completely, but can be reduced to some extent by
implementation of turbulators. This phenomenon also complicates mathematical modeling of
membrane systems since experimental determination of the boundary concentration is
exacting. Despite rapid progress in membrane technologies and gradual reduction of
operating costs, this way of desalination can still be financially unavailable particularly in
developing countries [50].
Another approach falls into the category "prevention" and lies in the application of
theoretical tools of chemical engineering, i.e., mathematical modeling of the chemicalphysical processes involved in particular technological procedures. In the case of salt curing it
means optimization of the main operating costs which is related to the determination of the
time necessary for proper curing and the consumption of salt, technological water and
energies. Mathematical description of the transport phenomena related to the transport of
NaCl in the hides has been so far mostly limited to soaking, which is in simple terms the
opposite of curing.
The first mathematical description of cattle hide soaking was published by O'Brien [51].
Detailed mathematical models of the soaking operation in a real industrial device (drum or
mixer) at repeated washing and a relatively low ratio of the volumes of the liquid and solid
phase, respectively, is given in [10]. The authors provided individual description of the initial
and later phase of soaking due to the different mechanisms of the said processes. They also
compared the values of transport parameter obtained from experimental data in fleshed
146
hides and hides without prior fleshing. The results of their work contain some important
conclusions that can be generalized also the curing; the authors state that the sorption of
sodium chloride to the hide matter (collagen) can be neglected, the diffusion takes place along
the real pore length which is not significantly influenced by hide swelling, the presence of
subcutaneous tissue substantially decelerates NaCl transport and soaking is slower in hides
with high percentage of dry matter. The said results were further applied in optimization and
control of the soaking operation [52]. Kolomaznk et al. [53] modeled soaking in tanning
drum as a non-isothermal and non-adiabatic reactor with implementation of the continuous
reaction model [54].
Most of published mathematical models of salt curing have been related to foodprocessing industry; sodium chloride diffusion has been described in meat and meat products
[55-57] and cheese [58]. There is also information on the experimental determination of the
effective diffusion coefficients, for example in cheese the values range between 1.0-5.3
1010 m2s1 at the temperatures between 10-15C, regardless on the cheese type and its
composition [59]. Experimental determinations of transport parameters are mostly based on
the relationships stated in Cranks excellent monograph [60]. Dehkordi et al. [61] presented
numerical solution of mathematical model of salt diffusion in potatoes and the description of
NaCl concentration fields in various times of curing.
There are practically no bibliographic records of mathematical modeling of raw hide
curing, with the exceptions of [13, 62]. The latter publication gives mathematical description
of concentration field and time dependence of NaCl concentration in a homogeneous sodium
chloride solution for various ratios of the liquid phase volume to the volume of raw hide
(soaking number). Minimal time necessary for proper curing is achieved by high values of
concentration gradient of NaCl on the hide surface, which is in the case of the said
publication possible at high soaking numbers. High concentration gradient leads to faster
curing and thus to saving on power consumption; on the other hand, it requires large quantity
of water and salt. Nevertheless, high values of concentration gradient can be also achieved by
the addition of solid salt into saturated brine solution. After termination of the curing process
there is a saturated brine solution left, which means that all the solid salt has been spent on the
curing [62].
DESALTING OF ANIMAL FLESHINGS

The "salt issue" in the leather industry is not restricted only to curing and soaking, but is
of great importance also in the processing of wastes generated by the said industry. Saline
liquid wastes and methods of salt regeneration have been already discussed above, but there is
also huge amount of solid waste to be taken into account. The possibilities of effective and
commercially interesting utilization of this waste, particularly primary waste generated in the
initial phase of raw hides processing, is a long-term global topic. Animal fleshings are a
typical example of such waste, representing more than 50 % of the total waste generated by
the leather industry [63] and at the same time the main protein solid waste of the said industry
[64]. The fleshings are produced during the fleshing operation, in which the remaining flesh
and fat are removed. The fleshings are referred to as green fleshings or pre-fleshings if
they are obtained before liming, or limed fleshings if hides are fleshed after the liming
147
procedure. Fleshing after liming brings practical advantages since the hides are de-haired, free
of major impurities and swollen after being placed for several hours in concentrated solution
of calcium hydroxide Ca(OH)2. However, this way also leads to creation of limed waste with
specific requirements for treatment and disposal, and limited utilization of the fat fraction
from limed fleshings. The fat partially hydrolyzes in strong alkali conditions of Ca(OH)2,
resulting in the losses of valuable raw stock. Moreover, with reduced fat increases the content
of free fatty acids which deteriorates the quality of the fat fraction.
Fleshings generally contain high portion of water and a balanced ratio of fat, protein and
carbohydrates [63]. In addition to that, green fleshings contain considerable amount of the
curing salt sodium chloride [65]. The protein content substantially complicates industrial
utilization of fleshings since it decomposes quickly and the decomposition products produce
unpleasant odors. For this reason, the majority of waste fleshings is incinerated or rendered.
Both ways are demanding from the viewpoint of both time and power consumption and lead
to economically uninteresting products. Incineration is frequently burdened with disposal fees
and also disputable from the environmental and public health aspect due to formation of toxic
dioxins in incineration products.
For the reasons described above, great efforts are being made recently to reduce the
health and environmental risks of fleshings processing as well as to find technologies to
convert fleshings into products with high economical potential. Examples of such attempt can
be found in [66], the authors of which treated fleshings with pancreatic enzymes; a
combination of enzymatic treatment and ultrasound is presented in [67] and fleshing
processing with acid hydrolysis using formic and propionic acids is described in [68].
Microbial treatment has been described as an interesting alternative to the chemical treatment
and is reported to be effective on both green and limed fleshings. The authors of [69] used
fleshings as a substrate for bacteria of the species Pseudomonas aeruginosa for the
production of alkaline protease, and Kumar et al. [70] tested microbial processing of tannery
protein waste for the production of mesophilic protease. To make a conclusion from the
above cited papers, the most frequently used ways of fleshings processing are chemical and
biological (or combinations of both), the products being used as fertilizers, feed additives, or
production of amino acids or enzymes. Great attention has been paid recently to utilization of
the fat fraction as an alternative source of energy (e.g., [71, 72]), the most promising [73] and
studied of which has been the production of biodiesel as an alternative to the existing
conventional biodiesel production from vegetable oils.
It is obvious from the available bibliographic sources on fleshing utilization that usually
only one of the two fractions (fat or protein) is processed. For overall and economically
profitable fleshing treatment it is advantageous to process both fractions simultaneously.
Research in this area has been very rare so far, with the exception of [63,64], or possibly [65].
The reasons for this are technological challenges to be overcome. One of the main
challenging tasks is the content of sodium chloride in the fleshings, which particularly
complicates effective processing of the protein fraction to commercial products such as
gelatin. Gelatin quality (and consequently its price) is derived from the gel strength (Bloom
value). This value decreases with higher ash content, in the case of fleshings the content of
sodium chloride. Desalting of fleshings is then one of the key operations in the technology for
its complex processing and gaining the maximal profit from the products.
In the following paragraph we would like to briefly summarize the background of our
research and set the objectives of our contribution. With reference to raw hide preservation,
148
most of the published papers deal with the properties of a particular preservation agent. The
most common way of preservation so far is curing with sodium chloride or its saturated
solution. Very few studies provide an engineering description of the curing process,
particularly by application of theoretical tools of chemical engineering for the description of
non-stationary concentration fields and time dependence of the salt concentration in the hides
or in the aqueous bath in the case of desalting. Quantitative relations of the said dependencies
can be then implemented in practical optimization for particular operation conditions. The
main purpose of our contribution is reducing the existing environmental burden related to the
worldwide use of sodium chloride for raw hide curing. The essential step is rationalization of
the curing process itself, since it determines the amount of salt to deal with in the subsequent
operations such as pre-soaking, soaking, after-soaking and desalting of animal fleshings
during their complex processing into valuable products. We focus on general application of
quantitative description of sodium chloride diffusion in various operations the mathematical
description is basically the same and differs only in the initial and boundary conditions.
MATHEMATICAL MODELING
Mathematical Model of Raw Hide Curing in Permanently Saturated Brine
Solution
Mathematical model of raw hide curing with pseudo-homogeneous sodium chloride
solution was first presented in [62] and is based on the model of continuous reaction [54].
Taking into account the observations from [1, 13], let us presume that the diffusion proceeds
asymmetrically into the hide inner volume from the flesh towards the grain side, forming a
non-stationary concentration field (Figure 1).
Figure 1. Mathematical model of sodium chloride diffusion into the hide iner volume during curing with
permanently saturated brine solution.
149
The model is represented by a partial differential equation of parabolic type (Flicks

Second Law) (1) under specific initial and boundary conditions. The complexity of the real
diffusion process is projected in the value of effective diffusion coefficient (Def) of sodium
chloride ions into the hide inner volume. The value of Def can be dependent on concentration
as well as on time. For a first approximation, let us assume that the value of Def does not
differ significantly with concentration. Experimental verification of this assumption is
described in the Experimental part. Considering the above stated limitation, the quantitative
model of raw hide curing can be described in the following form:
x, D
2c
x, 0
x 2
(1)
c
0, 0
x
(1a)
cb, cs
(1b)
cx,0 0
(1c)
Boundary condition (1a) says that the problem is not solved symmetrically, in other
words that the diffusion proceeds only from the flesh side towards the grain. Condition (1b)
expresses ideal mass transfer between the brine solution and the raw hide surface (the bath is
intensively stirred and the NaCl concentration in the bath is equal to the salt concentration in
the pores on the raw hide surface. Moreover, it is an open system where NaCl concentration
in the bath does not change with time and represents a permanently saturated brine solution
(which in practice is created by addition of solid salt into saturated brine solution. Initial
condition (1c) (i.e., when = 0) says that at the beginning of the curing process the
concentration of salt in the hide is zero. For the solution of the mathematical model it is
advantageous to introduce the following dimensionless parameter and variables:
c
cs
(2a)
x
b
(2b)
Fo
D
b2
(2c)
The dimensionless mathematical model together with the initial and boundary conditions
is represented by equations (3) (3c):
150
2
C
X , Fo C2 X , Fo Fo 0
Fo
X
(3)
C 1, Fo 1
(3a)
C
0, Fo 0
X
(3b)
C X ,0 0
(3c)
Taking into account that the presented mathematical model is linear, it is possible to
apply Laplace transformation for the solution of the partial differential equation. The
analytical solution (4) describes a dimensionless non-stationary concentration field of sodium
chloride in raw hide:
Fo 2 n 1
cos X 2n 1 2 e
C 1
2n 1 1n1
n1
2
2
(4)
Graphical expression of equation (4) is given in Figure 2:
Figure 2. Dimensionless concentration field of sodium chloride in hide during the curing process.
For the determination of time necessary to achieve certain degree of NaCl concentration
in the hide, we have introduced the integral mean concentration, which can be calculated
according to equation (5):
151
C C X , FodX
(5)
After integration, we get (6):
Fo 2 n 1
12 n3 e
C 1 2
2n 12 2
n 1
2
2
(6)
Dimensionless time dependence of the integral mean concentration is depicted in

Figure 3:
Figure 3. Dimensionless time dependence of the integral mean concentration of sodium chloride in raw
hide.
Mathematical Model of the Desalting of Animal Fleshings

Desalting is the first from the fleshing pre-treatment procedures in the complex
technology of industrial processing of fleshings into valuable products, both fat- and proteinbased. The fleshings are stirred in cold water, resulting in the formation of small spheres
pellets. Mathematical model of the desalting of fleshings was first published in [74] and
describes diffusion of sodium chloride from the pellet inner volume into the surrounding
aqueous bath (7):
152
2 cr , 2 cr ,
cr ,
0 r R1
D
r 2
r r
(7)
The model was solved under initial and boundary conditions given by equation (7a-e).
The following condition says that the problem is solved as symmetrical, in other words that
NaCl concentration is highest in the center of the pellet:
c0,
0
r
(7a)
We further assume that NaCl concentration in the beginning of the desalting process, i.e.,
when = 0, is constant for any point in the solid phase. This assumption is expressed by
boundary condition (7b).
cr,0 c p
(7b)
The following initial condition (7c) says that in the beginning of the desalting process
there is no salt present in the aqueous bath.
c0 0 0
(7c)
Equation (7d) stands for the assumption of an ideal mass transfer, which can be ensured
by ideal stirring in the reactor.
cR1 , c0
(7d)
Equation (7e) is the balance boundary condition which says that the diffusion flux of
NaCl on the pellet boundary is equal to the accumulation of the diffusion substance in the
volume of the surrounding aqueous bath (V0).
SD
cR1 ,
c
V0 0
r
(7e)
Again, we have introduced dimensionless parameters and variables defined by equations

(8a d).
cp c
cp
C0
c0
(8a)
(8b)
cp
Fo
D
R12
153
(8c)
r
R1
(8d)
By substitution of the said dimensionless variables into (7) we obtained mathematical

model of the desalting operation in dimensionless form (9), together with the related initial
and boundary conditions (9a-e):
C R, Fo 2 C R, Fo 2 C R, Fo

Fo
R
R
R 2
0 R 1
Fo 0
(9)
C 0, Fo
0
R
(9a)
C R,0 0
(9b)
C0 0 0
(9c)
C 1, Fo 1 C0
(9d)
C
1, Fo Na C0 Fo kde Na V0 , VS 4 R13 , S 4R12
3
R
3
Fo
VS
(9e)
By integration of (9) and implementation of the said conditions we obtained analytical

solutions of the model (10-13). Equation (10) represents dimensionless concentration field of
sodium chloride in the fleshing pellets:
sin R qn
exp Fo qn2
R qn
Na
2 Na
C

Na 3 n1
Na
1 Na
1 1
sin q n
3 cosqn 2
3qn qn qn
qn 3
(10),
where qn are roots of transcendent equation (11):
cotgqn
Na qn 1
3
qn
Graphical expression of equation (10) is given in the following Figure 4.
(11)
154
Equation (12) defines dimensionless concentration of NaCl in the surrounding aqueous

bath.
Figure 4. Dimensionless concentration field of sodium chloride in the fleshing pellets.
Figure 5. Time dependence of dimensionless salt concentration in the aqueous bath on dimensionless
water consumption (Na).
155
C0
Na
2 Na exp Fo qn2
3 n1 Na Na 2 qn2
1
9 2
(12)
The following Figure 5 shows the time dependence of dimensionless concentration of salt
in the bath for various dimensionless water consumptions (soaking number, Na).
One of the most important parameters in optimization of the desalting process is the
efficiency the degree of desalting (y). The efficiency can be calculated according to the
following equation (13):
Figure 6. Time dependence of the efficiency of the desalting process (y) for various soaking numbers
(Na).
V0 C0 NaC 0
Na
2 Na 2 exp Fo qn2
C pVS
Na 3 2 n1 Na Na 2 qn2
1
9 2
(13)
Symbol qn stands for the roots of transcendent equation (11) and Na denotes the ratio of
the volume of aqueous bath to the volume of solid phase (fleshings), also referred to as socalled soaking number.
Graphical expression of equation (13) is shown in Figure 6.
156
EXPERIMENTAL
Determination of the Effective Diffusion Coefficient of NaCl
As a reference value, we calculated the value of diffusion coefficient of sodium chloride
at infinite dilution according Nernst equation (14) [75]. This equation is sometimes referred to
as Nernst-Haskell equation [76], where the value of 8.9 10-10 is expressed as the universal
gas constant divided by Faraday constant, and the expression 0 stands for l l .
0
D0 8,93110
10
l0 l0 z z
T
0 z z

(14),
where D0 [cm2s1] is diffusion coefficient of NaCl at infinite dilution, T [K] is absolute

temperature, [Scm2mol1] stands for limit ionic conductances for cations and anions, 0
[Scm2mol1] represents the sum of limit ionic conductances of cations and anions and z+, z
[1] stand for the valences of cations and anions.
The value of diffusion coefficient of NaCl at infinite dilution and 20C calculated
according to equation (14) is 1.58 10-9 m2s-1.
Critical dimensionless time (Fourier diffusion criterion) FoK corresponding to the
required salt concentration in the hide can be read from Figure 3. For the calculation of the
real time () of the curing operation we need to know the value of the effective diffusion
coefficient (Def) and the thickness of raw hide (b). By implementation of the definition of
dimensionless Fourier criterion given by equation (2c), we obtain the following relation (15)
for the real time of curing:
where
FoK
(15),
D
.
b2
(15a)
We have introduced the important transport parameter that involves the hide thickness,
tortuosity and the effective diffusion coefficient. The transport parameter can be calculated
from experimental data obtained during the desalting of fleshings. In the case of the initial
phase of desalting and the assumption of very low values of effective diffusion coefficient
and relatively large particles of the solid phase, the time dependence of dimensionless salt
concentration in the bath can be calculated according to the following modified equation from
Crank [60]:
1 Na
Na
(16)
157
With rearrangement of (16) we get linear dependence of dimensionless concentration on

the square root of time (17) and the transport parameter can be estimated from the slope of
the straight line.
k Na

4 1 Na
(17)
The transport parameter is defined as diffusion coefficient at low concentrations divided

by the second power of the pore half-length. In our case, we can replace diffusion coefficient
with the value of the effective diffusion coefficient and the pore half-length with the
equivalent half-thickness of the fleshing pellets (Rm). Effective diffusion coefficient can then
be calculated as:
Def Rm 2
(18)
For the determination of the effective diffusion coefficient of salt in the inner volume of
the solid phase it was necessary to measure the conductivity of the bath on the square root of
time. After recalculation of conductivity to dimensionless concentration, we obtained the
graphical expression of equation (16). After linear regression of the data, we estimated the
value of the transport parameter from the slope of the straight line according to equation (17).
The following Figure 7 gives an example of the graph obtained from the experimental data:
Figure 7. Graph of the dependence of dimensionless salt concentration in the bath on the square root of
time during the desalting of fleshings.
The experiment work was carried out as follows: the electric conductivity was measured
in a mixture of animal fleshings obtained from a local tannery and distilled water. Initial
conditions of the experiment are given below. The heterogeneous mixture was intensively
158
stirred to eliminate the effect of inner diffusion. The conductivity was measured by a probe
every minute for one hour.
Example of the experiment:
Weight of the solid phase (fleshings)
Density of the solid phase
Equivalent half-thickness of the solid phase
Volume of the aqueous bath
Soaking number
Conductivity corresponding to the initial
concentration of the bath
Conductivity corresponding to the equilibrium
concentration of the bath
202 g
0.900 gcm-3
0.125 cm
600 ml
2.67
2 Scm-1
160 Scm-1
Dimensionless concentration was calculated from the measured conductivity divided by

the conductivity corresponding to equilibrium concentration, where from each member was
subtracted the value of the conductivity corresponding to the initial salt concentration in the
bath.
The resulting effective diffusion coefficient was 5.582 10-10 m2s-1.
OPTIMIZATION OF RAW HIDE CURING

The obtained effective diffusion coefficient can be approximated also for the case of raw
hide curing. Proceeding from equations (15) and (15a), the minimal time necessary for proper
curing can be calculated for raw hides of various thicknesses. The 85 % hide saturation with
salt, which is according to [33] the minimal value for proper curing, corresponds to the value
of FoK = 0.125. Implementing the value of Def = 5.582 10-10 m2s-1 and for the hide
thicknesses of b = 5; 10 and 15 mm, the corresponding minimal times for proper curing are
1.6; 6.2 and 14 h, respectively. In common practice according to [13] the hides are cured in
practically saturated brine solution for the minimum of 18 h at soaking numbers around 5.
The results of our work thus not only helps to save the time for which the hides must
remain in the curing raceway, but termination of the curing process right at the time of
reaching the 85 % saturation leads to considerable savings in the amount of the preservation
agent and electric power consumption. The fact that the cured hides do not contain
unnecessarily higher amount of salt also substantially reduces the amount of salt to deal with
in the effluents generated during the soaking operation and thus reduces the environmental
burden. Moreover, modeling of raw hide curing under the assumption that the maximal
concentration gradient is maintained by permanently saturated NaCl solution and not by high
soaking numbers is beneficial also from the viewpoint of water consumption.
The experimentally determined value of the effective diffusion coefficient is lower by
one order of magnitude than the theoretical value calculation according to Nernst equation at
infinite dilution (14), but is in good agreement with experimental values calculated for
soaking of cured hides [10, 77]. The speed of diffusion can be influenced by many factors,
one of the most important of which is the nature of the porous material itself, in other words
159
the arrangement of the collagen fibers in the hide, and its homogeneity. For comparison,
experimentally determined effective diffusion coefficients in meat and meat products, it
means materials composed mostly of highly organized molecules of myosin, were generally
in the same order of magnitude ( 10-10 m2s-1) as those estimated for raw hides, while in
potatoes (consisting mostly of polysaccharide starch) the diffusion coefficients were
ranging between 3.45 4.39 10-9 m2s-1 [61] in dependence on the initial salt concentration
in the curing bath. Other factors which can affect the speed of diffusion are for example poor
fleshing, agglutination of protein fibers, or high portion of dry matter in the hides (fleshings).
In contrast to soaking, the latter factor probably does not play important role in the curing
since it is unlikely that fresh hides overdry before curing.
ECONOMIC PARAMETERS OF THE DESALTING OF FLESHINGS

The basic economic parameters of the fleshing desalting operation have been described in
[74]. The main operating costs of the desalting involve the sum of the unit electric power
consumption necessary for stirring, and the overall washing water consumption:
N K E P KV VV
(19)
Consumption of the washing liquid (water) (VV) [m3] is an implicit function of time ()
[h], which is calculated according to equation (13) for the required desalting efficiency (y).
Symbol KE [USDkWh-1] denotes unit price of electric power, P [kW] is the input power the
electromotor for the mixer and KV [USDm-3] represents unit price of washing water. A
computer program has been elaborated which allows calculating the intersections for the
required desalting efficiency and various soaking numbers. These intersections are
subsequently implemented in equation (5.17), where the resulting cost function shows a
minimum. The purpose of rationalization is to control the desalting operation in this
minimum. The said publication gives also detailed description of experimental determination
of the fleshing desalting efficiency (y) during decantation washing and the related cost
functions for various levels of the required efficiency and various soaking numbers. The
results show that the proposed mathematical model can be implemented in the industrial
design of the desalting procedure for the calculated optimal conditions. The importance of
incorporation of the desalting step in the technology of complex processing of fleshings into
valuable products was proved by observation of the properties of gelatin prepared according
to patented technology of fleshing pre-treatment [78]. Gelatin obtained by the innovative
technology showed very low ash content and at the same time very high Bloom value
compared to gelatin produced without implementation of the desalting step.
CONCLUSION
Despite of global efforts to find economically viable and environmentally friendly
methods of raw hide curing with reduced or no involvement of sodium chloride, curing with
common salt still remains the most frequently used worldwide. Rationalization of the curing
160
process leads to shorter times necessary for proper curing and consequent reduction in the
consumption of water, energies and the preservation agent. Our contribution shows the
advantages of application of indirect modeling, particularly the theory of transport
phenomena for mathematical description of raw hide preservation for optimization of the said
technological operation. Based on the analytical solution of the mathematical model and
experimental determination of the effective diffusion coefficient of sodium chloride in the
hide (fleshings), we were able to estimate minimal time periods necessary for proper curing
of hides of various thicknesses. The acquired knowledge can be used in rationalization of
other technologies related to the leather industry and processing of its waste; in our case, we
give an example of application of the model on the desalting of fleshings during its
processing into valuable fat- and protein-based products such as quality biodiesel and glycerin
and commercial grade gelatin.
ACKNOWLEDGMENT
This work is a part of PhD thesis Barinova, M. Optimization of Raw Hide Preservation
[in Czech], Tomas Bata University in Zlin, Czech Republic, 2013. The work was financed by
the Ministry of Education, Youth and Sports of the Czech Republic, grant No. 7088352102
and ERDF Project CEBIA Tech No. CZ.1.05/2.1.00/03.0089. The authors would also like to
express great appreciation to the people from the Eastern Regional Research Center, USDA,
Wyndmoor, Pennsylvania, USA for a long-term beneficial cooperation.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
Bailey, D. G. The 44th John Arthur Wilson memorial lecture: Preservation of hides and
skins. J. Am. Leather Chem. As. 98, 308-319, 2003. ISSN 0002-9726.
Medium-term prospects for agricultural Commodities Projections To The Year 2010.
URL <http://www.fao.org/docrep/006/y5143e/y 5143e00.htm#Contents>.
Mwinyihija, M., Magero, J., Chamining'wa, G. N., Gnanamani, A. Characterization of
hides and skins curing process and rusultant effluent impact on soil profile at
Mariakani, Kenya. In II. International Leather Engineering Congress Innovative
Aspects for Leather Industry, May 12-13 2011, Izmir, Turkey.
Ozgunay, H., Colak, S., Mutlu, M. M., Akyuz, F. Characterization of Leather Industry
Wastes. Pol. J. Environ. Stud. 2007, vol. 16, p. 867-873.
Kolomaznk, K., Janov, D., Vaek, V., Blaha, A. Chemical Engineering and
Automatic Control in Leather Technology. In Advanced technologies researchdevelopment-application. Mammendorf: Verlag Robert Mayer-Scholz, 2006, s. 475516. ISBN 3-86611-197-5.
Kolomaznk, K., Furst, T., Uhlov, M. Relationship between mass transport and the
quality of cured hide. The Canadian Journal of Chemical Engineering, 2009, ro. 87, .
1, s. 60-68. ISSN 0008-4034.
Jeyapalina, Sujeevini. Studies on the hydro-thermal and viscoelastic properties of
leather. PhD thesis, University of Leicester, Great Britain, 2004.

[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
161
Lopot, Frantiek. Reologie a biomechanika. Aplikace model. Praha: Katedra anatomie

a biomechaniky FTVS UK. [in Czech]
Blaej, A., Galatk, A., Galatk, J., Mldek, M: Technologie ke a koein. SNTL
Praha, ALFA Bratislava, 1984, 451 pp. [in Czech]
Blaha, A., Kolomaznk, K. Mathematical model of soaking. Part I. J. Soc. Leath. Tech.
Ch. 1989, vol. 73, p. 136-140. ISSN 0144-0322.
Adzet, J. M. Short term preservation of raw hides and skins. World Leather 1997, vol.
10, No. 3, p. 59-60.
Endlweber, Hans. Preserving animal hides. United States Patent 4985039, 1991-01-15.
Hernandez Balada, E., Marmer, W. N., Kolomaznk, K., Cooke, P. H., Dudley, R. L.
Mathematical model of raw hide curing with brine. J. Am. Leather Chem. As. 2008,
vol. 103, p. 167-173. ISSN 0002-9726.
Todar, K. Todar`s Online Textbook of Bacteriology. University of Wisconsin, 2009.
Bailey, D. G., Birbir, M. The impact of halophilic organisms on the grain quality of
brine-cured cattle hides. J. Amer. Leather Chem. Ass. 1998, vol. 93, p. 121-131. ISSN
0002-9726.
Birbir, M., Eryilmaz, S. Prevention of halobacterial damage on hide caused by lipolytic
halophylic archaea with halocins, 2006. www.aaqtic.org.ar/congresos/istanbul2006/
Birbir, M., Sesal, C. Extremely halophilic bacterial communities in Sereflikochisar salt
lake in Turkey. Turk. J. Biol. 2003, vol. 27, p. 7-22.
International Union of Leather Technologists and Chemists Societies (IULTCS).
www.iultcs.org/leather_terms/r.asp.
CSIRO Division of Food Research, Meat Research Laboratory. Salt for hide
preservation: The preventiv of salt stains and salt stippen. Meat Research News Letter
1974, vol. 74, no. 2. http://www.meatupdate. csiro.au/data/MEAT_ RESEARCH_
NEWS_LETTER_74-2.pdf
The American Leather Chemists Association, Leather Discussion (online diskusn
forum). www.leatherchemists.org/forum/, September 30, 2007. Search: halophilic
bacteria.
Orlita A. Microbial biodeterioration of leather and its control: a review. Int.
Biodeterior. Biodegradation 2004, vol. 53, p. 157-163 ISSN: 0964-8305.
Vreeland R. H., Bailey D. G., Claunch R. W. Method of using bile salts to inhibit red
heat in stored brine-cured hides and skins. United States Patent No. 5,945,027, 199908-31.
Preethi V., Ramesh R., Chandra Babu N. K., Sehgal P. K. Efficient salt recovery and
total dissolved solids reduction in leather processing. J. Am. Leather Chem. As. 2006,
vol. 101., no. 4, p. 117-122. ISSN 0002-9726.
Salt in wastewater from leather manufacturing. URL <http://www. leathermag.com/
features/featuresalt-in-wastewater-from-leather-manufacturing/>
Hauber, C. Microbicide applications in the leather industry. Directory of Microbicides
for the Protection of Materials: A Handbook. Paulus, W. (Editor), 2005, p. 317-324,
online ISBN: 978-1-4020-2818-2.
Orlita, A., Ludvk, J., Navrtil, V: Krtkodob konzervace vepovic. Koastv 1986,
vol. 36, p. 78.
Russell, A, E., Tandt, H., Kohl, R: Liricure Powder biocide composition for hide and
skin preservation. J. Soc. Leath. Tech. Ch. 1987, vol. 81, p. 137-142. ISSN 0144-0322.
162
[28] Mitchell, J. W. Prevention of bacterial damage on brine cured and fresh cattlehides. J.
Am. Leather Chem. As. 1987, vol. 82, no. 12, 372-382. ISSN 0002-9726.
[29] Integrated Pollution, Prevention and Control (IPPC). Reference Document on Best
Available Techniques (BAT) for the Tanning of Hides and Skins. European
Commission, February 2003.
[30] Gattner, H., Lindner, W., Neuber, H. U: Mikrobieller Befall bei der Lederherstellung
und seine Kontrolle mit modernen Konservierungsmitteln. Das Leder 1988, vol. 39, no.
4, p. 66-73. ISSN 0024-0176.
[31] Hughes, I. R. Temporary preservation of hides using boric acid. J. Soc. Leath. Tech.
Ch. 1974, vol. 78, p. 18-53. ISSN 0144-0322.
[32] Bailey, D. G., Hopkins, W. J. Cattle hide preservation with sodium sulphite and acetic
acid. J. Am. Leather Chem. As. 1977, vol. 72, p. 334. ISSN 0002-9726.
[33] VANKAR, P. S., DWIVEDI, A. K. Sulphates for skin preservation - A novel approach
to reduce tannery effluent salinity hazards. J. Haz. Mater. 2009, vol. 163, no. 1, p. 207212. ISSN: 0304-3894.
[34] Gorems, A. Reduction of Total Dissolved Solids from Tannery Effluent by Optimum
Substitution of Common Salts with Sodium Sulphate for Hide/skin preservation. LAP
LAMBERT Academic Publishing 2012. 120 p. ISBN 978-3-8473-3387-6.
[35] Bailey D. G., Gosselin, J. The preservation of animal hides with potassium chloride. J.
Am. Leather Chem. As. 1996, vol. 91, p. 317-333. ISSN 0002-9726.
[36] Bailey, D. G. Gamma radiation preservation of cattle hides. A new twist on an old
story. J. Am. Leather Chem. As. 1999, vol. 94, no.7, p. 259-267. ISSN 0002-9726.
[37] Bailey, D. G., Dimaio, G. L., Gehring, A. G., Ross G. D. Electron beam irradiation
preservation of cattle hides in a commercial scale demonstration. J. Am. Leather Chem.
As. 2001, vol. 96, no. 10, p. 382-392. ISSN 0002-9726.
[38] Holicza, P. J. Method of preserving hides and skins. United States Patent US
2011/0135951 A1, 2011-06-09.
[39] Johnson, B., Anker, H., Meleney, F. Bacitracin: a new antibiotic produced by a
member of the B. subtilis group. Science 1945, vol. 102, p. 376-377. ISSN 0036-8075.
[40] Brosse, J., Sabatier, B. Use of superabsorbent polymers for treating raw skins,
corresponding compositions and methods and resulting treated skins. United States
Patent 6964745, 2005-11-15.
[41] Kanagaraj, J., Chandra Babu, N. K., Sadulla, S., Suseela RAJKUMAR, G., Visalakshi,
V., Chandrakumar, N. A new approach to less-salt preservation of raw skin/hide. J.
Am. Leather Chem. As. 2000, vol. 95, no. 11, p. 368-374. ISSN 0002-9726.
[42] Kanagaraj, J., Sastry, T. P., Rose, C. Effective preservation of raw goat skins for the
reduction of total dissolved solids. J. Clean. Prod. 2005, vol. 13, no. 9, p. 959-964.
ISSN: 0959-6526.
[43] Johnson, D. J., Mcaninch, T. L., Holzhauer, F. W. Hide-curing additive. United States
Patent 6451062, 2002-09-17.
[44] Kanagaraj, J., Sundar, V. J., Muralidharan, C., Sadulla, S. Alternatives to sodium
chloride in prevention of skin protein degradation - a case study. J. Clean. Prod. 2005,
vol. 13, no. 8, p. 825-831. ISSN: 0959-6526.
[45] Gautam, S. P. Recovery of better quality reusable salt from soak liquor of tanneries in
solar evaporation pans. Control of Urban Pollution Series: Cups/ 2009-10. India,
Central Pollution Control Board Ministry of Environment & Forests, January, 2009.
163
[46] International Union of Leather Technologists and Chemists Societies (IULTCS). IUE1: Recommendations on cleaner technologies for leather production, 2008.
www.iultcs.org/IUE1_2008.pdf.
[47] IDA Desalination Yearbook 2012-2013, ISBN 978-1-907467-19-6.
[48] Scholz, W. G., Roug, P., Bdalo, A., Leitz, U. Desalination of Mixed Tannery
Effluent with Membrane Bioreactor and Reverse Osmosis Treatment. Environ. Sci.
Technol. 2005, vol. 39, p. 85058511.
[49] HO, W. Membrane Handbook. 2nd ed. New York: Chapman & Hall, 1992, 954 s.
ISBN 0412988712.
[50] UNIDO. Introduction to treatment of tannery effluents. URL <http://www.unido.org/
resources/publications/poverty-reduction-through-productive-activities/agribusinessand-rural-entrepreneurship/introduction-to-treatment-of-tannery-effluents.html?
ucg_no64=1%2Fdata%2Fproject%2FDATA1%2Fdata%2Ffileadmin%2Ftemplates%2
Ftypo3conf%2Fext%2Fdoc%2Findex.php>
[51] OBrien, D. J. A mathematical model for unsteady state salt diffusion from brine-cured
cattlehides. J. Am. Leather Chem. As. 1983, vol. 78, p. 286-299. ISSN 0002-9726.
[52] Kolomaznk, K., Prokopov, Z., Vaek, V., Bailey, D. Development of a Control
Algorithm for the Optimized Soaking of Cured Hides. J. Am. Leather Chem. As. 2006,
vol. 101, no. 9, p. 309-316. ISSN 0002-9726.
[53] Kolomaznk, K., Frst, T., Uhlov, M. Relationship between mass transport and the
quality of cured hide. Can. J. Chem. Eng. 2009, vol. 87, no. 1, p. 60-68. ISSN 00084034.
[54] Levenspiel, O. Chemical Reaction Engineering, 3rd Ed., John Wiley & Sons, Inc., New
York, 1999. 578 pp. ISBN 978-0-4712-5424-9.
[55] Gravier, N., Pinotti, A., Califano, A., Zaritzky, N. Mathematical modeling of the
uptake of curing salts in pork meat. J. Food Eng. 2009, vol. 95, no. 4, p. 533-540. ISSN
0260-8774.
[56] Barat J. M., Baigts, D., Alio, M., Fernndez, F. J., Prez-Garca, V. M. Kinetics
studies during NaCl and KCl pork meat brining. J. Food Eng. 2011, vol. 106, p. 102110. ISSN 0260-8774.
[57] Bertram, H. C., Holdsworth, S. J., Whittaker, A. K., Andersen, H. J. Salt diffusion and
distribution in meat studied by 23Na nuclear magnetic resonance imaging and
relaxometry. J. Agric. Food Chem. 2005, vol. 53, p. 7814-7818. ISSN 1520-5118.
[58] Turhan, M., Kaletun, G. Modeling of salt diffusion in white cheese during long term
brining. J. Food Sci. 1992, vol. 57, no. 5, p. 1082-1085. ISSN 1750-3841.
[59] Floury, J., Jeanson, S., Aly, S., Lortal, S. Determination of the diffusion coefficients of
small solutes in cheese: A review. Dairy Sci. Technol. 2010, vol. 90, no. 5, p. 477-508.
ISSN 1958-5586.
[60] Crank, J. Mathematics of Diffusion, 2nd ed., USA, 1975, Oxford University Press, Inc.,
New York. 414 pp. ISBN 0-19-853411-6.
[61] Dehkordi, B. M., Hashemi, F., Mostafazadeh, R. Numerical solution of the equations of
salt diffusion into the potato tissues. International Journal of Chemical and Biological
Engineering 2010, vol. 3, no. 2, p. 78-81. ISSN 2010-3867.
[62] Bainov, M., Kolomaznk, K., Vaek, V., Matyaovsk, J., Jurkovi, P. Optimization
of raw hide curing using two-component counter-current diffusion model. J. Am.
Leather Chem. As. 2009, vol. 104, no. 12, p. 397-404. ISSN 0002-9726.
164
[63] Kanagaraj, J., Velappan, K., Chandra Babu, N. K., Sadulla, S. Solid wastes generation
in the leather industry and its utilization for cleaner environment-A review. J. Sci. Ind.
Res. 2006, vol. 65, p. 541-548. ISSN 0975-1084.
[64] Sundar, V. J., Gnanamani, A., Muralidharan, C., Chandra Babu, N. K., Mandal, A. B.
Recovery and utilization of proteinous wastes of leather making: A review. Rev.
Environ. Sci. Biotechnol. 2011, vol. 10, p. 151163. ISSN 1572-9826.
[65] Dalev, P. G., Simeonova, L. S. An enzyme biotechnology for the total utilization of
leather wastes. Biotechnol. Lett. 1992, vol. 14, p. 531-534.
[66] Kumaraguru, S., Sastry, T. P., Rose, C. Hydrolysis of tannery fleshings using
pancreatic enzymes: a biotechnological tool for solid waste management. J. Am.
Leather Chem. As. 1998, vol. 93, p. 3239. ISSN 0002-9726.
[67] Jian, S., Wenyi, T., Wuyong, C. Ultrasound-accelerated enzymatic hydrolysis of solid
leather waste. J. Clean. Prod. 2008, vol. 16, p. 591-597. ISSN 0959-6526.
[68] Rai, A. K., Nived, C., Sakhare, P. Z., Suresh, P. V., Bhaskar, N., Mahendrakar, N. S.
Optimization of acid hydrolysis conditions of delimed tannery fleshings by response
surface method. J. Sci. Ind. Res. 2009, vol. 68, p. 967-974.
[69] Kumar, G. A., Swarnalatha, S., Sairam, B., Sekaran, G. Production of alkaline protease
by Pseudomonas aeruginosa using proteinaceous solid waste generated from leather
manufacturing industries. Bioresour. Technol. 2008, vol. 99, p. 19391944. ISSN
0960-8524.
[70] Kumar, G. A., Venkatesan, R., Rao, B. P., Swarnalatha, S., Sekaran, G. Utilization of
tannery solid waste for protease production by Synergistes sp. In solid-state
fermentation and partial protease characterization. Eng. Life Sci. 2009, vol. 9, p. 6673.
ISSN 1618-2863.
[71] Aloy, M. Methane gas from tannery effluent. Leather 1987, vol. 189, p. 5354. ISSN
0023-9739.
[72] Shanmugham, P., Horan, N. J. Optimising the biogas production from leather fleshing
waste by co-digestion with MSW. Bioresour. Technol. 2009, vol. 100, p. 41174120.
ISSN 0960-8524.
[73] Kolomaznk, K., Pecha, J., Bainov, M., nek, L. Economic aspects of biodiesel
production from tannery waste fats. J. Am. Leather Chem. As. 2010, vol. 105, p. 327333. ISSN 0002-9726.
[74] Pecha, J., Kolomaznk, K., Bainov, M., nek, L. High Quality Biodiesel and
Glycerin from Fleshings. J. Am. Leather Chem. As. 2012, vol. 107, no. 10, p. 312-322.
ISSN 0002-9726.
[75] Chilton C. H., Perry R. H. (Eds.). Chemical Engineers Handbook, 5th ed., USA, 1973,
McGraw-Hill, Inc., New York. 1920 pp. ISBN 978-0-0704-9478-9.
[76] Reid, R. C., Prausnitz, J. M., Sherwood, T. K. The Properties of Gases and Liquids, 3rd
ed., USA, 1977, McGraw-Hill, New-York. 688 pp. ISBN 978-0-0705-1790-5.
[77] Janov, D. Nepm modelovn nmoku surovch k. PhD. Thesis. Vysok uen
technick v Brn, Zln, 1993. 115 p.
[78] Kolomaznk, K., Pecha, J., Vaek, V., Friebrov, V., Podzimek, P. Zpsob
deproteinizace odpadnch tuk a olej. Czech Patent, CZ303310B6. 2012-07-25. [in
Czech]

ISBN: 978-1-63117-329-5
Chapter 5
DEFUZZIFICATION OF FUZZY CONCEPTS

TO SUPPORT VULNERABILITY ASSESSMENTS
OF CLIMATE CHANGE IMPACTS
IN THE PHILIPPINES
Lilibeth A. Acosta1,2* and Jemimah Mae A. Eugenio3
1
Potsdam Institute for Climate Impact Research (PIK),

Telegraphenberg, Potsdam, Germany
2
School of Environmental Science and Management,
University of the Philippines in Los Banos (UPLB), Philippines
3
Institute of Mathematical Sciences and Physics,
College of Arts and Sciences,
UPLB, Philippines
ABSTRACT
Climate change is one of the most pressing global issues that require innovative
methods to address the complexity of human-environment interactions. Many aspects of
vulnerability to climate change and adaptation measures to address its adverse impacts
remain vague and unquantifiable. Vulnerability assessments require methods that can
reduce the vagueness and imprecision of interpretations of data and information in human
and environment systems.
This chapter illustrates an empirical application of fuzzy logic analysis and the utility
of this analytical tool in integrated modeling assessments in the context of climate
change. Using the intervulnerability framework, fuzzy logic models can be used to assess
trade-offs of adaptive capacity and hotspots of vulnerable regions. In particular, we used
data on socio-economic and ecological indicators that are relevant for the assessments of
adaptive capacity and vulnerability in the different provinces and regions in the
Philippines.
*
Corresponding author: Dr. Lilibeth A. Acosta, Potsdam Institute for Climate Impact Research (PIK),
Telegraphenberg A62, 14473 Potsdam, Germany. Tel.: +49 331 2882643; Fax: +49 331 2882695; E-mail:
lilibeth@pik-potsdam.de.
166

The empirical application in this country shows the advantages of fuzzy set theory in
terms of its (1) transparency, which allows explicit presentation of model assumptions
through inference rules; and (2) flexibility, which allows direct inclusion of informal and
expert knowledge in combining various indicator sets. The results of the fuzzy models
show that the types of indicators and determinants traded-off depend on the social and
economic conditions in the regions.
Vulnerable provinces are mostly located in northern and southern parts of the
Philippines. Vulnerability in the former can be reduced through improving water
availability for agriculture, whilst in the latter through improving peace and order
condition that affects socio-economic development.
1. INTRODUCTION
Climate change is one of the most pressing global issues that require innovative methods
to address the complexity of human-environment interactions. The Intergovernmental Panel
on Climate Change (IPCC), which was established in 1988 among others to provide scientific
support to climate change negotiations, is the leading international scientific body for the
assessment of climate change under the auspices of the United Nations (UN). The IPCC
(2007) defines climate change as: A change in the state of the climate that can be identified
(e.g., by using statistical tests) by changes in the mean and/or the variability of its properties
and that persists for an extended period, typically decades or longer. It may be due to natural
internal processes or external forcings, or to persistent anthropogenic changes in the
composition of the atmosphere or in land use. The IPCC differentiates climate change
problems in terms of its immediate (short-term) impacts like storms, drought, etc., and longterm impacts like sea level rise. Following its Assessment Reports (First AR, 1990; Second
AR, 1995; Third AR, 2001; Fourth AR, 2007), approaches to solving climate change are
generally categorised into two adaptation and mitigation. On the one hand, adaptation refers
to solutions for short-term impacts and, on the other hand, mitigation refers to measures for
reducing long-term impacts of climate change. Human and environmental systems that are
easily or highly exposed to the adverse effects of climate change impacts, whether in the
short-term or long-term, are considered to be vulnerable to climate change impacts.
Efforts to advance human dimensions in climate change research resulted in a shift from
impact assessments based on climate model scenarios to adaptation analyses based on an
understanding of vulnerability. The consequences of environmental change are now well
understood as a function of the ability of people and social systems to adapt to global
environmental change.
Thus, adaptation, like mitigation, became an important issue in addressing vulnerability
to global environmental change. For this reason, concepts and methods contributing to
increased knowledge on and understanding of vulnerability and adaptation have become
major foci of human dimensions research in the context of climate change. (Acosta and Galli,
2013) explained that new theoretical constructs and empirical methods that consider human
interaction with its environment are important for improving vulnerability assessments. In the
past decade, a number of interdisciplinary studies have captured the complexities of humanenvironment links such as the Social Vulnerability (Adger, 1999), Double Exposure (O'Brien
and Leichenko, 2000), Vulnerability-Resilience (Moss et al., 2001), Risk-Chain (Heitzmann
et al., 2002), Vulnerability for Sustainability (Turner et al., 2003), Eight-Step Approach
167
(Polsky et al., 2003), Intervulnerability (Acosta-Michlik and Rounsevell, 2005; AcostaMichlik and Espaldon, 2008; Acosta-Michlik and Espaldon, 2011), and Crisis Probability
Curves (CPC) (Acosta-Michlik et al., 2006; Acosta and Galli, 2013).
Among these studies, Acosta-Michlik and her colleagues applied fuzzy logic as one of
the important methods for the application of Intervulnerability and CPC frameworks. This
chapter will however focus only on the latter framework because it allows the application of
fuzzy logic models on the assessments of two important aspects of vulnerability trade-offs
pattern and hotspot regions.
The trade-offs pattern shows the sources of adaptive capacity for the society and hotspot
regions refer to the location of the most vulnerable people. The chapter aims to illustrate the
advantages of using fuzzy theory and methods for empirical research on adaptation and
vulnerability in view of its (1) transparency, which allows explicit presentation of model
assumptions through inference rules; and (2) flexibility, which allows direct inclusion of
informal and expert knowledge in combining various indicator sets. The chapter is structured
as follows: section 2 presents the concept of vulnerability and framework for
intervulnerability, section 3 discusses the fuzzy theory and methods that relates to their
applications in intervulnerability framework, section 4 checks the robustness of the fuzzy
logic models in terms of sensitivity of model outputs to changes in model inputs, section 5
presents the trade-offs pattern and hotspot regions generated from fuzzy logic models, and
section 6 provides conclusions.
2. CONCEPT AND FRAMEWORK

Vulnerability is not a new science, but it remains a much debated concept. As a result,
there are divergent definitions and frameworks for vulnerability available in literature.
Understanding vulnerability is very much influenced not only by the level, focus and methods
of analysis but also by the researchers field of expertise. The most widely used definition is
that of IPCC, which defines vulnerability as a function of adaptive capacity, sensitivity and
exposure (IPCC, 2001).
Exposure is the nature and degree to which a system is exposed to significant

climatic variations.
Sensitivity is the degree to which a system is affected, either adversely or
beneficially, by climate-related stimuli.
Adaptive capacity is the ability of a system to adjust to climate change (including
climate variability and extremes) to moderate potential damages, to take advantage
of opportunities, or to cope with the consequences.
The element of exposure is an integral part of vulnerability concept because it answers

the question vulnerable to what, the what being external stressors in the environment.
The degree of vulnerability to some environmental stressors depends on the sensitivity of the
system, from which the society depends for its existence (i.e., social, economic and natural
resources).
168
Vulnerability is also dependent on the adaptive capacity of the society. Sensitivity is the
most poorly defined element in vulnerability concept because it can hardly be disassociated
from exposure or adaptive capacity1. In view of this, many studies have combined sensitivity
with exposure to characterise natural environment that is fragile to the impacts of climate
change (e.g., Metzger et al., 2006; Acosta-Michlik et al., 2008).
The intervulnerability framework builds on the IPCCs vulnerability definition and
considers exposure and sensitivity as combined components of vulnerability. The framework
emphasises the importance of considering the interaction of the impacts of global processes
and the interconnection of global to local changes in assessing vulnerability (Acosta-Michlik
and Rounsevell, 2005).
Specifically, it aims to assist in merging the relevant socio-economic and biophysical
attributes of an agents environment, and thus in assessing the differential vulnerability of
local communities to interacting impacts of globalisation and climate change. The
intervulnerability framework follows stepwise approach to assess vulnerability indicatorbased, profile-based and agent-based (Figure 1).
This chapter focuses on the indicator-based approach, which applies fuzzy logic analysis
to understand the structure of adaptive capacity trade-offs and generate maps of hotspot
regions. In intervulnerability assessment, maps are used to guide the selection of case study
areas for the profile-based approach and the trade-offs structure can assist the selection of
adaptation options for the agent-based approach. The profile-based approach applies cluster
analysis to generate vulnerability profiles. The profiles are required to build the behavioural
model for the agent-based approach. Because agent-based models are processed-based, they
are useful for dynamic analysis of future vulnerabilities.
Estimating dynamic vulnerability is hardly possible using indicator-based and profilebased approaches as they only aggregate and stratify past and present information. Studies
that have projected vulnerability using indicator-based approach are based on comparativestatic, and not dynamic analysis.
Although it can only provide static view, the indicator-based approach remains very
useful in vulnerability assessments for the following reasons: (1) provides a synthesis of
complex state-of-affairs such as the vulnerability of regions, households or countries into a
single number that can then be easily used by policy (Hinkel, 2011); (2) provides scoping or
first look assessment to support identification of priority vulnerable coastal areas (Ramieri
et al., 2011), and (c) provides generalised knowledge across multiple spatial scales even
where data sources are limited (Acosta-Michlik and Rounsevell, 2009).
This statement is based on the discussions during the workshop of the START Advanced Institute on Vulnerability
to Global Environmental Change held in IIASA, Laxenburg, Austria on May 3-21, 2004.
Data Collection
Data Inputs
Secondary data
socio-economic indicators
biophysical indicators
GIS maps of land features
Primary data
household socio-economic
information (social survey)
farm boundaries (GPS)
Fuzzy logic analysis
Cluster analysis
social capacity
economic capacity
institutional capacity
soil quality
water availability
housedhold income & assets

farming & non-farming jobs
farm size and crops planted
age and educational level
source of information, etc.
Case study areas

market structure
farming system
social network
Select vulnerable region
Methods
Agent-based model
Build behavioural model Agents profiles
cognitive strategies
adaptive decisions
adaptation scenarios
Vulnerability maps
(2002)
Vulnerability profiles
(2005)
Vulnerability futures
(2005 - 2030)
Proportion of village residence per cluster
Model Outputs
100%
very high
80%
Gonzales
60%
Natatas
Calle
40%
high
moderate
low
traditional
diversified
subsistence
commercial
no policy
irrigation
market
Figure 1. Stepwise methods of the intervulnerability framework.
both policy
2025
2024
2023
2022
2021
2020
2019
2018
2017
2016
2015
2014
2013
2012
2011
2010
2009
2006
0%
2008
very low
20%
2007
B a ta n g a s
170
3. METHODS
3.1. Indicator-Based Approach
Indicator-based approaches to vulnerability assessments in climate change studies can be
traced back to earlier work on poverty mapping and food insecurity (Downing, 2001;
Ramachandran and Eastman, 1997; Henninger, 1998). Under this approach, the exposure
units are usually geographical areas, the vulnerabilities of which are captured by the
differences in their social, economic, institutional and environmental structure at a given point
in time. Composite vulnerability index, which is derived from aggregating socio-economic
and ecological indicators, is useful for identifying vulnerable countries, regions or
communities (Figure 2). Vulnerability indices are often presented in maps, which are a
convenient way of presenting spatial variation in vulnerability (e.g., OBrien et al., 2004;
Metzger et al., 2006; Liu et al., 2008; Fraser et al., 2013). The selection of indicators is
influenced by the availability of data and understanding of vulnerability concept. In this
chapter, relevant indicators of adaptive capacity were selected using theory-based (deductive)
approach. Quantitative assessment of a societys capacity to adapt to global environmental
changes has been largely based on the use of proxy variables for economic wealth, social
capital, and institutional infrastructure (e.g., Acosta-Michlik et al., 2008; Adger et al., 2004;
OBrien et al., 2004; Acosta et al., 2013; etc.). The indicators used for the vulnerability
assessment are presented in Figure 2 and the data used to represent these indicators are
presented in Appendix 1. The relevance of these indicators for adaptive capacity and
exposure/sensitivity are discussed below.
Income
indicators
Infrastructure
indicators
Good governance
indicators
Human security
indicators
Education
indicators
Economic
capacity
Institutional
capacity
Adaptive
Capacity
Social
capacity
Health
indicators
Groundwater supply
indicators
Rainwater supply
indicators
Soil erosion
indicators
Landuse change
indicators
Vulnerability
index
Water
availability
Sensitivity/
Exposure
Soil
quality
Figure 2. Indicator-based framework for vulnerability assessment.
171
Income per capita, measured by the ratio of GDP to total population, is the most widely
used indicator for economic well-being. However, GDP per capita is a crude measurement of
the populations personal wealth. This is because it does not disclose how much of the total
GDP accrue to what percentage of the population. The empirical relationship between income
per capita and the sense of basic need satisfaction can be extremely weak particularly in lowincome countries (Fuentes and Rojas, 2001; Shen and Williamson, 2001). In this chapter,
alternative indicators of economic capacity to adapt were thus used (Figure 2). Economic
development theorists argue that skewed distribution of income limits access to sufficient
food, although there are adequate food supplies at the national level, and restricts access to
basic services such as health and education. The shape of the distribution rather than the total
size of the national income help to account for observed variations in common indicators of
population health (Judge et al., 1997). Distribution of income and extent of poverty are thus
relevant indicators of economic capacity. In addition, indicators that directly reveal the
income level and purchasing power of a household are useful measure of economic capacity
to adapt to the impacts of climate change.
Infrastructure that supports effective transport system and clean water/energy supply is
important to increase adaptive capacity. Quality of roads and availability of ports are crucial
for creating cost-effective links between supplier and consumer agents in different
geographical scales. In the Philippines where there are rich water resources, hydropower,
which accounts for about 6 percent of the total energy produced domestically in 2009 (DOE,
2010), is one of the important sources of not only cheap but also clean energy. The river dams
are used not only for energy generation, but also to provide water for irrigation systems that
are vital for sustaining agricultural productivity. More recently, climate mitigation efforts to
reduce greenhouse gas emissions have promoted the use of renewable sources of energy like
hydropower. Access to clean water has long been considered as a key indicator of human
development because it improves health and standard of living.
Indicators for governance capacity were selected based on the work of Taenzler et al.
(2008). They used indicators such as tax revenue, social expenditure, and financial resources
to measure the governments ability to respond to crisis. According to Tnzler et al.
(2008:165), the general ability of states to collect taxes is a key function in order to pursue
specific policy goals. [T]he availability of financial resources is crucial to introduce
certain policy programs, administrative structures and more specifically early warning
systems in preparation for the occurrence of extreme weather events. However, financial
availability should be matched with state willingness to provide the services needed by the
population. The governments commitment to protect the people can be measured by the
proportion of fiscal resources spent for social services. Furthermore, indicators relating to
human security are also important measure of institutional capacity because they are
manifestations of weak governance.
Health and education are core to improving the social well-being of the people. They
provide the foundation for generating social capital. Education is essential for improving the
capacity of the people, for achieving awareness and skills, and for effective participation in
decision-making. Regular education, provided in state-governed institutional frameworks,
is, although not the sole provider of knowledge and competence, a key element in strategies to
ensure a broad participation of people in processes of socio-cultural, economic and
technological innovation (Kaiser et al., 2000:7). Through social services, the government
helps the people to acquire knowledge, create awareness and be innovative. These are all
172
indispensable to increase the ability to adapt to environmental stress. Similarly, more money
spent on health services will help to improve the physical condition of the population and to
increase their capacity to cope with health risks associated with environmental stress.
However, a number of studies point out that public subsidies on health have favoured the
better-off and failed to reach the deprived (Filmer et al., 1997; Filmer and Pritchett, 1999;
Castro-Leal et al., 2000; Gwatkin, 2003; Wang, 2003). For this reason, it is useful to consider
indicators that could assess the outreach of health and education services to the local people.
Impacts of climate change are affecting water availability and quality, whilst the impacts
of globalisation are influencing the land availability and land use. A significant part of the
global land area is already used for agriculture and most of the land use conversions between
1970 and 2000 were in favour of agriculture and related activities. According to Gomiero et
al. (2009), agriculture activities including improved pasture and co-adapted grassland account
for about 40% of land surface and nearly 85% of annual global water withdrawals. Thus, in
addition to extreme weather events (e.g., droughts and floods) due to changes in climate,
changes in land use are increasingly becoming a source of environmental exposure or causing
ecological sensitivity.
3.2. Fuzzy Logic Model

The analytical tool applied to derive composite indices of vulnerability based on the
above-mentioned indicator-based framework is fuzzy logic. Whilst fuzzy logic is now
increasingly used in other fields of agriculture and environment (e.g., Roberts, 1996; Wu et
al., 1996; Mays et al., 1997; Silvert, 2000; Mackay and Robinson, 2000; Kangas and Kangas,
2002), its application in vulnerability to climate change impacts is very limited. The first
fuzzy logic models for vulnerability have been used to assess susceptibility or lack of
adaptive capacity in selected regions in Portugal, Russia and India (Acosta-Michlik et al.,
2008; Krmker et al., 2008). These studies were extended to use the outputs from fuzzy
models to develop thresholds for vulnerability (Acosta-Michlik et al., 2006; Acosta & Galli,
2013). Another important application of fuzzy logic models is the development of scenarios
for adaptive capacity (Acosta et al., 2013), which are useful for integrated assessment
modelling of climate change impacts (Metzger et al., 2006). In these studies, fuzzy logic
models were only applied to develop adaptive capacity indices. But by using
intervulnerability framework in this chapter, the indices for both components of vulnerability
adaptive capacity and exposure/sensitivity, were generated from fuzzy logic models.
The fuzzy logic models are based on multi-valued logic producing indices between 0 and
1. Classical set theory that produces only two-logic values (i.e., either 0 or 1) will be able to
inform whether vulnerability exists or not. But the multi-logic approach of fuzzy set theory
can provide information on the degree of vulnerability, which is useful for identifying hotspot
regions through comparison of indices of adaptive capacity and exposure/sensitivity across
regions. Moreover, fuzzy logic models allow the use of linguistic values such as low,
moderate and high to certain index value ranges. Linguistic values are useful for fuzzy
concepts to quantify the vagueness and imprecision of interpretations (Mays et al., 1997;
Darbra et al., 2008). Such linguistic values have practical use for evaluating vulnerability,
which does not have an objective yardstick to assess its relative magnitude (Acosta-Michlik et
al., 2008). In this case, vulnerability assessments require transparency of model assumptions
173
and flexibility of model structure. On the one hand, assumptions are made transparent
because indicators can be combined to represent specific concepts (i.e., as in Figure 2) and
these concepts can be presented in inference rules (see section 3.1). On the other hand,
structure is made flexible because fuzzy logic allows inclusion of several indicators that
represent specific concept and these indicators can be included in different sets of fuzzy
models (i.e., different aggregation levels) to simplify the model. Vulnerability assessment
tools that are transparent and flexible translate vague and diverse information into a common
and comprehensible language, which is important in highly interdisciplinary fields like
climate change.
A fuzzy logic model has three components - input variables, inference rules and model
output. Figure 3 summarizes how these components are used in fuzzy logic analysis. The
analysis in fuzzy logic models consists of three steps - fuzzification, fuzzy inference and
defuzzification. Fuzzification translates data into linguistic values and defines the degree of a
membership A. A membership function is a curve that defines how each point in the input
space is mapped into a membership value (or degree of membership) between 0 and 1. The
fuzzy inference involves an implication and aggregation process (Cornelissen et al., 2001).
The implication process evaluates inference rules, which are if-then statements describing
the possible relationships between the input variables. For example, if water supply is low and
soil quality is low, then sensitivity/exposure is high. The aggregation process combines the
fuzzy conclusions (i.e., the area under the truncated membership functions) in each inference
rule. Finally, defuzzification converts the aggregated fuzzy conclusions into numerical
assessment, giving values between 0 and 1. The numerical assessment represents the index
value of the output variable. Details of these steps are available elsewhere (Eierdanz et al.,
2008). The fuzzy logic module of the MatLab software (The MathWorks, Inc., 2001) was
used in implementing the fuzzy logic models.
Figure 3. Components of fuzzy logic model and steps in fuzzy logic analysis.
174
In generating adaptive capacity, exposure/sensitivity and vulnerability indices, five levels

of aggregation (i.e., data, indicators, determinants, components, and vulnerability index) were
used to increase the transparency and decrease the complexity of vulnerability assessment
(Table 1). Each aggregation level represents different fuzzy logic models. In the first level of
aggregation, the input variables were the socio-economic and biophysical data, or proxy
variables, and the model outputs were the indices of the indicators. For example, data on
poverty incidence of families, food subsistence incidence of families and Gini coefficient
were used as inputs to the fuzzy logic model, which was applied to generate index for poverty
and inequality. At this level of aggregation, there were 14 fuzzy logic models corresponding
to 10 socio-economic indicators and 4 biophysical indicators. In the second level of
aggregation, the input variables were the model outputs from the first level of aggregation.
The model outputs from the second level of aggregation were the indices of the determinants
and/or components. There were 4 fuzzy logic models at this level of aggregation
corresponding to income level, infrastructure facilities, education level and services, and
health condition and services. For example, poverty and financial indices were used as inputs
to fuzzy logic model, which was applied to generate index for income level. There were no
corresponding determinants for indicators of governance and security, water supply, soil
erosion and land degradation because they were directly used as inputs to the third level of
aggregation.
In the third level of aggregation, the input variables were the model outputs from the
second level of aggregation, i.e., indices of the determinants. The model outputs were the
indices of vulnerability components. At this level of aggregation, there were 5 fuzzy logic
models corresponding to economic, institutional and social capacity as well as water
availability and soil quality. The fourth level of aggregation aimed to generate the indices of
adaptive capacity and exposure/sensitivity. There were thus 2 fuzzy logic models at this level
of aggregation. The input variables for the adaptive capacity model were economic,
institutional and social capacity and those for the exposure/sensitivity were water availability
and soil quality. Finally, the fifth level of aggregation consisted of one fuzzy logic model. It
combined the indices of adaptive capacity and exposure/sensitivity, which were the model
outputs from the previous aggregation level, to generate index of vulnerability, the output
from the last level of aggregation. At this point, there were 26 fuzzy models applied to
generate vulnerability index (Table 1). The models were applied in 81 provinces of the
Philippines for the year 2000, for which there was a complete dataset for all provinces.
Altogether, there were thus 2,106 fuzzy logic models to produce vulnerability indices for the
81 provinces.
3.3. The Case Study Area

The Philippines is an archipelago consisting of more than 7000 islands with a total land
area of 298,170 square kilometers (BAS, 2013). About 32 percent of the area is agricultural
land. The agricultural land is mainly planted to arable (51 percent) and permanent (44
percent) crops. Agriculture contributed about 11 percent of the 10,565 billion GDP in 2012.
Crops contribute to about 50 percent of the agricultural GDP, in particular rice, corn, banana
and coconut. The main agricultural exports are coconut oil (20 percent), banana fresh (13
percent) and pineapple and products (8 percent). Agricultural activities and services account
175
for only 7 percent of the agricultural GDP. The share of agriculture to total employment is
continuously declining, reaching only 32 percent in 2012. The Philippines has three major
islands Luzon, Visayas and Mindanao (Figure 4). It has a total 15 administrative regions, 6
in Luzon, 3 in Visayas and 6 in Mindanao.
Islands
Regions
Luzon
Visayas
Mindanao
Figure 4. Different regions in Luzon, Visayas and Mindanao islands in the Philippines.
In terms of land area, region 4 in Southern Luzon, which consists of Calabarzon and
Mimaropa, is the biggest with a total of 4.7 million hectares (Table 2). It has also the largest
number of population with more than 15 million people. This is followed by the National
Capital region (NCR) that covers the area of Metro Manila and has a population of 12 million
in 2010 (BAS 2013). The top agricultural export product (i.e., coconut) is widely cultivated in
region 4 (Calabarzon), region 5 (Bicol), region 8 (Eastern Visayas), region 11 (Davao) and
region 13 (Caraga). Prices of raw coconut products are however one of the lowest among crop
commodities in the Philippines so that daily wage is also low. The highest daily farm wage is
found in Central Luzon which is one of the regions with largest rice production. Rice is the
main staple food in the Philippines. The lowest daily farm wage is found in Central Visayas at
less than PhP100. Many regions in Mindanao have the highest poverty incidence of families
39.8 percent in region 13, 38.1 percent in region 15 and 36.6 in region 9. Poverty in these
regions is further exacerbated by local insurgence and civil conflicts. In region 15 or
Autonomous Region in Muslim Mindanao (ARMM), almost 70 percent of the population still
relies on agriculture for their living, more than double of the average employment figures in
the Philippines.
The Philippine climate is tropical and maritime, characterised by relatively high
temperature, high humidity and abundant rainfall (PAGASA, 2013). The average temperature
is 26.6 degrees centigrade, with the lowest mean temperature of 25.5 in January and highest
mean temperature of 28.3 in May. There is essentially no difference in the mean annual
temperature in the different regions in Luzon, Visayas and Mindanao. The high relative
humidity in the Philippines is due to high temperature and the surrounding bodies of water.
The average monthly relative humidity varies between 71 percent in March and 85 percent in
176
September. Rainfall is the most variable climatic element in the Philippines with different
rainfall distribution in different regions depending on wind direction and mountain locations.
The mean annual rainfall varies from 965 to 4,064 millimeters. Philippine climate is
categorised into four types based on the distribution of rainfall (Table 2): Type I has two
pronounced season - dry from November to April and wet during the rest of the year; Type II
has no dry season with a pronounced rainfall from November to January; Type III has no
pronounced seasons - relatively dry from November to April, and wet during the rest of the
year; and Type IV has more or less evenly rainfall distribution throughout the year. Type I is
typical climate in regions 1 and 6, type II in regions 7, 8, 10, 11 and 13, type III in region 2
and Type IV in region 12. All other regions have combined climate types.
4. MODEL VERIFICATION
Prior to the analysis of the results of the fuzzy logic models, we first verified the
sensitivity of the outputs to the input variables. A sensitivity analysis can help to gauge the
robustness of the indicators (Phillis and Andriantiatsaholiniaina, 2001; Baraldi et al., 2009;
Singh et al., 2012) and fuzzy logic models. It thus informs about the correctness of not only
the model structure, particularly in terms of constructing the membership functions, but also
the model inputs. Errors may result from the computation of standardized values and/or
preparation of database. It was necessary to do standardization1 because of large variability of
data range not only among indicators but also across regions. Because standardisation makes
data dimensionless (Gan et al., 2007), it is useful in defining standard indices for the different
indicators. Huge number and range of model inputs can cause uncertainties concerning the
data quality because information may be incomplete, imprecise, contradictory, not fully
reliable or vague (Janssen et al., 2010; Singh et al., 2012). Errors could have thus occurred in
up-/downloading and encoding data both by the data providers and users. The relevance and
accuracy of the data can be checked through sensitivity analysis. Information collected from
the analysis allow experts to see if model outputs are decreasing, increasing or stationary in
correspondence of a progressive increment or decrement of the input variables, and to verify
if such behaviour is in agreement with the experts expectations (Baraldi et al., 2009). We
checked for the sensitivity of the input variables to the fuzzy logic models by changing the
raw data for the indicators to generate new datasets with values corresponding to 5%, 10%,
25%, and 50%. Thus, in the addition to the reference model (i.e., actual data for 2000), the
26 fuzzy logic models were run eight times for 81 provinces using the new datasets.
The results of the sensitivity analysis for the indices of adaptive capacity,
exposure/sensitivity and vulnerability are presented in Figure 5. The adaptive capacity indices
show increasing trend as values of input variables are increased and decreasing trend as they
are reduced from 5 to 50 percent.
1
The following formula was used to standardise the data:
i ,0 1
X i X min
X max X min
where Xi refers to the original value of data point i, Xmin is the minimum or lowest value in the dataset X, X max
is the maximum or highest value in the same dataset and Xi represents the standardised data for each data
point i with values between zero and one.
Table 1. Fuzzy logic models for five levels of aggregation

Data
1st level
Family Poverty Incidence
Food Subsistence Incidence
Gini Coefficient
Average Annual Family Income
Average Annual Family Savings
Inflation Rate
Length Of National Roads
Length Of Poor Quality Roads
Total Number Of Ports
Large Scale Dams
Hydropower Schemes
% Population with Water Service
Literacy Rate
Higher Education Enrolment
Secondary Cohort Survival Rate
Number of Public Schools
Public Teacher-Student Ratio
Number of Water-Born Diseases
Access To Sanitary Toilet
Access To Safe Water Supply
Available Village Health Stations
Active Barangay Health Workers
Total Financial Resources perCapita
Non-Tax Revenue
% Social Services To Expenditures
Unemployment Rate
Indicators
2nd level
Determinants
3rd level
Components
4th level
Vulnerability26
5th level
Poverty &
inequality1
Income index15
Income &
purchasing power2
Economic
Capacity19
Road infrastructure3
Water/Energy
infrastructure4
Education situation5
Infrastructure
index16
Education
index17
Education services6
Health condition7
ADAPTIVE
CAPACITY24
Social Capacity20
Health index18
Health services8
Good governance index9
Institutional
Capacity21
Human security index10
Table 1. (Continued)
Data
Indicators
Determinants
1st level
2nd level
3rd level
Average Monthly Crime Rate
Crime Solution Efficiency
Amount Water Abstracted By Source
Groundwater supply index11
Physical Accounts Of Groundwater
Average Rainfall
Rainwater supply index12
Rainy Days Per Year
Lands Suffering From Erosion
Soil erosion index13
Nutrient Loss From On-Site Erosion
Forest Destruction
Land degradation index14
Land Use Conversion By Region
Note: Numbers in superscript refer to the number of fuzzy models.
Components
4th level
Vulnerability26
5th level
Water
availability22
EXPOSURE/
SENSITIVITY25
Soil quality23
Table 2. Different regions in the Philippines

Region Number
and Name
Land
Area1
Population
Daily FarmWage2
% Poverty
Incidence
Climate
Types
% Agric.
employ
1.3
4,748,372
161.20
17.8
38.5%
Tobacco,
Mango
2.8
3,229,163
140.76
14.50
III
57.9%
Corn
2.2
10,137737
172.87
12.0
I, II, III
21.6%
Rice
Sugarcane,
Coconut
Calamansi
Rice,
Coconut
Ilocos Region
Cagayan
Valley
Central Luzon
4a
Calabarzon
1.7
12,609,803
160.23
10.30
I, II, III, IV
15.9%
4b
Mimaropa
3.0
2,744,671
138.23
27.60
I, II
48.6%
Bicol Region
1.8
5,420,411
111.69
36
II, IV
40.7%
Main Crops
Region Number
and Name
Western
6
Visayas
Central
7
Visayas
Eastern
8
Visayas
Zamboanga
9
Peninsula
Northern
10
Mindanao
Land
Area1
Population
Daily FarmWage2
% Poverty
Incidence
2.1
7,102,438
118.23
23.80
39.7%
Sugarcane,
Rice
1.6
6,800,180
99.52
30.2
II
31.2%
Sugarcane
2.3
4,101,322
105.79
33.2
II
44.7%
Coconut
1.7
3,407,353
105.09
36.6
III (West)
IV (East)
49%
Rubber
2.1
4,297,323
109.22
32.80
II
43.1%
11
Davao Region
2.0
4,468,563
25.60
II
40.9%
12
Central
Mindanao
2.2
4,109,571
115.50
28.1
IV
49.5%
13
Caraga
2.1
2,429,224
126.12
39.80
II
38.6%
14
CAR
2.0
1,616,867
130.17
17.1
15
ARMM
3.4
3,256,140
2
Notes:
Million hectares, In Philippine Pesos (PhP).
Source: BAS 2013.
102.28
38.10
102.00
Climate
Types
II, III
III, IV
% Agric.
employ
Main Crops
Pineapple,
Banana
Banana,
Coconut
Pineapple,
Banana, Corn
Coconut,
Banana
50.1%
Cabbage
69.8%
Cassava
1In
180
Economic, institutional and social capacities have positive relationship with adaptive
capacity so both model inputs and outputs follow the same direction. At 50% level of
change the adaptive capacity indices increase and decrease by 12 percent. The
exposure/sensitivity indices show a decreasing trend as the input variables are increased, and
increasing trend as they are reduced from 5 to 50 percent. This is conceptually correct
because improving soil quality and increasing water availability should decrease
exposure/sensitivity. The vulnerability indices increase by 11 percent at +50% and by 7
percent at -50% level of change. Figure 4 show that vulnerability has positive relationship to
exposure/sensitivity and negative relationship to adaptive capacity, which are both
conceptually correct. The structure of the fuzzy logic models is thus robust and the model
inputs have no significant errors.
5. RESULTS AND DISCUSSION

5.1. Adaptive Capacity Trade-Offs
The results of fuzzy logic models for the determinants of adaptive capacity are presented
in web diagrams (Figure 6) and they correspond to the second level of aggregation (Table 1).
The larger the area of web diagram, the higher is the adaptive capacity with respect to these
socio-economic indicators. The selected provinces in Luzon and Visayas islands have
relatively higher level of adaptive capacity than those in Mindanao Island. Income indices are
lowest and education indices are highest in Luzon, particularly in the Batangas province.
Moreover, this province has the highest infrastructure index. Education and infrastructure are
thus traded-off against other determinants of adaptive capacity. Batangas belongs to region 4
in Calabarzon. Batangas has a very high level of economic capacity with an index of 0.65.
This can be attributed to the proximity and accessibility of the province to Manila, the
countrys center for foreign capital and investment. Many municipalities in Batangas province
are experiencing rapid rate of urbanization growth. Moreover, Batangas has an international
port that is suitable for industrial and commercial activities. The port is currently used for
shipment of foreign traded goods. Because the province is closely linked to international
market, it is very open to future opportunities and/or risks related to globalisation. Due to
these economic opportunities, which extend to the other provinces, poverty incidence is
lowest in the region (Table 2). Cagayan, a province in region 2 (Cagayan Valley) has the
lowest adaptive capacity among the selected provinces in Luzon (Figure 6). Unlike
Calabarzon, Cagayan and the rest of the region remain very much dependent on agriculture
with the sector providing about 58 percent of employment (Table 2). Health is however given
priority in this province as shown by its high index (Figure 2).
Some provinces in Visayas have higher adaptive capacity than those in Luzon (Figure 6).
Unlike in Luzon, there is no obvious trade-offs pattern among the different determinants. For
example, two provinces have high income indices and the other two have low income indices.
The sources of adaptive capacity are thus quite variable in the different provinces in Visayas.
Iloilo province in region 6 has the highest adaptive capacity in the Visayas Island. Except for
infrastructure, all adaptive capacity indices in Iloilo are higher than those in Cebu (region 7),
the capital of Visayas.
Defuzzification of Fuzy Concepts to Support Vulnerability
181
Adaptive Capacity
0,60
Adaptive capacity
economic capacity
institutional capacity
social capacity
0,55
Mean Values of Indices
0,50
0,45
0,40
0,35
0,30
0,25
-50%
-25%
-10%
-5%
Reference
5%
10%
25%
50%
10%
25%
50%
Percentage Level of Sensitivity Analysis
Exposure/Sensitivity
0,65
Exposure
soil quality
0,60
water availability
0,55
0,50
0,45
0,40
0,35
0,30
0,25
-50%
-25%
-10%
-5%
Reference
5%
Vulnerability
0,65
Vulnerability
0,60
Adaptive capacity
0,55
0,50
0,45
0,40
0,35
0,30
0,25
-50%
-25%
-10%
-5%
Reference
5%
10%
25%
50%
Figure 5. Results of the sensitivity analysis using 5%, 10%, 25%, and 50% changes from the
reference values.
Luzon Island
Income
Governance
1,00
1,00
0,80
0,80
0,80
0,60
0,60
0,60
0,40
0,40
Infrastructure
Governance
Infrastructure
0,20
0,00
Ilocos Norte
Quezon
Income
Income
1,00
0,20
Health
Mindanao Island
Visayas Island
0,40
Governance
0,20
0,00
0,00
Education
Cagayan
Batangas
Health
Education
Siquijor
Iloilo
Infrastructure
Leyte
Cebu
Health
Bukidnon
Compostela Valley
Figure 6. Trade-offs in determinants of adaptive capacity in selected provinces, by island, 2000.
Education
Sulu
Davao del Norte
183
Region 6 continued to be one of the top five fastest growing economies in the Philippines
attributed to a remarkable growth in agriculture sector at 14 percent and services sector at 4.3
percent between 2010 and 2011 (NEDA Region VI, 2013). Iloilo has an international port that
supports economic growth. Moreover, economic growth is supported by economic activities
and job-creating investments, which were generated by the business process outsourcing
companies, hotels and restaurant businesses, the regions top employment drivers in the last
three years. In Mindanao Island, the trade-offs among the different determinants of adaptive
capacity are more apparent. The province of Bukidnon in region 10 has highest index for
health but one of the lowest for governance and education. Davao del Norte in region 11 has
the highest index for education which can be ascribed to its proximity to Davao City, the
capital of Mindanao, where most of the big private and public universities are located. Health
is however traded-off against other determinants of adaptive capacity in Davao del Norte. The
province of Sulu has the lowest level of adaptive capacity, with very low indices particularly
for health. Sulu is a province in region 15 or Autonomous Region in Muslim Mindanao
(ARMM) which has the most severe social unrest due to ethnic/religious issues.
Figure 7 summarises the results of fuzzy models for the socio-economic and
environmental components of vulnerability (i.e., 4th level of aggregation). Social capacity is
highest in Luzon, revealing a general pattern of trading-off education and health against other
determinants of adaptive capacity in many regions in this island. Although social capacity is
also highest in Visayas, the level of trade-offs against the determinants of economic and
institutional capacity is not very high. In Mindanao, determinants of institutional capacity or
governance are traded-off against those of economic and social capacity. This is not
surprising because Mindanao remains to be affected by various political problems that require
effective governance. Improving institutional capacity is thus an important precondition to
improving the overall adaptive capacity in many regions in Mindanao. Another challenge in
Mindanao is poor soil quality, which affects economic productivity in many regions in this
island. Unlike in Mindanao, spatial differences in environmental problems related to water
availability and soil quality are not very significant in Luzon and Visayas.
0,60
0,50
0,40
Luzon
0,30
Visayas
Mindanao
0,20
0,10
0,00
economic
capacity
institutional
capacity
social capacity
water
availability
soil quality
Figure 7. Indices of vulnerability components for three major islands in the Philippines, 2000.
184
5.2. Vulnerability Hotspots

Figure 8 presents maps of adaptive capacity, exposure/sensitivity and vulnerability in the
Philippines. The first two maps were generated from 5th level and the latter from 6th (or last)
level of fuzzy aggregation. The geographical scale of aggregation is provincial level. In
Luzon, the provinces with high level of adaptive capacity are located in region 1 (i.e., Ilocos
Sur), region 4 (i.e., Cavite, Rizal, Romblon, Oriental Mindoro and Marinduque), region 5
(i.e., Catanduanes and Sorsogon) and region 14 (i.e., Abra and Kalinga). In Visayas, the
provinces with high level of adaptive capacity are located in region 6 (i.e., Aklan, Capiz and
Negros Occidental) and region 8 (i.e., Western Samar). Only the provinces of Zamboanga del
Norte in region 9 and Camiguin in region 10 have high level of adaptive capacity in
Mindanao. No province has very low adaptive capacity in Visayas Island. In Luzon Island
four provinces have very low adaptive capacity including Nueva Viscaya, Pampanga,
Palawan and Masbate. The most number of provinces with very low adaptive capacity is
located in Mindanao Island including Lanao del Sur, Sultan Kudarat, Davao del Sur, Basilan,
Tawi-Tawi and Sulu. Except for the last three provinces which are all located in the same
region, the other provinces belong to different regions. There is thus no pertinent spatial
pattern in adaptive capacity in the Philippines because it differs from one region to the other.
Unlike the levels of adaptive capacity, those of exposure/sensitivity show a similar
pattern for groups of provinces in the same regions (Figure 8). This is not surprising because
indicators of water availability and soil quality are influenced by geographical locations. The
highest number of provinces with very high level of exposure/sensitivity is found in
Mindanao. All provinces in regions 11 and 12 show very high level of exposure/sensitivity. In
addition, two provinces each in region 9 (i.e., Zamboanga del Norte and Zamboanga del Sur)
and region 10 (i.e., Lanao del Norte and Misamis Oriental) show very high level of
exposure/sensitivity. In Luzon, several provinces also show very high level of
exposure/sensitivity. For example in region 1 and region 5 (except for the province of
Catanduanes), all provinces have very high level of exposure/sensitivity. The NCR also
shows very high level of exposure/sensitivity of exposure, which is not surprising because of
the large number of population demanding land and water resources in very small area.
Whilst there is no province with very high level of exposure/sensitivity in Visayas Island,
there is no province with very low level of exposure/sensitivity in Mindanao Island. The areas
with very low level of exposure/sensitivity are mostly found in the middle of the Philippines,
covering several provinces in Visayas and Luzon Islands. All provinces in region 6 in Visayas
and almost all provinces in region 4 in Luzon have very low level of exposure/sensitivity.
The most vulnerable provinces in the Philippines are located in many regions in
Mindanao, followed by Luzon. The capacity of the people to adapt to the impacts of climate
change will be lower in Mindanao than in Luzon. As compared to many provinces in Luzon,
those in Mindanao have lower purchasing income and farmers depend mainly on their own
crops for food supply (Vinck and Bell, 2011). Moreover, nowhere in the Philippines is
poverty more widespread than in Mindanao where people are confronted not only with
economic but also social instability (Ringuet, 2002). In 2009 the families in National Capital
Region in Luzon had the highest average annual family income at 356,000 Pesos, whilst the
families in Autonomous Region in Muslim Mindanao (ARMM) had the lowest average
annual family income at 113,000 Pesos (NSO, 2011). In terms of source of employment,
more than 70% of the business establishments are located in Luzon and only 13% in
185
Mindanao (NSO, 2010). Vulnerability in many provinces in Mindanao can thus be reduced by
improving the institutional problems, which hinders socio-economic development. In Luzon,
vulnerability in many provinces can be reduced by reducing the level of exposure/sensitivity.
Improvement in irrigation systems in northern Luzon, particularly in region 2 where 57.9
percent of the labour force depends primarily on agriculture will help people to adapt to the
impacts of climate change. After region 3 (Central Luzon 17.32 percent), region 2 (Cagayan
Valley 16.48 percent) account for the largest irrigated areas in the Philippines in 2012
(BAS, 2013). But like in region 3, the remaining potential for irrigation development is
highest in region 2 at 14 percent. Provinces with very low level of vulnerability are located in
the southern regions in Luzon and western regions in Visayas, where levels of
exposure/sensitivity are very low.
Adaptive Capacity
Vulnerability
Figure 8. Spatial patterns in adaptive capacity, exposure/sensitivity and vulnerability in the Philippines,
2000.
CONCLUSION
Indicator-based approach to vulnerability assessment provides simple synthesis of
complex issues, rapid system for scoping and mapping, and generalisation of multiple spatial
scales. These advantages of the approach are often considered its weaknesses. Under this
approach, the indices are often generated through aggregation of socio-economic and
biophysical indicators. Such indicators, however, only inform either about the state of human
condition (e.g., level of income, health and education) and that of the environment (e.g., soil
quality, water stress) or about global environmental change (e.g., future climate and price
variability). The vulnerability indices are thus no more than aggregated information about
human and natural environment. Moreover, whilst the vulnerability maps provide information
about vulnerable regions, they are limited when identifying the most vulnerable people in
vulnerable places. The maps can provide only little knowledge on appropriate adaptation
policies to help the vulnerable people. Finally, maps can only describe the spatial variation in
vulnerability but not the dynamics of human (individuals or communities) vulnerability. Even
186
temporal progression of maps cannot measure the dynamics of vulnerability, unless human
adaptive behaviour, which contributes a lot to these dynamics, is taken into account in the
development of vulnerability indices. The vulnerability maps for the Philippines, for example,
can inform policy of the potential vulnerable provinces but not of vulnerable people. It will be
difficult to identify appropriate adaptation policy unless the groups of vulnerable people are
also known.
The forgoing does not imply however that indicator-based approach is completely
inappropriate for vulnerability assessment. Due to the simplicity, quickness and generality of
the approach, it is a useful component of an integrated vulnerability assessment framework
such as intervulnerability. As adaptation issue is core to human dimensions research on
vulnerability to global environmental change, vulnerability maps should be considered the
starting, and not the finishing point for vulnerability assessment. Knowledge generated from
indicator-based approach will make implementation of other approaches like agent-based
more efficient and focused. Whilst still in its infancy in the field of climate change, an agentbased approach is a very promising tool for vulnerability assessment in a changing global
environment because it provides great potential for extending our understanding of complex
social systems and how aggregate structures emerge from local rules of interaction. However,
models based on multi-agent systems are time-consuming and data hungry, which limit their
application to well documented case study areas. It is thus not a real alternative to indicatorbased approach, but a complementary approach to understand the knowledge generated from
indicators.
Vulnerability assessments using indicator-based approach rely on methods that can
combine a diverse and wide range of information on adaptive capacity and exposure/
sensitivity. The information is represented by various factors like social, economic,
institutional and ecological and covers various types like qualitative and quantitative.
Vulnerability assessments based on diverse and multitude indicators thus require a flexible
tool for aggregation of information. This chapter shows that fuzzy logic is a very useful and
flexible tool for assessing vulnerability using indicator-based approach. The empirical
application in the Philippines showed the advantages of fuzzy set theory in terms of its (1)
transparency, which allows explicit presentation of model assumptions through inference
rules; and (2) flexibility, which allows direct inclusion of informal and expert knowledge in
combining various indicator sets. Because of its flexibility, vulnerability assessment using
fuzzy logic facilitates not only identification of hotspots of vulnerable regions but also
comparison of trade-offs among sets of adaptive capacity indicators representing economic,
social, and institutional capacity.
REFERENCES
Acosta, L.A. & Galli, F. (2013) Crisis Probability Curves (CPCs): A Model for Assessing
Vulnerability Thresholds Across Space and Over Time. Journal of Environmental
Science and Management, 16, 36-49.
Acosta, L.A., Klein, R.J., Reidsma, P., Metzger, M.J., Rounsevell, M.D., Leemans, R. &
Schrter, D. (2013) A spatially explicit scenario-driven model of adaptive capacity to
global change in Europe. Global Environmental Change, 23, 12111224.
187
Acosta-Michlik, L. & Espaldon, V. (2008) Assessing vulnerability of selected farming

communities in the Philippines based on a behavioural model of agents adaptation to
global environmental change. Global Environmental Change, 18, 554563.
Acosta-Michlik, L. & Espaldon, V. (2011) Reducing vulnerability of rural communities in the
Philippines: Modelling social links between science and policy. Integrating Science and
Policy. Kasperson, R.E. & Berberian, M.), pp. 335-362. Earthscan, London, UK.
Acosta-Michlik, L. & Rounsevell, M. (2005) From Generic Indices to Adaptive
Agents:Shifting Foci in Assessing Vulnerability to the Combined Impacts of Climate
Change and Globalization. IHDP Update, 01, 14-16.
Acosta-Michlik, L. & Rounsevell, M. (2009) An Agent-based Framework for Assessing
Vulnerability Futures. Assessing Vulnerability to Global Environmental Change: Making
information useful for adaptation policy and decision-making. Patt, A., Schrter, D.,
Klein, R. & Vega-Leinert, A.D.), pp. 147-172. Earthscan, London.
Acosta-Michlik, L., Eierdanz, F., Alcamo, J., Krmker, D., Galli, F., Klein, R.J., Kumar,
K.K., Campe, S., Carius, A. & Tnzler, D. (2006) An Empirical Application of the
Security Diagram to Assess the Vulnerability of India to Climatic Stress. Die Erde, 137,
223-252.
Acosta-Michlik, L.A., Kumar, K.S., Klein, R.J. & Campe, S. (2008) Application of fuzzy
models to assess susceptibility to droughts from a socio-economic perspective. Regional
Environmental Change, 8, 151-160.
Adger, W.N. (1999) Social Vulnerability to Climate Change and Extremes in Coastal
Vietnam. World Development, 27, 249-269.
Adger, W.N., Brooks, N., Bentham, G., Agnew, M. & Eriksen, S. (2004) New indicators of
vulnerability and adaptive capacity. Tyndall Centre for Climate Change Research
Technical Report 7, Norwich, England.
Baraldi, P., Librizzi, M., Zio, E., Podofillini, L. & Dang, V.N. (2009) Expert Systems with
Applications. Expert Systems with Applications, 36, 12461-12471.
BAS (2013) CountrySTAT, Bureau of Agricultural Statistics (BAS), Quezon City,
Philippines. http://countrystat.bas.gov.ph/
Castro-Leal, F., J. Dayton, et al. (2000): "Public Spending on health care in Africa: do the
poor benefit?" Bulletin of the World Health Organization 78(1): 66-74.
Cornelissen, A., Van Den Berg, J., Koops, W., Grossman, M. & Udo, H. (2001) Assessment
of the contribution of sustainability indicators to sustainable development: a novel
approach using fuzzy set theory. Agriculture, Ecosystems and Environment, 86, 173-185.
Darbra, R.M., Eljarrat, E. & Barcelo, D. (2008) How to measure uncertainties in
environmental risk assessment. Trends in Analytical Chemistry, 27, 377-385.
DOE (2010) "Renewable Energy." City. http://www.doe.gov.ph/IPO web/linkedfiles/
2010/EIK10/biomass_biofuels.pdf.
Downing, T.E. (2001) Vulnerability to hunger in Africa: A climate change perspective.
Global Environmental Change, 1, 365380.
Eierdanz, F., Alcamo, J., Acosta-Michlik, L., Krmker, D. & Tnzler, D. (2008) Using fuzzy
set theory to address the uncertainty of susceptibility to drought. Regional Environmental
Change, 8, 197-205.
Filmer, D. and L. Pritchett (1999): "The impact of public spending on health: does
monmatter?" Social Science & Medicine 49: 13 09-1323.
188
Filmer, D., J. Hammer & L. Pritchett (1997): Health Policy in Poor Countries: Weak Links in
the Chain, Policy Research Working Papers, Washington, DC, World Bank: pp. 63.
http://www.worldbank.org/ poverty/health/library/papers.htm, 01/27/04.
Fraser, E.D., Simelton, E., Termansen, M., Gosling, S.N. & South, A. (2013) Vulnerability
hotspots: Integrating socio-economic and hydrological models to identify where cereal
production may decline in the future due to climate change induced drought. Agricultural
and Forest Meteorology, 170, 195-205.
Fuentes, N. and M. Rojas (2001): "Economic theory and subjective well-being: Mexico,
Social Indicators Research 53: 289-314.
Gan, G., C. Ma and J. Wu (2007) Data clustering: theory, algorithms and applications, ASASIAM Series on statistics & applied probability, SIAM, Philadelphia, ASA, Alexandria,
VA.
Gomiero, Tiziano, Maurizio G Paoletti, and David Pimentel (2010) Biofuels: Efficiency,
Ethics, and Limits to Human Appropriation of Ecosystem Services. Journal of
Agricultural and Environmental Ethics 23:403-434. http://www.springerlink.com/
content/v5267n80055l26q1/fulltext.pdf.
Gwatkin, D. R. (2003) Free government health services: are they the best way to reach the
poor? Washington, DC, World Bank: pp. 13. http://www.worldbank.org/ poverty/
health/library/papers.htm, 01/27/04.
Heitzmann, K., Canagarajah, R.S. & Siegel, P.B. (2002) Guidelines for Assessing the Sources
of Risk and Vulnerability. Washington, D.C.
Henninger, N. (1998) Mapping and Geographic Analysis of Human Welfare and Poverty -Review and Assessment. World Resources Institute, Washington, D.C.
Hinkel, J. (2011) Indicators of vulnerability and adaptive capacity: Towards a clarification
of the sciencepolicy interface. Global Environmental Change, 21, 198-208.
IPCC. (2001) Climate Change 2001: Impacts,Adaptation, And Vulnerability (Contribution of
Working Group II to the Third Assessment Report of the Intergovernmental Panel on
Climate Change) (JJ McCarthy, OF Canziani, NA Leary, DJ Dokken, and KS White).
Cambridge University Press, Cambridge, United Kingdom.
IPCC. (2007) Climate Change 2007: The Physical Science Basis (Contribution of Working
Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate
Change) (S Solomon, D Qin, M Manning, Z Chen, M Marquis, K Averyt, M Tignor, and
H Miller). Cambridge University Press, Cambridge, United Kingdom.
Janssen, J., Krol, M., Schielen, R., Hoekstra, A. & Kok, J.D. (2010) Assessment of
uncertainties in expert knowledge, illustrated in fuzzy rule-based models. Ecological
Modelling, 221, 1245-1251.
Judge, K., J.-A. Mulligan, et al. (1997) Income inequality and population health. SociScience
& Medicine 46(4-5): 567579.
Kaiser, F., L. v. d. Maat, et al. (2000) Signs of the times monitoring the position of
dutch education. Enschede, Center for Higher Education Policy Studies (CHEPS):
pp.123. http://www.utwente.nl/cheps/ publications/downloadable_publications/Down
loadablesenglish.doc/, 01/27/04.
Kangas, A. S. and J. Kangas (2004) Probability, possibility and evidence: approaches to
consider risk and uncertainty in forestry decision analysis. Forest Policy and Economics
6, 169188.
189
Krmker, D., Eierdanz, F. & Stolberg, A. (2008) Who is susceptible and why? An agentbased approach to assessing vulnerability to drought. Regional Environmental Change, 8,
173-185.
Liu, J., Fritz, S., Fuchs, M., You, L., Obersteiner, M. & Yang, H. (2008) Global and Planetary
Change. Global and Planetary Change, 64, 222-235.
Mackay, D. S. and V. B. Robinson (2000): A Multiple Criteria Decision Support System for
Testing Integrated Environmental Models. Fuzzy Sets and Systems 113: 53-67.
Mays, M. D., I. Bogardi and A. Bardossy (1997): Fuzzy Logic and Risk-Based Soil
Interpretations. Geoderma 77: 299-315.
Mays, M., Bogardi, I. & Bardossy, A. (1997) Fuzzy logic and risk-based soil interpretations.
Geoderma, 77, 299315.
Metzger, M., Rounsevell, M., Acosta-Michlik, L., Leemans, R. & Schrter, D. (2006) The
vulnerability of ecosystem services to land use change. EAgriculture, Ecosystems and
Environment, 114, 69-85.
Moss, R.H., Brenkert, A.L. & Malone, E.L. (2001) Vulnerability To Climate Change: A
Quantitative Approach. Online, 12.
NEDA Region VI 2013, Regional Development Council, National Economic Development
Authority (NEDA), Iloilo City, Province of Iloilo. www.neda-rdc6.ph/website/
index.php/99-latest-news-articles/24
NSO (2010) Annual survey of philippine business and industry (2008 Preliminary results),
National statistics office (NSO), Manila, Philippines; 2010. http:// www.census.gov.ph/
data/sectordata/2008/ aspbi08_04b.htm
NSO (2011) Family income and expenditure survey (Final results updated 2011). Income and
employment statistics division, national statistics office, Republic of the Philippines;
2011. http://www.census.gov.ph/ data/ pressrelease/2011/ie09frtx.html
OBrien, K.L., Leichenko, R., Kelkar, U., Venema, H., Aandahl, G., Tompkins, H., A. Javed,
S. & Bhadwal, S. Barg, L.N. (2004) Mapping vulnerability to multiple stressors: climate
change and globalization in India. Global Environmental Change, 14, 303-313.
O'Brien, K.L. & Leichenko, R.M. (2000) Double exposure: assessing the impacts of climate
change within the context of economic globalization. Global Environmental Change, 10,
221-232.
PAGASA (2013) Climate of the Philippines, Philippine Atmospheric, Geophysical and
Astronomical Services Administration (PAGASA). http://kidlat.pagasa. dost.gov.ph/cab/
climate.htm
Phillis, Y.A. & Andriantiatsaholiniaina, L.A. (2001) Sustainability: an ill-defined concept and
its assessment using fuzzy logic. Ecological Economics, 37, 435- 456.
Polsky, C., Patt, A., Gaffin, S., Martello, M.L., Neff, R., Pulsipher, A. and Selin, H. (2003)
Assessing Vulnerabilities to the Effects of Global Change: An Eight-Step Approach,
Belfer Center for Science & International Affairs. Cambridge, MA.
Ramachandran, M. and J.R. Eastman (1997): Applications of GIS to Vulnerability Mapping:
A West African Food Security Case Study. Applications of Geographic Information
Systems (GIS) Technology in Environmental Risk Assessment and Management, UNEP
and the Clark Labs for Cartographic Technology and Geographic Analysis.
Ramieri, E., Hartley, A., Barbanti, A., Santos, F.D., Gomes, A., Laihonen, P., Marinova, N. &
Santini, M. (2011) Methods for assessing coastal vulnerability to climate change.
190
Copenhagen. ETC CCA Technical Paper 1/2011, European Environment Agency,

Copenhagen.
Ringuet D.J. (2002) The continuation of civil unrest and poverty in Mindanao. Contemp
Southeast Asia 24(1):3349.
Roberts, D. W. (1996): Modelling Forest Dynamics with Vital Attributes and Fuzzy
SysteTheory. Ecological Modelling 90: 161-173.
Shen, C. and J. B. Williamson (2001): Accounting for crossnational differences in infant
mortality decline (1965-1991) among less developed countries: effects of women's status,
economic dependency, and state strength. Social Indicators of Research 53: 257-288.
Singh, R.K., Murty, H.R., Gupta, S.K. & Dikshit, A.K. (2012) Ecological Indicators.
Ecological Indicators, 15, 281-299.
Taenzler, D., Carius, A. & Maas, A. (2008) Assessing the susceptibility of societies to
droughts: a political science perspective. Regional Environmental Change, 8, 161-172.
The MathWorks, Inc. (2011) MATLAB and Fuzzy Logic Toolbox Release 2011b, The
MathWorks, Inc., Natick, Massachusetts, United States.
Turner, B.L., Kasperson, R.E., Matson, P.A., Mccarthy, J.J., Corell, R.W., Christensen, L.,
Eckley, N., Kasperson, J.X., Luers, A., Martello, M.L., Polsky, C., Pulsipher, A. &
Schiller, A. (2003) A framework for vulnerability analysis in sustainability science,
PNAS 100 (14):80748079.
Vinck P and Bell E. (2011)Violent conflicts and displacement in central Mindanao:
challenges to recovery and development. The World Food Programme and the World
Bank.
Wang, L. (2003): Determinants of child mortality in LDCs empirical findings from
demographic and health surveys. Health Policy, 2003, 65:277-299.
Wu, H.I.; B.L. Li, R. Stoker and Y. Li (1996): A Semi-Arid Grazing EcModel with
Probabilistic and Fuzzy Parameters. Ecological Modelling 90 : 147-160.
APPENDIX
Appendix 1. Data sources of socio-economic
and biophysical indicators
Determinants
Poverty and
inequality
Indicators
Poverty Incidence Of Families
(Unit: Percent)
Food Subsistence Incidence Of
Families
(Unit: Percent)
Gini Coefficient
(Unit: Range 0-1)
Data source
National Statistical Coordination
Board (2005)
Board (2005)
Board (2005)

Determinants
Income and
purchasing
power
Good
governance
Human
security
Education
situation
Health
condition
Indicators
Average Annual Family Income
(Unit: Pesos)
Savings: Average Annual
Family Less Expenditures
(Unit: Pesos)
Inflation Rate
(Unit: Percent)
Total Financial Resources Per
Capita
(Unit: Pesos)
Non-Tax Revenue
(Unite: Pesos)
Share Of Social Services
Expenditure To Total
Expenditures
(Unit: Percent)
Unemployment Rate
(Unit: Percent)
Average Monthly Crime Rate
(All Types)
(Unit: Number Of Incidents Per
100,000 Population
Crime Solution Efficiency
Percentage Of Solved Cases Out
Of Total Crime Cases
(Unit: Percent)
Literacy Rate
(Unit: Percent)
Higher Education Enrolment
(Unit: Number Of Students)
Cohort Survival Rate For
Secondary Level
(Unit: Percent)
Water-Born Diseases By Type
(Unit: Number Of Cases)
Proportion Of Households With
Access To Sanitary Toilet
(Unit: Percent)
Proportion Of Households With
Access To Safe Water Supply
(Unit: Percent)
Data source
Board (2002b)
Board (2002b)
Board (2002b)
Board (2002b)
Board (2002b)
Board (2002b)

Board (2002b)
Philippine Institute for
Development Studies (PIDS)


Board (2002b)
Board (2002a)
Board (2002b)
Board (2002b)
191
192

Appendix 1. (Continued)
Determinants
Education &
health services
Road
Infrastructure
Water
infrastructure
Groundwater
supply
Rainwater
supply
Soil erosion
Indicators
Public Elementary + Secondary
Schools
(Unit: Number)
Teacher-Student Ratio In Public
Secondary Schools
(Unit: Ratio)
Percent Of Barangay Health
Stations
To Total Barangays
(Unit: Percent)
Active Barangay Health
Workers
(Unit: Number)
Length Of National Roads
(Unit: Kilometer)
Length Of Poor Quality Roads
(Unit: Kilometer)
Total Number Of Ports
(Unit: Number)
Large Scale Dams
(Unit: Number And Capacity)
Hydropower Schemes
(Unit: Storage Capacity)
Water District Percent
Population Served
(Unit: Percent)
Amount Of Water Abstracted By
Source Of Water Supply
(Unit: Liters Per Second)
Physical Accounts Of
Groundwater
(Unit: Million Cubic Meters)
Average Rainfall
(Unit: Millimeter Per Year)
Rainy Days Per Year
(Unit: Number Of Days)
Lands Suffering From Moderate
(E2) To Severe (E3) Erosion
(Unit: Degree)
Estimated Nutrient Loss From
On-Site Erosion (ONSE) Due To
Upland Palay Farming
Data source
Board (2002b)
Board (2002b)
Board (2002b)

Board (2002b)
Board (2002a)
Board (2002a)
Board (2002a)
Board (2002a)
Board (2002a)
Board (2002a)
Board (2002a); National Statistical
Coordination Board (2000)
Board (1998)
Board (2002a)
Board (2002a)
Board (2002a); National Statistical
Coordination Board (1998)
Board (2000)

Determinants
Land use
change
Indicators
(Unit: Metric Tons)
Forest Destruction
(Unit: Hectares)
Land Use Conversion By Region
(Unit: In Hectares)
Data source
Board (1998)
Board (1998)
193

ISBN: 978-1-63117-329-5
Chapter 6
ECOLOGICAL RESILIENCE: IS IT READY FOR

OPERATIONALISATION IN FOREST MANAGEMENT?
Gerardo Reyes1,2* and Daniel Kneeshaw2
1
Department of Interdisciplinary Studies, Lakehead University,

Orillia, Ontario, Canada
2
Centre for Forest Research, Department of Biological Sciences,
University of Quebec in Montreal, Montreal, Quebec, Canada
ABSTRACT
Given the physiographic variability, variation in socio-political landscapes, and
differences in connectedness of people and communities associated with boreal forest
ecosystems, approaches to forest management that are flexible enough to accommodate
this variation are needed. Moreover, to ensure sustainable forest resource use, we need to
embrace the inherent complexity of boreal forest ecosystems rather than eliminate it, and
be prepared to adapt and adjust as environmental conditions change. While ecological
resilience may be a useful forest management objective to this end, developing general
guidelines to integrate it into practice remains elusive. We address a number of questions
often posed by managers when attempting to include ecological resilience into forest
management planning. Our goal is to determine if the theoretical foundation of ecological
resilience is sufficiently developed to provide a general framework that can be applied for
boreal forest management.
Keywords: Boreal forests, ecological resilience, stability and change, adaptation, forest
ecosystem management
E-mail : gpalomaresreyes@gmail.com; kneeshaw.daniel@uqam.ca.
196
1. INTRODUCTION
Given the overwhelming environmental, social, and economic importance of forests to
humankind, preoccupation is growing for promoting the sustainable use of forest ecosystem
resources. Because of expected rapid changes in global conditions over the next century
(Sokolov et al., 2009) and the potential consequences of these changes to our well-being, it is
imperative that we develop and implement forest management strategies that ensure forests
will continue to provide us with needed resources and services. Ecological resilience, an
ecosystems ability to re-organize and adapt to disturbance or environmental change without
shifting to an undesirable alternative state (Holling, 1973; Gunderson, 2000), is a concept that
has been proposed to help us to achieve this objective.
Ecological resilience was conceptualized to help explain unexpected and nonlinear
dynamics observed in complex adaptive systems (Holling, 1973; Gunderson and Holling,
2002), thus providing a theoretical foundation towards spatio-temporal understanding of how
boreal forest ecosystems may respond to any changes in climate, natural and anthropogenic
disturbances, invasive species, resource utilisation, and so forth. Managing for ecological
resilience is said to promote sustainability by enhancing a forest ecosystems adaptive
capacity (Gunderson, 2000; Allen and Holling, 2010), defined as the magnitude of an
ecosystems component species ability to respond and adapt to disturbance or change before
collapsing and shifting to a new stability domain, even as the shape or breadth of the domain
changes (Figure 1). In other words, maintaining or improving the ability of species within
ecosystems to respond to episodic disturbances or gradual change will improve an
ecosystems chance of avoiding progression towards an unwanted ecological state (Holling,
1973; Walker et al., 2004). Thus, forest ecosystems adapted to natural as well as imposed
anthropogenic disturbance regimes will have greater capacity to re-organize and retain
desired characteristics and functions, and by consequence be more resilient. Central to this
tenet is that while post-disturbance conditions in resilient ecosystems are not expected to be
exactly like those that existed prior to disturbance, as structural and compositional changes
occur, the same critical processes driving the system are upheld (e.g., photosynthetic capacity,
nutrient cycling, disturbance regime, etc.). Changes in critical processes can drive an
ecosystem into a new stability domain and thus it is imperative that we focus our attention on
understanding their roles in ecosystem maintenance.
Along with the direct changes to forest structure and natural ecological processes caused
by forest management, climate change presents new and unique challenges that will make
sustainable management of boreal forest ecosystems far more difficult to achieve given the
potential for it to interact with processes such as nutrient and hydrological cycling,
disturbance regimes, pollination, etc. (Bonan, 2008; Berggren et al., 2009, Huntington et al.,
2009). Even now, fundamental changes to environmental conditions are occurring at an
unprecedented rate (Bentz et al., 2010; Kilpelinen et al., 2010; Fettig et al., 2013) and we are
uncertain about the nature, magnitude, and timing of the effects. Given this uncertainty, an
adaptive approach for boreal forest ecosystem management is essential. To this end, the idea
of making forest ecosystems resilient to these challenges is certainly appealing. However,
operationalizing the concept; i.e., actively managing for resilience has a number of stumbling
blocks that require attention.
Ecological Resilience
197
Figure 1. Ball and cup conceptual model of ecological resilience and ecosystem state change. Balls
represent different stable ecological states, each within a domain of attraction controlled by a unique set
of processes. A threshold point is exceeded when a disturbance or change is so intense, severe, or
frequent that an ecosystem is driven into a qualitatively different stable ecosystem state and controlled by
a different set of ecological processes. In this example, grassland, boreal forest, and heathland
ecosystems are shown. In (A) ecological states shift into alternate stable states when disturbances of
sufficient magnitude or gradual changes drive them beyond ecological threshold points and into different
domains of attraction; (B) the domain itself can change in depth or width over time due to slow changes
in controlling processes (e.g., climate, acid rain), also potentially causing shifts in ecological state as well
as changing an ecosystems overall resilience. Red arrows with solid lines indicate changes within an
ecosystems natural range of variation. These shifts may be caused by natural disturbances such as fire or
insect outbreaks for which ecosystem components have developed adaptations to; i.e., the disturbances
have historical precedents. Red arrows with dotted lines indicate that restoration effort may be required if
attempting to shift a system from an unwanted ecological state back into another.
Modified from Gunderson (2000).
Our purpose here is to examine the applicability of ecological resilience as a management

option in boreal forest ecosystems. We address a number of questions directly related to
putting the concept on the ground for a hypothetical forest management unit. Ultimately, we
wish to determine if the theoretical foundation of ecological resilience is developed enough to
provide a general framework that can be applied for any boreal forest management unit.
198
2. INTEGRATING ECOLOGICAL RESILIENCE

INTO FOREST MANAGEMENT
Those involved with boreal forest management decisions usually raise questions such as:
i.
ii.
iii.
iv.
For what components of an ecosystem should we build ecological resilience?

What do we need to know to manage for ecological resilience?
At what spatio-temporal scales should we focus our management efforts? and
How do we determine if a system is resilient or not?
Proponents of resilience thinking have responded by stating that managing for ecological
resilience requires:
i. clearly defined stakeholder objectives;
ii. knowledge of critical processes and drivers that promote ecosystem stability or
ecosystem change;
iii. knowledge of the ecological impacts of cultivating, harvesting, or using various
ecosystem resources or services at multiple scales; and
iv. indicators of the adequacy of resilience via proxies such as biological diversity,
structural heterogeneity, response diversity, and ecological redundancy.
(Fischer et al. 2006, Campbell et al. 2009, Thompson et al. 2009)
For the remainder of this section, we address each of the above questions in relation to
the responses in more detail.
2.1. For What Components of an Ecosystem Should We Build Ecological

Resilience?
A starting point for operationalising ecological resilience is for stakeholders to determine
what objectives to manage for. The question of resilience of what to what? (Carpenter et al.,
2001) forces managers to clearly define objectives for the entire forest management unit and
explicitly specify their relative importance and spatio-temporal impacts across the landscape.
This can include managing for timber supply, maintaining biodiversity or old-growth forest,
provisioning of water, or providing opportunities for recreational activities. However, it
should be recognized that managing for one desired aspect of an ecosystem may reduce
resilience of another. This apparent paradox stems from what Holling and Meffe (1996)
called a command and control approach to managing resources. They note that managers
have simplified ecosystems to maximize the production of a desired resource; and that it this
simplification that reduces the adaptability of a system and thus the resilience of its nontargeted components.
When entire forest management units are managed for only one purpose, tradeoffs are
inevitable. We cannot maintain resilience for everything everywhere because of fundamental
differences in species life history requirements, feedbacks and interactions among species,
and conflicting stakeholder interests. For example, management plans may include provisions
199
to enhance white-tailed deer (Odocoileus virginianus) habitat. Large herd sizes provide
greater opportunities for hunters and naturalists but also result in heavy browsing damage to
regenerating commercial tree species (Rooney and Waller, 2003). Moreover, improving
hunting opportunities entails having a mix of favorable habitat types across the landscape that
includes conifer forest cover for shelter during winter, an abundance of clearings that provide
herbaceous plants, forbs, and browse for deer to forage, as well as maintaining logging roads
for human access (Voigt et al., 1997). Conversely, protecting pine marten (Martes americana)
populations in the same forest management unit may require maintaining large tracts of intact
mature mixed-coniferous forest containing spruce (Picea spp.), fir (Abies spp.), or cedar
(Thuja occidentalis), and limiting the fragmentation across the landscape that favours deer
(Watt et al., 1996). Many other associated plant and animal species also draw benefits or are
negatively impacted by conditions that promote elevated deer population densities (de Calesta
1994, Gill and Beardall, 2001). Extremely high population densities have, for example,
shifted the forest state on Anticosti Island from a balsam fir (Abies balsamea) to white spruce
(Picea glauca) dominated forest with concomitant losses or decreases of many herbaceous
species palatable to deer (Potvin et al., 2003; Morissette et al., 2009). Managing for a single
resource invariably reduces habitable conditions for other elements in the ecosystem and may
be a critical driver for shifting ecological states.
2.2. What Do We Need to Know to Manage for Ecological Resilience?

Whether our desire is to simply maintain a functioning forest ecosystem or to maintain a
specific type of forest ecosystem, building ecological resilience entails identifying the critical
processes that drive the ecosystem (Table 1). Species and ecosystems are adapted to
ecological processes that have historical precedents (Peterson, 2000; Read et al., 2004;
Johnstone et al., 2010). Retaining these processes is thus an approach that can be proactively
used to maintain ecological resilience. This is in fact, the original premise behind the
Emulating Natural Disturbance (END) concept (Gauthier et al., 2008). Moreover, if the focus
is centered on emulating processes rather than patterns END would escape some (but perhaps
not all) of the critiques of managing for past patterns in a changing environment (Klenk et al.,
2009). Understanding the natural variability in processes and species adaptations to them can
identify the type and range of processes that will maintain the stability of a desirable state, as
well as those that will lead to unwanted ecosystem state changes.
Natural processes that can lead to an ecosystem state change includes paludification,
which results in the conversion of conifer forests into peat bogs over time (Lavoie et al.,
2005). The process can be magnified by human activity when dominant or correcting
processes are not understood. For example, severe fires that burn into the moss layer can
reduce or reverse paludification whereas partial or less severe disturbances such as windthrow
or senescence (e.g., pathogen caused tree mortality) that do not disturb the soil (moss) layer
accelerate the process. Consequently, the blanket approach of using harvesting that protects
soils and advance regeneration (Leblanc and Pouliot, 2011) creates conditions favourable for
stand conversion whereas more aggressive silvicultural techniques that include scarification
would better emulate the soil disturbing processes that naturally control paludification.
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Table 1. Factors that impact ecological resilience at various spatial scales in boreal
forest ecosystems
scale
Process
Structure
Stand
seed dispersal,
natural
regeneration,
competition,
pollination,
herbivory, disease,
photosynthesis,
respiration, evapotranspiration,
nutrient cycling,
allelopathy,
mycorrhizal
association
Natural
disturbance,
succession,
nutrient cycling,
hydrological
cycling,
paludification
Primary
production climate
regulation
vertical,
horizontal, stand
density, relative
species mixes,
patch size &
shape
Landscape
Region
Other
environmental
factors
soil moisture,
pH, light
availability,
temperature,
nutrient
availability,
slope-aspect,
altitude, latitude,
anthropogenic
impacts
Variation in
forest types &
age class, stand
pattern &
connectivity
Soil moisture,
nutrient
availability,
physiography
Variation in
forest types &
age class, patch
pattern &
connectivity
temperature,
precipitation,
CO2, ozone, N
deposition &
uptake,
physiography
Fragmentation,
homogenization,
sedimentation &
waterflow
alteration,
climate change,
pollution
Fragmentation,
homogenization,
sedimentation &
waterflow
alteration,
climate change,
pollution
Timber harvest,
soil erosion,
compaction,
land conversion,
invasive species,
climate change,
conversion,
structural and
compositional
simplification,
pollution
Understanding the dominant processes and their interactions is clearly an important step
to effective management. Such an understanding will be critical when dealing with novel
combinations of disturbances such as the interaction of allelopathy, clearcutting, and fire that
have resulted in some conifer forest ecosystems to be converted to heathlands (Mallik, 1995;
Payette and Delwaide, 2003), invasive insect pests that can substantially alter forest structure
and composition (Dukes et al., 2009), and use of other inappropriate harvesting analogues
(Nitschke, 2005; Salonius, 2007; Taylor et al., 2013).
Unprecedented changes to the historical frequency or severity of natural disturbances is
also problematic. Fire regimes that are more frequent than the age of sexual maturity of tree
species, for example, can lead to ecosystem change. Increased frequency of stand-replacing
fires has resulted in conversion of aspen woodland to conifer forest (Strand et al., 2009) and
conifer forests to grasslands (Heinselman, 1981; Hogg and Hurdle, 1995; Beckage and
Ellingwood, 2008). Noble and Slatyer (1980) used knowledge of these processes and tree
201
functional attributes to identify when and why species shifts would occur as disturbance
processes changed. In fact, ecological research throughout history has been about identifying
shifts in ecosystem states due to changes in natural disturbances as well as those caused by
humans (Frelich and Reich, 1998). Clements (1928) was concerned about how the
agricultural practices of his time influenced the integrity of mid-plains ecosystems. Holling
(1978) identified the importance of disturbance in maintaining resilience; exemplified by the
spruce budworm (Choristoneura fumiferana) maintaining balsam fir forests in the Maritimes
by killing the canopy and releasing understory trees whereas fire, which is a rare disturbance
in this ecosystem, can lead to a different forest type. Thus, processes that can cause ecosystem
collapse usually do not have historical precedents and are often the result of anthropogenic
changes to the timing or severity of natural processes. Accordingly, human disturbances
should be evaluated in light of the processes they affect and the subsequent impacts on
species present across the landscape.
2.3. At What Spatio-temporal Scales Should We Focus Our Management

Efforts?
Ecological resilience changes over time and space. Thus, understanding the critical
processes driving a system must include knowledge of the spatio-temporal scales over which
they operate and interact (e.g., Heinselman, 1981; Gunderson and Holling, 2002; Mladenov et
al., 2008). Different ecological processes influence community structure and composition at
different spatial and temporal scales (Ricklefs, 1987; Herzog and Kessler, 2006; Sepp et al.,
2009) (Figure 2). Certain processes can also have impacts across scales of measure. These
processes often do not function in a simple linear fashion, nor do they function independently
of one another (Peterson et al., 1998; Frelich and Reich, 1999; Groffman et al., 2006).
Extrapolating ecosystem responses to these processes by scaling up or down may result in
erroneous assumptions and predictions due to non-linear relationships, differences in
environmental characteristics at different scales, and emergent properties (Peterson, 2000;
Turner et al., 2001). Therefore, we need to understand if and how critical processes impact
our forests at stand, management unit, and regional levels.
Effective management requires careful planning of how each desired objective is
distributed across the forest management unit. Thus, the scope should be large enough to
generate region-wide ecological benefits that compensate for impacts of an objective at a
single site as well as the cumulative impacts of multiple interventions of this and various
other objectives over time. For example, while the effects of logging are site specific, we need
to consider the spatio-temporal impacts on the forest management unit as a whole; not just
accommodate short-term and local needs or demands. If an associated objective is to maintain
structural complexity across the landscape, including large tracts of mature forest to provide
core habitat for wildlife and various aesthetic values, then a mixture of large and small cuts
arranged in an aggregated pattern across the management unit could allow for more intact,
interior forest conditions to be retained across the landscape relative to a strategy creating
smaller, uniform patches distributed systematically. Over time, a more fragmented landscape
with a greater edge-to-interior ratio may develop utilising a systematic approach (Turner et
al., 2001).
202
Figure 2. Some important processes affecting boreal forest ecosystems across spatio-temporal scales.
2.4. How Do We Determine If a System Is Resilient or Not?

At this time, ecological resilience can only be coarsely quantified using a proxy; i.e.,
measured in terms of the amount of biodiversity, structural heterogeneity, response diversity,
and ecological redundancy. Biodiversity and structural heterogeneity are defined as the
amount of variation in biological (genes, species, and ecosystems) and structural elements
(vertical strata of extant vegetation, spatial arrangement of patches, snags, coarse woody
debris, pit & mound topography, etc.), respectively (Hunter, 1999). Response diversity is the
variation in responses of functionally similar species to disturbance (Elmqvist et al., 2003);
for example, black spruce (Picea mariana) regenerates almost exclusively from the abundant
seed rain after severe fire while white birch (Betula papyrifera) and poplars (Populus spp.)
can reproduce via seed, but can also regenerate vegetatively. Ecological redundancy is the
extent to which a forest ecosystem structure, process, or function is substitutable if a
degradation or loss in the main species that provides that particular attribute occurs (Folke et
al., 2004). A system having greater quantities of a proxy is thought to be more resilient
(Loreau et al., 2003; Fischer et al., 2006). Response diversity and ecological redundancy are
deemed particularly important as multiple species performing the same critical function can
replace or compensate for substantial losses in a dominant species, as well as display
variation in responses to disturbance or gradual change (Thompson et al., 2009).
203
An abundance of research shows that the chances of shifting into another stability domain
increase when removal, reduction, or drastic changes to any of these proxies occurs (e.g.,
Naeem et al., 1995; Loreau et al., 2003; Contamin and Ellison, 2009). Larger impacts on
critical ecosystem processes are typically observed when there are fewer species present,
when the dominant or keystone species are strongly affected, or when functional redundancy
is low (Pastor et al., 1996; Lavorel et al., 2007; Rinawati et al., 2013). Thus, greater species
diversity may confer greater ecological resilience (Hooper et al., 2005; Fischer et al., 2006).
Yet this may not always be the case (e.g., Petchey and Gaston, 2009). Some boreal systems
with relatively low species diversity levels are also resilient. For example, black spruce
(Picea mariana) and balsam fir (Abies balsamea) forest ecosystems both have low functional
diversity and redundancy, yet are both highly resilient to catastrophic fire and insect
disturbance, respectively (Pollock and Payette, 2010; Boiffin and Munson, 2013).
Black spruce and balsam fir trees are well adapted to these severe disturbances and have
a broad genetic diversity that can tolerate a wide range of habitat conditions (Thompson et al.,
2009). Thus, while high levels of diversity may not be expressed at the species or community
levels of organization, at the genetic level, these species have the necessary components for
renewal and reorganization. However, questions remain as to how these ecosystems will
respond to climate change. Balsam fir, for example, regenerates poorly after fire (Asselin et
al., 2001) while jack pine (Pinus banksiana) regenerates poorly in its absence (Parisien et al.,
2004). Boiffin and Munson (2013) observed shifts in species dominance from black spruce to
jack pine after a period of unusually high fire activity that caused changes in microhabitat
suitability for germination. Large scale changes to species distribution patterns will likely
occur across the landscape if these periods of large fire years become more frequent. Other
concomitant effects of climate change are also of concern. Changes to habitat suitability for a
number of spruce beetle species (Dendroctonus spp.) along the west coast of North America
have expanded the potential for their impacts in both altitude and latitude (Bentz et al., 2010)
for example.
So how much diversity is enough to maintain resilience? Clearly there is still much to be
resolved with this aspect of ecological resilience. It is difficult to ascertain the quantity of a
proxy required for stability or which proxy is most important for any particular forest
management unit given that differences in local physiographic attributes, disturbance regimes,
and the spatial or temporal scale of measurement can change expected contributions (Loreau
et al., 2002; Lavorel et al., 2007). Further, knowledge of the functional roles of many species
remains incomplete (Grime, 1998; Scherer-Lorenzen et al., 2005), and thus it can be difficult
to judge the adequacy of response diversity or ecological redundancy.
Management is facilitated by clear objectives and by concrete numbers that support and
validate them; and ecological resilience theory, at this stage of its conceptual development
cannot provide them. In the ball and cup model of Figure 1, this equates to determining
exactly how close to a threshold edge an ecosystems current state is, how quickly it can
tumble towards it, and how much a proxy can keep it from drawing nearer or can drive it
away from collapse. Modeling that projects changes in critical processes into the future is
only beginning (e.g., Hirota et al., 2011; Gustafson, 2013; Lafond et al., 2013) so detecting or
predicting critical changes such as shifts between stable ecosystem states is still problematic.
Thus, it remains an enormous task to shift knowledge of the adequacy of ecological resilience
from hindsight to a useful predictive tool as we still dont know where thresholds are until
after they are crossed.
204
But do we really need to know exactly where thresholds lie or just the impacts of the
processes that lead to them? Shouldnt we be able to identify signals of tumbling towards
shifts in forest ecosystem states, and use these signals as qualitative indicators of the risks of
surpassing undesirable threshold points? As it is, we are not even able to effectively identify
key species or their response functions (e.g., be it whole plant, stem and below ground, or
regeneration functional traits) (Grime 1998, Scherer-Lorenzen et al., 2005; Lavorel et al.,
2007). Thus, the precautionary principle; n.b., Leopolds (1949) argument that the intelligent
rule to tinkering is not to get rid of any of the pieces, suggests that all species should be
maintained. Moreover, a recent synthesis (Cardinale et al., 2012) suggests that increased
diversity also begets increased ecosystem productivity, which implies that a call for
maintaining biodiversity does not need to be based on altruism or ethical considerations but
may be for our own best interest.
Perhaps another issue is that were expecting that managing for ecological resilience (or
any other management option) should account for everything a priori. Questions arise such
as: is management that promotes maintaining processes such as disturbance regimes within
natural historical ranges of variation even useful if the resultant patterns and relationships are
expected to change or decouple altogether with global change? How do we know if oncoming
novel disturbance types and/or disturbance interactions will be beyond what our forest
management unit can absorb? These are questions that perhaps no amount of management or
management approach can truly account for a priori. This may also require us to accept that
domain shifts will occur as conditions exceed the adaptations of local species. For example, if
conditions become too xeric for moisture sensitive species such as balsam fir. The ability to
adapt human institutions that depend on natural ecosystems will thus be tantamount to socioecological resilience as the ecosystems themselves re-organize.
3. PUTTING IT ALL TOGETHER: THE WAY FORWARD

Ecological resilience may eventually be an important management option. But at its
current conceptual iteration, there are too many details that require development or resolution
prior to it being used as a general operational tool. In particular, the lack of knowledge of a
number of critical processes and how they function and interact across spatio-temporal scales,
the uncertainty associated with relationships between resilience and the quantity of
biodiversity needed to maintain stability, as well as the lack of quantitative approaches to
determine an ecosystems position in state space relative to threshold points need addressing.
Despite this, ecological resilience can and does have an indirect role in managing our forests;
as there are several elements of ecological resilience already being used in contemporary
forest management paradigms. Objectives such as maintaining native biodiversity and
improving knowledge of processes that impact ecosystem functioning, for example, are
consistent with the guiding principles of Ecosystem Management, Emulating Natural
Disturbance, and Managing for Complexity (Holling, 1978; Grumbine, 1994; Perera et al.,
2007; Gauthier et al., 2008).
205
Figure 3. Conceptual diagram of the balance of social, economic, and environmental objectives under
Ecosystem Management linked across scales. We cannot manage for everything everywhere. In our
example here, the ball represents an objective. In (a) an economic objective takes precedence but overall
effects are within the adaptive capacity of the ecosystem at the microsite scale; (b) priority on social
measures is concomitantly beneficial to conservation but negatively impacts economic interests at the
stand scale. But since there are many stands across the landscape, stand-level impacts of this objective
will be balanced out by applying more intensive forestry on some sites and other social or conservation
measures on others; (c) shows multiple objectives across the region, each having a specific focus, but
impacts on other objectives are always considered. Ecosystem function is maintained by processes that
can interact and affect the ecosystem at one or a number of scales. Elimination of an objective occurs
when disturbance or slow change drives species responsible for providing objective beyond the tipping
point (i.e., threshold limit of resilience) at the regional scale (indicated by the dashed arrow).
Restoration is now required to re-introduce source or basis of objective. Ecosystem collapse can occur
when detrimental impacts of an objective are beyond the adaptive capacity of the groups of species
responsible for regulation of key ecosystem processes driving the system. Link between scales is
dependent on the connectivity and pattern of forest patches across scales and the processes controlling
them.
An approach based on Ecosystem Management (Grumbine, 1994), one that integrates

various aspects of other contemporary paradigms at multiple scales of focus will help
minimize risk of changing stability domains as well as maintain processes and attributes
identified when asking from what to what. Managing forest resources so that processes
remain within historic natural ranges of variability are stressed, but stakeholders should be
flexible enough to adapt strategies as more information becomes available. As in the TRIAD
approach to forestry management (Seymour and Hunter, 1992), the forest management unit
could be partitioned into zones where either social, economic, or conservation objectives are
emphasized, the proportion of which are pre-determined by stakeholder agreement, and this
206
pattern repeated across the landscape at various spatio-temporal scales (Figure 3). At each
scale of focus, an adaptive strategy is used. This is an iterative approach wherein the effects
of management policy and stakeholder actions are periodically evaluated and modified as
necessary; essentially, as outcomes from natural events and management actions become
better understood (Holling, 1978). Thus, it is a multidisciplinary, dynamic, and multi-scalar
approach to Ecosystem Management based on processes responsible for natural historic
ranges of variation. It emphasizes frequent communication, research, and information
exchange among stakeholders. The use and modification of procedures derived from
continuously updated knowledge of ecosystem dynamics is the underlying premise for
stakeholder exchanges.
Consistent with the requirements for building ecological resilience, this strategy
recognizes the importance of a range of variability in natural processes in contributing to
forest ecosystem functioning. The strength of the approach would be in the ability to identify
changes in conditions created by anthropogenic disturbances from multiple viewpoints and at
multiple scales. Moreover, complexity and variation of forest ecosystems are emphasized
rather than avoided while modeling and forecasting could incorporate spatial structure and
processes, in addition to traditional modeling parameters (Baskent and Yolasimaz, 2000). So
rather than focusing on attaining a single optimal ecosystem condition, a range of acceptable
outcomes is managed for, and thus, potentially reducing vulnerability to unforeseen
disturbance and gradual change across the entire forest management unit; n.b., similar to the
ball and cup metaphor, this is analogous to having a number of balls moving around in the
desired ecosystem state space at the same time (Figure 3).
CONCLUSION
Operationalising ecological resilience is an admirable goal. But at this stage of its
conceptual development, its use in management planning is limited. Instead it is perhaps best
used as a monitoring tool to evaluate the success of other strategies (e.g., TRIAD, Ecosystem
Management, Emulating Natural Disturbances). Until our understanding of critical processes
and ability to predict shifts in ecological states improves, current management approaches
that draw attention to the processes driving ecosystem dynamics across spatio-temporal
scales, as well as linking these processes with societal uses and values should be emphasized.
ACKNOWLEDGMENTS
Lively discussions and feedback from a number of individuals, including H. Archibald,
H. Chen, B. Freedman, T. Gooding, B. Harvey, K. Hylander, T. Jain, M. Kennedy, H.
Kimmins, N. Klenk, D. Kreutzweiser, L. Leal, C. Messier, A. Miller, A. Mosseler, A. Park,
K. Peterson, K. Puettmann, M. Willison, L. Van Damme, S. Woodley, and R. Tittler were
important in helping to develop ideas and clarify concepts presented here.
207
REFERENCES
Allen, C.R., and C. Holling 2010. Novelty, adaptive capacity, and resilience. Ecology and
Society 15(3): 24. [online] URL: http://www.ecologyandsociety.org/vol15/iss3/art24/
Asselin, H., Fortin, M.-J., and Y. Bergeron. 2001. Spatial distribution of late-successional
coniferous species regeneration following disturbance in southwestern Quebec boreal
forest. Forest Ecology and Management 140: 29-37.
Bakent, E.Z., and H.A. Yolasimaz. 2000. Exploring the concept of a forest landscape
management paradigm. Turkish Journal of Agriculture and Forestry 24: 443-451.
Beckage, B., and C. Ellingwood. 2008. Fire feedbacks with vegetation and alternate stable
states. Complex Systems 18: 159-172.
Bentz, B.J., Rgnire, J., Fettig, C.J., Hansen, E.M., Hayes, J.L., Hicke, J.A., Kelsey, R.G.,
Negron, J.F., and S.J. Seybold. 2010. Climate change and bark beetles of the western
United States and Canada: direct and indirect effects. BioScience 60: 602613.
Berggren, A., Bjrkman, C., Bylund, H., and M.P. Ayres. 2009. The distribution and
abundance of animal populations in a climate of uncertainty. Oikos 118: 1121-1126.
Boiffin, J., and A.D. Munson. 2013. Three large fire years threaten resilience of closed crown
black spruce forests in eastern Canada. Ecosphere 4(5):56, 20 p. http://dx.doi.org/
10.1890/ES13-00038.1
Bonan, G.B. 2008. Forests and climate change: forcings, feedbacks, and the climate benefits
of forests. Science 320: 1444-1449.
Campbell, E.M., Saunders, S.C., Coates, K.D., Meidinger, D.V., MacKinnon, A.J., ONeill,
G.A., MacKillop, D.J., and S.C. DeLong. 2009. Ecological resilience and complexity: a
theoretical framework for understanding and managing British Columbias forest
ecosystems in a changing climate. Technical Report 055. BC Ministry of Forests and
Range Forest Science Program, Victoria, BC, 36 p.
Campbell, J.L., Rustad, L.E., Boyer, E.W., Christopher, S.F., Driscoll, C.T., Fernandez, I.J.,
Groffman, P.M., Houle, D., Kiekbusch, J., Magill, A.H., Mitchell, M.J., and S.V.
Ollinger. 2009b. Consequences of climate change for biogeochemical cycling in forests
of northeastern North America. Canadian Journal of Forest Research 39(2): 264284.
Cardinale, B.J., Duffy, J.E., Gonzalez, A., Hooper, D.U., Perrings, C., Venail, P., Narwani,
A., Mace, G.M., Tilman, D., Wardle, D.A., Kinzig, A.P., Daily, G.C., Loreau, M., Grace,
J.B., Larigauderie, A., Srivastava, D.S., and S. Naeem. 2012. Biodiversity loss and its
impact on humanity. Nature 486: 59-67.
Carpenter, S.R., Walker, B., Anderies, J.M., and N. Abel. 2001. From metaphor to
measurement: resilience of what to what? Ecosystems 4: 765-781.
Clements, F.E. 1928. Plant Succession and Indicators: a definitive edition of plant succession
and plant indicators. The H.W. Wilson Co., New York, USA.
Contamin, R., and A.M. Ellison. 2009. Indicators of regime shifts in ecological systems: what
do we need to know and when do we need to know it? Ecological Applications 19(3):
799-816.
de Calesta, D.S. 1994. Effects of white-tailed deer on songbirds within managed forests in
Pennsylvania. Journal of Wildlife Management 58: 711718.
Dukes, J.S., Pontius, J., Orwig, D., Garnas, J.R., Rodgers, V.L., Brazee, N., Cooke, B.,
Theoharides, K.A., Stange, E.E., Harrington, R., Ehrenfeld, J., Gurevitch, J., Lerdau, M.,
208
Stinson, K., Wick, R., and M. Ayres. 2009. Responses of insect pests, pathogens, and
invasive plant species to climate change in the forests of northeastern North America:
what can we predict? Canadian Journal of Forest Research 39: 231-248.
Elmqvist, T., Folke, C., Nystrm, M., Peterson, G., Bengtsson, J., Walker, B., and J. Norberg.
2003. Response diversity, ecosystem change, and resilience. Frontiers in Ecology and the
Environment 1(9):488-494.
Fettig, C.J., Reid, M.L., Bentz, B., Sevanto, S., Spittlehouse, D.L., and T. Wang. 2013.
Changing climates, changing forests: a western North American perspective. Journal of
Forestry 111(3):214228. http://dx.doi.org/10.5849/jof.12-085
Fischer, J., Lindenmayer, D.B., and A.D. Manning. 2006. Biodiversity, ecosystem function,
and resilience: ten guiding principles for commodity production landscapes Frontiers in
Ecology and the Environment 4(2): 80-86.
Folke, C., Carpenter, S., Walker, B., Scheffer, M., Elmqvist, T., Gunderson, L., and C.S.
Holling. 2004. Regime shifts, resilience and biodiversity in ecosystem management.
Annual Review in Ecology, Evolution, and Systematics 35: 55758.
Frelich, L., E., and P.B. Reich. 1998. Disturbance severity and threshold responses in the
boreal forest. Conservation Ecology [online] 2(2):7. http://www.consecol.org./
vol2/iss2/art7
Frelich, L.E., and P.B. Reich 1999. Neighbourhood effects, disturbance severity, and
community stability in forests. Ecosystems 2: 151-166.
Gauthier, S., Vaillancourt, M.-A., Leduc, A., De Grandpr, L., Kneeshaw, D., Morin, H.,
Drapeau, P., and Y. Bergeron (eds.). 2008. Amnagement cosystemique en Fort
Borale. University of Quebec Press, Quebec, Canada, 600 p.
Gill, R.M.A., and V. Beardall. 2001. The impact of deer on woodlands: the effects of
browsing and seed dispersal on vegetation structure and composition. Forestry 74: 209
218.
Grime, J.P. 1998. Benefits of plant diversity to ecosystems: immediate, filter, and founder
effects. Journal of Ecology 86(6): 902-910.
Groffman, P.M., Baron, J.S., Blett, T., Gold, A.J., Goodman, I., Gunderson, L.H., Levinson,
B.M., Palmer, M.A., Paerl, H.W., Peterson, G.D., Poff, N.L., Rejeski, D.W., Reynolds,
J.F., Turner, M.G., Weathers, K.C., and J. Weins. 2006. Ecological thresholds: the key to
successful environmental management or an important concept with no practical
application? Ecosystems 9: 1-13.
Grumbine, R.E.1994. What is ecosystem management? Conservation Biology 8(1): 27-38.
Gustafson, E.J. 2013. When relationships estimated in the past cannot be used to predict the
future: using mechanistic models to predict landscape ecological dynamics in a changing
world. Landscape Ecology 28:14291437.
Gunderson, L.H. 2000. Ecological resilience in theory and application. Annual Review of
Ecology and Systematics 31: 425-439.
Gunderson, L.H., and C.S. Holling. 2002. Panarchy: Understanding Transformations in
Human and Natural Systems. Island Press, Washington, DC, USA, 507 p.
Heinselman, M.L. 1981. Fire and succession in the conifer forests of northern North America
In Forest succession: concepts and application Edited by D.C. West, H.H. Shugart, and
D.B. Botkin, Springer-Verlag, New York, USA, pp. 374-406.
209
Herzog, S.K., and M. Kessler. 2006. Local vs. regional control on species richness: a new
approach to test for competitive exclusion at the community level. Global Ecology and
Biogeography 15: 163172.
Hirota, M., Holmgren, M., van Nes, E.H., and M. Scheffer. 2011. Global resilience of tropical
forest and savanna to critical transitions. Science 334: 232235.
Hogg, E.H., and P.A. Hurdle. 1995. The aspen parkland in western Canada: a dry-climate
analogue for the future boreal forest? Water, Air and Soil Pollution 82: 391-400.
Holling, C.S. 1973. Resilience and stability of ecological systems. Annual Review of Ecology
and Evolution S4: 2-23.
Holling, C. S. 1978. Adaptive environmental assessment and management. John Wiley,
London, 377 p.
Holling, C.S., and G.K. Meffe. 1996. Command and control and the pathology of natural
resource management. Conservation Biology 10:328-337.
Hooper, D.U., Chapin III, F.S., Ewel, J.J., Hector, A., Inchausti, P., Lavorel, S., Lawton, J.H.,
Lodge, D.M., Loreau, M., Naeem, S., Schmid, B., Setl, H., Symstad, A.J., Vandermeer,
J., and D.A. Wardle. 2005. Effects of biodiversity on ecosystem functioning: a consensus
of current knowledge. Ecological Monographs 75(1): 3-35.
Hunter, M.L. 1999. Maintaining biodiversity in forest ecosystems. Cambridge University
Press, Cambridge, UK, 698 p.
Huntington, T.G., Richardson, A.D., McGuire, K.J., and K. Hayhoe. 2009. Climate and
hydrological changes in the northeastern United States: recent trends and implications for
forested and aquatic ecosystems. Canadian Journal of Forest Research 39(2): 199212.
Johnstone, J., Chapin III, F.S., Hollingsworth, T.N., Mack, M.C., Romanovsky, V., and M.
Turetsky. 2010. Fire, climate change, and forest resilience in interior Alaska. Canadian
Journal of Forest Research 40: 1302-1312.
Kilpelinen, A., Kellomki, S., Strandman, H., and A. Venlinen. 2010. Climate change
impacts on forest fire potential in boreal conditions in Finland. Climatic Change 103(3):
383-398 DOI 10.1007/s10584-009-9788-7
Klenk, N.L., G.Q. Bull and J.I. MacLellan. 2009. The emulation ofnatural disturbance
(END) management approach in Canadian forestry: A critical evaluation. The Forestry
Chronicle 85(3): 440445.
Lafond, V., Lagarrigues, G., Cordonnier, T., and B. Courbaud. 2013. Uneven-aged
management options to promote forest resilience for climate change adaptation: effects of
group selection and harvesting intensity. Annals of Forest Science [online first] DOI
10.1007/s13595-013-0291-y, 14 p.
Lavoie, M., Par, D., Fenton, N., Groot, A., and K. Taylor. 2005. Paludification and
management of forested peatlands in Canada: a literature review. Environmental Reviews
13(2): 21-50.
Lavorel, S., Daz, S., Cornelissen, J.H.C., Garnier, E., Harrison, S.P., McIntyre, S., Pausas,
J.G., Prez-Harguindeguy, N., Roumet, C., and C. Urcelay. 2007. Chapter 13. Plant
Functional Types: are we getting any closer to the holy grail? In Terrestrial Ecosystems
in a Changing World, IGBP Series Edited by J.G. Canadell, D. Pataki, and L. Pitelka,
Springer-Verlag, Berlin, Germany, pp 149-160.
Leblanc, M., and B. Pouliot. 2011. La coupe avec protection de la rgnration et des sols
avec rtention de bouquets - Fondements et excution oprationnelle, Ministre des
Ressources Naturelles et de la Faune, Qubec, Canada, 9 p.
210
Leopold, A. 1949. A Sand County Almanac: and sketches here and there. Oxford University
Press, UK, 240 p.
Loreau, M., Naeem, S., and P. Inchausti. 2002. Biodiversity and Ecosystem Functioning:
synthesis and perspectives, Oxford University Press, New York, USA, 294 p.
Loreau, M., Mouquet, N., and A. Gonzalez. 2003. Biodiversity as spatial insurance in
heterogenous landscapes. Proceedings of the National Academy of Sciences of the United
States of America 100(22): 12765-12770.
Mallik, A.U. 1995. Conversion f temperate forests into heaths: role of ecosystem disturbance
and ericaceous plants. Environmental Management 19(5): 675-684.
Mladenov, N., Pulido-Villena, E., Morales-Baquero, R., Ortega-Retuerta, E., Sommaruga, R.
and I. Reche. 2008. Spatiotemporal drivers of dissolved organic matter in high alpine
lakes: Role of Saharan dust inputs and bacterial activity. Journal of Geophysical
Research 113(G2): 9 p.G00D01, DOI: 10.1029/2008JG000699
Morissette, .-M., Lavoie, C., and J. Huot. 2009. Fairy slipper (Calypso bulbosa) on Anticosti
Island : the occurrence of a rare plant in an environment strongly modified by whitetailed deer. Botany 87: 1223-1231.
Naeem, S., Thomson, L.J., Lawlor, S.P., Lawton, J.H., and R.M. Woodfin. 1995. Empirical
evidence that declining species diversity may alter the performance of terrestrial
ecosystems. Philosophical Transactions: Biological Sciences 347(1321): 249-262.
Nitschke, C.R. 2005. Does harvesting emulate fire disturbance? A comparison of effects on
selected attributes in coniferous-dominated headwater systems. Forest Ecology and
Management 214: 305-319.
Noble, I.R., and R.O. Slatyer. 1980. The use of vital attributes to predict successional changes
in plant communities subject to recurrent disturbances. Vegetatio 43: 5-21.
Parisien, M.-A., Sirois, L., and M. Babeau. 2004. Distribution and dynamics of jack pine at its
longitudinal range limits in Quebec In Proceedings of the 22nd Tall Timbers Fire
Ecology Conference: fire in temperate, boreal and montane ecosystems, October 15-18,
2001, Kananaskis, Alberta Edited by R.T. Engstrom, K.E.M. Galley, and W.J. de Groot,
Tall Timbers Research Station, Tallahassee, Florida, USA, pp 247-257.
Pastor, J. Mladenoff, D.J., Hyla, Y., Bryant, J., and S. Payette. 1996. Biodiversity and
ecosystem processes in boreal regions In Functional Roles of Biodiversity: A Global
Perspective Edited by H.A. Mooney, J.H. Cushman, E. Medina, O.E. Sala, and E.-D.
Schulze, John Wiley and Sons, New York, NY, USA, pp 33-69.
Payette, S., and A. Delwaide. 2003. Shift to conifer boreal forest to lichen-heath parkland
caused by successive stand disturbances. Ecosystems 6: 540-550.
Perera, A.H., Buse, L.J., Weber, M.G., and T.R. Crow. 2007. Emulating natural forest
landscape disturbances a synthesis In Emulating Natural Forest Landscape
Disturbances: Concepts and Applications Edited by A.H. Perera, L.J. Buse, and M.G.
Weber, Columbia University Press, NY, USA, pp 265-274.
Petchey, O.L., and K.G. Gaston. 2009. Effects on ecosystem resilience of biodiversity,
extinctions, and the structure of regional species pools. Theoretical Ecology 2: 177-187.
Peterson, G.D. 2000. Scaling ecological dynamics: self-organisation, hierarchical structure,
and ecological resilience. Climatic Change 44: 291-309.
Peterson, G., Allen, C.R., and C.S. Holling. 1998. Ecological resilience, biodiversity, and
scale. Ecosystems 1: 6-18.
211
Pollock, S. L., and S. Payette. 2010. Stability in the patterns of long-term development and
growth of the Canadian spruce-moss forest. Journal of Biogeography 37:16841697.
Potvin, F., Beaupr, P., and G. Laprise. 2003. The eradication of balsam fir stands by whitetailed deer on Anticosti Island, Qubec: a 150-year process. coscience 10(4): 487-495.
Read, D.J., Leake, J.R., and J. Perez-Moreno. 2004. Mycorrhizal fungi as drivers of
ecosystem processes in heathland and boreal forest biomes. Canadian Journal of Botany
82: 1243-1263.
Ricklefs, R.E. 1987. Community diversity: relative roles of local and regional processes.
Science 235: 167-171.
Rinawati, F., Stein, K., and A. Lindner. 2013. Climate change impacts on biodiversity the
setting of a lingering global crisis. Diversity 5: 114-123.
Rooney, T.P., and D.M. Waller. 2003. Direct and indirect effects of white-tailed deer in forest
ecosystems. Forest Ecology and Management 181: 165-176.
Salonius, P. 2007. Silvicultural discipline to maintain Acadian forest resilience. Northern
Journal of Applied Forestry 24(2): 91-97.
Scherer-Lorenzen, M., Krner, C., and E.,-D. Schulze. 2005. Forest Diversity and Function:
temperate and boreal systems. Ecological Studies 176, Springer-Verlag Inc., New York,
NY, 400 p.
Sepp, H., Alenius, T., Bradshaw, R.H.W., Giesecke, T., Heikkil, M., and P. Muukkkonen.
2009. Invasion of Norway spruce (Picea abies) and the rise of the boreal ecosystem in
Fennoscandia. Journal of Ecology 97: 629-640.
Seymour, R.S., and M.L. Hunter Jr. 1992. New forestry in eastern spruce-fir forests:
principles and applications in Maine. Maine Agricultural and Forest Experiment Station
Miscellaneous Publication 716, 36 p.
Sokolov, A., Stone, P., Forest, C., Prinn, R., Sarofim, M., Webster, M., Paltsev, S., Schlosser,
C.A., Kicklighter, D., Dutkiewicz, S., Reilly, J., Wang, C., Felzer, B., Melillo, J., and H.
Jacoby. 2009. Probabilistic forecast for 21st century climate based on uncertainties in
emissions (without policy) and climate parameters. Journal of Climate 22(19): 51755204.
Strand, E.K., Vierling, L.A., Bunting, S.C., and P.E. Gessler. 2009. Quantifying successional
rates in western aspen woodlands: current conditions, future predictions. Forest Ecology
and Management 257: 1705-1715.
Taylor, A.R., Hart, T., and H.Y.H. Chen. 2013. Tree community structural development in
young boreal forests: a comparison of fire and harvesting disturbance. Forest Ecology
and Management 310: 19-26.
Thompson, I., Mackey, B., McNulty, S., and A. Mosseler. 2009. Forest Resilience,
Biodiversity, and Climate Change: a synthesis of the biodiversity/resilience/stability
relationship in forest ecosystems. Technical Series No. 43, Secretariat of the Convention
on Biological Diversity, Montreal, QC, 67 p
Turner, M.G., Gardner, R.H., and R.V. ONeil. 2001. Landscape Ecology in Theory and
Practice. Springer-Verlag Inc., New York, NY, 401 p.
Voigt, D.R., Broadfoot, J.D., and J.A. Baker. 1997. Forest management guidelines for the
provision of white-tailed deer habitat. Queens Printer for Ontario, Ontario, Canada, 33 p.
Watt, R.W., Baker, J.A., and D.M. Hogg. 1996. Forest management guidelines for the
provision of marten habitat. Queens Printer for Ontario, Ontario, Canada, 24 p.
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Walker, B., Holling, C.S., Carpenter, S.R., and A. Kinzig. 2004. Resilience, adaptability and
transformability in socialecological systems. Ecology and Society 9 (2): 5.
[online] URL: http://www.ecologyandsociety.org/vol9/iss2/art5/

ISBN: 978-1-63117-329-5
Chapter 7
CLIMATE CHANGE AND AN AUSTRALIAN

RAINFOREST CONIFER
Rohan Mellick
National Herbarium of NSW, The Royal Botanic Gardens and Domain Trust,
Sydney, NSW, Australia
ABSTRACT
Revealing the evolutionary trends of the recent past (late Quaternary) will allow
climate change science to anticipate the demographic response of species to future
disturbance. The genetic disjunctions and distribution of a long-lived rainforest conifer
provide a valuable signature of past demographic response to climate change a
biological autograph of time, climatic cycles and the environment. This chapter reviews
literature pertaining to three case studies. Case study one determines the level of genetic
diversity and structure within naturally occurring populations of Podocarpus elatus and
resolves the influence of historic and contemporary drivers on divergence. Case study
two explores the impact of glacial cycle climatic changes on the palaeodistribution of the
species: by combining population genetic analysis, coalescent-based analysis, the
observed fossil record and environmental niche modeling. Case study three hypothesizes
that future adaptive potential is indicative of genetic/demographic change and range
expansion/contraction trends in Podocarpus elatus associated with the Clarence River
Corridor. The final section of the chapter concludes the case studies and suggests
conservation strategies applicable to long-lived species allied with threatened
communities.
1. INTRODUCTION
The Podocarpaceae are an ancient coniferous family harboring traits that evolved with
extreme seasonality in high latitudes epochs ago (Brodribb and Hill, 1999, 2003; Quinn and
Price, 2003; Hill, 1994). These characters have proven resilient and have persisted despite
mass extinction events and many catastrophes. Although conifers are currently only a small
proportion of the total arboreal diversity on the planet, they once dominated the landscape
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with tall relatively closed forest. A high extinction rate has resulted in a rich fossil legacy and
record of biological response to environmental change.
Over time, the lack of landmass in the Southern Hemisphere and the inability to migrate
in response to pressure may have resulted in varied adaptive response and past diversification.
Many atypical coniferous taxa endure despite the vast majority having become extinct. In
particular, broad-leaved podocarps are incredibly diverse and are well represented in the
Gondwanan fossil record for over 144 million years (My) (Hill, 1994; Quilty, 1994).
These conifers are a remnant of a world dramatically different from the world we live in
today. In high latitudes, rainforests were then extremely seasonal and trees evolved to subannual periods of light and darkness (McLoughlin, 2001). Broad-evergreen foliage needed to
be tough and versatile to endure months of relentless cold and darkness.
The browsers and dispersers that evolved with Podocarpus in Australia (~65 million
years ago; Ma) are long extinct (Bartholomai and Molnar, 1981; Molnar, 1996), but elements
of this ancient environment remain. Dacrydium (Podocarpaceae) and associated swamp forest
in Australian Wet Tropics is believed to have gone extinct only six thousand years ago (ka)
(Kershaw et al., 2007a). Currently, Lagarostrobos franklinii (Podocarpaceae) forests extend
through South East Tasmania (the first Australasian landmass north of Antarctica), and of
coarse another southern hemisphere conifer Wollemia nobilis (Araucariaceae) was recently
rediscovered and thought to be extinct for 65 My - one population currently defies extinction
and persists 129km northwest of Sydney.
The Southern Hemisphere is dry due to a number of causes, such as northern tectonic
drift and the establishment of the Antarctic circumpolar current about 18 Ma (Barker and
Thomas, 2004). This has dramatically limited the fossil record in Australia due to the lack of
deposition, especially for the Quaternary (1.8 Ma to present). Interdisciplinarity may support
the current understanding of historical community structure.
Here we study a long-lived rainforest conifer, Podocarpus elatus (R.Br. ex Endl.). The
species ranges over 20 degrees of latitude, east of the Great Dividing Range (Eastern
Australia). The principle aim being to understand the effect of late Quaternary and future
climate change on the distribution, diversity and genetic disjunctions of a long-lived conifer
restricted to rainforest. Slow morphological adaptation (evolutionary senescence), restriction
to naturally fragmented mesic communities, and broad distribution makes P. elatus a valuable
tool to understand changes in community structure according to climate.
Understanding the effect of Quaternary climate change on the distribution, diversity and
divergence of Podocarpus elatus will contribute to the conservation of the east Australian
rainforests in light of increasing ecological damage, rapid human population growth and
anthropogenic-induced global warming. To know how intraspecific diversification in a wideranging long-lived species is impacted by climate change will improve our understanding of
how climatic-drivers are involved in the evolutionary process.
This chapter discusses the history of climate change in Australia, the family
Podocarpaceae, vegetation change during the Cenozoic, event histories, the East Australian
rainforest, palynology, marker development, domestication, cytoplasmic inheritance,
coalescent-based analyses environmental niche modeling, interdisciplinarity, general points of
interest and the following published case studies.
Case study one determines the level of genetic diversity and structure within naturally
occurring populations of Podocarpus elatus and resolves the influence of historic and
contemporary drivers on divergence.
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The objectives were to:

1
2
3
Determine genetic structure and how it corresponds to geographic and/or

environmental patterns.
Evaluate landscape-level habitat fragmentation and if there is loss of gene flow
among populations.
Identify genetic diversity within populations to see if there are measurable
differences across demographic age cohorts.
Case study two explores the impact of glacial cycle climatic changes on the
palaeodistribution of the species: by combining population genetic analysis, Bayesian
coalescence-based analysis, the observed fossil record and Environmental Niche Modeling
(ENM).
We endeavored to answer these questions:
1
2
3
Are the distributional changes predicted by ENM in agreement with the available
fossil record?
Are ENM and population genetic-based estimates of range contractions/expansions
and disjunctions in agreement?
In the context of the broad latitudinal and climatic distribution of the species, are the
northern and southern ranges likely to have experienced similar
expansion/contraction dynamics?
Case study three hypothesizes that genetic/demographic change and range

expansion/contraction trends in Podocarpus elatus associated with the Clarence River
Corridor are indicative of the future distribution and degree of adaptive potential in this longlived species. Future conservation strategies may be more successful if distributional and
demographic inference based upon reliable observational data is made.
Also we aimed to answer:
1
2
3
What are the coalescent-based estimates of ancestral demographic patterns and

divergence times in Podocarpus elatus and how do these relate to climate change?
What is the predicted distribution of P. elatus for the IPCC 4th Assessment Report
climatic estimates of 2050?
Based on these findings, what are the appropriate conservation and management
strategies for P. elatus?
The final section of the chapter will conclude the case studies and suggest conservation
strategies applicable to threatened species and habitats.
2. THE AUSTRALIAN VEGETATION

The Australian vegetation today is the consequence of a dynamic history of climate
change, latitudinal change, continental isolation, interaction with an evolving fauna, fire and
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more recently anthropogenic affects (Hill, 1994). Community turnover (including

distributional change) between drier rainforest types, containing Araucaria and Podocarpus
species, and wetter types containing Nothofagus species have been successional in response
to recent glacial cycles along the east coast of Australia (Mellick et al. 2013a, Kershaw et al.
1994; Hill, 1994).
The Quaternary (1.8 Ma to present) is a period of particular importance due to extant
plants and animals coming to establish broader communities and to reside within their
environmental limits of tolerance (environmental niche). The fossil record indicates some
species, including Podocarpus, have a similar ecology, co-occur with palaeo-counterparts and
rely on mesic habitats such as they did since and during the Tertiary (65 - 0 Ma), largely
unaffected by the changing environment (Brodribb and Hill, 2003) that is not to say changes
in distribution have not facilitated their survival and trait preservation.
Throughout the Quaternary in the Australian Wet Tropics (AWT), rainforest was the
dominant vegetation type with large tracts of dry rainforest fringing areas of complex
rainforest in wetter areas (Kershaw et al., 2005) similar in type to present-day dry rainforest
communities typified by Araucarian emergents. Information from the fossil record indicates
these dry Araucarian forests were the major habitat type of Podocarpus species. These
transitional communities fringed floristically complex rainforest core areas, and where
reduced angiosperm competition allowed for slower growing rainforest gymnosperms to
establish, and in some circumstances thrive.
Australian vegetation is very diverse and reflective of the heterogeneous landscape and
diversity of ecosystems that occur across the continent. This diversity is primarily due to the
huge variation in rainfall across the landscape which over time has changed considerably and
promoted rapid adaptation and extinction of a variety of plant taxa.
Increasing aridity during the Neogene (33.71.8 Ma) into the Quaternary is responsible
for the transformation of the Australian landscape from one dominated by broad-leaf
rainforest communities to one composed predominantly of open vegetation communities
(sclerophyllous-type) with wetter rainforest restricted to present day locally moist areas
(Kershaw et al., 1994; Hill, 2004; Martin, 2006). Detailed information of the Australian
climate throughout the Cretaceous and Cenozoic (145.5 Ma to present) has emerged over the
last few decades but there is limited data to document short term climatic cycles (Kershaw et
al., 2007a), particularly for the Quaternary from eastern Australia where fossil evidence is
sporadic and poorly dated (Quilty, 1994).
The change in distribution of major forest types provides a good assessment of abiotic
change (e.g., climate, soil and fire). Biotic conditions (e.g., competition, pathogens,
symbionts and people) also influence the expansion/contraction of plant communities. A plant
taxon requires a suitable abiotic environment for growth yet biotic interactions are varied.
Adaptability governs response to change so migration out of a residing area can be viewed as
an inability to adapt to that area over time.
Past climatic change is inferred from evidence incorporated into deposits and especially
from contained fossils (Hill, 1994; Quilty, 1994). If palaeoclimate is reconstructed solely on
that indicated by fossil plants, it is susceptible to false interpretation. It is ideal to reach the
same conclusion from a number of sources of evidence that are independent. Australia is
deprived of palaeoclimatic data sources, especially ice cores that provide unique archives of
past climate and environmental changes. Environmental niche modeling, used in this study, is
217
reliant on known global fluctuations of climate, which for the large part has been sourced
from Antarctic ice cores.
Australia is a continent where continuous onshore sedimentary records, particularly of
those deposits that accumulated in a non-marine environment, are uncommon, and research
often depends on the offshore marine sequences, themselves incomplete, around the continent
margins, supplemented by other diverse convoluted records (Quilty, 1994). While carbonate
deposition has characterized the offshore history during the Cretaceous to Cenozoic, they are
gallingly incomplete in so far as records of onshore conditions (Quilty, 1994). The Australian
paucity of reliable chronostratigraphic records emphasizes the need for exploration of further
palaeo-data sources and techniques for inferring Quaternary community structure.
3. THE HISTORY OF PODOCARPACEAE

Extant lineages are only a minutiae of past coniferous diversity - when angiosperms were
rare and conifers covered Gondwana (~65 million years ago; Ma). Gymnosperms were once
dominant in the Australian landscape, now, Podocarpaceae are one of only a few
gymnosperm families to still occur in angiosperm dominated tropical rainforests (Hill, 1994).
Historically they were a major component of the Gondwanan flora, but a changing physical
environment, a mass extinction event (Creataceous-Paleogene boundary ~ 65 Ma), and rapid
diversification of the angiosperms, resulted in the displacement and consequential extinction
of many coniferous lineages. In comparison to the flowering plants, which when all taxonomy
is finally done may add up to 300 000 species, conifers are currently a diminutive group of
woody seed plants, with only 630 species (Hill, 1994).
Extant Podocarpaceae in particular are only a very small representation of a once highly
diverse group (Hill, 1994). The family-wide morphology has stayed conserved through
evolutionary time (Biffin et al., 2012), yet recent radiations of the family suggest Podocarpus
is more dynamic and adaptive than other podocarp genera (Biffin et al., 2011). Over time the
lack of landmass in the Southern Hemisphere and the inability to migrate in response to
pressure may have resulted in varied adaptive response and past diversification in the group.
The community associations of the podocarps have also stayed conserved (e.g.,
Araucariaceae, Nothofagaceae and Cunoniaceae); even in peripheral ranges such as Central
America they continue co-occurring with their palaeo-counterparts (Brodribb and Hill, 2003).
The ecological and environmental requirements of Podocarpaceae are specific, with
almost all species restricted to wet montane and rainforest environments (Brodribb and Hill,
2003). Regeneration is usually continual recruitment of shade-tolerant seedlings, or in less
shade tolerant species it is reliant on small-scale disturbances or topographic features such as
ecotones, rivers and ridgelines to open the canopy (Brodribb and Hill, 2003).
3.1. Taxonomy of Podocarpaceae

Podocarpaceae is comprised mainly of Southern Hemisphere conifers and is a large
family of 18 genera and 173 species (Hill, 1994; Quinn et al., 2003). Podocarpus is by far the
largest genus with 110 species, with the next largest genus being Dacrydium with 16. Of the
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18 genera of Podocarpaceae only seven are represented in Australia, with most species
restricted to northeast Queensland and Tasmania (Hill, 1994). The family was endemic to the
ancient super continent of Gondwana and is a classic member of Antarctic flora (Quinn et al.,
2003). The main centre of diversity is Australasia, mainly New Caledonia, Tasmania and
New Zealand, and to a smaller extent, Malesia and South America.
Podocarpus has a lancolate leaf with a prominent mid-vein with no secondary venation
(Fig. 1). Retrophyllum has opposing leaflets arranged so the abaxial surface on one side is up
and on the other is down (Hill and Pole, 1992). This possibly is a light-harvesting trait left
over from its high-latitude origin, where the sun remains low in the sky (Ed Biffin, University
of Adelaide, pers. comm.).
Figure 1. Variation in leaf morphology of shade-tolerant genera from the family Podocarpaceae
(Modified from source: Tim Brodribb, University of Tasmania).
Podocarpaceae members are evergreen shrubs or trees usually with a straight trunk and
mostly horizontal branches. The leaves are usually spirally arranged and are sometimes
opposite. The leaves are scale-like, needle-like or flat and leaf-like, and are linear to
lanceolate. Members are dioecious or rarely monoecious trees or shrubs with spirally inserted
(opposite in Microcachrys) oblong to scale-like leaves (functionally replaced by flattened
branches in Phyllocladus). Pollen cones are catkin-like and have many stamens. Male cones
are terminal on axillary shoots including numerous spirally arranged sporophylls every one
with two abaxial microsporangia (Mcarthy, 1998; http://www.ibiblio.org/pic/GymnospKey
/gymnosperm_key_glossary.html).
Pollen grains are winged (saccate or bisaccate). Female cones are pendant and mature in
one year. They are terminal on branches or terminal on short axillary shoots. Scales are
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persistent or deciduous and including axes are fleshy or dry and not woody at maturity. The
seeds are completely covered by a fleshy structure referred to as an epimatium and are
wingless (Mcarthy, 1998). Epimatium and integument sometimes connate and form a leathery
testa. Germination is phanerocotular with two cotyledons and two parallel vascular bundles
(Van Royen, 1979; Pocknall, 1981; Silba, 1984).
3.2. The Origin of Podocarpaceae

Podocarpaceae originated in the Southern Hemisphere about 242 million years ago (Ma)
and later migrated north of the equator probably during the last 15 million years (My) when
the Australian plate contacted the Southeast Asian plate (Quilty 1994; Hill and Brodribb
1999). They also migrated further north through Central America to Mexico during the same
period. The podocarps appeared in the fossil record at the beginning of the Triassic when the
great super continent Pangaea broke up. They grew alongside araucarians, ginkophytes,
cycads, tree ferns, giant club mosses and horsetails (Quilty, 1994; Hill and Brodribb, 1999),
and were likely to be browsed and dispersed by dinosaurs (Bartholomai and Molnar, 1981;
Molnar, 1996).
The Cenozoic macrofossil record of the Podocarpaceae is extensive, especially in
southeastern Australia, where the majority of the extant genera have been recorded (Hill and
Brodribb, 1999). A few extinct genera (i.e., Podosporites, Willungia and perhaps Coronelia)
have also been reported from across high southern latitudes, confirming an extremely diverse
and widespread suite of Podocarpaceae during the Cenozoic in the region (Hill and Brodribb,
1999). The origins and relationships of the Podocarpaceae are unclear (Hill 1994) but
attempts to explain the phylogeny have improved over time (Kelch, 1997; Conran et al.,
2000; Biffin et al., 2011). Essentially the Podocarpaceae are a Southern Hemisphere family
though macrofossils are found in the Northern Hemisphere (Hill and Brodribb, 1999; Hill,
1994) suggesting a northern expansion. The earlier Mesozoic and Tertiary floras of the
Northern Hemisphere contain no Nothofagus or Podocarpaceae (Couper, 1960).
By the onset of the Mesozoic, the evolution of the Podocarpaceae is shown by the genus
Rissikia, evident from the Triassic (248-206 Ma) of Madagascar, South Africa, Australia and
Antarctica (Hill, 1994). Other early southern conifers, such as the Jurassic Nothodacrium and
Mataia (Townrow, 1967a; 1967b) are most probably podocarps, although, their relationship
to extant genera warrants classification (Stockey, 1990). Podocarps were still prominent in the
Cretaceous, albeit in Australia they were members of extinct genera (Hill, 1994), e.g.,
Bellarinea barklyi from the Early Cretaceous of Victoria (Drinnan and Chambers, 1986). Mill
(2003) discusses the biogeography of Podocarpaceae pertaining to extant/fossil taxa and the
palaeogeography of areas presently occupied by podocarps.
Molecular systematic studies using the locus rbcL for the Podocarpaceae show they are
monophyletic but with low overall main branch support, although most genera in the
phylogeny hold together as clades (Conran et al., 2000). Phyllocladaceae are nested inside
Podocarpaceae and Podocarpus is one genus with both subgenera positioned as clades
(Conran et al., 2000).
Podocarpus were abundant in Antarctic/Australian rift valley during the Cretaceous
(Dettmann and Jarzen, 1990; Hill, 1994). A number of extant podocarpaceous genera are
recorded as macrofossils in Australia during the early Tertiary (Hill, 1994). The majority of
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those genera, e.g., Podocarpus, Falcatifolium, Acmopyle, Dacrycarpus, Dacrydium,

Lepidothamnus and Phyllocladus, occur in southeastern Australia, but Retrophyllum has been
found in the southwest of Australia (Hill, 1994).
There are some shrubby species of Podocarpus that do presently occur within opencanopied communities, particularly heath (i.e., P. spinulosus, P. drouynianus and P.
lawrencei), but like a number of taxa whose affinities are with rainforests, opinion is divided
as to whether these are regarded as particularly tolerant and adaptable remnants of rainforests
or are true components of open communities (Kershaw et al., 1994; Hill, 1994). Australasia
and Malaysia have the greatest diversity of living podocarps, where South America,
Antarctica and New Zealand have the greatest diversities of fossil podocarps. The fossil
podocarp flora of New Zealand is more recent and probably derived from that of Australia,
which has fewer living or endemic fossil genera (Hill, 1994; Mill, 2003; Wagstaff, 2004,
Jordan et al., 2011).
3.3. Podocarpaceae, Pinaceae and Pangaea

In the Southern Hemisphere today conifers achieve greatest abundance in wet forests,
where there ability to compete successfully with broad-leaved angiosperms is due in part to
their production of broad, flat photosynthetic shoots (Hill and Brodribb, 1999; Brodribb and
Hill, 2003). The Podocarpaceae produce large leaves (Fig. 1) and they have superior light
harvesting ability than the Pinaceae. The tall closed canopy forests of the equatorial region
have remained accessible due to this leaf morphology. The Pinaceae (with the exception of
Pinus krempfii) are shade-intolerant and have not been able to colonize south of the equator
(Hill and Brodribb, 1999; Brodribb and Hill, 2003).
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Figure 2. The unsuccessful colonization of Pinaceae into Southeast Asia (red), and the successful
colonization of Podocarpaceae (black) (Modified from source: Tim Brodribb, University of Tasmania).
The colonization of Southeast Asia and subsequently Australia by Pinaceae has been
blocked by the equatorial evergreen rainforests (Fig. 2). Pines are physiologically incapable
of traversing this region due to shade-intolerance (Brodribb and Hill, 2003). In contrast, the
Podocarpaceae are shade-tolerant and can propagate under a canopy making them capable of
colonizing the equatorial zone and beyond (Hill and Brodribb, 1999; Brodribb and Hill,
2003).
3.4. Migration, Adaptation or Extinction

Shade tolerance, and the ability to propagate under a canopy, is a common character of
the Southern Hemisphere conifers. Possibly, high-latitude rainforest origin and the ability to
senesce over seasonal periods of darkness, is associated with the evolution of shade-tolerance
in the present members of Podocarpaceae. Relative to the southern supercontinent Gondwana,
the northern Laurasian supercontinent stayed together and allowed range shift across the
landmass in response to a changing environment (McLoughlin, 2001).
It has been shown from fossil and molecular systematic studies that conifers are a
monophyletic group and a common ancestor between the Northern and Southern Hemisphere
conifers occurred (Chaw et al., 1997: Stephanovic et al., 1998). The Northern Hemisphere
family Pinaceae is shade-intolerant, possibly a result of the ability to migrate in latitude,
where the relative lack of restriction did not necessitate significant adaptation to a changing
environment. While, the Southern Hemisphere conifers were restricted in distribution and
needed to adapt to the changing environment or, as many did, become extinct (Enright and
Hill, 1995).
Palynological records show that Northern Hemisphere tree populations are capable of
rapid migration in response to a warming climate. The Northern Hemisphere fossil pollen
record has revealed rapid migration rates of many temperate tree species of 1001000 m/yr
during the early Holocene (McLachlan et al., 2005). The migration rates you would imagine
would be comparable to Southern Hemisphere tree populations, but detailed palynology to
record past migrations is absent, or of poor quality to record such events here in Australia.
Possibly, the relative lack of land mass in the Southern Hemisphere has necessitated
adaptation rather than migration in response to competitive exclusion. The high latitude
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circumpolar Taiga Forests of the Northern Hemisphere are devoid of arboreal angiosperms.
The distribution illustrates the ancestral retreat of gymnosperms away from increased
angiosperm competition at lower latitudes (Enright and Hill, 1995). While in the Southern
Hemisphere, the lack of migration routes south toward the pole may have caused the
remarkable adaptation of the southern conifers in response to increased angiosperm
competition (Fig. 1: broad leaves and shade tolerance; Enright and Hill, 1995; Brodribb and
Hill, 2003; Biffin, et al. 2011). Strong selection may account for the extinction of many
coniferous genera in the Southern Hemisphere, as recorded in the Mesozoic fossil record
(Hill, 1994; 2004).
3.5. Podocarpus
Podocarpus was first described in 1807 by LHeritier. The genus comprises 110 species
the majority of which are restricted to lowland and montane forests of warm temperate to
tropical areas in the Southern Hemisphere. Seven species are endemic to Australia: P.
dispermus, P. drouynianus, P. elatus, P. grayae, P. lawrencei, P. smithii, and P. spinulosus.
Podocarpus has two subgenera, subgenus Podocarpus and subgenus Foliolatus. The
subgenus Podocarpus have cones that are not subtended by lanceolate bracts and the seed
usually has an apical ridge, and a florin ring around stomata. While Foliolatus has a cone
subtended by two lanceolate bracts and the seed usually is without an apical ridge (Mcarthy,
1998).
Distribution of the subgenus Podocarpus is in the temperate forests of Tasmania, New
Zealand, southern Chile, with some species extending into the tropical highlands of Africa
and the Americas (Mcarthy, 1998). While Foliolatus, generally has a tropical and subtropical
distribution, concentrated in east and Southeast Asia and Malesia, overlapping with subgenus
Podocarpus in northeastern Australia and New Caledonia (Van Royen, 1979; Silba, 1984;
Harden, 1990).
3.5.1. Podocarpus: A Climatic Indicator

Podocarps are important to the study of the effect of long-term climatic change on, leaf
morphology (Sporne, 1965; Biffin, et al. 2011; Hill and Pole, 1992), physiology (Brodribb
and Hill, 2003), taxonomic make-up during the Cenozoic (Hill, 1994), distribution (Ledru et
al., 2007) and diversity (Quiroga and Premoli, 2007; Quiroga and Premoli, 2010). The
concentration of conifers in wet forest habitats left them vulnerable to Cenozoic climate
change and decreases in diversity have occurred since the Paleogene in all areas where fossil
records are available (Hill and Brodribb, 1999).
Podocarpus fossils have been used by palynologists and palaeo-climatologists to
reconstruct Quaternary climate in tropical South America even though the factors involved in
their modern distribution are not well understood (Enright and Hill, 1995). The moist
ecosystems where the vast majority of the genus grow are well defined climatically and their
bisaccate pollen grain are unmistakable. Pollen analysis using light microscopy has not yet
been able to identify to the species level reliably, so palynological interpretations are the
subject to several hypotheses (Enright and Hill, 1995).
For decades, palynologists working in tropical South America have been using the genus
Podocarpus as a climate indicator (Ledru et al., 2007). The combination of botany, pollen and
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molecular analysis has proved to be reliable for determining population groups and their
regional evolution within tropical ecosystems. The refugia of rainforest communities
identified as crucial hotspots has allowed the Atlantic forests to survive under unfavorable
climatic conditions and are likely to offer the opportunity for this type of forest to expand in
the event of future climate change (Ledru et al., 2007).
Investigation of the long-term responses to climate changes in Podocarpus parlatorei, a
cold-tolerant tree species from the subtropics in South America, using distribution patterns of
isozyme variation has inferred northern expansion of the species during glacial periods
(Quiroga and Premoli, 2007). Podocarpus parlatorei is restricted to montane forests within
the Yungas, a cloud forest of the subtropics of northwestern Argentina and southern Bolivia.
It consists of disjunct population groups that are ecologically subdivided according to
latitude. These groups were expected to be genetically divergent from one another as a result
of historical isolation. The effective number of alleles and observed heterozygosity increased
with latitude, with the southern populations tending to be more variable and genetically
distinct. A positive association between genetic and geographic distances was detected and
reduction in diversity towards the north and high-elevation mountains are consistent with
evidence of patterns of forest migration resulting from climate change during the Late
Quaternary (Quiroga and Premoli, 2007).
3.5.2. Stand Dynamics

Stand dynamic studies on Podocarpus species have revealed that on poorly-drained,
nutrient-poor and high altitude sites where most of associated species were fairly shade
intolerant and light crowned, dense all-aged populations and the presence of numerous
saplings beneath the canopy suggested continuous regeneration (Lusk, 1996). Conversely, on
more favorable sites, were several of the associated angiosperms were highly shade-tolerant
and dense crowned, Podocarpus species were less abundant, and there regeneration from seed
appeared to be sporadic (Lusk, 1996).
Great longevity of shade tolerant conifers is probably crucial to their persistence strategy
in competition with shade-tolerant broad leaved species in undisturbed stands on favorable
sites (Lusk, 1996). A review of literature on southern temperate forests (Enright and Hill,
1995; Enright and Ogden, 1995; Lusk, 1996) disputes the hypothesis that heavily shaded,
infrequently disturbed habitats are an evolutionary refuge for conifers (Bond, 1989).
Sites likely to have high leaf area indices and infrequent disturbance are more
successfully exploited by shade-tolerant angiosperms (Lusk, 1996). Regeneration can take the
form of continual recruitment of shade-tolerant seedlings, or in less shade tolerant species it is
reliant on small-scale disturbances or topographic features such as rivers and ridgelines to
open the canopy (Brodribb and Hill, 2003).
The Myall Lakes and Jervis Bay populations of P. elatus are regularly burnt and
considerable recruitment is observed post-burning (Chris Quinn, The Royal Botanic Gardens
and Domain Trust, Sydney, pers. comm.). Podocarpus drouynianus and P. spinulosus are
probably fire adaptable remnants of rainforest. They resprout from lignotubers and are fire
tolerant. It is also shown for P. lawrencei that recruitment is favored after fire (Macdonald,
2004).
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3.6. Podocarpus elatus R.Br. Ex Endl

Eukaryota; Viridiplantae; Streptophyta; Embryophyta; Tracheophyta; Spermatophyta;
Coniferopsida; Pinales; Podocarpaceae; Podocarpus; Foliolatus; elatus.
Podocarpus elatus is an evergreen conifer that was abundant across the warmer wetter
parts of present day Australia before the arrival of Europeans. Indigenous people possibly
referred to P. elatus as Djerren Djerren in the Eora dialect of the Gadigal nation but there is
no known dreaming or song lines associated with the species (Clarence Slockee, The Royal
Botanic Gardens and Domain Trust, Sydney, pers. comm.). Podocarpus is derived from two
Greek words pous (foot) and karpos (fruit), referring to the fleshy fruit stems. The species
name elatus, is Latin for 'tall', refers to how tall the trees grow (http://www.
anbg.gov.au/anbg/conifers/Podocarpus-elatus.html).
Figure 3. The distribution of Podocarpus elatus based on a compilation of collections made for all major
herbaria in Australia since 1818. The Clarence River Corridor is a regional genetic boundary between
northern and southern populations (indicated by bar) (Source: Mellick et al. 2011). Photos: Podocarpus
elatus fruiting and mature tree.
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The species ranges from New South Wales to Queensland and prefers habitat in and
around rainforest north of the Beecroft Peninsula, Jervis Bay, NSW (Harden, 1990), in the
south, to Cape York Peninsula, QLD, in the north (Fig. 3). It prefers subtropical, gallery and
littoral rainforest habitats, with rich, moist, non-alkaline soils but the species is usually more
successfully established on poorer sites where competition is less vigorous. Plants will
tolerate salt spray and frosts to -7oC so long as they have adequate moisture levels and
humidity. Maturing in 8-10 years, P. elatus is fast growing once established (Harden, 1990).
Populations observed along the East Coast of NSW exhibited little recruitment with most
populations being composed of a few mature trees with no seedlings or saplings present.
It is commonly referred to as the Plum Pine, Illawarra Plum or Pine, Brown Pine
(Harden, 1990) and Turpentine Pine in the timber industry. Growing to 40m with brown bark
(fibrous) that is often fissured and scaly on old trees. It is a dioecious species having separate
male and female trees. The fruits are a purple black color and composed of two segments. The
edible portion is a grape-like (10mm diameter), sweet with a juniper-like flavor but
mucilaginous that ripens from March to July (Harden, 1990). The inedible part of the fruit is
the hard dark seed that is situated externally on top of the swollen stalk. The fruit has a high
ascorbic acid content (vitamin C), contains minerals, fat, protein, and are high in energy. The
leaves are lanceolate, oblong to linear (6-18mm wide, 5-14cm long) and the midvein is
prominent (Harden, 1990). Leaves can grow to 25cm long on young trees. The male cones are
narrow-cylindrical, catkin-like, to 3cm long, and are in sessile clusters (Harden, 1990).
Female cones are stalked, and solitary; scales are few, fleshy, uniting with the stalk to form a
fleshy receptacle (Harden, 1990).
3.6.1. Reproductive Biology of Podocarpus elatus

Podocarpus elatus has a reproductive cycle of one year and is a dioecious species with
separate male and female plants. Information specific to P. elatus is limited. The closest
phylogenetic species with information available is P. neriifolius, which exhibits
underdeveloped embryos at time of dispersal, although germination is usually rapid with seed
quickly losing viability (i.e., 20-60 days) so that there is no persistent soil-stored seed bank
(Enright and Jaffr, 2011). Podocarpus totara is a large tree of New Zealand and is a member
of the sub-genus Podocarpus, while P. elatus is a member of Foliolatus. Podocarpus totara
in New Zealand has a reproductive cycle of two years, and strobilus initiation is in
September, followed by a nine-month period of winter dormancy until emergence during the
growth flush in July-August of the following year (Wilson, 1999). Pollination in P. totara
occurs in mid-October to mid-November at the megaspore tetrad stage, where female strobili
bear only one or two ovules. During December pollen germination and fertilization occur
quickly and the pollen tube carries the body cell which branches out after reaching the
archegonia. Embryo maturation is complete by February (Wilson, 1999).
3.6.2. Podocarpus elatus Timber and Cultivation
The early loggers targeted Podocarpus elatus extensively for it is a useful timber that has
wide applications from boat building to cabinet making. The wood has a very fine, even
texture and a straight grain with faint growth rings, making it desirable for tabletops,
furniture, musical instruments (piano keys and violin bellies) and wood turning. Commonly
referred to as Brown Pine, the yellow wood turns brown in color shortly after being exposed
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(Barker et al., 2004). It has not been widely planted as a timber tree due to not being as light
and strong as its relative Araucaria cunninghamii. It has however been widely clonally
cultivated for roadside plantings (David Bateman, Waverly Council, Sydney, pers. comm.), as
an ornamental shade tree and now more commonly for the native bush food market. There is
horticultural development research published on P. elatus (Ahmed and Johnson, 2000)
although the majority of cultivation of the species is now clonal with preference for male
ramets due to not dropping fruit. This practice may be homogenizing the P. elatus pollen
cloud.
3.7. Fire and Ecotonal Specialization

Bowmans book (Bowman, 2000), titled Australian Rainforests: islands of green in a
land of fire emphasizes the existence of Australian rainforests is largely owed to the patterns
and processes responsible for the sharp boundaries between drier rainforest-types and fire
promoting communities. The capacity of the fragmented East Australian rainforests to resist
destruction by fire is partially a consequence of the species composition and structure of the
surrounding, frequently disturbed drier rainforest communities.
Podocarpus elatus exhibits a comparative advantage in drier communities, fringing more
floristically complex core communities. Larger dense populations are usually found on the
southern side of a break in the rainforest canopy with a northern aspect. This drier more
frequently burnt rainforest boundary would seemingly select against longer-lived species,
though for P. elatus, thick bark and waxy leaf cuticle, gravity seed dispersal, shade-tolerance
(i.e., rapid and dense propagation under female trees), the ability to senesce as a sapling for
long periods and possibly leaf chemistry may aid it in occupying these fire prone areas where
other rainforest trees are less able.
Podocarpus elatus is known as Turpentine Pine, due to the high concentration of
turpentinol compounds in the foliage, as are found in Pinus species. The evolution of these
compounds is likely a response to increased herbivory. Turpentinols increase flammability
and possibly these compounds in the species may also be a result of frequent burning. It
would be interesting to know if P. spinulosus, a co-occurring fire adapted podocarp, has
similar leaf chemistry to P. elatus. Understanding the past expansion/contraction of dry
rainforest communities will aid in understanding the seemingly precarious existence of these
relatively fragile-wet communities in such a harsh-dry landscape.
Evidence suggests large herbivorous dinosaurs browsed on, and subsequently dispersed,
the Australian podocarps (Bartholomai and Molnar, 1981; Molnar, 1996), which may have
contributed to the podocarps ecotonal habitat preference (Hill and Brodribb, 1999), as heavily
forested areas would restrict the movement and dispersal from such browsers. It is worth
briefly mentioning that the rapid extinction of mega fauna possibly increased fire frequency
due to biomass gain from reduced browsing (Rule et al., 2012), indicating that extinct mega
fauna may have had a considerable influence on rainforest fragmentation.
Drier rainforest communities, typified by Araucarian emergents and Podocarpus species,
are sensitive to effects of fire. Kershaw et al. (2005) postulated that dry rainforest
communities fringed wetter core rainforest communities in the Australian Wet Tropics
(AWT), and expansion and contraction of these communities are seasonal and climate driven.
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Precipitation gradients are largely responsible for successional community turnover from wet
rainforest to dry rainforest and eventually to sclerophyllous forest during dry periods.
During wet periods, wetter rainforest would encroach into previously dry rainforest and
the lack of fire would allow dry rainforest to expand into areas previously occupied by
sclerophyllous forest. Evidence for the latter can be found throughout the rainforests of
northern NSW (central range of P. elatus) where old Eucalyptus grandis trees tower over wet
rainforest communities far from fire prone boundaries.
These boundaries are an important parameter of climate change. With increasing
fragmentation (associated with aridification), the abundance of plant communities associated
with these boundaries may also increase, because of increasing surface area. Past changes in
species composition and extent of these communities have been showed to be correlated to
the glacial cycles of the Quaternary period (Kershaw et al., 2007a).
Podocarpus species are known to senesce for periods up to a decade with very little
growth (Brodribb and Hill, 2003). The species exhibits remarkable traits to survive in such a
highly diverse, dynamic and competitive environment. Possibly, high-latitude rainforest
origin of Podocarpaceae and the need to senesce over seasonal periods of darkness is
associated with the evolution of shade-tolerance in the present members of the family.
CASE STUDY ONE: CONSEQUENCES OF LONG- AND SHORT-TERM

FRAGMENTATION ON THE GENETIC DIVERSITY AND
DIFFERENTIATION OF A LATE SUCCESSIONAL RAINFOREST CONIFER
The east Australian rainforests provide an informative system with which to study
historic climate-driven habitat fragmentation. The long life cycle of rainforest conifers and
consequent lag effects on genetic variation, offer insights into demographic stochasticity in
small populations and persistence in increasingly fragmented systems. Microsatellite markers
were used to investigate the genetic diversity and structure of Podocarpus elatus
(Podocarpaceae), a long-lived rainforest conifer endemic to Australia (Mellick et al., 2011).
The markers used in the study were developed and characterized in Almany et al. (2009) and
assessed in Mellick et al. (2011). Twenty-seven populations throughout the east Australian
rainforests were screened and two divergent regions separated by the dry Clarence River
valley (New South Wales) were found (Fig. 4).
This new biogeographic barrier may be called the Clarence River Corridor (CRC). Niche
modeling techniques were employed to verify the incidence of habitat divergence between the
two population groups (Fig. 5).
Significantly high inbreeding was detected throughout the species range with no evidence
of contemporary bottlenecks. Most of the diversity in the species resides between individuals
within populations that suggest the species would be sensitive to the adverse effects of
inbreeding, though evidence suggests that these populations have been small for several
generations (Mellick et al., 2011). Higher diversity estimates were found in the southern
region, yet it is likely that the species survived historic population contraction in dispersed
refugia within each of these genetically differentiated regions.
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Figure 4. Results based on K= 2 using the Bayesian framework implemented by STRUCTURE across
individuals from the 27 populations of Podocarpus elatus.(ordered according to latitude). (a) All
individuals were used in the analysis that clustered them into two regions representing: Southern Region
(NSW) and Northern Region (Northern NSW/Qld). (b) Results based on K= 2 using the same Bayesian
framework on juvenile individuals and (c) on the mature individuals (Source: Mellick et al., 2011).
Figure 5. The regional climatic models for Podocarpus elatus based on collection data (National
Herbaria, YETI database and ATLAS database) and environmental data (WORLDCLIM). Darker areas
indicate a higher probability of occurrence (white indicates 020% and black indicates 80100%). The
black bar shows the Clarence River Corridor (Source: Mellick et al., 2011).
Mellick et al. (2011) is the first study reporting regional genetic structure either side of
the Clarence River Corridor in a plant. Environmental niche modeling of the separate regions
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has shown distinct differences between the climatic niches of each region. Primarily, the
southern model is associated with winter (uniform) rainfall patterns and northern with
summer rainfall patterns (Mellick et al., 2011). Some overlap between the two distinct niches
coincides geographically with the Macleay McPherson Overlap Zone that allowed for
validation of each regional model (i.e., each model predicted small areas of high probability
of occurrence in the neighboring region in the absence of occurrence data). These climatic
differences may underline long-term divergent processes between the two regional groups. In
the shorter term and at a regional scale, anthropogenic habitat clearing (i.e., Big Scrub
rainforest, Nth NSW) is also likely to contribute to the differences measured between regions
and among generational cohorts (Mellick et al., 2011).
The lower diversity and distributional pattern of the northern populations could suggest
that the current distribution is the result of an earlier northern expansion from a narrower
genetic pool (Mellick et al., 2011). This theory has been investigated in a phylogeographic
study combining genetic and palynological data that will helped identify migration routes and
date expansion/contraction events (case study two; Mellick et al. 2012). The projection of the
spatial distribution models generated for the northern and southern population groups onto
past climatic conditions provides support to adaptive divergence between the regions, and
elucidates the contrasting expansion/contraction climatic response of the species in relation to
early successional rainforest taxa (Mellick et al., 2011).
4. VEGETATION CHANGE IN AUSTRALIA DURING THE CENOZOIC

The Australian landscape has not always been arid, and the central desert was once wellvegetated (McLoughlin, 2001; Martin, 2006). At the start of the Cenozoic (65 Ma), Australia
had a warm/humid climate and the vegetation was predominantly warm to cool temperate
rainforest (Martin, 2006). The history shaping the eastern Australian rainforest communities
involved, high southern latitude of the continent at the end of the Cretaceous period (65 Ma)
and its gradual movement north toward the equator; general global aridification over the last
65 My amidst short term fluctuations and the evolution from ancestral Gondwanan lineages
of most taxa, but also immigration onto the continent by both plant and animal lineages from
different geographic sources at several times (Martin, 1982; Greenwood and Christophel,
2005; Sniderman and Jordan, 2011).
Separation of Australia from Antarctica started at the end of the Paleocene (54.8 Ma)
with the formation of a narrow strait, but it was the mid-Oligocene (31.1 Ma) when the first
channel was formed between the continents (McLoughlin, 2001). This allowed for the
Antarctic Circumpolar Current (ACC) to be created due to the removal of the block caused by
the South Tasman Rise, which cooled the continent and increased the size of the west
Antarctic ice cap, which removed the available atmospheric moisture and reduced
precipitation globally (Martin, 1982). The magnitude of the ACC as we know it today was
established about 18 Ma. This started the rapid cooling of Antarctic and the eventual demise
of the rich Antarctic flora.
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4.1. Cenozoic Summary

In the Palaeocene (6554.8 Ma), the Australian continent was warm/wet, and the
vegetation was mostly rainforest, except the northwest where there was limited aridity and
central Australia where aridity would have been seasonal (Martin, 2006). Gymnosperms were
the predominant vegetation type of south-eastern Australia but angiosperms were dominant in
central Australia (Martin, 2006). Podocarpaceous gymnosperms dominated the Palaeocene
vegetation due to the cool temperate climate similar to Tasmania and New Zealand today.
The early Eocene (54.8 Ma) was hot/humid ensuing angiosperm diversification and
dominance, and the increase of mega-thermal taxa in south-eastern Australia (Martin, 2006).
Rainforest gymnosperms were less abundant than the Palaeocene.
In the mid-late Eocene (4941 Ma) there was a decrease in temperature the vegetation
was mainly rainforest, but in central Australia there were some open vegetation and
sclerophyllous taxa (Martin, 2006). Sclerophylly developed as a response to infertile soils,
long before the climate became dry (Martin, 2006). Nothofagus became the dominant pollen
type, especially in the southeast, and Lauraceae the dominant leaf type (Martin, 2006).
There was a rapid cooling during the early Oligocene (33.7 Ma), the result of opening of
the seaway between Australia and Antarctica and strengthening of the Antarctic Circumpolar
Current (Martin, 2006; Quilty, 1994) Angiosperm diversity decreased and Nothofagus pollen
became more prominent (Martin, 2006).
During the Oligocene (33.723.7 Ma) temperature and angiosperm diversity increased,
and the occurrence of swamps in south-eastern Australia were more common, indicating that
rainfall was particularly high at this time (Martin, 2006).
The early Miocene (23.7 Ma) saw an increase in temperatures and the vegetation became
more variable in south-eastern Australia and in central Australia, rainforest was limited to
small pockets. The Miocene remains the warmest and most humid period during the Cenozoic
(Martin, 2006).
The mid-Miocene (16.4 Ma) is when regular flows in palaeo-drainage systems over much
of western and central Australia ceased, and alkaline lakes of inland basins in central
Australia deposited dolomite indicating high rates of evaporation and a well-marked dry
season (Martin, 2006).
The climate became colder and drier during the late Miocene (11.2 Ma), reducing the
abundance of rainforest in Australia and increasing the fire tolerant Myrtaceae flora especially
Eucalyptus (Martin, 2006).
A brief warming period and increased precipitation in the early Pliocene (5.3 Ma) caused
an expansion of rainforest in river valleys of the western slopes and south-eastern Australia
(Martin, 2006).
The climate increasingly became drier during the late Pliocene (3.6 Ma) (Fig. 6) and
rainforest taxa contracted further to the wetter coastal and highland regions. Grasslands
became more prevalent in inland areas and the modern climate was established, but it still was
considerably wetter than today (Martin, 2006).
The Pleistocene (1.80.01 Ma) fluctuated between drier glacial and wetter interglacial
periods. About 0.5 Ma, there was a marked shift to a dry climate (Martin 2006). The present
interglacial is drier than the previous interglacial (130 ka), with the last glacial maximum
(LGM: 21 ka) being particularly adverse. Although conditions have improved, precipitation
has not returned to the levels of the previous interglacial period (Martin, 2006).
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Figure 6. The build-up of arid cycles during the last 56 million years (Source: Bowler 1982).
The earth's climate has become cooler through the Tertiary (65-1.8 Ma) with frequent
oscillations that increased in amplitude (Fig. 6) and lead to the series of major ice ages of the
Quaternary (Hewitt, 2000).
The surviving rainforest taxa have had to migrate into areas (refuges) that have conserved
favorable environmental conditions for survival, and the ranges of many Gondwanan lineages
has decreased dramatically. The present genetic structure of populations, species and
communities has been primarily formed by the Quaternary ice ages, and genetic, fossil and
environmental data combined can greatly help our understanding of how organisms were
affected (Bennett, 1997; Hewitt, 2000).
4.2. Quaternary Vegetation

The Quaternary is a period in which modern life as we know it have evolved, or have
persisted from the Tertiary largely unaffected by environmental change (Hope, 1994; Hewitt,
2000). The Quaternary chronology is not based on widespread evolutionary changes, as are
older periods, but instead uses climatic changes, such as the growth of ice sheets and the
spread of cold surface water (Hope, 1994; Wright Jr, 1984). Fluctuations of heavy isotope
oxygen (18O) from marine sediments and ice cores, records a series of cyclic changes of
periods of 100 ky, being glacial maximums alternating with inter-glacial periods. This record
shows in the last 600 ky there have been six glacials periods (Fig. 6).
The two divisions of the Quaternary are the Pleistocene from 1.8 Ma to 10 ka, and the
Holocene, which includes the present inter-glacial. The Pleistocene represents the period of
establishment of our current landscapes, climatic patterns and diversity, and the adaptation of
the Tertiary biota to these new environments (Hope, 1994). Vegetation history of the
Quaternary is of particular importance when comparing extant flora, or recent extinctions, to
fossil flora (Hill, 1994; Hill, 2004; Hope, 1994; Wright Jr, 1984).
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4.3. East Australian Rainforests

World Heritage Listing of the east Australian rainforests (isolated sub-tropical and
tropical forests that occur above 300m) was awarded largely due to the rare assemblage of
Lepidozamia hopei, Agathis robusta, Prumnopitys ladei, Podocarpus grayae and Podocarpus
elatus which includes the closest living counterparts of Jurassic-age fossils. The members of
Podocarpaceae in the rainforests of tropical Australia are Podocarpus dispermus, Podocarpus
elatus, Podocarpus grayae, Podocarpus smithii, Prumnopitys ladei and Sundacarpus amara.
All occur in the Wet Tropics, although P. elatus is very rare in the Wet Tropics. It should
however be included, as it is more typical of somewhat drier (Araucarian) rainforest
(Greenwood and Christophel, 2005).
Tenuous persistence of the Australia Wet Tropics (AWT) rainforest communities under
increasing aridification can be attributed to orographic uplift and subsequent increase in
precipitation in those areas as a result of the Great Dividing Range (GDR). The vast tracts of
rainforest that once occurred throughout Australia contracted to these areas of high
precipitation (Kershaw et al., 2007b). Floristic interchange with Southeast Asian rainforests
may have occurred (Sniderman and Jordan 2011) but possibly was prevented by a dry
corridor in the northern Australian-Sahul Shelf region (Kershaw et al., 2005).
The aridification of the continent, decline of mega fauna and advent of indigenous
burning increased the exposure of the relatively fire susceptible drier rainforest communities.
Araucarian forest appears to have remained intact until it was progressively replaced by
sclerophyllous vegetation as a result of increased burning over the last 200,000 years
(Kershaw et al., 2005). Kershaw et al., (2005, 2007a) provides excellent evidence of
community turnover in the Australian Wet Tropics (AWT) in response to recent glacial cycles
of the Quaternary. His extensive work has provided invaluable records of fossil pollen over
the last 230 ky (Fig. 7).
During interglacial periods in the AWT the occurrence of Podocarpus pollen is
dramatically reduced when compared to glacial periods, indicating a preference for cooler
drier environments, and/or susceptibility to angiosperm competition. Possibly, the genus
persists during periods of angiosperm dominance (interglacials), due to association with drier
fringing communities around core rainforest communities, where angiosperms are present yet
are not as competitive (Lusk, 1996).
On another front it can be observed that during glacial periods the sclerophyllous taxa
become more abundant. This fire promoting vegetation could be encroaching on drier
rainforest, and accordingly drier rainforests communities may infringe wetter rainforests
during glacial periods.
Kershaw et al. (2007a) on completion of the Lynchs crater sequence (Fig. 7), maintains
the pattern of complex rainforest expansion during wetter interglacial periods is replaced by
drier rainforest and sclerophyll vegetation during drier glacials. Araucaria and Podocarpus
(drier rainforest) incur cyclic changes in abundance coinciding with the last two glacial
cycles. During the last glacial period, these genera are replaced by more fire-tolerant
elements, as is understood from the recorded increase in fire frequency during this period.
The decline in a more fire sensitive sclerophyll taxon Callitris, may suggest an earlier,
more regional increase in burning, a feature not inconsistent with the evidence in the offshore
fossil record, that regionally Araucariaceae had an initial decline about 130 ka, after some 10
My of near dominance in the landscape (Kershaw et al., 2007a).
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Figure 7. A pollen record of the last 230 ka from Lynch's Crater (AWT), north-eastern Australia
(modified from Kershaw et al., 2007a), showing the relative proportions of the major groups of arboreal
forest taxa and percentages of major contributors to these groups. All percentages of individual taxa are
based on the arboreal forest taxon sum for individual spectra. Corresponding change in temperature (two
glacial cycles) according to Vostok (Antarctica) ice core data (modified from Petit et al., 1999) is
provided on the left (Source: Kershaw et al., 2007a; Petit et al., 1999).
The impact of these changes on the current landscape is that Araucaria (dry rainforest) is
now restricted to small isolated patches that are unlikely to regain their previous dominance
(Kershaw et al., 2005).
The extinction of Dacrydium from the continent, whose closest morphological type
occurs as in New Caledonia, is clearly related but its presence in the AWT record may
suggest it was associated with a different community a peat land or swamp forest that is
now extinct in Australia (Kershaw et al., 2007a).
In AWT there are four occurring Podocarpus species (Fig. 7) associated with different
mesic habitats and this poses a problem when assessing species-level dynamics because the
pollen record is recorded at the generic-level, and does not account for differences in habitat
preference among the species.
Podocarpus elatus is very rare in AWT and only occurs in dry rainforest at high
elevations, where it co-occurs with Podocarpus grayae, which also expands in to lowland
areas. Podocarpus dispermus occurs in wet rainforest at lower elevations and Podocarpus
smithii occurs in wet rainforest at high elevations.
So there is a problem assessing species-level dynamics and community turn-over from a
generic profile, the signatures of four Podocarpus species are compounded within Fig. 7.
Shimeld (1995, 2004) provides evidence of long-term decline of Podocarpus elatus since
the previous interglacial (130 ka) from central areas of the species current range (Fig. 8).
Two adjacent deposits were used and chronology was replicated. The only other co-occurring
podocarp is Podocarpus spinulosus, which is expected to contribute little to the pollen profile
because it is a dry adapted shrub with different community associations.
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Figure 8. Fossil observations at Moffats Swamp/Creek, Port Stephens, NSW (130 ka to present)
showing an overall decline of Podocarpus elatus pollen since the previous interglacial (130 ka)
(Source: Shimeld 1995).
4.4. Palynology
Pollen analysis has been well-established as a means for reconstructing vegetation history
(Brewer et al., 2002; Hill, 1994, 2004; Kershaw et al. 2007b, 2007a, 2005, 1994; Shimeld
1995, 2004, Woods and Davis, 1989). The pollen grains and spores produced by plants are
preserved well in anoxic environments (e.g., lake deposits, forest hollows, peat bogs) and may
be extracted from these deposits by sampling exposed sections or by taking sediment cores
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(Brewer et al., 2002). The variation in the pollen assemblage are normally presented in the
form of a pollen diagram (Fig. 7) with the changes in pollen percentages of each taxon plotted
against depth, enables the temporal changes in the representation of individual taxa and the
type of surrounding vegetation communities to be determined.
Kershaw et al. (1994) indicates that it is not always possible to separate different genera
on their pollen morphology. Ledru et al. (2007) has found it impossible to classify
Podocarpus pollen grains at the species-level using light microscopy. Techniques used in
forensic palynology (Lynn Milne, University of Western Australia, Perth, pers. comm.) made
need to be incorporated into current methodology, if species-level identification using light
microscopy is important in reconstructing past community structure.
Fossil pollen sampled from sediment cores taken from the bottom of Lake Euramoo
(AWT) has revealed that there has been a gradual change in the surrounding vegetation from
dry adaptive species to rainforest species (Haberle, 2005). This vegetation change peaked at
about 7300 years ago during the Holocene Climatic Optimum and has since been in decline.
This is consistent with the habitat becoming wetter until the shift towards competitive
dominance of taxa adapted to drought and fire, which may be a response to the intensification
of El Nino-related climatic cycles (Haberle, 2005).
In north-eastern Australia, recent pollen spectra from the Ocean Drilling Program (ODP)
have sufficient in common with the riverine samples to suggest that rivers are contributing a
major pollen component to the offshore sediments (Moss et al., 2005). This would suggest
riparian vegetation (gallery forest) and associated taxa would be well-represented in the
offshore fossil record. Recent pollen samples from core tops taken from the Grafton Passage
on the continental shelf, that was thought to be the major passage for pollen transport to ODP
Site 820 (1638S, 14618E), show significant differences to both riverine/ODP samples and
suggest that pollen is dispersed across the continental shelf and through the outer Great
Barrier Reef system in an unanticipated fashion (Moss et al., 2005).
4.4.1. Podocarpus Pollen Morphology

Species-level taxonomic resolution is limited for Podocarpus pollen and understanding of
past community structure and relative abundance of species from the fossil pollen record is
not reliable (M. K. Macphail, Australian National University, Canberra, pers. comm.).
Podocarpus pollen grains are monads, heteropolar, bilateral; vesiculate and bisaccate
(Pocknall, 1981). Podocarpaceae pollen mostly have sacci (Wodehouse, 1935), small bladder
like structures flanking the corpus (Fig. 9). Their likely function is to increase buoyancy to
facilitate migration of the pollen grain through the pollination fluid in the micropylar canal,
tending to orientate the grain so that the germinal furrow contacts the female gamete (Doyle,
1945). Sacci structures may also be involved with flight, increasing the dispersal distance of
pollen and aiding pollination (Proctor et al., 1996). Sacci are always associated anatomically
with the furrow and may function in protecting it in periods of water stress (Pocknall, 1981).
Podocarpus pollen is easily identifiable due to distinctive bi-saccate grains (Fig. 9).
Although bi-sacci is a synapomorphic trait shared with other coniferous flora, it is unique to
Podocarpus in Australian fossil deposits. The mesic ecosystems where the trees grow are
climatically well defined, so the broad distribution patterns can be extrapolated from point
locations of fossil remains, due to distinct climatological requirements.
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Figure 9. Bilateral cross-section of Podocarpus elatus bi-saccate pollen.
5. PHYLOGEOGRAPHY AND POPULATION GENETICS

Phylogeography is a term coined by Avise et al. (1987) to illustrate the spatial
distributions of phylogenies. Phylogeography is used to determine common responses of
organisms to historical biogeography so to understand divergence and speciation, and to
comprehend geographic distributions of genealogical lineages including those at the
intraspecific level (Avise, 2000). Phylogeography interprets current genetic structure,
phylogenetic relatedness of alleles and their spatial arrangement among and within
populations to reveal historical components of gene flow (Avise, 2000).
Individual species phylogeography provides identification of geographic areas containing
high genetic diversity or distinct evolutionary units for that species (Byrne, 2007). These
areas are usually inferred as refugia, although past migration of diversity may have an
influence. Phylogeographic data collected from wide-ranging species allows for phylogenetic
estimates of gene flow to be made (Lowe et al., 2004). Phylogeography is a critical juncture
between established fields and effectively weights the influences of dispersal versus
vicariance in shaping the geographic distributions of genetic traits (Avise, 2000).
The field takes a population genetics and phylogenetic perspective on biogeography. An
explicit focus on a species biogeographical past sets phylogeography apart from classical
population genetics and phylogenetics (Knowles and Maddison, 2002). Past events including
population expansion/contraction, bottlenecks, vicariance and migration can be identified.
Recently developed approaches integrating coalescent theory, environmental niche modeling
and genealogical history of alleles can accurately address the relative roles of these historical
events in shaping current patterns (Cruzan and Templeton, 2000).
The field can inform conservation strategies through the assessment of genetic diversity
that incorporates an evolutionary perspective, and allows evaluation within a geographical
context, so providing integration with other biogeographical information (Byrne et al., 2011).
A number of studies have been interested in the spatial and temporal response of organisms to
climate driven distributional fluctuation (e.g., Bell et al., 2007; Mellick, et al. 20011, 2012,
2013a, 2013b; Pease et al., 2009; Petit, 2002, Petit et al. 2002, 2003; Richards et al., 2007;
Rissler et al., 2006; Scoble and Lowe, 2010).
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5.1. Population Genetics

Population genetics is the study of the allele frequency distribution and change under the
influence of the four evolutionary forces: natural selection, genetic drift, mutation and gene
flow (Hartl and Clark, 1997; Lowe et al., 2004). It takes account of population subdivision
and population structure in space, and attempts to explain such phenomena as adaptation and
speciation. Population genetics was a vital ingredient in the modern evolutionary synthesis;
its primary founders were Sewall Wright (Wright, 1921, 1931), J. B. S. Haldane and R. A.
Fisher (1930), who also laid the foundations for the related discipline of quantitative genetics
(Falconer and Mackay, 1996; Hartl and Clark, 1997).
5.1.1. Hardy-Weinberg Principal

The HardyWeinberg principle or equilibrium (HWE) states that the genotype
frequencies in a population remain constant or are in equilibrium from generation to
generation unless specific influences are introduced (Lowe et al., 2004). For example in a
random mating diploid organism, AA + 2Aa + aa = 1 genotype proportions are expected.
Those influences include non-random mating, mutations, natural selection, limited
population size, random genetic drift and gene flow. Genetic equilibrium is a basic principle
of population genetics (Emigh, 1980); it is achieved in one generation, and requires the
assumption of random mating with an infinite population size (Hartl and Clark, 1997).
5.1.2. Genetic Distance
Genetic distance is a measure of the dissimilarity of genetic material between different
species or individuals of the same species (Pollock and Goldstein, 1995). It is a degree of
similarity between a pair of individuals, populations or species were values range between
zero (identical) and one (completely different) (Lowe et al., 2004). By comparing the
percentage difference between the same genes or neutral loci of different species, a figure can
be obtained, which is a measure of genetic distance. Depending upon the difference and
correcting for known rates of evolution, genetic distance can be used as a cladistic tool.
5.1.3. Heterozygosity
Quantification of within population genetic variation is central in the interpretation of
genetic differentiation between populations. Heterozygosity (Ho) is a measure of genetic
diversity, being the frequency of heterozygotes for one locus within a population (Page and
Holmes, 1998). A heterozygote is an individual with two (diploid) or more (polyploidy)
alleles at a locus. In understanding how genetic diversity is partitioned within a population, it
is important to determine how many alleles are present at a single locus. Usually the observed
(Ho) and expected (He) heterozygosities are compared through the determination of allelic
frequencies. Deviation away from the expected HWE frequencies indicates that the
population is not randomly breeding and some degree of assortative mating is occurring
(Lowe et al., 2004).
5.1.4. The Fixation Index
In 1921 what is known as the fixation index was defined (Wright, 1921). The purpose of
which is to quantify the inbreeding effect of population sub-structure (Lowe et al., 2004). The
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index equals the reduction in heterozygosity expected with random mating at anyone level of
a population hierarchy relative to another (Hartl and Clark, 1997). It quantifies genetic
differentiation and proves useful because it allows for an objective comparison of the overall
effect of population substructure among different organisms (Lowe et al., 2004). F-statistics
describe genetic differentiation by partitioning variation into three levels: total population,
sub-population and individual (Lowe et al., 2004). FST and RST statistics refer to analysis of
variance in allele frequencies and in repeat numbers respectively and are used to illustrate
quantitatively the degree of genetic structure (Prez et al., 2002).
5.1.5. Inbreeding Depression and Heterosis

Inbreeding depression is a term indicating reduced fitness in a given population as a
result of breeding of related individuals (Lowe et al., 2004). Although inbreeding to some
degree accounts for all the diversity that we see today, it is a double edged sword and
breeding between closely related individuals, called inbreeding, results in more recessive
deleterious traits manifesting themselves. The more related the breeding pair the more
deleterious genes the offspring will have (i.e., increased genetic load), resulting in unfit
individuals. Genetic load is a term widely used in domestication and one that will become
more familiar to conservation efforts as natural populations become smaller and more
fragmented.
The effects of inbreeding depression can be dramatic between selfed and out-crossed
families (Fig. 10) depending on the genetic load. In a population where inbreeding occurs
frequently, fatal recessives alleles would be rare, due to promptly being eliminated from a
population. With infrequent inbreeding, recessive deleterious alleles will be masked by
heterozygosity, and so heterozygotes will not be selected against (assuming dominance).
Obligate outcrossers, such as trees, are more susceptible to inbreeding depression.
Heterosis is the advantageous effects of hybridization (introgression), and to some
degree, admixture, between two inbred lines with different deleterious genes. By crossing
such lines in a diploid species, the genetic load is dramatically decreased and the fitness of the
offspring increases in comparison to the parents. Many domestication efforts have utilized
this phenomenon (Fig. 10: Shepherd et al. 2005). If an offspring of two highly inbreed lines is
selfed, the offspring produced (assuming sufficient fecundity) will largely exhibit genotypic
proportions expected under HardyWeinberg equilibrium.
5.2. Coalescent Theory

The application of coalescence theory to genealogical relationships within species
provides information into the process of diversification and the influence of biogeography on
distributional patterns (Cruzan and Templeton, 2000). The coalescent theory is a retrospective
model of population genetics that traces all alleles of a gene from a population to a single
ancestral copy shared by all members of the population, known as the Most Recent Common
Ancestor (MRCA) (Donnelly and Tavar, 1995). Under conditions of genetic drift alone,
every finite set of genes or alleles has a coalescent point at which all descendants converge to
a single ancestor (Cannings, 1974; Donnelly and Tavar, 1995).
Selfed
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Outcrossed
Figure 10. The effect of inbreeding depression (left) and heterosis (right) on the vegetative propagation
of the Pinus elliottii x P. caribaea hybrid (Study and photo: R. Mellick).
Some properties of the coalescent theory are: the larger the number of samples (genes)
the greater the rate of coalescence (the more lineages there are the greater the probability that
two will coalesce), the larger the population size the slower the rate of coalescence, time to
coalescence gets longer as the process moves toward the MRCA, smaller sample sizes have a
high probability of including the MRCA of the population, and time cannot be measured
directly with genetic data but genetic divergence can. Considering the assumption of selective
neutrality (Kimura, 1968) it is possible to model the history of a sample, that is, without
regard to the rest of the population. Selection can be accommodated easily if it is strong,
while coalescent models of weak selection are more complicated. Chloroplast and nuclear
genes will coalesce at different rates due to the difference in inheritance between chloroplast
and nuclear DNA as a result of recombination.
The coalescent, as it is typically presented in population genetics, makes all the usual
assumptions of the Wright-Fisher model of a population (Donnelly and Tavar, 1995; Fisher,
1930; Wright, 1931). As coalescent theory was developed, so were the within-species
molecular data sets resulting from the development and availability of molecular techniques
(Crandall and Templeton, 1993; Kingman, 2000).
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We now have access to Second Generation Sequencing or Next Generation Sequencing,

where potential exists to develop 1000s of informative markers from a single sequencing run.
Recently the resolution and sheer number of molecular markers available has increased
confidence of inferred molecular history through coalescent-based analyses. Coupled with
environmental models that can be projected onto historical climatic estimates an
interdisciplinary evolutionary history can be acquired for a species (Mellick et al., 2012,
2013b).
CASE STUDY TWO: PALAEODISTRIBUTION MODELING AND GENETIC

EVIDENCE HIGHLIGHT DIFFERENTIAL POST-GLACIAL RANGE
SHIFTS OF A RAINFOREST CONIFER DISTRIBUTED ACROSS
A LATITUDINAL GRADIENT
We examined range dynamics during the last glacial cycle of the late-successional
tropical rainforest conifer Podocarpus elatus using a combination of modeling and molecular
marker analyses. In particular, we tested whether distributional changes predicted by
environmental niche modeling are in agreement with the glacial maximum contractions
inferred from the southern fossil record, and population genetic-based estimates of range
disjunctions and demographic dynamics. Also, we tested whether northern and southern
ranges are likely to have experienced similar expansion/contraction dynamics. The study
location is the Eastern Australian tropical and subtropical rainforests (Mellick et al., 2012).
Environmental niche modeling was completed for three time periods during the last
glacial cycle and was interpreted in light of the available fossil record (Fig. 11; Mellick et al.,
2012). We collected 109 samples from 32 populations across the entire range of P. elatus. Six
microsatellite loci and Bayesian coalescence analysis were used to infer population
expansion/contraction dynamics, and five sequenced loci (one plastid and four nuclear) were
used to quantify genetic structure/diversity (Fig. 12; Mellick et al., 2012). Environmental
niche modeling showed that the northern and southern ranges of P. elatus experienced
different expansion/contraction dynamics. In the northern range, after persisting in a small
refugial area during the Last Glacial Maximum (LGM; 21 ka), the habitat suitable for P.
elatus expanded during the post-glacial period. Conversely in the south, suitable habitat was
widespread during the LGM but since has contracted. These differential dynamics were
supported by coalescent-based analysis of the population genetic data (northern dispersal) and
are consistent with the higher genetic diversity in the south compared to the north. A contact
zone between the two genetically divergent groups (corresponding to the Macleay Overlap
Zone) was supported by environmental niche modeling and molecular analyses (Fig. 11 and
12; Mellick et al., 2012).
The climatic changes of the Quaternary have differentially impacted the northern and
southern ranges of this broadly distributed rainforest tree in Australia. Recurrent
contraction/expansion cycles contributed to the genetic distinction between northern and
southern distributions of P. elatus (Mellick et al., 2012). By combining molecular and
environmental niche modeling evidence, this study questions the general assumption that
broadly distributed species respond in a uniform way to climate change.
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Figure 11. Environmental niche models for Podocarpus elatus north (a, b and c), and south (d, e and f),
of the Clarence River Corridor biogeographic barrier in eastern Australia based on the Model for
Interdisciplinary Research on Climate (MIROC) global climatic model for 21 ka Last Glacial Maximum
(a and d), 6 ka Holocene Climatic Optimum (b and e) and the 0 ka pre-industrial (c and f) time periods.
Dark blue indicates low probability of occurrence and warmer colours indicate high probability of
occurrence (Source: Mellick et al., 2012).
Niche-modeling indicated (Fig. 11) that at the Last Glacial Maximum (21 ka), the
habitats suiting the two genetically differentiated regions of P. elatus were geographically
disjunct (Mellick et al., 2012). The northern distributional region persisted through the LGM
in a small refugial area, which during post-glacial periods has expanded. Conversely, the
southern range followed the opposite trend and has contracted since the LGM, but overall had
higher genetic diversity (Fig. 12). Coalescent-based analysis supported these differential
dynamics across the distribution of the species (Mellick et al., 2012).
In this study we coupled molecular (cpDNA and nDNA) and environmental niche
modeling (ENM) data to compare the distribution histories of two genetically differentiated
groups of the widespread Australian rainforest tree Podocarpus elatus. Molecular and ENM
results were congruent in suggesting that north/south divergence can be explained by
differential range-shift responses between these two genetic clusters separated by the
Clarence River Corridor. The differential range shift response of the species in northern
versus southern distributions is likely to be illustrative of differing climatic drivers between
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the southern subtropical and northern tropical rainforests. Stronger seasonality in the south
might have contributed in maintaining this divergence, and while the species occupies such a
broad environmental envelope, the degree of gene flow between the population groups has
been sufficient to maintain the species integrity (Mellick et al., 2012).
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Figure 12. Podocarpus elatus sequence haplotype distribution and haplotype networks for each of the
five loci (ae) used in the study. The Clarence River Corridor (CRC: curved line) is a microsatellite
genetic boundary (K = 2), where the north includes both Macleay Overlap Zone and northern
populations. Pie charts are coloured according to the haplotypes present in each population, and are
proportional to the sample size, were the smallest circles represent n = 1 and the largest n = 7. The
networks are shaded according to region and are sized relative to abundance of each haplotype. The
proportion of each haplotype present in the southern populations (112) is white, the Macleay Overlap
Zone (1325) is grey and in the northern populations (2632) is black. Only two haplotypes were found
at locus A45 (b) and therefore no network was generated. Locus B37 (c) is a chloroplast locus and the
remaining loci are nuclear (Source: Mellick et al., 2012).
6. MOLECULAR ANALYSIS
6.1. Nucleic Markers Including Microsatellites
The flanking sequence of nuclear microsatellites (SSRs) has proved informative to
evolutionary studies (Rossetto et al., 2008, 2009). Inferring genealogical relationships from
SSR allelic size data alone is weak due to the mutational mechanisms involved (Estoup et al.,
2002) but the regions flanking the repeat itself provide a tractable source of phylogenetic
information that is well suited to cross-population and phylogeographic studies (Rossetto et
al. 2002; Hey et al., 2004). The fact that these flanking regions are conserved to a degree
necessary to allow for primer annealing and Polymerase Chain Reaction (PCR), yet more
variable as the sequence approaches the SSR (within the amplicon), give these markers an
advantage over other co-dominant marker systems. This is due to being able to score
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haplotypes from the flanking sequence, and in some circumstances link to repeat length
variation, i.e., HapSTR (Haplotype Short Tandem Repeat; Hey et al., 2004, Mellick et al.,
2013b).
Microsatellites, or Simple Sequence Repeats (SSRs), are polymorphic loci present in
nuclear DNA and organelle DNA that consist of repeating units of one to four base pairs in
length (Turnpenny and Ellard, 2005). They are co-dominant molecular markers that have
wide-ranging applications in the field of genetics, including kinship and population studies.
These markers often show high levels of inter- and intra-specific polymorphism, particularly
when tandem repeats number ten or greater (Queller et al., 1993). Microsatellites owe their
variability to an increased rate of mutation compared to other neutral regions of DNA. These
high rates of mutation can be explained most frequently by slipped strand mispairing
(slippage) during DNA replication on a single DNA strand. Mutation may also occur during
recombination during meiosis (Blouin et al., 1996). Some errors in slippage are rectified by
biomolecular proofreading mechanisms within the nucleus, but some mutations can escape
repair.
Commonly it is found that a number of nucleic microsatellite loci distinguish between
individuals of a rare or threatened organism. Microsatellite library construction is problematic
in conifers due to their large genome size and the high proportion of duplicated DNA (Elsik
and Williams, 2001; Scott et al., 1999; Scott et al., 2003). Nucleic microsatellite libraries
were developed for Podocarpus elatus (Almany et al., 2009) and P. lawrencii.
6.2. Plastid DNA Markers

Plastid analysis provides a deeper historical observation than nucleic DNA, due to not
undergoing recombination and being of a more conserved nature (Powell et al., 1995). This
conservation allows for historical events to be recorded as signatures in the DNA sequence.
Chloroplast genomes are predominantly maternally inherited in angiosperms and paternally
inherited in gymnosperms. They are powerful in determining gene flow from seed versus
pollen movement and reconstructing phylogeographic colonization (Petit et al., 2003).
Intergenic spacers and introns of chloroplast DNA are commonly used as markers in
phylogenetic studies focusing on species-level relationships in plants. In order to attain
informative variation at this low taxonomic level, a large number of nucleotide bases and,
therefore, a great many regions must be investigated. The great majority of loci investigated
for this project were plastid, and only one polymorphic locus was found (PeB37BGT:
Almany et al., 2009).
6.3. Cytoplasmic Inheritance in Podocarpus

The pattern of cytoplasmic inheritance in Podocarpus totara confirms a predominantly
paternal inheritance of plastids, common in all conifer families, and inheritance of
mitochondria is dependant on the mechanism of fertilization and the structure of male and
female gametes found in each family (Owens and Morris, 1990; Wilson and Owens, 2003).
Wilson and Owen (2003) inform that Podocarpaceae display a cytoplasmic inheritance
mechanism similar to that of the Pinaceae and Taxaceae. Bi-parental inheritance in
245
Podocarpus elatus is therefore likely, with cpDNA being paternally inherited and mtDNA
being maternally inherited. An extensive search for polymorphic mtDNA loci in the P. elatus
was warranted due to populations being clumped and maternal structure being likely but none
were found. Discovery of polymorphic plastid loci has improved since the advent of Next
Generation Sequencing and will serve gene discovery in organisms with large sized genomes
where paraology is likely.
6.4. Interdisciplinary Studies

Interdisciplinary studies that use multiple sources of information to infer past genetic
structure, such as molecular and palynological data, are commonly used (Petit et al., 2002,
2003). The methods are complementary, so that the limitations from one method are often
compensated for by evidence from the other method. For instance, the taxonomic resolution
using palynological tools is limited, whereas some insights on the dynamics within species
can only be obtained using molecular tools. Furthermore, genetic surveys can have a greater
spatial resolution yet fossil data provide greater temporal resolution (Petit et al., 2002, 2003).
Macro-fossil data in most taxa provides more taxonomic certainty, while palynology provides
much more fossil data but is subject to scrutiny when it comes to reliable species
identification.
Petit et al. (2002) identified refugia and post-glacial colonization routes of European
White Oaks (Quercus spp.) based on both chloroplast DNA (cpDNA) and fossil pollen
evidence. Geographic distribution of 32 cpDNA variants belonging to eight Quercus species
sampled from 2613 populations is presented by Petit et al. (2002). Clear-cut geographic
patterns were revealed in the distribution of cpDNA haplotypes. Combined with
palynological data, colonization routes out of glacial period refugia were able to be identified.
Integration of genetic and climatic data (Pease et al., 2009; Scoble and Lowe, 2010, Mellick
et al., 2011, 2012, 2013a, 2013b) with fossil data will further improve our understanding of
the underlying environmental factors that maintain genetic structure.
7. ENVIRONMENTAL NICHE MODELING

Environmental Niche Modeling (ENM) techniques endeavor to define a conceptual
envelope that best describes the limits to a species actual distribution by correlating
occurrence records to environmental variables. It is a process using computer algorithms to
predict the geographic distribution of species on the basis of a mathematical representation of
their known distribution in environmental space (Beaumont and Hughes, 2002; Heikkinen et
al., 2006). Environmental suitability is largely governed by climate in particular temperature
and precipitation gradients. Variables can be relatively constant, such as soil type, or dynamic
like climate and land use, so a prior knowledge of the study area and study system need to be
considered for reliable predictions.
The development of Geographic Information Systems (GIS) has allowed researchers to
investigate these environmental factors through ENM in detail. This has made it possible to
model the spatial patterns of climatic suitability for organisms based on their current
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Rohan Mellick
distributions and to project these conditions onto mapped estimates of historical and future
climates. Allowing for inference of refugial areas based solely on environmental data alone.
Figure 13. Climate-based prediction and constraints on species distributions (Modified from source:
Cunningham, 2004).
Prediction of species distributions is integral to various ecological, evolutionary and

conservation applications in science (Elith et al., 2006; Elith and Leathwick, 2009).
Applications include field collection, predicting demographic history and forecasting future
threats. Environmental Niche Modeling is now a common tool for assessing the potential
impact of climate change on species ranges (Beaumont et al., 2008).
Many of the questions in phylogeographic studies pertain to how environmental variation
over space and time shape patterns of genetic divergence (Pease et al., 2009; Scoble and
Lowe, 2010). One of these questions is the identification of environmental barriers to
dispersal and gene flow. Environmental niche modeling can answer the question: Is
environmental variation causing range disjunction and reproductive isolation of fragmented
populations? This can be tested by determining genetic connectivity between populations
located in different environmental envelopes.
Modelers are often faced with a problem when the fundamental niche (potential
distribution) of a species does not correspond with a realized niche (actual distribution) and
for this reason either an error in the construction of the fundamental niche (the abiotic
thresholds for a species) has been made or that there are genuine factors affecting the actual
distribution of the species, such as competition, predation and pathogens (Fig. 13). This
discrepancy between the two often provides the basis of the more interesting hypotheses.
247
7.1. Landscape Genetics

Environmental and historical data are now being combined to understand geographic
patterns of genetic diversity in the emerging discipline landscape genetics (Scoble and
Lowe, 2010). It integrates population genetics, spatial statistics and landscape ecology. Just
coming into existence and beginning to display signs of future potential, landscape genetics
research explicitly quantifies the effects of landscape composition, configuration and matrix
quality on gene flow and spatial genetic variation (Storfer et al., 2007). The matrix can be
perceived as the hostile are between areas of increased habitat suitability and associated
fragmented habitats. Niche modeling has contributed to such efforts by allowing species
environmental associations to be projected into the past so that hypotheses about historical
vicariance can be generated and tested independently with genetic data (Pease et al., 2009).
Recent episodes of environmentally mediated divergence are unlikely to be shown as a
molecular signature, however, utilizing environmental models associated with divergent
population groups reveals the history of genetic disjunctions and how climate and the
landscape drives evolution.
Speculation has been made that rainforest communities (Hilbert, et al., 2007;
VanDerWal, et al., 2009) and alliances (Mellick et al., 2013a) fluctuate independently in
response to climate depending on their species specific ecology in the context of their abiotic
environment. Byrne et al. (2011) suggests that plants respond to Quaternary climatic change
as species, not as associations or biomes. Population isolation/migration and
vicariance/admixture processes over time, brought about by enduring glacial periods to the
brief interglacials like the present, add to the evolutionary complexity in fragmented highly
biodiverse areas.
Figure 14. Environmental niche models (altitudinal range shift) for Nothofagus moorei (blue) and
Elaeocarpus grandis (yellow) in far-eastern Australia (Mt Warning Caldera) for 21 thousand years ago
(fossil record support) during the Last Glacial Maximum (LGM) time period based on the Model for
Interdisciplinary Research on Climate (MIROC 3.2.2) global climatic model, the current time period
based on WorldClim data (1966present) and an average of 13 global climatic models for 2050 (Mellick
et al., 2013a; Mellick et al., 2013b ). Darker shading indicates areas of higher elevation and lighter
shading indicates areas of lower elevation (Source: Mellick et al., 2013a).
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Rohan Mellick
Figure 15. a. Boxplots of area of overlap at each time for 10 paired replicate models. Area of overlap was
measured as number of overlapping grid cells marked as core climate conditions for each species. b.
Histograms of frequency of altitude values in the core climate condition grid cells for each species.
Elaeocarpus grandis data is to the left and Nothofagus moorei to the right in each panel. Histograms of
altitude in 100 m bands were based on the core climate suitability grid cells for each species pooled
across the 10 replicates at each time. The dashed line on each plot indicates the mean altitude for each
species. c. The entire (northern and southern) Nothofagus moorei occurrences (YETI and Atlas of NSW
Wildlife), including genetic structure and diversity across whole range that comprises four major
highland population groups. Darker shading indicates areas of higher elevation and lighter shading
indicates areas of lower elevation (Source: Mellick et al., 2013a).
7.2. Past-Current-Future Distribution

Distributional changes facilitate adaptation and forge the evolutionary trends responsible
for incipient speciation. Palaeodistribution modeling projects the envelope created from
current occurrence records onto historical climatic estimates (Mellick et al., 2012). Used in
conjunction with molecular data the method combines independent data to locate glacial and
interglacial refugia (Hilbert et al., 2007). Recently research on the turnover along altitudinal
gradients from cool-temperate (Nothofagus spp.) to warm subtropical rainforest (Elaeocarpus
spp.) in far-eastern Australia has revealed post-glacial trends (Mellick et al., 2013a).
The potential distributions of the two species closely associated with different rainforest
types were modeled to infer the potential contribution of post-glacial warming on spatial
distribution and altitudinal range shift (Mellick et al., 2013a: Fig. 14 and 15). Environmental
niche models were used to infer range shift differences between the two species in the past
(21 thousand years ago), current and future (2050) scenarios, and to provide a framework to
explain observed genetic diversity/structure (Fig. 15a, b and c). The models suggest
continuing contraction of the highland cool temperate climatic envelope and expansion of the
lowland warm subtropical envelope, with both showing a core average increase in elevation
in response to post-glacial warming (Figure 15b).
249
7.3. Predicting Future Distribution of Genetic Diversity

Modeling and monitoring studies over the last 20 years have provided considerable
evidence that global climate change is already affecting and will continue to affect many
species and ecosystems, resulting in declines and extinctions of many species (Dunlop and
Brown, 2008). It is usually the most threatened species and habitats that are going to respond
first to these climatic changes. Nonetheless, because of the interacting nature of ecological
systems the impacts on biodiversity to future environmental change are not clear.
We know that adaptive potential is associated with genetic diversity and that distributions
follow environmental gradients. Through modeling both molecular and environmental data,
we can anticipate future spatial changes in genetic diversity. Recently the resolution and sheer
number of molecular markers available has increased confidence of inferred molecular
history through coalescent-based analyses. Coupled with environmental models that can be
projected onto future climatic estimates an interdisciplinary forecast can be acquired for a
species. Next Generation Sequencing will provide additional tools to reliably predict future
changes in genetic diversity and therefore the adaptive potential of species to the rapid
environmental changes anticipated this century.
Table 1. Details of the 13 atmospheric oceanic global circulation models (AOGCMs)
used to create an ensemble (average) for projecting MaxEnt models onto 2050 future
climate conditions (Source: Mellick et al., 2013b)
Climate Model Inter-comparison
Project 3(CMIP3) identifier
Originating institution or collective
BCCR-BCM2.0
CGCM3.1(T63)
Bjerknes Centre for Climate Research, Norway

Canadian Centre for Climate Modeling and Analysis, Canada
CNRM-CM3
Mto-France / Centre National de Recherches

Mtorologiques, France
CSIRO Atmospheric Research, Australia
Max Planck Institute for Meteorology, Germany
Meteorological Institute of the University of Bonn,
Germany; Meteorological
Research Institute of the Korean Meteorological Agency,
Korea
Geophysical Fluid Dynamics Laboratory, NOAA, Dept. of
Commerce USA
Goddard Institute for Space Studies NASA USA
Instituto Nazionale di Geofisica e Vulcanologia, Italy
Institute for Numerical Mathematics, Russia
Institut Pierre Simon Laplace, France
Center for Climate System Research (The University of
Tokyo), National Institute for Environmental Studies, and
Frontier Research Center for Global Change (JAMSTEC),
Japan
Meteorological Research Institute, Japan
CSIRO-Mk3.5
ECHAM5/MPI-OM
ECHO-G
GFDL-CM2.1
GISS-ER
INGV-SXG
INM-CM3.0
IPSL-CM4
MIROC3.2(medres)
MRI-CGCM2.3.2
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Studies have supported the prediction that species with narrower climatic niches will be
more sensitive to climate-induced range contraction (Sexton et al., 2009; Bell, 2007).
Potential impacts of projected climate change on biodiversity are often assessed using singlespecies Environmental Niche Models (ENM) (Heikkinen et al., 2006). Predicting the
probability of successful establishment of plant species by correlating distribution to
climatic/environmental variables, has considerable potential as supporting methodology to
reinforce palynological and phylogeographic studies. In the future, deeper ecological and
physiological understanding may allow competition effects to be quantified and included in
species distribution modeling. Future biogeographical ranges of species are constructed by
applying the models based on climatic variables that best describe the current equilibrium
distributions to simulate future distributions under selected climate changes scenarios
(Bakkenes et al., 2002; Solomon et al., 2007). Bakkenes (2002) suggests that in reviewing
possible future trends, it was found that European plant species, in general, would find their
current climate envelopes further northeast by 2050, implying maximum temperature
threshold may restrict species lower latitude range limits.
Araujo and New (2007) suggests added confidence in ENM output can be achieved
through projection of the trained environmental envelope onto an ensemble of different
atmospheric oceanic global circulation models (AOGCMs). The selection of climate
scenarios for impact assessments should not be undertaken arbitrarily - strengths and
weakness of different climate models should be considered (Beaumont et al., 2008). To
account for uncertainties in predictions of future climate data, we derived data from 13 global
climate models (Table 1: Mellick et al., 2013a, 2013b) used in the Fourth Assessment Report
of the Inter-governmental Panel on Climate Change (IPCC).
7.4. Correlative and Mechanistic Modeling

Environmental niche models are correlative (statistical) models. They relate observed
presences of a species to values of environmental variables across the geographic extent of
the species range. Some models use absence data, which is very hard and expensive to
collect but the most commonly used models use presence-only data, perhaps together with
random background data. In contrast, mechanistic (or process-based) models assess the biophysiological aspects of a species to generate the conditions in which the species can ideally
survive, based on a species traits and observations made in laboratory or controlled field
studies (Bresson et al., 2011). Mechanistic modeling defines the abiotic limits of a species
range through the physiological tolerances of the species, e.g., Podocarpus auxiliary xylem
tissue collapses at certain water-stress thresholds and therefore the species distribution is
limited by a trade-off between water use and photosynthetic efficiency (Brodribb and Hill,
1999).
It may be possible to combine mechanistic and correlative approaches to alleviate the
expense required for mechanistic data collection and gain the convenience of correlative
modeling. The development of phenotype-genotype correlation between the physiological
traits associated with climatic tolerance and a marker suite linked to such characters may
allow this. Possibly, selective genotyping (i.e., genotyping the best and worse individuals of
physiological quantitative traits), candidate gene analysis and/or quantitative trait loci
analysis could achieve the phenotype-genotype correlation required. Then the correlative
251
modeling approach could be applied to the geographic distribution of markers associated with
such traits.
Figure 16. The distribution of Podocarpus elatus showing genetically differentiated population groups;
southern group is red and northern is green (Mellick et al., 2011). The Clarence River Corridor dividing
the groups is shown. The three populations used for the coalescent-based analysis are shown and the
sizes of their representative circles are relative to allelic richness (Rs) x unbiased heterozygosity (uh)
(Source: Mellick et al., 2013b).
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Rohan Mellick
CASE STUDY THREE: INTRASPECIFIC DIVERGENCE ASSOCIATED

WITH A BIOGEOGRAPHIC BARRIER AND CLIMATIC MODELS SHOW
FUTURE THREATS AND LONG-TERM DECLINE OF
A RAINFOREST CONIFER
A capacity to foresee the shift in species range and the demographic response to future
climate change is integral to effective conservation planning (Mellick et al., 2013b). Here we
model the future climate-driven range shift, and compare it with past range shift, along a
latitudinal gradient in two population groups of a late-successional rainforest conifer
(Podocarpus elatus), genetically differentiated over the Clarence River Corridor
biogeographic barrier (Northern NSW, East Australian Rainforests). Environmental niche
modeling of the past-current-future distributions of the two groups and a coalescent-based
isolation-with-migration model investigated divergence times and effective population sizes
among the current genetic disjunctions in the species. This suggests differential range shift
(i.e., expansion in the north and contraction in the south) will continue in the future, with a
southern range shift also occurring in both climatic models. The origin of the Clarence River
Corridor (Fig. 16) dividing the two population groups was inferred by molecular analysis to
be prior to the last glacial maximum (Table 2). Another divergence in the south (19 ka) is
indicative of slow consistent habitat contractions since the last glacial maximum (LGM: 21
ka). We recommend the southern and Macleay Overlap Zone (far-eastern Australia)
populations as priority areas for protection based upon intraspecific diversity and pastcurrent-future habitat suitability. The integrated approach shows that this widely distributed
species is more at risk than expected from current climate change and other anthropogenic
effects (Mellick et al., 2013b).
Past-current-future modeling (Table 2 and Fig. 17) suggests that the two population
groups respond differently to climate change, and that both are subjected to
expansion/contractions cycles indicative of community turnover (Mellick et al., 2013a;
Kershaw et al., 2007a). This emphasizes the sensitivity of this species to climatic fluctuation
and, when considering its fragmented distribution along a broad latitudinal range, the
likelihood that this species may survive climatic cycles within dispersed refugia and
microhabitats (e.g., ecotones, ridgelines, rainforest remnants; Mellick et al., 2013b; Brodribb
and Hill, 2003).
Although the species has long generation periods, possibly of 600 years or more,
successful recruitment and establishment are reliant on abiotic factors (e.g., fire frequency
and climate) as well as biotic factors (e.g., competition and light availability). Observed
spatial displacement to boundary communities (Mellick et al., 2011, Harden et al., 2006)
away from the increased competition of core communities (Lusk, 1996) may have facilitated
the survival of populations in the past, yet may now expose P. elatus to increased
anthropogenic disturbance, such as more frequent burning and non-indigenous invasive
species (Mellick et al., 2013b).
The nature of these ecotonal communities (e.g., nutrient poor areas, fire prone, less
competition) affords Podocarpus an advantage (Brodribb and Hill, 2003; Lusk, 1996). The
micro-environmental character and the sheltered ecology of ecotonal micro-habitats may have
facilitated survival in areas of low climatic suitability (Mellick et al., 2013b). These
fragmented habitats considering the outcrossing nature of the tree are especially vulnerable to
253
the effects of isolation, genetic drift and inbreeding (Mellick et al., 2011) as shown in other
Australian rainforest conifers (Peakall et al., 2003, Shapcott, 1997). Although Podocarpus
elatus is common to the East Australian rainforests, its existence is closely allied to habitats
that are threatened by future climate change. Seeing localized extinction and population
decline has been documented in other rainforest podocarps (Shapcott, 1997) and drier
rainforest conifers (Peakall et al., 2003; Pye and Gadek, 2004), we should consider P. elatus
as potentially at future risk (Mellick et al., 2013b).
Table 2. The inferred genetic history of three Podocarpus elatus populations
representing the southern [1. southern New South Wales (Sth NSW) and 2. northern
New South Wales (Nth NSW)] and northern [3. southern Queensland (Sth QLD)] ranges
either side of the Clarence River Corridor (CRC) biogeographic barrier
DATA SET
Sth NSW 1 Nth NSW 2Sth QLD 3NSW ancestral 4All ancestral 5t1
MLE
0.1825
0.1673
0.5655
0.888
34.04
0.0475
HPD95 Low
0.0075
0.01425
0.1905
0
21.8
0.0175
HPD95 High
2.918
0.7748
1.556
12.11
54.44
0.1475
rescaled population size (: individuals) and time (t:1000 years) parameter units
MLE
938.6
837.3
2831
4443
170406
105.127
HPD95 Low
37.55
71.34
953.7
0
109132
35.042
HPD95 High
14605
3878
7787
60636
272530
295.357
t2
0.0095
0.0015
0.0435
19.023
3.004
87.105
The 95% highest posterior density intervals (HPD95 low HPD95 high) are tabulated for effective
population sizes (1- 5) and splitting times (t1; first split either side of the CRC between Sth QLD
and NSW ancestral populations: t2; second split between Sth and Nth NSW). The maximum
likelihood estimate (MLE) is the curve height (i.e., mode) of marginal posterior probability for
each parameter. The difference between the original parameter values (i.e., curve height of
marginal posterior probability) and the rescaled population size and time parameter values are that
the latter use marginal distribution values in demographic units. None of the migration parameters
converged and were left out of the table accordingly (Source: Mellick et al., 2013b)
CONCLUSION
The case studies underpinning this chapter aim to understand how the distribution of
Podocarpus elatus has responded to recent climatic change of the Quaternary and the likely
response to future climate change. Using the fossil record, molecular observation/inference
and Environmental Niche Modeling (ENM), an interdisciplinary signal has been obtained of
how past climate change has affected distribution and diversity of this rainforest conifer.
Seeing a common genetic and environmental boundary has been observed (Fig. 5), future
changes in the distribution of genetic diversity have been predicted (Fig. 16).
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Rohan Mellick
Figure 17. Environmental niche models for Podocarpus elatus north (a, b, c and d) and south (e, f, g and
h) of the Clarence River Corridor biogeographic barrier in eastern Australia for 21 ka Last Glacial
Maximum (a and e), 6 ka Holocene Climatic Optimum (b and f), 0 ka Pre-industrial (c and g), including
the location of the three populations under study, and A2 2050 future time periods (d and h). Red borders
around projected distributions do not reflect probability of occurrence (Source: Mellick et al., 2013b).
Agreement between the climatic data (i.e., ENMs: Fig. 5, 11 and 16) and regional
distribution either side of the Clarence River Corridor (CRC) suggests genetic divergence is
climate-driven, as the decline in the observed fossil record suggests (Black et al., 2006; Black
and Mooney, 2007; Kershaw et al., 2007; Shimeld, 1995, 2004; Williams et al., 2006).
Rainforest herpetofauna (Burns et al., 2007; Schauble and Moritz 2001) show genetic
divergences over the CRC that suggest the differential climatic drivers identified in P. elatus
may support broader rainforest associations.
Due to the study being based on separate independent sources of evidence, the
conclusions made are reliable and will provide a basis to interpret the environmental drivers
255
and biological processes that have led to present-day genetic diversity and structure. The
method used here to reconstruct community turnover has been tailored to the inadequacies of
the east Australia Quaternary fossil record (i.e., abundance, chronology and taxonomy).
Interdisciplinarity will improve our theoretical understanding of the response of threatened
communities to climate change as well as informing future conservation strategies.
The majority of the genetic diversity (microsatellite, nDNA and cpDNA sequence) in P.
elatus is found in the southern and central ranges. The northern distribution is impoverished
and very fragmented. The species is rare in the Australian Wet Tropics (Fig. 16). The lower
diversity and distributional pattern of the northern populations could suggest that the current
distribution is the result of an earlier northern expansion from a narrower genetic pool (case
study one).
Podocarpus have traits that originated in extreme seasonality (Brodribb and Hill, 1999,
2003; Quinn and Price, 2003; Hill, 1994) and since have served expansion into equatorial
regions (Fig. 2). The surviving podocarps are remnants of a world dramatically different from
the one they occupy today. Although past Antarctic climates were seasonally hot and wet, the
change in day length for the genus over time has been dramatic.
The current wide latitudinal range of the species is linked to the availability of rainforest
boundary communities. This has given P. elatus a continental wide range yet a narrow
microhabitat requirement. Over time population expansion and contraction cycles have been
influence by climate. Differential range shift response is shown between the northern and
southern population groups (Fig. 11 and 17) illustrative of differing climatic drivers between
the southern subtropical and northern tropical rainforests. These differing climatic conditions
may underline long-term divergent processes between the two regional groups. In the shorter
term and at a regional scale, anthropogenic habitat clearing (i.e., Big scrub Rainforest) is also
likely to contribute to the differences measured between regions and among generational
cohorts (Fig. 4).
The location and aridity of the Clarence River Corridor would have restricted dispersal
during expansion phases of each latitudinally distributed region. These successional waves of
diversity in opposing directions resulted in the populations flanking the barrier to be
genetically distinct and of high diversity, with the majority of unique allele genotypes found
close to the barrier (Fig. 12). Due to the huge climatic variation across its current range,
periods of admixture (expansion) and vicariance (contraction) between populations have been
different between southern and northern ranges. Differential range shift response shown in P.
elatus may be caused by stronger seasonality in the south. Although the species occupies such
a broad environmental envelope, the degree of gene flow between the population groups has
been sufficient to maintain the species integrity (case study two).
The future climate-induced range shift (Fig. 16 d and h) of the two genetically
differentiated regions were shown to follow a similar pattern to that observed during the
Holocene Climatic Optimum (6 ka: Fig. 11b and e, Fig. 17 b and f) when the climate was
hotter and wetter. Expansion/contraction dynamics suggest the southern diverse region is
under threat of future climate change and sea-level rises expected this century (case study
three).
Locally adapted genetic variants may be harbored by threatened populations and these
variants may offer genetic variation that may reduce the genetic load of other inbreed
populations (Mellick et al., 2011). Conservation strategies may involve the extension of
habitat corridors to accommodate future range-shift and assisted migration of genetically rich
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Rohan Mellick
stock under threat of localized extinction into areas of high habitat suitability (Mellick et al.,
2013b).
Climatic change has made naturally disjunct populations of Podocarpus elatus
genetically inbreed and divergent from one another, suggesting local genetic seed should be
used in the restoration of degraded habitats. The approach of using locally sourced seed to
revegetate areas may be appropriate for areas of relatively high diversity but where
genetically impoverished, success will depend on seed viability and, once established, on
resilience to forecasted changes and further disturbance. We need to promote admixture
between divergent population groups to reduce genetic load and reduce the adverse effects of
inbreeding. If natural selective gradients are in place then this local increase in diversity will
not hinder selective filtering and the natural processes present in the species, rather it would
aid it through survival.
It was found that P. elatus is considerably more threatened than shown by its current
distribution, and I suggest the use, and extension, of habitat corridors to accommodate future
climate-induced range shift of fragmented rainforest habitats along the east coast of Australia.
The future design of habitat corridors could take on a broader evolutionary application by
linking fragmented habitats along predicted avenues of range shift, and understanding natural
gene flow patterns will allow for genotype selection and assisted migration along these
avenues. Range shift is part of the natural adaptive process (Moritz, 2002) but during previous
climate fluctuations, range shift has been unhindered by human land-use. In order to conserve
the natural genetic constitution and adaptive potential of species in general, protected avenues
along which migration is assisted will need to be integrated into the human land-use matrix.
Our data suggest that conservation and management should be focused around the
southern populations and Macleay Overlap Zone; where most of the species diversity resides
and where sustained habitat suitability in response to post-glacial warming and future
scenarios occurs (Fig. 17 d and h). The southern populations (Fig. 17h) are under threat of
localized extinction, and therefore should be a target of conservation strategies. The general
decline of rainforest conifers from the fossil record is a consequence of a changing
environment and has occurred since the previous interglacial (130 ka: Kershaw, 2005; et al.,
2007a; Shimeld, 1995, 2004).
Predictive distributional modeling and the understanding of gene flow dynamics provide
a method to interpret current distribution patterns and potentially anticipate, and
accommodate, rapid migration rates as a result of projected anthropogenic-induced climate
change.
Species worldwide are a result of natural evolution that has afforded them a genetic
constitution and an ability to survive natural climatic cycles and environmental extremes. The
consequences of our interference (artificial selection through anthropogenic effects) may be a
reduction in the adaptive potential and natural genetic constitution to deal with natural
climatic cycles and environmental pressures.
Complex evolutionary processes occur in the World Heritage listed central east
Australian Rainforests, the majority of which are surrounded by a human land use matrix with
little means of altitudinal or latitudinal range shifts in response to anthropogenic-induced
climate change. Understanding the manner of intraspecific divergence and adaptation along
latitudinal temperature/precipitation gradients within these confined rainforests is integral to
their conservation.
257
ACKNOWLEDGMENTS
Thank you to Tim Brodribb, Robert S. Hill, Andrew Lowe, Ed Biffin, Chris Allen, Peter
D. Wilson and Maurizio Rossetto. I acknowledge the University of Adelaide, Faculty of
Science, for funding the research (Divisional Scholarship). This research was also funded by
the Australian Research Council Discovery Grant (DP0665859). Thank you to the National
Herbarium of NSW, The Royal Botanic Gardens and Domain Trust, Sydney. I particularly
thank Andrew Ford (CSIRO, Atherton), Rebecca Johnson, Bob Coveny, David Bateman,
Phillip Greenwood, NSW National Parks and Wildlife and Robert Kooyman for their
assistance in undertaking collections and observations; Simon Ho (The University of Sydney)
and Paul Rymer (The University of Western Sydney) for their support with regard to multilocus coalescence-based analysis; Peter Kershaw, Peter Shimeld, Sandy Harrison, Scott
Mooney and Nicole Williams for providing palynological data.
REFERENCES
Ahmed AK, Johnson KA (2000) TURNER REVIEW No. 3. Horticultural development of
Australian native edible plants. Australian Journal of Botany 48, 417-426.
Almany GR, De Arruda MP, Arthofer W (2009). Permanent Genetic Resources added to
Molecular Ecology Resources Database 1 May 2009-31 July 2009. Molecular Ecology
Resources 9, 1460-1466.
Araujo MB, New M (2007). Ensemble forecasting of species distributions. Trends in Ecology
and Evolution 22(1): 42-47.
Avise JC (2000). 'Phylogeography: the history and formation of species.' (Harvard University
Press)
Avise JC, Arnold J, Ball RM Jr., Bermingham E, Lamb T, Neigel JE, Reed CA, Saunders NC
(1987). Intraspecific phylogeography: the mitochondrial DNA bridge between population
genetics and systematics. Annual Review of Ecology and Systematics 18, 489522.
Bakkenes M, Alkemade JRM, Ihle F, Leemans R, Latour JB (2002). Assessing effects of
forecasted climate change on the diversity and distribution of European higher plants for
2050. Global Change Biology 8, 390-407.
Barker NP, Muller EM, Mill RR (2004). A yellowwood by any other name: molecular
systematics and the taxonomy of Podocarpus and the Podocarpaceae in southern Africa.
South African Journal of Science 100, 629-632.
Barker PF, Thomas E (2004). Origin, signature and palaeoclimatic influence of the Antarctic
Circumpolar Current. Earth-Science Reviews 66, 143-162.
Bartholomai A, Molnar RE (1981). Muttaburrasaurus, a new iguanodontid (Ornithischia:
Ornithopoda) dinosaur from the Lower Cretaceous of Queensland. Memoirs of the
Queensland Museum 20, 319-349.
Beaumont LJ, Hughes L (2002). Potential changes in the distributions of latitudinally
restricted Australian butterfly species in response to climate change. Global Change
Biology 8, 954-971.
Beaumont LJ, Hughes L, Pitman AJ (2008). Why is the choice of future climate scenarios for
species distribution modeling important? Ecology Letters 11, 1135-1146.
258
Rohan Mellick
Bell KL, Moritz, C., Moussalli, A. and Yeates, D.K. (2007). Comparative phylogeography
and speciation of dung beetles from the Australian Wet Tropics rainforest. Molecular
Ecology 16, 4984 -4998.
Bennett KD (1997). 'Evolution and Ecology: The pace of life.' (Cambridge University Press:
Cambridge, U.K.)
Biffin E, Brodribb TJ, Hill RS, Thomas P, Lowe AJ (2012). Leaf evolution in Southern
Hemisphere conifers tracks the angiosperm ecological radiation. Proceedings of the
Royal Society B: Biological Sciences.
Biffin E, Conran J, Lowe A (2011). Podocarp Evolution: A Molecular Phylogenetic
Perspective. In Ecology of the Podocarpaceae in Tropical Forests. (Eds BL Turner and
LA Cernusak) pp. 120. Smithsonian Contributions to Botany, No. 95. (Smithsonian
Institution Scholarly Press: Washington D.C.)
Black MP, Mooney SD (2007). The response of aboriginal burning practices to population
levels and El Nino-Southern oscillation events during the mid- to late-Holocene: a case
study from the Sydney basin using charcoal and pollen analysis. Austral. Geo. 38, 37-52
Black, M.P., Mooney, S.D., Martin, H.A. 2006. A >43,000-year vegetation and fire history
from Lake Baraba, New South Wales, Australia. Quaternary Science Review 25, 30033016.
Blouin MS, Parsons M, Lacaille V, Lotz S (1996). Use of microsatellite loci to classify
individuals by relatedness. Molecular Ecology 5, 393-401.
Bond WJ (1989). The tortoise and the hare - ecology of angiosperm dominance and
gymnosperm persistence. Biological Journal of the Linnean Society 36, 227-249.
Bowler JM, (1982). Aridity in the late tertiary and quaternary of Australia. In: Evolution of
the flora and fauna of arid Australia. Barker WR and Greenslade PJM (eds) (Peacock
Publications, South Australia).
Bowman D (2000) 'Australian Rainforests: Islands of Green in the Land of Fire.' Cambridge
University Press, Cambridge.
Bresson, CC, Vitasse Y, Kremer A, Delzon S (2011). To what extent is altitudinal variation
of functional traits driven by genetic adaptation in European oak and beech? Tree
Physiology 31, 1164-1174.
Brewer S, Cheddadi R, de Beaulieu JL, Reille M (2002). The spread of deciduous Quercus
throughout Europe since the last glacial period. Forest ecology and management 156, 2748.
Brodribb T, Hill RS (1999). The importance of xylem constraints in the distribution of conifer
species. New Phytologist 143, 365-372.
Brodribb TJ, Hill RS (2003). The rise and fall of the Podocarpaceae in Australia: a
physiological explanation. In 'Evolution of plant physiology'. (Eds A Hemsley and I
Poole) pp. 381-399. (Academic: London)
Burns EL, Eldridge MDB, Crayn DM, Houlden BA (2007). Low phylogeographic structure
in a wide spread endangered Australian frog Litoria aurea (Anura : Hylidae).
Conservation Genetics 8, 17-32.
Byrne M (2007). Phylogeography provides an evolutionary context for the conservation of a
diverse and ancient flora. Australian Journal of Botany 55, 316-325.
Byrne M, Steane DA, Joseph L, Yeates DK, Jordan GJ, Crayn D, Aplin K, Cantrill DJ, Cook
LG, Crisp MD, Scott Keogh J, Melville J, Moritz C, Porch N, Sniderman K, Sunnacks P,
259
Weston PH (2011) Decline of a biome: evolution, contraction, fragmentation, extinction

and invasion of the Australian mesic zone biota. Journal of Biogeography 38, 1635-1656.
Cannings C (1974). The Latent Roots of Certain Markov Chains Arising in Genetics: A New
Approach, I. Haploid Models. Advances in Applied Probability 6, 260-290.
Chambers TC, Drinnan AN, McLoughlin S (1998). Some morphological features of Wollemi
Pine (Wollemia nobilis: Araucariaceae) and their comparison to cretaceous plant fossils.
International Journal of Plant Sciences 159, 160-171.
Chaw SM, Zharkikh A, Sung HM, Lau TC, Li WH (1997). Molecular phylogeny of extant
Gymnosprems and seed plant evolution: analyisi of nuclear 18s rRNA sequences.
Molecular Biology and Evolution 14, 56-68.
Conran JG, Wood GM, Martin PG, Dowd JM, Quinn CJ, Gadek PA, Price RA (2000).
Generic relationships within and between the gymnosperm families Podocarpaceae and
Phyllocladaceae based on an analysis of the chloroplast gene rbcL. Australian Journal of
Botany 48, 715-724.
Couper RA (1960). Southern Hemisphere Mesozoic and Tertiary Podocarpaceae and
Fagaceae and their palaeogeographic significance. Proceedings of the Royal Society of
London. Series B, Biological Sciences 152, 491-500.
Crandall KA, Templeton AR (1993). Empirical tests of some predictions from the Coalescent
Theory with applications to intraspecific Phylogeny reconstruction. Genetics 134, 959969.
Cruzan MB, Templeton AR (2000). Paleoecology and coalescence: phylogeographic analysis
of hypotheses from the fossil record. Trends in Ecology and Evolution 15, 491-496.
Cunningham S (2004). Climatic impacts on biodiversity: how useful are current predictions.
CSIRO entomology presentation.
Demesure B, Sodzi N, Petit RJ (1995). A set of universal primers for amplification of
polymorphic noncoding regions of mitochondrial and chloroplast DNA in plants
Molecular Ecology 4, 129-131.
Dettmann ME, Jarzen DM (1990). The Antarctic/Australian rift valley: Late cretaceous cradle
of nortteastern Australasian relicts? Review of Palaeobotany and Palynology 65: 131144.
Donnelly P, Tavar S (1995). Coalescents and genealogical structure under neutrality. Annual
Review of Genetics 29, 401-421.
Doyle J (1945). Development lines in pollination mechanisms in the Coniferales. Scientific
proceedings of the Royal Dublin Society 24, 43-62.
Drinnan AN, Chambers TC (1986). Flora of the Lower Cretaceous Koonwarra Fossil Bed
(korumburra Group) south Gippsland. T. C. Mem. Ass. Australas. Palaeontols 3, 177.
Dunlop M, Brown PR (2008). ' Implications of climate change for Australia's National
Reserve System: a preliminary assessment. Technical Report.' Department of Climate
Change, Canberra.
Elith J, Graham CH, et al. (2006) Novel methods improve prediction of species' distributions
from occurrence data. Ecography 29, 129-151.
Elith J, Leathwick JR (2009). Species Distribution Models: ecological explanation and
prediction across space and time. In 'Annual Review of Ecology Evolution and
Systematics' pp. 677-697. (Annual Reviews: Palo Alto)
Elsik CG, Williams CG (2001). Low-copy microsatellite recovery from a conifer genome.
TAG Theoretical and Applied Genetics 103, 1189-1195.
260
Rohan Mellick
Emigh TH (1980). A comparison of tests for Hardy-Weinberg Equilibrium. Biometrics 36,

627-642.
Enright NJ, Hill RS (1995). 'Ecology of the southern conifers.' (Melbourne University Press.:
Melbourne)
Enright NJ, Jaffr T (2011). Ecology and Distribution of the Malesian Podocarps. In Ecology
of the Podocarpaceae in Tropical Forests. (Eds BL Turner and LA
Cernusak) pp. 5777. Smithsonian Contributions to Botany, No. 95. (Smithsonian Institution
Scholarly Press: Washington D.C.)
Enright NJ, Ogden J (1995). The southern conifers- a synthesis. In 'Ecology of the southern
conifers'. (Eds NJ Enright and RS Hill) pp. 271-287. (Melbourne University Press:
Melbourne )
Estoup A, Jarne P, Cornuet JM (2002). Homoplasy and mutation model at microsatellite loci
and their consequences for population genetics analysis. Molecular Ecology 11, 15911604.
Ewens W (1990). Population genetics theory - the past and the future. In 'Mathematical and
Statistical developments of Evolutionary Theory'. (Ed. S Lessard) pp. 177-227. (Kluwer
Academic Publishers: New York)
Falconer DS, Mackay TFC (1996). 'Introduction to quantitative genetics.' (Addison Wesley
Longman Limitied: Harlow)
Fisher RA (1930). 'The genetical theory of natural selection.' (Clarendon Press: Oxford)
Greenwood DR. Christophel DC (2005). The origins and tertiary history of Australian
Tropical Rainforests. Tropical Rainforests: past, present and future. D. a. M.
Bermingham.
Haberle SG (2005). A 23,000-yr pollen record from Lake Euramoo, Wet Tropics of NE
Queensland, Australia. Quaternary Research 64, 343-356.
Harden GJ (1990). 'Flora of New South Wales.' (University of NSW press: Sydney)
Hartl DL, Clark AG (1997). 'Principals of Population Genetics (3rd ed).' (Sinauer Associates,
Inc: MA)
Heikkinen RK, Luoto M, Araujo MB, Virkkala R, Thuiller W, Sykes MT (2006). Methods
and uncertainties in bioclimatic envelope modeling under climate change. Progress in
Physical Geography 30, 751-777.
Hewitt G (2000). The genetic legacy of the Quaternary ice ages. Nature 405, 907-913.
Hey J, Won YJ, Sivasundar A, Nielsen R, Markert JA (2004). Using nuclear haplotypes with
microsatellites to study gene flow between recently separated Cichlid species. Molecular
Ecology 13, 909-919.
Hilbert D, Graham A, Hopkins M (2007). Glacial and interglacial refugia within a long-term
rainforest refugium: The wet tropics bioregion of NE Queensland, Australia.
Palaeogeography Palaeoclimatology Palaeoecology 251(1): 104-118.
Hill RS (1994). The history of selected Australian taxa. In 'History of the Australian
Vegetation: Cretaceous to Recent '. (Ed. RS Hill) pp. 390-419. (Cambridge University
Press: Cambridge)
Hill RS (2004). Origins of the southeastern Australian vegetation. Philosophical Transactions
of the Royal Society of London Series B-Biological Sciences 359, 1537-1549.
Hill RS, Brodribb TJ (1999). Turner Review No. 2 - Southern conifers in time and space.
Australian Journal of Botany 47, 639-696.
261
Hill RS, Pole MS (1992). Leaf and shoot morphology of extant Afrocarpus, Nageia and
Retrophyllum (Podocarpaceae) species, and species with similar leaf arrangement, from
tertiary sediments in Australia. Australian Systematic Botany 5, 337-358.
Hope GS, Kershaw P, Kenyon C, McKenzie M, Williams N (2010). Late Quaternary fire
regimes of Australasia. Quaternary Science Reviews 30, 28-46.
Hope GS (1994). Quaternary vegetation. In 'History of the Australian Vegetation: Cretaceous
to Recent'. (Ed. RS Hill). (Cambridge University Press: Cambridge)
Jordan GJ, Carpenter RJ, Bannister JM, Lee DE, Mildenhall DC, Hill RS (2011). High
conifer diversity in Oligo-Miocene New Zealand. Australian Systematic Botany 24, 121136.
Kelch DG (1997). The phylogeny of the podocarpaceae based on morphological evidence.
Systematic Botany 22, 113-131.
Kershaw AP, van der Kaars S, Flenley JF (2007b). The Quaternary history of far eastern
rainforests. In 'Tropical Rainforest Responses to Climate Change'. (Eds MB Bush and JF
Flenley) pp. 77-115. (Springer-Praxis: Berlin)
Kershaw AP, Bretherton SC, van der Kaars S (2007a). A complete pollen record of the last
230 Ka from Lynch's Crater, north-eastern Australia. Palaeogeography
Palaeoclimatology Palaeoecology 251, 23-45.
Kershaw AP, Moss PT, Wild R (2005). Patterns and Causes of Vegetation Change in the
Australian Wet Tropics Region over the last 10 Million Years. In 'Tropical Rainforests:
past, present and future'. (Ed. DaM Bermingham))
Kershaw AP, Martin HA, McEwen Mason JRC (1994). The Neogene: a period of transition.
In 'History of the Australian Vegetation: Cretaceous to Recent'. (Ed. RS Hill) pp. 299328. Cambridge University Press, Cambridge.
Kimura M (1968). Evolutionary Rate at the Molecular Level. Nature 217, 624-626.
Kingman JFC (2000). Origins of the Coalescent: 19741982. Genetics 156, 1461-1463.
Knowles LL, Maddison WP (2002). Statistical phylogeography. Molecular Ecology 11(12):
2623-2635.
Ledru MP, Salatino MLF, Ceccantini G, Salatino A, Pinheiro F, Pintaud JC (2007). Regional
assessment of the impact of climatic change on the distribution of a tropical conifer in the
lowlands of South America. Diversity and Distributions 13, 761-771.
Lowe A, Harris S, Ashton P (2004). Ecological genetics: design, analysis and application.
(Blackwell Science Ltd.)
Lusk CH (1996). Stand dynamics of the shade-tolerant conifers Podocarpus nubigena and
Saxegothaea conspicua in Chilean temperate rainforest. Journal of Vegetation Science 7,
549-558.
Macdonald T (2004). Fire biodiversity in the Australian Alps Workshop proceedings, Albury
NSW.
Martin HA (2006). Cenozoic climatic change and the development of the arid vegetation in
Australia. Journal of Arid Environments 66, 533-563.
Martin HA (1982). Changing Cenozoic Barriers and the Australian Paleobotanical Record.
Annals of the Missouri Botanical Garden 69, 625-667.
McLachlan JS, Clark JS, Manos PS (2005). Molecular Indicators of Tree Migration Capacity
under Rapid Climate Change. Ecology 86(8): 2088-2098.
McLoughlin S (2001). The breakup history of Gondwana and its impact on pre-Cenozoic
floristic provincialism. Australian Journal of Botany 49, 271-300.
262
Rohan Mellick
Mellick R, Rossetto M, Allen C, Wilson PD, Hill RS, Lowe A (2013b) Intraspecific
divergence associated with a biogeographic barrier and climatic models show future
threats and long-term decline of a rainforest conifer. The Open Conservation Biology
Journal 7, 1-10.
Mellick R, Wilson PD, Rossetto M (2013a). Post-glacial spatial dynamics in a rainforest
biodiversity hot spot. Diversity 5: 124-138.
Mellick R, Lowe A, Allen CD, Hill RS, Rossetto M (2012). Palaeodistribution modeling and
genetic evidence highlight differential post-glacial range shifts of a rainforest conifer
distributed across a latitudinal gradient. Journal of Biogeography 39(12): 2292-2302.
Mellick R, Lowe A, Rossetto M (2011) Consequences of long- and short-term fragmentation
on the genetic diversity and differentiation of a late successional rainforest conifer.
Australian Journal of Botany 59, 351-362.
Mill RR (2003). Towards a biogeography of Podocarpaceae. In 'Acta Hort. (ISHS)' pp.
615:137-147.
Molnar RE (1996). Observations on the Australian ornithopod dinosaur Muttaburrasaurus.
Memoirs of the Queensland Museum 39, 639-652.
Mooney SD, Harrison SP, Bartlein PJ, Daniau AL, Stevenson J, Brownlie KC, Buckman S,
Cupper M, Luly J, Black M, Colhoun E, Costa D, Dodson J, Haberle S, Hope GS,
Kershaw P, Kenyon C, McKenzie M, Williams N (2010). Late Quaternary fire regimes of
Australasia. Quaternary Science Reviews 30, 28-46.
Moritz C (2002). Strategies to protect biological diversity and the evolutionary processes that
sustain it. Syst Biol 51: 238-54.
Moss PT, Kershaw AP, Grindrod J (2005). Pollen transport and deposition in riverine and
marine environments within the humid tropics of northeastern Australia. Review of
Palaeobotany and Palynology 134, 55-69.
Nix HA (1991). Biogeography: Patterns and process. In ' Rainforest animals. Atlas of
vertebrates endemic to Australias Wet Tropics'. (Eds HA Nix and M Switzer) pp. 11-39.
(ANPWS: Canberra, Australia.)
Owens JN, Morris SJ (1990). Cytological Basis for Cytoplasmic Inheritance in Pseudotsuga
menziesii. I. Pollen Tube and Archegonial Development. American Journal of Botany 77,
433-445.
Page RDM, Holmes EC (1998). 'Molecular evolution: A phylogentic approach.' (Blackwell
Science: Cambridge)
Peakall, R, Ebert, D, Scott, L.J, Meagher, P.F, Offord, C.A. (2003). Comparative genetic
study confirms exceptionally low genetic variation in the ancient and endangered
relictual conifer, Wollemia nobilis (Araucariaceae). Molecular Ecology 12, 23-31.
Pease KM, Freedman AH, Pollinger JP, McCormack JE, Buermann W, Rodzen J, Banks J,
Meredith E, Bleich VC, Schaefer RJ, Jones K, Wayne RK (2009). Landscape genetics of
California mule deer (Odocoileus hemionus): the roles of ecological and historical factors
in generating differentiation. Molecular Ecology 18, 1848-1862.
Prez T, Albornoz J, Dominguez A (2002). Phylogeography of chamois (Rupicapra spp.)
inferred from microsatellites. Molecular Phylogenetics and Evolution 25, 524-534.
Petit JR, Jouzel J, et al. (1999). Climate and atmospheric history of the past 420,000 years
from the Vostok ice core, Antarctica. Nature 399, 429-436.
263
Petit RJ (2002). Chloroplast DNA variation in European white oaks Phylogeography and
patterns of diversity based on data form over 2600 populations. Forest Ecology and
Management 156, 5-26.
Petit RJ, Brewer S, et al. (2002). Identification of refugia and post-glacial colonisation routes
of European white oaks based on chloroplast DNA and fossil pollen evidence. Forest
Ecology and Management 156, 49-74.
Petit RJ, Csaikl UM, et al. (2003). Chloroplast DNA variation in European white oaks
phylogeography and patterns of diversity based on data from over 2600 populations (vol
156, pg 5, 2002). Forest Ecology and Management 176, 595-599.
Pocknall DT (1981). Pollen morphology of the New Zealand species of Dacrydium Solander,
Podocarpus L'Heritier, and Dacrycarpus Endlicher (Podocarpaceae). New Zealand
Journal of Botany 19: 67.
Pollock DD, Goldstein DB (1995). A comparison of two methods for constructing
evolutionary distances from a weighted contribution of transition and transversion
differences. Molecular Biology and Evolution 12, 713-717.
Powell W, Morgante M, Andre C, McNicol JW, Machray GC, Doyle JJ, Tingey SV, Rafalski
JA (1995). Hypervariable microsateliites provide a general source of polymorphic DNA
markers for the chloroplast genome Current Biology 5, 1023-1029.
Proctor M, Yeo P, Lack A (1996). 'The natural history of pollination'. Timber Press, Portland.
Pye MG, Gadek PA (2004). Genetic diversity, differentiation and conservation in Araucaria
bidwillii (Araucariaceae), Australia's Bunya pine. Conservation Genetics 5, 619-629.
Queller DC, Strassmann JE, Hughes CR (1993). Microsatellites and kinship. Trends in
Ecology and Evolution 8, 285-288.
Quilty PG (1994). The background: 144 million years of Australian palaeoclimate and
palaeogeography. In ' History of Australian Vegetation: cretaceous to recent'. (Ed. RS
Hill))
Quinn CJ, Price RA (2003) Phylogeny of the Southern Hemisphere Conifers. In Proc. Fourth
International Conifer Conference 129-136.
Quiroga MP, Premoli AC (2007). Genetic patterns in Podocarpus parlatorei reveal the longterm persistence of cold-tolerant elements in the southern Yungas. Journal of
Biogeography 34, 447-455.
Quiroga MP, Premoli AC (2010). Genetic structure of Podocarpus nubigena (Podocarpaceae)
provides evidence of Quaternary and ancient historical events. Palaeogeography,
Palaeoclimatology, Palaeoecology 285, 186-193.
Rahmstorf S (2007). A semi-empirical approach to projecting future sea-level rise. Science
315, 368-370.
Richards CL, Carstens, BC, Knowles, LL (2007). Distribution modeling and statistical
phylogeography: an integrative frame work for generating and testing alternative
biogeographical hypotheses. Journal of Biogeography 34, 1833-1845.
Rissler L, Hijmans, R.J., Graham, C.H., Moritz, C., Wake, D.B. (2006). Phylogeographic
lineages and species comparisons in conservation analyses: A case study of California
herpetofauna. The American Naturalist 167 (5), p. 655.
Rossetto M, Crayn D, Ford A, Mellick R, Sommerville K (2009). The influence of
environment and life-history traits on the distribution of genes and individuals: a
comparative study of 11 rainforest trees. Molecular Ecology 18, 14221438.
264
Rohan Mellick
Rossetto M, Kooyman R, Sherwin W, Jones R (2008). Dispersal limitations, rather than

bottlenecks or habitat specificity, can restrict the distribution of rare and endemic
rainforest trees. American Journal of Botany 95, 321-329.
Rossetto M, Jones RS, McNally J (2002). Isolation of microsatellite loci from a rainforest
tree, Elaeocarpus grandis (Elaeocarpaceae), and amplification across closely related taxa.
Molecular Ecology Notes 2(2): 179-181.
Rule S, Brook BW, Haberle SG, Turney CSM, Kershaw AP, Johnson CN (2012) The
Aftermath of Megafaunal Extinction: Ecosystem Transformation in Pleistocene Australia.
Science 335, 1483-1486.
Schauble CS, Moritz C (2001) Comparative phylogeography of two open forest frogs from
eastern Australia. Biological Journal of the Linnean Society 74, 157-170.
Scoble J, Lowe AJ (2010). A case for incorporating phylogeography and landscape genetics
into species distribution modeling approaches to improve climate adaptation and
conservation planning. Diversity and Distributions 16, 343-353.
Scott LJ, Shepherd M, Henry RJ (2003). Characterization of highly conserved microsatellite
loci in Araucaria cunninghamii and related species. Plant Systematics and Evolution 236,
115-123.
Scott LJ, Cross M, Shepherd M, Maguire T, Henry RJ (1999). Increasing the efficiency of
microsatellite discovery from poorly enriched libraries in coniferous forest species. Plant
Molecular Biology Reporter 17, 351-354.
Sexton JP, McIntyre PJ, Angert AL, Rice KJ (2009). Evolution and Ecology of Species
Range Limits. In 'Annual Review of Ecology Evolution and Systematics' pp. 415-436.
(Annual Reviews: Palo Alto)
Shapcott A (1997) Population genetics of the long-lived Huon pine Lagarostrobos franklinii:
An endemic Tasmanian temperate rainforest tree. Biological Conservation 80, 169-179.
Shepherd M, Mellick R, Toon P, Dale G, Dieters M (2005). Genetic control of adventitious
rooting on stem cuttings in two Pinus elliottii x Pinus caribaea hybrid families. Annals of
Forest Science 62, 403-412
Shimeld P (2004). The Last Interglacial at Port Stephens, New South Wales. In 'Australasian
Quaternary Association Biennial Conference'. Cradle Mountain Tasmania. (Eds S
Haberle and J Stevenson). (AQUA 2004 Program and Abstracts)
Shimeld P (1995) A late Quaternary vegetation and climate history of Port Stephens and the
lower Hunter Valley, N.S.W. Thesis, University of Tasmania, Hobart.
Silba J (1984). An international census of Coniferae. Phytologia memoir 7, 1-79.
Sniderman JMK, Jordan GJ (2011). Extent and timing of floristic exchange between
Australian and Asian rainforests. Journal of Biogeography 38, 1445-1455.
Solomon S, Qin D, Manning M, Marquis M, Averyt K, Tignor MMB, Miller Jr HL, Chen Z
(2007). Climate change 2007: The physical science basis. Cambridge University Press,
Cambridge, U.K.
Sporne KR (1965). 'The morphology of gymnosperms. ' (Hutchinson and Co. Ltd.: London)
Stockey RA (1990). Antarctic and Gondwana conifers. In 'Antarctic Paleobiology: Its Role in
the Recontruction of Gondwana' (Ed. T Taylor). 179-191. (Springer-Verlag: New York).
Storfer A, Murphy MA, Evans JS, Goldberg CS, Robinson S, Spear SF, Dezzani R, Delmelle
E, Vierling L, Waits LP (2007) Putting landscape in landscape genetics. Heredity 98,
128142
265
Townrow JA (1967b). On Rissikia and Mataia podocarpaceous conifers from the Lower
Mesozoic of southern lands. Pap. Proc. Roy. Soc. Tasmania 101, 103-36.
Townrow JA (1967a). The Brachyphyllum crassum complex of fossil conifers. Pap. Proc.
roy. Soc. Tasmania 101, 149-72.
Turnpenny P, Ellard S (2005). 'Emery's Elements of Medical Genetics.' (Elsevier: London)
Van Royen P (1979). 'The alpine flora of New Guinea ' (J. Kramer: Berlin)
VanDerWal J, Shoo LP, Williams SE (2009). New approaches to understanding late
Quaternary climate fluctuations and refugial dynamics in Australian wet tropical
rainforests. Journal of Biogeography 36, 291-301.
Wagstaff SJ (2004). Evolution and biogeography of the austral genus Phyllocladus
(Podocarpaceae). Journal of Biogeography 31, 1569-1577.
Williams NJ, Harle KJ, Gale SJ, Heijnis H (2006) The vegetation history of the last glacialinterglacial cycle in eastern New South Wales, Australia. Journal of Quaternary Science
21, 735-750.
Wilson VR, Owens JN (2003). Cytoplasmic inheritance in Podocarpus totara
(Podocarpaceae). Proceedings of the Fourth International Conifer Conference - Conifers
for the Future? R. R. Mill: 171-172.
Wilson VR, Owens JN (2003). Cytoplasmic inheritance in Podocarpus totara
(Podocarpaceae). Acta Hort. (ISHS).
Wilson VR, Owens JN (1999). The reproductive biology of totara (Podocarpus totara)
(Podocarpaceae). Annals of Botany 83(4): 401-411.
Wodehouse R (1935). 'Pollen Grains. Their Structure, Identification and Significance in
Science and Medicine.' (McGraw-Hill: New York)
Woods KD, Davis MB (1989). Paleoecology of range limits-Beech in the Upper Peninsula of
Michigan Ecology 70, 681-696.
Wright Jr HE (1984). Sensitivity and response time of natural systems to climate change in
the Late Quaternary. Quat. Sei. Rev. 3, 91-131.
Wright S (1931). Evolution in Mendelian populations. Genetics 16, 97-159.
Wright S (1921). Systems of mating. Genetics 6, 111-178

ISBN: 978-1-63117-329-5
Chapter 8
A NOVEL THERMAL SEAWATER DESALINATION

PROCESS BASED ON SELF-HEAT RECUPERATION
Institute of Industrial Science, Collaborative Research Center for Energy Engineering,
The University of Tokyo, Komaba, Meguro-ku, Tokyo, Japan
ABSTRACT
Thermal desalination processes, which separate pure water from seawater by
evaporation, have been used throughout the world. Thermal desalination typically
comprises either multi-stage flash or multi-effect desalination processes. These processes
have the following characteristics: the product water salinity is low enough for industrial
use and seawater quality does not seriously affect the operating conditions. However,
heat is not recovered perfectly by either process and is partly discarded to cooling water.
Therefore, energy consumption in conventional thermal processes is large.
A novel thermal desalination process based on self-heat recuperation, which is a
technology designed to save energy, has been proposed recently. In this process, all of the
heat is recirculated and energy is required only for producing a temperature difference in
the heat exchangers. As a result, the energy consumption can be dramatically reduced. At
the same time, it has been reported that the specific energy consumption, defined as the
total energy added divided by the product water flow rate, may be further decreased by
increasing the recovery ratio (the product water flow rate / the feed water flow rate).
In this chapter, we describe a novel desalination process based on self-heat
recuperation technology and explain its potential for saving energy compared with its
conventional counterparts. In addition, we summarize recent development of the process.
Keywords: Desalination, self-heat recuperation, energy saving, fluidized bed
Corresponding Author address: Email: a-tsu2mi@iis.u-tokyo.ac.jp.
268
INTRODUCTION
Water shortages are becoming more serious globally. In fact, more than 1/10 of the global
population cannot access potable water (UN, 2012). Furthermore, because of the high growth
rates of both population and industrial development, it is predicted that increasing numbers of
people will face water shortage problems (Cotruvo et al., 2010). To solve this problem,
increased attention has been paid recently to desalination processes.
To date, many desalination processes have been investigated (Park et al., 2011;
Charcosset, 2009; Younos et al., 2005). Amongst these, membrane desalination and thermal
desalination processes have generally been used (Voutchkov et al., 2010). Reverse Osmosis
(RO) desalination is a membrane process that separates pure water from seawater using a
semi-permeable membrane. RO is the most widely used desalination process, accounting for
51% of global desalination capacity, simply because the energy consumption of this process
is relatively low (Lattemann, 2010). In fact, the reported energy required by RO is between
9.0 and 25.2 kJ/ kg-water (Lattemann, 2010). However, the product water salinity is high
(Fritzmann et al., 2007). Hence, to use the product as industrial water, multiple RO stages are
required (Greenlee et al., 2009). Moreover, when the feed water contains high solids content,
undesirable fouling can occur, which restricts the permeation rate through the membrane.
Thus, the RO process requires a higher degree of pretreatment than the thermal desalination
process, which separates potable water from seawater by evaporation. Thermal desalination
can be classified into two processes: multistage flash distillation (MSF) and multiple effect
distillation (MED) (El-Dessouky et al., 1998; Al-Shammiri et al., 1999). The major difference
between these is the evaporation method. In the MSF process, seawater is vaporized by flash
evaporation, whereas in the MED process, seawater evaporation is achieved by heat transfer
through a heat exchanger. Thus, in the MSF process, it is generally accepted that scale
deposition, which leads to a decrease in heat transfer rates in the heat exchanger, is less likely
to occur. Thus, MSF is used more widely than the MED process. In fact MSF comprises 32%
of the reported global desalination capacity, while MED comprises only 8% (Lattemann,
2010).
Advantages of thermal process are as follows: 1) seawater quality does not seriously
affect the operating conditions. Hence, they do not require physical pretreatment, such as
filters or screens, other than what is provided by the intake. 2) Product water salinity is low
because vapor contains little solids (Voutchkov et al., 2010). However, thermal processes
consume considerably more energy than RO process. The reported energy consumption of
MSF is between 250 and 330 kJ/kg-water and that of MED is between 145 and 390 kJ/kgwater (Lattemann, 2010). Thus, energy saving technologies for thermal desalination processes
are required. Recently, Kansha et al. proposed self-heat recuperation technology to save
energy (Kansha et al., 2009). They reported that the energy requirements of industrial thermal
processes could be considerably reduced, by 1/3 1/22, using such technology (Aziz et al.,
2011; Kansha et al., 2010; Kishimoto et al., 2012; Matsuda et al., 2011; Matsuda et al., 2010).
Figure 1 shows a flow diagram and temperature-heat diagram of a vapor/liquid stream
thermal process, with heat recovery achieved using a feed-effluent heat exchanger as a
conventional thermal process (self-heat exchange process). The feed stream passes through
the heat exchanger (12), in which the heat of the effluent is recuperated. The stream is then
heated and flows into a reactor (23). The effluent stream from the reactor can be used to
269
preheat the feed stream (45). However, a finite temperature difference is needed to transfer
heat from one medium to another. Thus, most of the latent heat during phase transition cannot
be recovered. Hence, the heat exchange load, QHX, is small. The effluent stream is then
cooled using cooling water (56). Figure 2 shows a flow diagram and temperature-heat
diagram of the thermal process based on self-heat recuperation. The feed stream passes
through a heat exchanger (12) and flows into the reactor (23). The effluent stream from
the reactor is then compressed adiabatically (34) to provide the temperature difference in
the heat exchanger. Because the boiling temperature of the effluent stream is raised by
compression, all of the heat is circulated (45). Therefore, the energy requirement is
dramatically reduced. The effluent stream is depressurized by a valve (56) and then cooled
by cooling water (67).
Figure 1. Configuration of a conventional thermal process.
Figure 2. Configuration of a thermal process based on self-heat recuperation.
270
Recently, Mizuno et al. proposed a novel thermal desalination process based on self-heat
recuperation (Mizuno et al., in press). They reported that the energy consumption of their
proposed process could be reduced to approximately 1/4 that of a corresponding conventional
thermal process. Furthermore, they found that the energy required for the proposed thermal
desalination process is comparable with that of RO desalination.
In this chapter, we describe a thermal desalination process based on self-heat
recuperation technology and explain the reason for its low energy consumption compared
with the conventional thermal process (MSF process) using the law of conservation of energy.
Furthermore, parameters that influence the energy consumption of this process are examined
and differing features between the process and RO are summarized. Finally, the latest
research on thermal desalination using self-heat recuperation technology is introduced.
PROCESS DESCRIPTION OF SELF-HEAT

RECUPERATIVE THERMAL DESALINATION
Figure 3 shows the configuration of the conventional thermal process (MSF process). The
feed stream flows into a heat exchanger in each stage and it is preheated. Then, the stream is
heated by an additional heater. The heated feed stream flows into a flash column, with
depressurization to lower-than-saturated vapor pressure. Then, flash evaporation occurs. The
vapor is cooled by the heat exchanger and becomes product. The brine flows into the next
flash column whose operating pressure is slightly lower than the previous one, and flash
evaporation occurs again. By repeating flash evaporation, product water is separated from
seawater. The energy consumption of this process was calculated by the commercial process
simulator Pro/II Ver. 9.0 (Invensys). The reported energy was 325 kJ/kg-water (Mizuno et
al., in press).
Figure 4 shows the thermal desalination process based on self-heat recuperation. This
process comprises three heat exchangers (HX), one separator (S), one compressor (CM), one
valve (V) and two coolers (CL). The seawater is divided into two streams (12, 3) and flows
into the first two heat exchangers (22, 33), where the heat from the product and brine
streams is recovered. The stream then passes through heat exchanger 3 (2, 34) and
receives latent heat. The generated vapor and the brines are separated from the heated stream
by the separator (S) (45, 6). The vapor is adiabatically compressed by the compressor (CM)
(57) to produce a temperature difference in the heat exchangers. The latent heat of the
compressed vapor stream is exchanged in heat exchanger 3 (78) and the stream condenses.
These streams (6, 8) then exchange their sensible heat with the feed stream in heat exchangers
1 and 2 (610, 89). The pressure of stream 9 is adjusted to ambient pressure by the valve
(V) (911). These streams (10, 11) are cooled to ambient temperature by the coolers (CL1,
CL2)(1013, 1112). Stream 13 contains rejected brine and stream 12 is product water.
The energy consumption of this process was calculated under conditions where the adiabatic
efficiency of the compressor was 100%, the recovery ratio, defined as the product water flow
rate divided by the feed water flow rate, was 30% and the minimum internal temperature
difference in the heat exchanger was 5 K. The reported energy was 70 kJ/kg-water and the
energy was 1/4 of that of the conventional thermal process (MSF process).
271
Figure 3. A multi-stage flash desalination process.
Figure 4. The thermal desalination process based on self-heat recuperation.
The specific energy consumption of the thermal desalination process based on self-heat
recuperation is quite small compared with that of the conventional process because in the
former, the sensible heat of the product and rejected brine streams as well as latent heat is
recirculated. That is, all of the heat is recuperated and recycled. On the other hand, in the
conventional process, only latent heat is recovered. Thus, larger energy consumption is
required because of the no recovering of the sensible heat.
The specific energy consumption difference between these two processes can be
understood using temperature-heat diagrams. Figure 5 shows a temperature-heat diagram for
the conventional thermal process (MSF). The solid and dotted streams represent for the cold
(feed) and hot (product) side streams, respectively. From this figure, it can be seen that in
each stage, only latent heat is recovered, while sensible heat is not recovered because of the
structure of MSF. Thus, from conservation of energy, additional heat equal to the discarded
sensible heat is required.
Figure 6 shows the temperature-heat diagram of the thermal process based on self-heat
recuperation. The solid and dotted lines represent the cold (feed) and hot (product and
rejected brine) side streams, respectively. From this figure, it can be seen that the sensible
heat from the feed stream is exchanged with that of the product and rejected brine streams at
heat exchangers 1 and 2. The feed stream receives the latent heat from the product stream at
heat exchanger 3 and is evaporated.
272
Figure 5. Temperature-heat diagram for MSF.
Figure 6. Temperature-heat diagram for the thermal seawater process based on self-heat recuperation.
Thus, both sensible heat and latent heat can be recirculated, leading to the drastic
reduction of the energy consumption compared to the conventional thermal process. The
required energy is used only for producing temperature differences in the heat exchangers.
The energy consumption of MED is also large compared with thermal seawater
desalination process based on self-heat recuperation. This is because, in the MED process,
only latent heat is recovered at the heat exchanger and sensible heat is not recovered, the
same as for the MSF process because of the structure of the MED process. Thus, external
heating load is required and the specific energy consumption is also larger.
SIMULATION RESULTS AND DISCUSSION

Adiabatic Efficiency
In the simulation, the adiabatic efficiency was assumed to be 100%. However, in real
compressors, it is approximately 70%. In this section, the influence of adiabatic efficiency on
the energy consumption of the thermal process based on self-heat recuperation is examined.
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Adiabatic efficiency is defined as the ratio of ideal to actual work. Thus, this value represents
the ratio of additional energy used to increase the pressure of the gas stream. The increased
pressure of the stream increases the condensation temperature and produces a temperature
difference in the latent heat exchanger. Hence, the temperature difference in the latent heat
exchanger decreases as adiabatic efficiency decreases for constant additional energy. Figure 7
shows the temperature-heat diagrams for the thermal seawater desalination process based on
self-heat recuperation with 100% and 70% adiabatic efficiencies. The solid and dotted lines
represent the cold (feed) and hot (product and rejected brine) streams, respectively. From this
figure, it can be seen that the temperature difference between the hot and cold streams in heat
exchangers 1 and 2 are the same in each process, while that in heat exchanger 3 varies with
adiabatic efficiency. In this simulation, the important thing to note is that the specific energy
consumption remains nearly unchanged, while the temperature difference in the heat
exchanger varies with adiabatic efficiency and the amount of heat exchanged in HX 3 is the
same at each process. This is because in these processes, perfect internal heat circulation is
achieved and conservation of energy demands that the energy required is used only to
produce a temperature difference in the heat exchangers.
The reported temperature difference during the change in phase of a real desalination
process is very small, at 2 K (Darwish et al., 2002). Thus, it can be considered that, while the
higher adiabatic efficiency a compressor has, the better it is, the current compressor
specification is not to low to develop a highly energy efficient thermal desalination process.
Figure 7. Temperature-heat diagram with different adiabatic efficiencies.
Recovery Ratio and Minimum Internal Temperature Difference

It has been reported that the recovery ratio has a large influence on specific energy
consumption (Mizuno et al., 2012). The recovery ratio is defined as the product water flow
rate divided by the feed water flow rate. In other words, a 30% recovery ratio for a process
means 70% of the feed stream is rejected as brine and the remainder is product water. We
mentioned above that specific energy consumption decreases as the recovery ratio increases.
274
In fact, the specific energy consumption with a 30% recovery ratio was 70 kJ/kg-water and
that with a 70% recovery ratio was 30 kJ/kg-water. This is because when the feed stream
(seawater) flow rate and the minimum internal temperature difference in heat exchangers are
fixed, the energy consumption of the compressor (kW) is constant for a given recovery ratio.
The specific energy consumption (kJ/kg-water) is defined as the required energy (kW), which
is equal to the amount of discarded heat from conservation of energy, divided by the product
water flow rate (kg/s) and the discarded energy can be expressed by the following equation:
productC p T m
rejected brineC p T
Qdiscarded m
(1)
where m
product and m
rejected brine represent the flow rates of product and rejected brine streams,
respectively. C p is the specific heat at constant pressure and T is the temperature
difference between the product and rejected brine streams and feed water stream. Although
the recovery ratio varies, the discarded heat (kW) from this process is almost constant
because C p is fairly constant. Moreover, T is reasonably constant for a process design
based on self-heat recuperation, which leads to perfect internal heat circulation and the
minimum internal temperature difference is assumed to be constant. Furthermore, when the
rejected brine are constant. Thus, because of
product plus m
feed stream is constant, the values of m
the conservation of energy, the energy required by the compressor (kW) is constant at any
recovery ratio. However, when the recovery ratio is changed, the product water flow rate also
changes. Therefore, the higher the recovery ratio, the less specific energy (kJ/kg-water) is
consumed.
Mizuno et al. also reported the influence of minimum internal temperature difference in
heat exchangers on specific energy consumption (Mizuno et al., in press). The specific energy
consumption grows proportionally with increasing minimum internal temperature difference
in the heat exchanger. In fact, when the recovery ratio was assumed to be 30%, the energy
consumption of the proposed process with a 2 K minimum internal temperature difference
was 28 kJ/kg-water, because as you can see from the above equation, the temperature
difference is proportional to the energy required in the compressor.
Thus, it can be said that the minimum internal temperature difference in the heat
exchanger has a large impact on specific energy consumption.
To develop a highly energy efficient thermal desalination process, one must increase the
recovery ratio and decrease the temperature difference in the heat exchangers.
Comparison with RO Process

The reported specific energy consumption of the proposed thermal desalination process
using self-heat recuperation technology is in the approximate range 30 70 kJ/kg-water.
Thus, it can be seen that an RO process is superior to thermal desalination process from the
energy consumption point of view because the reported energy consumption of an RO
process is in the range 9.0 25.2 kJ/kg-water. However, some conditions, such as product
275
water salinity and recovery ratio, differ between the two processes. Hence, when we evaluate
the specific energy consumption, these differences in condition must be taken into account.
Product water salinity from an RO process is approximately 10 times higher than that of
the proposed process because RO separation is based on a rate-governed mechanism, while
the thermal process is based on vapor-liquid equilibrium. In an RO process, both salts and
water molecules can permeate the membrane. Thus, the product water salinity is relatively
high. In contrast, in the thermal process, because salts are not volatile, the salinity of the
product water can be very low. The product water salinity is important, especially for
industrial and agricultural use, which require values below approximately 10 ppm (Tanaka et
al., 2009). Hence, to use the product of the RO process as industrial or agricultural water, the
permeate water must pass through multiple RO stages, which leads to an increase of the
specific energy consumption because of the need for additional pumps. In the thermal
desalination process, the product water salinity is sufficiently low for industrial and
agricultural usage. Thus, to gain low salinity water, there is no need for additional processes.
The recovery ratio also differs between the two processes. The high recovery ratio
process enables the cost of pretreatment to be reduced and the impact of rejected brine on the
environment to be minimized. Thus, from the viewpoints of cost reduction and environmental
protection, enhancement of the recovery ratio is required. The recovery ratio from an RO
process is restricted to below 50%. This value is determined by the total permeate flux
through the membrane, J , which can be expressed by the following equation (Meyer et al.,
2008):
J Lp pf pp f p
(2)
where Lp , p and represent water flux, stream pressure and osmotic pressure, respectively.
The subscripts f and p indicate feed and permeate streams. From this equation, under
conditions where the operating pressure and osmotic pressure of the permeate stream are held
constant, the total flux rate increases with increasing feed stream pressure, which is applied
by a pump. However, the osmotic pressure of the feed stream is not constant but increases as
the recovery ratio increases because of the concentration of seawater. Thus, as the pressure
applied by the pump increases, the rate of increase in total permeate flux rate slows.
Furthermore, the maximum applicable pressure to membrane is limited to approximately
7000 kPa because of limitations in the mechanical strength of the RO module. Thus, the
recovery ratio in RO processes is limited to 60% (Greenlee et al., 2009). On the other hand, in
the thermal desalination process based on self-heat recuperation, the recovery ratio can be
easily varied by changing the amount of heat exchanged in the latent heat exchanger. Thus,
for achieving a high recovery ratio desalination process, it can be concluded that the thermal
process is more suitable than an RO process. (The problem of scale deposition is discussed in
following section.)
As you have seen, it is difficult to definitely determine which desalination process is the
lowest energy consumption. Thus, in the future, a new model that includes these parameters
must be developed.
In any case, it can be concluded that the energy consumption of the proposed thermal
process is comparable with that of an RO process under some conditions and the novel
276
desalination process can potentially be installed in regions where it is not feasible to introduce
a desalination process because of problems with feed water quality and energy cost.
Self-Heat Recuperative Evaporation

To realize a high recovery ratio thermal desalination process, the problem of scale
deposition must be solved. Scale, which is caused by the precipitation of salts in seawater that
exceed their saturation limits, deposits on a heated surface and leads to a reduction in heat
transfer coefficient within heat exchangers (Andritsos et al., 2003; Wade, 1979; Paakkonen et
al., 2009). It has been reported that calcium carbonate, calcium sulfate and sodium chloride
are the main contributors to scale deposition, and these begin to precipitate when 50%, 70%
and 90% of seawater is evaporated, respectively (The salt industry center of Japan, 2006). In
an actual thermal desalination process, the recovery ratio is generally limited to 30% to avoid
scale deposition. However, as mentioned above, the specific energy consumption decreases as
the recovery ratio increases in thermal desalination processes based on self-heat recuperation.
Furthermore, to reduce operating costs and the impact of the desalination plant on the
environment, a novel heat exchange method that can work at a high recovery ratio is required.
In the latest research on thermal desalination based on self-heat recuperation, to solve the
scale deposition problem and develop a highly energy efficient thermal desalination process,
a novel desalination process that uses a fluidized bed evaporator has been investigated. In this
process, it can be considered that seawater evaporation occurs on heated particles. Thus, scale
does not deposit on the heated surface. Furthermore, even if the scale deposition takes place
on the heat transfer surface, fluidized particles should erode the scale from the surface.
Currently, experiments on the anti-scale performance of fluidized bed evaporators have been
conducted, aimed at enabling the practical use of this desalination process.
The self-heat recuperative desalination process using a fluidized bed evaporator can be
applied to waste water treatment, medicine manufacturing, food concentration and other
applications, in addition to desalination. Although self-heat recuperation technology has
significant energy saving potential, it has been applied to date only in processes in which the
scale deposition problem does not occur, such as distillation and gas separation processes.
When a novel thermal desalination process using fluidized bed evaporators is finally
implemented, it will be possible to widen the applications of self-heat recuperation
technology and to further enhance energy savings in production processes. Therefore, it can
be said that research on self-heat recuperative thermal desalination using a fluidized bed
evaporator has significant potential for realizing an eco-friendly society as well as solving the
water shortage problems around the world.
CONCLUSION
In this chapter, a new thermal seawater desalination process based on self-heat
recuperation technology was introduced and the differences between the proposed process
and conventional processes were examined. It was found that the energy consumption of the
proposed process is reduced to 1/4 of that of a conventional thermal process. Furthermore, it
277
was shown that the higher the recovery ratio, the less specific energy is consumed. To enable
a high recovery ratio desalination process, the problem of scale deposition must be overcome.
To this end, a novel self-heat recuperative desalination process using a fluidized bed
evaporator has been examined.
This research has barely begun and further research is needed to implement the process.
It can be said that this is a very promising process for solving water shortage problems around
the world.
REFERENCES
Al-Shammiri M., Safar M. (1999). Multi-effect distillation plants: state of the art,
Desalination, 126(1-3), 4559. doi:10.1016/S0011-9164(99)00154-X.
Andritsos N., Karabelas A. J. (2003) Calcium carbonate scaling in a plate heat exchanger in
the presence of particles, International Journal of Heat and Mass Transfer 46(24), 4613
4627. doi:10.1016/S0017-9310(03)00308-9.
Aziz M, Kansha Y, Tsutsumi A (2011) Self-heat recuperative fluidized bed drying of brown
coal, Chemical Engineering and Processing 50, 944-951. doi: 10.1016/j.cep.2011.07.005.
Cotruvo J., Abouzaid H. (2010) Desalination Technology. CRC press, Florida, chapter 1.
Charcosset C (2009) a review of membrane processes and renewable energies for
desalination, Desalination 245, 214-231. doi: 10.1016/ j.desal.2008.06.020.
Darwish M.A., Asfour F. Al., Al-Najem N. (2002) Energy consumption in equivalent work
by different desalting methods : case study for Kuwait, Deaslination 152, 8392.
El-Dessouky H, Alatiqi I, Ettouney H (1998) Process synthesis: the multi-stage flash
desalination system, Desalination 115, 155-179. doi: 10.1016/ S0011-9164(98)00035-6.
Fritzmann C, Lowenberg J, Wintgens T, Melin T, (2007) State-of-the-art of reverse osmosis
desalination, Desalination 216, 1-76. doi: 10.1016/ j.desal.2006.12.009.
Greenlee L. F., Lawler D. F., Freeman B. D., Marrot B., Moulin P. (2009) Reverse osmosis
desalination: water sources, technology, and todays challenges, Water research, 43(9),
231748. doi:10.1016/ j.watres.2009.03.010.
Kansha Y, Tsuru N, Sato K, Fushimi C, Tsutsumi A (2009) Self-Heat recuperation
technology for energy saving in chemical processes, Industrial and Engineering
Chemistry Research 48,7682-7686. doi:10.1021/j.ces.2009.05.001.
Kansha Y, Tsuru N, Fushimi C, Shimogawara K, Tsutsumi A (2010) An innovative
modularity of heat circulation for fractional distillation, Chemical Engineering Science
65, 330-334. doi: 10.1016/ j.ces.2009.05.001.
Kishimoto A, Kansha Y, Fushimi C, Tsutsumi A (2012) Exergy recuperative CO2 gas
separation in pre-combustion capture, Clean Technol. and Environ. Policy 14, 465-474.
doi: 10.1007/s10098-011-0428-3.
Lattemann S (2010) Development of an environmental impact assessment and decision
support system for seawater desalination plants, Dissertation, Delft University.
Meyer D. E., Williams M., Bhattacharyya D. (2008) Separation Technology second edition,
Wiley interscience, New Jersey.
Matsuda K., Kawazuishi K., Hirochi Y., Sato R., Kansha Y., Shikatani Y., Kunikiyo H.,
Tsutsumi A. (2010) Advanced energy saving in the reaction section of the hydro-
278
desulfurization process with self-heat recuperation technology, Applied thermal

engineering 30, 2300-2305. doi:10.1016/ j.applthermaleng.2010.05.003.
Matsuda K., kawazuishi K., Kansha Y., Fushimi C., Nagao M., Kunikiyo H., Masuda F.,
Tsutsumi A. (2011) Advanced energy saving in distillation process with self-heat
recuperation technology, Energy 36, 4640- 4645. doi:10.1016/j.energy.2011.03.042.
Mizuno H., Kansha Y., Kishimoto A., Tsutsumi A. Thermal seawater desalination based on
self-heat recuperation, Clean Technology and Environmental Policy, in press.
doi:1007/s10098-012-0539-5.
Mizuno H., Kansha Y., Kishimoto A., Tsutsumi A. (2012) Thermal Desalination Process
Based on Self-heat Recuperation, Chemical Engineering Transactions 29, 379-384. doi:
10.3303/CET1229064.
Paakkonen T. M., Riihimaki M., Puhakka E., Muurinen E., Simonson C. J., Keiski R. L.
(2009) Crystallization fouling of CaCO3 effecty of bulk precipitation on mass
deposition on the heat transfer suface, Proceedings of international conference on heat
exchanger fouling and cleaning, Published online www.heatexchanger-fouling.com.
Park K, Hong SY, Lee JW, Kang KC, Lee YC, Ha M, Lee JD (2011) A new apparatus for
seawater desalination by gas hydrate process and removal characteristics of dissolved
minerals (Na+, Mg2+, Ca2+, K+, B3+), Desalination 274, 91-96. doi: 10.1016/
j.desal.2011.01.084.
Tanaka K., Matsui K., Hori T., Iwahashi H., Takeuchi K., Ito Y. (2009) The First Large Full
Triple Pass RO Seawater Desalination Plant in the World, Mitsubishi Heavy Industries
Technical Review 46, 13-15 (in Japanese).
The Salt Industry Center of Japan (2006) Data Book for Seawater Science and Salt
Production, The Salt Industry Center of Japan, Tokyo, chapter 1 (in Japanese).
UN (2012) WATER, United Nations Web sites, http://www.un.org/en/ globalissues/water/
Accessed 29 July 2013.
Voutchkov N, Sommariva C, Pankratz T, Tonner J (2010) Desalination Technology. CRC
press, Florida, chapter 2.
Wade N M (1979) a review of scale control methods, desalination 31,309-320.
Younos T, Tulou KE (2005) Overview of desalination techniques, Journal of contemporary
water research and education 132, 3-10. doi: 10.1111/ j.1936-704X.2005.
mp132001002.x.

ISBN: 978-1-63117-329-5
Chapter 9
BIOCHEMICAL GAS SENSOR BIO-SNIFFER

AND IMAGING SYSTEM FOR MEDICAL
AND HEALTH CARE SCIENCE
Tokyo Medical and Dental University, Tokyo, Japan
ABSTRACT
We introduce biochemical gas sensors bio-sniffer which leverage biochemical
reactions and characteristics of various enzymes. Volatile substances associated with
diseases and breath odors are released from human body. Hence, highly sensitive and
highly selective bio-sniffers have been developed and demonstrated in biomedical and
health care applications utilizing enzymes as biomarkers of related diseases. We present
three topics of bio-sniffer techniques for monitoring of gaseous components of methyl
mercaptan, formaldehyde and ethanol. A bio-sniffer for gaseous methyl mercaptan (MM)
is applied to measure halitosis (oral odor) in breath. MM is known as one of the
important chemicals of halitosis in oral care. And then, a fiber-optic biochemical gas
sensor for assessment of indoor environment is fabricated and demonstrated in
monitoring of formaldehyde. Finally, two-dimensional visualization system of gaseous
ethanol is demonstrated in spatial and temporal imaging of gaseous components of
exhaled breath. In this chapter, we describe the details and future prospects of
biochemical gas sensors for environmental analysis, medical and health care.
1. INTRODUCTION
In last decade, a measurement of gaseous components from human body plays an
important role in a non-invasive, painless and attractive diagnostic method of monitoring
disease states without risk of blood collection to patients. Exhalation diagnosis and human
body odor were reported to be helpful in diagnosis of diseases by monitoring for volatile
organic compounds (VOCs) [1, 2]. Additionally, Health damages from formaldehyde, a wellknown representative of volatile organic compounds, are caused by human activities and
280
products. The main emission sources of indoor formaldehyde are urea-formaldehyde resins in
pressed wood products in cabinetry and furniture. A combination of respiratory disease and
allergic dermatitis, so-called sick building syndrome is associated with chronic exposure to
formaldehyde [3, 4]. Hence, instant and simple methods are strongly desired to discriminate
volatile organic compounds from human body, indoor environment and so on. However, gas
chromatography methods are required time consuming, expensive and large-scale equipment.
It is difficult for low selective semiconductor gas sensor to arrest density and a change in the
space precisely. Therefore, continuous and easy monitoring system for various gas
components behavior in spatial localization is strongly required. Some technology has been
developed for gas sensor employing enzymatic reaction, such as biochemical gas sensors for
ethanol, acetaldehyde, formaldehyde and various volatile organic compounds and a NADHdependent fiber-optic biosensor bio-sniffer for determination of gaseous components [5].
Also the enzyme-based biosensors are highly selective and sensitive for target chemicals.
We introduce biochemical gas sensors bio-sniffer by exploiting biochemical reactions
and characteristics of various enzymes. Firstly, optical bio-sniffer (gas sensor) for gaseous
methyl mercaptan (MM) was applied to measure halitosis (oral odor) in breath. MM is known
as one of the important chemicals of halitosis in oral care. The MM bio-sniffer was fabricated
a oxygen-sensitive optical fiber with a ruthenium organic complex, a monoamine oxidase
type-A (MAO-A) immobilized membrane and a reaction unit, which consists of liquid and
gaseous compartments, separated by a hydrophobic porous polytetrafluoroethylene (PTFE)
diaphragm membrane. This sensor was applied for halitosis measurement.
Secondly, gaseous formaldehyde is well known as one of the harmful volatile organic
compounds, which causes health damages of so-called sick building syndrome. A fiber-optic
biochemical gas sensor for assessment of indoor environment was fabricated and tested in
monitoring of formaldehyde. The bio-sniffer measures formaldehyde vapor as fluorescence of
reduced NADH, which is the product of enzymatic reaction of formaldehyde dehydrogenase
(FALDH). We employed a micro flow-cell with a FALDH immobilized membrane to prevent
the FALDH from deactivation at the optode. An ultraviolet light emitting diode (UV-LED)
with peak emission of 335 nm was employed as an excitation light source. Emission of the
UV-LED was introduced to the optode through an optical fiber and fluorescence of NADH
was picked up coaxially at the optode. Continuous formaldehyde monitoring with
biochemical method was successfully conducted with high selectivity at sub-ppb level.
Finally, two-dimensional imaging system of gaseous ethanol was demonstrated in spatial
and temporal imaging of gaseous components of exhaled breath for a non-invasive diagnostic
method of monitoring disease states without risk to patients. We applied alcohol oxidase
(AOD), catalyzes low molecular weight alcohols by molecular oxygen into aldehydes with
the production of hydrogen peroxide, which can be led to the HRP-luminol-H2O2 system for
the chemiluminescence analysis. The chemiluminescence generated by the catalytic reaction
of gaseous ethanol was analyzed. Rebuilding an image analysis of chemiluminesce allows it
to visualize spatial and temporal image of gaseous ethanol. The metabolism capability of
alcohol in volunteers was successfully evaluated by the illustrated images of ethanol
chemiluminescence noninvasively.
281
2. BIO-SNIFFER FOR METHYL MERCAPTAN IN HALITOSIS

Halitosis diagnosis is important in the medical and dental fields. Methyl mercaptan (MM)
is one of typical causation for halitosis [6, 7]. The American Conference of Governmental
Industrial Hygienists and the Environment Agency Government of Japan had specified the
MM as a typical volatile organic compounds (VOCs) and malodorous substance. The
maximum permissible concentration of gaseous MM in the work place is 5.0 ppm (threshold
limit value-time weighted average concentration) and 0.5 ppm. We have constructed an
optical bio-sniffer for the measurement of MM as major odorous chemical in bad breath using
monoamine oxidase. After the evaluation of the sensor characteristics using a batch
measurement system, the optical sniffer was applied to the halitosis analysis as a
physiological application.
From Analytica Chimica Acta 573574 (2006) 7580.

Figure 1. Schematic image and photograph of methyl mercaptan bio-sniffer with a sensor cleaning
system in the gas phase and the device components.
282
The schematic image and photograph of an optical bio-sniffer for MM in the gas phase
was shown in Figure 1. The sniffer device constructed with an enzyme immobilized
membrane for detection of MM, a flow cell and a commercial available oxygen-sensitive
optical fiber with a ruthenium-organic complex. The optical fiber was coated in a solgel
process with the ruthenium-organic complex that is subjected to an optical quenching
(excitation wavelength: 470 nm, fluorescent wavelength: 600 nm) in the presence of oxygen.
Monoamine oxidase type A (MAO-A, E.C.1.4.3.4) was used as the MM recognition material
for the halitosis bio-sniffer. MAO-A was mixed with PVA-SbQ solution (UV cross-linkable
polyvinyl alcohol) to a dialysis membrane for enzyme immobilization, and then irradiated
with a fluorescent lamp for photo-crosslink the solution and immobilizing the enzyme
membrane. The MAO-A immobilized membrane was removed from the glass plate and
immersed in phosphate buffer. The flow cell was constructed by connecting two t-tubes to
both sides of a stainless steel pipe. The enzyme membrane, which was cut to the required
dimensions using a scalpel, was used to close one of the open edges of the flow cell and
secured with a supporting nylon mesh net and a rubber O-ring. Figure 2 illustrates a batch
flow measurement system with valve connecting to a gas generator for evaluating the
characteristics of the optical bio-sniffer and to a sampling bag for the breath analysis.
Standard gaseous MM and sample of human breath and phosphate buffer solution could be
injected individually through the flow cell in the detection system. A spectrophotometer was
optically connected to the bio-sniffer and monitoring the fluorescent quenching, resulting
from oxygen consumption caused by MAO-A catalytic reaction with MM.

Figure 2. Breath analysis procedure and system by the optical bio-sniffer with MAO-A for methyl
mercaptan in the gas phase.
The performance of the bio-sniffer for MM vapor was evaluated with the batch flow
measurement system. The output increased rapidly following application of MM vapor and
reached to a steady-state output within 3 minutes. The reduction of optical quenching of the
ruthenium-organic complex emission induced by the consumption of oxygen was caused by
the MAO-A catalytic reaction with methyl mercaptan. The calibration curve of the bio-sniffer
for methyl mercaptan in the gas-phase is shown in Figure 3. The calibration range of the bio-
283
sniffer for MM vapor was from 8.7 to 11500 ppb (correlation coefficient 0.977) including a
MM threshold (200 ppb) of pathologic halitosis and the human sense of smell level 3.5 (10.0
ppb). As the physiological application, breath samples from healthy male volunteer subjects
were provided to the gas measurement system with the optical bio-sniffer for monitoring
halitosis. Exhausted breath gases in five subjects were sampled every hour and the process of
concentration change of MM was monitored [8-11].

Figure 3. Calibration curve of the bio-sniffer for methyl mercaptan in the gas phase. (200 ppb MM as
threshold of pathologic halitosis).
3. BIO-SNIFFER FOR FORMALDEHYDE IN ENVIRONMENTAL ANALYSIS

Formaldehyde is a reactive and flammable chemical, which is well known as one of the
volatile organic compounds (VOCs). Formaldehyde was upgraded in classification from
group 2A (probably carcinogenic to humans) to group 1 (carcinogenic to humans) by
International Agency for Research on Cancer (IARC) in 2004 [12]. Health damages for longterm exposure to formaldehyde are also reported. A combination of respiratory disease,
allergic dermatitis and other ailments, so-called sick building syndrome, is associated with
chronic exposure to low concentrations of formaldehyde [13]. For this reason, the World
Health Organization sets guideline level of formaldehyde exposure to 80 ppb. Nonetheless,
formaldehyde is widely used for many industrial purposes. It is typically used in pressedwood products, adhesives and coatings. Outgassing from resins in furniture, wallpaper or
paints can be the major indoor formaldehyde emission sources. Formaldehyde emissions in
residential atmosphere cause sick building syndrome even in lower concentrations than 80
ppb [14].
In the previous study, we reported a biochemical gas-sensor with formaldehyde
dehydrogenase (FALDH) for convenient analysis of gaseous formaldehyde with highly gasselectivity. The bio-sniffer for formaldehyde in the gas phase was constructed by
immobilizing FALDH to a Pt-electrode coated hydrophilic PTFE membrane. The oxidation
284
current of NADH produced by the enzymatic reactions was measured by amperometric

analysis [15]. Biochemical recognition system allows highly selective and highly sensitive
gas monitoring with a simplified structure.
We introduce a highly sensitive fiber-optic bio-sniffer using FALDH immobilized
membrane for gaseous formaldehyde monitoring. The bio-sniffer measures formaldehyde
concentration as fluorescence of NADH. In order to obtain sufficient sensitivity for indoor
formaldehyde monitoring, a photomultiplier tube (PMT) was employed as a fluorescence
detector. The UV-LED based excitation system enabled the bio-sniffer to be a simplified and
miniaturized gas sensor for its low power consumption and low heat generation. LEDs also
provided advantages in security and controllability compared with general UV lamps. The
construction, characteristics and possible applications of the fiber-optic bio-sniffer was
reported [16].
FALDH immobilized membrane was prepared by immobilizing FALDH (EC 1.2.1.1)
onto a hydrophilic PTFE membrane filter [17]. 2-methacryloyloxyethyl phosphorylcholine
(MPC) copolymerized with 2-ethylhexyl methacrylate (EHMA) was used for enzyme
immobilization. MPC-co-EHMA (PMEH) was synthesized using free radical-polymerization
method. NADH (-nicotinamide adenine dinucleotide, reduced from disodium salt) was
prepared for characterization of the NADH measurement system. Phosphate buffer solution
containing 20 mmol/L NAD+ (-NAD) was prepared in order to wet the enzymeimmobilized membrane during gas measurement. a fiber-optic NADH measurement system
was constructed.
formaldehyde + NAD + H 2O FALDH

fomicacid + NADH + 2H +
(1)
A UV-LED (= 335 nm) was employed as an excitation light source. Emission of the
UV-LED was coupled into a branched optical fiber using custom-fabricated UV-LED power
supply with an adjustable optical fiber connector. A PMT was connected to the other
branched terminal. An optical fiber probe was connected to the assembled terminal of the
branched optical fiber. In order to reduce background level, excitation light and fluorescence
were filtered using band-pass filters (330350 nm and 490510 nm), respectively. Thus,
fluorescence of NADH at the neighborhood of the optical fiber probe could be measured
coaxially by the PMT [18, 19].
From Biosensors and Bioelectronics 26 (2010) 854858.

Figure 4 Construction of the fiber-optic bio-sniffer and FALDH immobilization for continuous
monitoring of formaldehyde.
285
A formaldehyde-sensitive optode was constructed by attaching a flow cell with FALDH

immobilized membrane onto the optical fiber probe. The flow cell was fabricated by
assembling a silicone tube (2 mm) and a cylindrical PMMA cell (4 mm) with inlet/outlet as
shown in Figure 4.
FALDH immobilized membrane was prepared by curing a mixture of PMEH solution (1
L/cm2) and FALDH (50 units/cm2), which was spread on the H-PTFE membrane filter, for
180 min under 4 degree C. The FALDH membrane was cut into 1 cm 1 cm and tightly
fixed onto the end of the PMMA tube using a silicone O-ring.
Measurement of gaseous formaldehyde was carried out using the standard formaldehyde
measurement system. Gaseous formaldehyde was applied to the optode with a flow rate of
200 mL/min. Fluorescent signal immediately increased after application of gaseous
formaldehyde and attained steady state within 2 min. Fluorescent intensities of the steady
state are determined by the balance of NADH production rate and the rinse effect of PB.
Sufficient recovery of initial state when formaldehyde gas was eliminated from the optode
was also confirmed. The response curves indicated that the bio-sniffer was stable enough to
be used for continuous formaldehyde monitoring.

Figure 5. Calibration curve for formaldehyde vapor using formaldehyde bio-sniffer. The fluorescent
intensity related to formaldehyde concentrations from 2.5 to 10 ppb. The small box shows typical
responses to gaseous formaldehyde.
The calibration curve of the FALDH bio-sniffer for gaseous formaldehyde is shown in
Figure 5. The output fluorescence was related to the formaldehyde concentration from 2.5
ppb to 10 ppm. The bio-sniffer also showed high reproducibility. The calibration range
included both the guideline value of WHO (80 ppb, signed in the figure). Considering the
following capability of fluctuation of formaldehyde level, the bio-sniffer showed comparative
sensitivity with above system and higher detection limit than that of commercial
formaldehyde sensors. For instance, modern commercial solid-state sensors for real-time
286
monitoring are available from several tens of ppb. The lower detection limit of the FALDH
bio-sniffer can be improved by some realistic approaches. For instance, excitation with
multiple LEDs is considered to be one of the most effective approaches. Thicker optical fibers
are also useful to enhance fluorescence signal because the effective region of the enzyme
membrane increases. These improvements may enhance the sensitivity down to sub-ppb level
considering the present SN ratio. On the other hand, the optical system can be easily
miniaturized using a photo-diode as a detector instead of the PMT.
Gas selectivity for various chemical substances was also investigated. Acetaldehyde is a
useful reference to assess gas selectivity of a formaldehyde sensor because of similar
structure. Figure 6 shows the relative fluorescent intensities of the FALDH bio-sniffer for
formaldehyde, acetaldehyde, acetone, benzene, methanol and ethanol (5.0 ppm). As a result,
the fluorescent intensity for acetaldehyde was only 1.3% of output for formaldehyde, and no
fluorescence was detected for other gaseous substances. Considering the selectivity for
formaldehyde, the selectivity of the FALDH bio-sniffer was approximately 10 fold higher
than that of a conventional formaldehyde gas sensor. Such a high selectivity of the bio-sniffer
was induced by the specificity of FALDH. Since the FALDH bio-sniffer measures
formaldehyde as a concentration of NADH, it is also possible to measure other volatile
chemical substances with high selectivity by replacing enzyme with similar system (i.e.,
alcohol dehydrogenase for ethanol monitoring).
In addition, we are applying the NADH based biosensor technique with UV-LED to
many application of detection of gaseous ethanol [5] and amino acid solution of L-leucine
[20] and phenylalanine [21]. Especially, this NADH-detecting biosensor with enzyme
immobilized membrane that permits to contribute various diagnosis of amino acid in blood
and urine by applying to point of care testing. In the future, we will apply the biosensor with
UV-LED excitation system to the combined multiple dehydrogenase enzyme-immobilized
biosensor for determination of various amino acids.

Figure 6. Comparison of gas selectivity of FALDH bio-sniffer and conventional FA sensor.
287
4. TWO-DIMENSIONAL VISUALIZATION SYSTEM OF

GASEOUS ETHANOL
Breath gas analysis plays a role important method for non-invasive information of
clinical state of volatile organic compounds (VOCs) present in the exhaled breath, which is
faster and safer than blood or urine analyses. Compared to traditional diagnostic methods,
breath analysis is painless and requires no special medical skills [22]. Approximately 3000
VOCs have been found in human breath using gas chromatography; 200 of these have been
linked to various diseases such as lung cancer, breast cancer, diabetes, and liver diseases [23,
24]. For example, methanol, ethanol, acetone, and ethylene are all VOCs that are known to be
diagnostic for certain diseases. Ethane and methylated hydrocarbons are related to oxidative
stress and lung or breast cancers, respectively, and exhaled carbon monoxide is a marker for
cardiovascular diseases. Many investigations have been carried out to characterize and
identify the substances found in breath samples. Gas chromatography and mass spectrometry
was used to identify 42 VOCs that act as lung cancer biomarkers [25]. As a result of such
extensive studies, several breath markers have been successfully used in the diagnosis of
diseases. Breath gas screening is a highly desirable diagnostic technique because it is a noninvasive, convenient, and rapid diagnostic method that links VOCs found in exhaled breath to
medical conditions [26, 27]. A straight-forward continuous monitoring system for various gas
components is therefore required. We fabricate and demonstrated a non-invasive spatial
visualization system of exhaled ethanol for real-time analysis of alcohol metabolism. We
have focused on alcohol oxidase (AOD). AOD catalyzes the reaction of low molecular weight
alcohols with molecular oxygen, producing aldehydes and hydrogen peroxide, which can in
turn be consumed in the HRP-luminol-H2O2 reaction for CL analysis (Figure 7). CL was
generated by the catalytic reaction of breath gaseous ethanol was detected and analyzed using
standard gas and breath gas sample. The system for imaging the spatial movement of gas was
developed. AOD and HRP enzyme and PVA-SbQ mixture was coated onto the mesh
substrate, spread, cured, and treated with ultraviolet radiation. Enzyme-immobilized supports
were stored at 4oC. AOD and HRP were used together to generate the CL signal from gaseous
ethanol. Tris-HCl buffer solution was the medium of the AOD catalytic reaction, and HRP
catalyzed the CL reaction. Ethanol is oxidized to acetaldehyde by AOD in the presence of
oxygen.
Figure 7. Schematic view of gaseous ethanol imaging system, consisting of ethanol gas generator, mass
flow controller, enzyme immobilized mesh and EM-CCD recoding system. Fabrication process of AOD
and HRP enzymes and UV-cross-linkable PVA-SVQ immobilized mesh substrate.
288
From Analyst, 136 (2011) 3680-3685.

Figure 8. Temporal changes of various concentrations of standard gaseous ethanol.
The peroxide then reacts with the luminol solution catalyzed by HRP, ultimately
generating chemiluminescence (= 460 nm). The reactions are as follows [28]:
ethanol+O2 AOD
acetaldehyde+H2O2
(2)
3-aminophthate+2H2O+N2 +hn
luminol+H2O2 +2OH- HRP
(3)
The temporal changes of various concentrations of standard gaseous ethanol are shown in
Figure 8 with the images of maximum intensity processed. As Figure 8 indicates, the CL
intensities increased rapidly following the loads of standard gaseous ethanol. The peaks
appeared within 90 s and faded away within 180 second. And the images showed that the area
became bigger and the CL intensities became higher as a result of the increments in the
amount of standard gaseous ethanol. The development of the system showed rapid and
accurate responses and a visible measurement in real time. Figure 9 shows the calibration
curve of the system for standard gaseous ethanol measurement. The peaks of average CL
intensities detected by the system were related to the concentrations of gaseous ethanol from
30 to 400 ppm. This system showed a wide calibration range covered the concentration of
exhaled breath ethanol from drunk driving to acute toxicosis of alcohol [29, 30].
CL of gaseous ethanol (300 ppm) and ethanol in exhaled breath sample (30 min after
ethanol oral administration) of volunteer with ALDH2 (-) are illustrated in Figure 6. The
spatiotemporal changes of ethanol in exhaled breath (right) were detected and recorded as the
gaseous ethanol (left). The upper images were processed to show the different information of
CL of exhaled ethanol in a 3D profile. The lower ones were processed to show CL intensity in
RGB. Ethanol in exhaled breath after oral administration was selectively detected and
289
measured. Compared with the gas detector tube for exhaled ethanol after oral administration,
the system showed a better sensitivity. Exhaled ethanol in breath can be visibility evaluated
with the system in real time, which cannot be evaluated with other ethanol sensors.
From Analyst, 136 (2011) 3680-3685.

Figure 9. Calibration curve of the imaging system for standard gaseous ethanol. The peak of average
intensity related to the concentration of gaseous ethanol from 30 to 400 ppm.
From Analyst, 136 (2011) 3680-3685.

Figure 10. Chemiluminescence of gaseous ethanol (left) and ethanol in exhaled breath (right). The
spatiotemporal changes of ethanol in exhaled breath were detected and recorded as gaseous ethanol.
290
The pharmacokinetic profiles of mean exhaled ethanol are shown in Figure 11. The
exhaled breath samples of 10 volunteers (ALDH2 (+), n=5; ALDH2 (-), n=5) were
demonstrated. The lines illustrate the regression line based on data points from 75 min and
onward according to zero-order kinetics for the time variation profile. Exhaled ethanol
concentrations in all volunteers rapidly increased after oral administration and the peaks
appeared at 30 min and then gradually decreased until the end of sample collection at 120
min. During the first 30 min, the time variation profile showed the absorption and distribution
function after oral administration, and the values thereafter showed the elimination function.
Due to the deficiency in ALDH2, acetaldehyde (oxidation product of ethanol) could not be
metabolized. The ethanol concentration in volunteers with ALDH2 (+) was lower than that in
volunteers with ALDH2 (-). Ethanol that had not even been metabolized was egested in
exhaled breath and was detected and illustrated by the visualization system. ALDH2 was
considered to be the main enzyme in acetaldehyde oxidization related to ethanol metabolism.
Hence, in volunteers with ALDH2 (-), it results in increased acetaldehyde levels and leads to
ethanol being metabolized with a slower rate than volunteers with ALDH2 (+) [29, 30]. We
applied this imaging system to a non-invasive method of directly imaging exhaled gaseous
ethanol using chemiluminescence and used in the analysis of alcohol metabolism [31]. This
imaging system will be useful and significant for the diagnosis of diseases using exhaled
human breath. In addition, the rate of ethanol metabolism by ALDH2(+) and ALDH2(-)
human subjects was also determined using direct gaseous ethanol imaging using flow control
unit, over 300 minutes after the oral administration of alcohol.
From Analyst, 136 (2011) 3680-3685.

Figure 11. Pharmacokinetic profile of exhaled ethanol concentration of 10 healthy volunteers.
291
CONCLUSION
We introduce biochemical gas sensors bio-sniffer using biochemical reactions and
characteristics of various enzymes for determination of methyl mercaptan, formaldehyde and
gaseous ethanol. We apply the bio-sniffer to highly sensitive and highly selective gas sensor
for biomedical and health care applications utilizing enzymes as biomarkers of related
diseases. In future work, the sensing and imaging system of gaseous components from human
body and breath will apply for imaging of volatile organic components information from
human, transdermal analysis, halitosis and non-invasive screening.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
J. P. Spinhirne, J. A. Koziel, N. K. Chirase, A device for noninvasive on-site sampling

of cattle breath with solid phase microextraction, Biosystems Engineering, 84(2), 239
246, 2003.
A. W. Boots, J. J. B. N. Berkel, J. W. Dallinga, A. Smolinska, E. F. Wouters, F. J.
Schooten, The versatile use of exhaled volatile organic compounds in human health and
disease, J. Breath Res. 6 027108, 2012.
J. Gamble, Effects of formaldehyde on the respiratory system. In: Gibson JE, ed.
Formaldehyde toxicity. Hemisphere & McGraw Hill, Washington DC, 1983, 175-197.
M. Ritchie and R. G. Lehnen, Formaldehyde-related Health Complaints of Residents
Living in Mobile and Conventional Homes, Am. J. Public Health, 77, pp. 323-328,
1987.
H. Kudo, M. Sawai, Y. Suzuki, X. Wang, T. Gessei, D. Takahashi, T. Arakawa, K.
Mitsubayashi, Fiber-optic bio-sniffer (biochemical gas sensor) for high-selective
monitoring of ethanol vapor using 335 nm UV-LED, Sensor Actuator B Chem., 132(2),
676-680, 2010.
J. Tonzetich, P. A. Carpenter, Arch. Oral Biol. 16 (1971) 599607.
N. F. Schmidt, S. R. Missan, W. J. Tarbet, Oral Surg. Oral Med. Oral Pathol. 45
(1978) 560567.
K. Mitsubayashi, T. Minamide, K. Otsuka, H. Kudo, H. Saito, Optical bio-sniffer for
methyl mercaptan in halitosis, Analytica Chimica Acta 573574 (2006) 7580.
T. Minamide, K. Mitsubayashi, H. Saito, Bioelectronic sniffer with monoamine
oxidase for methyl mercaptan vapor, Sensors and Actuators B 108 (2005) 639645.
K. Mitsubayashi, Y. Hashimoto, Bioelectronic nose for methyl mercaptan vapor using
xenobiotic metabolizing enzyme: avin-containing monooxygenase, Sensors and
Actuators B 83 (2002) 35-40.
T. Minamide, K. Mitsubayashi, N. Jaffrezic-Renault, K. Hibi, H. Endo, H. Saito,
Bioelectronic detector with monoamine oxidase for halitosis monitoring, Analyst 130
11 (2005) 1490-1494.
V. J. Cogliano, Y. Grosse, R. A. Baan, K. Straif, M. B. Secretan, F. El Ghissassi,
Working Group for Volume 88, Environ. Health Perspect. 113, (2005) 12051208.
L.E. Beane Freeman, A. Blair, J.H. Lubin, P.A. Stewart, R. B. Hayes, R.N. Hoover, M.
Hauptmann, Mortality from lymphohematopoietic malignancies among workers in
292
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]

formaldehyde industries: the National Cancer Institute cohort, J. Natl. Cancer Inst.
101, (2009) 751761.
J.R. Beall, A.G. Ulsamer, Formaldehyde, Formaldehyde and hepatotoxicity: a review,
J. Toxicol. Environ. Health 14, (1984) 121.
K. Mitsubayashi, G. Nishio, M. Sawai, E. Kazawa, H. Yoshida, T. Saito, H. Kudo, K.
Otsuka, M. Takao, H. Saito, A biochemical sniffer-chip for convenient analysis of
gaseous formaldehyde from timber materials, Microchim. Acta (2008) 160: 427433.
H. Kudo, T. Yagi, M.X. Chu, H. Saito, N. Morimoto, Y. Iwasaki, K. Akiyoshi, K.
Mitsubayashi, Glucose sensor using phospholipid polymer based enzyme
immobilization method, Anal. Bioanal. Chem. 391, (2008) 12691274.
H. Kudo, Y. Suzuki, T. Gessei, D. Takahashi, T. Arakawa, K. Mitsubayashi,
Biochemical gas sensor (bio-sniffer) for ultrahigh-sensitive gaseous formaldehyde
monitoring, Biosensors and Bioelectronics 26 (2010) 854858.
H. Kudo, X. Wang, Y. Suzuki, M. Ye, T. Yamashita, T. Gessei, K. Miyajima, T.
Arakawa, K. Mitsubayashi, Fiber-optic biochemical gas sensor (bio-sniffer) for subppb monitoring of formaldehyde vapor, Sensors and Actuators B 161 (2012) 486492.
H. Kudo, T. Yamashita, K. Miyajima, T. Arakawa, K. Mitsubayashi,, NADHfluorometric Biochemical Gas Sensor (Bio-Sniffer) for Evaluation of Indoor Air
Quality, IEEE Sensors Journal, 13 8 (2013) 2828-2833.
T. Koshida, T. Arakawa, T. Gessei, D. Takahashi, H. Kudo, H. Saito, K. Yano, K.
Mitsubayashi, Fluorescence biosensing system with a UV-LED excitation for Lleucine detection Sensors and Actuators B 146 (2010) 177-182.
T. Arakawa, T. Koshida, T. Gessei, K. Miyajima, D. Takahashi, H. Kudo, H. Saito, K.
Yano, K. Mitsubayashi, Biosensor for L-phenylalanine based on the optical detection
of NADH using a UV light emitting diode, Microchimica Acta, 173 (2011) 199-205.
J. P. Spinhirne, J. A. Koziel, N. K. Chirase, A device for noninvasive on-site sampling
of cattle breath with solid phase microextraction, Biosystems Engineering, 84(2), 239
246, 2003.
A. W. Boots, J. J. B. N. Berkel, J. W. Dallinga, A. Smolinska, E. F. Wouters, F. J.
Schooten, The versatile use of exhaled volatile organic compounds in human health and
disease, J. Breath Res. 6 027108, 2012.
G. Shuster, Z. Gallimidi, A. H. Reiss, E. Dovgolevsky, S. Billan, R. A-Bortnyak, A.
Kuten, A. Engel, A. Shiban, U. Tisch, H. Haick, Classification of breast cancer
precursors through exhaled breath, Breast Cancer Research and Treatment, 126, 3,
791-796, 2011.
G. Peng, U. Tisch, O. Adams, M. Hakim, N. Shehada, Y. Y. Broza, S. Billan, R. A.
Bortnyak, A. Kuten, H. Haick, Diagnosing lung cancer in exhaled breath using gold
nanoparticles, Nature Nanotech., 14 669-673, 2010.
P. J. Mazzone, Exhaled breath volatile organic compound biomarkers in lung cancer J.
Breath Res., 6, 027106, 2012.
M. Philips, Method for the collection and assay of volatile organic compounds in breath
Anal. Biochem., 247, 2272-2278, 1997.
P. Fletcher, K. N. Andrew, A. C. Calokerinos, S. Forbes, P. J. Worsfold, Applications
of Flow Injection Chemiluminescence Detection - A review Luminescence, 16, 1-23,
2001.
293
[29] X. Wang, E. Ando, D. Takahashi, T. Arakawa, H. Kudo, H. Saito, K. Mitsubayashi, 2D

spatiotemporal visualization system of expired gaseous ethanol after oral administration
for real-time illustrated analysis of alcohol metabolism, Talanta, 82, 892898, 2010.
[30] X. Wang, E. Ando, D. Takahashi, T. Arakawa, H. Kudo, H. Saito, K. Mitsubayashi,
Non-invasive spatial visualization system of exhaled ethanol for real-time analysis of
ALDH2 related alcohol metabolism, Analyst, 136 (2011) 3680-3685.
[31] T. Arakawa, X. Wang, T Kajiro, K. Miyajima, S. Takeuchi, H. Kudo, K. Yano, K.
Mitsubayashi, A direct gaseous ethanol imaging system for analysis of alcohol
metabolism from exhaled breath, Sensors and Actuators B: Chemical, 186 (2013)
2733.

ISBN: 978-1-63117-329-5
Chapter 10
DESALINATION OF BRACKISH WATER BY

ELECTRODIALYSIS: EFFECTS OF OPERATIONAL
PARAMETERS AND WATER COMPOSITION ON
PROCESS EFFICIENCY
Mourad Ben Sik Ali*, Amor Hafiane,
Mahmoud Dhahbi and Bchir Hamrouni
Desalination and Water Treatment Research Unit, Chemistry Department,
Faculty of Sciences of Tunis, University of El Manar, Manar II, Tunisia
Engineering Preparatory Institute of Nabeul, University of Carthage,
Merazka, Nabeul, Tunisia
Water Researches and Technologies Center, Soliman, Tunisia
ABSTRACT
Electrodialysis is an electro-membrane process for separation of ions across charged
membranes from one solution to another under the influence of an electrical potential
difference used as a driving force. The transfer of the charged species is carried out
according to a mechanism of exchanges of ions between the ions of the solution and the
counter ions of the membrane.
This chapter is dealing with the effectiveness of the desalination of brackish water by
this process. A laboratory scale electrodialysis cell was used for this purpose.
The desalination of brackish solutions containing only one salt according to the
continuous mode (single pass process) was carried out initially. This study revealed that
the effectiveness of the process is dependent on the operational parameters of the
electrodialysis cell. But the rate of desalination is relatively weak. This rate does not
exceed 50% and sometimes does not allow reaching the awaited results.
Study of another configuration was carried out. This configuration is the
discontinuous mode or total recirculation mode (batch process). In this mode, the
solutions are recycled in the cell until the desired concentration is reached. While
* Desalination and Water Treatment Research Unit, Chemistry Department, Faculty of Sciences of Tunis, 2092
Manar II, Tunisia. Email: mourad.bensikali@gmail.com.
296
Mourad Ben Sik Ali, Amor Hafiane, Mahmoud Dhahbi et al.

working with this mode, the desalination rates of various solutions reached quickly high
values. Indeed, they exceeded the 75% rate in few minutes.
This study concluded also that the composition of the solution itself influences the
effectiveness of desalination process. Indeed, the transfer of the ions from one
compartment to another depends on the various ionic species present in solution.
The presence of the calcium ions largely decreases the transfer of the magnesium
ions and vice versa. This is explained by the competition effect between two ions of same
valence during their transfers through exchanging membranes.
Moreover, the rates of transfer of the cations and more precisely calcium and
magnesium ions undergo reductions in the presence of anions and in particular sulfate
ions. The desired rates of desalination are also obtained for longer handling times which
have an immediate effect on energy consumption. In fact, the consumption of energy is
more important for more complex solutions.
Keywords: Brackish water, desalination, operational parameters, water composition, process

efficiency
INTRODUCTION
The drinking water is an invaluable and vital product. The vast majority of the water of
the sphere consists of sea water. Approximately 2.5 % are fresh water, and the two-thirds of
this one are in the form of icecaps (El-Dessouky & Ettouney, 2002).
Rivers and lakes contain a small percentage of planet water but this surface water is
crucial. Like certain aquifers, they are constantly renewed by the water cycle.
The groundwater reserves constitute an important source of water for many people. The
groundwater is often subject of water quality deterioration. The coastal aquifers can contain
sea water since prehistory, when their sediments settled. The sea water intrusion is also
possible because of the excessive pumping of the fresh water. The aquifers of the arid regions
can also contain brackish water. In this case, salts are usually concentrated by the evaporation
of closed basins or by depressions.
Modern technologies of desalination can extract salts from sea water and brackish water,
thus ensuring a new source of fresh water. The desalination processes available on the market
are divided into two main categories: thermal processes and membrane processes (Alghoul,
Poovanaesvaran, Sopian, & Sulaiman, 2009; Greenlee, Lawler, Freeman, Marrot, & Moulin,
2009; Sadrzadeh & Mohammadi, 2008).
Among the thermal processes, distillation is distinguished. It is one of the most frequently
employed methods. Approximately half of the de-salted water in the world is produced by
means of heat being used to distill fresh water starting from sea water. The distillation process
reproduces the natural cycle of water since it consists in heating salt water for the production
of steam which is in its turn condensed to form fresh water (El-Dessouky & Ettouney, 2002).
In nature, the membranes play a big role to separate salts. Indeed, dialysis and osmosis
processes occur in the living organisms (Baker, 2004; Noble & Stern, 1995). The membranes
are used for water treatment in two important processes: electrodialysis (ED) and reverse
osmosis (RO).
These membrane processes belong to new technologies which can play an important role
for the treatment of wastewater and the production of drinking water. However, the
Desalination of Brackish Water by Electrodialysis
297
application of the membrane processes and especially reverse osmosis encounter difficulties.
This is due to the formations of polarization layer and then membrane fouling. This
phenomenon presents the acutest problem of membrane filtration. It reduces the productivity
of the membranes and thus contributes to increase the energy expenses, to increase the
frequency of washings and to possibly reduce the lifespan of the membranes (Ct, Weirun,
Gierlich, Natarajan, & Taniguchi, 1996; Danis, 2003; Greenlee et al., 2009; Matsuura, 2001).
Electrodialysis is an electro-membrane process for separation of ions across charged
membranes from one solution to another under the influence of an electrical potential
difference used as a driving force. The transfer of the charged species is carried out according
to a mechanism of exchange of ions between the ions of the solution and the counter ions of
the membrane.
This process has been widely used for production of drinking and process water from
brackish water and seawater, treatment of industrial effluents, recovery of useful materials
from effluents and salt production (Danis, 2003; Matsuura, 2001; SenGupta, 2007;
Zagorodni, 2007). This chemical-free technology competes with reverse osmosis. It shows
better resistance to fouling and scaling. It also has an economical advantage in desalination of
low salinity solution (less than 5 g L-1 as total dissolved salts (TDS)). Also it should be kept
in mind that because of low chemicals consumption, ED is an environmental friendly process
for water desalination (Dardel, 1998).
In this chapter we are interested to study the effectiveness of the desalination process by
ED of synthetic solutions and real sample. The various parameters which can influence this
process were studied. These parameters include those related to the operation of the pilot of
electrodialysis and those related to the nature of the solution and its composition. An
energetically approach was carried out.
ELECTRO-MEMBRANE PROCESSES: OVERVIEW

The electro-membrane techniques are separative techniques implementing the ions
exchange membranes. The driving force in these processes is a gradient of electric potential
which causes an electric current and by consequence leads to the separation of ionic species.
Ion exchange is a process wherein ions of a certain charge contained in a solution (eg
cation) are removed from the solution by adsorption on a solid material (the ion exchanger),
to be replaced with an equivalent amount of other ions of similar charge emitted from the
solid. The opposite charged ions are not affected (Inglezakis & Poulopoulos, 2006; SenGupta,
2007; Zagorodni, 2007).
The ion exchange reactions are reversible and selective; they are governed by the law of
chemical equilibrium. They take place until the concentrations of various ions reach certain
specific proportions (Zagorodni, 2007).
An ion exchange membrane (IEM), also known as "ion-permeable membrane" or "ionic
membrane" generally consists of a macromolecular material, more or less crosslinked in a
three-dimensional network insoluble in water, to which are covalently attached ionized or
ionizable functional groups also called fixed ions. These groups are electrically neutralized by
mobile ions of opposite sign called compensating ions or counter ions. The co-ions are ions
having the same charge sign as the fixed sites. They are ideally excluded from transfers
298
through the membrane. Counter ions and co-ions are components of the electrolyte solution
(Figure 1). (Baker, 2004; C. Hannachi, Hamrouni, & Dhahbi, 2009; Ch Hannachi,
Bouguecha, Hamrouni, & Dhahbi, 2008; Kontturi, Murtomki, & Manzanares, 2008; Noble
& Stern, 1995; Heiner Strathmann, 2004; Yoshinobu Tanaka, 2007). The fixed ions are the
basis of the specificity of the membrane. If they are negatively charged, membrane is then
selective to cations and is then called cation exchange membrane (CEM), otherwise it is an
anion exchange membrane (AEM).
Figure 1. Structure of an ion exchange membrane (case of CEM) (Krol, 1997).
The transfer of the charged species is carried out according to a mechanism of ions
exchange between the ions of the solution and counter ions of the membrane (Baker, 2004;
Hoffman, 2003; Kontturi et al., 2008; Matsuura, 2001; Nagarale, Gohil & Shahi, 2006; Noble
& Stern, 1995; Sadrzadeh & Mohammadi, 2008; Shaposhnik, Zubets, Mill & Strigina, 2001;
H. Strathmann, 2004; Yoshinobu Tanaka, 2007; Wilhelm, 2001).
In the case of a cation exchange membrane, under the effect of an electric field,
positively charged ions (for example Na+) will move in the network of the immobilized anion
functional groups and thus will cross the membrane.
The anions for their part (for example Cl-) will be retained by the cation exchange
membrane. Effectively they will be repulsed by the anionic functional groups forming the
membrane.
In the case of an anion exchange membrane, the anions (as Cl-) will move in the network
of the cation functional group of the membrane.
Figure 2. Principle of operation of an (a) anion and (b) cation exchange membrane.
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Figure 2 illustrates the principle of operation of an (a) anion and (b) cation exchange
membrane.
Electro-membrane techniques have seen for a few years their potential fields of
application widening in an important way. This is explained by the appearance on the market
of new generations of membranes having an improved chemical resistance (Nagarale et al.,
2006).
Among these techniques we distinguish mainly:
- Electrodialysis (ED) known as conventional electrodialysis
- Electrodialysis with bipolar membrane (EDBP)
- Electro-electrodialysis (EED)
- Electrodeionisation (EDI)
THE CONVENTIONAL ELECTRODIALYSIS

1. Principle
Conventional electrodialysis (ED) is the most applied configuration among
electromembrane processes. Its basic principle was discussed earlier and is shown in figure 2.
In an electrodialysis unit, the cationic membranes (CEM, cation permeable) and anionic
membranes (AEM, anion permeable) are arranged in a parallel and alternate way.
The injection of current in the system is assured by two parallel electrodes to membranes
plan. They are placed at the ends of the electrodialysis cell.
Figure 3. Principle of conventional electrodialysis.
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The ionized dissolved species, such as salts, acids or bases, are transported across the
ionic membrane under the action of an electric current. The CEM blocks the anions and let
passing only cations. Whereas AEM blocks the cations and let anions transfers. As
consequence, two diffrents compartiments are created: concentrating compartment
(concentrate) and dilution compartement (dilute). Solutions are renewed in the compartments
by a fluid circulation parallel to membrane plan.
The principle of conventional electrodialysis is presented by Figure 3.
In industrial plants, stacks can reach several hundreds of unitaire cells in filter press
assemblies (Heiner Strathmann, 2004).
2. Operation Modes
There are four different operation modes under which can works the electrodialysis
process (MOOTGUY, 1999):
a. Continuous Mode with Direct Passage

The solution passes only once in the cell (figure 4). To achieve the desired output
concentration, a cascade of cells is used. This type of operation is also called "single pass
process."
Figure 4. Schematic diagram of a continuous process with direct passage.
b. Discontinuous Mode or Total Recirculation

The solutions are recycled in the cell until the desired output concentration is reached
(figure 5). This type of operation is also called "batch process".
Figure 5. Schematic diagram of a "batch process".
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c. Partial Recycling Mode

It is a combination of the previous two modes. A portion of the solution outlet of the cell
is recycled to the inlet (figure 6). It is also called "feed and bleed."
Figure 6. Schematic diagram of a "feed & bleed process".
d. Semi-Continuous Mode
One compartment operates continuously (direct or feed & bleed) while the other operates
in discontinuous. (Figure 7)
Figure 7. Schematic diagram of a "semi-continuous process".
3. Electrdodialysis Limitation: The Limiting Current

In electrodialysis, concentration polarization can take place at the membrane surface. The
magnitude of the concentration polarization is a function of various parameters including the
applied current density, the feed flow velocity parallel to the membrane surface, the cell
design, and the membrane properties (Ben Sik Ali, Mnif, Hamrouni, & Dhahbi, 2010; Lee,
Sarfert, Strathmann, & Moon, 2002; Lee, Strathmann, & Moon, 2006; Y. Tanaka, 2002,
2005). The transport of charged species to the anode or cathode through a set of ion exchange
membranes leads to a concentration decrease of counter-ions in the laminar boundary layer at
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the membrane surface facing the dilute cell (Csd) and an increase at the surface facing the
concentrate cell (Csc). When the ion concentration at membrane surface will approach to zero,
the current density will approach to the maximum value. At this condition the applied current
is defined as the limiting current density (LCD) (Lee et al., 2006).
Figure 8. Schematic diagram of concentration polarization in electrodialysis process.
The limiting current density in the electrodialysis process is an important parameter

which determines the electrical resistance and the current utilization. It is generally believed
that an electrodialysis process shows higher electrical resistance or lower current utilization
when operated at above LCD. It also can give rise to problems such as water dissociation or
salt precipitation. It is necessary, therefore, to determine the LCD to prevent problems and
operate the electrodialyzer successfully (Y. Tanaka, 2002).
MATERIAL AND METHODS

1. Electrodialysis Equipment and Membranes
The ED setup consists of: a power DC, a brine tank, a feed tank, an electrode rinse tank,
three centrifugal pumps (P = 84W, total head = 4.2 m) equipped each with a flowmeter and
three valves to control feed flow rate in the compartments of ED cell. Figure 9 shows a
simplified diagram of the ED setup working in continuous mode and recirculation mode.
The electrodialysis operation was carried out on a laboratory stack PCCell ED 64 002
supplied by PCA-Polymerchemie Altmeier GmbH and PCCell GmbH, Heusweiler, Germany.
ED cell is packed with ion exchange membranes (cation and anion), spacers and a pair of
electrodes (anode and cathode). Both electrodes are made of Pt/Ir- coated Titanium. The
membranes and spacers are stacked between the two electrode-end blocks. Plastic separators
are placed between the membranes to form the flow paths of the dilute and concentrate
streams. These spacers are designed to minimize boundary layer effects and are arranged in
the stack so that all the dilute and concentrate streams are manifolded separately. In this way
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a repeating section called a cell pair is formed; it consists of a cation exchange membrane, a
dilute flow spacer, an anion-exchange membrane, and a concentrate flow spacer. In this
chapter, experiments were carried out by this stack equipped with three cation exchange
membranes (CEM) and two anion exchange membranes (AEM).
Figure 9. Schematic of the ED system used in this study (a) continuous mode (b) batch recirculation
mode.
For each membrane, the active surface area is 0.0064 m2 and the flow channel width
between two membranes is 0.5 mm.
Figure 10. Schematic of the ED cell.
Table 1. Information on PCA standard cation and anion exchange membranes
Membrane
Thickness
(m)
PC-SK
PC-SA
130
90-130
Ion exchange
capacity
(meq g-1)
~1
~1.5
Chemical
stability
(pH)
0-11
0-9
Permselectivity
Functional
groups
Surface potential
( cm2)
> 0.93
> 0.96
-SO3-NR4-
0.75-3
1-1.5
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PC-SK standard cation exchange membranes and PC-SA standard anion exchange
membranes are used in the stack. Information about the membranes is given in Table 1, which
was supported by the manufacturer.
2. Reagents
Analytical grade sodium chloride, magnesium chloride, calcium chloride and sodium
sulfate salts are used in all experiments to produce solutions with known amount of salts and
electrode rinse solution. Distilled water was used throughout.
ANALYTICAL METHODS
In all the experiments, Magnesium (Mg) and calcium (Ca) amounts were determined by
atomic absorption spectroscopy using an analytical AAS Vario 6 spectrometer.
Sodium (Na) and potassium (K) were evaluated by atomic emission spectroscopy using a
Jenway PFP 7 spectrometer.
Sulfate and chloride anions were determined by ion chromatography using a Metrohm
761 Compact IC with conductivity detection (Metrohm AG, Switzerland) and chemical
suppression. The anion measurements were performed with a Metrosep anion dual 2 column
(4.675 mm) with a particle diameter of 6 m.
A conductometer (712 Conductometer, Metrohm AG, made in Switzerland) was used to
measure the electrical conductivity and temperature of samples. Water conductivity directly
depends on its salt content.
654 pH-metre (Metrohm AG, Switzerland) equipped with a glass electrode was used for
measuring pH solutions
DATA ANALYSIS
The purpose of the experiments was to study the effects of operational parameters
(voltage, flow rate, circulation mode) and water composition on ED cell performance.
All figures and tables refer to concentration changes in the dilute. The mass balance of
the ions present in the feed solution was verified for dilute, concentrate and electrode rinse
solution. Thus, data for concentrate and electrode rinse solution will not be presented in this
chapter.
1. Determination of the Demineralization Rate

In this study, the quality characteristic was the demineralization rate which can be
calculated as follow (Casademont, Farias, Pourcelly, & Bazinet, 2008; Wang, Ying, Jiang,
Yang, & Jahangir, 2009):
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ECt
DR (%) 100 1
EC0
Where DR is the demineralization rate expressed in percentage, EC0 and ECt are,
respectively, the initial and conductivity of the dilute, expressed in S cm-1.
2. Determination of the Ionics Transport Flux

The flux values were evaluated for all experimental conditions in order to compare the
transport of ions from feed to receiver phase. The flux of ion (J) was determined by using the
following equation (Ergun, Tor, Cengeloglu, & Kocak, 2008):
V C
J (mol cm2 s 1 )
A T
Where V is the volume of receiver phase (L), A is the effective membrane area (cm2),
C is the transported amount of ions at a time (mol L-1) and T is the period time (s).
3. Determination of the Specific Power Consumption
Specific power consumption (SPC) can be described as the energy needed to treat unit
volume of solution. SPC was calculated for each experimental condition using the following
equation (Kabay, Arar, Samatya, Yksel, & Yksel, 2008):
t
SPC
E I (t ) dt
0
Where E is the applied potential, I the current, V the dilute stream volume and t is the
time.
The SPC is a key parameter of desalination by electrodialysis in competing with the other
membrane processes.
4. Determination of the Limiting Current

The limiting current can be determined experimentally by plotting the electrical
resistance across the membrane stack (E I-1) or the pH value in the dilute cell as a function of
the reciprocal electric current (I-1). This is called a CowanBrown plot after its original
developers (Baker, 2004; Y. Tanaka, 2002).
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Usually, the limiting current depends on membrane and solution properties as well as on
the electrodialysis stack construction and various operational parameters such as the flow
velocity (flow rate) of the dilute solution. The set of primary tests was done to determine the
limiting current density for the operating conditions to be adopted in the study when we work
at batch recirculation mode.
Figure 11. Experimental determination of Ilim by the CowanBrown method.
RESULTS AND DISCUSSION

Desalination of Synthetic Solution
Synthetic brackish water solutions with known amount of compounds were prepared by
dissolving Sodium chloride, Calcium chloride, Magnisium chloride and Sodium sulfate in
distilled water. Ionic strength was fixed by adjusting the concentration of sodium chloride.
Prior to the experiments, pH was adjusted by the addition of 1 M HCl and/or NaOH.
In order to prevent the generation of chlorine or hypochlorite, which could be hazardous
for the electrodes, 0.1 M Na2SO4 solution, prepared by dissolving Sodium sulfate salt in
distilled water, was used as electrode rinse solution circulating in electrode compartments.
Flow rate of electrode rinse solution was fixed to 80 L h-1 for all experiments.
During the experiments, the same synthetic brackish water solutions were used as initial
concentrate and dilute solutions. Their flow rates (dilute and concentrate) were fixed at the
beginning of experiment. Total voltage drop, including voltage drop in the membrane stack as
well as on the electrodes, was also fixed at the start of the experiment.
In this chapter, only single pass process and batch process modes were studied.
Samples, to be analyzed, were collected at the inlet (before treatment) and outlet (after
treatment) of each compartment of electrodialysis cell.
In order to remove any deposits, cleaning solutions of 0.1 M HCl, 0.1 M NaOH and
distilled water were circulated through the ED cell for 30 min each at the end of experiment.
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a. Single Pass Process Mode

Effects of Applied Voltage
To study the effect of applied voltage, the ionic strength, pH, and the inlet velocity of
feed solution were fixed respectively to 0.025 M, 5, and 17 L h-1.
Conductivity and consequently salts concentration change in the dilute solution as
function of applied voltage is presented in figure 12.
We note that applied potential difference has a direct influence on the evolution of the
conductivity in dilute compartment. Indeed, an increase of this parameter leads to a decrease
of the dilute conductivity and so the salt concentration in this compartment.
Figure 12. Effect of applied voltage on dilute solution conductivity (ionic strength 0.025 M; pH 5; feed
flow rate 17 L h-1).
Figure 13. Effect of applied voltage on the demineralization rate (ionic strength 0.025 M; pH 5; feed flow
rate 17 L h-1).
308
This can be explained by the transfer of these entities between the two compartments:
dilute and concentrate. There will be a migration of ions from dilute to concentrate. This
migration is exacerbated by the increase of the applied potential across the stack.
The influence of applied voltages on the demineralization rate is presented in figure 13.
Figure 13 shows that the demineralization rate strongly depends on the applied voltage.
There are three distinguished parts in this curve. In the first part (E < 2 V) the
demineralization increases only marginally with the increasing voltage drop. Previous work
(Ben Sik Ali, Ennigrou, & Hamrouni, 2013; Ben Sik Ali et al., 2010) showed that in this
region the resistance of the stack is relatively high. The applied voltage is not so important to
overcome the resistance of membranes and to induce the transport of several ions. At these
conditions there are few transports of ions between the dilute and concentrate compartments.
This is also confirmed in figure14 which present the effect of applied voltage on ionic
transport or ionic flux. Effectively low ionic fluxes are obtained in this region.
Figure 14. Effect of applied voltage on the ionic transport (ionic strength 0.025 M; pH 5, feed flow rate
17 L h-1).
In the second part (2 V < E < 12 V), Figure 13 and 14 shows a more or less linear
increase of the demineralization rate and ionic flux. The transport of ions between the
compartments of cell is proportional to current.
In the third part (E > 12 V), the increase in the applied voltage does not lead to a
significant increase in the demineralization rate and ionic flux. At this point the limiting
current density is reached and there is no increase in the current density neither ionic transport
from dilute to concentrate compartment when the applied voltage increases. In this range of
applied voltage and as it is shown in Figure 15, the current efficiency decreases by increasing
the applied voltage. The induced current is not only used to ions transport but also to split
water. Same results were obtained by Ben Sik Ali et al.(Ben Sik Ali et al., 2013; Ben Sik Ali
et al., 2010).
As shown in Figure 16, the specific power consumption increases by increasing the
applied voltage. It is low in the first region (0-2 V). This is expected because the specific
power consumption depends of the applied voltage and current which were weak.
309
Figure 15. Effect of applied voltage on the current efficiency (ionic strength 0.025 M; pH 5; feed flow
rate 17 L h-1).
Figure 16. Effect of applied voltage on the specific power consumption (ionic strength 0.025 M; pH 5;
feed flow rate 17 L h-1).
Effects of Flow Rate

The ionic strength and pH of feed solution were fixed respectively at 0.025 M and 7. The
flow rate of dilute compartment was varied from 5 to 15 L h-1. Experiments were performed
by applying 2, 5 and 8 V each time across the entire assembly. The influences of the flow rate
on the ED performances are illustrated in figure 17, 18, 19 and 20.
In figure 17 we notice that the DR decreases with an increase of the flow rate. This can
be explained by the remaining time of ions inside the different compartments of the cell. In
fact the ions have more time to be transferred from one compartment to another thought the
membrane when the velocity or flow rate is lower. This can lead to an increase of the total
amount of salts transferred and consequently to an increase of separation percentage. These
310
interpretations are confirmed in figure 18. In fact the ionic flux transport of salts decreases by
the increase of the feed flow rates. For that, low flow rates are recommended to get maximum
separation
Figure 17. Effect of flow rate on the demineralization rate (ionic strength 0.025 M; pH 7).
Figure 18. Effect of flow rate on the ionic flux (ionic strength 0.025 M; pH 7).
311
Figure 19. Effect of flow rate on current efficiency (ionic strength 0.025 M; pH 7).
Figure 20. Effect of flow rate on the specific power consumption (ionic strength 0.025 M; ; pH 7).
In other hand and as depicted in figure 19 the current efficiency is not affected by the
variation of flow rate in these conditions. All current was used to transport salts.
As illustrated in figure 20 the specific power consumption is higher for low flow rate.
However, in this case, SPC amount is still relatively low.
Effects of Ionic Strength

The effect of the feed solution ionic strength on the removal of salts was investigated
using aqueous solutions at various concentrations of NaCl salt. The ionic strength of feed
solution was varied from 5 10-4 M to 5 10-2 M. The pH of prepared solutions was fixed to 7.
The flow rate of dilute and concentrate were fixed to 12 L h-1. 2, 5 and 8 V was respectively
312
applied across the entire assembly. Figures 21, 22, and 23 represent the effects of the ionic
strength of feed solution on electrodialysis performances.
As shown in figure 21 the demineralization rate has a considerable dependency on the
feed solution ionic strength. Effectively at some hydrodynamique and electrical conditions an
increase of the initial ionic strength or salts concentration leads to the decrease of the DR. As
depicted on figure 22 the number of ions transported through the membranes is almost the
same but total amounts of salts are quite different from the different treated solution. As
known the calculation of DR depends strongly on the initial feed concentrations and the
amount of transported ions. So the DR evolves reciprocally to the initial feed concentration at
some hydrodynamique and electrical conditions.
Figure 21. Effect of ionic strength on the demineralization rate (flow rate 12 L h-1; pH 7).
Figure 22. Effect of ionic strength on the ionic flux (flow rate 12 L h-1; pH 7).
313
Figure 23. Effect of ionic strength on the specific power consumption (flow rate 12 L h-1; pH 7).
Figure 24. Experimental determination of Ilim by the CowanBrown method. (ionic strength 0.01 M; feed
flow rate 15 L h-1).
314
As depicted in figure 23 the specific power consumption are low for lowest initial feed
concentration and mainly for lowest applied voltage. In other hand the current efficiency is
not affected by the variation of flow rate in these conditions. All current was used to transport
salts.
It was not possible to increase the ionic strength of initial feed solution above 0.05 M
since an electrode overheating appeared in the present system as a result of the increase of
cell conductivity. The DR was very low and insignificant. For these reasons it is suitable to
use this process for the demineralization of solution with salinity under 0.05 M.
b. Batch Process Mode

Determination of the Limiting Current (Ilim)
In this study the limiting current (Ilim) was determined by measuring the potential and the
cell resistance as a function of the applied current. Figure 24 shows the curves illustrating the
determination of the limiting current from the experimental result obtained with a 0.01 M
NaCl solution and a feed flow velocity of 15 L h-1. In the relationship between the dilute pH
and the current in figure 24 (a), the limiting current was determined where the slope was
changed due to water dissociation on the surface of ion exchange membranes (Baker, 2004;
Lee et al., 2006). In addition, the limiting current was determined from the graph showing the
cell resistance versus the reciprocal of the current (figure 24 (b)).
NaCl Solutions with different concentrations were used to determine these values at
different flow rates. The obtained results were summarized in Table 2.
Table 2. Limiting current values as function of flow rate and feed concentration
Flow rate (L h-1)
5
15
25
30
Feed solution concentration (g L-1)

0.5
1
1.5
0.2
0.4
0.82
0.34
0.62
0.98
0.46
0.86
1.15
0.52
1
1.26
2.5
1.16
1.52
1.96
2.2
The applied current in all experiment was fixed from the beginning to a value below the limiting current
(I = 0.8 Ilim)(Balmann & Casademont, 2006).
Effect of Initial Feed Concentration

The effect of initial feed concentration on the desalination process was investigated using
aqueous solutions at various concentrations of NaCl salt (0.01, 0.02, 0.03 and 0.05 M) and
fixed flow rate of 25 L h-1. As shown in Figures 25, 26 and 27, the initial salt concentration
has a significant effect on the process efficiency. The most important observation is that total
process time increased by increasing initial concentration in the feed. Consequently the
specific power consumption is closely depending on it as seen in Figure 27.
The ionic flux also is closely depending on the initial ionic strength of solution. Higher
ions transfert were obtained for highest initial concentration. These results can be explained
by the increase of number of ions in solutions when the concentration of salts increases. As a
result a better transfer throught membrane can appear.
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Figure 25. Effect of ionic strength on the demineralization rate (flow rate 25 L h-1).
Figure 26. Effect of ionic strength on the ionic flux (flow rate 25 L h-1).
Effect of Feed Flow Rate

The operation was carried out using different feed flow rates (5, 15, 25 and 30 L h-1) and
a solution with 0.05 M as ionic strength.
As seen in figure 28, flow rate has a significant effect on desalination process in the range
studied. Fewer flow rates were better for the performance of ED as was believed by
Sadrzadeh et al. (2007) (Sadrzadeh, Razmi, & Mohammadi, 2007). This was because the
treated solution could stay longer in the ED device and the ions could transfer freely in the
membrane. However, the ions had relative shorter retention time in the dilute tank at high
flow rate, which resulted in lower removal efficiency (Wang et al., 2009).
In other hand and as depicted in figure 29 the specific power consumption depends also
on this parameter. The SPC is lower for low flow rate. In fact the SPC depends mainly on two
parameters: the applied current and the time of experiment. Firstly the applied current (the
limiting current) is depending on the flow rate as shown in Table 3. It is lower for low flow
rate. Secondly the experiment time to obtain the same results (removal 85 % of salt)
augmented by increasing the flow rate.
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Figure 27. Effect of ionic strength on the specific power consumption (flow rate 25 L h-1).
Figure 28. Effect of flow rate on the demineralization rate (ionic strength 0.05 M).
Figure 29. Effect of flow rate on the specific power consumption (ionic strength 0.05 M).
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Effect of Coexisting Ions

In this section, we will study the demineralization of saline solutions containing multiple
anionic and cationic species. These solutions were prepared by dissolving: NaCl, MgCl2,
CaCl2 and Na2SO4 in distilled water.
The total salt concentration of different solutions and their flow rates were set at the
starting of the experiment respectively to 3 g L-1 and 25 L h-1.
The current between the electrodes was imposed and maintained constant. It was equal to
80% of the limiting current. The end of the experiment was announced by the obtention of a
dilute solution with a total salt concentration less than 0.5 g L-1 or conductivity lower than
400 S cm-1.
Figure 30 illustrates the variation of demineralization rates over time during the
desalination of solutions of different compositions. From these curves we find that the
presence of several salts affects the demineralization rate. Indeed, at same total dissolved salts
amount (TDS), demineralization rate decreases when more various salts are present. As
consequence, the duration of the desalination process increases.
The evolution of the energy consumption and the desalination process total duration of
studied solutions are presented in figure 31.
Figure 30. Demineralization rate variation as a function of time during the desalination of solutions of
different compositions (ionic strength 0.05 M; I: 1.96 A; feed flow rate 25 L h-1)
From this figure we see that the total duration of the process increases with the addition
of salts. In fact, for a solution containing only sodium chloride, the dilute can achieve
desirable salinity after 60 min, when 90 min is required to achieve the same salinity for a
solution containing a mixture of several salts.
What is also remarkable is that the energy consumption increases for solutions containing
various salts. This is expected since the energy consumption is defined as a function of time
on the one hand and the increase in cell resistance on the other hand.
We proposed to study the behavior of each species during the desalination of a brackish
solution containing various salts. For this we have traced the evolution of the ion flux of each
species over time in Figure 32.
318
Figure 31. Evolution of the specific power consumption and the desalination process duration of
solutions with different compositions (ionic strength 0.05 M; I 1.96 A; feed flow rate 25 L h-1).
Figure 32. Variation of the ionic flux of Ca2+, Mg2+ and SO42- versus time during the desalination
process. (Flow rate 25 L h-1, TDS 3 g L-1, I 1.96 A).
From this curve, we see that the ion fluxes of cations (Ca2+ and Mg2+) are relatively
higher than those of anions (SO42-). In addition, in the presence of calcium, magnisium ions
were preferentially transported. This is reflected by their higher fluxes.
It was found that all ion fluxes decreased over time. This is due to the depletion of the
solution from salts.
As shown in Figure 33, the effect of magnesium ions is clearly visible on the calcium
ions transfer. Indeed, the presence of magnesium ions greatly reduces the transfer of calcium
ions especially at the beginning of the desalination process.
319
Figure 33. Variation of the Ca2+ ionic flux versus time during the desalination process of solutions with
various compositions. (Flow rate 25 L h-1; TDS 3 g L-1; [Ca2+] 0.01 M; I 1.96 A).
This indicates that there is competition between these two ions with same valence during
their transfer through ion exchange membranes. This competition is reduced at the end of the
process because the solution is depleted of ions at this level.
The competition between the two ionic species can also be deduced from the figure 34
showing the variation of the current efficiency for the transport of calcium ions as a function
of time for solutions containing different fractions of magnesium ions. Indeed, the increase in
this fraction causes the decrease of current efficiency. Thus, the current is no longer used only
for the transport of Ca2+ ions, but it is divided between the two species.
Figure 34. Variation of the current efficiency for the calcium ions transport as a function of time for
solutions containing different fractions of magnesium ions (Flow rate 25 L h-1; TDS 3 g L-1; [Ca2+] 0.01
M; I 1.96 A).
320
Figure 35. Variation of specific power consumption as a function of time for solutions containing
different fractions of magnesium ions (Flow rate 25 L h-1; TDS 3 g L-1; [Ca2+] 0.01 M; I 1.96 A).
Concerning energy consumption, the addition of Mg ions does not have a significant
effect on this parameter as shown in Figure 35. But, as the demineralization rate, it causes a
slight increase in the total duration of the desalination process.
The presence of divalent anions may also have an effect on the desalination process. To
perform the study we have prepared solutions with different amounts of sulfates. Calcium
concentration and total dissolved salts were respectively set at 0.01 M and 0.05 M. We added
sulfate ions at different fraction by dissolving Na2SO4 in these solutions.
Figure 36 illustrates the variation of demineralization rate as function of time during the
desalination of prepared solutions. From these curves we find that the presence of sulfate ions
affects the demineralization rate. Indeed, the addition of these anions decreases the process
efficiency. It causes also a slight increase in the total duration of the desalination process.
But the effect of sulfate ions is clearly visible on the calcium ionic transfer as is shown in
Figure 37. Indeed, the presence of these anions largely reduces the transfer of calcium ions
especially at the beginning of the desalination process. An increase in the fraction, especially
beyond seventh, sulfate ions reduces the transfer of calcium ions at very low fluxes. These
rates remain fairly constant over time. This result encouraged us to study the transfer of
calcium and sulfate ions analogous as shown in Figure 38.
From figure 38, we find that calcium ions transfer fluxes increases slightly over time
unlike that of sulfate ions.
We also note that these fluxes are relatively low (~10-8 mol cm-2 s-1) when compared to
those in the absence of sulfate ions (~ 10-7 mol cm-2 s-1).
This result can be interpreted by the fact that in the presence of bivalent anions, Ca ions
are retained in the dilute. Apparently the mobility of these cations is decreased. A mutual
interaction between the oppositely charged ions can take place.
As shown in figure 39, the effect of the addition of anions on the current efficiency for
the transport of Ca2+ is also clear.
321
This efficiency decreases more and more with increasing the molar fraction of the SO42ions in the solution. Thus the current is no longer used only for the transport of Ca2+ ions, but
it is divided between the two species.
Concerning energy consumption, the addition of sulfate ions does not have a significant
effect on this parameter as shown in Figure 40. But, as the demineralization rate, it causes a
slight increase in the total duration of the desalination process.
Figure 36. Variation of demineralization rate as a function of time for solutions containing different
fractions of sulfate ions (Flow rate 25 L h-1; TDS 3 g L-1; [Ca2+] 0.01 M; I 1.96 A).
Figure 37. Variation of the Ca2+ ionic flux versus time during the desalination process of solutions with
various compositions. (Flow rate 25 L h-1; TDS 3 g L-1; [Ca2+] 0.01 M; I 1.96 A).
322
Figure 38. Variation of the Ca2+ and SO42- ionic fluxes versus time during the desalination process.
(Flow rate 25 L h-1, TDS 3 g L-1, [Ca2+] 0.01 M; [SO42-] 0.002 M; I 1.96 A).
Figure 39. Variation of the current efficiency for the transport of calcium ions as a function of time for
solutions containing different fractions of sulfate ions (Flow rate 25 L h-1, TDS 3 g L-1, [Ca2+] 0.01 M; I
1.96 A).
c. Desalination of the Real Water Sample

Brackish water sample with total dissolved salts TDS around 15 g L-1 was taken from
groundwater in the region of Borj-Cdria (Tunis City - Tunisia). Since an electrode
overheating can occur in the ED system for the treatment of solution with relatively high
323
salinity (TDS over 5 g L-1), the sample was diluted by mixing it with raw water to reduce the
total salinity until 5 g L-1. The physico-chemistry characteristics of obtained sample are given
in Table 3.
Figure 40. Variation of specific power consumption as a function of time for solutions containing
different fractions of sulfate ions (Flow rate 25 L h-1, TDS 3 g L-1, [Ca2+] 0.01 M; I 1.96 A).
Table 3. Composition, pH and conductivity of brackish water Sample

Physico-chemistry parameter
Conductivity at 25 C (S cm-1)
pH
F- (mg L-1)
Cl- (mg L-1)
HCO3- (mg L-1)
NO3- (mg L-1)
SO42- (mg L-1)
Na+ (mg L-1)
K+ (mg L-1)
Ca2+ (mg L-1)
Mg2+ (mg L-1)
TDS (mg L-1)
5 008
7.2
2.9
2 674
202
225
707
1041
300
235
127.6
5 424
From this table, we can see that the water is rich in sulfate as well as chloride ions. It also
contains high levels of calcium and magnesium.
The present section is dealing with the desalination of the resulting solution by
electrodialysis in batch process mode. The flow rates were set at the outset to 25 L h-1. An
electric current of 1.96 A is applied and maintained constant between the electrodes cell
terminals.
324
We followed the changes in the demineralization rate and ionic fluxes of predominant
species namely calcium, magnesium and sulfate in solution over time.
Figure 41 illustrates the variation in demineralization rate as function of time during the
desalination process.
Figure 41. Variation of demineralization rate as a function of time during the desalination of brackish
solution (I 1.96 A; Flow rate 25 L h-1).
From this graph we see that the demineralization rate increases over time. The desired
salinity is practically obtained after 85 min.
Figure 42. Variation of ionic flux as a function of time during the desalination of brackish solution (I
1.96 A; Flow rate 25 L h-1).
We proposed to study the behavior of each species in these conditions. For this purpose,
we have traced the evolution of the ionic flux of each species over time in Figure 42.
From Figure 42, we note that the ionic fluxes of cations (Ca2+ and Mg2+) are relatively in
the same order of scale (10-8 mol cm-2 s-1) and even slightly lower than those of anions
325
(sulfates). This result is different from what was found in thedesalination of synthetic
solutions containing a mixture of these three ions. This can be explained by the fact that other
ions in solution, such as bicarbonates and nitrates, also influence the transport of the studied
species. Concerning the energy consumption, there is an increase in this parameter over time.
Energy consumption at the end of the experiment (about 35 W h L-1) is equivalent to that
found in the case of desalination of a synthetic solution containing a mixture of calcium,
magnesium and sulfate ions.
Figure 43. Variation of specific power consumption as a function of time during the desalination of
brackish solution (I 1.96 A; Flow rate 25 L h-1).
Table 4. Composition, pH and conductivity of brackish water sample,

treated solution and WHO recommended solution for drinking water
Physico-chemistry parameter
Conductivity at 25 C (S cm )
pH
F- (mg L-1)
Cl- (mg L-1)
5 008
7.2
2.9
2 674
Treated
solution
0.808
5.1
0.22
189
HCO3- (mg L-1)

NO3- (mg L-1)
SO42- (mg L-1)
Na+ (mg L-1)
202
225
707
1041
202
25.5
24.67
49.92
50
400
250
K+ (mg L-1)
Ca2+ (mg L-1)
Mg2+ (mg L-1)
300
235
127.6
24.23
14.03
12.72
TDS (mg L-1)
5 424
350
500
Sample
-1
Who recommendation
6.5-8.5
1.5
250
326
The physico-chemical characteristics of the sample, the desalted solution and

recommendations of the World Health Organization (WHO) for drinking water are
summarized in the following table (WHO, 2008):
Comparing different solutions, we find that the resulting solution with a pH adjustment is
consistent with the recommendations of the World Health Organization for drinking water.
This proves the efficiency of electrodialysis process for the desalination of brackish water to
produce drinking water.
CONCLUSION
In this chapter it has been showed that the desalination of brackish water by conventional
electrodialysis is depending on several parameters.
The applied voltage, the feed flow rate and the ionic strength of the feed solution have a
significant effect on the process efficiency and mainly on the demineralization rate and power
consumption.
Working in single pass process mode, on which the solution passes only once in the
electrodialysis cell, the decrease of the flow rate and ionic strength induces better
performances. However an increase of applied voltage and taking into account to work under
limiting current density gives acceptable efficiency.
In this configuration, the maximum desalination rate does not exceed the 55% and a
second electrodialysis stage is required to enhance the process efficiency.
A study of another configuration was carried out. This configuration is the discontinuous
mode or total recirculation mode (batch process). In this mode, the solutions are recycled in
the cell until the desired concentration is reached.
In the first configuration, the applied voltage, the feed flow rate and the ionic strength of
the feed solution have also significant effect on the process efficiency. While working with
this mode, the desalination rates of various solutions reached quickly high values. Indeed,
they exceeded the 75% in a few minutes.
This study also revealed that the composition of the solution itself influences the
effectiveness of desalination process. In fact, the transfer of ions from a compartment to
another depends on the various ionic species present in solution.
The presence of the calcium ions largely decreased the transfer of the magnesium ions
and vice versa. This is interpreted by the fact that two ions of same valence enter in
competition during their transfers through exchanging membranes.
Moreover, the rates of transfer of the cations and more precisely calcium and magnesium
ions undergo reductions in the presence of anions and in particular sulfate ions. The desired
rates of desalination are also obtained for longer handling times. The consequence is
immediate on energy consumption. Indeed the consumption of energy is more important for
more complex solutions.
The process was applied for the treatment of real brackish water sample. With 30 W h L-1
as specific power consumption, the concentrations of different species in the obtained treated
water are below the recommended amounts by World Health Organization for drinking water.
327
REFERENCES
Alghoul, M. A., Poovanaesvaran, P., Sopian, K., & Sulaiman, M. Y. (2009). Review of
brackish water reverse osmosis (BWRO) system designs. Renewable and Sustainable
Energy Reviews, 13(9), 2661-2667.
Baker, R. W. (2004). Membrane technology and applications (2 ed.). England: John Wiley &
Sons, Ltd.
Balmann, Hlne Roux De, & Casademont, Ernest. (2006). lectrodialyse. Techniques de
lIngnieur, J 2840(J 2840).
Ben Sik Ali, M., Ennigrou, D. J., & Hamrouni, B. (2013). Iron removal from brackish water
by electrodialysis. Environmental Technology (United Kingdom).
Ben Sik Ali, M., Mnif, A., Hamrouni, B., & Dhahbi, M. (2010). Electrodialytic desalination
of brackish water: effect of process parameters and water characteristics. Ionics, 1-9.
Casademont, C., Farias, M. A., Pourcelly, G., & Bazinet, L. (2008). Impact of electrodialytic
parameters on cation migration kinetics and fouling nature of ion-exchange membranes
during treatment of solutions with different magnesium/calcium ratios. Journal of
Membrane Science, 325(2), 570-579.
Ct, P., Weirun, Z., Gierlich, H. H., Natarajan, P., & Taniguchi, Y. (1996). State-of-the-art
techniques in reverse osmosis, nanofiltration and 1 electrodialysis in drinking-water
supply. Water Supply, 14(3-4), 289-319.
Danis, Patrick. (2003). Dessalement de leau de mer Techniques de lIngnieur, trait Gnie
des procds, J2700.
Dardel, Franois De. (1998). change dions Principes de base. Techniques de lIngnieur,
trait Gnie des procds, J 2 783.
El-Dessouky, Hisham T., & Ettouney, Hisham M. (2002). Fundamentals of Salt Water
Desalination. Amsterdam, The Netherlands: Elsevier Science B.V.
Ergun, E., Tor, A., Cengeloglu, Y., & Kocak, I. (2008). Electrodialytic removal of fluoride
from water: Effects of process parameters and accompanying anions. Separation and
Purification Technology, 64(2), 147-153.
Greenlee, Lauren F., Lawler, Desmond F., Freeman, Benny D., Marrot, Benoit, & Moulin,
Philippe. (2009). Reverse osmosis desalination: Water sources, technology, and today's
challenges. Water Research, 43(9), 2317-2348.
Hannachi, C., Hamrouni, B., & Dhahbi, M. (2009). Ion exchange equilibrium between cation
exchange membranes and aqueous solutions of K+/Na+, K+/Ca2+, and Na+/Ca2+.
Ionics, 15(4), 445-451.
Hannachi, Ch, Bouguecha, S., Hamrouni, B., & Dhahbi, M. (2008). Ion exchange equilibrium
between ion exchange membrane and electrolyte solutions. Desalination, 221(1-3), 448454.
Hoffman, E. J. (2003). Membrane Separations Technology: Single-Stage, Multistage, and
Differential Permeation: Elsevier Science & Technology Books
Inglezakis, V.J., & Poulopoulos, S.G. (2006). Adsorption, Ion Exchange and Catalysis:
Design of Operations and Environmental Applications. Amesterdam, The Netherlands:
Elsevier Science.
328
Kabay, Nalan, Arar, zgr, Samatya, Saba, Yksel, mran, & Yksel, Mithat. (2008).
Separation of fluoride from aqueous solution by electrodialysis: Effect of process
parameters and other ionic species. Journal of Hazardous Materials, 153(1-2), 107-113.
Kontturi, Kysti, Murtomki, Lasse, & Manzanares, Jos A. (2008). Ionic Transport
Processes In Electrochemistry and Membrane Science. New York: Oxford University
Press Inc.
Krol, John Jacco. (1997). Monoplolar and bipolar ion exchange membranes: Mass transport
limitations. (Thesis), Universit Twente.
Lee, Hong-Joo, Sarfert, F., Strathmann, H., & Moon, Seung-Hyeon. (2002). Designing of an
electrodialysis desalination plant. Desalination, 142(3), 267-286.
Lee, Hong-Joo, Strathmann, Heiner, & Moon, Seung-Hyeon. (2006). Determination of the
limiting current density in electrodialysis desalination as an empirical function of linear
velocity. Desalination, 190(1-3), 43-50.
Matsuura, Takeshi. (2001). Progress in membrane science and technology for seawater
desalination -- a review. Desalination, 134(1-3), 47-54.
Mootguy, Philippe. (1999). Modlisation du fonctionnement d'une lectrodialyseur
membrane l'aide du logiciel Flux-Expert. (Thesis), cole Centrale de Paris Paris.
Nagarale, R. K., Gohil, G. S., & Shahi, V. K. (2006). Recent developments on ion-exchange
membranes and electro-membrane processes. Advances in Colloid and Interface Science,
119(2-3), 97-130.
Noble, Richard D., & Stern, S. Alexander. (1995). Membrane separations technologies
Principles and Applications Amsterdam: Elsevier Science B.V.
Sadrzadeh, M., & Mohammadi, T. (2008). Sea water desalination using electrodialysis.
Desalination, 221(1-3), 440-447.
Sadrzadeh, M., Razmi, A., & Mohammadi, T. (2007). Separation of different ions from
wastewater at various operating conditions using electrodialysis. Separation and
Purification Technology, 54(2), 147-156.
SenGupta, Arup K. (2007). Ion exchange and solvant extraction A Series of Advances (Vol.
18). Boca Raton, Florida: CRC Press.
Shaposhnik, V. A., Zubets, N. N., Mill, B. E., & Strigina, I. P. (2001). Demineralization of
water by electrodialysis with ion-exchange membranes, grains and nets. Desalination,
133(3), 211-214.
Strathmann, H. (2004). Ion-Exchange Membrane Separation Processes (Vol. 9). Amsterdam,
The Netherlands Elsevier.
Strathmann, Heiner. (2004). Ion-exchange membranes separation processes (Vol. 9).
Amsterdam: Elsevier B.V.
Tanaka, Y. (2002). Current density distribution, limiting current density and saturation
current density in an ion-exchange membrane electrodialyzer. Journal of Membrane
Science, 210(1), 65-75.
Tanaka, Y. (2005). Limiting current density of an ion-exchange membrane and of an
electrodialyzer. Journal of Membrane Science, 266(1-2), 6-17.
Tanaka, Yoshinobu. (2007). Ion Exchange Membranes: Fundamentals and Applications (Vol.
12). Oxford, UK: Elsevier.
Wang, Q., Ying, T., Jiang, T., Yang, D., & Jahangir, M. M. (2009). Demineralization of
soybean oligosaccharides extract from sweet slurry by conventional electrodialysis.
Journal of Food Engineering, 95(3), 410-415.
329
WHO. (2008). Guidelines for drinking-water quality. In W. H. Organization (Ed.), (3 ed.,

Vol. 1, pp. 375-492).
Wilhelm, Friedrich Georg. (2001). Bipolar Membrane Electrodialysis: Membrane
development and transport caracteristics. (Ph.D. thesis), University of Twente,
Enschede, the Netherlands. Retrieved from www.tup.utwente.nl/uk/catalogue/
technical/electrodialysis
Zagorodni, Andrei A. (2007). Ion Exchange Materials Properties and Applications. Oxford,
UK: Elsevier BV.

ISBN: 978-1-63117-329-5
Chapter 11
APPROPRIATE TIME SCALE FOR AGGREGATING

CLIMATIC DATA TO PREDICT FLOWERING
AND BOLL SETTING BEHAVIOR OF COTTON
Zakaria M. Sawan*
Cotton Research Institute, Agricultural Research Center,
Ministry of Agriculture and Land Reclamation, Giza, Egypt
ABSTRACT
This study covers the predicted effects of climatic factors during convenient intervals
(in days) on cotton flower and boll production compared with daily observations.
maximum air temperature, are the important climatic factors that significantly affect
flower and boll production. The least important variables were found to be surface soil
temperature at 0600 h and minimum temperature. The five-day interval was found to be
more adequately and sensibly related to yield parameters. There was a negative
correlation between flower and boll production and either evaporation or sunshine
duration, while that correlation with minimum relative humidity was positive. Higher
minimum relative humidity, short period of sunshine duration, and low temperatures
enhanced flower and boll formation.
Keywords: Cotton flower and boll production, boll retention, evaporation, relative humidity,
sunshine duration, temperature
ABBREVIATIONS
ET
ETmax
Evapotranspiration
Maximum Evapotranspiration
* Email: zmsawan@hotmail.com
332
Zakaria M. Sawan
PGR
TKW
plant growth regulator

thermal kinetic window
1. INTRODUCTION
Climate affects crop growth interactively, sometimes resulting in unexpected responses to
prevailing conditions. Many factors, such as length of the growing season, climate (including
solar radiation, temperature, light, wind, rainfall, and dew), cultivar, availability of nutrients
and soil moisture, pests and cultural practices affect cotton growth (El-Zik, 1980). The
balance between vegetative and reproductive development can be influenced by soil fertility,
soil moisture, cloudy weather, spacing and perhaps other factors such as temperature and
relative humidity (Guinn, 1982). Weather, soil, cultivars, and cultural practices affect crop
growth interactively, sometimes resulting in plants responding in unexpected ways to their
conditions (Hodges et al. 1993).
Water is a primary factor controlling plant growth. Xiao et al. (2000) stated that, when
water was applied at 0.85, 0.70, 0.55 or 0.40 ET (evapotranspiration) to cotton plants grown
in pots, there was a close relationship between plant development and water supply. The fruitbearing branches, square and boll numbers and boll size were increased with increased water
supply. Barbour and Farquhar (2000) reported on greenhouse pot trials where cotton cv. CS50
plants were grown at 43 or 76% relative humidity (RH) and sprayed daily with abscisic acid
(ABA) or distilled water. Plants grown at lower RH had higher transpiration rates, lower leaf
temperatures and lower stomatal conductance. Plant biomass was also reduced at the lower
RH. Within each RH environment, increasing ABA concentration generally reduced stomatal
conductance, evaporation rates, superficial leaf density and plant biomass, and increased leaf
temperature and specific leaf area.
Temperature is also a primary factor controlling rates of plant growth and development.
Burke et al. (1988) has defined the optimum temperature range for biochemical and metabolic
activities of plants as the thermal kinetic window (TKW). Plant temperatures above or below
the TKW result in stress that limits growth and yield. The TKW for cotton growth is 23.5 to
32C, with an optimum temperature of 28C. Biomass production is directly related to the
amount of time that foliage temperature is within the TKW.
Reddy et al. (1995) in growth chamber experiments found that Pima cotton cv. S-6
produced lower total biomass at 35.5C than at 26.9C and no bolls were produced at the
higher temperature of 40C. Schrader et al. (2004) stated that high temperatures that plants
are likely to experience inhibit photosynthesis. Zhou et al. (2000) indicated that light duration
is the key meteorological factor influencing the wheat-cotton cropping pattern and position of
the bolls, while temperature had an important function on upper (node 7 to 9) and top (node
10) bolls, especially for double cropping patterns with early maturing varieties.
In Texas, Guo et al. (1994) found that plant growth and yield of the cotton cv. DPL-50
(Upland cotton) were less in a humid area than in an arid area with low humidity. Under arid
conditions, high vapor pressure deficit resulted in a high transpiration rates, low leaf water
potential and lower leaf temperatures. Gipson and Joham (1968) mentioned that cool
temperatures (< 20C) at night slowed boll development. Fisher (1975) found that high
temperatures can cause male sterility in cotton flowers, and could have caused increased boll
Appropriate Time Scale for Aggregating Climatic Data to Predict Flowering
333
shedding in the late fruiting season. Zhao (1981) indicated that temperature was the main
climatic factor affecting cotton production and 20-30C was the optimum temperature for
cotton growth.
Hodges et al. (1993) found that the optimum temperature for cotton stem and leaf growth,
seedling development, and fruiting was almost 30C, with fruit retention decreasing rapidly
as the time of exposure to 40C increased.
Reddy et al. (1998) found that when Upland cotton (G. hirsutum) cv. DPL-51 was grown
in naturally lit plant growth chambers at 30/22C day/night temperatures from sowing until
flower bud production, and at 20/12, 25/17, 30/22, 35/27 and 40/32C for 42 days after flower
bud production, fruit retention was severely curtailed at the two higher temperatures
compared with 30/22C. Species/cultivars that retain fruits at high temperatures would be
more productive both in the present-day cotton production environments and even more in
future warmer world.
This study aimed at predicting effects of climatic factors during different convenient
intervals (in days) on cotton flower and boll production compared with daily observations.
The study presents a rich effort focused on evaluating the efficacy of regression equations
between cotton crop data and climatic data grouped at different time intervals, to determine
the appropriate time scale for aggregating climate data to be used for predicting flower and
boll production in cotton (Sawan et al., 2006). This could result in formulating advanced
predictions as for the effect of certain climatic conditions on production of Egyptian cotton.
Minimizing the deleterious effects of the factors through utilizing proper cultural practices
will lead to improved cotton yield (Sawan et al., 2010).
2. DATA AND METHODS

Two uniform field trials were conducted at the experimental farm of the Agricultural
Research Center, Ministry of Agriculture, Giza, Egypt (30oN, 31o: 28E at an altitude of 19
m), using the cotton cultivar Giza 75 (Gossypium barbadense L.) in 2 successive seasons (I
and II). The soil texture was a clay loam, with an alluvial substratum (pH = 8.07, 42.13%
clay, 27.35% silt, 22.54% fine sand, 3.22% coarse sand, 2.94% calcium carbonate and 1.70%
organic matter) (Sawan et al., 2010).
In Egypt, there are no rain-fed areas for cultivating cotton. Water for the field trials was
applied using surface irrigation. Total water consumed during each of two growing seasons
supplied by surface irrigation was about 6,000-m h-1. The criteria used to determine amount
of water applied to the crop depended on soil water status. Irrigation was applied when soil
water content reached about 35% of field capacity (0-60 cm). In season I, the field was
irrigated on 15 March (at planting), 8 April (first irrigation), 29 April, 17 May, 31 May, 14
June, 1 July, 16 July, and 12 August. In season II, the field was irrigated on 23 March
(planting date), 20 April (first irrigation), 8 May, 22 May, 1 June, 18 June, 3 July, 20 July, 7
August and 28 August. Techniques normally used for growing cotton in Egypt were followed.
Each experimental plot contained 13 to 15 ridges to facilitate proper surface irrigation. Ridge
width was 60 cm and length was 4 m. Seeds were sown on 15 and 23 March in seasons I and
II, respectively, in hills 20 cm apart on one side of the ridge. Seedlings were thinned to 2
plants per hill 6 weeks after planting, resulting in a plant density of about 166,000 plants ha-1.
334
Zakaria M. Sawan
Phosphorus fertilizer was applied at a rate of 54 kg P2O5 ha-1 as calcium super phosphate
during land preparation. Potassium fertilizer was applied at a rate of 57 kg K2O ha-1 as
potassium sulfate before the first irrigation (as a concentrated band close to the seed ridge).
Nitrogen fertilizer was applied at a rate of 144 kg N ha-1 as ammonium nitrate in two equal
doses: the first was applied after thinning just before the second irrigation and the second was
applied before the third irrigation. Rates of phosphorus, potassium, and nitrogen fertilizer
were the same in both seasons. These amounts were determined based on the use of soil tests
(Sawan et al., 2010).
After thinning, 261 and 358 plants were randomly selected (precaution of border effect
was taken into consideration by discarding the cotton plants in the first and last two hills of
each ridge) from 9 and 11 inner ridges of the plot in seasons I, and II respectively. Pest
control management was carried out on an-as-needed basis, according to the local practices
performed at the experimental station (Sawan et al., 2010).
Flowers on all selected plants were tagged in order to count and record the number of
open flowers, and set bolls on a daily basis. The flowering season commenced on the date of
the first flower appearance and continued until the end of flowering season (31 August). The
period of whole September (30 days) until the 20th of October (harvest date) allowed a
minimum of 50 days to develop mature bolls. In season I, the flowering period extended from
17 June to 31 August, whereas in season II, the flowering period was from 21 June to 31
August. Flowers produced after 31 August were not expected to form sound harvestable bolls,
and therefore were not taken into account (Sawan et al., 2010).
For statistical analysis, the following data of the dependent variables were collected:
number of tagged flowers separately counted each day on all selected plants (Y1), number of
retained bolls obtained from the total daily tagged flowers on all selected plants at harvest
(Y2), and (Y3) percentage of boll retention ([number of retained bolls obtained from the total
number of daily tagged flowers in all selected plants at harvest]/[daily number of tagged
flowers on each day in all selected plants] x 100).
As a rule, observations were recorded when the number of flowers on a given day was at
least 5 flowers found in a population of 100 plants and this continued for at least five
consecutive days. This rule omitted eight observations in the first season and ten observations
in the second season. The number of observations (n) was 68 (23 June through 29 August)
and 62 (29 June through 29 August) for the two seasons, respectively (Sawan et al., 2010).
The climatic factors (independent variables) considered were daily data of: maximum air
temperature (C, X1); minimum air temperature (C, X2); maximum-minimum air
temperature (diurnal temperature range) (C, X3); evaporation (expressed as Piche
evaporation) (mm day-1, X4); surface soil temperature, grass temperature or green cover
temperature at 0600 h (C, X5) and 1800 h (C, X6); sunshine duration (h day-1, X7);
maximum relative humidity (maxRH) (%, X8), minimum relative humidity (minRH) (%, X9)
and wind speed (m s-1, X10) in season II only. The source of the climatic data was the
Agricultural Meteorological Station of the Agricultural Research Station, Agricultural
Research Center, Giza, Egypt. No rainfall occurred during the two growing seasons. Range
and mean values of the climatic parameters recorded during the production stage for both
seasons and overall data are listed in Table 1. Daily number of flowers and number of bolls
per plant which survived till maturity (dependent variables) during the production stage in the
two seasons are graphically illustrated in Figures 1 and 2 (Sawan et al., 2006).
335
Table 1. Range and mean values of the independent variables for the two seasons
and overall data
First season*
Climatic factor's
Max Temp (C), (X1) Min
Temp (C), (X2) Max-Min
Temp (C), (X3)
Evap (mm d-1), (X4)
0600 h Temp (C), (X5)
1800 h Temp (C), (X6)
Sunshine (h d-1), (X7) Max
RH (%), (X8) Min RH (%),
(X9) Wind speed (m s-1),
(X10)
Range
31.0-44.0
18.6-24.5
9.4-20.9
7.6-15.2
14.0-21.5
19.6-27.0
10.3-12.9
62-96
11-45
ND
Second season**
Mean
34.3
21.9
12.4
10.0
17.8
24.0
11.7
85.4
30.8
ND
Range
30.6-38.8
18.4-23.9
8.5-17.6
4.1-9.8
13.3-22.4
20.6-27.4
9.7-13.0
51-84
23-52
2.2-7.8
(Sawan et al. 2006).
Diurnal temperature range. ND not determined.

*
Flower and boll stage (68 days, from 23 June through 29 August).
from 29 June through 29 August).
Mean
34.1
21.8
12.2
6.0
18.0
24.2
11.9
73.2
39.8
4.6
**
Over all data

(Two seasons)
Range
Mean
30.6-44.0
34.2
18.4-24.5
21.8
8.5-20.9
12.3
4.1-15.2
8.0
13.3-22.4
17.9
19.6-27.4
24.1
9.7-13.0
11.8
51-96
79.6
11-52
35.1
ND
ND
Flower and boll stage (62 days,
Sawan et al., 2006.

Figure 1. Daily number of flowers and bolls during the production stage (68 days) in the first season (I)
for the Egyptian cotton cultivar Giza 75 (Gossypium barbadense L.) grown in uniform field trial at the
experimental farm of the Agricultural Research Centre, Giza (30N, 31:28'E), Egypt. The soil texture
was a clay loam, with an alluvial substratum, (pH = 8.07). Total water consumptive use during the
growing season supplied by surface irrigation was about 6000 m3ha-1. No rainfall occurred during the
growing season. The sampling size was 261 plants.
336
Zakaria M. Sawan
Sawan et al., 2006.

Figure 2 Daily number of flowers and bolls during the production stage (62 days) in the second season
(II) for the Egyptian cotton cultivar Giza 75 (Gossypium barbadense L.) grown in uniform field trial at
the experimental farm of the Agricultural Research Centre, Giza (30N, 31:28'E), Egypt. The soil
texture was a clay loam, with an alluvial substratum, (pH = 8.07). Total water consumptive use during
the growing season supplied by surface irrigation was about 6000 m3ha-1. No rainfall occurred during the
growing season. The sampling size was 358 plants.
2.1. Statistical Analysis

Statistical analysis was conducted using the procedures outlined in the general linear
model (GLM, SAS Institute, Inc., 1985). Data of dependent and independent variables,
collected for each day of the production stage (60 days in each season), were summed up into
intervals of 2, 3, 4, 5, 6 or 10 days. Data from these intervals were used to compute
relationships between the dependent variables (flower and boll setting and boll retention) and
the independent variables (climatic factors) in the form of simple correlation coefficients for
each season. Comparisons between the values of r were done to determine the best interval
of days for determining effective relationships. The -level for significance was P < 0.15. The
climatic factors attaining a probability level of significance not exceeding 0.15 were deemed
important (affecting the dependent variables), selected and combined with dependent variable
in multiple regression analysis to obtain a convenient predictive equation (Cady and Allen,
1972). Multiple linear regression equations (using stepwise method) comprising selected
predictive variables were computed for the determined interval and coefficients of multiple
determinations (R) were calculated to measure the efficiency of the regression models in
explaining the variation in data. Correlation and regression analyses were computed
according to Draper and Smith (1966) (Sawan et al., 2006).
337
3. RESULTS AND DISCUSSION

3.1. Response of Flower and Boll Development to Climatic Factors on the
Anthesis Day
Daily number of flowers and number of bolls per plant which survived to maturity
(dependent variables) during the production stage of the two seasons (68 days and 62 days in
the first and the second seasons, respectively) are graphically illustrated in Figures 1 and 2.
The flower- and boll-curves reached their peaks during the middle two weeks of August, and
then descended steadily till the end of the season. Specific differences in the shape of these
curves in the two seasons may be due to the growth-reactions of environment, where climatic
factors (Table 1) (Sawan et al., 2006) represent an important part of the environmental effects
(Miller et al., 1996).
3.2. Correlation Estimates

Significant simple correlation coefficients were estimated between the production
variables and studied climatic factors for different intervals of days (combined data of the 2
seasons) (Table 2) (Sawan et al., 2006).
Evaporation was the most important climatic factor affecting flower and boll production
in Egyptian cotton. The negative correlation means that high evaporation ratio significantly
reduced flower and boll production. High evaporation rates could result in water stress that
would slow growth and increase shedding rate of flowers and bolls (Sawan et al., 2006). Kaur
and Singh (1992) found in cotton that flower number was decreased by water stress,
particularly when existing at flowering stage. Seed cotton yield was decreased by about 50%
when water stress was present at flowering stage, slightly decreased by stress at boll
formation stage, and not significantly affected by stress in the vegetative stage (6-7 weeks
after sowing).
The second most important climatic factor was minimum humidity, which had a high
positive correlation with flower and boll production, and retention ratio. The positive
correlation means that increased humidity would bring about better boll production (Sawan et
al., 2006).
The third most important climatic factor in our study was sunshine duration, which
showed a significant negative relationship with flower and boll production only (Sawan et al.,
2006). The negative relationship between sunshine duration and cotton production may be
due to the fact that the species of the genus Gossypium are known to be short day plants
(Hearn and Constable, 1984), so, an increase of sunshine duration above that sufficient to
attain good plant growth will decrease flower and boll production. Bhatt (1977) found that
exposure to daylight over 14 hours and high day temperature, individually or in combination,
delayed flowering of the Upland cotton cv. J34. Although average sunshine duration in our
study was only 11.7 h, yet it could reach 13 h, which, in combination with high maximum
temperatures (up to 38.8C), may have adversely affected reproductive growth.
Table 2. Significant simple correlation coefficient values between the production variables and the studied climatic factors for the daily
and different intervals of days combined over both seasons
Max
(X1)
Min
(X2)
Max-Min
(X3)
Climatic factorsz
Surface soil
Evap
temp (C)
(mm d-1)
0600 h 1800 h
(X4)
(X5)
(X6)
Flower
Boll
Boll ret. rat.
-0.15++
NS
NS
NS
NS
NS
-0.26**
-0.25**
NS
-0.33**
-0.43**
-0.56**
NS
NS
NS
-0.20*
-0.19++
NS
-0.23*
-0.18++
NS
NS
NS
NS
0.30**
0.36**
0.34**
2 Days (n# = 60)
Flower
Boll
Boll ret. rat.
-0.31++
-0.29++
NS
NS
NS
NS
-0.32*
-0.30++
NS
-0.36**
-0.46**
-0.61**
NS
NS
NS
-0.24+
-0.21+
NS
-0.36**
-0.31*
NS
NS
NS
NS
0.37**
0.44**
0.40**
3 Days (n# = 40)
Flower
Boll
Boll ret. rat.
-0.34*
-0.32*
NS
NS
NS
NS
-0.34*
-0.32*
NS
-0.33*
-0.48**
-0.63**
NS
NS
NS
-0.28++
-0.24+
NS
-0.39*
-0.36*
NS
NS
NS
NS
0.34*
0.45**
0.40*
4 Days (n# = 30)
Flower
Boll
Boll ret. rat.
-0.31++
-0.31++
NS
NS
NS
NS
-0.35++
-0.33++
NS
-0.33++
-0.48**
-0.64**
NS
NS
NS
-0.28+
-0.23+
NS
-0.39*
-0.38*
NS
NS
NS
NS
0.34++
0.45*
0.42*
5 Days (n# = 24)
Flower
Boll
Boll ret. rat.
-0.35++
-0.33+
NS
NS
NS
NS
-0.37++
-0.35++
NS
-0.39++
-0.49*
-0.66**
NS
NS
NS
-0.39++
-0.35++
NS
-0.52**
-0.44*
NS
NS
NS
NS
0.41*
0.47**
0.43*
Daily and intervals

of days
Production
variables
Daily (n = 120)
Air temp (C)
Sunshine
duration
(h d-1)
(X7)
Relative humidity
(%)
Max
Min
(X8)
(X9)
Flower
Boll
Boll ret. rat.
Max
(X1)
-0.37++
-0.37++
NS
Min
(X2)
NS
NS
NS
Max-Min
(X3)
-0.41++
-0.40++
NS
Climatic factorsz
Surface soil
Evap
temp (C)
(mm d-1)
0600 h 1800 h
(X4)
(X5)
(X6)
-0.38++
NS
NS
-0.49*
NS
NS
-0.69**
NS
NS
Flower
Boll
Boll ret. rat.
NS
NS
NS
NS
NS
NS
-0.45++
-0.43++
NS
-0.40+
-0.51++
-0.74**
Daily and intervals

of days
Production
variables
6 Days (n# = 20)
10 Days (n# = 12)
Air temp (C)
NS
NS
NS
-0.55*
-0.53++
NS
Sunshine
duration
(h d-1)
(X7)
-0.54**
-0.46*
NS
Relative humidity
(%)
Max
Min
(X8)
(X9)
NS
0.42*
NS
0.49*
NS
0.45*
-0.65*
-0.57*
NS
NS
NS
NS
(Sawan et al. 2006).

z
Wind speed did not show significant effect upon the studied production variables, so is not reported.
**
Significant at 1 % probability level, * Significant at 5 % probability level.
++
Significant at 10 % probability level, + Significant at 15 % probability level.
NS Means simple correlation coefficient is not significant at the 15% probability level.
#
n = Number of data pairs used in calculation.
0.43++
0.51++
0.55*
340
Zakaria M. Sawan
Maximum air temperature, temperature magnitude and surface soil temperature at 1800 h
show significant negative relationships with flower and boll production only. Meanwhile, the
least important factors were surface soil temperature at 0600 h and minimum air temperature
(Sawan et al., 2006).
Our results indicate that evaporation was the most effective climatic factor affecting
cotton boll production. As the sign of the relationship was negative, this means that an
increase in evaporation caused a significant reduction in boll number (Sawan et al., 2006).
Thus, applying specific treatments, such as an additional irrigation or the use of plant growth
regulators (PGR) that would decrease the deleterious effect of evaporation after boll
formation, could contribute to an increase in cotton boll production and retention, and
consequently an increase in cotton yield. In this connection, Meek et al. (1999) in a field
experiment in Arkansas found that application of 3 or 6 kg glycine betaine (PGR) ha-1 to
cotton plants under mild water stress increased yield.
Comparing results for the different intervals of days with those from daily observation
(Table 2) (Sawan et al., 2006), the 5-day interval appeared to be the most suitable interval,
which actually revealed a more solid and more obvious relationships between climatic factors
and production characters. This was in fact indicated by the higher R2 values obtained when
using the 5-day intervals. The 5-day interval may be the most suitable interval for diminishing
the daily fluctuations between the factors under study to clear these relations comparing with
the other intervals. However, it seems that this conception is true provided that the
fluctuations in climatic conditions are limited or minimal. Therefore, it would be the most
efficient interval used to help circumvent the unfavorable effect of climatic factors. This
finding gives researchers and producers a chance to deal with condensed rather than daily
weather data (Sawan et al., 2006).
3. REGRESSION MODELS
Multiple linear regression equations were estimated using the stepwise multiple
regression technique to express the relation between cotton production variables [number of
flowers (Y1); bolls per plant (Y2); and boll retention ratio (Y3)] and the studied climatic
factors (Table 3) (Sawan et al., 2006).
Evaporation and surface soil temperature at 1800 h, sunshine duration and minimum
humidity accounted for a highly significant amount of variation (P < 0.05) in cotton
production variables, with the equation obtained for the 5-day interval showing a high degree
of certainty. The R values for the 5-day interval were higher than those obtained from daily
data for each of the cotton production variables. Also, the 5-day interval gave more efficient
and stable estimates than the other studied intervals (data not shown) (Sawan et al., 2006).
The R values for these equations clearly indicate the importance of such equations since
the climatic factors involved explained about 59 to 62% of the variation found in the
dependent variables (Sawan et al., 2006).
341
Table 3. The equations obtained for each of the studied cotton production variables for
the five-day intervals and daily intervals combined over both seasons
Equationz
R
Significance
Five-day intervals
Y1 = 23.78 0.5362X4 0.1429X6 0.1654X7 + 0.0613X9
0.6237
**
Y2 = 15.89 0.4762X4 0.1583X6 0.1141X7 + 0.0634X9
0.5945
**
Y3 = 72.65 0.0833X4 0.1647X6 + 0.2278X9
0.6126
**
Daily intervals
Y1 = 19.78 0.181X3 0.069X4 0.164X6 0.182X7 + 0.010X9
0.4117
**
Y2 = 14.96 0.173X3 0.075X4 0.176X6 0.129X7 + 0.098X9
0.4461
**
Y3 = 52.36 3.601X4 0.2352X7 + 4.511X9
0.3587
**
Sawan et al., 2006.
z
Where Y1 = number of flowers per plant, Y2 = number of bolls per plant, Y3 = boll retention ratio, X3 =
maximum minimum temperature C, X4 = evaporation mm day-1, X6 = surface soil temperature
C at 1800 h., X7 = sunshine duration h day-1, and X9 = minimum relative humidity %.
During the production stage, an accurate weather forecast for the next 10 days would
provide an opportunity to avoid any adverse effect for weather factors on cotton production
through applying appropriate cultural practices such as adequate irrigation regime or
utilization of plant growth regulators. This proposal would be true if the fluctuations in
weather conditions were not extreme. Our recommendation would be the accumulation 5-day
climatic data, and use this information to select the adequate cultural practices (such as an
additional irrigation or utilization of plant growth regulators) that would help circumvent the
unfavorable effects of climatic factors. In case of sharp fluctuations in climatic factors, data
could be collected daily, and when stability of climatic conditions is restored, the 5-day
accumulation of weather data could be used again (Sawan et al., 2006).
Relative humidity showed the highest contribution to the variation in both flower and boll
production. This finding can be explained in the light of results found by Ward and Bunce
(1986) in sunflower (Helianthus annuus). They stated that decreases of relative humidity on
both leaf surfaces reduced photosynthetic rate of the whole leaf for plants grown under a
moderate temperature and medium light level.
Reddy et al. (1993) found that cotton (Gossypium hirsutum) fruit retention decreased
rapidly as the time of exposure to 40C increased. Warner and Burke (1993) indicated that the
cool-night inhibition of cotton (Gossypium hirsutum) growth is correlated with biochemical
limitation on starch mobilization in source leaves, which result in a secondary inhibition of
photosynthesis, even under optimal temperature during the day. Gutirrez and Lpez (2003)
studied the effects of heat on the yield of cotton in Andalucia, Spain, during 1991-98, and
found that high temperatures were implicated in the reduction of unit production. There was a
significant negative relationship between average production and number of days with
temperatures greater than 40C and the number of days with minimum temperatures greater
than 20C. Wise et al. (2004) indicated that restrictions to photosynthesis could limit plant
growth at high temperature in a variety of ways. In addition to increasing photorespiration,
high temperatures (35-42C) can cause direct injury to the photosynthetic apparatus. Both
carbon metabolism and thylakoid reactions have been suggested as the primary site of injury
at these temperatures.
342
Zakaria M. Sawan
Regression models obtained explained a sensible proportion of the variation in flower and
boll production, as indicated by their R2, which ranged between 0.53-0.72 (Sawan et al.,
2010). These results agree with Miller et al. (1996) in their regression study of the relation of
yield with rainfall and temperature. They suggested that the other R2 0.50 of variation was
related to management practices, which coincide with the findings of this study. Thus, an
accurate climatic forecast for the effect of the 5-7 day period during flowering may provide
an opportunity to avoid possible adverse effects of unusual climatic conditions before
flowering or after boll formation by utilizing additional treatments and/or adopting proper
precautions to avoid flower and boll reduction.
Temperature conditions during the reproduction growth stage of cotton in Egypt do not
appear to limit this growth even though they are above the optimum for cotton growth (Sawan
et al., 2010). This is contradictory to the finding of Holaday et al. (1997). A possible reason
for that contradiction is that the effects of soil moisture status and relative humidity were not
taken into consideration in the research studies conducted by other researchers in other
countries. Since temperature and evaporation are closely related to each other, the higher
evaporation rate could possibly mask the effect of temperature. Sunshine duration and
minimum relative humidity appeared to have secondary effects, yet they are in fact important
factors. The importance of sunshine duration has been eluded by Moseley et al. (1994) and
Oosterhuis (1997).
CONCLUSION
maximum temperature, were the most significant climatic factors affecting flower and boll
production of Egyptian cotton. The negative correlation between each of evaporation and
sunshine duration with flower and boll formation along with the positive correlation between
minimum relative humidity value and flower and boll production, indicate that low
evaporation rate, short period of sunshine duration and high value of minimum humidity
would enhance flower and boll formation. Temperature appeared to be less important in the
reproduction growth stage of cotton in Egypt than evaporation (water stress), sunshine
duration and minimum humidity. These findings concur with those of other researchers
except for the importance of temperature. A possible reason for that contradiction is that the
effects of evaporation rate and relative humidity were not taken into consideration in the
research studies conducted by other researchers in other countries. The matter of fact is that
temperature and evaporation are closely related to each other to such an extent that the higher
evaporation rate could possibly mask the effect of temperature. Water stress is in fact the
main player and other authors have suggested means for overcoming its adverse effect which
could be utilized in the Egyptian cotton. It must be kept in mind that although the reliable
prediction of the effects of the aforementioned climatic factors could lead to higher yields of
cotton, yet only 50% of the variation in yield could be statistically explained by these factors
and hence consideration should also be given to the management practices presently in use.
The 5-day interval was found to give adequate and sensible relationships between climatic
factors and cotton production growth under Egyptian conditions when compared with other
intervals and daily observations (Sawan et al., 2006). It may be concluded that the 5-day
343
accumulation of climatic data during the production stage, in the absence of sharp fluctuations
in these factors, could be satisfactorily used to forecast adverse effects on cotton production
and the application of appropriate production practices circumvent possible production
shortage.
Finally, the early prediction of possible adverse effects of climatic factors might modify
their effect on production of Egyptian cotton. Minimizing deleterious effects through the
application of proper management practices, such as, adequate irrigation regime, and
utilization of specific plant growth regulators could limit the negative effects of some climatic
factors (Sawan et al., 2010).
REFERENCES
Barbour MM, Farquhar GD (2000) Relative humidity- and ABA-induced variation in carbon
and oxygen isotope ratios of cotton leaves. Plant, Cell and Environment 23: 473-485.
Bhatt JG (1977) Growth and flowering of cotton (Gossypium hirsutum L.) as affected by
daylength and temperature. Journal of Agricultural Science 89: 583-588.
Burke JJ, Mahan JR, Hatfield JL (1988) Crop specific thermal kinetic windows in relation to
wheat and cotton biomass production. Agron J 80: 553-556.
Cady FB, Allen DM (1972) Combining experiments to predict future yield data. Agron J 64:
211-214.
Draper NR, Smith H (1966) Applied Regression Analysis. John Wiley & Sons Ltd., New
York, NY. 407 pp.
El-Zik KM (1980) The cotton plant - its growth and development. Western Cotton Prod.
Conf. Summary Proc., Fresno, CA, p. 18-21.
Fisher WD (1975) Heat induced sterility in Upland cotton. Proc 27th Cotton Improvement
Conf. 85.
Gipson LR, Joham HE (1968) Influence of night temperature on growth and development of
cotton (Gossypium hirsutum L.): I. Fruiting and boll development. Agron J 60: 292-295.
Guinn G (1982) Causes of square and boll shedding in cotton. USDA Tech. Bull. 1672.
USDA, Washington, DC.
Guo Y, Landivar JA, Hanggeler JC, Moore J (1994) Response of cotton leaf water potential
and transpiration to vapor pressure deficit and salinity under arid and humid climate
conditions. In Proceedings Beltwide Cotton Conferences, January 5-8, San Diego,
California, USA. Memphis, USA, National Cotton Council, 1301-1308.
Gutirrez Mas JC, Lpez M (2003) Heat, limitation of yields of cotton in Andalucia.
Agricultura, Revista Agropecuaria 72: 690-692.
Hearn AB, Constable GA (1984) The Physiology of Tropical Food Crops. Chapter 14:
Cotton. P. 495-527 (Edited by Goldsworth, P.R.; Fisher, N.M.), John Wiley & Sons Ltd.,
NY. 664 pp.
Hodges HF, Reddy KR, McKinion JM, Reddy VR (1993) Temperature effects on cotton.
Bulletin Mississippi Agricultural and Forestry Experiment Station No. 990: 15.
Holaday AS, Haigler CH, Srinivas NG, Martin LK, Taylor JG (1997) Alterations of leaf
photosynthesis and fiber cellulose synthesis by cool night temperatures. In Proceedings
344
Zakaria M. Sawan
Beltwide Cotton Conferences, January 6-10, New Orleans, LA, National Cotton Council,
TN pp 1435-1436.
Kaur R, Singh OS (1992) Response of growth stages of cotton varieties to moisture stress.
Indian J Plant Physiol 35: 182-185.
Meek CR, Oosterhuis DM, Steger AT (1999) Drought tolerance and foliar sprays of glycine
betaine. In Proceedings Beltwide Cotton Conferences, January 3-7, Orlando, FL, USA.
Memphis, USA. National Cotton Council, 559-561.
Miller JK, Krieg DR, Paterson RE (1996) Relationship between dryland cotton yields and
weather parameters on the Southern Hig Plains. In Proceedings Beltwide Cotton
Conferences, January 9-12, Nashville, TN, USA, Memphis, USA, National Cotton
Council, 1165-1166.
Moseley D, Landivar JA, Locke D (1994) Evaluation of the effect of methanol on cotton
growth and yield under dry-land and irrigated conditions. In Proceedings Beltwide Cotton
Conferences, January 5-8, San Diego, CA, USA. Memphis, USA. National Cotton
Council, 1293-1294.
Oosterhuis DM (1997) Effect of temperature extremes on cotton yields in Arkansas. In
Proceedings of the Cotton Research Meeting, held at Monticello, Arkansas, USA,
February 13 [Edited by Oosterhuis, D.M.; Stewart, J.M.]. Special Report-Agricultural
Experiment Station, Division of Agriculture, University of Arkansas, No. 183: 94-98.
Reddy KR, Hodges HF, McKinion JM (1993) Temperature effects on Pima cotton leaf
growth. Agron J 85: 681-686.
Reddy KR, Hodges HF, McKinion JM (1995) Carbon dioxide and temperature effects on
pima cotton growth. Agriculture Ecosystems & Environment 54: 17-29.
Reddy KR, Robana RR, Hodges HF, Liu XJ, Mckinion JM (1998) Interactions of CO 2
enrichment and temperature on cotton growth and leaf characteristics. Environ Exp Bot
39: 117-129
SAS Institute, Inc (1985) SAS Users Guide: Statistics. 5th ed. SAS Institute, Inc., Cary, NC.
pp. 433-506.
Sawan ZM, Hanna LI, McCuistions WL (2006) Appropriate time scale for aggregating
climatic data to predict flowering and boll setting behaviour of cotton in Egypt.
Communication in Biometry and Crop Science 1: 11-19.
Sawan ZM, Hanna LI, McCuistions WL, Foote RJ (2010) Egyptian cotton (Gossypium
barbadense) flower and boll production as affected by climatic factors and soil moisture
status. Theoretical and Applied Climatology 99: 217-227.
Schrader SM, Wise RR, Wacholtz WF, Ort DR, Sharkey TD (2004) Thylakoid membrane
responses to moderately high leaf temperature in Pima Cotton. Plant, Cell and
Environment 27: 725-735.
Ward DA, Bunce JA (1986) Responses of net photosynthesis and conductance to independent
changes in the humidity environments of the upper and lower surfaces of leaves of
sunflower and soybean. J Exper Botany 37: 1842-1853.
Warner DA, Burke JJ (1993) Cool night temperatures alter leaf starch and photosystem II
Chlorophyll fluorescence in cotton. Agron J 85: 836-840.
Wise RR, Olson AJ, Schrader SM, Sharkey TD (2004) Electron transport is the functional
limitation of photosynthesis in field-grown Pima cotton plants at high temperature. Plant,
Cell and Environment 27: 717-724.
345
Xiao J-F, Liu Z-G, Yu X-G, Zhang J-Y, Duan A-W (2000) Effects of different water
application on lint yield and fiber quality of cotton under drip irrigation. Acta Gossypii
Sinica 12: 194-197.
Zhao Y-Z (1981) Climate in Liaoning and cotton production. Liaoning Agricultural Science
No. 5: 1-5.
Zhou Z-G, Meng Y-L, Shi Pei, Shen Y-Q, Jia Z-K (2000) Study of the relationship between
boll weight in wheat-cotton double cropping and meteorological factors at boll-forming
stage. Acta Gossypii Sinica 12: 122-126.
INDEX
#
21st century, 211
A
abstraction, 139
access, 31, 171, 199, 240
accessibility, 181
accountability, 31
acetic acid, 143, 162
acetonitrile, 9, 11, 12
acid, 2, 3, 11, 13, 16, 17, 20, 52, 143, 144, 147, 162,
164, 197, 225
ACs, 75
adaptability, 198, 212
adaptation(s), viii, ix, 103, 116, 165, 166, 167, 168,
186, 187, 188, 195, 197, 199, 204, 209, 214, 216,
221, 231, 237, 248, 256, 258
additives, 144, 147
adsorption, 36, 38, 41, 42
adverse conditions, 88
adverse effects, 166, 227, 256
aerosols, 2, 3, 16, 18, 20
aesthetic(s), 110, 113, 201
Africa, 39, 133, 143, 188, 219, 222, 257
age, 200, 215, 232
agencies, 122
agglutination, 159
aggregation, 173, 174, 178, 181, 184, 185, 186, 187
aggregation process, 173
agricultural exports, 174
agriculture, ix, 114, 118, 135, 166, 172, 175, 181,
184, 186
AIBN, 17
air pollutants, 51, 52
air quality, 52
air temperature, xi, 63, 87, 90, 97, 112
Alaska, 209
allele, 237, 238, 255
alternative energy, 106, 128
altruism, 204
aluminium, 93
ambient air, 46, 50, 52
amino acid(s), 147
ammonia, 78, 82, 83
amplitude, 32, 231
anaerobic digestion, 108
angiosperm, 216, 217, 222, 230, 232, 258
animal fleshings, viii, ix, 137, 148, 157
animal husbandry, 108, 133
annealing, 243
antibiotic, 162
antibody, 16
antigen, 16
appropriate technology, 134
architects, 104, 115, 134
Argentina, 223
argon, 17
arid conditions, viii, 137, 138, 332
arsenic, 36
ascorbic acid, 225
Asia, 190, 221, 222
assessment, xi, 105, 115, 166, 168, 170, 172, 173,
174, 186, 187, 188, 190, 209, 216, 236, 259, 261
assessment tools, 173
ATLAS, 228
atmosphere, 26, 30, 39, 70, 73, 75, 112, 166
attitudes, 112
Australasia, 218, 220, 261, 262
authorities, 126
avoidance, 110
awareness, 26, 117, 118, 133, 171
348
Index
B
Bacillus subtilis, 144
bacteria, 141, 142, 143, 144, 145, 147, 161
bacteriostatic, 143
banks, 110
barriers, 73, 83, 118, 246
base, 4, 10, 14, 39, 126, 190
base pair, 244
basic services, 171
batteries, 108
beetles, 207, 258
beneficial effect, 66
benefits, 31, 70, 83, 86, 105, 110, 111, 112, 199,
201, 207
benign, 26
benzene, 17
bias, 12, 14
bilateral, 236
bile, 142, 161
biodiesel, ix, 138, 147, 160, 164
biodiversity, 39, 198, 202, 204, 208, 209, 210, 211,
249, 250, 259, 261, 262
biogas, viii, 103, 104, 108, 133, 164
biogeography, 219, 236, 238, 262
biological processes, 255
biomarkers, x
biomass, viii, 103, 104, 122, 133, 188, 226
biotechnology, 164
biotic, 216
biotic factor, 252
blends, viii, 23, 96, 99
boilers, viii, 24, 27, 95, 99
Bolivia, 223
bonding, 100
boreal forest, ix, 195, 196, 197, 198, 200, 202, 207,
208, 209, 210, 211
boreholes, 94, 99
boric acid, 143, 144, 162
breeding, 237, 238
Britain, 25, 160
bromine, 70
browsing, 199, 208, 226
buffalo, 143
building blocks, 109
burn, 108, 199
businesses, 98, 184
C
cadmium, 36
calcium, xi, 142, 147
calculus, 48
calibration, 12, 14, 17, 18, 19, 20
cancer, 52
capacity indicators, 187
capillary, 2
carbohydrates, 147
carbon, viii, 24, 95
carbon dioxide, 25, 75, 108, 115
case study(ies), x, 134, 162, 168, 187, 213, 214, 215,
229, 253, 255, 258
casting, 105, 128
catalysis, 16
catastrophes, 213
cattle, 141, 143, 144, 145, 161, 162
CCA, 190
centigrade, 175
challenges, 147, 191, 196
changing environment, 199, 216, 221, 256
cheese, 138, 146, 163
chemical(s), ix, 1, 2, 4, 5, 6, 8, 11, 16, 20, 26, 39, 43,
51, 69, 137, 139, 140, 141, 142, 143, 145, 147,
148
chemical stability, 69
child mortality, 191
children, 121
Chile, 222
chlorine, 13, 14, 70
chloroplast, 239, 243, 244, 245, 259, 263
chromatography, 2
chromium, 36
circulation, 69, 85, 99, 249, 250
Clarence River Corridor, x, 213, 215, 224, 227, 228,
241, 243, 251, 252, 253, 254, 255
classification, 28, 135, 219
clean energy, 171
cleaning, 38
clients, 112
climate change, vii, ix, x, 30, 39, 165, 166, 167, 168,
170, 171, 172, 173, 186, 187, 188, 190, 196, 200,
203, 207, 208, 209, 213, 214, 215, 222, 223, 227,
240, 246, 249, 250, 252, 253, 255, 256, 257, 259,
260
climates, 73, 93, 208, 246, 255
climatic factors, xi
closure, 140
cluster analysis, 168
clustering, 189
clusters, 116, 138, 225, 241
CO2, viii, 24, 27, 51, 52, 70, 71, 95, 96, 108, 115,
200
coatings, 17
cobalt, 36
coconut oil, 174
349
Index
collagen, 140, 146, 159
colonization, 221, 244, 245, 263
color, 225
combustion, 36, 51, 96, 108
commercial, vii, 23, 69, 70, 74, 98, 134, 144, 147,
160, 162, 181, 199
commodity, 208
communication, 104, 132, 206
community(ies), ix, x, 108, 161, 168, 170, 186, 187,
195, 201, 203, 208, 209, 210, 211, 213, 214, 216,
217, 220, 223, 226, 227, 229, 231, 232, 233, 235,
247, 252, 255
compaction, 200
comparative advantage, 226
comparative costs, 119
compensation, 38
competition, xi, 106, 200, 216, 222, 223, 225, 232,
246, 250, 252
compilation, 224
complexity, ix, 104, 149, 165, 166, 174, 195, 201,
206, 207, 247
composition, xi, 40, 54, 68, 146, 161, 166, 200, 201,
208, 226, 227, 247
compounds, 2, 4, 9, 20, 70, 142, 226
compressibility, 48
compression, viii, 24, 51, 56, 58, 59, 61, 62, 63, 76,
85, 86
computation, 176
computer, 159, 245
conceptual model, 197
concreteness, 113
condensation, 4, 8, 11, 14, 54, 61, 94
conditioning, 26, 27, 32, 52, 63, 70, 83, 90, 98, 100,
106, 109, 110, 111, 116, 117, 129, 135
conductivity, 100, 157, 158
configuration, xi, 28, 33, 96, 247
congress, 134, 135, 160
conifer, x, 199, 200, 208, 210, 213, 214, 224, 227,
240, 244, 252, 253, 258, 259, 261, 262
connectivity, 200, 205, 246
consensus, 209
conservation, x, 26, 36, 43, 44, 93, 104, 110, 112,
126, 128, 134, 135, 205, 213, 214, 215, 236, 238,
244, 246, 252, 255, 256, 258, 263
construction, 69, 72, 75, 105, 107, 108, 111, 112,
113, 114, 115, 118, 121, 244, 246
consumers, 70, 83, 92, 105, 112, 118
consumption, vii, viii, x, xi, 2, 23, 27, 30, 31, 32, 51,
69, 70, 71, 72, 73, 74, 83, 97, 105, 107, 109, 110,
111, 114, 118, 121, 126, 127, 133, 135, 137, 139,
145, 146, 147, 154, 158, 159, 160
contact time, 18, 19
containers, 26, 144
contamination, 37, 38, 134, 142, 145

Convention on Biological Diversity, 211
cooking, 108
cooling, vii, x, 6, 23, 25, 26, 27, 31, 46, 52, 65, 69,
70, 71, 72, 73, 75, 83, 84, 89, 90, 91, 94, 95, 96,
97, 98, 99, 100, 109, 111, 112, 117, 134, 141,
229, 230
cooperation, 106, 160
coordination, 108
copolymer, 17
copper, 4, 36, 94
correlation(s), xi, 118, 121, 132, 142, 250
corrosion, 29, 53, 69, 88, 142
cost, 2, 30, 36, 43, 57, 68, 72, 74, 86, 89, 92, 94, 95,
98, 99, 104, 106, 107, 108, 114, 119, 126, 127,
128, 129, 159, 171
cost saving, 110, 112
cotton, xi
covering, 185
CPC, 167
crop(s), 38, 174, 175, 186
crown, 207
crystalline, 141
crystals, 17, 145
CSD, 101
CT, 10, 14, 126
cultivation, 226
culture, 117
cure, 138, 145
curing process, viii, ix, 137, 143, 146, 148, 149, 150,
158, 160
customers, 92
cuticle, 226
CWA, 18
cycles, x, 24, 46, 47, 52, 53, 54, 62, 63, 64, 65, 66,
68, 76, 77, 86, 87, 101, 213, 216, 227, 231, 232,
233, 235, 240, 252, 255, 256
cycling, 86, 117, 196, 200, 207
cytoplasmic inheritance, 214, 244
Czech Republic, 137, 160
D
damages, 38, 167
data collection, 250
data set, 239
database, 176, 228
decay, 141
decision-making process, 115
decomposition, 147
defence, 72
deficiencies, 107
degradation, 12, 14, 52, 138, 144, 162, 174, 179, 202
350
Index
dehydration, 144
demographic change, x, 213, 215
denuder extraction, vii, 1, 3
deposition, 200, 214, 217, 262
deposits, 29, 216, 217, 233, 234, 235
depression, 238, 239
depth, 27, 32, 94, 108, 125, 197, 235
desalting process, ix, 138, 152, 155
designers, 75, 111, 112, 114
desorption, 36, 42, 52
destruction, 35, 52, 103, 226
detection, vii, 1, 2, 3, 9, 16, 17, 18, 19, 20
developed countries, 191
developing countries, 104, 107, 145
deviation, 17, 66
dew, 54
diesel engines, 51
diesel fuel, 106
diffusion, ix, 42, 137, 140, 144, 146, 148, 151, 152,
156, 157, 158, 160, 163
diffusion process, 149
diffusivity, 32, 69
digestion, 108, 164
diluent, 5
dinosaurs, 219, 226
diploid, 237, 238
directives, 51
discomfort, 27, 83
diseases, x
displacement, 11, 58, 62, 191, 217, 252
disposition, 115
distilled water, 13, 157
distribution, x, 3, 29, 72, 94, 95, 97, 99, 100, 105,
140, 163, 171, 176, 203, 207, 213, 214, 215, 216,
221, 222, 223, 224, 229, 235, 237, 241, 243, 245,
246, 248, 250, 251, 252, 253, 254, 255, 256, 257,
258, 261
distribution of income, 171
divergence, x, 213, 214, 215, 227, 229, 236, 239,
241, 246, 247, 252, 254, 256, 262
diversification, 122, 214, 217, 230, 238
diversity, x, 198, 202, 203, 204, 208, 210, 211, 213,
214, 215, 216, 217, 218, 220, 222, 223, 227, 229,
230, 231, 236, 237, 238, 240, 241, 247, 248, 249,
252, 253, 255, 256, 257, 261, 262, 263
DMF, 52
DNA, 239, 244, 245, 259, 263
DOI, 209, 210
domestication, 214, 238
dominance, 203, 230, 232, 233, 235, 238, 258
dosage, 143
drainage, 37, 96, 230
drawing, 203
dreaming, 224
drinking water, 108
drought, 166, 188, 189, 235
dry ice, 141
dry matter, 146, 159
drying, 140, 141, 142
durability, 89, 115
dusts, 136
dynamic factors, 3
E
early warning, 171
Earth Summit, 114, 134
ecological indicators, ix, 165, 170
ecological processes, 196, 197, 199, 201
ecological systems, 207, 209, 212, 249
ecology, 216, 247, 252, 258
economic damage(s), 38
economic development, viii, ix, 103, 114, 166, 186
economic growth, 30, 106, 129, 184
economic indicator, 174, 181
economic well-being, 171
economics, 108
ecosystem, vii, 23, 52, 69, 70, 142, 190, 195, 196,
197, 198, 199, 200, 201, 202, 203, 204, 205, 206,
208, 209, 210, 211
education, viii, 103, 117, 118, 121, 171, 174, 181,
184, 186, 189
effluent, 18, 51, 160, 162, 164
effluents, ix, 37, 137, 139, 142, 144, 158, 163
Egypt, 39
elastin, 140
electric conductivity, 157
electric power, ix, 75, 108, 137, 158, 159
electrical potential, xi, 295, 297
electricity, viii, 24, 27, 31, 83, 95, 97, 98, 104, 106,
108, 109, 118, 121, 129, 132
electrode surface, 13
electrodes, vii, 1, 3, 13, 14, 16, 20
electrolyte, 140
electron, 139, 143
electroplating, 36
emergency, 86, 87
emission, 115
empirical methods, 166
employment, 110, 175, 181, 184, 186, 190
encoding, 176
endangered, 258, 262
energy conservation, 26, 36, 104, 110, 112
energy consumption, x, xi, 31, 32, 71, 72, 83, 97,
104, 110, 111, 114, 118, 135
351
Index
energy efficiency, vii, 23, 69, 70, 75, 83, 89, 104,
106, 109, 113, 116, 118, 129, 135
energy expenditure, 27, 83
energy input, 46, 104, 105
energy recovery, 117
energy supply, 31, 104, 116, 171
enforcement, 117
engineering, ix, 2, 26, 44, 111, 132, 137, 145, 148
England, 188
entrepreneurship, 163
entropy, 24, 29, 35, 36, 42, 43, 45, 48, 49, 50, 53, 54,
55, 57, 65, 76
environmental change, 166, 170, 186, 187, 196, 214,
216, 231, 249
environmental characteristics, 201
environmental conditions, x, 104, 106, 107, 129,
195, 196, 231
environmental control, 116
environmental degradation, 51
environmental factors, 115, 200, 245
environmental impact, ix, 31, 51, 73, 83, 95, 98, 115,
132, 137, 138, 143
environmental issues, 112
environmental management, 208
environmental protection, vii, 71, 83, 135
environmental quality, 106, 129, 132
environmental regulations, 111
environmental stress, 167, 172
environmental sustainability, 104, 106, 128
environmental variables, 245, 250
environments, 16, 26, 51, 108, 110, 111, 141, 217,
231, 232, 234
enzyme(s), x, 147, 164
equality, 64
equilibrium, 2, 41, 42, 43, 47, 76, 81, 82, 158, 237,
238, 250
equipment, 26, 28, 34, 36, 64, 68, 87, 89, 90, 96, 99,
104, 105, 107, 117, 142
erosion, 174, 179, 193, 200
ethanol, x
EU, 26, 50, 51
Europe, 25, 39, 114, 126, 127, 141, 187, 258
European Commission, 144, 162
europium, 16
evaporation, x, xi, 4, 6, 54, 60, 94, 138, 162, 230
evidence, 51, 189, 210, 216, 223, 227, 232, 233, 240,
245, 249, 254, 261, 262, 263
evolution, 219, 221, 223, 226, 227, 229, 237, 247,
258, 259, 262
exclusion, 209, 221
exercise, vii, 23, 69, 70
experimental design, 139
expertise, 167
exploitation, 105, 112, 128

exports, 174
exposure, 109, 167, 168, 170, 172, 173, 174, 176,
181, 184, 185, 186, 187, 190, 232
expressiveness, 113
external environment, 52
extinction, 213, 214, 216, 217, 222, 226, 233, 253,
256, 259
extraction, vii, 1, 3, 20
extreme weather events, 171, 172
F
fabrication, 100
families, 174, 175, 186, 217, 238, 244, 259
family income, 186
farmers, 38, 186
farms, 108, 121
fat, 140, 141, 146, 147, 151, 160, 225
fatty acids, 147
fauna, 215, 226, 232
feed additives, 147
fermentation, 108, 164
fertilization, 225, 244
fertilizers, 147
fever, 52
fiber(s), xi, 17, 18, 19, 140, 159
filters, 3, 88
financial, 31, 106, 129, 139, 174
financial intermediaries, 122
financial resources, 171
Finland, 134, 209
fire fighting, 2
fires, 199, 200
fish, 51, 52, 144
fishing, 144
fitness, 238
fixation, 237
flame, 17
flammability, 226
flavor, 225
flex, 93
flexibility, ix, 166, 167, 173, 187
flight, 235
floods, 172
flora, 217, 218, 220, 229, 230, 231, 235, 258
flora and fauna, 258
flowering period, 38
fluctuations, 126, 217, 229, 256
fluid, 25, 28, 29, 32, 33, 35, 36, 37, 43, 60, 66, 98,
235
fluorine, 70
food, 26, 75, 146, 170, 171, 174, 175, 186, 226
352
Index
food security, 75
forbs, 199
force, xi, 97, 186
forecasting, 206, 246, 257
foreign affairs, 106
forest ecosystem, ix, 195, 196, 197, 199, 200, 202,
203, 204, 206, 207, 209, 211
forest fire, 209
forest habitats, 222
forest management, ix, 195, 196, 197, 198, 201, 203,
204, 205, 206
forest resources, 205
formaldehyde, x, 279, 280, 283, 284, 285, 286, 291,
292
formation, xi, 39, 69, 87, 142, 145, 147, 151, 229,
257
formula, 35, 116, 118, 126
fossil record, x, 213, 214, 215, 216, 219, 222, 232,
235, 240, 247, 253, 254, 255, 256, 259
fossils, 216, 222, 232, 259
fouling, 29, 145
foundations, 237
founder effect, 208
fractal theory, 29
France, 135, 249
free energy, 42
free volume, 140
freedom, 16
freezing, 140, 141
frequency distribution, 237
freshwater, 51
frost, 87, 97
fruits, 225
fuel consumption, 27, 109, 126, 127
fuel efficiency, 109
fuel prices, 106, 128
funding, 257
fungi, 211
fuzzy set theory, ix, 166, 172, 187, 188
G
gamete, 235
gamma rays, 144
gas injection technology, vii, 1
gas sensors, vii, x
gaseous ethanol, xi, 279, 280, 286, 287, 288, 289,
290, 291, 293
GDP, 174
GDP per capita, 171
gel, 147
genes, 202, 237, 238, 239
genetic diversity, x, 203, 213, 214, 215, 227, 236,

237, 240, 241, 247, 248, 249, 253, 255, 262
genetic drift, 237, 238, 253
genetic load, 238, 255, 256
genetic traits, 236
genetics, 236, 237, 238, 239, 244, 247, 257, 260,
261, 262
genome, 244, 259, 263
genotype, 237, 250, 256
genotyping, 250
genus, 217, 219, 222, 225, 232, 255
Geographic Information System (GIS), 190, 245
geothermal heat pump, 27, 96, 100
Germany, 165, 209, 249
germination, 203, 225
GHG, 39
GHP, 96
global climate change, 249
global warming, viii, 23, 52, 70, 75, 96, 214
globalization, 190
glycerin, 160
glycol, 40
governance, 171, 174, 178, 184, 192
governments, 31
grants, 133
graph, 91, 157
grasslands, 200
gravity, 24, 43, 94, 226
Great Britain, 160
green buildings, 115
green electricity, viii, 24, 95
greener world, vii, 23, 69, 70
greenhouse gas(es), 30, 106, 112, 129, 171
greenhouse gas emissions, 30, 106, 129, 171
grid electricity, viii, 24, 95
groundwater, 37, 100
growth, viii, 13, 14, 30, 39, 75, 103, 105, 106, 114,
115, 116, 122, 129, 132, 141, 181, 184, 198, 211,
214, 216, 225, 227, 231
growth rate, 103
growth rings, 225
guidelines, x, 93, 107, 114, 115, 195, 211
guiding principles, 204, 208
gymnosperm, 217, 218, 258, 259
H
habitat(s), 141, 199, 201, 203, 211, 215, 216, 222,
223, 225, 226, 227, 229, 233, 235, 240, 241, 247,
249, 252, 255, 256
halitosis, xi
haplotypes, 243, 244, 245, 260
harmony, 110
353
Index
harvesting, 198, 199, 200, 209, 210, 211, 218, 220
hazardous air pollutants, 51, 52
hazards, 52, 162
health care, x, 188
health condition, 174
health risks, 143, 172
health services, 172, 189, 192
heat capacity, 35, 54
heat loss, 68, 72, 76, 82, 93, 94, 97, 109, 110, 135
heat pump cycle, 89
heat pumps, viii, 24, 25, 26, 27, 86, 87, 88, 90, 91,
96, 97, 98, 99, 100
heat transfer, 24, 25, 26, 28, 29, 32, 33, 36, 45, 56,
58, 85, 100, 111, 135
heavy metals, 36
height, 109, 124, 125, 253
hemisphere, 214
herpetofauna, 254
heterogeneity, 37, 198, 202
heterosis, 239
heterozygote, 237
highlands, 222
historical data, 247
history, 198, 201, 214, 215, 217, 229, 231, 234, 236,
239, 240, 246, 247, 249, 253, 257, 258, 260, 261,
262, 263
Holocene, 221, 231, 235, 241, 254, 255, 258
homeowners, 96
homes, 90, 96, 98
homogeneity, 159
hotels, 184
hotspots, ix, 165, 187, 188, 223
House, 95, 135
household sector, 133
housing, 32, 134
human, ix, x, 31, 39, 51, 72, 108, 113, 114, 165, 166,
171, 186, 187, 199, 201, 204, 214, 256
human activity, 199
human body, x
human condition, 186
human development, 171
human dimensions, 166, 187
human health, 39
human security, 171
humidity, xi, 90, 97, 98, 106, 129, 142, 175, 225
Hunter, 202, 205, 209, 211
hunting, 199
husband, 121
husbandry, 108, 133
hybrid, 239
hybridization, 238
hydrocarbons, 48, 71
hydrochloroflurocarbons, viii, 23, 96
hydrogen, 13, 20
hydrogen bromide, 20
hydrogen chloride, 20
hydrogen fluoride, 20
hydrolysis, 16, 147, 164
hydrothermal synthesis, 40
hydroxide, 13, 17, 147
hypothesis, 223
I
IAM, 189
ideal, 34, 45, 47, 57, 63, 64, 65, 66, 67, 91, 101, 105,
126, 149, 152, 216
identification, 168, 187, 235, 236, 245, 246
IEA, 101
illiteracy, 121
image, 17
immigration, 229
impact assessment, 166, 250
imprinting, 16, 17
impurities, 4, 5, 6, 8, 38, 88, 145, 147
inbreeding, 227, 237, 238, 239, 253, 256
incidence, 174, 175, 181, 227
income, 121, 171, 174, 181, 186, 190
increased competition, 252
India, 100, 162, 172, 188, 190
indirect effect, 207, 211
individuals, 186, 206, 227, 228, 237, 238, 244, 250,
253, 258
industrial chemicals, 5
industrial processing, 151
industrialisation, viii, 103
industries, 26, 36, 139, 164
industry, vii, viii, 23, 36, 69, 70, 72, 73, 75, 83, 122,
137, 138, 139, 143, 144, 146, 160, 161, 164, 190,
225
inequality, 174, 189, 191
inertia, 28
infancy, 187
infant mortality, 191
information exchange, 115, 206
infrastructure, 39, 109, 122, 125, 126, 170, 174, 181,
193
ingredients, 113
inheritance, 214, 239, 244
inhibitor, 100
initiation, 225
insects, 141
insecurity, 170
institutional infrastructure, 125, 170
institutions, 122, 204
insulation, 4, 52, 72, 89, 91, 93
354
Index
integration, 17, 45, 53, 104, 151, 153, 236

integrity, 201, 242, 255
integument, 219
interface, 28, 189
interference, 256
intermediaries, 122
internal processes, 166
internalised, 31
intervention, 122
introns, 244
investment(s), 126, 144, 181, 184
ion adsorption, 36
ions, xi, 13, 16, 36, 38, 43, 142, 149
IPO, 188
iron, 36, 39
irradiation, 113, 143, 162
irrigation, 125, 171, 186
islands, 174, 175, 181, 184, 185, 226
isolation, 110, 114, 215, 223, 246, 247, 252, 253
isotherms, 37, 42
isotope, 231
isozyme, 223
issues, ix, 2, 30, 31, 91, 105, 106, 110, 112, 113,
114, 129, 134, 165, 166, 184, 186
Italy, 249
iteration, 204
J
Japan, 39, 249
joint ventures, 122
joints, 93
Jordan, 118, 134, 220, 229, 232, 258, 261
K
Kenya, 39, 138, 160
kerosene, 26, 118
kinetic model, 41
kinship, 244, 263
KOH, 13
Korea, 249
L
labour force, 186
lakes, 138, 142, 210, 230
landscape(s), ix, 116, 117, 195, 198, 199, 201, 203,
205, 206, 207, 208, 210, 213, 215, 216, 217, 226,
229, 232, 231, 233, 247
laws, 46, 65
LC-MS, vii, 1, 3, 9, 11, 12, 13, 19, 20
LDCs, 191
lead, 2, 28, 36, 39, 67, 104, 109, 114, 139, 142, 147,
199, 200, 204, 231
leakage, viii, 24, 26, 91, 93, 96, 99, 115
leaks, 93
learning, 122
legislation, 117
legs, 93
lichen, 210
life cycle, 115, 227
lifetime, 126, 128
light, 18, 31, 32, 87, 110, 112, 144, 200, 201, 214,
218, 220, 222, 223, 226, 235, 240, 252
linear dependence, 157
liquid chromatography, 2
liquid phase, 2, 54, 84, 146
liquids, 88
lithium, 75, 76, 77, 78, 79, 80, 81
livestock, 136
living conditions, 104
loans, 133
loci, 237, 240, 243, 244, 245, 250, 258, 260
locus, 219, 237, 243, 244, 257
logging, 199, 201
longevity, 86, 223
low temperatures, xi
LPG, 95, 118, 121
luminescence, 17
Luo, 100
M
machinery, 38, 144
macromolecules, 140
magnesium, xi, 142
magnetic refrigeration, vii, 23, 69, 70
magnetic resonance, 163
magnetic resonance imaging, 163
magnitude, 28, 36, 59, 158, 172, 196, 197, 229
majority, 140, 145, 147, 214, 219, 222, 226, 244,
255, 256
Malaysia, 101, 220
man, 51, 52, 72, 83, 97
management, viii, x, 38, 103, 111, 114, 121, 133,
164, 195, 196, 197, 198, 199, 200, 201, 203, 204,
205, 206, 207, 208, 209, 211, 215, 256, 258
manganese, 36
manufacturing, 37, 104, 107, 113, 115, 138, 139,
161, 164
mapping, 170, 186
marginal distribution, 253
marine environment, 217, 262
market access, 31
355
Index
marketing, 115
mass, 2, 8, 14, 24, 28, 29, 33, 42, 43, 44, 45, 46, 47,
51, 56, 58, 62, 69, 111, 112, 114, 117, 118, 149,
152, 160, 163, 213, 217, 221
material resources, 114
materials, vii, 1, 2, 4, 5, 6, 9, 13, 16, 20, 26, 31, 39,
69, 70, 73, 83, 104, 105, 107, 108, 114, 115, 132,
140, 143, 159
matrix, 16, 247, 256
matter, 40, 47, 113, 117, 121, 139, 146, 159, 210
maximum likelihood estimate (MLE), 253
MB, 257, 259, 260, 261
measurement(s), 12, 13, 14, 17, 20, 34, 113, 171,
203, 207
meat, 138, 146, 159, 163
mechanical properties, 140
mechanical ventilation, 31, 72
media, 40
median, 39
medical, xi, 108
medicine, 138
Mediterranean, 111
megaspore, 225
meiosis, 244
membership, 173, 176
membranes, xi, 145
mercury, 8, 12, 36
Mercury, 21
messages, 113
metabisulfite, 144
metal ion(s), 36, 38, 43
metals, 16, 36, 37
metaphor, 206, 207
meter, 108
methanol, 7, 17
methodology, 100, 235, 250
Mexico, 189, 219
microclimate, 105
microfabrication, 28
microhabitats, 252
micrometer, 28
microorganisms, 140, 141, 142
microsatellites, 243, 260, 262
microscope, 139
microscopy, 222, 235
migration, 216, 221, 223, 229, 235, 236, 247, 252,
253, 255, 256
migration routes, 222, 229
milligrams, 2
miniature, 17, 18, 20
Ministry of Education, 160
Miocene, 230, 261
MIP, 16, 17, 18, 19, 20
mission(s), 27, 39, 96, 115

Missouri, 261
mitochondria, 244
mitochondrial DNA, 257
mixing, 105
modelling, 29, 68, 111, 116, 139, 172
models, ix, 36, 109, 116, 139, 145, 146, 165, 166,
167, 168, 172, 173, 174, 176, 178, 179, 181, 184,
187, 188, 189, 208, 228, 229, 239, 240, 241, 247,
248, 249, 250, 252, 254, 262
modern society, 104
modifications, 111
modules, 29
moisture, 88, 140, 200, 204, 225, 229
moisture content, 140
mole, 17, 54
molecular mass, 47
molecular sensors, 16
molecules, 17, 43, 159
momentum, 106, 128
monolayer, 37
morphology, 217, 218, 220, 222, 235, 261, 263
mortality, 191, 199
MPI, 249
MRI, 249
MSW, 164
mtDNA, 245
mutation(s), 237, 244, 260
myosin, 159
N
NaCl, 13, 138, 140, 141, 143, 144, 145, 146, 149,
150, 152, 154, 156, 158, 163
nanocrystals, 40
nanomaterials, 41
nanoparticles, 36, 39, 40, 43
naphthalene, 142
National Academy of Sciences, 210
national income, 171
natural disturbance, 197, 200
natural evolution, 256
natural gas, 74, 95
natural resource management, 209
natural resources, viii, 70, 83, 103, 115, 167
natural selection, 237, 260
negative effects, 109, 132
negative relation, 181
neglect, 111
nerve, 16
Netherlands, 106, 133
neutral, 237, 244
New South Wales, 225, 227, 253, 258, 260
356
Index
New Zealand, 218, 220, 222, 225, 230, 261, 263

NGOs, 122
nickel, 36
Nigeria, 39
nitrates, 40, 52
nitrogen, 8, 12, 17
NOAA, 249
nonlinear dynamics, 196
North America, 39, 203, 207, 208
Norway, 211, 249
Norway spruce, 211
nuclear magnetic resonance, 163
nucleus, 132, 244
nutrient, 196, 200, 223, 252
O
oil, viii, 24, 25, 26, 49, 51, 72, 88, 94, 95, 96, 104,
133, 174, 216
oil boiler, viii, 24, 96
openness, 106, 128
operating costs, 86, 99, 145, 159
operations, viii, 36, 137, 147, 148
opportunities, 30, 72, 110, 116, 133, 167, 181, 198,
199
optical fiber, 17
optimization, ix, 137, 138, 139, 143, 145, 146, 148,
155, 160
ores, 17, 234, 235
organelle, 244
organic matter, 210
organism, 237, 244
organize, 196, 204
organs, 113
oscillation, 258
osmosis, 145
outreach, 172
outsourcing, 184
overlap, 229, 248
oxide nanoparticles, 39
oxygen, 40, 70, 231
ozone, 52, 70, 200
P
paints, 36
palaeodistribution, x, 213, 215
parallel, 32, 81, 92, 99, 110, 219
parents, 238
pasture, 172
pathogens, 208, 216, 246
pathology, 209
PCR, 243
peace, ix, 166
peat, 199, 233, 234
peptide(s), 140, 144
peptide chain, 140
permeability, 100, 111
Perth, 235
pests, 200, 208
petroleum, 26, 104
pH, 13, 17, 18, 36, 38, 40, 144, 200
phase transformation, 40
phenotype, 250
Philadelphia, 189
Philippines, v, vii, ix, 165, 166, 171, 174, 175, 179,
184, 185, 186, 187, 188, 190
phosphate, 3, 6, 13
photosynthesis, 200
physical environment, 113, 217
physical properties, 140
physiology, 222, 258
piano, 225
Pie chart, 243
plants, vii, 23, 51, 69, 70, 73, 75, 106, 116, 126, 127,
129, 138, 143, 145, 199, 210, 216, 217, 225, 234,
244, 247, 257, 259
plastid, 240, 244, 245
platform, 3, 17, 20
Pliocene, 230
polarization, 145
policy, 29, 111, 168, 171, 186, 187, 188, 189, 206,
211
policy issues, 30
political problems, 184
politics, 30
pollen, 221, 222, 225, 226, 230, 232, 233, 234, 235,
236, 244, 245, 258, 260, 261, 263
pollen tube, 225
pollination, 38, 196, 200, 235, 259, 263
pollutants, 51, 52, 135
pollution, viii, 24, 30, 36, 37, 52, 95, 101, 108, 113,
200
polymer(s), 3, 16, 17, 20, 144, 162
polymer matrix, 16
polymorphism, 244
polyploidy, 237
polysaccharide, 159
pools, 98, 210
poor performance, 114
population density, 103, 108, 109, 117
population group, 223, 227, 229, 242, 247, 248, 251,
252, 255, 256
population growth, viii, 103, 105, 115, 122, 214
population size, 237, 239, 252, 253
357
Index
population structure, 237
porosity, 140
porous materials, 140
portability, 20
Portugal, 136, 172
positive relationship, 181
potassium, 13, 143, 162
potato, 163
poverty, 163, 170, 171, 174, 175, 181, 186, 188, 189,
190
power generation, 108
precedents, 197, 199, 201
precipitation, 39, 40, 200, 229, 230, 232, 245, 256
predation, 246
preparation, 2, 3, 143, 171, 176
preservation, ix, 137, 138, 139, 141, 142, 143, 144,
147, 158, 160, 161, 162, 216
prevention, 69, 138, 144, 145, 162
principles, 2, 47, 115, 116, 134, 204, 208, 211
prior knowledge, 245
probability, 110, 118, 120, 189, 228, 229, 239, 241,
250, 253, 254
probe, 158
process control, 28
producers, 38, 105
professionals, 104, 112
profit, 147
profitability, 116
project, 101, 106, 107, 133, 244, 246
propagation, 38, 226, 239
propane, 71
protection, vii, 71, 83, 135, 209, 252
proteins, 144
prototype, 134
Pseudomonas aeruginosa, 147, 164
PTFE, 4, 9, 10, 13, 14
public administration, 38
public awareness, 117, 133
public health, 147
public sector, viii, 103
public service, 104
pulp, 37
pumps, viii, 11, 14, 24, 25, 26, 27, 52, 81, 82, 86, 87,
88, 90, 91, 94, 96, 97, 98, 99, 100, 103, 104, 106,
107, 117, 123, 124, 126, 127, 132, 133
purchasing power, 171, 178, 191
pure water, x, 76, 81
purity, 7, 11
Q
quality control, 107, 134
quality standards, 51
Queensland, 218, 225, 253, 257, 260, 262
R
radiation, 52, 73, 104, 107, 108, 118, 143, 162, 258
rainfall, 175, 216, 229, 230
rainforest, vii, x, 213, 214, 216, 217, 221, 223, 225,
226, 227, 229, 230, 231, 232, 233, 235, 240, 241,
247, 248, 252, 253, 254, 255, 256, 258, 260, 261,
262
random mating, 237, 238
ratepayers, 86
raw materials, 143
reaction temperature, 40
reactions, x, 16
real time, vii, 1, 20, 156
reality, 51, 104, 113
receptacle, 225
receptors, 16
recognition, 31
recombination, 239, 244
reconstruction, 259
recovery, x, 52, 117, 161, 191, 259
recreational, 198
recycling, 37, 99, 115, 133, 143
redundancy, 198, 202, 203
refrigerant, vii, viii, 23, 25, 26, 49, 51, 53, 56, 57, 58,
60, 61, 62, 66, 68, 69, 70, 71, 75, 76, 81, 83, 84,
85, 87, 88, 89, 92, 94, 96, 99
regenerate, 202
regeneration, 5, 36, 38, 145, 146, 199, 200, 204, 207,
223
regions of the world, 106, 129
regression, 157
regulations, 38, 111
rejection, 29, 30, 53, 56, 65, 73
relative humidity, xi, 106, 129, 175, 331, 332, 334,
341, 342
relevance, 170, 176
reliability, 14, 26
remodelling, 115
renewable energy, viii, 24, 27, 29, 31, 32, 73, 83, 95,
96, 103, 104, 105, 112, 116, 117, 118, 122, 128
renewable energy technologies, viii, 30, 103, 106,
128
repair, 31, 32, 127, 244
replication, 244
requirements, 2, 57, 68, 90, 104, 105, 109, 116, 135,
147, 198, 206, 217, 235
research institutions, 122
researchers, 167, 245
residues, 118, 143
358
Index
resilience, vii, x, 195, 196, 197, 198, 199, 200, 201,

202, 203, 204, 205, 206, 207, 208, 209, 210, 211,
256
resistance, 28
resolution, 17, 204, 235, 240, 245, 249
resource management, 133, 209
resources, vii, viii, 31, 32, 70, 83, 103, 104, 106,
112, 114, 115, 116, 128, 132, 134, 163, 167, 171,
185, 196, 198, 205
respiration, 200
response, x, 6, 14, 17, 18, 28, 112, 164, 198, 202,
203, 204, 213, 214, 216, 217, 221, 226, 229, 230,
232, 235, 236, 241, 247, 248, 252, 253, 255, 256,
257, 258
response time, 17, 18, 28
responsiveness, 117
restoration, 197, 256
RETs, 106, 128
revenue, 171
reverse osmosis, 145
rings, 4, 14, 225
risk(s), 26, 51, 114, 143, 147, 172, 181, 188, 189,
190, 204, 205, 252, 253
risk assessment, 188
room temperature, 4, 39, 92
root(s), 153, 155, 157
roughness, 29
routes, 222, 229, 245, 263
rowing, 225
Royal Society, 258, 259, 260
rules, ix, 105, 166, 167, 173, 187
rural areas, viii, 103, 108, 121, 133
rural population, 121
Russia, 172, 249
S
SAB, 125
safety, 26, 31, 75, 87, 108
saline water, 138
salinity, x, 107, 138, 162
salt concentration, 141, 148, 149, 154, 156, 157, 158,
159
salts, 142, 145, 161, 163
SAP, 144
saturation, viii, 24, 37, 56, 59, 84, 158
savings, viii, 24, 27, 31, 83, 86, 91, 93, 95, 98, 110,
111, 112, 158
scale system, 20
scaling, 201
science, x, 2, 51, 111, 113, 167, 187, 189, 191, 213,
246
scientific knowledge, 37
scope, 201
sea level, 52, 166, 255
sea-level rise, 255
seasonality, 213, 242, 255
second generation, 100
second virial coefficient, 47
security, 28, 72, 75, 171, 174, 178, 192
sediment(s), 231, 234, 235, 261
sedimentary records, 217
sedimentation, 200
seed, 38, 125, 200, 202, 208, 217, 222, 223, 225,
226, 244, 256, 259
seedlings, 217, 223, 225
segregation, 38
senescence, 199, 214
senses, 18
sensing, 17
sensitivity, 3, 20, 167, 168, 170, 172, 173, 174, 176,
181, 182, 184, 185, 186, 187, 252
sensors, vii, xi, 3, 16, 17, 20, 87
sequencing, 240
services, 31, 32, 69, 104, 106, 132, 171, 172, 174,
184, 189, 190, 192, 196, 198
set theory, ix, 166, 172, 187, 188
settlements, 104, 114
sewage, 37, 109
shade, 27, 83, 217, 218, 220, 221, 222, 223, 226,
227, 261
shape, 16, 40, 76, 108, 112, 171, 196, 200, 246
sheep, 138
shelter, 199
shock, 139
shoot(s), 218, 220, 261
shortage, 116
showing, 233, 234, 248, 251
shrubs, 94, 218
signals, 11, 204
signs, 143, 247
simulation(s), 49, 77, 78, 111, 116
siphon, 10
skin, 140, 161, 162
slag, 37
sludge, 37, 51, 108, 143
small communities, 108
social capital, 170, 171
social expenditure, 171
social services, 171
society, 104, 167, 168, 170
sodium, viii, 3, 13, 14, 17, 137, 138, 141, 142, 143,
144, 146, 147, 148, 149, 150, 151, 153, 154, 156,
159, 162
359
Index
sodium chloride, viii, 13, 137, 138, 141, 143, 146,
147, 148, 149, 150, 151, 153, 154, 156, 159, 162,
276, 304, 306, 317
sodium hydroxide, 17
software, 8, 12, 18, 173
soil erosion, 174, 200
soil pollution, 37
soil type, 96, 245
solar collectors, 117
solid phase, 41, 84, 145, 152, 155, 156, 157, 158
solid waste, 52, 138, 146, 164
solubility, 7, 9, 68, 143
solution, vii, ix, xi, 1, 2, 3, 4, 6, 9, 10, 11, 12, 13, 14,
16, 17, 18, 19, 23, 25, 33, 36, 38, 40, 68, 69, 70,
75, 76, 81, 82, 83, 96, 98, 99, 106, 110, 129, 138,
141, 142, 143, 144, 145, 146, 147, 148, 149, 150,
158, 160, 163
solvent stream, vii, 1, 2
solvents, 52
sorption, 41, 66, 139, 146
sorption process, 139
South Africa, 39, 143, 219, 257
South America, 218, 220, 222, 223, 261
Southeast Asia, 190, 219, 221, 222, 232
speciation, 236, 237, 248, 258
species richness, 209
specific heat, 24, 28, 29, 33, 49, 53
specifications, 92, 125
spending, 188
spontaneity, 42
stability, 36, 43, 53, 69, 75, 195, 196, 198, 199, 203,
204, 205, 208, 209, 211
stabilization, 140
stable states, 197, 207
stakeholders, 198, 205
stamens, 218
standard deviation, 17
standard of living, 31, 32, 171
standardization, 176
starch, 159
state(s), 19, 33, 40, 44, 47, 49, 51, 53, 56, 58, 64, 78,
81, 82, 84, 94, 132, 141, 144, 146, 163, 164, 166,
168, 171, 186, 191, 196, 197, 199, 201, 203, 204,
206, 207, 237
statistics, 189, 190, 238, 247
steel, 4
stock, 12, 39, 116, 144, 256
stomata, 222
storage, 38, 95, 96, 116, 126, 127, 135, 138, 142
storms, 52, 166
strategic planning, 132
stress, 72, 109, 172, 186, 235, 250
stressors, 167, 190
structural changes, 140

structure, x, 97, 104, 108, 115, 140, 142, 168, 170,
173, 176, 181, 196, 200, 201, 202, 206, 208, 210,
213, 214, 215, 217, 219, 226, 227, 228, 231, 235,
236, 237, 240, 244, 245, 248, 255, 258, 259
style, 110, 136
styrene, 17
subcutaneous tissue, 141, 146
subjective well-being, 189
subsistence, 174
substitution, 142, 144, 153
substrate, 147
succession, 200, 207, 208
Sudan, viii, 103, 104, 106, 107, 118, 120, 124, 126,
127, 132, 133, 134
sulfate, xi, 143
sulfuric acid, 144
sulphur, 52
supervision, 99
supplier(s), viii, 24, 95, 171
surface area, 24, 28, 36, 43, 99, 227
surface tension, 69
surfactant, 13
surfactants, 144
survival, 216, 231, 252, 256
susceptibility, 172, 188, 191, 232
sustainability, 104, 106, 114, 115, 116, 128, 188,
191, 196
sustainable development, 31, 32, 105, 101, 114, 128,
188
sustainable energy, 122
swelling, 100, 140, 146
syndrome, 134
synthesis, 2, 36, 40, 43, 168, 186, 204, 210, 211,
237, 260
T
tandem repeats, 244
target, 5, 16, 18, 104, 113, 256
tariff, viii, 24, 95
taxa, 214, 216, 219, 220, 229, 230, 231, 232, 233,
235, 245, 260
taxes, 171
taxonomy, 217, 255, 257
TBP, 6
techniques, x, 4, 20, 28, 32, 73, 75, 110, 115, 116,
133, 134, 144, 199, 217, 227, 239, 245
technology transfer, 122
tenants, 99
tensile strength, 140
tension, 69
terminals, 92
360
Index
terrestrial ecosystems, 210

testing, 2, 5, 8, 11, 19, 107, 134
tetrad, 225
texture, 139, 140, 225
TFE, 52
Thermal desalination, x, 267, 268
thermal energy, 46, 63, 64, 108
thermodynamic equilibrium, 47
thermodynamic parameters, 42
thermodynamic properties, vii, 49, 50, 68
thermodynamics, 40, 43, 45, 46, 64, 101
threats, 246, 262
time periods, 138, 160, 240, 241, 254
tissue, 141, 146, 250
total energy, x, 104, 132, 171
toxicity, 144
tracks, 258
trade, ix, 103, 165, 167, 168, 181, 184, 187, 250
trade-off, ix, 165, 167, 168, 181, 184, 187, 250
traditions, 113
training, viii, 103, 119, 122, 133
traits, 204, 213, 227, 236, 238, 250, 255, 258
trajectory, vii, 23, 69, 70
transformation, 40, 150, 216
transformations, 40
transparency, ix, 166, 167, 172, 174, 187
transpiration, 200
transport, vii, viii, 1, 2, 20, 38, 51, 98, 101, 105, 109,
116, 117, 132, 137, 139, 140, 145, 146, 156, 157,
160, 163, 171, 235, 262
transport processes, ix, 137
transportation, 105, 109, 138, 141, 142, 144
treatment, 104, 143, 144, 145, 147, 151, 159, 163
tributyl phosphate, 6
tropical forests, 232
Turkey, 134, 160, 161
turnover, 116, 216, 227, 232, 248, 252, 255
twist, 162
U
ultrasound, 147
uniform, 17, 29, 40, 44, 201, 229, 240
universal gas constant, 47, 156
universities, 184
urban areas, 108, 109, 116
urban densities, 105
urbanisation, viii, 103, 104
urbanization, 181
USDA, 160
UV, 17
V
vacuum, 2, 4, 6, 10, 14, 18, 75
valence, xi
validation, 3, 5, 13, 229
valuation, 135
valve, 4, 10, 11, 14, 27, 29, 30, 31, 57, 58
vapor, vii, 1, 2, 3, 4, 5, 6, 8, 9, 11, 12, 13, 14, 20
vapour absorption, vii, 23, 69, 70
variables, xi, 149, 152, 153, 170, 173, 174, 176, 181,
245, 250
variations, 167, 171
varieties, 93
vascular bundle, 219
vegetable oil, 147
vegetation, 113, 202, 207, 208, 214, 215, 216, 229,
230, 232, 234, 235, 258, 260, 261
vehicles, 109
vein, 218
velocity, 43, 92, 108
ventilation, 31, 32, 73, 109, 111, 112, 114, 116, 117,
134, 135
vertebrates, 262
Vietnam, 188
viscoelastic properties, 160
viscosity, 69
visualization, xi
vitamin C, 225
volatility, 2, 4, 5, 8, 9, 75
vulnerability, ix, 165, 166, 167, 168, 170, 172, 174,
176, 181, 184, 185, 186, 187, 188, 189, 190, 191,
206
vulnerable people, 167, 186
W
Wales, 225, 227, 253
walking, 117
warning systems, 171
Washington, 188, 189, 208, 258, 260
waste, 4, 8, 10, 27, 36, 37, 52, 64, 70, 83, 87, 97,
108, 114, 115, 138, 141, 143, 144, 146, 147, 160,
164
waste disposal, 52
waste heat, 27, 64, 97
waste management, 164
waste water, 138, 143, 144
wastewater, 36, 43, 51, 161
water absorption, 78, 83
water heater, 96
water quality, 51
water resources, 171, 185
361
Index
water supplies, 107
wavelengths, 73
weakness, 250
wealth, 133, 170, 171
wear, 89
web, 181, 188
well-being, 171, 189, 196
wells, 96
West Africa, 190
Western Australia, 235
Western Europe, 39
wetting, 13, 14
white oak, 263
wildlife, 201
wind power, 118, 124, 134
wind speed(s), 107, 118, 120, 124, 125, 126, 131,
132
windows, 89, 91, 94, 115
wood, 107, 118, 121, 225
woodland, 200
World Bank, 188, 189, 191

World Health Organization, 188
worldwide, viii, 26, 73, 83, 135, 137, 138, 148, 159,
256
X
xylem, 250, 258
Y
Yemen, 134
yield, xi, 49
Z
zinc, 36, 142

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ADVANCES IN ENVIRONMENTAL RESEARCH

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ADVANCES IN ENVIRONMENTAL RESEARCH

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ADVANCES IN ENVIRONMENTAL RESEARCH

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Improved Gas and Vapor Detection Using Denuder Technology

Environmental Protection from Thermodynamic Properties,

Some Aspects of Solar and Wind Energy Resources

Rationalization of Salt-Related Processes in the

Defuzzification of Fuzzy Concepts to Support Vulnerability

Ecological Resilience: Is It Ready for Operationalisation

Climate Change and an Australian Rainforest Conifer

A Novel Thermal Seawater Desalination Process

Biochemical Gas Sensor Bio-Sniffer and Imaging System

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Appropriate Time Scale for Aggregating Climatic Data

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In: Advances in Environmental Research. Volume 32

IMPROVED GAS AND VAPOR DETECTION USING

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Improved Gas and Vapor Detection Using Denuder Technology

VERIFICATION OF DENUDER COLLECTION EFFICIENCY

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VAPOR GENERATOR PREPARATION

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Improved Gas and Vapor Detection Using Denuder Technology

Figure 2. Schematic of the packed-bed vapor generator.

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Improved Gas and Vapor Detection Using Denuder Technology

Figure 4. GC-MS from VX during generation demonstrating purity of the sample.

Figure 5. Output of the VX generator at 16 C.

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Figure 6. Schematic of the packed-bed vapor generator.

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Improved Gas and Vapor Detection Using Denuder Technology

Figure 7. The denuder system flow schematic.

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Figure 8. The denuder sampling apparatus.

Figure 9. Sample transfer schematic.

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Improved Gas and Vapor Detection Using Denuder Technology

Figure 10. Second stage of the denuder sample-collection system.

Table 1. LC-MS Instrument Settings

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Figure 11. Example of the VX calibration curve.

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Improved Gas and Vapor Detection Using Denuder Technology

8 Advances in Environmental Research Vol 32 - Reyes & Kneeshaw 2014

8 Advances in Environmental Research Vol 32 - Reyes & Kneeshaw 2014