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Chorine Reactivity with Concrete Pipe Surfaces

John Woolschlager, Ph.D.1 and William J. Soucie, M.S.2


1
Assistant Professor of Civil Engineering, University of North Florida, 4567 Saint Johns Bluff Road,
Jacksonville, FL 32224, phone: (904) 620-1399; fax (904) 620-1391; e-mail: jwoolsch@unf.edu
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2
Water Quality Laboratory Supervisor, Central Lake County Joint Action Water Agency, 200
Rockland Road, Lake Bluff, IL 60044, phone: (847) 295-7788; fax: (847) 295-6853; e-mail:
soucie@clcjawa.com

Abstract

Chlorine disinfectants can dissipate dramatically within distribution systems. The


purpose of this study is to examine the loss of free chlorine to reactions with concrete
pipe surfaces. The distribution system examined in this study is owned by the Central
Lake County Joint Action Water Agency (CLCJAWA), a water distributor with 16
discrete delivery points supplying water to several suburban communities north of
Chicago. Field measurements taken from the distribution system included free and
total chlorine residual, pressure, and flow rates measured at the treatment plant and
the 16 water delivery points. The bulk water reactivity of the chlorine was
determined using batch tests. A hydraulic and water quality model of the distribution
system was established and calibrated for the specific days when the measurements
were taken from the distribution system. The bulk reactivity coefficient derived from
the batch tests was input to the model and the wall reactivity was calibrated to fit the
measured data. The results of this study showed that an average of 23 percent of the
free chlorine loss could be attributed to wall reactions with concrete pipes. Since the
finished water is very low in organics, the wall reactions can be attributed directly to
the concrete materials. Concrete is a composite material that contains a high fraction
of aluminates and silicates. Aluminates and silicates, over time, can form acidified
surfaces by splitting water, supplying a free proton that can catalyze acid-sensitive
reactions. Free chlorine exists as HOCl or OCl-, depending on the pH, with a pKa of
7.5. Because the pH is buffered much higher than 7.5, OCl- is the dominant form of
free chlorine in the CLCJAWA distribution system. If the concrete surfaces donate
protons, OCl- would shift to the more reactive HOCl, explaining the accelerated loss
of free chlorine at the concrete wall surfaces.

Introduction

Chlorine disinfectants are well known to dissipate within distribution systems. The
loss of chorine residuals can occur through reactions with constituents in the bulk
water and through reactions with pipe materials. Typical reactions that can occur on
pipe surfaces include the oxidation of Fe2+ to Fe3+ as part of the corrosion process of
iron pipes and oxidation of organics in biofilms attached to pipe surfaces. Concrete
pipe materials, previously thought to be inert, have shown to play a role in chlorine
decay in recent studies. In a study documented elsewhere (Woolschlager, 2000),
chloramines were shown to be highly reactive with reinforced concrete and concrete

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lined pipes. In fact up to 40 percent of the chloramine loss was linked to catalysis
reactions on the surface concrete materials. The purpose of this study is to examine
the loss of free chlorine (HOCl and OCl-) to reactions with concrete pipe surfaces.
The distribution system examined in this study is owned by the Central Lake County
Joint Action Water Agency (CLCJAWA), a water distributor with 16 discrete
delivery points supplying water to several suburban communities north of Chicago.
There are several features of the CLCJAWA distribution system that make it an ideal
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system to study the reactivity of free chlorine with concrete pipe surfaces: (1) the
hydraulics of the distribution system are very well defined; (2) pipes are composed
almost completely of reinforced concrete; (3) the finished water is very low in
organic carbon, so low that positive biofilms growth is not supported; and (4) free
chlorine is used as the residual disinfectant; and (5) built in 1992, the system is
relatively new. The project involved three logical tasks, which are described in the
following sections.

• Task 1 Distribution System Sampling


• Task 2 Establishment of a Hydraulic and Water Quality Model.
• Task 3 Analyses of the Causes of Disinfectant Loss.

Task 1—Distribution System Sampling

Weekly samples were taken from the treatment plant effluent and the delivery points
at the extents of the distribution system during the summer of 2001. Distribution
system samples were tested for all components that can trace disinfectant reactivity
and water quality decay in the distribution system. The measurements taken from the
samples are listed in Table 1. The analytical methods suggested are described in
Standard Methods for Water and Wastewater (APHA/AWWA, 1998).

Table 1
Field Testing Measurement Methods
Measurement Proposed Method
Disinfectant DPD Colorimetric per Standard Method 4500-Cl G.
Dissolved Organic Carbon Combustion-Infrared technique per Standard Method 5310 B.
Heterotrophic Plate Count R2A agar per Standard Method 9215.
Dissolved Oxygen Membrane Electrode Standard Method-O G.
Alkalinity Titration Method per Standard Method 2320 B.
Biodegradable Organic Matter BDOC technique developed by Joret et al. (1985).

The distribution system was sampled during the summer because this is a time when
disinfectant decay is highest. Each distribution sample was taken applying the
following steps: (1) Flush tap until temperature stabilizes before taking the first
sample; allow 3 minutes between subsequent samples; (2) Collect samples at each
location in sterile glass containers; (3) In the field, measure and record temperature

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and pH; (4) Note time, date, and location of each sample; (5) Transport samples to
laboratory at 4°C; (6) Analyze samples within 8 hours.

During the distribution system-sampling period, batch samples were taken from the
treatment plant effluent to determine chlorine reactivity in the bulk water. These
values are compared to the chlorine residuals measured in the distribution system.
The difference between the decay rate in the bulk water and the distribution system
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can be attributed to reactions with the pipe wall. Each batch sample was tested
applying the following steps: (1) obtain 5 one-liter samples from the treatment plant
effluent; (2) Incubate the one-liter samples and perform the tests listed in Table 1
after an incubation period of 0, 3, 7, 14, and 21 days.

Task 2—Establishment of a Hydraulic and Water Quality Model

A hydraulic and water quality model was established to evaluate disinfectant


reactively in the distribution system. Establishing the hydraulic and water quality
model requires two steps. First, a physical representation of the distribution system
must be established in the model, including the length and diameter of each pipe, the
geometry of pipe connections, and location and size of storage facilities. Second, the
model must be calibrated to fit measured data from the distribution system.

WaterCAD Version 5 (Haestad Methods, 2001) was selected to model the distribution
system. As with most hydraulic and water quality models, the physical features of
distribution systems are modeled in WaterCAD using links and nodes. A link
represents a pipe, while a node represents a pipe junction. Nodes must be established
at pipe junctions and where pipe diameters change. Once the basic network is
established, pumps, valves, storage tanks, and reservoirs can be added in the model,
usually located at model nodes. Finally, the system demands are defined at the water
withdrawal points in the system. The physical features of the CLCJAWA distribution
system include six 7.2 MGD finished water pumps, 30 miles of reinforced concrete
pipe ranging from 12 to 48 inches in diameter, three 13.5 MGD booster pumps, three
3-million gallon storage tanks, and sixteen demand points.

Two demand scenarios were developed from the year 2000 flow data: (1) an average
flow day, and (2) a maximum flow day. The average flow day and maximum flow day
were determined by taking the hourly average and maximum flows for the year. The
average day flow was 17.7 mgd and the maximum day flow was 30.8 mgd. The
results of the hydraulic calibration for the average day calibration were within 10
percent of the measured pressures, with an average pressure difference of 3.0 percent.
The maximum day model scenario fit the measured pressures within an average of 3.6
percent for all sites, but had two points that fell outside 10 percent of the measured
pressure. Several factors could explain why these two points seem to fall out of
calibration. First, there could be an undocumented feature that is causing head loss
(pressure drops) in the system, such as a half open or throttling valve. Another cause
could be inaccuracy in pressure measurements at these locations. Accuracy of
pressure measurements are affected by height of the pressure meter relative to the

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pipe, atmospheric pressure in the room around the meter, or a meter that is out of
calibration. Although the maximum day scenario had two points that did not fit the
measured data well, the overall calibration is a good fit to the data. Results of the
water quality calibration are discussed in the next section.

Task 3— Analyses of the Causes of Disinfectant Loss


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The main task of this study is to identify the causes of disinfectant loss in a
distribution system that contains concrete pipes. From the results of the water quality
model analysis, the causes of chlorine loss in the distribution system were evaluated.
Potential loss mechanisms of free chlorine include:

1. Oxidation reactions with organic matter in the finished water.


2. Oxidation reactions with iron in pipes (not applicable to CLCJAWA, since
iron pipe is not used extensively).
3. Surface catalysis on concrete pipe surfaces.

The third mechanism of chlorine loss is especially pertinent to the CLCJAWA, since
the distribution system is composed mostly of reinforced concrete pipe. Although
disinfectant reactions with concrete surfaces may seem far-fetched, this mechanism
was found to be the major cause of disinfectant loss in a recent distribution system
study where chloramines are used (Woolschlager, 2000).

The tool used in this study to analyze disinfectant loss patterns was the water quality
module of the WaterCAD model. WaterCAD has the capability of modeling
advective transport and constituent reactions in a water distribution system. A
detailed discussion of the water quality module contained in WaterCAD is found in
Appendix B-4 of the WaterCAD software manual (Haestad Methods, Inc., 2002).

The chlorine bulk water decay constant was derived from batch tests where water
samples were taken from the treatment plant effluent and the chlorine residual was
measured over a number of days. A first-order decay equation was fit to this data to
derive the first-order bulk water decay constant used by WaterCAD. Figure 1 shows
a first-order fit to one of the batch data sets, yielding a bulk water decay constant of
0.22 per day.

The bulk reaction rate was entered into the WaterCAD model with an initial pipe
reaction rate of zero. The model was run and the results were compared to the
measured chlorine in the distribution system. If the modeled chlorine is greater than
the measured chlorine, then reactions are taking place on the pipe surfaces and the
WaterCAD pipe reaction coefficient must be increased until the modeled chlorine fits
the measured chlorine. The calibration values from the water quality modeling
results show a first-order pipe wall decay rate of 0.08 ft/day. This level of wall
reaction accounts for 23 percent of the total chlorine decay among all sites in the
distribution system, while the remaining 77 percent of the chlorine loss occurs in the

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bulk water. To understand these trends, it is important to examine the specific
mechanisms of chlorine loss that can occur in the bulk water and at pipe surfaces.

1.20
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1.00
Batch test
Free Chlorine (mg/L)

0.80 First-order fit

0.60

0.40

0.20

0.00
0 5 10 15 20 25
Time (days)

Figure 1. Derivation of the chlorine bulk water reaction rate constant from
batch tests of the treatment plant effluent. The derived bulk water decay
constant is 0.22 per day.

Bulk Water Reactions: In the bulk water, free chlorine (HOCl and OCl-) can decay
through reactions with ammonia and organic matter. Any ammonia present when
free chlorine is added will form monochloramine (NH2Cl) though the following
generalized reaction (Leao and Selleck, 1983):

HOCl + NH3 ↔ NH2Cl + H2O

If excess free chlorine exists once all ammonia has been converted to
monochloramine, it is oxidized through a complex set of reactions termed the
breakpoint reactions as described by the work of Saunier and Selleck (1979) and
Jafvert and Valentine (1992). Although these reactions involve many complex steps,
the overall breakpoint reaction stoichiometry is approximately the following:

2 NH 2 Cl + HOCl ⇔ N 2(g) +3H + + 3Cl + H 2 O

Although ammonia can decrease free chlorine residuals significantly, these reactions
are relatively rapid and are complete before the water leaves the treatment plant.

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Therefore, they are not normally considered a contributor in the bulk water decay
within the distribution system.

The principle causes of free chlorine loss in the bulk water within the distribution
system are reactions with organic matter. These reactions are highly variable
depending on the properties of the organic matter. The organic content of treated
drinking water is primarily humic-type substances resulting from the decay of natural
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biomass in the source water (Aiken et al., 1987). These humic-type substances are
labeled natural organic matter (NOM). Strong oxidants like HOCl preferentially
attack electron-rich sites on NOM compounds, such as activated aromatic rings and
phenolic carbon sites (Korshin et al., 1996). Since NOM from different sources will
have different distributions of electron rich sites, they will also have differing reaction
rates with chlorine. Therefore, the bulk reaction rate changes by location and even by
season at the same location. Since Lake Michigan, the water source for CLCJAWA,
has relatively low organic carbon concentrations, the bulk reaction rate is lower than
most treated waters, which can vary from 0.10 to over 10.0 per day (Vasconcelos et
al., 1997). The bulk reaction rate of this study is 0.22 per day, which is very close to
the low end of the range of possible bulk reaction rates.

Pipe Reactions: Once the treated water enters the distribution system, free chlorine
can react with reduced iron released by corrosion processes. The reactive species of
iron is Fe2+, which is oxidized to Fe3+ based on the research of Piriou et al. (1997):

1 + 2+
1
2 HOCl + 2 H + Fe → Fe 3+ + 21 H 2 O + 21 Cl −

Reaction with corrosion products typically is the dominant disinfectant decay


mechanism in distribution systems where free chlorine contacts iron pipes. However,
this mechanism should not be issue for CLCJAWA, where the pipes are almost all
reinforced concrete.

Another possible source of pipe wall reactions arise from biofilm formation on pipe
surfaces. The microorganisms in these biofilms are composed of organic matter,
which can react with chlorine in the same way as it does in the bulk water. This can
be a significant source of disinfectant decay (Kiene et al., 1998). However, for low-
carbon water such as delivered by CLCJAWA, biofilm growth is expected to be low.

Finally, another possible source of wall reactions is chemical catalysis that can occur
on concrete surfaces. Concrete is mostly calcium silicates and aluminates. Silicates
and aluminates are weak acids in their pure forms and can donate protons supporting
acid catalysis reactions. This is especially true for aluminates that have a zero point-
of-charge at a pH of 9.1, being protonated in the normal pH of drinking water of 7.0
to 9.0.

Although silicates and aluminates can donate protons individually, they become a
much stronger proton donor when mixed. Combinations of silicate and aluminate
(aluminosilicates) can form a “super acid” surface by reacting with water as shown by

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Figure 2 (Campbell, 1988). The formation of super acid surfaces on aluminosilicates
is explained by the examining the different coordination requirements of aluminum
(threefold) and silicon (fourfold) in the polymeric oxide structure. If silica is the
major component, it enforces the fourfold coordination on the aluminum centers.
This creates a site on the aluminum atoms where a pair of electrons can be accepted
with ease to form the needed fourth bond. When aluminosilicates are in contact with
water, a pair of electrons can be donated from the hydroxide ion, conferring a
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negative charge on the aluminum atom. The proton lost from the water molecule
achieves bonding with the neighboring oxygen atom by accepting the electron density
associated with one of its lone pairs. This proton is easily donated, which increases
the rate of the acid-catalyzed reactions, which greatly increases the rate of
disinfectant decay.

H+ OH

Si O Al + H2O Si O Al-

Figure 2. Super-acid surface formation mechanism in mixtures of silicates


and aluminates (Campbell, 1988).

In a recent study, it was shown that acid-catalysis reactions accounted for up to 60


percent of the loss of monochloramine in a distribution system with concrete and
concrete-lined pipes (Woolschlager, 2000). The acid-catalysis of monochloramine is
well established as demonstrated by the increase in monochloramine decay at lower
pH (Jafvert and Valentine, 1992), but no evidence currently exists supporting the acid
catalysis of free chlorine species, although it is likely caused by the transformation of
OCl- to HOCl on acidified surfaces. Free chlorine exists at HOCl or OCl-, depending
on the pH, with a pKa of 7.5. In the CLCJAWA distribution system, the pH is
buffered much higher than 7.5, causing OCl- to be the dominant form of free chlorine.
If the concrete surfaces donate protons, OCl- would shift to the more reactive HOCl,
explaining the accelerated loss of free chlorine at the concrete wall surfaces. This
study shows the strong support for this type of reaction, but detailed bench studies are
needed to fully establish this fact. Bench studies examining this potential reaction
will be completed by the summer of 2003.

Conclusions

Although concrete pipe surfaces were thought to be inert, this study suggests that
concrete pipe surfaces can strongly influence the decay of disinfectants in the
distribution system. The mechanism of this influence is likely acid catalysis driven
by the splitting of water by the aluminosilicates contained in concrete, which shifts
free chlorine to its more reactive form – HOCl. Since many utilities are selecting

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concrete or concrete-lined pipes for their distribution system, this discovery should be
further studied to fully establish the impact of concrete materials on disinfectant
decay.

References:
Aiken, G., McKnight, D., Wershaw, R., and MacCarthy, P. (1987). Humic
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Substances in Soil, Sediment, and Water. Wiley-Interscience, New York.


Campbell, I. M. (1988). Catalysis at Surfaces. Chapman and Hall, London.
Haestad Methods, Inc, (2002). WaterCAD for Windows – Version 5. Haestad Press,
Waterbury, Connecticut.
Jafvert, C., and Valentine, R. (1992). Reaction scheme for the chlorination of
ammoniacal water. Environ. Sci. Technol., 26 (3), 577-586.
Joret, J., Levi, Y., and Volk, C., (1991). Biodegradable Dissolved Organic Carbon
(BDOC) Content of Drinking Water and Potential Regrowth of Bacteria. Wat. Sci.
Tech., 24(2),95-100.
Kiene, L., Lu, W., and Levi, Y. (1998). Relative importance of the phenomena
responsible for chlorine decay in drinking water distribution systems. Water Sci.
Technol., 38(6), 219-227.
Korshin, G., Li, C., and Benjamin, M. (1996). Use of UV spectroscopy to study
chlorination of natural organic matter. In: Water Disinfection and Natural Organic
Matter, R. Miner and G. Amy (eds.). American Chemical Society, Washington, D.C.,
pp. 182-195.
Leao, S. and Selleck, R. (1983). Chemistry of combined residual chlorination. In:
Water Chlorination: Enviromental Impact and Health Effects, R. Jolley (ed.), vol 3.
Ann Arbor Sci., pp. 139-149.
Piriou, P., Kiene, L., and Levi, Y. (1997). Study and modeling of drinking water
quality evolution using a pipe loop system. Proceedings of the Annual Meeting of the
American Water Works Association. (June 15-19, 1997; Atlanta, Georgia).
Saunier, B., and Selleck R. (1979). The kinetics of breakpoint chlorination in
continuous flow systems. J. of Am. Wat. Works. Asso., 71(3), 164-172.
Standard Methods for the Examination of Water and Wastewater (1998). APHA,
AWWA, and WPCF. Washington, D.C.
Vasconcelos, J. J., Rossman, L. A., Grayman, W. M., Boulos, P. F., and Clark, R. M.
(1997). Kinetics of chlorine decay. J. of Am. Water Works Assoc., 89(7), 54-65.
Woolschlager, J. (2000). A Comprehensive Disinfection and Water Quality Model.
Ph.D. Dissertation. Northwestern University, Evanston, Illinois, USA.

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