International Journal of Engineering Sciences, 2(5) May 2013, Pages: 145-153

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ISSN
2306-6474

International Journal of Engineering Sciences

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A Synopsis on Biogenic and Anthropogenic Volatile Organic

Compounds Emissions: Hazards and Control
Abdullahi Mohammed Evuti
Department of Chemical Engineering, University of Abuja-Nigeria.
AR TIC LE INF O

AB STR AC T

Keywords:

The growing interest on volatile organic compounds is because of their harmful effects to humans
and the environment. This paper discusses the consequences and documents a simple synopsis of
the various hazardous effects of these compounds to humans and environment. These include toxic
and carcinogenic human effects, stratospheric ozone depletion and ground level photochemical
ozone formation, enhancement of global greenhouse effect and accumulation and persistence in the
environment. The various control measures were also discussed.

VOCs
Biogenic
Anthropogenic
Emission
Hazards
Control

1.

2013 Int. j. eng. sci. All rights reserved for TI Journals.

Introduction

The monitoring of volatile organic compounds (VOCs) in ambient air has received substantial attention over the past several years because
certain VOCs are known to be hazardous to human health and the environment [1]. Biogenic VOCs are produced by plants, animals,
microbes and fungi [2] while anthropogenic VOCs are primarily emitted by chemical process industries (CPI) dealing with the
manufacture, storage, handling and distribution of paints, lubricants and liquid fuels; and the combustion processes [3]. With continued
global industrialization, the atmospheric concentrations of VOCs due to primary as well as fugitive emissions have constantly been on rise.
Enhanced emissions of VOCs from various biogenic and anthropogenic sources have not only reduced the air quality within source regions,
but also have altered the composition of the atmosphere in remote regions through medium- and long-distance (trans-boundary) transport
[4]. The toxicity of VOCs even at very low concentrations makes their removal from air and wastewater or contaminated ground water an
important issue in our industries and homes [5-6]. VOCs are dangerous to human health and also trigger serious environment problems
such as ozone layer depletion, offensive odour, photochemical smog and acid rain [2, 7-8]. This has led to the enactment of stringent
environmental laws; especially in industrialized countries which have forced industries to search for effective abatement technologies that
can comply with these laws.
Over the years, a lot of researches have been done on the development of technology for the treatment of VOCs. However, due to the
negative impact of the exposure to these compounds, there is a continuous need for researches in this area. This paper is aimed at
reviewing the hazards of VOCs to both human and the environment and the current status of researches on the various hazards control
measures.

2.

VOCs sources

VOCs are part of the large hydrocarbon family, a vast array of aliphatic, aromatic hydrocarbons, their halogenated derivatives, alcohols,
ketones and aldehydes. VOCs have a property of conversion into vapour or gas without any chemical change due to their low boiling points
[9]. Many VOCs are human- made chemicals that are used or produced in the manufacture of paints, adhesives, petroleum products,
pharmaceuticals and refrigerants. Many are also compounds of fuels, solvents, hydraulic fluids, paint thinners and dry cleaning agents
commonly used in urban settings such as bleach [10]. Some are also produced by plants, animals, microbes and fungi. According Goldstein
and Galbally, biological sources emit an estimated 1150 teragrams of carbon per year in the form of VOCs. The majority of VOCs are
produced by plants with isoprene as the main compound [2]. For example, a 62,000 km 2 area of forest in US state of Pennsylvania emits an
estimated 3400000 kilograms of terpenes on a single day in august during growing season [11]. Research result also shows that
anthropogenic sources emit about 142 teragrams of carbon per year in the form of VOCs [2]. Mller reported that the total global
anthropogenic non-methane VOC emissions are about 150 Tg yr1 [12]. However, the relative emission varies from region to region
depending on the level of industrial activities, climate and the vegetation. For example, in the densely forested Nordic areas, especially in
Finland, the biogenic VOC emissions are generally higher than the anthropogenic emissions [13]. The regional breakdown of total global
anthropogenic non-methane VOC emission is shown in Figure 1 below.

* Corresponding author.
Email address: evutimohd@yahoo.com

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Inter nat ional Journal of Engineer ing Sci ences, 2(5) May 2013

Figure 1: Regional breakdown of total global anthropogenic non-methane VOC emission [14]

The global emission of non-methane VOCs (NMVOC) for the year 1990 is 153,244 ktones while in 1995 the amount increased to 159,634
ktones as shown in Table 1 below.
Table 1: National VOCs emissions in Ktonnes [15]

COUNTRY
AUSTRALIA
JAPAN
MALAYSIA
SINGAPORE
THAILAND
UNITED KINGDOM
UNITED STATES

1990

1995

2,377.01
5,435.64
1,636.93
124.66
898.9
3,360.80
19,626.79

2,390.73
5,851.56
1,938.23
156.11
1,195.96
3,567.10
19,497.00

The contribution made by different sectors to emissions of NMVOCs as shown on Figure 2 reveals that solvent and product use accounts
for the highest NMVOCs with a value of 35.8%.

Figure 2: Contributions of various sectors to emission of NMVOCs [15]

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3.

VOCs hazards

VOCs play important role in the following environmental problems.

A. Toxic or carcinogenic human health effects
Based on the epidemiological studies, the United States Environmental Protection Agency (USEPA) has identified some of the VOCs as air
toxics or carcinogens [16]. Exposure to VOCs concentrations above the allowable limit usually result in acute and chronic health effects.
These include eye, nose and throat irritation, headaches, vomiting, dizziness cancer, liver damage, kidney damage, nervous system damage
and asthma exacerbation [17]. For example, exposure to air containing 600 ppm of toluene for more than 8 hours causes headache and
dizziness [18]. Another hazard of VOCs is formation of odours. Researches have shown that the presence of odors is also associated with
VOC emissions. A wide number of VOCs such as 2-butanone, -pinene, tetrachloroethylene, dimethyl disulfide, -pinene, limonene,
phenol and benzoic acid have been identified important classes compounds with high odor impact [19]. The health effects of some VOCs
are shown in Table 2.
Table 2: Some VOCs and their harmful effects [17]

VOCs

HARMFUL EFFECTS

Benzene
Toluene
Xylene

Carcinogenic
Headache and dizziness
Eye and respiratory tract irritation, narcotic effect, nervous system depression and death

Chloroform
Ethylene, Styrene
Acetaldehyde, acetone
Phenol
Epoxides
Ethers
Vinyl chloride, freon
Nitrogen containing compounds (Amines)

Affect central nervous system causing depression, dizziness, liver and kidney damages, skin infection
Depletion of ozone layer
Respiratory and eye irritation
Offensive odour and toxicity
Toxic, carcinogenic, explosive
Producing peroxides, affecting the reproductive system
Ozone hole formation, carcinogenic, toxic, greenhouse effect, climate changes
Bad odour, carcinogenic (affecting urinary bladder)

B. Stratospheric ozone depletion

VOCs also cause stratospheric ozone layer depletion, formation of highly toxic secondary pollutants (i.e tropospheric ozone and
peroxyacetylnitrate) leading to global green-house effect [20]. Many organic compounds are stable enough to persist in the atmosphere, to
survive tropospheric removal processes, and to reach the stratosphere. VOCs containing chlorine or bromine substituents undergo
stratospheric photolysis and hydroxyl radical destruction which lead to the release of active ozone-destroying chain carriers and further
stimulation of stratospheric ozone layer depletion and Antarctic ozone hole formation. Examples are chlorinated solvents and refrigerants,
bromine-containing fire retardants and fire extinguishers [21].
C. Ground level photochemical ozone formation
VOCs undergo complex photochemical reactions in the presence of sunlight and oxides of nitrogen to form ozone, a major component of
urban air smog [16]. O3 is produced from the photolytic decomposition of NO 2 when the oxygen atom formed rapidly recombines with
molecular oxygen (O2) as follows.

NO2 HV NO O

(1)

O O2 O3

(2)

The reaction of VOCs with sunlight and NOx also produces ozone analogous to the reactions starting with CO or CH4, but the reaction
mechanism is much more complicated. The steps involved are [14]:

Ozone undergoes photolysis to form O* (O singlet D), which reacts with water to form two hydroxyl radicals:
O 3 + h O2 + O*
(3)
Followed by
O* + H2O 2 OH
(4)
Two VOC (the carbon source, here indicated as R-H) molecules react with OH radicals followed by oxygen to form RO2 (peroxy
radicals):
R-H + OH R + OH
(5)
Followed by
R + O2 RO 2
(6)
The peroxy radicals react with NO to form NO2 : RO2 + NO RO + NO2
(7)
The NO2 molecules absorb light to form O atoms: NO2 + h NO + O
(8)
The O atoms attach to O2 to form O3 : O + O2 O3
(9)

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Inter nat ional Journal of Engineer ing Sci ences, 2(5) May 2013

It can be observed that one ozone molecule produces two OH radicals, and each OH radical results in the formation of two ozone
molecules. Thus, the reaction is a branched chain reaction. In addition, each VOC molecule can start many chain reactions, since, in
general, each VOC molecule has several hydrogen atoms to react; i.e., the left over RO radical can enter into more reactions to form ozone.
This can be represented by Figure 3 below.

Figure 3: Series of reaction with VOCs to form ozone (14)

Ground level ozone is of concern not only with respect to human health but also because of its effects on crops, plants, and trees. Elevated
ozone concentrations during summertime photochemical pollution episodes may exceed environmental criteria set to protect both human
health and natural ecosystems. It is these concerns which led to the formulation of the Geneva Protocol and which underpin the reductions
in emissions and control actions which it stipulates (21) .
D. Enhancing the global greenhouse effect
Processes that interfere with the earths radiation budget result in the phenomenon of global warming otherwise referred to as climate
change or the greenhouse effect [22]. The earth absorbs energy in the form of ultraviolet, visible and infrared radiation from the sun and
emits infrared radiation to outer space. These two processes are always in balance. Certain atmospheric trace gases, the radiatively-active
trace gases, absorb some of the outgoing infrared radiation and so disturb this radiative balance. The earths surface and atmosphere react to
this disturbance by warming and so as to re-establish the radiative balance. This process is called radiative forcing and the warming is the
greenhouse effect. The most important radiatively-active trace gases in the atmosphere are water vapour and carbon dioxide. Their presence
accounts for the natural greenhouse effect that is estimated to be about 30 oC (21-23).
There are possible climate change consequences of VOC emissions to the atmosphere and from their control by incineration [22]. The
relative effectiveness of a compound to cause global warming compared with carbon dioxide can be expressed in term of Global Warming
Potentials (GWPs). The GWP of a trace gas can therefore be defined as the ratio of the radiative forcing from a given mass emission of the
trace gas compared to that from the same mass emission of carbon dioxide, integrated over a given time horizon. Simply stated, the GWP
of a VOC is a measure of its climate change impact relative to carbon dioxide [22-23]. Table 3 shows the GWPs of some common VOCs.
Many organic compounds are not themselves radiatively active gases, but they do have the property of potentially being able to perturb the
global distributions of other radiatively active gases. If they exhibit this property, then they can be classes as secondary greenhouse gases
and indirect GWPs may be defined for them. Organic compounds can behave as secondary greenhouse gases by: reacting to produce ozone
in the troposphere; increasing or decreasing the tropospheric *OH distribution and hence perturbing the distribution of methane [21].
If the VOC is destroyed in an incinerator using a fossil fuel to complete combustion or thermal oxidation, then the CO 2 equivalent
emissions have a contribution from the carbon in the VOC that is released from the incinerator as CO2 and the carbon in the fossil fuel used
to complete combustion. However, the CO2 equivalent emissions may be offset by a reduction in primary fossil fuel combustion used
elsewhere in the installation to generate heat if heat is recovered from the incinerator [22].

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Table 3: Global warming potential of some common VOCs in a 100-year time horizon [22]
VOLATILE ORGANIC COMPOUNDS
dimethylether
Dichloromethane
Chloromethane
Bromomethane
1,1,1-Trichloroethane
Chlorodifluoromethane
Dichlorotrifluoroethane
Chlorotetrafluoroethane
Dichlorofluoroethane
Chlorodifluoroethane
Dichloropentafluoropropane
Dichloropentafluoropropane
Trifluoromethane
Difluoromethane
Pentafluoroethane
1,1,1,2-Tetrafluoroethane
1,1,1-Trifluoroethane
1,1-Difluoroethane
1,1,1,2,3,3,3-Heptafluoropropane
1,1,1,3,3,3-Hexafluoropropane
1,1,1,3,3-Pentafluoropropane
1,1,1,3,3-Pentafluorobutane
1,1,1,2,3,4,4,5,5,5-Decafluoropentane
ethane
propane
butane
ethylene
propylene

GLOBAL WARMING PONTENTIAL

1
10
16
5
144
1780
76
599
713
2270
120
586
14310
670
3450
1410
4400
122
3140
9500
1020
782
1610
8.4
6.3
7.0
6.8
4.9

E. Accumulation and persistence in the environment

Some of the higher molecular mass organic compounds are persistent enough to survive oxidation and removal processes in the boundary
layer and may be transported over large distances before being removed in rain. The semi-volatile VOCs with high molecular size and
complexity tend to become adsorbed onto the surface of suspended particulate matter. In this form they undergo long-range transport and
may be removed in rain remote from their point of original emission. Once deposited in rain, they may re-evaporate back into the
atmosphere and begin the cycle all over again. Ultimately this material may be recycled through the atmosphere before reaching its more
permanent sink in the colder aquatic environments in Polar Regions. Biological accumulation in these sensitive environments can lead to
toxic levels in human foodstuffs in areas exceedingly remote from the point of original emission. Examples of these compounds are PCBs,
PCTs, and phthalic acid and its derivatives [21].
Soil VOCs are of concern primarily as a potential source of ground-water contamination. They may contribute to inhalation exposure,
which can result when volatile emissions emanate from the soil surface. Soil VOCs also may be associated with ingestion exposure, which
can occur when children play in contaminated soil or when the compounds are absorbed into the edible portion of agricultural plants [24].

4.

VOCs hazard control philosophy

The release of anthropogenic VOCs may occur at various stages such as during production, use, storage, degradation of material and from
wastewaters. This will then be transmitted through air path to the receiver as shown in Figure 4 below. Hazard control program consist of
all steps necessary to protect worker from exposure to a substance or system. The controls are usually placed at the source (where the
hazard comes from), along the path (where the hazards travels) and at the worker [25].

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Source
Elimination
Substitution
Enclosure
Process change

Transmission
Shielding
Distance
Dilution ventilation

Receiver
Remove worker
Reduce exposure
Enclose worker
Reduce no. of worker
Personal Protective
Equipment

Figure 4: Transmission of VOCs from source to the receiver [25]

The principles of Hazard control are shown in Figure 5. The first step which is elimination of the hazard is the best option; if elimination is
not possible then substitution should be considered.

Figure 5: Hierarchy of Hazard control

Engineering control is applied to control hazards by engineering modifications in the process if there is no suitable substitute. The next
principle advocate the management (administrative) control by making some administrative mechanism in the work place to keep away
hazards from human and workplace. The application of all four control measures with the use of personal protective equipment (PPEs)
reduces the hazards significantly in workplace and outside the unit [26].
A. Elimination
Elimination is the most effective way to control hazards because hazard is controlled at the source. It is important to consider health and
safety aspects when work processes are still in the planning stages [26]. The plant should be designed to eliminate emission of VOCs. The
only way to avoid environmental harm from waste is to prevent its generation. Pollution prevention means changing the way activities are
conducted and eliminating the source of the problem. It does not mean doing without, but doing differently. For example, preventing waste
pollution from litter caused by disposable beverage containers does not mean doing without beverages; it just means using refillable bottles.
Elimination of hazards can be achieved through sustainable design [27]. Sustainable design (also called environmental design,

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environmentally sustainable design, environmentally conscious design, etc.) is the philosophy of designing physical objects, the built
environment, and services to comply with the principles of social, economic and ecological sustainability. The intention of sustainable
design is to "eliminate negative environmental impact completely through skillful, sensitive design [27]. Sustainable design is mostly a
general reaction to global environmental crises, the rapid growth of economic activity and human population, depletion of natural
resources, damage to ecosystems, and loss of biodiversity [28].
B. Substitution
This involves trying to replace a particular dangerous chemical or work process with a safer substitute [26, 29]. An example of substitution
includes using less hazardous solvents instead of toxic ones, such as using dichloromethane or fluorochlorohydrocarbon instead of carbon
tetrachloride; and toluene, cyclohexane or ketones instead of benzene [25-26].
C. Engineering Control
Engineering control include the following measure; enclosure, isolation and ventilation [25-26].
i. Enclosure
Many hazards can be controlled by partially or totally enclosing the work process. Highly toxic materials that can be released into the air
should be totally enclosed, usually by using a mechanical handling device or a closed glove system that can be operated from the outside
[25].
ii. Isolation
Isolation can be an effective method of control if a hazardous job can be moved to a part of the workplace where fewer people will be
exposed, or if a job can be changed to a shift when fewer people are exposed (such as a weekend or midnight shift). The worker can also be
isolated from a hazardous job, for example by working in an air-conditioned control booth. It is also important to limit the length of time
and the amount of a substance(s) to which workers are exposed if they must work in the hazardous area. For example, dust-producing work
should be isolated from other work areas to prevent other workers from being exposed. At the same time, workers in the dusty areas must
be protected and restricted to only a short time working in those areas. Isolation is also possible by using PPEs in the hazardous areas [2526].
iii. Ventilation
Ventilation helps to prevent the work environment from being too hot, cold, dry or humid and eliminate or lower the level of hazardous airborne contaminants or flammable vapours at source [30]. There are two types of ventilation: local exhaust ventilation and general
ventilation. Whatever the type, ventilation should be used together with other methods of control. Local exhaust control usually uses
suction, based on the principle of a vacuum cleaner, to remove pollutants from the air. The fumes may be sucked into an open tank and then
transferred to a disposal point away from the workers or fumes may be sucked into a canopy hood which hangs over a contaminant and
forced out through a ventilation duct [25-26].
General ventilation which is also referred to as dilution ventilation [30] which is used for keeping the workplace comfortable is one of the
least effective methods of controlling hazards but one of the most commonly used. The purpose of any general ventilation system is to
remove contaminated air and replace it with fresh air. This system does not really remove hazardous agents from the air; it simply
reduces the amounts in the air to levels that are considered safe for breathing. The effectiveness of a general ventilation system depends
on several things, like: how quickly the hazardous agent is being released into the air; how much and how quickly fresh air is coming in;
and how the contaminated air is being removed [25-26].
The contaminant equilibrium level depends on the volume flow rate of the ventilation air and on the rate at which contaminants are
introduced into the room space. Assuming that the volume flow rate of the contaminants is very small in comparison with the ventilation air
flow rate, it is possible to determine the contaminant equilibrium level using equation 10 [30]. Equation 10 applies equally to viable and
non-viable contaminants and a variety of units can be used for the contaminant equilibrium level (e.g. ppm, mg/m3 and cfu/m3).

Ce

Qch
N vent *V

Where:
Qch = Rate at which contaminants are introduced into the room space per hour (cfu/h)
Nvent = Number of air changes per hour due to ventilation system (h-1)
V
= Room Volume (m3)

(10)

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D. Administrative Control
Administrative controls limits the duration of working time of the workers at a hazardous place [31]. Some examples of administrative
controls include: changing work schedules (for example, two people may be able to work for four hours each at a job instead of one person
working for eight hours at that job); giving workers longer rest periods or shorter work shifts to reduce exposure time; moving a hazardous
work process to an area where fewer people will be exposed; changing a work process to a shift when fewer people are working. Other
measures include clear and readable signage, compliance to the regulatory provisions, motivations in form of bonus to those who regard
safety and follow the safety instructions and disclosure of the hazards and risk to civil administration to get help in real emergency [25-26].
E. Personal protective equipment
Personal protective equipment (PPE) is the least effective method of controlling occupational hazards and should be used only when other
methods cannot control hazards sufficiently. PPE can be uncomfortable, can decrease work performance and can create new health and
safety hazards. For example, ear protectors can prevent from hearing warning signals, respirators can make it harder to breathe, earplugs
may cause infection, and leaky gloves can trap hazardous chemicals against the skin. PPEs should be used in addition to other control
hazards methods. However, if it is impossible to reduce hazards in spite of the, elimination, substitution, engineering and administrative
controls then PPEs should be used to save lives of workers and even community. Examples of PPE include: safety glasses, ear protectors,
respirators with filters, dust masks, gloves, protective suits and safety shoes [25-26].
PPE is also mandated by Occupational Safety and Health Administration (OSHA) standards:
- OSHA standard 1910.132(a) says that, "Protective equipment, including personal protective equipment for eyes, face, head, and
extremities, protective clothing, respiratory devices, and protective shields and barriers, shall be provided, used, and maintained in a
sanitary and reliable condition wherever it is necessary by reason of hazards of processes or environment, chemical hazards, radiological
hazards, or mechanical irritants encountered in a manner capable of causing injury or impairment in the function of any part of the body
through absorption, inhalation or physical contact" [32].

5.

Conclusion

VOCs are produced from both biogenic and anthropogenic emissions. While biogenic emissions are the highest global VOC source,
emissions from human activities plays the dominant role in human and environmental hazards. These include toxic and carcinogenic human
effects, stratospheric ozone depletion and ground level photochemical ozone formation, enhancement of global greenhouse effect and
accumulation and persistence in the environment. Hazard control program consist of all steps necessary to protect worker from exposure to
a substance or system. The controls are usually placed at the source (where the hazard comes from), along the path (where the hazards
travels) and at the worker. The review shows that the following steps are necessary for effective hazard control; assessment, analysis,
proper judgment of the right control methods, appropriate control methods recommendation, proper implementation and monitoring of the
whole process.

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