Recent Advances in Disinfection By-Products
Recent Advances in Disinfection By-Products
Recent Advances in Disinfection By-Products
Disinfection By-Products
Recent Advances in
Disinfection By-Products
Clemson University
Anderson, South Carolina
Sponsored by the
ACS Division of Environmental Chemistry, Inc.
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by-products (DBP) research around the world. The current book is based on
a symposium entitled Occurrence, Formation, Health Effects and Control of
Disinfection By-Products in Drinking Water, held at the 248th National Meeting
of the ACS Division of Environmental Chemistry, in San Francisco, California,
on August 10-14, 2014.
The formation, control, and health effects of DBPs in drinking water are
issues of international concern because of the health effects (e.g., bladder
cancer and potential adverse reproductive-development impacts) associated with
exposure to certain DBPs. As a result, many countries, as well as the World Health
Organization, have regulations and/or guidelines on acceptable concentrations of
DBPs in water.
In recent years, DBP research worldwide has focused on determining
the possible adverse health effects of emerging, yet unregulated, DBPs,
specifically halogenated (e.g., iodinated) and non-halogenated nitrogenous (e.g.,
nitrosamines) DBPs. The breadth of DBP research is very broad from source
waters (e.g., wastewater, wildfire, seawater intrusion influences) to treatment
strategies and technologies, followed by distribution system and point of entry
issues (e.g., biofilms, heating, swimming pools), as well as health effects and
analytical method developments. Recent research is helping to understand factors
controlling formation and to develop a cost-effective control of a wide range of
regulated and emerging DBPs. Furthermore, the pace of research on emerging
DBP toxicity has increased and generated diverse findings, with comparative
toxicity and the molecular mechanisms leading to improved understanding of
their toxicity pathways and potential adverse biological effects.
This book represents the latest research efforts to understanding these
important DBP-related issues. The authors of the chapters in this book are a
multidisciplinary group of scientists and engineers, who are conducting studies
in many parts of the world. The chapters in this book address both regulated and
emerging DBPs and are organized under the sections on DBP toxicology and
health effects, modeling of DBP formation, precursors and reactions involving
nitrosamines, and formation of halogenated DBPs. This book will be of interest
to researchers, drinking water utility scientists and engineers, toxicologists,
epidemiologists, and regulators interested in the formation and control of and
exposure to DBPs.
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In Recent Advances in Disinfection By-Products; Xie, et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
We wish to thank all individuals who served as peer reviewers of our
chapter manuscripts. We also wish to gratefully acknowledge the Water Research
Foundation for their financial assistance in support of the symposium, and the
Association of Environmental Engineering and Science Professors for their
assistance in disseminating information on the symposium.
Tanju Karanfil
Department of Environmental Engineering and Earth Sciences
Clemson University
Anderson, South Carolina 29625
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Bill Mitch
Department of Civil and Environmental Engineering
Stanford University
Stanford, California 94305
Paul Westerhoff
School of Sustainable Engineering and The Built Environment
Arizona State University
Tempe, Arizona 85287-3005
Yuefeng Xie
Civil and Environmental Engineering Programs
Capital College
The Pennsylvania State University
Middletown, Pennsylvania 17057
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Chapter 1
Department of Crop Sciences and the Center of Advanced Materials for the
Purification of Water with Systems, Safe Global Water Institute, University
of Illinois at Urbana-Champaign, Urbana, Illinois 61801
*E-mail: [email protected].
Introduction
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In 2002 the U.S. EPA published a landmark study commonly referred to as the
Nationwide Occurrence Study (36, 37). In this study, novel quantitative analytical
methods were developed for measuring the priority DBPs; the occurrence of a
wide variety of DBPs in drinking waters throughout the U.S. was determined; the
effect of source water and treatment conditions on DBP formation was measured;
the fate and transport of these DBPs in the distribution system were studied; and
the identification of new DBPs was reported. This study clearly demonstrated
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that hundreds of DBPs were differentially distributed in drinking waters within
the U.S. However, the Nationwide Occurrence Study did not identify the toxicity
of the water samples. In concert with the data generated by the Nationwide
Occurrence Study, our laboratory developed mammalian cell microplate-based
assays and generated in vitro, systematic, analytical, comparative databases
on the chronic cytotoxicity and genotoxicity of individual DBPs. To date we
have analyzed 87 DBPs (Table I). Their comparative cytotoxicity in Chinese
hamster ovary (CHO) cells (LC50) is presented in Figure 1 (carbon-based DBPs)
and Figure 2 (nitrogen-containing DBPs). Their comparative genotoxicity is
presented in Figure 3. These data provide a direct comparison of the cytotoxicity
and genotoxicity of DBPs within a chemical class and among chemical classes
and allow for detailed structure activity relationships to be studied by integrating
analytical chemistry and analytical biology. The data for Figures 1-3 were
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published (12, 24–27, 29–31, 33, 38–43) and represent the largest toxicity
database for DBPs. This work as well as recent bioanalytical research will
provide a foundation to identify forcing agents that contribute to the toxicity of
disinfected water.
Figure 1. CHO cell chronic cytotoxicity analyses of carbon based DBPs. The abbreviations for the DBPs are listed in Table I. Each DBP is
repre-sented as its LC50 concentration (50% cell density as compared to the negative control).
Figure 2. CHO cell chronic cytotoxicity analyses of N-DBPs. The abbreviations for the DBPs are listed in Table I. Each DBP is represented
as its LC50 concentration (50% cell density as compared to the negative control).
Figure 3. CHO cell genotoxicity analyses of DBPs. The abbreviations for the DBPs are listed in Table I. Each DBP is represented as its
midpoint of the SCGE genotoxicity concentration-response curve or its 50%Tail DNA metric.
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Table I. (Continued). DBPs Analyzed for CHO Cell Cytotoxicity and
Genotoxicity and Abbreviations
Abbreviation DBP Abbreviation DBP
2-Bromo-3-
2B3MBTDA BNM Bromonitromethane
methylbutenedioic acid
CNM Chloronitromethane
DBNM Dibromonitromethane
HPYL Halophenolics DCNM Dichloronitromethane
BCNM Bromochloronitromethane
4-Hydroxy-3-iodo-1-
4HIPOLA TBNM Tribromonitromethane
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phenolic acid
TIPOL 2,4,6-Triiodo-1-phenol TCNM Trichloronitromethane
Bromodichloroni-
BDCNM
tromethane
Dibromochloroni-
HAN Haloacetonitriles DBCNM
tromethane
BAN Bromoacetonitrile
CAN Chloroacetonitrile HAcAm Haloacetamides
IAN Iodoacetonitrile BAcAm Bromoacetamide
DBAN Dibromoacetonitrile CAcAm Chloroacetamide
DCAN Dichloroacetonitrile IAcAm Iodoacetamide
Bromochloroacetoni-
BCAN DBAcAm Dibromoacetamide
trile
TCAN Trichloroacetonitrile DCAcAm Dichloroacetamide
DIAcAm Diiodoacetamide
CN Cyanogen Halides BIAcAm Bromoiodoacetamide
BN Cyanogen Bromide CIAcAm Chloroiodoacetamide
CN Cyanogen Chloride BCAcAm Bromochloroacetamide
IN Cyanogen Iodide TBAcAm Tribromoacetamide
TCAcAm Trichloroacetamide
NA Nitrosamines DBCAcAm Dibromochloroacetamide
N-nitrosodimethy-
NDMA BDCAcAm Bromodichloroacetamide
lamine
NDPhA N-nitrosodiphenylamine N2DCAcAm N,N-Dichloroacetamide
NPIP N-nitrosopiperidine NCAcAm N-Chloroacetamide
NMOR N-nitrosomorpholine
Continued on next page.
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Table I. (Continued). DBPs Analyzed for CHO Cell Cytotoxicity and
Genotoxicity and Abbreviations
Abbreviation DBP Abbreviation DBP
Other DBPs
Bromate Bromate
3-chloro-4(dichloromethyl)-
MX
5-hydroxy-2[5H]-furanone
4-Hydroxy-3,5-diiodo-1-
4HDINB
nitrobenzene
TBPy Tribromopyrrole
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Conclusion
DBP exposure is a constant in modern life. Every time you take a drink of
water, every time you prepare food, take a shower or swim in a swimming pool
you are exposed to DBPs. The level of concern of the adverse health effects of
these toxic agents is increasing with the increased level of compromised source
waters used in the generation of drinking water. With the advent of climate
change-mediated drought, increased reliance upon direct or indirect wastewater
recycling or disinfected desalinated water, new emerging DBP classes are entering
the drinking water stream.
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Chapter 2
Introduction
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Sample Extraction
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Table 1. Analytical Methodologies Used for HAL Analysis in Water
Analyte extraction Analyte detection LOD
HALs Sample preservation Reference
(Sample volume) (GC column) (μg/L)
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GC-ECD
LLE with MTBE or pentane (50 DB-1 (30 m, 0.25 mm i.d, 1
CH Sodium sulfite (100 mg/L) 0.011** (29)
mL) μm) and Rtx-1301 (30 m, 0.25
mm i.d, 1 μm)
GC-ECD / GC-MS
DCAL, BCAL, DBAL,
AscAc (35 mg/L) SPE (Bond Elut PPL) (36 mL) DB-5 and DB-1 (30 m, 0.32 1-2.5 (for
BDCAL, DBCAL, CH, (23)
pH=3-4 LLE with MTBE (30 mL) * mm i.d, 1 μm) / Rtx 1 (30 m, SPE)**
TBAL
0.25 mm i.d, 1 μm)
DCAL, BCAL, DBAL, LVI-PTV-GC-MS
0.006 -
BDCAL, DBCAL, CH, pH = 3-3.5 MLLE with ethyl acetate (9 mL) HP-5 MS (30 m, 0.25 mm i.d., (26)
0.020
29
mono- and di-HALs (11, 24), which in their native form, are almost impossible
to extract from water. This method consisted of the derivatization of these
compounds with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and
subsequent LLE of the oximes formed with hexane. The derivatization reaction is
shown in Scheme 1. This is also the analytical strategy selected for the extraction
of the very polar IAL from water. Limits of detection achieved for mono- and
di-HALs with this approach ranged between 0.05 µg/L and 0.25 µg/L (24).
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Analyte Detection
Regardless of the extraction method followed, HAL detection was always
achieved by means of GC coupled to either ECD or MS. In most of the ECD
based methods, due to the low specificity of this technique, a secondary column in
addition to the primary analytical column was used for analyte confirmation (20,
23, 29, 33, 35, 44). GC/MS analysis was also used by Koudjonou and Lebel (20)
for analyte confirmation. Electron ionization (EI) was used to acquire the analyte
spectra, and chemical ionization (CI) was used to confirm the molecular weights
of the compounds (20).
Although less sensitive than GC-ECD detection, selective GC/EI-MS
detection was also commonly used in the selected ion monitoring (SIM) mode
for HAL identification and quantification (23–27, 36, 37, 45). Serrano et al (26)
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Table 2. (Continued). Occurrence of HALs in Disinfected Water
HALs Concentration (μg/L)** Country Reference
2.1*-12.2 ds (42)
China
n.d.-10.4 ef+ds (41)
0.2-19 ds Australia (61)
n.d.-8.6 ds Poland (45)
0.4-8.9 ds Poland (55)
n.d.-12.6 ef (24)
U.S.
n.d.-3 ef / n.d.-2 ds (11)
TBAL n.d.-1.5 ef / n.d ds (20)
Canada
n.d.-2 ef / n.d-1.6 ds (28)
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source water, as previously reported by Koudjonou et al. (28). In this regard,
the lowest concentrations, and thus, contributions to total HAL levels, of the
chlorine-based HAL species, CAL, DCAL, TCAL, and BDCAL, were measured
in disinfected waters that originated from the highest bromide content source
waters (24).
Besides haloacetaldehydes, additional halogenated aldehydes, i.e.,
iodobutanal, dichloropropenal, and 4-chloro-2-butenal, were identified in the U.S.
Nationwide DBP Occurrence Study (5, 11). However, their concentrations and
formation mechanisms have not been investigated yet.
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Haloacetaldehyde Toxicity
As reviewed in the Introduction, toxicological studies were previously only
conducted on CAL, BAL, DCAL, CH and TBAL. A recent study examined the
genotoxicity and cytotoxicity of the complete set of the ten HALs, including IAL
(24). These toxicity assays were performed in mammalian cells as described in
the next subsections. Results obtained allowed comparison of the toxic potencies
of individual HALs and of this DBP class with other DBP classes.
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Toxicity Assays
Chinese hamster ovary (CHO) cell line AS52, clone 11-4-8 was used for
the toxicity studies (62–64) and was maintained in modified Ham’s F12 medium
(Mediatech, Inc., Manassas, VA) supplemented with 5% heat-inactivated fetal
bovine serum (FBS), 1% L-glutamine and 1% antibiotic-antimycotic solution
(Invitrogen, Carlsbad, CA) at 37°C in a humidified atmosphere of 5% CO2. The
cells exhibit normal morphology, express cell contact inhibition, and grow as a
monolayer without expressing neoplastic foci.
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We compared the CHO cell toxic potencies of the HALs to other DBP
chemical classes with their calculated cytotoxicity and genotoxicity indices.
The cytotoxicity index was determined by calculating the mean LC50 value of
all of the individual compounds of a single class of DBPs. The genotoxicity
index was determined by calculating the mean SCGE genotoxic potency value,
which is defined by the midpoint of the SCGE tail moment or the 50% Tail
DNA values from the individual compounds within a single class of DBPs (22).
Six DBP chemical classes were compared, including the THMs, HAAs, HALs,
halonitromethanes, haloacetonitriles, and haloacetamides. As summarized in
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Table 4, HALs constitute the second most cytotoxic DBP class, whereas they rank
as the second least genotoxic DBP class.
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Figure 3. The mean bootstrap a) CHO cell cytotoxic index values (±SE) and b)
CHO cell genotoxic index values (±SE) of the HALs (24).
Conclusions
Different analytical methods have been used to determine HALs in disinfected
waters. Due to their very different physical-chemical properties, the complete
set of nine chloro and bromo HALs and IAL cannot be analyzed by a unique
approach. Regardless of the extraction approach followed, analyte detection
is carried out by GC coupled to ECD or MS detection. The evaluation of the
occurrence of HALs in drinking waters allowed this DBP class to be identified
as the third largest group by weight of DBPs reported. Besides CH (TCAL),
which is currently the most abundant HAL in drinking water, bromo containing
acetaldehydes and IAL may be relevant in chloraminated waters that contain
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high levels of bromide and iodide. Despite the fact that HAL concentrations
may increase in preozonation-based systems, individual HAL concentrations in
disinfected water strongly depend on the source water quality and the type of
disinfection treatment applied. A systematic quantitative comparative study of
their acute cytotoxicity and chronic genotoxicity to mammalian cells revealed
HALs as the second most cytotoxic class of DBPs after haloacetamides. Taking
all this into account, it is important to determine their potential health risks and
to investigate their formation mechanisms to control their presence in drinking
waters.
Acknowledgments
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We would like to thank the drinking water treatment plants for generously
providing us with samples. This work was supported by the EPA STAR Grant
R834867. We appreciate support by the Center of Advanced Materials for
the Purification of Water with Systems (WaterCAMPWS), a National Science
Foundation Science and Technology Center, under Award CTS-0120978. C.J. was
supported by a NIEHS Pre-doctoral Fellowship under Grant No. T32 ES007326.
C.P. acknowledges support from the European Union Seventh Framework
Programme (FP7/2007-2013) under grant agreement n° 274379 (Marie Curie
IOF). This work has been financially supported by the Generalitat de Catalunya
(Consolidated Research Groups “2014 SGR 418 - Water and Soil Quality Unit”
and 2014 SGR 291 - ICRA). This work reflects only the author’s views. The EU
is not liable for any use that may be made of the information contained therein.
This work does not reflect EPA policy.
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Chapter 3
Introduction
With the purpose of inactivating harmful microorganisms and eradicating
waterborne diseases, disinfection has been applied in drinking water treatment.
Chlorine is a widely used disinfectant for drinking water. Chlorine-disinfected
drinking water is distributed to households via a public water distribution system,
in which a certain level of chlorine residual should be maintained to prevent
regrowth of microorganisms in the water, especially when breaks or cracks
occur in the pipeline. However, chlorinated disinfection by-products (DBPs)
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unintentionally form (from the reaction between hypochlorous acid and natural
organic matter in source water) during chlorination in a drinking water treatment
plant and in a water distribution system. Besides, source waters contain bromide
ions resulting from geologic dissolution, seawater intrusion and human activities
(1). During chlorination, hypochlorous acid can oxidize bromide to hypobromous
acid, which subsequently reacts with natural organic matter in source water to
generate brominated DBPs. Brominated DBPs have been reported to exhibit
significantly higher toxicity than their chlorinated analogues (2–6).
Humans are unavoidably exposed to DBPs via water ingestion. It has
been reported that the total cancer risks from the commonly known haloacetic
acids and trihalomethanes mainly result from tap water ingestion (7). In most
Western nations, tap water is directly drunk, whereas in some Asian nations,
people are used to boiling tap water before drinking. Boiling has its own
advantages, including effectively removing chlorine or chloramine residual
and thus eliminating chlorinous taste and odor of the water (8); inactivating
chlorine-resistant pathogenic protozoa Cryptosporidium and Giardia (9); and
reducing some major DBPs (including trihalomethanes, haloacetic acids,
haloketones, haloacetonitriles, haloaldehydes, and halonitromethanes) (10–12).
Recently, a powerful precursor ion scan (PIS) approach with electrospray
ionization-triple quadrupole mass spectrometry coupled with ultra performance
liquid chromatography (UPLC/ESI-tqMS) has been developed for selectively
detecting polar halogenated DBPs (13–19). By using this approach, the authors’
group has studied the effect of boiling on the halogenated DBPs in a simulated
tap water, and found that boiling for 5 min significantly reduced the halogenated
DBPs and cytotoxicity of the water (20). However, a real tap water may be
different from the simulated tap water because a real tap water originates from
a real source water, which may contain a variety of organic and inorganic
components including (micro)pollutants. Accordingly, the purpose of this study
was to determine the effect of boiling on the halogenated DBPs and toxicity in
real tap waters.
Hutchinson’s group developed an in vivo assay using the sensitive
embryo-larval stages of a polychaete, Platynereis dumerilii, which is a
cosmopolitan species, extending from the tropics to cold temperate latitudes
in both hemispheres (21, 22). The authors’ group modified Hutchinson et al.’s
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method and significantly lowered the relative standard deviation to <5% (5). The
improved bioassay becomes a sensitive metric and has been successfully applied
in determining the comparative developmental toxicity of individual DBPs
(5, 23). In this study, P. dumerilii was employed to evaluate the comparative
developmental toxicity of real tap waters without and with boiling.
Experimental Methods
Water Sampling and Characterization
Two source water samples (source waters 1 and 2) were collected at the inlets
of two drinking water treatment plants. Correspondingly, two tap water samples
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that originated from the two drinking water treatment plants were collected at
two faucets on the same day. Tap waters 1 and 2 corresponded to source waters
1 and 2, respectively. The collected water samples were filtered through 0.45 μm
membrane. Dissolved organic carbon (DOC), UV absorbance, pH, and bromide
concentration of each source water sample were measured with a total organic
carbon analyzer (Model TOC-Vcsh, Shimadzu), a UV/visible spectrophotometer
(GE healthcare, Ultrospec 4300 pro), a pH meter, and an ion chromatograph
(Dionex DX500), respectively. Alkalinity in each source water sample and
chlorine residual in each tap water sample were determined according to the
Standard Methods (24). The characteristics of the source water samples were
summarized in Table 1. The chlorine residual levels in tap waters 1 and 2 were
0.75 and 0.63 mg/L as Cl2, respectively. For comparison, the characteristics of
the simulated source water used in the previous study were also listed in Table
1. This simulated source water was disinfected with 5 mg/L NaOCl as Cl2 in
darkness at ~21 ºC for 15 h to generate the simulated tap water. No chlorine
residual was detectable in the simulated tap water (20).
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Chemicals and Seawater
Our previous study showed that boiling for 5 min obviously reduced the
halogenated DBPs and toxicity of the simulated tap water (20). Accordingly,
for either tap water 1 or tap water 2, two parallel samples (3.4 L each) were
heated to boiling (at 100 ºC) in open 5 L glass beakers, and kept boiling for 5
min. Afterwards, both boiled water samples were cooled to ambient temperature
quickly in an ice bath (to minimize the variation of the sample components during
cooling). Then, both samples were brought to 3.4 L by adding ultrapure water,
and the chlorine residual in each sample was measured (24). After boiling, no
chlorine residual was detectable, which was consistent with Zhang’s results (8).
One of the parallel samples was divided into two aliquots (300 mL and
3000 mL). The 300 mL aliquot was subjected to total organic halogen (TOX)
measurement, and the 3000 mL aliquot was pretreated per Zhang et al.’s procedure
(25). In brief, it was further divided into three 1000 mL aliquots, and each aliquot
was first acidified to pH 0.5 with 70% (v/v) aqueous sulfuric acid, followed by the
addition of sodium sulfate to saturation. Then, the acidified sample was extracted
with 100 mL MtBE, and 70 mL of the organic layer was transferred to a rotary
evaporator and concentrated to 0.5 mL. The 0.5 mL MtBE solutions obtained
from three aliquots were combined together (totally ~1.5 mL) and mixed with
20 mL acetonitrile. The mixture was concentrated to 1 mL, and stored at 4 °C.
Prior to UPLC/ESI-tqMS measurement, the acetonitrile solution was diluted to
2 mL with ultrapure water, and filtered with 0.45 μm membrane. For the other
parallel sample, 3000 mL was pretreated following the procedure above, except
that after evaporation, the 0.5 mL MtBE solutions obtained from three aliquots
were combined together and dried with nitrogen sparging. The solid obtained
was stored at 4 °C and dissolved in seawater 1 h prior to the toxicity test as a
toxicity test stock solution. This stock solution was diluted by seawater to various
concentration factors (in comparison with the original water sample).
For comparison, two 3.4 L parallel aliquots of each tap water sample without
boiling were pretreated following the procedure above, except that the chlorine
residual in the 300 mL aliquot for TOX measurement was quenched with NaAsO2
at 105% of the stoichiometric amount of the chlorine residual (26).
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TOX Measurement
TOX was measured according to Standard Method 5320B (24), except that
an off-line ion chromatograph was used as a halide separator and detector for the
measurement of total organic chlorine (TOCl) and total organic bromine (TOBr)
(26–28). Total organic iodine (TOI) was not included in this study because the
TOI levels in the two tap waters were very low (about 1.3 µg/L as I) (29). Each
300 mL tap water sample without or with boiling was adjusted to pH 2 with
nitric acid. A 3-channel adsorption module (Mitsubishi Chemical Analytech)
was used for activated carbon adsorption. After adsorption, the activated carbon
columns were rinsed with 10 mL of 5000 mg/L KNO3 as NO3− to remove
inorganic halides and were subsequently subjected to pyrolysis at 1000 °C with
an AQF-100 automatic quick furnace (Mitsubishi Chemical Analytech). The
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hydrogen halide and halogen gases produced from pyrolysis were absorbed in a 5
mL 0.003% H2O2 solution, which contained 2 mg/L KH2PO4 as PO43− serving as
an internal standard to estimate the volume variations introduced by the GA-100
gas absorption unit (Mitsubishi Chemical Analytech). Thus, TOCl and TOBr
in the original water sample were converted and transferred into the absorption
solution in the form of Cl− and Br−, respectively. One mL of the absorption
solution was analyzed by an ICS-3000 ion chromatograph (Dionex) with an
IonPac analytical column (AS19, 4×250 mm) and a guard column (AG19, 4×50
mm). A KOH eluent was generated by the EGC KOH cartridge (Dionex) at a flow
rate of 1 mL/min. Chloride and bromide were separated with an isocratic eluent
of 10 mM KOH from 0 to 10 min followed by a linear gradient eluent of 10-45
mM KOH from 10 to 25 min. The concentrations of the halides were quantified
with a conductivity detector. The practical quantitation limits for TOCl and TOBr
were 0.002 mg/L as Cl and 0.002 mg/L as Br, respectively (26). Each sample was
subjected to triplicate TOX analyses.
(UPLC/)ESI-tqMS Analyses
and bromide ions to form chlorinated and brominated DBPs during heating.
However, chlorine residual decreases quickly with the increase of temperature,
and it almost completely decays at 100 °C (8). Besides, the formed DBPs might
decompose during the subsequent 5 min boiling at 100 °C (20). Accordingly, the
“apparent” reduction of TOX after boiling was the combined result of formation,
volatilization and decomposition.
Figure 1. TOCl and TOBr concentrations in (a) tap water 1 and (b) tap water 2
without boiling and with 5 min boiling. Each datum presents the average and
standard deviations of triplicate measurements.
tap water, while tribromoacetic acid was not detected and trichloroacetic acid
was detected in both real tap waters. Third, 2,4,6-tribromophenol, which has
been confirmed in the simulated tap water, was not detected in either real tap
water. However, ion clusters m/z 283/285/287 (with the isotopic abundance
ratio of 1:2:1) and m/z 239/241/243 (with the isotopic abundance ratio of 3:4:1)
were detected in PISs m/z 35 of both real tap waters, and they were proposed
to be 2,4,6-dibromochlorophenol and 2,4,6-bromodichlorophenol, respectively.
Fourth, ion cluster m/z 285/287 was detected in PIS m/z 79 of the simulated
tap water, and it was proposed to be dibromomethylbutenedioic acid. This ion
cluster was only detected in tap water 1, and ion clusters m/z 241/243 (with the
isotopic abundance ratio of 3:1 in PIS m/z 79) and m/z 197/199 (with the isotopic
abundance ratio of 3:1 in PIS m/z 35) were detected in both real tap waters.
These two ion clusters were proposed to be bromochloromethylbutenedioic
acid and dichloromethylbutenedioic acid. Additionally, some saturated aliphatic
DBPs (which did not form in the simulated tap water) were detected in
both real tap waters, including bromopropanoic acid, bromobutanedioic acid,
bromochlorobutanedioic acid and dichlorobutanedioic acid.
Figure 4 shows the effect of boiling on the concentrations of the halogenated
DBPs in the two real tap waters, based on the peak areas of the corresponding
ion clusters in the UPLC/ESI-tqMS MRM chromatograms. More than
half of the listed DBPs decomposed during boiling, including trihaloacetic
acids (i.e., dibromochloro-, bromodichloro-, and trichloro-acetic acids),
butenedioic acids (i.e., bromochloro-, dibromomethyl-, bromochloromethyl-,
dichloromethyl-, trichloromethyl-butenedioic acids), butanedioic acids (i.e.,
bromochloro- and dichloro-butanedioic acids), and 2,4,6-trihalophenols
(i.e., 2,4,6-dibromochlorophenol and 2,4,6-bromodichlorophenol). The
decomposition mechanisms of trihaloacetic acids, dihalobutenedioic acids,
dihalomethylbutenedioic acids, and trihalomethylbutenedioic acids included
decarboxylation and hydrolysis (20).
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Figure 2. ESI-tqMS PIS spectra of m/z 79 of (a) tap water 1 without boiling, (b)
tap water 1 with 5 min boiling, (c) tap water 2 without boiling, and (d) tap water
2 with 5 min boiling. The y-axes are on the same scale. Above the spectra shows
the corresponding structures, of which bromoacetic acid, bromodichloroacetic
acid, bromochloroacetic acid, bromobutenedioic acid, dibromochloroacetic acid,
dibromoacetic acid and 3,5-dibromo-4-hydroxybenzaldehyde were confirmed
with the standard compounds, while others were proposed structures.
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Figure 3. ESI-tqMS PIS spectra of m/z 35 of (a) tap water 1 without boiling, (b)
tap water 1 with 5 min boiling, (c) tap water 2 without boiling, and (d) tap water
2 with 5 min boiling. The y-axes are on the same scale. Above the spectra shows
the corresponding structures, of which dichloroacetic acid and trichloroacetic
acid were confirmed with the standard compounds, while others were proposed
structures.
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Boiling also resulted in accumulation of a few DBPs, including bromoacetic
acid, dihaloacetic acids, bromobutenedioic acid, bromobutanedioic acid, and
bromopropanoic acid. For some DBPs, boiling showed different impacts
in the two real tap waters: The levels of bromo- and chloro-propenoic
acids increased in tap water 1, but decreased in tap water 2; the level of
3,5-dibromo-4-hydroxybenzaldehyde decreased in tap water 1, but increased in
tap water 2. Monohalopropenoic acids and monohalobutenedioic acids were
found to decompose during boiling in the simulated tap water (20). However, in
the real tap waters, their levels increased, possibly due to the continued reaction
between chlorine residual and the organic matter and bromide ions during heating.
It was also reported that some aromatic DBPs in the simulated tap water increased
during boiling because of the degradation of their precursors (20). Tap water
2 might also contain the precursors of 3,5-dibromo-4-hydroxybenzaldehyde,
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leading to the increase of its level after boiling. Tap water 1 might not contain
the precursors of 3,5-dibromo-4-hydroxybenzaldehyde, and both tap waters 1
and 2 might not contain the precursors of 2,4,6-dibromochlorophenol and 2,4,6-
bromodichlorophenol. Besides, the decomposition of 2,4,6-dibromochlorophenol
and 2,4,6-bromodichlorophenol caused the additional formation of dibromo-,
bromochloro- and dichloro-acetic acids, following the mechanism proposed by
Zhai and Zhang (13).
Total ion intensity (TII) in the ESI-tqMS PIS spectrum of m/z 79 (or m/z 35)
can be approximately proportional to the total quantity of polar brominated (or
chlorinated) DBPs in a water sample. It was defined as the sum of ion intensities
from m/z 100 to 500 in the PIS spectrum of m/z 79 (or from m/z 50 to 400 in the
PIS spectrum of m/z 35). After boiling, for tap water 1, the TII values in the PIS
spectra of m/z 79 and m/z 35 decreased by 28.0% and 51.3%, respectively; for tap
water 2, the TII values in the PIS spectra of m/z 79 and m/z 35 decreased by 17.4%
and 36.4%, respectively.
Since the levels of TOX and polar halogenated DBPs in the two tap waters
were substantially reduced by 5 min boiling, the toxicity of the boiled tap waters
was expected to be lower. Figure 5 shows the concentration factor-response
curves of the developmental toxicity (against the polychaete P. dumerilii) of the
two tap waters without and with boiling. A lower normal development percentage
indicates a higher toxicity. Through regression analysis of the concentration
factor-response curve, the EC50 value for each tap water without/with boiling
was calculated (Table 2). A lower EC50 value represents a higher developmental
toxicity potential (5, 23). Considering the EC50 values, the developmental toxicity
of tap waters 1 and 2 was decreased by 53.0% and 57.1%, respectively, after
boiling. These indicate that boiling is an effective “detoxification” method for
real tap waters.
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Figure 5. Concentration factor-response curves of the developmental toxicity
against the polychaete P. dumerilii of (a) tap water 1 without boiling and with 5
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min boiling, and (b) tap water 2 without boiling and with 5 min boiling. Each
datum presents the mean of duplicate measurements and the difference between
the mean and the measured value.
Conclusions
The results of TOX measurements and (UPLC/)ESI-tqMS analyses obtained
in this study demonstrated that boiling for 5 min substantially reduced the
brominated and chlorinated DBPs in real tap waters. Accordingly, boiling is an
effective method for reducing human exposure to halogenated DBPs through tap
water ingestion. From the data of developmental toxicity against the polychaete
P. dumerilii, 5 min boiling significantly decreased the toxicity of tap waters.
To further investigate the effect of boiling on “detoxification” of tap water,
additional toxicity tests may be conducted with different bioassays, and relevant
epidemiological studies may also be needed.
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Acknowledgments
This research was supported by grants from the Research Grants Council of
Hong Kong, China (projects 622412, 622913 and FSGRF12EG60). The authors
thank Jingyi Jiang for her assistance in the DOC measurement, Dave Ho for
his daily maintenance of the TOX analyzer, and Adriaan W. C. Dorresteijn (at
the Johannes Gutenberg-Universität Mainz, Germany) for providing parental P.
dumerilii.
References
1. Amy, G. L.; Siddiqui, M. S. Strategies to Control Bromate and Bromide;
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16. Zhai, H. Y.; Zhang, X. A new method for differentiating adducts of common
drinking water DBPs from higher molecular weight DBPs in electrospray
ionization-mass spectrometry analysis. Water Res. 2009, 43, 2093–2100.
17. Xiao, F.; Zhang, X.; Zhai, H.; Yang, M.; Lo, I. M. C. Effects of enhanced
coagulation on polar halogenated disinfection byproducts in drinking water.
Sep. Purif. Technol. 2010, 76, 26–32.
18. Xiao, F.; Zhang, X.; Zhai, H.; Lo, I. M. C.; Tipoe, G. L.; Yang, M.; Pan, Y.;
Chen, G. H. New halogenated disinfection byproducts in swimming pool
water and their permeability across skin. Environ. Sci. Technol. 2012, 46,
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19. Ding, G.; Zhang, X.; Yang, M.; Pan, Y. Formation of new brominated
disinfection byproducts during chlorination of saline sewage effluents.
Water Res. 2013, 47, 2710–2718.
20. Pan, Y.; Zhang, X.; Wagner, E. D.; Osiol, J.; Plewa, M. J. Boiling of
simulated tap water: effect on polar brominated disinfection byproducts,
halogen speciation, and cytotoxicity. Environ. Sci. Technol. 2014, 48,
149–156.
21. Hutchinson, T. H.; Jha, A. N.; Dixon, D. R. The polychaete, Platynereis
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hazardous potential of chemicals in the marine environment. Ecotoxicol.
Environ. Saf. 1995, 31, 271–281.
22. Jha, A. N.; Hutchinson, T. H.; Mackay, J. M.; Elliott, B. M.; Dixon, D.
R. Evaluation of the genotoxicity of municipal sewage effluent using the
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Genet. Toxicol. Environ. Mutagen. 1997, 391, 179–188.
23. Yang, M.; Zhang, X. Halopyrroles: A new group of highly toxic DBPs
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11846–11852.
24. APHA, AWWA, WEF. Standard Methods for the Examination of Water and
Wastewater, 22th ed.; Washington, DC, 2012.
25. Zhang, X.; Talley, J. W.; Boggess, B.; Ding, G.; Birdsell, D. Fast selective
detection of polar brominated disinfection byproducts in drinking water using
precursor ion scans. Environ. Sci. Technol. 2008, 42, 6598–6603.
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ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
26. Liu, J.; Zhang, X. Effect of quenching time and quenching agent dose on
total organic halogen measurement. Int. J. Environ. Anal. Chem. 2013, 93,
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27. Hua, G.; Reckhow, D. A. Determination of TOCl, TOBr and TOI in drinking
water by pyrolysis and off-line ion chromatography. Anal. Bioanal. Chem.
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28. Li, Y.; Zhang, X.; Shang, C. Effect of reductive property of activated
carbon on total organic halogen analysis. Environ. Sci. Technol. 2010, 44,
2105–2111.
29. Gong, T.; Zhang, X. Determination of iodide, iodate and organo-iodine in
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2013, 47, 6660–6669.
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Chapter 4
Background
Disinfection of drinking water by chlorine has dramatically reduced the
transmission of potentially fatal waterborne diseases. The main issues that
affect current chlorination practices include the limited efficiency of chlorine
against some pathogens and formation of toxic disinfection by-products (DBPs)
(1) formed as a result of reactions of chlorine and other halogen species with
natural organic matter (NOM) to produce chlorinated, brominated and, in much
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been shown to be independent vs. chlorine doses, reaction times and temperature
(25) but affected by pH or bromide concentration (26).
In this study we pursued the development of a combined approach that
incorporates a kinetic model to represent changes of ΔA272 values as a function
of time and bromide concentration while concentrations of individual DBPs are
obtained in this approach by incorporating DBP vs. ΔA272 relationships. This
approach was applied to the formation of three highly important classes of DBPs
(THMs, HAAs and haloacetonitriles, HANs) generated for a highly varying
reaction times and bromide levels.
Experimental
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Chlorination was carried out with free chlorine at pH 7.0 in the presence of
0.03 mol/L phosphate buffer in headspace-free 1.6 L PTFE sampling bags, which
were used to prevent the loss of volatile DPBs when samples were taken at different
reaction times (10 minutes to 7 days). Selected experiments were carried out at
varying bromide concentrations (from its background levels to 2 mg/L) at chlorine
dose of 1.5 mg Cl2 per mg DOC. Chlorinated samples were analyzed for DBPs only
if chlorine residual was found. Requisite amount of Na2SO3 or NH4Cl were used
to quench residual chlorine. Chlorine concentrations were determined using the
DPD colorimetric method. Absorbance spectra were obtained with a Perkin-Elmer
Lambda 18 spectrophotometer using 5 cm quartz cells. All reported spectra were
normalized to the cell length of 1 cm. TOC was analyzed using an O.I. Analytical
1010 or a Shimadzu VCSH organic carbon analyzer. Concentrations of THMs,
HANs and HAAs were determined using standard analytical procedures (EPA
methods 551.1 and 552.2) and a Perkin-Elmer AutoSystem gas chromatograph
equipped with an electron capture detector. Other aspects of these analyses are
described in our previous publications (27, 28).
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Results and Discussion
Kinetics of DBP Formation in Chlorinated Water
In agreement with the data of prior research (e.g., (2, 22, 25, 27)),
concentrations of THMs, HAAs and dihaloacetonitriles (DHANs) increased
gradually with time at given chlorine dose. Higher chlorine doses or temperatures
caused higher levels of these DBPs species (25). For instance, Figure 1 shows
the formation kinetics of CHCl3, CHCl2Br and CHClBr2 for chlorinated Ancipa
water. Similar behaviour was observed for the other investigated individual DBPs
formed in chlorinated Ancipa and LW water.
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the very fast, fast and slow sites, respectively. These values are comparable with
those reported in prior research in formal descriptions of the speciation of THMs
and HAAs (9, 19, 20, 22, 23).
The use of the above approach allowed achieving precise modelling of the
changes of differential absorbance from the entire range of reactions (from 10
minutes to 3 days) and bromine concentrations (from 0.04 to 2.04 mg/L). This
allowed using this model for predicting concentrations of individual DBPs species
once ΔA272 values have been measured experimentally or calculated using the
model. This aspect of our approach is discussed in the sections that follow.
In the above expression, DBPi stands for the concentration of any target
individual DBP compound, ki is the proportionality coefficient specific to this
species while x is the parameter of the fitting power function. As will be explained
below, the parameters x was determined to have the same value for all examined
DBPs.
Eq.2 can be useful for modelling concentrations of any target DBP (DBPi)
because it allows simplifying the number of water quality parameters that need to
be taken into account. For a constant pH, Eq.2 can be simplified as:
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Fitting the experimental DBPs and ΔA272 values with Eq.3 at varying bromide
concentrations showed that a single value of x=1.7 can be used to fit the data for
all the investigated DBPs and waters. This is demonstrated in Figure 3-6 for data
sets showing these correlations for trichloroacetic acid (TCAA) and tribromoacetic
acid (TBAA) formed in Lk. Washington water at bromide concentrations 0.1 and
1.0 mg/L. This result allows reducing Eq. 3 to the following simple form:
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Similarly to the results for Lk. Washington water, DBP concentrations found
in chlorinated Ancipa water could be well fitted by using Eq. 4, as shown in Figure
1 for the formation kinetics of CHCl3, CHCl2Br and CHClBr2.
When represented vs. the concentration of bromide, values of the ki
proportionality coefficients obtained via the fitting of the experimental DBP
and ΔA272 data exhibited a type of functional dependence similar to that of the
dimensionless speciation coefficients for THMs, HAAs and HANs reported in
prior studies (9, 19, 22, 23). This is demonstrated in Figure 7 and 8 that present the
ki coefficients for the trihalogenated (THAA) and dihalogenated HAAs (DHAA),
respectively, formed in chlorinated LW water. As a result, the proportionality
coefficients, ki, are speciation coefficients which can be determined by the
correlations between DBPs and differential absorbance, alternatively to the formal
modeling, which employs dimensionless ratios of bromination/chlorination
reaction rates.
The ki coefficients have also been found to be strongly correlated with the
logarithms of bromide concentrations (Figure 9-11). The fitting shown in these
figures was achieved using second-order polynomial curves. In the case of DBPs
containing only chlorine or bromine, the fitting predicted a gradual decrease or
increases, respectively, of the ki coefficients while for mixed compounds the
behavior of these coefficients was non-monotonic (Figure 9-11).
The use of logarithms of bromide concentration and correlating them with the
ki coefficients appears to be a reasonably straightforward procedure that is expected
to be applicable to any water quality. Further studies will demonstrate the extent
of effects of NOM site-specificity on these correlations of NOM as well as on the
absolute values of ki coefficients.
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Conclusions
This study examined the formation of THM, HAA and HAN species and
concurrent NOM transformations reactions based on the kinetic analysis of DBPs
data and also via differential spectroscopy. The approach treated the differential
absorbance (ΔAλ) as master parameter that can be used to predicts concentrations
of any selected individual DBP compounds. The kinetics of ΔAλ changes was
determined to be sensitive to the presence of bromide. It also reflected the
fact of a faster bromination of NOM reactive sites, compared with the rates
of chlorination. Comparison of ΔAλ values and concurrently measured DBP
concentrations showed that DBPs levels were correlated with ΔAλ by a uniformly
applicable power function having a 1.7 power coefficient but this function also
contains a proportionality coefficient which is compound specific and varies
with the bromide level. The proportionality coefficients were found to behave
similarly to the formal speciation coefficients reported in prior research and are
strongly correlated with logarithms of the bromide concentrations.
The joint interpretation of the kinetic DBP and differential absorbance data
confirmed the applicability of the DBPs speciation model. The results indicate that
both the absolute levels and speciation of several classes or bromine-containing
DBPs can be interpreted and modeled based on the presented approach. Further
research is needed to expand the modeling of DBPs formation to a wider range
of surface waters as well as to examine its performance for chloraminated waters
containing bromide and/or iodide.
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Acknowledgments
This study was partially supported by the Water Research Foundation
(Project #2597), the United States EPA/Cadmus (grant 069-UW-1), and the Italian
Ministry of Instruction, University, and Research (MIUR), through the Research
Projects of National Interest - PRIN 2009 (grant 20092MES7A_002). Paolo
Roccaro and Gregory Korshin acknowledge the U.S.-Italy Fulbright Commission
for supporting their research in the U.S. and in Italy, respectively. Views expressed
in this paper do not necessarily reflect those of the funding agencies.
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Popilevsky, I.; Juraev, O.; Glezer, V.; McKague, A. B.; Plewa, M. J.;
Wagner, E. D. Tribromopyrrole, brominated acids, and other disinfection
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4. Hua, G.; Reckhow, D. A.; Kim, J. Effect of bromide and iodide ions on
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consumption – part I: compliance with European water quality standards.
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Sclimenti, M. J.; Onstad, G. D.; Thruston, A. D. Occurrence of a new
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10. Obolensky, A.; Singer, P. C. Halogen substitution patterns among
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11. Zhang, L.; Xu, L.; Zeng, Q.; Zhang, S.-H.; Xie, H.; Liu, A.-L.; Lu, W.-
Q. Comparison of DNA damage in human-derived hepatoma line (HepG2)
exposed to the fifteen drinking water disinfection byproducts using the single
cell gel electrophoresis assay. Mutat. Res. 2012, 741, 89–94.
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halogenated dbps in a chlorinated saline sewage effluent to the marine
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13. Heller-Grossman, L.; Idin, A.; Relis, B. L.; Rebhun, M. Formation
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25. Roccaro, P.; Chang, H.-S.; Vagliasindi, F. G. A.; Korshin, G. V. Differential
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Chapter 5
Introduction
Over the past decades, N-nitrosamines (NAs), which form as disinfection
by-products during chlorination, in particular chloramination, have emerged as
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((1) and (2) in figure 1) and the latter successfully predicted NDMA formation
over a range of conditions (15). A statistical model was proposed to predict
NDMA formation kinetics from pharmaceutical compounds such as ranitidine
in various water matrices (23). In addition, natural organic matter (NOM) was
also investigated as a source of precursors in a NDMA formation model (28).
No attempt has been ever made to model NDMA formation in wastewater or
wastewater-impacted waters. The challenge for a model development lies in the
multitude of precursors and precursor types present and hence the possibility of
having various mechanisms, with distinct kinetics occurring simultaneously.
The aim of this work is to formulate and evaluate a NDMA formation kinetics
model that is applicable to different water sources and model compounds. A
simple second-order kinetic reaction model was developed for NDMA formation.
In this model, the precursor concentration, quantified as the maximum NDMA
concentration formed during chloramination under specific water conditions, and
chloramine decay were used to predict transformation of precursors to NDMA.
The model was parameterized using NDMA formation data from literature data
on NOM and model precursor compounds (i.e. ranitidine). The optimization of
the kinetic model parameters and the resulting model performance are discussed.
Model Description
NDMA Formation Model
As detailed in the introduction, three different pathways for NDMA formation
have been proposed (Figure 1). The original concept of the model was that
different types of precursors may proceed along different mechanistic pathways
with different chloramine species and the reactions may potentially involve
oxygen to produce NDMA. Such a model would classify NDMA precursors
(nM quantities) as having either higher or lower yields and presumably different
reaction rates with different chloramine species. In a first step, using data obtained
from our research of NDMA formation in wastewater, we developed a simple
second-order model for the reaction of NDMA precursors (P) in the presence of
monochloramine (NH2Cl):
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where [NH2Cl], [NHCl2] = monochloramine or dichloramine concentration at time
t
[P] = NDMA precursor concentration at time t
kmono, kdi = rate constant of NDMA formation from monochloramine or
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dichloramine
kapp = second order rate constant of NDMA formation in our model
α = ratio of dichloramine and monochloramine
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related to the maximum amount of NDMA precursors available for reaction in an
experiment ( [P]0 = [NDMAmax] ) as follows:
Monochloramine Degradation
Chen et al. modeled NDMA formation from reactions between NOM and
monochloramine (28). They suggested that NOM in surface waters could be
oxidized involving two types of reactive sites of monochloramine loss. A portion
of the dissolved organic carbon (DOC) could react with monochloramine rapidly
within hours and the other part had a much slower reaction with free chlorine
(over days). However, their model had five parameters (i.e. fast and slow reactive
fractions of NOM) to be optimized which would vary between water sources.
Here we fitted their experimental data with our model. The monochloramine
decay was modeled as a first order reaction in Equation 2 and the monochloramine
decay rate constants are shown in Table 2. The decay rate of monochloramine
increased when pH was reduced from 9 to 7 since at low pH monochloramine
would decay to dichloramine more easily (Reaction 5, Table 1).
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The NDMA formation data in surface waters with various Cl/N ratios in
Chen’s work was also fitted with our model. Both monochloramine decay
and NDMA formation were well predicted (Figure 3). Results showed that a
decreasing Cl/N ratio reduced monochloramine decay rates, NDMA formation
rates and NDMA yields. This was the result of dichloramine formation being
favored at high Cl/N ratios (low ammonia concentrations) according to reaction
3 in Table 1 With the monochloramine degradation measurements shown in
Chen’s work (28), the model successfully predicted NDMA formation over time
in surface waters from pH 7 to 9 and in conditions of Cl/N ratio from 0.1 to 0.7.
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Although kapp× [NH2Cl] was greater in the FP tests, indicating a faster NDMA
formation in FP conditions than in SDS conditions, the optimized rate constants
(kapp) in the FP tests were less than under SDS conditions, by an order of magnitude
for model compounds. Compared to amine precursor concentrations (200nM) in
Selbes’ work, the monochloramine concentrations (1.4mM) were more than 5000
times the precursor concentrations in the FP test. Thus, in the FP test, there is a
substantial excess of monochloramine present that reduced the rate constant. Rate
constants kapp of ranitidine, DMBzA and DMA are similar and that of DMiPA
is much smaller. The similar kapp between ranitidine and DMA was unexpected
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since DMA and ranitidine have very different yields (<3% and 80% respectively)
and different proposed NDMA formation mechanisms. In SDS conditions with
excess ammonia, optimized kapp for both ranitidine and DMBzA are less than those
under SDS conditions, suggesting dichloramine reactions may be important. The
dichloramine reaction rate constant, which is the difference between kapp between
two conditions, was found to be greater than the monochloramine rate constant.
Table 3. Optimized Rate Constant kapp for Model Compounds under Various
Reaction Conditions. (NDMA data from Selbes, 2014 (35))
Compounds kapp M-1s-1 (R2)
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formation (23). In addition, dichloramine has a lower electron density on nitrogen
due to two chlorine atoms so it would be a more preferable species to interact
with negatively charged NOM. Thus in the presence of NOM, dichloramine could
more easily react with NOM compared to monochloramine and hence NDMA
formation from dichloramine would be suppressed by NOM.
To better understand how NOM affects NDMA formation rates, our proposed
model was adjusted to fit the kinetics data. As there is no NDMA formed during
the lag-time, we start the model simulation at the end of the NDMA formation
lag. The lag time was removed and the kinetics data was refitted with our model.
The model fits the experimental data better for all four pharmaceutical compounds
(Figure 6) and the optimized rate constants were listed in Table 3. The optimized
second-order rate constants kapp were found to decrease with increasing TOC
concentrations. This can be explained by a competition between NOM and model
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compounds to react with mono- and/or di- chloramine. In the river water samples
(TOC=6mg/L), the optimized rate constants kapp for the pharmaceutical model
compounds were in the range of 0.08 to 0.25M-1s-1 (Table 4) and were comparable
to the rate constants (0.02 to 0.09 M-1s-1) of NDMA formation from NOM in
surface waters with similar TOC concentration (TOC=3.4mg/L) in Chen’s work
we discussed previously. By using the lag model, we were able to compare the
rate constant of NDMA formation at different DOC concentrations and reveal
how the DOC impacted the NDMA formation kinetics.
Acknowledgments
This research was supported by the Water Research Foundation (Project 4499,
managed by Djanette Khiari), American Water Works Association Abel Wolman
Fellowship, Water Environment Federation Canham Scholarship, and the Arizona
State University Fulton School of Engineering Dean’s Fellowship.
References
1. Krasner, S. W.; Mitch, W.; McCurry, D. L.; Westerhoff, P.; Hanigan, D.
Formation, Precursors, Control, and Occurrence of Nitrosamines in Drinking
Water: A Review. Water Res. 2013, 47, 4433–4450.
2. EPA, U. Contaminant Candidate List 3 (CCL3); 2009, http://water.epa.gov/
scitech/drinkingwater/dws/ccl/ccl3.cfm (accessed September 26th, 2014).
3. OEHHA. Public Health Goal for Chemicals in Drinking Water:
N-Nitrosodimethylamine; California Environmental Protection Agency:
Sacramento, CA, 2006.
4. Mitch, W.; Kraner, S.; Westerhoff, P.; Dotson, A. Occurence and Formation
of Nitrogenous Disinfection By-products. Water Research Foundation
Report; Water Research Foundation: Denver, CO, 2009.
5. Boyd, J. M.; Hrudey, S. E.; Richardson, S. D.; Li, X. F. Solid-phase extraction
and high-performance liquid chromatography mass spectrometry analysis of
nitrosamines in treated drinking water and wastewater. Trends Anal. Chem.
2011, 30 (9), 1410–1421.
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6. Russell, C. G.; Blute, N. K.; Via, S.; Wu, X.; Chowdhury, Z.; More, R.
Nationwide assessment of nitrosamine occurrence and trends. J. AWWA
2012, 104 (3), 57–58.
7. Krasner, S. W.; Westerhoff, P.; Mitch, W. A.; Skadsen, J. Case Studies on
Nitrosamine Formation and Control at Full-Scale Drinking Water Treatment
Plants. Presented at 2012 AWWA Wat. Qual. Technol. Conf., Toronto,
Ontario, 2012.
8. Valentine, R. L.; Choi, J.; Chen, Z.; Barrett, S. E.; Hwang, C. J.; Guo, Y.;
Wehner, M.; Fitzsimmons, S.; Andrews, S. A.; Werker, A. G.; Brubacher,
C.; Kohut, K. D., Factors affecting the formation of NDMA in water and
occurrence. AWWA Research Foundation: Denver, CO, 2005.
9. Krasner, S. W.; Westerhoff, P.; Chen, B.; Rittmann, B. E.; Amy, G.
Occurrence of disinfection byproducts in united states wastewater treatment
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21. Le Roux, J.; Gallard, H.; Croue, J. P. Chloramination of nitrogenous
contaminants (pharmaceuticals and pesticides): NDMA and halogenated
DBPs formation. Water Res. 2011, 45 (10), 3164–3174.
22. Shen, R.; Andrews, S. A. Demonstration of 20 pharmaceuticals and
personal care products (PPCPs) as nitrosamine precursors during chloramine
disinfection. Water Res. 2011, 45 (2), 944–952.
23. Shen, R. Q.; Andrews, S. A. NDMA formation kinetics from three
pharmaceuticals in four water matrices. Water Res. 2011, 45 (17),
5687–5694.
24. Selbes, M.; Kim, D.; Ates, N.; Karanfil, T. The Roles Of Tertiary Amine
Structure, Background Organic Matter And Chloramine Species On NDMA
Formation. Water Res. 2013, 47 (2), 945–953.25.
25. Choi, J.; Valentine, R. L. Formation of N-nitrosodimethylamine (NDMA)
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Chapter 6
1. Introduction
Numerous empirical models have been developed to predict the formation
of disinfection by-products (DBPs) (1–5). The majority of the models are on the
formation of THM4 (i.e., the sum of the four chlorine- and bromine-containing
trihalomethanes) following chlorination of natural waters. The THM4 and
other DBP formation models are typically developed using multiple regression
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2. Methods
Previously published chlorine-based THM4 formation models were collected
from peer-reviewed journal articles and reports as described in detail elsewhere
(6). The models evaluated in this research are listed in Table 1. The models
follow the multiple-parameter power function format or log-transformed power
function format. The model number is the same as used in previous work (6).
For subsequent analysis, the THM4 formation models were divided into two
categories; those that included bromide as an explanatory variable and those that
did not include bromide as an explanatory variable. The predictive capability of
the THM4 formation models was assessed by log (base 10) transformation of the
power function models to a common format, i.e., log y = a + b1log x1 + bplog xp,
where y is the predicted THM4 concentration (in µg/L), x1 to xp are explanatory
variables, a and b1 to bp are regression coefficients, and p is the number of
explanatory variables. The power function models were log transformed to
linearize all models, which was the original form of the models used in the
multiple regression analysis, and to allow for graphical display of all THM4 data,
which ranged from 1 to 1000 µg/L. For each model, the predicted log10(THM4)
was compared with the measured log10(THM4) using the following statistical
metrics: linear coefficient of determination or R-squared (R2), adjusted R-squared
(adj-R2), standard error (SE), and mean absolute percentage error (MAPE).
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Table 1. Summary of THM4 Formation Models Evaluated in this Work
No.a Modelb Ref
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Statistical analysis was conducted on log transformed (base 10) models. b Units: THM4 (µg/L), Br− (µg/L) unless noted otherwise, DOC (mg/L), TOC
101
(mg/L), UV254 (1/cm), pH (–), T (° C), t (h), Cl2 (mg/L), SUVA (L/mg·m). c NH3 term neglected. d Br− (mg/L). e Combined terms separated following
logarithm rules. f Not corrected for pH to maintain consistent format with other log transformed models. g All terms divided by ln(10) to convert model to
log base 10.
same units as the response variable. The smaller the value of SE, the higher the
accuracy of the prediction. SE was calculated in Microsoft Excel using the sum of
squares of differences function as SQRT(SUMXMY2(log10(THM4i) measured,
log10(THM4i) predicted)/n). The MAPE is a measure of the accuracy of the
predictions, and has the formula ∑abs[(log10(THM4i) measured – log10(THM4i)
predicted)/log10(THM4i) measured]/n where the summation is over all data and
the final value is expressed as a percent. The MAPE formula was calculated in
Microsoft Excel. The smaller the value of MAPE, the more accurate the prediction
by the model.
The measured THM4 data and corresponding water quality and chlorination
conditions came from a national study of bromide in U.S. drinking water
supplies (12). The subset of THM4 formation models that included bromide
as an explanatory variable were evaluated for their sensitivity to changing
bromide concentration. The bromide-containing THM4 formation models were
evaluated using a data set that measured THM4 formation for increasing bromide
concentration with all other water quality and chlorination conditions constant
(13). Finally, the bromide-containing THM4 formation models were used to
simulate the change in THM4 concentration that would occur for different
scenarios of seawater intrusion based on a bromide to total dissolved solids (TDS)
mass ratio of 0.0019134 for standard seawater (14).
water inputs (13). The predictive capability of several of the models, e.g., 8 and
12, could be improved by increasing the constant while keeping the same value
for the regression coefficients for the explanatory variables. This represents a
hybrid approach in which a water utility could slightly modify an existing THM4
formation model using historic water quality and THM4 formation data but not
redo the multiple regression analysis to develop an entirely new model.
Table 2 provides a summary of the goodness of fit statistics that quantify the
predictive capability of the log (base 10) transformed THM4 formation models.
The models with the lowest SE were models 21 (SE = 0.226), 22 (SE = 0.230),
16 (SE = 0.232), 30 (SE = 0.234)), 17 (SE = 0.235), 5 (SE = .241), and 9 (SE =
0.262). It is important to recognize that the SE values are for log10(THM4), i.e.,
log base 10 scale, such that a small value in SE can translate to a large variation
in THM4 concentration depending on the magnitude of log10(THM4). Table 3
illustrates the accuracy of the model estimates for log10(THM4) = 1.6 (40 µg/
L) and log10(THM4) = 1.9 (80 µg/L). For example, for a log10(THM4) model
prediction of 1.6, the model prediction ± one SE is 24 to 67 µg/L after anti-log
transformation. However, for a log10(THM4) model prediction of 1.9, the model
prediction ± one SE is 48 to 135 µg/L after anti-log transformation, which is
too wide of a range to be useful for regulatory compliance. Among the models
with the lowest SE discussed above, model 9 had the lowest MAPE (30%) and
model 22 had the highest adjusted R2. Models 5, 16, 17, 21, and 22 included
Br−, UV254, Cl2, and t as common explanatory variables. These four explanatory
variables represent the minimum set of explanatory variables needed to accurately
predict THM4 formation. For instance, Br− and UV254 represent both inorganic
and organic precursor material in THM4 formation, and Cl2 and t dictate the extent
of the chlorination reaction.
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Table 2. Summary of Goodness of Fit Statistics for Log (Base 10)
Transformed THM4 Formation Models.
Modela SE MAPE R2 adj-R2 p Bromide
2 0.346 36% 0.759 0.752 4 no
5 0.241 38% 0.749 0.736 7 yes
6 0.500 56% 0.759 0.754 3 no
7 0.563 31% 0.726 0.719 4 no
8 0.669 36% 0.671 0.664 3 no
9 0.262 30% 0.704 0.696 4 no
10 0.294 34% 0.766 0.756 6 yes
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Table 3. Illustration of Predictive Accuracy of Model 21 (SE = 0.226) and Model 9 (SE = 0.262).
THM4, log10(THM4) SE log10(THM4) Anti- log10(THM4) Anti-
µg/L – SE log(log10(THM4) + SE log(log10(THM4)
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variable (see Table 1). Model 5 was the only model that could relatively accurately
predict THM4 formation at low and high bromide concentrations, which was
indicated in Figure 2a and by the low SE of 0.092. However, despite model 5
being the most accurate model, the predicted data showed a different trend than
the measured data in terms of increasing THM4 concentration with increasing
bromide. Model 35 predicted increasing THM4 concentration with increasing
bromide concentration; however, the predictions were not accurate as shown in
Figure 2a and by the high SE of 1.264. In summary, at bromide concentration in
the range of 50–100 µg/L, there were models that both under predicted and over
predicted THM4 formation (see Figure 2b). This was because other factors are
more important than bromide on THM4 formation at low bromide concentrations,
such as the concentration and character of DOC. At bromide concentration greater
than 500 µg/L, all models under predicted THM4 formation. Thus, there is a clear
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need for THM4 formation models that are calibrated using water quality data sets
that contain bromide in the range of 500 µg/L to great than 1 mg/L.
Given that model 5, among the models considered, showed the best agreement
between predicted THM4 concentration and measured THM4 concentration
for the condition of increasing bromide concentration, it was used to predict
THM4 formation under a more generalized scenario of seawater intrusion. In
particular, Figure 3 shows THM4 formation as a function of increasing TDS
where the bromide concentration was calculated from the bromide-to-TDS ratio
for standard seawater (14). Model 5 includes TOC, UV254, Br−, Cl2, t, pH, and T
as explanatory variables; the value used for each variable is given in the caption
to Figure 3. The variables represent reasonable values for finished drinking water,
e.g., 1 mg/L TOC and Cl2-to-TOC mass ratio of 2 (25). Figure 3 shows that
THM4 increases steadily with increasing TDS, which is due to the increasing
bromide concentration as shown in Figure 2b. An interesting data point in Figure
3 is 500 mg/L TDS, which is equivalent to THM4 formation of 144 µg/L. Thus, at
the secondary standard for TDS, THM4 formation exceeds its primary maximum
contaminant level. This is significant because secondary drinking water standards
are not health-based, whereas primary drinking water standards are in place to
protect public health (28). Hence, the model predictions in Figure 3 suggest that
seawater intrusion, and in particular the co-transport of bromide with chloride,
will be problematic in terms of increasing the formation of THM4 well before
the water would become unpalatable due to high TDS. Furthermore, laboratory
studies have shown that high chloride concentrations can catalyze the formation
of highly reactive bromine species during chlorination, which further increases
the formation of brominated DBPs (29). Overall, the results in Figure 3 illustrate
a new and unique challenge for drinking water treatment because there are a
limited number of processes that can effectively remove bromide and seawater
intrusion is expected to increase in many coastal areas due over pumping, changes
in recharge, and sea-level rise (30, 31).
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4. Conclusions
Several previously published THM4 formation models were determined
to be moderately robust in their model development and calibration such that
the models could be applied at the water utility scale using water quality and
chlorination conditions separate from the original calibration data set. For
example, the anti-log transformation of log10(THM4) ± SE for log10(40) = 1.6
± 0.226 gives an accuracy of 24 to 67 µg/L for a target THM4 concentration
of 40 µg/L. This example used the highest level of accuracy that was obtained
in this work, so there is the potential for some of these models to be used
at the water utility scale. In particular, the more statistically robust THM4
formation models determined in this work are expected to be useful for small
water systems and water systems experiencing frequent changes in water quality,
such as variable TOC concentrations. With minimal to no modification, water
utilities can use these models to predict THM4 and help inform short-term
operation and long-term planning. One caveat to the THM4 formation models
evaluated in this work was the low sensitivity of many of the models to increasing
bromide concentration. Hence, previously published THM4 formation models
should be used with caution if the application of the model is predicting THM4
concentration under conditions of variable bromide concentration, such as the
case of seawater intrusion. An important side result of the bromide sensitivity
analysis was the illustration that THM4 concentration could reach problematic
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levels (> 100 µg/L) when the TDS was at or below its secondary standard of
500 mg/L. This highlights a new challenge for drinking water treatment whereby
seawater intrusion, with its drivers in urbanization and global climate change, can
alter the water matrix and dramatically increase the formation of DBPs, especially
brominated DBPs.
Acknowledgments
This publication is based upon work supported by the University of Florida
Research Opportunity Seed Fund award: Florida as a Laboratory for Global
Urbanization, Sea Level Rise, and Future Health Risks of Drinking Water Sources.
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disinfection byproduct (DBP) formation in drinking waters: A chronological
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2. Chowdhury, S.; Champagne, P.; McLellan, P. J. Investigating effects of
bromide ions on trihalomethanes and developing model for predicting
bromodichloromethane in drinking water. Water Res. 2010, 44, 2349–2359.
3. Lu, O.; Krasner, S. W.; Liang, S. Modeling approach to treatability analyses
of an existing treatment plant. J. Am. Water Work Assoc. 2011, 103, 103–117.
4. Sohn, J.; Amy, G.; Cho, J.; Lee, Y.; Yoon, Y. Disinfectant decay and
disinfection by-products formation model development: chlorination and
ozonation by-products. Water Res. 2004, 38, 2461–2478.
5. Amy, G. L.; Siddiqui, M.; Ozekin, K.; Zhu, H. W.; Wang, C. Empirical
based models for predicting chlorination and ozonation byproducts:
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Environmental Protection Agency: Washington, D.C., 1998.
6. Ged, E. C.; Chadik, P. A.; Boyer, T. H. Predictive capability of chlorination
disinfection byproducts models. J. Environ. Manage. 2015, 149, 253–262.
7. Nikolaou, A. D.; Golfinopoulos, S. K.; Arhonditsis, G. B.; Kolovoyiannis, V.;
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8. Uyak, V.; Ozdemir, K.; Toroz, I. Multiple linear regression modeling of
disinfection by-products formation in Istanbul drinking water reservoirs.
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9. Gallard, H.; von Gunten, U. Chlorination of natural organic matter: kinetics
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Chapter 7
Introduction
The Sacramento-San Joaquin Delta (Delta) is at the nexus of a California
statewide water system, which provides a critical water supply (State Project Water
[SPW]) to 23 million people in California. The Delta is at the confluence of the
Sacramento and San Joaquin Rivers (Figure 1). The Delta empties into the Pacific
se (4).
Nitrosamines are known to be probable human carcinogens, and they have
gained a lot of attention from health and regulatory agencies in the United
States (U.S.) and internationally (5). Although there is no federal regulation for
nitrosamines in drinking water, the California State Water Resources Control
Board Division of Drinking Water (DDW) set a notification level of 10 ng/L each
for NDMA and two other nitrosamines (6). The objective of this study was to
evaluate the presence and fate of NDMA, other nitrosamines, their precursors,
and selected PPCPs in the Delta, including seasonal and year-to-year variability.
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Experimental
Overview of Study
The sampling sites in this study included locations upstream and downstream
of the Stockton and Sacramento Regional WWTPs, and WWTP effluent or river
water immediately adjacent to the discharge. Table 1 lists the sampling locations.
There were a total of eight sampling events: both watersheds were sampled in six
of them, covering summer, fall, and winter seasons over a two-year period; only the
San Joaquin River and the Stockton WWTP were sampled in two additional events.
The samples were analyzed for eight nitrosamines, including NDMA, NMOR, and
N-nitrosopyrridine (NPYR). Certain PPCPs found in wastewater can be used as
conservative indicators of wastewater impacts in drinking water supplies. The
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indicators used in this project were primidone (an anticonvulsant drug) (7, 8)
and sucralose (an artificial sweetener - Splenda®) (9). The percentage of treated
wastewater in the rivers was calculated as the ratio of the concentrations of these
indicators in the rivers against their concentrations in the WWTP effluents. In
addition, modeling of volumetric contributions of the WWTP discharges to the
river flow was estimated using a simulation model.
Study Sites
Stockton WWTP
The Stockton WWTP was a tertiary treatment plant. The advanced treatment
units included oxidation ponds, wetlands, nitrifying biotowers, dissolved air
floatation (DAF), and mix media filters. The effluent was chlorinated and
ammonia was added (if needed; ammonia was present or not, depending on how
well the biotowers nitrified the water to form chloramines). The tertiary processes
provided additional treatment to clean up the wastewater, including removal of
ammonia, algae, and a final filtering through sand, gravel, and anthracite coal to
remove more organic material and fine suspended particles.
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Sacramento Regional WWTP
Analytical Methods
Nitrosamines
Nitrosamine Precursors
PPCPs
Sucralose
Filtered (0.45-μm) water samples were injected directly onto the C18 HPLC
column equipped with a 2.0-mm C18 guard column. The MS was operated under
an electrospray negative ion mode. Sucralose was identified as were other PPCPs.
An isotope dilution technique was used for quantitation with d6-sucralose. The
MRL was 0.2 µg/L.
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Figure 3. NDMA and NMOR in the San Joaquin River and at the Stockton
WWTP (bottom and top of the box = 25th to 75th percentile, line through the box
= median, bottom and top of the whiskers = 10th to 90th percentile).
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Wastewater Indicators in WWTPs and Estimated Wastewater Effluent
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Figure 7. NDMA precursors in the San Joaquin River and in the Stockton WWTP
effluent (reverse flows during the November 2011 and July 2012 sample events).
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Table 2. Concentrations of the Wastewater Indicators and NDMA FP in the
San Joaquin River and in the Stockton WWTP Effluent (November 2012)
NDMA FP Primidone Sucralose
ng/L ng/L µg/L
Upstream 25 9.5 2.6
WWTP 283 132 34.9
Downstream 45 18.6 5.3
Estimated % Effluent 10 % 7% 8%
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Figure 9 shows the percent wastewater effluent in these two rivers as estimated
by the model. The data from the model was a daily average of the river flow,
whereas the data from our sampling events were based on grab samples. In the San
Joaquin River, the percent WWTP effluent in the downstream location fluctuated
from 2 to 14%, whereas the Sacramento River percentage remained steady at 2-4%.
This was due to the higher river flow of the Sacramento River. The average annual
river flow of Sacramento River was 23,469 cubic foot per second (cfs), whereas
in the San Joaquin River it was 4,460 cfs.
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Figure 10 shows that both wastewater indicators had good agreement in the
estimation of percent WWTP effluent in the downstream locations in these two
rivers. Moreover, the estimations based on wastewater indicators matched well
with the hydraulic flow-calculated contributions.
Conclusions
Effluents from the two largest WWTPs in the Delta were shown to be an
important source of NDMA precursors in a major source of drinking water for
23 million Californians. NDMA precursor loadings in the river were detected
downstream of the WWTPs at higher levels than at the upstream sites, where the
increase was consistent with the percent of river flow due to the WWTP discharge.
However, due to river dilution and/or solar photolysis, the nitrosamines formed or
present at the WWTP were not detected at or above the MRLs downstream of these
WWTPs. The anticonvulsant primidone and the artificial sweetener sucralose were
found to be good wastewater indicators, and the percentage of treated wastewater
in the rivers was determined based on these indicators. In addition, the volumetric
wastewater contribution to river flow was determined using a hydraulic simulation
model, which matched the percent effluent estimations based on the wastewater
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indicators. A good relationship was found between the level of NDMA precursors
in the river/WWTP systems and the wastewater indicators, where the slope of
the trend line was steeper for the river system with the WWTP with secondary
treatment as compared to the system with the tertiary treatment process.
Acknowledgments
The authors gratefully acknowledge support from the staff of the California
DWR and the City of Stockton, with special thanks going to Carol DiGiorgio
(DWR) and Laura Lazzelle (City of Stockton).
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11. Krasner, S. W.; Sclimenti, M. J.; Guo, Y. C.; Hwang, C. J.; Westerhoff, P.
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12. Krasner, S. W.; Sclimenti, M. J.; Mitch, W. A.; Westerhoff, P.; Dotson,
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Chapter 8
National Occurrence of
N-Nitrosodimethylamine (NDMA)
An Investigation of 38 Australian Drinking Water Supplies
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Introduction
The formation of N-nitrosodimethylamine (NDMA) in disinfected water
supplies has attracted worldwide attention, given it has been classified as a potent
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carcinogen (1). Health guidelines for NDMA adopted by agencies around the
world range from between 9 and 100 ng/L (2–6). NDMA has been detected in both
chlorinated and chloraminated drinking waters, although higher concentrations
have generally been associated with systems using chloramine as the disinfectant
(7–9). While reported NDMA concentrations in drinking water supplies have
tended to be lower than 10 ng/L (10), higher concentrations (>100 ng/L) have
been observed with increasing residence time in the distribution system (11–13).
Some studies have also reported the presence of NDMA in some raw waters (i.e.
without disinfection) (12, 14). Factors that impact NDMA formation in drinking
water include source water quality and the presence of precursors (15–17), choice
of disinfectant (8, 12, 14), operational parameters such as pH or disinfectant dose
(16), use of ion-exchange resins or certain nitrogen-containing coagulants (7, 18),
and the residence time in distribution systems (11–13).
While some monitoring programs have been established by state water
authorities or water utilities, there are limited published data on NDMA
occurrences in Australian drinking water. This paper consolidates results of
NDMA occurrence surveys collected across five states and one territory in
Australia between 2007-2013, representing the most comprehensive analysis
of NDMA concentrations in Australian drinking water supplies. Survey data
were analysed to determine the impact of water treatment processes on NDMA
formation, and to identify key factors in the formation of NDMA in Australian
drinking water treatment plants (DWTPs).
Methods
Sample Sites
A total of 211 samples were collected from 38 DWTPs around Australia (five
states and one territory) between 2007 and 2013, with the majority (85%) collected
between 2009 and 2011. The samples were collected as part of individual
studies or monitoring programs undertaken by research organisations across
Australia, and data were subsequently combined for this study. The DWTPs
studied included ten from Victoria, three from New South Wales, two from South
Australia, all studied by the Australian Water Quality Centre (AWQC), ten from
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Western Australia and three from the Northern Territory, studied by the Curtin
Water Quality Research Centre (CWQRC), and ten from Queensland, studied
by the Smart Water Research Centre (SWRC) at Griffith University, and the
Advanced Water Management Centre (AWMC) at the University of Queensland.
While some studies did test for other N-nitrosamines in addition to NDMA, there
were significant variations in analytical method and limits of reporting. Therefore
this paper discusses NDMA occurrence only as it was the only N-nitrosamine
measured in all studies.
In terms of disinfection, 18 of the 38 DWTPs tested used chlorine and 14
DWTPs used chloramine. Six plants used mixed disinfection treatment trains;
four plants used pre-ozonation followed by chlorination or chloramination
(DWTPs 29, 31, 37 and 38) and two plants used UV disinfection in addition
to chlorine or chloramine disinfection for additional microbial protection
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(DWTPs 14 and 24). Figure 1 shows the general classification of these DWTPs
according to pre-treatment process before disinfection. Disinfection (chlorination
or chloramination) was the sole treatment process for eight DWTPs (21%),
while four plants (11%) utilised filtration (e.g., granulated activated carbon or
membrane filtration) or sedimentation without coagulation before disinfection.
One disinfection-only plant (DWTP 15) that utilised chloramine is unusual
because the raw water reservoir includes pre-treated groundwater, surface
water and desalinated water, and both chloramination and chlorination are used
in the large distribution system to maintain residual. All other DWTPs (26,
68%) utilised coagulation for treatment, with 15 plants following a relatively
conventional treatment process (coagulation, flocculation, sedimentation,
filtration and disinfection, with pH adjustment and pre-chlorination as required).
Four plants (DWTPs 2, 3, 23, and 30) utilised coagulation and direct filtration
(e.g. membranes or dissolved air flotation and filtration) instead of clarification
by sedimentation. Seven DWTPs had atypical aspects to their pre-treament,
including incorporation of desalinated water (DWTPs 5 and 36), use of ion
exchange resins for NOM removal (DWTP 21), and ozonation throughout the
treatment process (DWTPs 29, 31, 37 and 38). The target chlorine or chloramine
residuals leaving each DWTP were generally between 1 and 3 mg/L, although
three chloramination plants (DWTP 14, 15 and 26) servicing large distribution
systems had treatment plant target residuals of between 3 and 4.5 mg/L.
In addition to sampling, operational data were collected for each plant,
including description of the treatment regime, the use and dose of primary
coagulants and coagulant aids, disinfection dose(s), pH, target disinfectant
residual leaving the plant, and system detention time at the sampling point. In
the case of chloramination, details of the order and time between chlorine and
ammonia addition were also obtained. Where possible, operational parameters
were obtained for the exact dates when samples were collected, although for
some DWTPs or systems little or no data were available and collection of
operational data were challenging for systems where the water authorities
providing distribution system water samples were not responsible for initial water
treatment. Physicochemical characteristics such as pH, total dissolved solids
(TDS), temperature, dissolved organic carbon (DOC) and disinfectant residuals
were also recorded for raw and treated water samples, where possible.
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Table 1. Details of Sampling and Analytical Methods for NDMA for Each
Laboratory
Laboratory AWQC CWQRC QHFSS
Preservation Sodium Ascorbic acid Sodium
Agent thiosulphate 20 mg/L thiosulphate
pentahydrate 80-100 mg/L
120 mg/L
Sample volume 500 mL 1000 mL 1000 mL
Blanks Tap water treated Ultrapure water and Ultrapure water
with UV light quenching agent
SPE cartridge 35-50 mesh LiChrolut® EN and Coconut charcoal
resin activated charcoal Carboxen™ 572
Ionisation mode Positive CI with Positive CI with Positive CI with
(GC-MS) isobutane ammonia ammonia
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Samples were collected in glass amber bottles or aluminium foil-covered
polyethylene bottles containing a quenching agent, kept cool and in the dark in
an ice box during transport to the laboratory, and then refrigerated in the dark at
4°C until extraction. All laboratories used laboratory blank samples to quantify
contamination introduced through the analytical process. In addition, CWQRC
also included trip and field blanks in each sampling event to determine if there
was any contamination through the sampling process, storage and transport.
Trip blanks remained unopened until analysis, and field blanks were opened at
each sampling location. Samples were then analysed for NDMA at one of three
laboratories, AWQC, CWQRC or Queensland Health Forensic and Scientific
Services (QHFSS). Analysis was carried out using solid-phase extraction (SPE)
followed by gas chromatography-mass spectrometry (GC-MS), with minor
variations between laboratories. Details of small variations between the sampling
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protocol and analytical method used by each laboratory are listed in Table 1. The
concentration of NDMA was quantified against a deuterated internal standard
(isotope dilution procedure) and the limits of reporting (LOR) ranged between 1
ng/L and 5 ng/L.
All three laboratories undertook two rounds of inter-laboratory comparison
testing as part of the NDMA survey undertaken by the AWQC and funded by Water
Quality Research Australia (WQRA, now known as Water Research Australia
Ltd). During each round, duplicate samples containing between 10 and 130 ng/L
NDMA were sent to each independent laboratory for analysis. Results obtained
from CWQRC and QHFSS compared well with those of the AWQC. With the
exception of one sample, all results were within 13% relative standard deviation
(RSD) (19).
Data Analysis
All data, excluding blanks and replicates, were pooled into a common dataset.
The normality of the dataset was tested by calculation of the Kolmogorov-Smirnov
Statistic and the Shapiro-Wilk Statistic (SPSS Statistics v20) and the data were
found to have a poor fit to the normal distribution curve. Therefore median was
chosen for data analysis rather than average because it is less affected by outliers
and because it is more suited for data that does not follow a normal distribution.
As the LOR for NDMA analyses varied for each of the testing laboratories, the
highest LOR was chosen as the limit for all samples. Therefore if a result was < 5
ng/L then it was allocated a value of < 5 ng/L (i.e. zero for calculations), and this
will influence percentage detection calculations and other statistics.
Calculation of median concentrations incorporated all data points including
samples reported to be below LOR, and these were assumed to be equal to the
LOR for the purposes of that calculation. While this conservative approach will
overestimate the actual median concentration of chemicals reported below LOR
in more than 50% of samples, it was deemed appropriate given our primary goal
of assessing the safety of treated drinking water. As most samples (>80%) did
not contain NDMA above the LOR, average and median concentrations were also
calculated solely based on samples in which NDMA ≥ 5 ng/L.
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Results and Discussion
Overview of Occurrence Data
A total of 211 post-disinfection samples were collected and analysed in this
study. Of these, 95 samples were collected at, or within 2km of, the treatment
plant and 116 were collected in the distribution system. The Australian Drinking
Water Guidelines recommend maintaining a chlorine or chloramine residual
greater than 0.5 mg/L for control of Naegleria fowleri (1) and therefore we
expected disinfectant residual throughout the distribution system. Disinfectant
residual data collected in 27 of the 38 DWTP confirmed this, although the residual
was not always > 0.5 mg/L.
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Figure 2 shows that the majority (80%, n = 169) of all samples contained
NDMA concentrations below 5 ng/L, while 12% (n = 25) contained NDMA
concentrations between 5 and 10 ng/L. As the majority of all disinfected samples
measured NDMA below 5 ng/L, the median concentration of all disinfected
samples was also < 5 ng/L. Of the 211 disinfected samples, 126 were from
chloraminated systems while the remaining 85 were from chlorinated systems.
Figure 2 shows that only 5% of samples (n = 4) from chlorinated systems
contained NDMA above 5 ng/L. On the other hand, 30% (n = 38) of samples
from chloraminated systems were measured with NDMA levels of 5 ng/L or
higher. Chloraminated samples also recorded a much higher maximum NDMA
concentration (74 ng/L) than the chlorinated samples (14 ng/L).
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Further data analysis demonstrated that all NDMA detects ≥ 5 ng/L were from
nine specific DWTPs, where 48% of all samples (n = 88) contained NDMA > 5
ng/L (Table 2). There was a wide variation in observed NDMA levels, with two
DWTPs (4 and 14) exhibiting significantly higher levels of NDMA (up to 46 ng/L
and 74 ng/L, respectively) than the other plants. The high NDMA concentrations
measured in DWTP 4 and 14 have previously been studied, and were attributed
to factors that include poor source water quality, the method of chloramination
and DWTP management practices (20). Despite these results, all detections were
below the Australian Drinking Water Guideline of 100 ng/L for NDMA.
As shown in Table 2, where NDMA was present at ≥ 5 ng/L, the median
concentration for distribution system samples was generally higher than for
treatment plant samples, with the exception of DWTP 4. In addition, a higher
percentage of distribution system samples contained NDMA compared to the
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treatment plant samples (30% versus 8%). This is consistent with results of other
surveys suggesting that NDMA can continue to form and increase with time in
the distribution system (11–13).
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Influence of Operational Parameters on NDMA Formation in Chloraminated
Systems
Polymer
Raw Water
Median used as Addition of
Plant No. DOC
NDMA ng/L coagulant ammonia first
>10 mg/L
aids
2 3 Y N n.a.
3 4 Y Y N
4 53 N Y Y
5 7 Y Y Y
6 n.d. N n.a. n.a.
7 n.d. N n.a. n.a.
8 n.d. N n.a. n.a.
12 n.d. Y N N
13 7 Y N Y
14 19 Y Y Y
15 3 N Y N
25 n.d. N N n.a.
26 n.d. N N n.a.
27 n.d. N N n.a.
36 n.d. Y N n.a.
38 n.d. N N n.a.
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of chloramination practice (order of reagent addition and contact time), use of
nitrogen-containing coagulants and coagulant aids, as well as raw water chemistry
on NDMA formation. Table 3 presents a summary of the key factors and NDMA
concentrations in the 16 DWTPs using chloramination. The influence of these
factors on formation of NDMA are discussed in detail below.
Chloramination Practice
In contrast, the addition of chlorine after ammonia has been shown to enhance
NDMA formation from dimethylamine, a model NDMA precursor, by up to an
order of magnitude (22). This increase was attributed to the localised formation
of dichloramine at the point of chlorine addition, due to high localised Cl:N ratio.
NDMA formation from dichloramine is higher than from monochloramine.
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Coagulation and Coagulation Aids
Most of the DWTPs in this study (25 out of 38) used coagulation as part of
their water treatment process. Alum was the most commonly used coagulant,
but other coagulants such as ferric chloride and Magnasol 489, a mixture of
polyaluminium chlorohydrate and polydiallyldimethyl ammonium chloride
(polyDADMAC), were also used. The primary coagulant dose varied greatly,
ranging from 5 mg/L to 240 mg/L. There was no correlation observed between
the primary coagulant dose and NDMA concentration in the treated water. In
some instances where no coagulant was used, NDMA was still observed in the
final product water suggesting the presence of precursors in the raw water.
Fifteen of the DWTPs also employed various coagulant aids, which varied in
dose, ranging from 0.005 mg/L to 4.7 mg/L. Even though higher coagulant doses
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can potentially remove more NDMA precursors, the use of certain coagulant aids
can potentially add NDMA precursors to the water. For example, polyDADMAC,
a nitrogen-based polymeric coagulant has received attention for its reported
propensity to form NDMA during chloramination (18, 25). PolyDADMAC was
used in some water treatment plants in South Australia and Queensland, including
some of the DWTPs presented here.
While there was no clear evidence to suggest that the generic use of coagulant
aids resulted in higher level of NDMA in the disinfected water, when coagulant
aids were utilised, NDMA was only observed when polyDADMAC and/or
Magnafloc LT22 was used in chloraminating DWTPs. NDMA was not detected
in DWTPs that used other coagulant aids (e.g. Flopam AN 910 PWG, Magnafloc
LT20, Magnafloc LT21, Magnafloc LT25, Nalco 44560, Nalco 3482, Magnafloc
LT425, SNF AN 905). Among the six DWTPs utilizing PolyDADMAC, NDMA
was detected in two of the three chloraminating plants between 7-46 ng/L,
but was not detected in any of the three plants using chlorine disinfection.
PolyDADMAC consists of quaternary amines with dimethylamine-functional
groups and it has been proposed that NDMA formation can occur from both
the dimethylamine-moieties (25, 26) or the quaternary amines themselves (27),
which act as NDMA precursors. In this study higher NDMA concentrations
were observed in plants using polyDADMAC, when chloramination was the
disinfection process and not chlorination. This suggests that polyDADMAC
may have an influence in forming NDMA in DWTPs, but only when chloramine
disinfection is used.
Only four DWTPs utilised Magnafloc LT22 as the exclusive coagulant
aid, all of which practiced chloramination, and all of which detected NDMA
at least once. Magnafloc LT22 is a polyacrylamide-based polymer and there
have been no studies to-date relating NDMA formation to its use. However,
certain polyacrylamides used in water treatment have been reported to form
NDMA also through the dimethylamine-moieties in the polymer structure (25,
26). While the exact composition of Magnafloc LT22 was unknown, it is possible
that its structure contains dimethylamine-moieties which can explain the NDMA
formation observed in these plants.
In order to assess the contribution of these nitrogen-based polymers towards
NDMA formation during water treatment, NDMA formation potentials (FP)
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were determined from different commercially available coagulant aids used
in Australia. Coagulant aids (10 mg/L) were dosed with a high concentration
of monochloramine and analysed for NDMA after seven days of contact time,
based on the procedure by Mitch et al. (28). Of the five coagulant aids tested,
only polyDADMAC and Magnafloc LT22 formed > 10 ng/L NDMA (Table 5).
PolyDADMAC showed an extremely high NDMA FP of 15,000 ng/L, several
orders of magnitude higher than any of the other coagulant aids. While Magnafloc
LT22 had a high NDMA FP (160 ng/L), formation was much lower than that
from polyDADMAC. While both polymers may have the potential to form
NDMA during chloramination, the extent of their impact will depend on specific
water treatment conditions. Doses of chloramine and coagulant aids used in the
DWTPs are much lower than the conditions of the FP procedure. Therefore the
contribution of Magnafloc LT22 to NDMA formation may not be significant; on
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the other hand, the use of polyDADMAC could still have significant potential for
NDMA formation under DWTP conditions due to its high FP.
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Raw Water Chemistry
Raw water parameters, including pH, TDS, temperature, DOC and turbidity,
were evaluated for relationships with NDMA concentrations, by calculation of
Spearmans’s correlation coefficients (R). There were no correlations observed
between NDMA concentrations and any raw water parameters, except for DOC.
As shown in Table 3, it appears that higher NDMA concentrations (> 5 ng/L)
were found in plants with higher raw water DOC (> 10 mg/L). Raw water DOC
showed a significant positive correlation with average NDMA concentrations (R
= 0.9, p <0.01, data not shown) However, the relationship was heavily skewed
by the significantly higher NDMA concentrations reported in DWTP 4, and there
was no significant correlation observed when data from DWTP 4 was removed.
Furthermore, six of the eight DWTPs practised some form of conventional
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treatment and/or filtration before disinfection, and therefore some DOC removal is
expected before disinfection. Raw water DOC therefore cannot be directly related
to NDMA formation in these cases. Another limitation is that the concentrations
of NDMA and its precursors are typically orders of magnitude lower than DOC
(ng/L compared with mg/L), and may not be directly comparable.
DWTP 4, which did not use any form of coagulation, exhibited the highest
NDMA concentrations. A previous study (20) has also identified that DWTP
4 had poor source water quality, and the treatment process (microfiltration)
was not effective in removing DOC. However, laboratory tests using DWTP 4
source water demonstrated that, even with alum coagulation, NDMA precursors
were not effectively removed compared with total DOC (20). This is consistent
with previous findings that NDMA precursors are usually low molecular weight
hydrophilic compounds (31), and are therefore unlikely to be effectively removed
through conventional treatment processes.
There are clearly limitations in assessing NDMA formation according to bulk
parameters such as DOC and organic nitrogen. Rather, the nature of natural organic
matter in the source water is more important for determining NDMA and and can
vary for each water source. Measurements of NDMA precursors (i.e. NDMA-FP)
may be a more useful indication of the potential of a source water to produce
NDMA under certain water treatment conditions.
Conclusions
The concentration of NDMA in Australian drinking water was variable, but
all detections were below the Australian Drinking Water Guideline of 100 ng/L.
As expected, chloraminating plants were found to have higher concentrations,
and more frequent detections of NDMA than chlorinating plants. The order
of reagent addition during chloramination had a significant impact on NDMA
formation, where the addition of ammonia before chlorine typically led to higher
NDMA concentrations, as compared to addition of chlorine first. Under certain
conditions, some nitrogen-containing coagulant aids may provide precursors for
NDMA formation upon chloramination. Employing free chlorine contact time
before ammonia addition can help to control NDMA formation in chloraminating
systems. These findings are the first demonstration of the influence of operational
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factors on NDMA formation in Australian DWTPs at the full-scale, and overall
they are consistent with previously reported findings from both laboratory studies
and other drinking water systems worldwide.
Acknowledgments
We acknowledge the following people for their technical assistance: Andrew
Chan and Geoff Chidlow of CWQRC; Con Kapralos, Jules Leach and Najwa
Slyman of AWQC; Neil Holling of QHFSS; Claire McInnes from Water Research
Australia. We thank the following people for their sampling assistance: Liza
Breckler, Ralph Henderson and Fern Burgess of Water Corporation (WA), Deb
Gale of Seqwater and other Seqwater staff. Thanks also goes to Adam Holman for
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his study on water treatment polymers, and Glendon Shaw and Kalinda Watson
for research support at SWRC. CWQRC research was funded by the Australian
Research Council (LP110100548), Water Research Australia Ltd and the Water
Corporation of Western Australia (WCWA). AWQC research was part of Water
Research Australia Project 1018-09 and thanks the participating water authorities
. SWRC research was funded by the Urban Water Security Research Alliance.
AWMC acknowledges the tailored collaboration between Seqwater and Water
Research Foundation, and would like to thank Djanette Khiari, manager of Water
Research Foundation Project #4484, and the project advisory committee for their
support. Dr Maria Jose Farre also acknowledges the European Commission for
funding project 623711 under the FP7-PEOPLE-2013-IIF - Marie Curie Action:
“International Incoming Fellowships”.
References
1. IARC, Some N-Nitroso compounds. IARC Monographs on the Evaluation
of Carcinogenic Risks to Humans; International Agency for Research on
Cancer, World Health Organisation: Lyon, France, 1978; Vol. 17, p 365.
2. Boyd, J. M.; Charrois, J. W. A.; Hofmann, R.; Hrudey, S. E. NDMA and other
N-nitrosamines – health risk assessment and management. In Disinfection
By-Products – Relevance to Human Health; Hrudey, S., Charrois, J. W. A.,
Eds.; IWA Publishing: London, 2012; pp 125−144.
3. Ontario Regulation 169/03, Schedule 2, Chemical Standards, Ontario Safe
Drinking Water Act; Ontario Ministry of Environment: Toronto, 2002.
4. Guidelines for Canadian Drinking Water Quality – Summary Table; Water,
Air and Climate Change Bureau, Healthy Environments and Consumer
Safety Branch, Health Canada: Ottawa, Ontario, 2012.
5. Guidance on the Water Supply (Water Quality) Regulations 2000 specific
to N-nitrosodimethylamine (NDMA) concentrations in drinking water;
Drinking Water Inspectorate: London, U.K., 2008.
6. Australian Drinking Water Guidelines 6; National Health and Medical
Research Council, National Resource Management Ministerial Council:
Canberra, Australia, 2011.
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7. Najm, I.; Trussell, R. R. NDMA Formation in Water and Wastewater. J. Am.
Water Works Assoc. 2001, 93, 92–99.
8. Valentine, R. L.; Choi, J.; Chen, Z.; Barrett, E.; Hwang, C. Factors Affecting
the Formation of NDMA in Water and Occurrence; AWWA Research
Foundation: Denver, CO, 2005.
9. Liew, D.; Linge, K. L.; Heitz, A.; Joll, C. A. Nitrogenous DBPs in drinking
water: toxicity, regulation, analysis, occurrence and control. In Disinfection
By-Products – Relevance to Human Health; Hrudey, S., Charrois, J. W. A.,
Eds.; IWA Publishing: London, 2012; pp 83−124.
10. Mitch, W. A.; Sharp, J. O.; Trussell, R. R.; Valentine, R. L.; Alvarez-
Cohen, L.; Sedlak, D. L. N-nitrosodimethylamine (NDMA) as a drinking
water contaminant: a review. Environ. Eng. Sci. 2003, 20, 389–404.
11. Zhao, Y. Y.; Boyd, J.; Hrudey, S. E.; Li, X. F. Characterization of New
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Water. OzWater’12 Conference Proceedings, Sydney, Australia, May 8−10,
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21. Mitch, W. A.; Oelker, G. L.; Hawley, E. L.; Deeb, R. A.; Sedlak, D. L.
Minimization of NDMA formation during chlorine disinfection of municipal
wastewater by application of pre-formed chloramines. Environ. Eng. Sci.
2005, 22, 882–890.
22. Schreiber, I. M.; Mitch, W. A. Influence of the Order of Reagent Addition on
NDMA Formation during Chloramination. Environ. Sci. Technol. 2005, 39,
3811–3818.
23. Charrois, J. W. A.; Hrudey, S. E. Breakpoint chlorination and free-chlorine
contact time: Implications for drinking water N-nitrosodimethylamine
concentrations. Water Res. 2007, 41, 674–682.
24. Mitch, W. A.; Sedlak, D. L. Formation of N-Nitrosodimethylamine (NDMA)
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Chapter 9
process configuration since these oxidants are also associated with the formation
of both regulated DBPs and NDMA (without chloramination). The objective
of this chapter is to provide a literature review on the oxidant applications for
controlling NDMA formation during drinking water treatment.
Chlorine
The first pathway that has been suggested to form NDMA is through
nitrosation of nitrogen-containing compounds. Nitrosation involves introducing
a nitroso group (-NO) into an organic compound causing the formation of
nitroso compounds. By N-nitrosation of nitrogen-containing organic compounds,
nitrosamines are formed. Possible nitrosating agents include nitrous acid (HNO2),
nitrogen oxides (N2O3, N2O4), and some others (4). For example, the nitrosation
reaction induced by nitrite is as follows: “Under acidic conditions, nitrite (NO2-)
is transformed to nitrous acid (HNO2), which is not stable in aqueous solution
but decomposes either to the nitrosyl cation (NO+) or to dinitrogen trioxide
(N2O3). Both of which are capable of reacting with nitrogen-containing organic
compounds to form nitrosamines (4).
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Table 1. Some of the Structures of NDMA Precursors
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Chlorine Dioxide
Andrzejewski and Nawrocki (15) have shown that chlorine dioxide reaction
with DMA led to the formation of NDMA. The highest observed yield was 0.2%
molar conversion under very high chlorine dioxide concentrations (i.e., 36 mg/L)
at pH 8.0. Compared to chloramination or other oxidants, however, this much
yield is expected to be negligible under drinking water treatment conditions.
Ozone
Ozonation of DMA forms NDMA but yields generally are <0.02% at neutral
pH (16). The yield of reaction was somewhat higher than 0.02% yet still below
0.4% molar conversion with the increasing pH (16). In another study of NDMA
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formation, Yang et al. (17) used a nitrosation pathway to generate the formation
of NDMA from DMA at pH level of 3.4. They also observed, through an
unknown pathway, the formation of NDMA during ozonation at a level of pH
greater than 7.0. Subsequent studies of NDMA formation during ozonation
showed that 1,1-Dimethyl Hydrazine (UDMH), daminozide and semicarbazide,
both with UDMH-like functional groups, formed NDMA at yields >50% (5, 18,
19). The ozonation of N,N-Dimethylsulfamide (DMS), a transformation product
of the fungicide tolylfluanide, was observed to form NDMA at a 52% yield
(18). Lastly, the ozonation of polyDADMAC, a polymer used in water treatment
plants also formed NDMA (20). These results clearly indicate that the ozonation
of polyDADMAC can release the DMA moiety while concurrently forming
hydroxylamines. The simultaneous reaction of these two products could form
UDMH, at which point the formed UDMHs would be converted to NDMA in the
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presence of ozone.
Permanganate
UV Irradiation
The high reaction kinetics of both chlorine and amines (i.e., NDMA
precursors) makes pre-chlorination an effective strategy for minimizing NDMA
formation (25). However, the use of chlorine also leads to the formation
of halogenated DBPs, of which the trihalomethanes (THMs) and haloacetic
acids (HAAs) are regulated, which may limit the application of chlorine as a
pre-oxidant.
The chlorination of wastewaters with ammonia can also cause the formation
of chloramines, which can react with certain forms of organic nitrogen to produce
NDMA. This phenomenon in turn causes the formation of NDMA in secondary
wastewater effluents (2). Therefore, prior to the application of chlorine for
controlling NDMA formation, the ammonia levels in the water should be analyzed
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because high levels of ammonia can hinder the inactivation of NDMA precursors.
Lauer (26) observed this phenomenon while investigating the use of oxidants
for controlling the discharge of NDMA precursors in wastewaters. Presence of
ammonia higher than 0.5 mg/L in wastewater samples was sufficient to negate the
chlorine at doses 5-10 mg/L. Only after the breakpoint chlorination, removal of
NDMA precursors was observed which was achieved at 20 mg/L chlorine dose.
However, the wastewater samples that contained ammonia levels lower than 0.5
mg/L, even 5 mg/L of chlorine dose achieved the removal of NDMA precursors
by 25 to 50% in two minutes of contact time. Higher NDMA precursors removal
(70-95%) with increasing chlorine doses and contact times (26). The distinct
effect of ammonia, however, precluded the mention of studies in this review that
concern unintended chloramination during the pre-chlorination process.
Charrois and Hrudrey (27) investigated two full-scale water treatment plants
as well as some bench-scale experiments with samples collected from those
treatment plants. Their results have showed that 2 mg/L free-chlorine contact of
two hours followed by an additional 2 mg/L chloramine, resulted in lower NDMA
levels (16±3.5 ng/L) compared to no free-chlorine contact time (51±8.3 ng/L). In
these bench-scale experiments, they found that a higher dose of free chlorine (4
mg/L) applied for two hours followed by a 4 mg/L chloramine dose, resulted in
even lower NDMA formation (3±0.7 ng/L). In samples collected from surface
water and the Iowa River (Total Organic Carbon [TOC] = 3.4 mg/L), Chen and
Valentine (28) found that NDMA formation decreased with the application of
free chlorine. The samples were exposed to 0.08 mM of free chlorine at pH 7.0,
which reduced NDMA formation from ~32 ng/L to ~12 ng/L within 5 minutes of
contact time and reached the lowest NDMA formation potential (FP) of ~6 ng/L
after 120 minutes. Furthermore, the amount formed decreased with an increase
pre-chlorination dosage for a fixed free chlorine contact time. One hour contact
time with chlorine doses of 0.035, 0.05, 0.06, and 0.08 mM reduced NDMA
FP to ~26, ~18, ~10 and ~6 ng/L, respectively, from the original NDMA FP of
~33 ng/L (with no chlorine exposure). In their studies, they determined that an
increase in both the chlorine dose and contact time decreased the formation of
NDMA during subsequent chloramination.
In another study, grab samples were collected upstream of any oxidant
addition for 10 source waters (29). Following pre-chlorination, samples were
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chloraminated for 72 hours under uniform formation conditions (UFC) and then
analyzed for NDMA formation. In general their findings have shown that chlorine
can reduce the NDMA formation by more than 50% within a concentration×time
(CT) of <70 mg×min/L. For instance, pre-chlorination of one of the samples
(pH=8.3, TOC=5.0 mg/L, Br-=170 µg/L, NH4+=0.06 mg/L) reduced NDMA
formation from 25 to 5 ng/L by a CT of 37 mg×min/L (29). They also determined
that the pre-oxidation with chlorine at a low exposure followed by chloramination
increased NDMA formation for three wastewater-impacted source waters. In
all three samples, the NDMA formation increased significantly at the lowest
exposure, representing a 3 minute contact time with chlorine before ammonia
addition, but declined at higher exposures (29). Because all three sample waters
contained some level of nitrite, it was hypothesized that NDMA formation was
perhaps due to the reaction of chlorine with nitrite that formed N2O4 (29), a
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nitrosating agent linked to the NDMA formation. It was also possible that the
increase in NDMA at low exposures was because the chlorination converted
NDMA precursors to more potent forms, an effect observed by Chen and
Valentine (28). At higher exposures, however NDMA formation declined, likely
because of the deactivation of these more potent NDMA precursors (29).
In separate study of samples at a water facility, Uzun et al. also reported
a decrease in NDMA formation in chlorine treated waters (30). In the utilities
they surveyed even small doses of chlorine (i.e., 0.5 mg/L) used for maintenance
purposes were found to decrease NDMA FP by an average of 10%. Furthermore,
the application of chlorine prior to the addition of ammonia in clearwells resulted in
a removal rate of 10 to 65%. The minimum and maximum chlorination CT in these
clearwells was 101 mg×min/L and 504 mg×min/L, respectively. However, no
strong correlation was observed between the chlorine CT and NDMA FP reduction
at the full-scale plants surveyed.
Several mechanistic studies have also been undertaken to elucidate the
pre-oxidation of NDMA precursors. These studies can be classified based
on the group of amines investigated: (i) Secondary Amines: The NDMA
formation from the secondary amine, namely DMA, decreased from 1.6% to
1.1% within 5 minutes (CT of 15 mg×min/L) of contact time with chlorine.
This increased chlorine contact time (CT of 180 mg×min/L) did not result in
a further decrease in NDMA formation (19). Previous studies also indicated
the high reactivity of DMA with chlorine (kapp at pH 7 ≈ 104 M-1 s-1), which
caused the formation of chlorinated-DMA (23, 25, 31). Therefore, formed
chlorinated-DMAs could remain in the solution and still form NDMA during
sequential chloramination. (ii) Tertiary Amines: Research performed by Shen and
Andrews (32) examined the impact of pre-chlorination on NDMA formation from
tertiary amines (amine-based pharmaceuticals). Here, eight pharmaceuticals (i.e.
ranitidine, nizatidine, tetracycline, doxylamine, chlorphenamine, carbinoxamine,
diltiazem, and sumatriptan) were examined under contact times of 0.5 to 120
minutes with chlorine ([Cl2]0 = 2.5 mg/L). Their results showed no change in
the rate of NDMA formation from diltiazem upon pre-chlorination. Surprisingly,
however, the chlorination of sumatriptan resulted in a three-fold increase of the
initial yield. Except for those two precursors, the NDMA formation from other
pharmaceuticals decreased by 10 to 90% with an increases in the pre-chlorination
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contact time (32). In their investigation of the interactions between chlorine
and tertiary amines, Selbes et al. (19) examined the pre-chlorination at different
contact times (5 to 60 minutes) with chlorine ([Cl2]0 = 3 mg/L) at pH 7.5 from
a wide array of NDMA precursors. After chlorination, with the exception of
compounds in both the carbonyl and sulfonyl groups, an overall decrease in the
NDMA formation rate was observed, which was influenced by the selected tertiary
amines. The NDMA yield of the former compounds decreased to approximately
half of the initial yield during pre-chlorination within 5 to 15 minutes, resulting
in a corresponding CT of 15 to 45 mg×min/L (19). (iii) Quaternary Amines:
There are mixed findings for the pre-chlorination of quaternary amines, and the
reasons for those differences remain unclear. Chlorination had no distinct effect
on the NDMA yields from quaternary amines (polyDADMAC, polyamine and
polyACRYL), because the positive charge on the nitrogen atoms of the polymers
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hindered the nucleophilic substitution (9, 19). A separate analysis however, did
indicate that the pre-chlorination of polyDADMAC and polyAMINE did decrease
NDMA formation within 10 minutes of contact time (33). The decrease was
attributed to the structural changes of either the polymers or the DMAs, which
made them less reactive to further chloramination.
Overall, the effectiveness of pre-oxidation with chlorine is highly dependent
on the type of precursors, a finding supported by mechanistic studies. There are
also precursors that exhibit no reactivity with chlorine. Indeed, chlorination has
caused an increase in NDMA formation, which occurred i) in the presence of nitrite
from chlorine-triggered nitrosation pathways, or ii) or in the presence of ammonia-
forming chloramines that then directly created NDMAs.
Chlorine Dioxide
Chlorine dioxide is sometimes used in lieu of chlorine in water treatment
processes as it produces fewer chlorinated organic substances, does not form
THMs, and significantly suppresses the formation of HAAs. A potential drawback,
however, associated with the use of chlorine dioxide is that approximately 70%
of the compound is reduced to chlorite (ClO2-), which is a regulated DBP in
the United States. Chlorate (ClO3-) may also form, which while not currently
regulated, is associated with adverse health effects at elevated concentrations (34).
Lee et al. (3) also used chlorine dioxide to investigate the effect of
pre-oxidation on the NDMA FPs in natural waters from the Rhein, Neckar, and
Pfinz rivers in central Europe and in Lake Greifensee, a small lake near Zurich,
Switzerland. In experiments performed under typical drinking water treatment
conditions an initial dose of 2.1 mg/L of chlorine dioxide at pH 7.0 were added
to the samples. Subsequent results showed that the residual chlorine dioxide was
quenched after 5 minutes. The samples were then chloraminated for NDMA FP
analyses, which showed an NDMA FP removal rate ranging from 32 to 94%
depending upon the water sample from a given river. In another study, grab
samples were collected upstream of any oxidant addition for several source waters
(29). Following pre-oxidation, samples were chloraminated for 72 hours under
UFC conditions. After 72 hours, the chloramine residual was quenched, and
the DBPs were analyzed. The results showed that a pre-oxidation with chlorine
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dioxide exposure (mg×min/L) resulted in a reduction in NDMA formation in
some samples by an average of 50% (29). Pre-oxidation with chlorine dioxide
reduced the NDMA formation to approximately 7-9 ng/L at the highest exposure.
These results, however, were not concurrent with all source waters sampled
in the study. Pre-oxidation with chlorine dioxide increased NDMA formation
by an average of 50%. The water samples with an elevated level of NDMAs
were affected by wastewaters, polyDADMAC polymers, and anion exchange
resin-related precursors, making it likely that pretreatment with chlorine dioxide
converted the precursors in these source waters to more potent forms (29).
In another study, 12 water sources (9 surface water, 1 groundwater, and 2
wastewater effluents) were exposed to pre-oxidation with chlorine dioxide at a
dose of 1.0 mg/L at pH 6.0 to 7.0 (35). After chlorine dioxide pretreatment,
reductions in NDMA FP were observed in most of the samples (with a top range of
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~33%). Although and average reduction of 58% was observed in the wastewaters
under study, in other samples NDMA FP either remained relatively constant or
increased (with a top range of ~140%).
In a recent study to determine the effect of pre-oxidation, Uzun et al. (36)
conducted experiments using chlorine dioxide on NDMA FPs in pristine surface
waters blended with wastewaters at different facilities. While they found that
chlorine dioxide both increased and decreased in the levels of NDMA FP,
chlorine dioxide oxidation was more effective in NDMA formation in wastewater
impacted sources than non-impacted sources. Also, the percentage of the NDMA
precursor removed using chlorine dioxide increased with an increase in the
level of wastewater (36). They also observed a rapid oxidation of chlorine
dioxide oxidation (<10 min. contact time), which resulted in a maximum level
of NDMA FP removal in all waters in their study. Lauer (26) investigated the
effect of pre-oxidation in five wastewater samples collected prior to disinfection
and exposed them to 2.5, 5, and 10 mg/L at contact times of 2-60 minutes.
Chlorine dioxide was observed to be the most efficient in removing NDMA
precursors with the highest removal (~90%) at a dose of 10 mg/L. At a dose
of 2.5 and 5 mg/L, however, the removal rate was much greater, ranging from
19% to 90% depending on the dose, contact time and background organic matter
concentrations. These lower reductions at the lower doses was perhaps due to a
competition for the chlorine dioxide between the background organic matter and
the NDMA precursors (26).
There are also model compound studies in the literature that can provide
insight regarding these mixed results regarding chlorine dioxide pre-oxidation in
natural water samples. For example, in their 2007 study to determine the change
rate of NDMA FP in eight model precursors (i.e., DMA, trimethylamine) to 0.5
or 1.0 mM of chlorine dioxide at pH 7.0, they observed no distinct difference
in the DMA in the NDMA FP. However, pre-oxidation with chlorine dioxide of
the other tertiary amines did reduce the presence of NDMA FP from 41 to 63%
(3). In another comprehensive mechanistic study recently conducted by Selbes et
al. (19), they examined the effectiveness of pre-oxidation with chlorine dioxide
([ClO2]0 = 1 mg/L) at different contact times (5 to 30 minutes) and in a pH range
of 7.5 for 15 NDMA precursors, including secondary amines, tertiary amines
and quaternary amines. They observed no obvious reactivity of the DMA to the
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chlorine dioxide. The exposure of chlorine dioxide to a high level of NDMA
yielded (>5%) precursors, which in turn decreased the formation of NDMA
formation. However, upon contact with chlorine dioxide, tertiary amines (e.g.
methylene blue) with a low NDMA formation (<1%) increased the level of the
NDMA FP. This increase was attributed to a release of the DMA moiety from
the parent compound, which transformed the moiety into a more potent form.
These findings suggest that the origin of the various deactivation efficiencies
of precursors may be attributed to one single major product, namely DMA.
Consequently, the application of chlorine dioxide as a pre-oxidant to control
NDMA formation could be effective in source waters with high levels of NDMA
yielding precursors (i.e., >5%). For source waters containing either DMA or
lower NDMA yielding precursors than DMA as major precursors (i.e., <1%),
however, the application would be redundant (19). These findings are supported
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by studies from both Selbes et al. (19) and Park et al. (33), who reported
that the pre-oxidation of quaternary amines (polyDADMAC, polyAMINE, and
polyACRYL) with chlorine dioxide did not affect the overall NDMA yields.
These findings indicate that pre-oxidation with chlorine dioxide can either
increase or decrease NDMA formation. It is more likely that the chlorine dioxide
treatment would be beneficial for utilities if the water does have a wastewater
content. The use of chlorine dioxide may be detrimental, however, for those
utilities with a low level of reactivity precursors in their source waters.
Ozone
Ozone is a strong oxidizing agent that can oxidize many organic and inorganic
compounds in water. While ozone does not lead to the formation of halogenated
DBPs, it can lead to the formation bromate (BrO3-), which is a regulated DBP in
the United States.
Previous studies with ozone have provided some promising results to
reduce NDMA formation, despite some observations reporting enhanced NDMA
formation (3, 19, 27–29, 37, 38). The overall body of research here shows ozone
an effective oxidant for reducing NDMA formation, likely because of the high
reaction rate constants with amines, especially in their deprotonated forms (25).
For example, ozone reduced NDMA formation by over 50% within a very short
contact time (i.e., CT ≤0.5 mg×min/L) (3, 28, 29), with only a few cases of
ozonation actually causing the formation of NDMA (18, 39).
In their study to determine pre-oxidation in the Rhein, Neckar, and Pfinz rivers
and in Lake Greifensee, Lee et al. also investigated the effect of pre-ozonation
on the NDMA FPs in those waters (3). Oxidation treatments were performed
under typical drinking water treatment conditions with 1 and 2 mg/L of ozone
at pH 7.0. The NDMA FPs of the treated natural waters was then measured
after a complete depletion of the ozone, with a removal rate ranging from 32 to
94% depending on the natural water. There was however, no distinct difference
between two ozone doses. In another study to determine the effects of treated
wastewaters, polyDADMAC polymers, and anion exchange resin on ten different
natural systems, Shah et al. (29) observed that ozone similarly reduced NDMA
formation by as much as 50% and at exposures as low as 0.4 mg×min/L.
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Zhao et al. (40) used ozone as an oxidant to control the formation of NDMA
in two source waters, with the contact time set as the length of time required
to achieve the desired dose (CT = 10 mg×min/L). In both instances, higher
concentrations of NDMA were recorded compare to the untreated source waters
used as the control. The DMA pathway reported by Andrzejewski et al. (16) was
found to be cause of this NDMA formation during ozonation. In a similar study
supporting these finds, Zhao et al. (40) also investigated ozonation followed by
chlorination in two separate water bodies, and observed higher concentrations of
NDMA over the ozone treatment alone.
These results suggested that the ozone oxidation of natural organic matter
may release precursors into the source waters that can react with chlorine to
form NDMA. Although Zhao (40) examined ozonation only and then ozonation
followed by chlorination, the increasing trend involving the use of ozonation
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closely agrees with more recent analysis. In one German study detailing how
elevated NDMA formation potentials might affect ozonation in areas of the
country under intense agricultural cultivation, DMS, was detected in ground and
surface waters at concentrations ranging from 100-1000 ng/L and 50-90 ng/L,
respectively (5). Batch ozonation experiments in ultrapure buffered water, surface
water, and tap water found that 52% of the DMS, created from the degradation
of the tolylfluanide fungicide, was converted to NDMA (5). The researchers
also identified the following precursors that exhibited high NDMA conversions
during ozonation: N,N-dimethyl-N′-(4-methylphenyl)-sulfamide, tolylfluanid,
daminozid. The authors also found that a 54% molar conversion rate of the
NDMA yield for an initial concentration of DMS (5). Similarly, von Gunten et
al. (18) examined how bromide, from DMS, might affect NDMA formation.
Although the initial ozonation of DMS in samples of phosphate-buffered ultrapure
water (pH = 7.0) yielded a low rate of NDMA conversions (<3%), the addition of
a few µg/L of bromide substantially enhanced the NDMA formation during the
ozonation process. Notably, this addition of bromide to levels of 15 – 20 µg/L,
which are typical for drinking waters, greatly enhanced the maximum NDMA
yield to approximately 50%.
A similar study, but in Japan, was undertaken to determine the association
of NDMA formation (2.2-10 ng/L) and ozonation in finished drinking waters
from the Yodo River (37). Relatively high concentrations of NDMA were
found after ozonation of water samples taken from wastewater treatment plants
located upstream of the water intake points of the drinking water treatment plants
in the Yodo River basin, and the NDMA formation was associated with the
anti-yellowing agents used by the industries.
In the United States, ozone induced NDMA formation in drinking water
treatment plants have not been observed so far. In 10 water samples, ozone
reduced NDMA formation by over 50% within a very short contact time (i.e.,
CT ≤0.5 mg×min/L) (29). Recently, Lauer (26) investigated the effect of
pre-ozonation in five wastewater samples collected prior to disinfection and
exposed them to 2.5, 5, and 10 mg/L at contact times of 2, 5, and 10 minutes.
Ozone was highly effective at removing NDMA precursors, and reacted very
quickly. A higher than 90% decrease in NDMA FP was observed with a 2.5
mg/L ozone dose and 2 minutes of contact time, with little to no further removal
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observed after 2 minutes or higher doses of ozone. However, ozonation can lead
to the formation of NDMA in some wastewater discharges (41, 42). In selected
wastewaters the net direct formation of NDMA of 6-33 ng/L was observed after
ozonation by Pisarenko et al. (41). Similar findings, reported by Gerrity et al.
(42) indicated that ozonation may lead to the direct formation of both NDMA
and some other nitrosamines (i.e., N-nitrosomorpholine). A recent survey also
indicates that the de facto use of wastewater in drinking water treatments is
increasing in the US (43). In the light of these studies, ozone triggered NDMA
formation may well occur in US drinking water treatment plants impacted by
wastewaters in the near-future.
A number of mechanistic studies connected ozonation to the significant
removal of NDMA precursors at low CT values (<1 mg×min/L) (3, 19). Other
studies, however, indicate the occurrence of NDMA formation during ozonation,
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Other Oxidants/Disinfectants
Other oxidants/disinfectants, such as potassium permanganate (KMnO4),
hydrogen peroxide (H2O2), ferrate, and UV irradiation, are all viable disinfectant
alternatives in drinking water treatment processes. A brief overview of these
oxidants/disinfectants and certain treatment strategies are elucidated in this
section.
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Chen and Valentine (28) examined the influence of three pre-oxidation
strategies (sun simulation, hydrogen peroxide and potassium permanganate)
on the NDMA formation in the Iowa River to determine any correlation in
specific UV absorbance (SUVA) caused by oxidation. They observed in sample
concentrates (TOC = 3.4 mg/L, pH = 7.0, [NH2Cl]0 = 0.05 mM), a decrease in
NDMA formation for both oxidants. The application of 10 mg/L permanganate
for a contact time of one hour reduced NDMA formation by approximately 50%
compared to samples not subjected to pre-oxidation. Although a notable decrease,
it was achieved with permanganate doses much greater than used in typical
drinking water treatment strategies. Overall, the standard dosage of permanganate
in drinking water treatment protocols neither contributed to NDMA formation
nor did it destroy NDMA precursors.
Ferrate was also the subject of study regarding its use as a pre-oxidant
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reaction would in turn either decrease precursor reactivity or destroy any formed
NDMAs during ozonation. Indeed, a recent study conducted by Pisarenko et al.
(41), reported that the use of ozone/peroxide was 20% more effective in removing
NDMA precursors than with ozone alone.
pH
Temperature
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Background Ions
As discussed previously, nitrite also reacts with chlorine to form NDMA
without chloramination (14, 26, 29). The presence of ammonia can also cause the
formation of chloramines which would decrease the efficiency of pre-oxidation
result in the direct formation of NDMA (2, 26). The presence of background
ammonia may also shift the chloramine speciation which would influence the
overall NDMA formation (10). Bromide can also enhance the formation of
NDMA during chloramination at concentrations higher than 400μg/L (8, 29).
Furthermore, ozone can also react with bromide and act as a catalyst for the
formation of NDMA from DMS at low concentrations (15-20 μg/L) (5, 18).
Background Organics
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Background organics can compete for chloramine species and decrease the
NDMA formation from some NDMA precursors (10). Furthermore, it is expected
that the presence of background organic matter would create competition with
NDMA precursors for the pre-oxidants. Consequently, this competition would
affect the overall efficiency and the kinetics of NDMA precursor inactivation. This
impact can be clearly seen during the pre-oxidation of surface waters spiked with
NDMA precursors in which the removal of NDMA precursors have been reported
to be lower compared to lab grade water (3, 32). This hindrance was also observed
during pre-oxidation with chlorine dioxide in waters (30) and wastewaters (26).
However, there has been no systematic investigation to determine the effect of
organic matter, on NDMA formation especially during pre-oxidation of NDMA
precursors.
Conclusions
As a review of the studies in this chapter clearly show, the use of pre-oxidation
prior to disinfection with chloramines is a promising NDMA control strategy
for some utilities. However, each oxidant has its own associated regulated DBP
formation and has a varying degree of efficiency in reducing NDMA formation.
Key findings from the literature are summarized in Table 2.
Although an increase of the CT of chlorine prior to chloramination did
decrease the amount of NDMA formation, utilities employing this method of
precursor control must be cautious, as regulated carbonaceous-DBPs (i.e., THMs
and HAAs) may result. In studies of several wastewater sources, pre-chlorination
caused an increase in NDMA formation due to the nitrosation pathway facilitated
by the presence of nitrite. Even though ozonation is very effective in destroying
NDMA precursors at low CT values, ozonation still leads to an increase in NDMA
via direct formation from specific precursors (i.e., amides). Although chlorine
dioxide is a potential mechanism for controlling NDMA formation, it may
increase the overall NDMA formation-like ozone depending on the precursors
in the source water. Both chlorine dioxide and ozone may convert precursors
into more potent forms (by liberating the DMA moiety). Thus, there is no single
oxidant that is effective for controlling NDMA in all water types, but rather
their effectiveness is highly dependent upon the characteristics of the existing
precursors in source waters. Furthermore, each of those oxidants is associated
with a regulated DBP formation (THMs, HAAs, chlorite, bromate), which results
in a trade-off between the destruction of NDMA precursors and other DBPs
formation. The other oxidants/disinfectants including permanganate, ferrate,
peroxide and UV, did, however exhibit a negligible effect on NDMA precursors.
Of these, UV was found quite effective in the destruction of formed NDMAs.
The selection of pre-oxidant type, dose and application location for NDMA
control will be site-specific. Managers in water utilities that intend to use pre-
oxidation as a strategy for NDMA control should also assess the effects on the
formation of regulated DBPs as well as other unintended consequences inherent
with the use of oxidants.
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Table 2. Summary of Key Findings from the Literature
Pre-Oxidants/ Disinfectants Effect on NDMA Precursors Other
Reaction with
NDMA Formation DBPs of
NDMA
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Direct NDMA
formation has been
reported (21) but · Not effective at doses relevant to
Potassium unlikely to be drinking water treatment (28).
NA NA NA
Permanganate significant compared · Can remove ~50% of NDMA FP
to chloramination at high doses (10 mg/L) (28).
in drinking water
treatment conditions.
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Chapter 10
conducted at 100 rpm. After the addition of certain amounts of PAC, the timer was
started. After certain spans of adsorption time, the jar test was stopped. The PAC
was removed from the solution by glass-fiber filtration. The residual concentration
of known NDMA precursors or NDMA FP and other water quality indices of the
water samples were measured.
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Table 2. Basic Water Quality of Water Samples
DOC UV DON NDMA FP NDEA FP
Water Tested
(mg/L) (cm-1) (mg N/L) (ng/L) (ng/L)
Blended (80/20)
river/wastewater 3.7 0.073 0.69 195 ND
(Arizona)
Aquacuture-
impacted lake
4.8 0.106 0.33 198 106
water (Yangtze
River Delta)
Note: DOC = Dissolved organic carbon, DON = dissolved organic nitrogen, UV =
ultraviolet absorbance at 254 nm. DON = TDN - NH3-N - NO3-N - NO2-N, where TDN is
total dissolved nitrogen. NDMA and NDEA FP were measured by the method described
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2.2. Tests with an Aquaculture-Impacted Lake Water
At pH 3, PAC removed 83% of the NDMA precursors and 89% of the NDEA
precursors. At pH 7 or 8, PAC removed ~60% of the NDMA precursors and
~75% of the NDEA precursors. At pH 11, PAC removed only 34% of the NDMA
precursors and 51% of the NDEA precursors. Contrary to the trend shown in
Section 2.1, nitrosamine precursor removal in this aquaculture-impacted lake
water gradually decreased as pH increased. This indicates that the behavior of
NA precursor with PAC adsorption can be quite site-specific.
Removal of bulk organic matter from the water samples was similar to that
in Section 2.1. The DOC, UV254, and DON removal gradually decreased as pH
increased, which followed the same trend of the nitrosamine precursors in this lake
water. In almost all cases, NA precursors were removed by PAC more effectively
than the bulk organic matter. In general, the removal trend was as follows: NDEA
FP > NDMA FP > UV254 > DON ~ DOC.
The adsorption capacities of the NDMA FP in the two waters was very
different. The capacity in the blended river/wastewater at pH 8 was 13.2 ng
NDMA FP/mg PAC with Ce = 89.4 ng/L (Figure 1b) and the capacity for the
aquaculture-impacted lake water NDMA precursors was 3.6 ng NDMA FP/mg
PAC with the same Ce at the same pH (28% of the capacity for the blended
river/wastewater precursors). The difference was likely due to the different
charactersitcs of NDMA precursors in the two water samples.
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3. pH Effect on Removal of Model NDMA Precursors with
PAC Adsorption
The experiments above indicate that the removal of nitrosamine precursors
in real waters with PAC adsorption is complex and site-specific. Therefore, two
model NDMA precursors that are PPCPs, ranitidine and chloropheniramine (3),
were used to simplify the investigation of the fate of NA precursors during the
PAC adsorption process.
Figure 3 shows the removal of the model NDMA precursors with PAC at
varying pH levels and with different PAC doses (model compound concentrations
= 0.01 mM each).
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At pH 11, both model NDMA precursors quickly broke through the SCX
cartridge, with low adsorption affinity. The capacity of each was ~90-100% at
pH 3 and 7: The SCX cartridges retained almost all of the chemicals at acidic or
neutral pH levels, even after a 40-mL filtration.
In Figures 4 and 5, the removal of the two chemicals by C18 matched well
with the neutral species distribution of ranitidine or chlorpheniramine at varying
pH levels. C18 also adsorbed the monovalent cation species of chlorpheniramine
(CA+). In addition, the removal of the two model compounds by SCX coincided
with the presence of the two cationic species.
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The two model NDMA precursors both have amine functional groups that are
protonated at low pH. For example, the pKa values of ranitidine are 2.7 and 8.2,
respectively. When the pH was greater than 10, the molecule was deprotonated
or neutral and did not sorb via ion exchange. When the pH was less than 6, the
molecule was protonated and thus amenable to ion exchange.
The adsorption capacities of the two chemicals at pH 7 were different.
Ranitidine was still recalcitrant to C18 adsorption at pH 7, whereas
chlorpheniramine was retained better by the C18 cartridge. The difference could
be attributed to the pKa of the two chemicals, which are 9.2 (chlorpheniramine)
and 8.2 (ranitidine).
In general, the neutral species were more easily adsorbed by the C18 cartridge,
but were recalcitrant to SCX. The positive charged species were sorbed to the SCX
media, but were excluded from C18 sorption.
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5. Mechanism of pH Effect on NA Precursor Removal with
PAC in Natural Waters
Figure 6 illustrates a scheme around our hypothesis that pH influences
the removal of NA precursors on PAC. The NA precursors likely have at least
one dialkylamine functional group, which is a potential target for oxidant
attack and nitrosamine formation. In addition to the basic secondary amines,
such as dimethylamine and diethylamine, other NA precursors have longer
carbon chains and potentially contain functional groups such as carboxyl and
hydroxyl. Therefore, we give a model structure formula for NDMA precursors
with dimethylamine, followed by a carbon chain (Rm) containing carboxyl and
hydroxyl groups, as shown in Figure 6.
Both van der Waals forces and electrostatic interaction influence the
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adsorption of organic contaminants on PAC. Van der Waals forces are favored for
nonpolar moieties. The electrostatic interactions are stronger than van der Waals
and, thus, will dominate for charged groups. The pH effect on NA precursor
removal by PAC can be explained by their net effect.
The majority of the fractions of aquatic NOM has carboxyl and hydroxyl
functional groups, bringing about the acidity of the NOM. These functional groups
are negatively charged at neutral or alkaline conditions, but become protonated at
lower pH levels (i.e., below the pKa values common to carboxylic and hydroxyl
groups). On the PAC side, high pH also makes the carboxyl and hydroxyl groups
on the carbon surface depronate or become negatively charged, which excludes the
organic matter. Other major fractions of NOM behave as net neutral molecules,
and a very small amount of the NOM behave as basic molecules. The nonpolar
adsorption by PAC will decline as pH increases, as shown in Figure 1a-1d (blended
river/wastewater) and Figure 2 (aquaculture-impacted lake water).
6. Conclusion
The following conclusions can be drawn according to the results of this
investigation.
(1) Experiments with different water samples and model NDMA precursors
indicated that removal of NDMA precursors by PAC adsorption is pH
dependent and site-specific. The removal of two model precursors
(ranitidine and chloropheniramine) and the NDMA FP in a blended
river/wastwater with PAC adsorption increased with higher pH. However,
the NDMA FP in an aquaculture-impacted lake water had declining
NDMA FP reduction with PAC adsorption with increasing pH.
(2) PRAM indicated that the pH effect on PAC adsorption of NDMA
precursors is potentially attributable to the protonization or charge of the
precursors. Alkaline conditions deprotonate amine functional groups
on model precursors and favor adsorption onto PAC, whereas acidic
or neutral conditions result in a precursor with positive charge, which
reduces the affinity for PAC.
Acknowledgments
The testing of the aquaculture-impacted lake water was supported by the
National Natural Science Foundation of China (Grant No. 21477059 and
51290284) and Tsinghua University Initiative Scientific Research Program (Grant
No. 20131089247). The testing of the blended river/wastewater was supported
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by the Water Research Foundation, Denver, Colo., U.S.A. (project 4370, under
the management of Djanette Khiari).
We highly appreciate Rita Chang from UCLA and Yueying Ouyang from
Tsinghua University, who volunteered to be the laboratory interns and contributed
much to the laboratory work of PRAM.
References
1. Krasner, S. W.; Westerhoff, P.; Chen, B.; Rittmann, B. E.; Amy, G.
Occurrence of disinfection byproducts in United States wastewater treatment
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13. USEPA. Method 521: Determination of nitrosamines in drinking water by
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Chapter 11
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Table 1. Examples of DBPs Generated by Water Pollutants
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Table 1. (Continued). Examples of DBPs Generated by Water Pollutants
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Table 2. Examples of DBP Classes Identified (with N-DBPs Highlighted)
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In addition to cancer, adverse birth outcomes, and asthma, there are some
newer concerns concerning severe skin rashes, and respiratory and digestive issues
surrounding chloraminated drinking water. To-date, there has not been a controlled
scientific study to investigate these newer adverse effects. Chloramination has
become increasingly popular in the U.S., as drinking water utilities have struggled
to meet the tightened DBP regulations (4). Chloramination is also popular in other
countries, including the UK and Australia. Switching from chlorine to chloramines
can result in ~90% reduction in the levels of regulated trihalomethanes (THMs)
and haloacetic acids (HAAs), and it is also beneficial to utilities for maintaining
disinfection in the distribution system.
The nature and quantity of DBPs formed depends on the type of disinfectant,
dose, and the type of organic matter or other constituents present in the water (1,
28–31). Formation mechanisms for several DBPs and DBP classes have been
investigated, including iodo-DBPs, halonitromethanes, nitrosamines, haloamides,
halopyrroles, and halobenzoquinones (Figures 1-8). The state of the science for
their formation follows.
Iodo-DBPs
Iodo-DBPs identified to-date are shown in Figure 1. They include iodo-THMs
(dichloroiodomethane, bromochloroiodomethane, dibromoiodomethane,
chlorodiiodomethane, bromodiiodomethane, and iodoform); iodo-acids
(iodoacetic acid, bromoiodoacetic acid, chloroiodoacetic acid, diiodoacetic
acid, (Z)-3-bromo-3-iodopropenoic acid, (E)-3-bromo-3-iodopropenoic
acid, and (E)-2-iodo-3-methylbutenedioic acid) (5, 32–35); iodo-amides
(bromoiodoacetamide and chloroiodoacetamide) (1, 13, 36); and the recently
reported iodoacetaldehyde (37, 38).
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Iodo-THMs
Lifestraw®), the highest levels were formed with iodine tincture treatments (46).
Finally, new research has revealed that hydraulic fracturing (HF) wastewater can
produce iodo-THMs when treated with chlorine or monochloramine (47). This is
likely due to the high levels of iodide present in HF wastewater (47).
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Iodo-acids
Iodo-acids, which are the most genotoxic of the iodo-DBPs (34, 35), were
first identified as part of a U.S. Nationwide Occurrence Study (5, 35, 44).
Levels up to 1.7 µg/L were reported in a 23 city survey of chloraminated and
chlorinated drinking water from the U.S. and Canada (34). Chlorine dioxide
was also reported to form iodoacetic acid when reacted with source waters (45).
Iodo-acids were also tentatively identified in simulated drinking waters treated
with chlorine, monochloramine, and chlorine-chloramine (32). The authors
used ultra-performance liquid chromatography (UPLC)/electrospray ionization
(ESI)-tandem mass spectrometry (MS/MS) with precursor ion scanning for the
m/z 127 ion of iodine to broadly detect iodo-DBPs formed in these reactions.
This research revealed the presence of iodoacetic acid, chloroiodoacetic acid,
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Iodo-amides
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Iodo-DBP Formation Mechanisms
hypoiodous acid (HOI), which can then react further with chlorine to form
iodite and iodate (Figure 2). These reactions are much faster than the competing
reactions to form organic iodo-DBPs (e.g., iodo-THMs and iodo-acids), such that
chlorination favors the formation of iodate over organic iodo-DBPs. However, the
reactions of monochloramine with HOI to form iodite and iodate are much slower
than the corresponding reactions of chlorine with HOI, such that monochloramine
favors the formation of organic iodo-DBPs over iodate.
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New research shows that ozone pretreatment at lower pH can be used to
minimize iodo-DBP (and bromate) formation by selectively oxidizing iodide to
iodate (61). Ozone could also be used to oxidize iodo-THMs that might already
be present in the water.
Iodide salt is believed to be the major source of iodine in the formation of
iodo-DBPs. But, new research has revealed that compounds used for medical
imaging, i.e., iodinated X-ray contrast media (ICM) can also be a source of iodine
(48, 49, 62). ICM are excreted within ~24 h after medical imaging, and they are
stable during wastewater treatment, which has resulted in levels up to 100 µg/L
in rivers and creeks (63) and up to 2.7 µg/L in drinking water reservoirs (49).
These ICM compounds have a triiodobenzene core structure with 3 amide side
chains, and research shows that chlorine or chloramine can react with ICM to form
iodo-THMs and to a lesser extent, iodo-acids. NOM and pH substantially affect
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the formation, and OCl- is believed to be the reacting species. In addition, new
controlled laboratory studies indicate that iodo-THMs are favored at low chlorine
doses, but are suppressed at higher doses (62).
To-date, iopamidol appears to be the most reactive, with much less formation
of iodo-DBPs from other ICM investigated (e.g., iopromide, iohexol, iomeprol,
diatrizoate, hiztodenz, and iodixanol) (48, 49, 62). New research using liquid
chromatography (LC)-high resolution MS/MS and nuclear magnetic resonance
(NMR) spectroscopy is revealing the initial points of reaction on the iopamidol
structure, along with the initial high molecular weight DBPs formed (Figure
3) (48). The proposed reactions involve cleavage of one of the side chains,
substitution of chlorine for iodine on the benzene ring, amide hydrolysis, cleavage
of the other side chains, and oxidation of NH2 to NO2 (Figure 3). Structures for
19 high molecular weight DBPs were deduced in the reaction pathway.
indicates that the nitrosamines identified to-date only represent 5-10% of the
total nitrosamines formed in drinking water and recreational waters (70, 71).
The identity of these other nitrosamines is currently unknown. Interestingly,
algal-derived organic matter was an insignificant precursor for EPA Method
521 nitrosamines during chloramination, but a potent precursor for other,
uncharacterized N-nitrosamines, as measured using the TONO assay. In 2014,
tobacco-specific nitrosamines —4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone
and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol— were also discovered to be
chloramination DBPs (72).
NDMA is regulated in California at 10 ng/L (73) and Ontario, Canada at 9
ng/L (74). A Canadian national drinking water guideline has also recently been
established, which limits NDMA to 40 ng/L in drinking water (75), and the U.S.
EPA is considering its regulation in the United States. NDMA was included in
the U.S. EPA’s second Unregulated Contaminants Monitoring Rule (UCMR-2),
along with 5 other nitrosamines (N-nitrosodiethylamine, N-nitrosodibutylamine,
N-nitrosodipropylamine, N-nitrosomethylethylamine, and N-nitrosopyrrolidine).
National occurrence data are currently available (16). These new data revealed a
maximum level of 530 ng/L for NDMA in chloraminated drinking water, which
surpasses the previous maximum (180 ng/L) observed in Canadian chloraminated
drinking water (68). In addition, NDMA and 4 other nitrosamines are also on the
U.S. EPA’s Contaminant Candidate List (CCL-3), a priority list of drinking water
contaminants (76).
NDMA (94).
Finally for the tobacco-specific nitrosamines just identified in 2014, tobacco
alkaloids, including nicotine, nornicotine, and anabasine were determined to be
precursors to their formation in chloraminated drinking water (72).
Haloamides
Haloamides are formed by both chlorine and chloramine, (5, 13, 44,
97, 98), but preferentially by monochloramine (56). The mechanism can
involve the hydrolysis of the corresponding haloacetonitriles (54, 55), or
reaction of monochloramine with organic nitrogen precursors (56) (Figure
5). Experiments involving 15N-labeled monochloramine indicated initial
rapid formation of both dichloroacetamide and dichloroacetonitrile, where
the nitrogen originated from organic nitrogen precursors. However, slower
formation occurs by pathways involving chloramine incorporation into organic
precursors. In addition, experiments with asparagine as a model precursor also
suggested that dichloroacetamide can be formed without a dichloroacetonitrile
intermediate, and humic materials were found to be more potent precursors for
dichloroacetamide formation, while wastewater effluents and algal substances
were more potent precursors for dichloroacetonitrile formation (56). Therefore,
there are independent mechanisms involved in the formation of haloacetamides,
beyond the hydrolysis of the haloacetonitriles.
Several amino acids were also recently found to be precursors of haloamides,
with aspartic acid, histidine, tyrosine, tryptophan, glutamine, asparagine, and
phenylalanine reacting with chlorine to form dichloroacetamide (99).
Halonitromethanes
Nine chloro/bromo halonitromethanes have been identified to date (Figure
6). Chloropicrin (trichloronitromethane) is the most commonly measured
example in this class, but it has not been a concern for toxicity in drinking
water. Brominated nitromethanes, however, have shown significant toxicity
(100) and have been found in drinking water up to 3 μg/L individually
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(5, 44, 100–102). Bromonitromethanes are more cytotoxic and genotoxic
than most DBPs currently regulated (100). Dibromonitromethane is more
than an order of magnitude more genotoxic to mammalian cells than MX
(3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone, a carcinogenic DBP),
and is more genotoxic than all of the regulated DBPs, except for monobromoacetic
acid. Other brominated forms are also potent in this assay. Halonitromethanes
are also mutagenic in the Salmonella bacterial cell assay (103), with mutagenic
potencies greater than that of the regulated THMs (104). The halonitromethanes
are also at least 10x more cytotoxic than the THMs, and the greater cytotoxic and
mutagenic activities of the halonitromethanes was indicated to be likely due to
the greater intrinsic reactivity conferred by the nitro group (104).
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Halopyrroles
A halogenated pyrrole —2,3,5-tribromopyrrole (Figure 7)— was first
reported as a DBP in 2003 (107). It was found in finished drinking water
from Israel that was treated with pre-chlorination followed by treatment with
combined chlorine dioxide-chlorine or chlorine dioxide-chloramine. The source
water contained exceptionally high bromide levels (approximately 2 ppm). This
identification resulted from the first study of chlorine dioxide DBPs formed
under high bromide/iodide conditions. Bromide levels in U.S. source waters
generally range up to a maximum of approximately 0.5 ppm, and to-date, this
tribromopyrrole has not been identified in drinking waters from the United States.
Tribromopyrrole is 8x more cytotoxic than dibromoacetic acid (a regulated
DBP) and has about the same genotoxic potency as MX (107), which is also
an animal carcinogen (109). Formation studies of different NOM precursors
revealed that tribromopyrrole forms primarily from humic acid (vs. fulvic acid),
and this isolated humic acid contained a greater contribution of nitrogen in its
chemical structure than the isolated fulvic acid. It is interesting to note that a
soil humic model proposed by Schulten and Schnitzer (110) includes a pyrrole
group in its structure (110), but tribromopyrrole represented the first time a
halopyrrole was reported as a DBP. In none of the samplings from this research
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was tribromopyrrole found in pre-chlorinated waters (with chlorine treatment
only). Thus, the combination of chlorine dioxide and chlorine (or chloramines)
may be necessary for its formation. It is also possible that chloramination alone
may also be important for its formation.
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New research has revealed that halopyrroles can form as DBPs in chlorinated
saline wastewater effluents (108). Tri- and tetra-halopyrroles were identified,
including brominated, chlorinated, and iodinated analogues (Figure 7). In
mechanistic experiments, chlorophyllin (which contains pyrrole units in its
structure) was found to be an important precursor in their formation. The
chlorinated saline wastewaters were also found to be developmentally toxic to
marine polychaetes (108).
Halobenzoquinones
Halobenzoquinones (HBQs) are a new class of DBP recently identified
(Figure 8). Four HBQs —2,6-dichlorobenzoquinone, 2,6-dibromobenzoquinone,
2,6-dichloro-3-methylbenzoquinone, and 2,3,6-trichlorobenzoquinone— were
initially identified in drinking waters treated with chlorine, chloramines, chlorine-
chloramines, ozone-chloramines, and chloramines-UV (111, 112). Levels ranged
up to 275 ng/L. 2,6-Dichlorobenzoquinone, 2,3,6-trichloro-1,4-benzoquinone,
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2,3-dibromo-5,6-dimethyl-1,4-benzoquinone, and 2,6-dibromo-1,4-benzoquinone
were also formed in chlorinated swimming pools (113). And, subsequent work
has also revealed the formation of hydroxylated HBQs with UV treatment (114).
Quantitative structure-toxicity relationship (QSTR) analysis had predicted that
haloquinones are highly toxic and may be formed during drinking water treatment.
The chronic lowest observed adverse effect levels (LOAELs) of haloquinones are
predicted to be in the low µg/kg body weight per day range, which is 1000x lower
than most regulated DBPs, except bromate.
Separate controlled laboratory studies using phenol as a precursor
demonstrated that chlorination produced the highest levels of
2,6-dichlorobenzoquinone, while preozonation increased the formation of
2,6-dibromobenzoquinone in the presence of bromide. UV filters and other
aromatic compounds found in lotions and sunscreens were also determined to be
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Conclusions
In conclusion, the nature and quantity of DBPs formed depends on the type
of disinfectant, dose, and the type of organic matter or other constituents present
in the water. Due to the significant occurrence and toxicity of many emerging
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DBPs, it is important to understand their formation so that treatment methods
can be developed to minimize them in drinking water. For example, formation
of several of these DBPs is enhanced by chloramination, which is a popular
disinfection alternative that many treatment plants have switched to in order to
minimize regulated THMs and HAAs. However, due to the significant toxicity
associated with several chloraminated DBPs, such as NDMA, iodoacetic acid,
and haloamides, it may be wise to investigate other treatment technologies,
such as granular activated carbon (GAC) or membranes, which could be used
in combination with chlorine or chlorine dioxide to potentially minimize both
emerging chloramination DBPs and regulated DBPs. However, research is
needed to ensure that these treatment changes do not cause other unintended
consequences, such as increased brominated DBP formation. In this regard, when
exploring new treatment methods, it is wise to combine chemistry and toxicology.
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Acknowledgments
C.P. acknowledges support from the European Union Seventh Framework
Programme (FP7/2007-2013) under grant agreement no. 274379 (Marie Curie
IOF). This work has been financially supported by the Generalitat de Catalunya
(Consolidated Research Groups “2014 SGR 418 - Water and Soil Quality Unit”
and 2014 SGR 291 - ICRA). This work reflects only the author’s views. The EU
is not liable for any use that may be made of the information contained therein.
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107. Richardson, S. D.; Thruston, Jr., A. D.; Rav-Acha, C.; Groisman, L.;
Popilevsky, I.; Juraev, O.; Glezer, V.; McKague, A. B.; Plewa, M. J.;
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Chapter 12
2.6% of the dissolved organic carbon (DOC) and 35% of the dissolved organic
nitrogen (DON) in some lakes. Hagedorn and colleagues (8) observed in their
studies of catchment runoff a 20% to greater than 75% of the DON of the total
AAs observed. Elevated amino acid levels were also found in the presence of
algae blooms, the degradation of which is a major cause of increased AA levels
in natural waters (7, 9–11). In a recent survey of sixteen water treatment plants
in the United States, the total AA concentrations, identified as glycine, glutamic
acid, alanine, aspartic acid, leucine, proline and serine, constituted an average
15% of the DON in the source waters (2, 7, 12–14).
The presence of AAs in raw and treated waters requires substantial amounts
of chlorine for treatment (15, 16). The relative chlorine reactivity of the AAs
depends on the side chain groups attached to the α-carbon. Studies conducted for
purposes of reacting AAs with chlorine clearly indicated the formation of various
classes of DBPs including haloacetaldehydes, haloacetonitriles (HANs), cyanogen
chloride, trihalomethanes (THMs) and haloacetic acids (HAAs) (15, 17, 18). A
recent study showed that AAs with activated aromatic structures (e.g. tryptophan,
tyrosine) were potent precursors of THMs and HAAs (17). Additionally, absent
the reactive ring structure, aspartic acid and asparagines produced high levels of
HAAs.
Investigations conducted on the reaction(s) of ozone with AAs determined
that the side chains of AAs were responsible for the high ozone reactivity in
polypeptide structures (19). Structures that possess side groups such as amino
nitrogen or activated aromatic ring were identified as the most reactive AAs.
This AA ozonation leads to the formation of aldehydes such as formaldehyde,
acetaldehyde, glyoxal and glyoxal derivatives.
Unlike the carbonaceous DBPs (C-DBPs), very little is known regarding
how N-DBPs form from amino acids, especially for halonitromethanes (HNMs)
and N-nitrosamines. HNM constitutes one group of N-DBPs that exhibits high
degrees of cyto- and geno-toxicity (1, 21). Drinking waters and wastewater
effluents under chloramination conditions are a particularly relevant medium in
which nitrosamine, especially N-nitrosodimethylamine (NDMA), can form (20).
Nitrosamines, which have been classified as a probable human carcinogen by
the United States Environmental Protection Agency, can pose important health
risks even at ng/L concentrations. As a result, the Canada Ontario Ministry of
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the Environmental and Energy established a maximum allowable concentration
of 9 ng/L for NDMA, and the California Department of Health Service set an
interim action level of 10 ng/L. Although nitrosamines are not currently regulated
in the United States, NDMA and four other nitrosamines [N-nitrosodiethylamine
(NDEA), N-nitroso-di-n-propylamine (NDPA), N-nitrosodiphenylamine
(NDPhA), N-nitrosopyrrolidine (NPYR)] are on the USEPA’s Contaminant
Candidate List-3, and are monitored under the Unregulated Contaminant
Monitoring Rule 2.
Recent studies on the formation potentials of HNMs in natural waters found
that HNM yields increased with decreasing DOC/DON ratios (i.e., increasing
organic nitrogen content per organic carbon in water) during ozonation followed
by chlorination (3). The hydrophilic components of dissolved NOM, especially
nitrogenous organic compounds, are important precursors of HNMs in the NOM
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pool (2, 3). Only a limited number of studies, however, have been conducted to
elucidate trichloronitromethane (TCNM) formation by AAs during chlorination,
using glycine (4, 22), tyrosine (4), tryptophan and aspartic acid (23). Similarly,
very little is known about of the formation of NDMAs caused by AAs, aside
from that undertaken by Mitch et al. (4). Specifically, they observed nitrosamine
formation (NDMA, NMEA and NDEA) in aspartic acid, proline and histidine
after chloramination (24); and NDMA formation of <2ng/L in glycine after
chloramination (4).
Produced during chlorination HANs consist of an acetate derivative group,
known as a cyano (-CN) group, and up to three halogens replacing the hydrogen
atoms. Dichloroacetonitrile (DCAN), the most prevalent of the HANs, was
detected at 0.3-8.1 µg/L in 10 chlorinated drinking waters in southern Ontario
(25), and at median and maximum concentrations of 1 and 12 µg/L, in 12
wastewater treatment plans in the US (26). In both studies, DCAN levels were
10% of the molar concentration for THMs. DCAN formation also occurred when
amino acid moieties were used to during the chlorination of AAs, polypeptides,
and hydrophobic substances (27). Moreover, aspartic acid (16, 23) and alanine
(28) used in chlorination has caused the formation of HANs from AAs.
Since AAs constitute an important fraction of organic nitrogen pool in natural
waters, and previous studies have mainly focused on the formation regulated C-
DBPs (e.g., THM and/or HAA) from AAs mostly for chlorination, the objective of
this study was to concurrently investigate formation potential of both regulated C-
DBPs (THMs and HAAs) and selected N-DBPs (HANs, HNMs and nitrosamines)
from AAs ozonation, chloramination and chlorination conditions. The results were
also used to provide additional insight to the DBP formation mechanisms from
AAs.
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Amino acids were purchased from a certified vendor (Sigma-Aldrich) and a
500 mg/L stock solution of each AA was prepared in deionized distilled water. For
the formation potential (FP) tests, 1 mg/L (and 10 mg /L in selected experiments)
AA sample solutions were prepared with dilution from the main stock. These
solutions were buffered at pH 6.0 or 8.0 using 4 mM sodium bicarbonate and
adjusted with 1M HCl or NaOH. The AA concentrations (1 or 10 mg/L) in the
diluted solutions were confirmed using a TOC analyzer (Shimadzu Corp., USA).
Although these AA concentrations are higher than their typical occurrence levels
in fresh waters, they were intentionally selected at these high levels to magnify
and better examine the DBP formation; an approach that has been used in previous
studies (4, 29).
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Based on the Equation 1, typical chlorine doses were around 11-12 mg/L for 1
mg/L AA concentration. Ozonation was carried out by adding ozone stock solution
to the samples approximately at 4 mg/L (Equation 3). Following ozone addition,
the samples were mixed on a stir plate for 5 min. After 5 minutes, they were also
exposed same doses of chlorine. Prior to chlorination presence of residual ozone
confirmed and thus, ozone was not a limiting factor during ozonation period. Since
10 mg/L AA concentration was used for nitrosamine FP test conditions, initial
chloramine dose was 10-15 mg/L. Although AAs have high oxidant demands
(i.e., chlorine, ozone), the levels of oxidants were sufficient to maintain a residual
concentration at the end of the reaction time.
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Table 2. Analytical Methods and Minimum Reporting Levels
Parameter Unit Measurement Method Instrument MRL or Accuracya
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DOCb mg/L SM 5310B TOC-VCHS & TNM-1, Shimadzu Corp., Japan 0.1
DN (=DON)c mg/L High Temperature Combustion TOC-VCHS & TNM-1, Shimadzu Corp., Japan 0.1
pH - SM 4500-H+ 420A, Orion Corp., USA ±0.01d
THMs & HANse µg/L US EPA Method 551.1 6890 GC-ECD, Agilent, USA 1.0
HAAsf µg/L SM 6251 Bg 6890 GC- ECD, Agilent, USA 1.0
HNMsg µg/L US EPA Method 551.1 6850 GC-ECD, Agilent, USA 0.7
Nitrosaminesh ng/L US EPA 521 Varian GC/MS/MS 3.0
FAC mg/L SM 4500-Cl F NA 0.1
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a MRLs were determined in the lab in previous works (31). Accuracy as reported by the manufacturer. b Reagent grade potassium hydrogen phthalate
was used to prepare external standards. c Reagent grade potassium nitrate was used to prepare external standards. Since there was no inorganic nitrogen
present, measured DN values were equal to DON. d Accuracy (pH units). e THMs and HANs were extracted by liquid-liquid extraction with methyl-
tert butyl ether (MtBE) and analyzed by GC-μECD. f HAAs were extracted by liquid-liquid extraction with MtBE, derivatized with diazomethane and
analyzed by GC-μECD. g HNM were extracted by liquid-liquid extraction with MtBE and analyzed by GC-μECD. h Nitrosamines were extracted by solid
phase extraction, eluted with dichloromethane and analyzed by GC-MS. DOC (Dissolved Organic Carbon), DN (Dissolved Nitrogen), DON (Dissolved
Organic Nitrogen), THM (Trihalomethanes), HAN (Haloacetonitriles), HAA (Haloacetic acids), HNM (halonitromethanes), SM (Standard Methods), EPA
(Environmental Protection Agency), GC (Gas Chromatography), MS (Mass Spectrometer), FAC (Free Available Chlorine), NA (Not Applicable).
Analytical Methods
The analytical methods used in the study and their respective minimum
reporting levels (MRLs) are provided in Table 2. Either standard methods (SM)
or USEPA methods were used in the DBP analyses with minor modifications.
The detailed information about these methods can be found elsewhere (31). For
DOC, DN and DBP analyses, samples were analyzed in duplicates. The error
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bars in all the graphs show the variability due to multiple analysis (n=2) under
the same conditions.
Nitrogenous-DBPs
Halonitromethanes (HNMs)
The formation of all HNM species from nine amino acids after chlorination
was below MRL, which is in agreement with the reports in the literature. Merlet
et al. (22) reported <0.01% mole/mole yield rate (<0.7 µg/mg-C) of TCNM from
glycine after chlorination at pH 7.1. A recent report by Mitch et al. (4) also
showed low yields of TCNM from glycine and tyrosine during chlorination FP
tests (0.8 µg/L from 64 µM glycine (4.8mg/L)). No TCNM formation was found
from chlorinated tryptophan and aspartic acid (23).
Ozonation followed by chlorination was more favorable than chlorination
for HNM formation, as previously observed in natural waters (3, 26, 32–35).
Furthermore, trihalogenated HNMs (i.e., TCNM) was the major species detected
which is consistent with the literature (34). The ozonation of amines in aqueous
solutions can lead to oxidation at both the amine and on the side chain of
the molecule (19, 36). The higher TCNM formation caused by AAs during
pre-ozonation may be due to the oxidation of the amine group by the strong
oxidant ozone to form a nitro group (22, 37). The nitro compound will, then, be
further substituted to form nitromethanes and react with chlorine. TCNM was the
only HNM species formed in our study, with glycine showing remarkably high
TCNM formation (223.4 µg/L), followed by lysine and proline (14.6 and 17.2
µg/L). We also detected a small amount of TCNM in glutamic acid (0.8 µg/L)
and serine (0.9 µg/L), while for the remainder of the AAs examined, the HNM
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concentrations were either below MRL or were not detected. A comparison
of our AA result are plotted and normalized in Figure 1 based on their DOC
(µg-TCNM/mg-DOC). The levels of TCNM during ozonation-chlorination were
comparable with our previously reported findings (32).
These findings were used to provide additional insight to the formation
mechanism of TCNM from glycine. The ozonation of glycine is known to
form nitrate, form, formic acid and carbon dioxide as by-products (38). Under
certain conditions, the formation of formic acid can be relatively high (>0.05
mM formed from 1.5 mM O3 vs. 1.1 mM glycine, in the presence of 0.2 mM
hydrogenocarbonate ions) (29), suggesting the possible rupture of the C-C
bond and the subsequent formation of nitromethanes. It has been hypothesized
that the rupture of the C-C bond may occur with the formation of a strongly
reducing α-aminoradical in an unprotonated amino group; this rupture may
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occur when the electron abstraction from the amine nitrogen is then re-arranged
with decarboxylation (39). It is also hypothesized that the reaction follows the
oxidation carboxyl from ozone to peroxide (37), followed by decarboxylation
(29, 39), which in turn causes the oxidation of the amine group to the nitro group
(22, 37). A halogenation reaction with chlorine, which causes TCNM formation,
is the result.
The greater TCNM yield from lysine after ozonation-chlorination was
attributed to the production of glycine and glycine-like intermediates formed
during ozonation. The long chain structure of α-C of lysine makes the breakage
of the C-C bond easier compared to other amino acids examined in this study.
In this study, we also observed aspartic acid to form high levels of DCAN
(549.2 µg/mg-C) during chlorination at a pH of 8.0, with histidine the second most
reactive AA, forming 173.7 µg/mg-C (seen Figure 2). The high level of DCAN
FP of aspartic acid has been validated in two previous studies: that of Trehy et
al. (16) in which they used 158 µg/mg-C at pH of 6.4; and that of Bond et al.
(23) in which they used 0.06 mol/mol 130 µg/mg-C) at pH of 7. Both studies
concur with a study by Ram et al. in which the chlorination of AAs, polypeptides,
and hydrophobic substances with amino acid moieties were used to create DCAN
(27). Although Chu et al. (28) reported the formation of non-detectable HANs
(DCAN and TCAN) in 0.1 mM of alanine after chlorination, in our study we
observed a DCAN formation level of only 3.9 µg/mg-C DCAN after chlorination.
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Figure 2. DCAN formation potential results from amino acids during chlorination
and ozonation-chlorination at pH 8.0 (DOC = 0.3 ~ 0.5 mg/L, DON = 0.04 ~
0.30 mg/L).
Nitrosamines
Initial nitrosamines FP test for three selected AAs at 1.0 mg/L concentration
did not produce measurable nitrosamines. To further confirm the results, it was
decided to magnify the initial concentration of AAs during the experiments by
increasing to 10.0 mg/L. Three different oxidation scenarios, monochloramination,
ozonation and ozonation-chloramination were tested for all nine AAs. Ozonation
was also examined independently because of the recently reported NDMA
formation after ozonation in both the lab (40, 41) and in full scale ozonation
plants (42, 43).
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Despite this increase to 10 mg/L, NDMA and NDBA FP concentrations
remained very low at levels of 5 ng/L NDBA from lysine after chloramination
(Table 3). Mitch and co-workers reported non-detectable nitrosamine (NDMA,
NMEA and NDEA) formation from aspartic acid, proline and histidine during
chloramination (24); and NDMA formation of <2 ng/L from glycine and tyrosine
during chloramination (4).
Principally all amines with the exception of primary amines (i.e., amino
acids) have the potential to form nitrosamines (44). During chloramination,
only lysine was observed to form NDBA (5 ng/L). This may be due to reaction
of butyl chains of two lysine’s with chloramines. Since ozone is a stronger
oxidant, it is likely to form intermediates that are more prone to reaction (45).
Thus, during ozonation-chloramination NDBA yield from lysine increased to 9
ng/L. In addition, during ozonation-chloramination, NDBA formation of 3 ng/L
from proline and serine was also observed. Proline also lead to formation of
4 ng/L NPYR during both ozonation and ozonation-chloramination conditions.
Other nitrosamines were undetected. NPYR is formed from proline because
of its structure; once ozonation causes the decarboxylation of proline followed
by nitrosation, the nitrogen of the nitrosating agent is likely sourced from the
oxidation of the nitrogen atom in the proline’s ring. The direct formation of
nitrosamines during ozonation hasl also occurred with other precursors (45). The
authors observed very low nitrosamine yields of AAs during the FP tests (<0.01%
molar conversion). Considering the occurrence concentrations of total AAs in
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natural waters, it is unlikely that AAs will play a role in the formation of NDMA
and other nitrosamines during chloramination, ozonation, and ozonation that is
followed by chloramination.
Carbonaceous-DBPs
Trihalomethanes (THMs)
Trichloromethane (TCM) was the only THM species observed during both
chlorination and ozonation-chlorination (Figure 4), with the selected AAs in this
study forming TCMs within the range of <MRL-13.5 µg/L after chlorination.
These values are consistent with that previously reported by the authors (32).
Ozonation can increase in TCM formation. Bond et al. (23) reported that 0.02
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mol TCM formed from 1 mol aspartic acid after chlorination (i.e., 49.7 µg/mg-C),
which is relatively comparable to the yield observed in this study, 18.8 µg/mg-
C. Chu et al. (28) reported a yield rate of 0.23% (i.e., 5.7 µg/mg-C) for TCM
formation from 0.1 mM alanine after chlorination, while no TCM formation from
alanine was measurable during chlorination in this study. Hong et al. (17) studied
chlorination of all 20 amino acids at pH 7 and found low THM formation (<4.9
µg/mg-C), except for tryptophan and tyrosine. The results of our study showed
that pre-ozonation prior to chlorination had a drastic effect on TCM formation
from glycine and lysine which was similar to HNMs. TCMs formation of glycine
and lysine increased from <MRL to 83.4 and 33.9 µg/L, respectively. Other AA’s
TCM formations during ozonation-chlorination were comparable and were within
the range of 6.7-11.8 µg/L.
Reaction sequences have been developed for the molecular ozone attack on
amines (46), which suggests that amides and formylamine are caused by i) the
breakdown of the carbon-nitrogen bond, ii) the formation of inorganic nitrogen
and hydroxylamine, oxime or amine oxide, and iii) by the oxidation of the
carbon.. All these reactions were shown to involve decarboxylation. Specifically,
a study of glycine (29) determined that, for AAs, the intermediate created from
the addition of ozone either released oxygen to create monohydroxylamine or
caused carbon oxidation via a probable ozonide intermediate. Also the presence
of oxamic and oxalic acids indicates that these reactions can occur without
decarboxylation. Based on these findings reported in the literature, ozone
should first launch an electrophilic attack on nitrogen and followed by two steps
of oxidation on N with or without decarboxylation to form hydroxylamines
(R-NHOH) and hypothetical hydronitrous acid, N(OH)2•. Then oxime will be
formed through dehydration and further oxidized to form aldehyde which has
been previously reported in the literature (29). Since aldehyde could be generated
by the hydrolysis of dihalogenated compound, the backward reaction could lead
the formaldehyde to TCM with further halogenation during chlorination.
A significant amount of THM formation in lysine after ozonation-chlorination
(Figure 4), prompted a comparison of the molar yields of DBP/amino acid of TCM
and TCNM from glycine and lysine under ozonation-chlorination. The yields for
glycine was 5.24% mole TCM and 10.20% mole TCNM per mole of glycine,
respectively, and 4.15% mole TCM and only 1.29% of TCNM for lysine. These
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results suggested that the mechanism for TCM formation from lysine may not
follow the pathway proposed for TCNM. It is possible that intermediates other
than glycine may form. In their study of the formation trends of THM and HNM
Hu et al. (34) also observed a divergence in formation pathways. The findings of
this study would explain these previously observed trends.
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Figure 4. TCM formation potential results from amino acids during chlorination
and ozonation-chlorination at pH 8.0 (DOC = 0.3 ~ 0.5 mg/L, DON = 0.04 ~
0.30 mg/L).
The most reactive AA that caused DCAA formation was aspartic acid, which
yielded a formation of 992.5 µg/mg-C during chlorination (Figure 5), followed
by histidine, which yielded a formation of 336.3 µg/mg-C. These results were
validated by the earlier study of Hong et al. (17), who also confirmed that of the
20 amino acids studied, aspartic acid and histidine caused the highest DCAA
formation during chlorination at pH 7.0. Also since the DCAN produces DCAA
after hydrolysis, these results were also consistent with HAN findings (15, 16, 47).
Aspartic acid is also known to function as a reactive DCAA precursor, forming
0.26 mol/mol (693 µg/mg-C) after chlorination at pH 7.0 (23). Its reactivity
is thought to result from the formation of a β-keto acid intermediate upon
chlorination, a moiety known to have a high DCAA FP (15, 48). In terms of HAA
speciation, aspartic acid and histidine (basic and hydrophilic AAs) formed very
high concentrations of DCAA, whereas the formation of TCAA was significantly
lower. This finding may be partially the result of the hydrophobicity of the
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surrogate which was reported by Bond et al. (23). In that study, it was determined
that the hydrophilic-acid or transphilic-acid surrogates (i.e., aspartic acid) formed
predominantly DCAA during chlorination. In contrast, the hydrophobic-acid and
hydrophobic-neutral surrogates (i.e., tryptophan and tyrosine) formed mainly
TCAA.
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Figure 5. DCAA and TCAA formation potential results from amino acids during
chlorination and ozonation-chlorination at pH 8.0 (DOC = 0.3 ~ 0.5 mg/L, DON
= 0.04 ~ 0.30 mg/L).
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Table 4. DBP FPs of AAs Tested in This Study at pH 6.0 and 8.0
TCNM DCAN TCM DCAA TCAA
Amino DOC DON (µg/L) (µg/L) (µg/L) (µg/L) (µg/L)
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Glycine 0.32 0.19 <MRL <MRL <MRL <MRL <MRL <MRL <MRL <MRL <MRL <MRL
Histidine 0.46 0.27 <MRL <MRL 73.2 79.9 2.1 13.5 42.4 154.7 13.6 20.9
Lysine 0.49 0.19 <MRL <MRL <MRL <MRL 2.5 <MRL <MRL 1.9 <MRL 1.4
Proline 0.52 0.12 <MRL <MRL <MRL 1.5 <MRL 1.3 <MRL 5.9 <MRL 2.1
Serine 0.34 0.13 <MRL <MRL <MRL <MRL <MRL <MRL <MRL 3.5 <MRL 1.4
Continued on next page.
Glycine 0.32 0.19 25.9 223.4 <MRL 2.5 7.4 83.4 <MRL <MRL <MRL <MRL
nation
Histidine 0.46 0.27 <MRL <MRL 6.4 3.8 1.1 6.9 12.7 33.3 3.3 8.5
Lysine 0.49 0.19 12.0 14.6 1.5 <MRL 10.5 33.9 12.9 9.8 1.5 3.1
Proline 0.52 0.12 16.4 17.3 <MRL <MRL 5.0 11.5 7.2 16.6 1.2 2.5
Serine 0.34 0.13 <MRL 0.9 <MRL <MRL 2.0 8.4 1.3 1.5 1.1 <MRL
*Initial concentration of AA’s were 1mg/L. DOC and DON values are calculated based AA concentration and AA formulas. MRL: Minimum Reporting
Limit.
The results show that the THMs and HAAs formation increased with
increasing pH (Table 4). It has been previously reported in the drinking water
literature that THM formation decreases with a decrease in pH, while this
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Conclusions
The C-DBP and N-DBP formation potentials of AAs tested in this study
were summarized in Table 4. Of the nine AAs analyzed, aspartic acid, glycine
and histidine showed the highest reactivity, which contributed to the formation
of N-DBPs and C-DBPs. Aspartic acid also exhibited the highest DCAN and
DCAA formation during both chlorination and ozonation-chlorination. Under the
same conditions, the highest HNM and THM formation was formed from glycine,
although it did not yield HNM and THM during chlorination. HNM formation
from glycine under ozonation-chlorination condition was remarkably higher than
all AAs tested. Further, although a substantial amount of TCM, DCAA, TCAA
and DCAN was formed with the introduction of histidine during chlorination,
the reactivity was lower for chlorination after ozonation. All other AAs showed
very low C-DBP and N-DBP yields, with nitrosamine yields from all nine AAs
during chlorination either being very low or below the minimum reporting levels.
Furthermore, the DBP yield of the selected AAs was higher at pH 8.0 than 6.0
with the only exception of DCAN formation from aspartic acid.
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Aspartic acid and glycine are the most commonly detected AAs in natural
waters. Although the total AA concentrations in natural waters were low, their
elevated concentrations during seasonal events (e.g., algae blooms, die-off, run
off) and the presence of aspartic acid and glycine type structures in the organic
nitrogen molecules in natural waters caused a partial generation of certain C-DBPs
and N-DBPs depending on the oxidation conditions. The results from this study
indicate that AAs are an unlikely contributor to NDMA formation because of the
very low yields generated during chloramination.
Acknowledgments
This work was partly supported by a research grant from the National Science
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Foundation (CBET 106657). However, the manuscript has not been subjected to
the peer and policy review of the agency and therefore does not necessarily reflect
its views.
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Chapter 13
1. Introduction
Adding disinfectants in drinking water treatment is a common practice
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of a variety of organic compounds which can release into water after cell lysis.
This BOM can react with excess disinfectants in water to form DBPs. Moreover,
BOM is relatively enriched in nitrogen than other sources of NOM in natural
waters (26, 27). Therefore, BOM could be an important precursor in forming
nitrogenous DBPs (N-DBPs) such as HANs and NDMA, which could be more
hazardous compared to currently regulated DBPs (i.e. THMs and HAAs) in
finished drinking waters (6, 28, 29).
In this study, we hypothesize that BOM is a DBP precursor and it can
react with chlorine to form a variety of DBP during bacterial disinfection. We
conducted a series of controlled laboratory experiments to evaluate the effect
of water pH, chlorine dosage, and concentrations of NOM on the disinfection
efficiency and DBP formation. The objective of this study is to illustrate the
relationship between bacteria and DBP contaminations in chlorination processes,
as demonstrated in Figure 1. Results of the study could be useful for water
engineers and microbiologists to define the end point of bacterial disinfection and
provide referable information to balance the risk between microbial control and
production of DBPs in finished waters.
2. Experimental
2.1. Chemicals
All the stock solutions and supplies including pipette tips and filter papers for
disinfection experiment were autoclaved (at 121°C for 20 min) to avoid culture
contamination. All glassware were soaked in 5% DECON for 24 h, washed with
Milli-Q water (Millipore, USA), and placed in a furnace at 500°C for 5 h to
eliminate organic contaminants. All the working solutions were conducted in the
phosphate buffered saline (PBS) prepared by suspending 8.01 g of NaCl, 0.20 g
of KCl , 1.78 g of Na2HPO4•2H2O, 0.27 g of KH2PO4 into 1 L Milli-Q water.
Suwannee River Humic Acid (HA) was purchased from International Humic
Substances Society. A stock solution of 100 mg/L of HA was prepared in 0.01
M KCl. The stock solution was filtered through 0.45 μm membrane filter and
kept in clean and glass-topped amber bottle in a refrigerator set at 4°C. The stock
solution was diluted with Milli-Q water to 2 or 4 mg/L of HA for the disinfection
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studies. The 2 or 4 mg/L of HA solution was equivalent to 0.92 or 1.84 mg/L of
dissolved organic carbon (DOC), respectively, based on our measurements using
Shimadzu TOC analyzer.
Seven bacteria commonly found in soil and water, including three gram
positive strains (Bacillus cereus, Bacillus subtilis, and Staphylococcus sciuri)
and four gram negative strains (Acinetobacter junii, Aeromonas hydrophila,
Escherichia coli, and Shigella sonnei), were examined in this study. After a
pre-incubation test to determine the time span of the stationary phase for each
bacterial species, seven strains of bacteria were inoculated individually into
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nutrient broth (10% of the instructed dosage) and grown overnight (16 - 20 h)
to reach the stationary phase. Aliquots of bacterial cultures were centrifuged
at 11,600 x g for 5 min, and bacterial cells were collected and washed three
times with saline solution (0.9% of NaCl) to remove the nutrient broth. The
cell pellets were re-suspended in deionized water in Duran bottles to obtain a
cell density in the range of 104–107 colony forming units per milliliter (cfu/mL)
for the chlorination test. Total organic carbon of cell pellets were tested in
SSM-5000A solid sample combustion unit connected to Shimadzu TOC analyzer.
The relationships between total organic carbon and bacterial count of the seven
bacterial strains are summarized in Table 1. To study the effects of pH, chlorine
dosage, and NOM levels, E. coli was inoculated in a low level and a high level
for each parameter as summarized in Table 2.
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Table 2. A Low Level and a High Level of pH, Chlorine Dosage, and NOM
Were Tested in This Study
Low Level High Level
pH 5 8
Chlorine Dosage (mg/L) 0.5 1.5
Humic Acid (mg/L) 2 4
Free chlorine (HOCl) stock solution (3,000 mg/L of Cl2) was prepared by
diluting ≥4% sodium hypochlorite (NaOCl) (Aldrich) and buffered to pH to 8.0 ±
0.2. For the effects of pH and chlorine dosage on DBP formation and disinfection
efficiency, working solutions of 0.5 and 1.5 mg/L of HOCl were prepared by
diluting stocking solutions with PBS solution. Their pH was adjusted to 5.0 or
8.0 ± 0.2 using 2 mM of sodium hydroxide or 1 mM of sulfuric acid. The HOCl
concentration was tested daily with a HACH chlorine pocket colorimeter (Hach
Co., Loveland, CO) in accordance with Standard Method 4500-Cl B.
Chlorination was conducted in 60-mL glass bottles. The bottles were all
covered in order to prevent chlorine degradation from light. Bottles were placed
in a shaker with a constant vibration frequency to prevent cell settling. For the
effects of pH, chlorine dosage, and NOM levels, the final concentration of E. coli
was adjusted to 1.5×107 cfu/mL. Bacteria and/or HA spiked into the solution and
mixed continuously at room temperature. An aliquot of 0.5 mL of treated mixture
was sampled at 5, 20, 40, and 80 min during the reaction. The mixture was then
quickly diluted with sterilized saline solution. Each 0.1 mL of original or diluted
sample was then immediately placed on the sterilized and dry nutrient agar. Agar
plates were incubated at 37°C for 24 h. The bacteria cell density at each time
interval was computed by the colonies counted on the agar plates.
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2.5. DBP Analysis
3. Results
3.1. DBP Formation During Bacteria Inactivation
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Figure 3. (a) Fluorescence EEM of water solution containing E. coli: (a) before
disinfection treatment, (b) after 80-min treatment with 0.5 mg/L Cl2 at pH 8,
and (c) after 80-min treatment with 1.5 mg/L Cl2 at pH 8. Quenching solution
Na2S2O3 was added after 80-min treatment before fluorescence measurement
was taken.
Both HA and BOM can react with chlorine in forming DBPs. The formations
of DBPs were generally increased with the chlorine dosage (Figures 5). For pure
E.coli culture solution with 1.5×107 cfu/mL at pH 8, 1.1 and 5.7 μg/L of THMs
were produced at 0.5 and 1.5 mg/L of chlorine, respectively. For the pure NOM
solutions with 2 and 4 mg/L of HA at pH 8, 5.0 – 5.2 µg/L and 33.4 – 40.1 µg/
L of THMs were produced at 0.5 and 1.5 mg/L of chlorine, respectively. Other
types of DBPs were also produced but their levels were in ng/L range. The water
solutions containing both E. coli and HA generated less THMs than pure E.coli or
pure HA water solutions at pH 8. Fluorescence EEM demonstrated that different
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characteristics of BOM and HA. A strong humic acid-like peak was observed in
Ex = 250 nm / Em 450 nm in pure HA solution (Figure 6a) but a strong microbial
by-product-like peak was observed in Ex = 280 nm / Em = 250 nm when bacteria
was added into the solution (Figure 6b).
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Figure 4. Effects of humic acid and pH on E. coli cell density in water solution
during 80-min chlorination.
Figure 6. Fluorescence EEM of water solution after chlorination with initial 1.5
mg/L of Cl2 at pH=8 for 80 min (a) 4 mg/L Humic acid only (b) 4 mg/L Humic
acid + 107 cfu/mL E.coli K-12. Quenching solution Na2S2O3 was added after
80-min treatment before fluorescence measurement was taken.
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4. Discussions
4.1. Microbial Cells and Cellular Components as DBPs Precursor
Many studies had examined biological molecules such as amino acids,
nucleic acids, carbohydrates on DBP formation and concluded that they are
reactive DBP precursors (23–25, 34, 35). Generally specific THM formation of
these biomolecules usually low than 10 μg-THM/mg-C except few exceptions
such as tryptophan and tyrosine which can be over 100 μg-THM/mg-C (34, 35).
Differences from other previous studies, we examined DBP formation directly
disinfecting bacterial cells. Our results showed the specific THM formation from
bacterial cells ranged from 6.1 to 37.6 μg/mg-C and specific HAN formation from
3.6 to 16.3 μg/mg-C. These numbers are generally comparable to those monomers
or standard chemicals studies as discussed above. The results confirmed that that
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these bacterial components can also be the DBP precursor as long as halogenating
reagent exists. We have also demonstrated that there is a positive correlation
between DBP formation and the log-reduction of E. coli by both chlorination and
chloramination (33). The results further confirmed that the DOM released from
the breakdown of bacteria can contribute to DBP formation.
In addition to the source waters, bacteria existed as biofilm are commonly
observed within water delivery systems (36). Disinfectants could react with
extracellular polymeric substance (EPS) released from biofilm in forming DBPs
(37). Not only do the quantity and quality of EPS affect the yield of DBPs, but
also they determine the speciation of DBP formation. For example, the surrogate
protein of EPS favors the formation of HAA formation while the surrogate lipid
favors THM formation. In addition, the bacterial phenotypes and the materials
on which biofilm attached also have a great impact on the bacterial derived DBP
formation. Our research group demonstrated that planktonic cells formed 7-11
times greater THMs per carbon that those from biofilm Furthermore, biofilms
on the polyvinyl chloride consumed comparable chlorine but produced more
THMs than those on galvanized zinc surface (33). All these results indicated the
important of BOM in the DBP formation in the drinking water supply.
There is no obvious difference on the bacteria type, such as Gram staining,
size or source of the bacteria, on the DBP formation of chlorination. However,
as mentioned, the quality of cell components (i.e. EPS) would have great impact
on the DBP formation. Therefore, the DBP formation potential of bacteria maybe
mainly affect by the quality of cell components instead of the thickness of cell
wall. Therefore, no obvious trend is observed in this study.
biological molecules such as amino acid and nucleic acid are N-rich. With a lower
C/N ratio, BOM could have a higher reactivity in forming more toxic N-DBPs
when comparing with other sources of NOM (34).
The addition of HA would inhibit the disinfection efficiency as HA
competed for chlorine during the process, resulting in a lower effective chlorine
concentration for bacterial inactivation in water solutions. Chlorine could react
with either E. coli or HA to form DBPs. However, E. coli and HA do not exhibit
an additive effect in DBP formation when they co-existed in the water solutions,
although both of them are DBP precursors. In some cases, the existence of E. coli
in HA solution even resulted a lower DBP formation than the HA solution alone
(Figure 5). A simple competitive reaction model (i.e. E. coli and HA compete
for free chlorine) may not explain the phenomenon when there was excess
chlorine in water. This observation could also attribute to N-rich organic matter
from bacterial cells. N-rich BOM could affect the residual chlorine in water
throughout forming organic chlorine and breakpoint reaction, depending on the
Cl-to-N ratio (40). In fact, studies had demonstrated that organic N could reduce
THM formation during water chlorination (41). These experiments demonstrated
“competition” relationships of HA and bacteria during water chlorination. HA
reduces bacterial inactivation efficiency by consuming reactive chlorine whereas
BOM from lysed cells changes the chlorine chemistry in water and reduces THM
formation from HA. The combined effects showed less disinfection efficiency
and less DBP formation than HA or E. coli existed alone in water. In natural
source waters, other organic matters such as fulvic acid also exist but HA is
generally larger in size than fulvic acid and it should have a greater shielding
effect protecting bacteria from disinfection.
increase the operation costs. More important, the recovery and the impacts of
nanoparticles are still uncertain.
5. Conclusions
The results of this study confirmed our hypothesis that BOM is a DBP
precursor and it can react with chlorine to form a variety of DBP during
bacterial disinfection. Since bacteria in source water are ubiquitous, their relative
contribution to DBP formation in water disinfection has been overlooked. The
DBP formation from inactivating bacterial cells is greatly affected by different
factors, such as types and dosages of disinfectants, water pH, physiology and
phenotypes of bacteria, etc. Results of this study also suggested that a lower
DBP formation and better inactivation efficiency could be achieved in the acidic
condition.
Acknowledgments
This work was funded by the Research Grant Council of Hong Kong SAR
Government (CUHK 477610). P.K. Wong was also supported by the CAS/SAFEA
International Partnership Program for Creative Research Teams, Chinese
Academy of Sciences, China. This research is also based upon work supported
by NIFA/USDA under the project number SC-1700489 and SCN-2013-02784,
and Joint Fire Science Program 14-1-06-19. This manuscript is a technical
contribution no. 6349 of the Clemson University Experimental Station.
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Chapter 14
Introduction
In 1902, for the first time in the United States, chlorine was added to drinking
water (DW) to protect the public from water-borne diseases (1). Since then,
countless lives have been saved by this potent microbicidal agent. Not until
the 1970s, however, were the unintended consequences of DW chlorination
discovered (2, 3). In addition to inactivating bacteria and viruses, chlorine can
where kHOBr is a second-order rate constant (M-1 s-1), [HOBr] is the concentration
of HOBr (mol/L), [Org-H] is the concentration of the parental organic compound
(mol/L), and [Org-Br] is the concentration of the brominated product (mol/L).
When HOBr is present in large excess, kHOBr can be calculated by eq 3:
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where kobs is a pseudo-first-order rate constant (s-1). Apparent rate constants (kapp)
are also commonly reported for bromination reactions:
where [Br(I)]tot denotes the total concentration of free bromine. Values of kapp
typically vary as a function of pH (e.g., due to the weak-acid character of HOBr).
That BrO- possesses a net negative charge and requires expulsion of a weakly-
labile leaving group (O2-) suggests HOBr will be a more reactive brominating agent
than BrO- (53).
The kinetic models represented by eqs 3 and 4 do not account for the
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Catalysis by Chloride
Although commonly overlooked, bromination rates of organic compounds
can depend on the concentration of chloride ions (53, 55–57). For example,
a recent investigation involving the herbicide dimethenamid (a substituted
thiophene) revealed that rates of bromination in solutions of free bromine
increased linearly with the concentration of added chloride (Figure 1) (53). The
influence of chloride on rates of dimethenamid bromination (represented by the
slopes in Figure 1) increased with decreasing pH. These findings are consistent
with the participation of BrCl as a brominating agent, whose concentration is
proportional to the concentration of chloride (eq 7):
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Although an additional free bromine species (BrCl2-) can also form in the
presence of chloride (58), the formal negative charge on BrCl2- is anticipated to
render this species significantly less electrophilic compared to neutral free bromine
species (e.g., BrCl and HOBr) (55).
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BrCl has an inherent reactivity 3.6 x 106- and 1.4 x 107-times greater than
HOBr toward dimethenamid (53) and the para position of anisole, respectively
(55). As such, the potency of chloride as a bromination catalyst can be substantial.
The median chloride concentration in raw DW is approximately 10 mg/L (59).
Treatment processes (e.g., coagulation) can increase the chloride concentration
of DW. For example, addition of FeCl3 at 2 mM (~300 mg/L) as a coagulant
concomitantly increases the chloride concentration by ~200 mg/L. This additional
chloride is sufficient to increase bromination rates of anisole and dimethenamid
by more than a factor of 11 (Figure 2).
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As with BrCl, the partial positive charge on the bromine atom of BrOCl and
the greater leaving group ability of ClO- (relative to BrO-) suggest this mixed
halogen will function as a brominating agent (53). As HOCl is a product of
aromatic bromination reactions involving BrOCl (53, 55), HOCl can be viewed as
a bromination catalyst. Catalysis of bromination by HOCl has also been reported
for reactions of anisole in solutions prepared by adding excess free chlorine to
sodium bromide (Figure 5) (55).
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Sivey et al. (53) suggested that the participation of Br2O (eq 12) as a
brominating agent could account for the measured reaction rates exhibiting a
greater-than-first-order dependence on total free bromine.
Figure 8. Speciation of free bromine for a model water containing bromide (160
µg/L) that undergoes disinfection by (A) free chlorine and (B) a sufficient amount
of ozone to convert 95% of initial bromide into free bromine, Br(I), and assuming
higher oxidation products of bromine (e.g., bromate) are not formed. Data from
reference (55) and sources cited therein.
Overall, recent literature reports (53, 55, 56) suggest kinetic models that do not
account for the less abundant free bromine species (BrCl, Br2, Br2O, and BrOCl)
are unable to satisfactorily explain the effects of solution chemistry conditions
on measured bromination rates of modestly nucleophilic aromatic compounds.
Accordingly, caution should be exerted when interpreting published rate constants
(e.g., kapp and kHOBr) that include (often untested) assumptions about the effects
of halides and hypochlorous acid on rates of bromination. The extent to which
catalysis by halides (via formation of BrCl and Br2) and hypochlorous acid (via
formation of BrOCl) influences formation rates of regulated DBPs merits future
research. Such catalysis might be particularly influential, for example, during
reactions involving the “slowly reacting fraction” of trihalomethane precursors
(78).
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Chapter 15
Introduction
Forests are critically important to the supply of clean drinking water in the
United States. National forests and grasslands, which represent 30% of the forest
area in the U.S., provide drinking water for over 60 million people (1). The
number of people served by all forests and grasslands in the U.S. are far greater
than this number. Hot temperatures and longer dry periods due to climate change
will increase the likelihood of larger and more severe wildfires (2). Forest fire
rapidly modifies the chemical composition of the detritus layer on the forest
floor, converting lignin and polysaccharide rich and relatively degradable carbon
pools to polycyclic aromatic and charcoal rich and recalcitrant black carbon
(BC) (3). Dissolved organic matter (DOM) leaching from pyrogenic organic
matter (PyOM), or dissolved BC, could have different treatability and reactivity
in disinfection by-product (DBP) formation compared to the DOM leaching from
unburned detritus layer. In contrast to wildfire, prescribed fire is low-intensity
burning of accumulated detritus materials to reduce the fuel amount on forest floor
to prevent catastrophic wildfires (4). It is often conducted when soil is moderately
moist to reduce the intensity, and it brings benefits to decrease the invasive species
and release different nutrients from plant materials (5). While forested ecosystems
have been identified as persistent sinks for atmospheric carbon (6), prescribed
burns can affect forest’s capacity to sequester carbon and carbon quality and
quantity in soil organic matter pools (7, 8). For example, forest fire converts plant
biomass into forms of BC such as polycyclic aromatic hydrocarbons (PAHs) that
are resistant to microbial attack and persist in the soil for thousands of years (9).
These new compounds are the products of incomplete combustion of biomass,
which usually had lower H/C and O/C ratios (10). Hockaday, et al. (2007) (11)
found that export of BC from soils via dissolution and biological transformation
could constitute an important C loss mechanism. In fact, charred plant materials
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can cause accelerated breakdown of simple carbohydrates (12) and enhance
the loss of forest humus (13). As detritus in forest floor is one major source of
terrestrial DOM (14), export of these newly formed and modified compounds
is of great concern because they may alter the water quality by changing DOM
quantity and quality.
The well-documented toxicological properties of DBPs suggested that
exposure to DBPs in disinfected water may increase the risk of cancers such
as bladder and colorectal cancers (15, 16). As DOM is an important precursor
reacting with disinfectants during water treatment to yield carbonaceous (e.g.,
trihalomethanes; THMs) and nitrogenous disinfection by-products (N-DBPs)
(e.g., haloacetonitriles; HANs) (17–19) increasing studies are focusing on the
sources of DOM and the associated chlorine reactivity (20, 21). Litters have
been identified as a significant watershed source of DOM contributing to the
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downstream water supply and DBP precursors (14, 22–24). Different plant
species can have a diverse amount and composition of organic compounds such
as polysaccharides, lignin, tannin, and aliphatic biopolymers (25). Thus, variation
in plant species can affect the DOM composition and may affect the budget and
speciation of DBPs in water treatment process. Burning of diverse plant materials
would affect the quality and quantity of DOM and the subsequent DBP formation
as well, which, however, has not been well studied.
In order to understand the effects of low intensity prescribed forest fire
on the productions of DOM and DBP precursors in forested watersheds, we
conducted a controlled laboratory study (Part I) and a controlled field study (Part
II) independently. In this chapter we present Part I, the laboratory study where
we compared characteristics of water extractable organic matter (WEOM) from
raw and laboratory-controlled burned foliar litters of six plant species commonly
found in the southeastern United States, including baldcypress (Taxodium
distichum), boxelder (Acer negundo), longleaf pine (Pinus palustris), pop ash
(Fraxinus caroliniana), sweetgum (Liquidambar styraciflua), and water tupelo
(Nyssa aquatica), and evaluated their DBP formation using a uniform formation
condition test. Results of this study would illustrate the productions of DOM
and DBP precursors among different tree species under prescribed fire practices.
Results of this controlled experiment would also be used to compare to the real
prescribed fire practices (Part II), as described in the other chapter of Part II.
Statistical Analyses
All statistical analyses conducted in “R” version 2.15.0 (Copyright (C) 2012
The R Foundation for Statistical Computing). Relationships were considered to
be significant at P < 0.05. Pearson’s correlation was used to examine correlation
between different parameters.
Figure 1. Chemical composition of original (white bars) and burned (gray bars)
litters as determined from pyrolysis gas chromatography mass spectrometry
(Py-GC/MS).
Fluorescence Spectrometry
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Table 3. Pearson’s Correlation Coefficients (r) between Measured Parameters of Litters before Burn. Significant Correlations
(p < 0.05) Are Highlighted in Bold.
Specific
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which was highest for boxelder (0.007±0.000 mmol/mol-C) and did not show
difference among other plant species (0.003-0.005 mmol/mol-C).
After burning, both the specific THM formation and specific HAN formation
were significantly altered, which is in agreement with the results of field studies
of prescribed fire (Part II) and wildfire. The specific chloroform formation
decreased by 12%-60% for all plant species (56). However, the specific
dichlorobromomethane formation increased for baldcypress (52%), boxelder
(55%), pop ash (347%), and water tupelo (69%). Different from chloroform,
the specific haloacetonitriles formation increased for all species. While the
specific dichloroacetonitrile formation increased by 30%-1457%, the specific
trichloroacetonitrile formation increased by 7%-73%. There was no correlation
between the percent decrease of specific THM formation and the percent decrease
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of specific HAN formation, suggesting that the fire’s effects on the THM precursor
and HAN precursor were independent. However, correlation between specific
HAN formation and percent fluorescence response of region IV was significant
for both before and after burn (Table 3). This may provide a fast easy method for
prediction of specific HAN formation both before and after burn.
Multiplying the specific DBP formation with the WEOC, we can estimate
the DBP precursor yield (μg/g-original-litter) from the litter material (Figure
4). Before burn, the litter materials can potentially produce THMs ranging
from 82.3±1.0 μg-THMs/g-original-litter μg-THMs/g-original-litter (pop ash)
to 706.4±93.7 μg-THMs/g-original-litter (sweetgum). After burn, the THM
yield decreased by 70%-98% for all species (Figure 4a). For HANs, these litter
materials had the HAN yield ranging from 3.72±0.24 μg-HANs/g-original-litter
(water tupelo) to 10.40±0.14 μg-HANs/g-original-litter (boxelder). As the
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specific HAN formation has increased after burn, there was a much less decrease
in HAN yield compared to THM yield after burn. The HAN yield dropped by
29%-69%, for all species (Figure 4b).
The results demonstrated the effects of low intensity burning (i.e. 340 °C) on
changes in quantity and quality of DBP precursors on the forest floor. Because
fire can largely consume organic matter in detritus layer, WEOM (i.e. WEOC
and WETN) decreased after burn. Such consumption of litter materials is likely
an overriding effect to reduce the DBP precursors, which resulted in the overall
reduction in DBP yield from litter materials (Figure 4). Chlorine reactivity of
the burned litter in forming HANs is much higher than that of original litter.
As the HANs have been documented to be much more toxic than the common
carbonaceous DBPs such as THMs and haloacetic acids, attention should be
placed on the nitrogenous DBPs in water treatment of fire-affected DOM.
The study revealed the effect of vegetation cover on the potential DBP
export. We found that among the major plant species within the watershed, the
sweetgum has a much larger content of DBP precursor because its litter has
high WEOM that is also very reactive in forming DBPs (ranking 1st for THM
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yield and the 2nd for HAN yield; Figure 4). In contrast, the pop ash is a species
with much less contribution to the watershed export of DBP precursor, with
only 12% THM formation and 61% HAN formation relative to the sweetgum.
The response of DBP precursors in litter materials is highly dependent upon
plant species as shown in Figure 4. Therefore, the knowledge acquired in one
watershed about the fire effect on the DBP export may not be directly applicable
to estimate the DBP export in another watershed that has quite different dominant
plant species. The controlled lab study here is designed for elucidating the
effects of simulated burning on the DBP precursor in litter materials without
any interference from other environmental factors such as mixes of vegetations,
fuel moistures, decomposition stages, etc. To evaluate a real suitation on DBP
precursor production from a burnt forest, our research team conducted a controlled
burning experiment and natural exposure of WEOM in a natural forest at Hobcaw
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Bonary, Georgetown SC. Results and findings of the controlled field study, as the
Part II of this prescribed fire study, are discussed in the following chapter.
Acknowledgments
Jun-Jian Wang received financial support from the China Scholarship Council
(CSC[2011]3010). Portions of this study were also supported by NIFA/USDA
under project number SC1700489 and 2014-67019-21615, Joint Fire Science
Program 14-1-06-19, and NSF Rapid Grant 1264579 as presented in technical
contribution number 6359 of the Clemson University Experiment Station.
Appendix
Table A1. The Categorization of Pyrogenic Products from Results of
Pyrolysis Gas Chromatography Mass Spectrometry: Ar = aromatics; Lg =
lignins; Lp = lipids; Ps = polysaccharides; N = nitrogens; PAHs = polycyclic
aromatic hydrocarbons; Ph = phenolics.
Ty-
# Compound # Compound Type
pe
1 Phenol, 2-methoxy- Lg 77 Heptadecane Lp
2 Phenol,2-methoxy-4-methyl- Lg 78 1-Eicosene Lp
3 Phenol,4-methoxy-3-methyl- Lg 79 1-Nonene Lp
4 1,2-Benzenediol,3-methoxy- Lg 80 Tridecane Lp
5 Phenol,4-ethyl-2-methoxy- Lg 81 Heptadecane Lp
6 4-Hydroxy-3-methoxystyrene Lg 82 Toluene Ar
7 Phenol,3-methoxy-5-methyl- Lg 83 Ethylbenzene Ar
8 Phenol, 2,6-dimethoxy- Lg 84 P-Xylene Ar
Phenol,2-methoxy-4-(1-
9 Lg 85 P-Xylene Ar
propenyl)-
Continued on next page.
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Table A1. (Continued). The Categorization of Pyrogenic Products from
Results of Pyrolysis Gas Chromatography Mass Spectrometry: Ar =
aromatics; Lg = lignins; Lp = lipids; Ps = polysaccharides; N = nitrogens;
PAHs = polycyclic aromatic hydrocarbons; Ph = phenolics.
Ty-
# Compound # Compound Type
pe
10 3,4-Dimethoxyphenol Lg 86 Benzene, Popyle- Ar
11 Vanillin Lg 87 4-Ethyltoluene Ar
12 Eugenol Lg 88 1,2,4-Trimethylbenzene Ar
Phenol,2-methoxy-4-(1E)-1-
13 Lg 89 2-Ethyltoluene Ar
propenyl-
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4-methoxy-3-hydroxyacetophe-
14 Lg 90 2-Methylstyrene Ar
none
3-methoxy-2,4,6-trimethyl- Benzene,1-methyl-2-(1-
15 Lg 91 Ar
phenol methylethyl)-
2-Propanone,1-(4-hydroxy-3-
16 Lg 92 Benzene, 2-propynyl Ar
methoxyphenyl)-
Phenol,2,6-dimethoxy-4-(2- Benzene,1-methyl-4-(1-
17 Lg 93 Ar
propenyl)- methylethenyl)-
3,5-Dimethoxy-4-
18 Lg 94 Benzene, 1-butynyl- Ar
hydroxybenzaldehyde
Phenol,2,6-dimethoxy-4-(2- Benzene,(1-methylene-2-
19 Lg 95 Ar
propenyl)- propenyl)
20 4-Ethyl-2-methoxyphenol Lg 96 Resorcinol Ar
1-ethyl-2,4,5-trimethyl-
21 1,2,4-Trimethoxybenzene Lg 97 Ar
benzene
Benzene, 1,3,5-trimethyl-
22 Phenol, 3,5-dimethoxy- Lg 98 Ar
2-(1,2-propadienyl)-
Benzene, (1-ethynyl-2-
23 Vanillyl ethyl ether Lg 99 Ar
methyl-1-propenyl)-
24 2,5-Dimethylfuran Ps 100 Mesitylene Ar
25 2(5H)-Furanone Ps 101 Benzene Ar
26 Furfural Ps 102 Benzene, 1-propynyl- Ar
Cyclopentene,1-(1-
27 Ps 103 Cinnamaldehyde Ar
methylethyl)-
28 2-Cyclopenten-1-one,2-methyl- Ps 104 Mesitaldehyde Ar
29 Furfuryl alcohol Ps 105 1-Indanone Ar
2-Furancarboxaldehyde,5-
30 Ps 106 Benzene, octyl- Ar
methyl-
Continued on next page.
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Table A1. (Continued). The Categorization of Pyrogenic Products from
Results of Pyrolysis Gas Chromatography Mass Spectrometry: Ar =
aromatics; Lg = lignins; Lp = lipids; Ps = polysaccharides; N = nitrogens;
PAHs = polycyclic aromatic hydrocarbons; Ph = phenolics.
Ty-
# Compound # Compound Type
pe
31 2(5H)-Furanone,3-methyl- Ps 107 Phenol Ph
32 Furan, 2,4-dimethyl- Ps 108 2,5-Dimethylphenol Ph
33 2(3H)-Furanone,5-methyl- Ps 109 Phenol,3,5-dimethyl- Ph
34 2,5-Dimethyl furane Ps 110 Phenol,2-ethyl-5-methyl- Ph
35 Furan, 2-ethenyl- Ps 111 Phenol,4-ethyl-3-methyl- Ph
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2H-Pyran-2-one,
36 Ps 112 Hydroquinone Ph
4-ethenyltetrahydro-
1,2-Benzenediol,4-
37 2H-Pyran-2-one Ps 113 Ph
methyl-
38 2-Cyclopenten-1-one,2-methyl- Ps 114 1,2-Benzenediol,4-ethyl- Ph
Phenol,4-(2-propen-1-
39 2-Acetylfuran Ps 115 Ph
yl)-
1,4-Benzene-
40 2(3H)-Furanone Ps 116 Ph
diol,dimethyl-
2H-Pyran-2-one,
41 Ps 117 1,2-Benzenediol,4-ethyl- Ph
5,6-dihydro-3,5,5-trimethyl-
42 Furfuryl alcohol Ps 118 Pyrogallol Ph
43 3-Methyl-2-cyclopenten-1-one Ps 119 Methylparaben Ph
2-Cyclopenten-1-one,2,3- 1,4-Benzenediol,2,3,5,6-
44 Ps 120 Ph
dimethyl- tetramethyl-
1,2-Benzenediol,4-
45 2-Cyclopentenone Ps 121 Ph
methyl-
46 Pyridine N 122 1,3-Benzenediol,4-ethyl- Ph
47 Benzonitrile N 123 Pyrogallol Ph
1,4-Benzenediol,2,3,5-
48 Oxazole,2-ethyl-4,5-dihydro- N 124 Ph
trimethyl-
49 1H-Pyrrole, 1-methyl- N 125 m-Tolualdehyde Ph
50 N-Methyl pyrrole N 126 3-Ethylphenol Ph
51 Pyrrole N 127 Phenol,2-methyl- Ph
2-Oxocyclohexanepropiononi-
52 N 128 Phenol,4-methyl- Ph
trile
54 3-Pyrazolidinone, 1,4-dimethyl- N 129 2,3-Dimethylphenol Ph
Continued on next page.
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Table A1. (Continued). The Categorization of Pyrogenic Products from
Results of Pyrolysis Gas Chromatography Mass Spectrometry: Ar =
aromatics; Lg = lignins; Lp = lipids; Ps = polysaccharides; N = nitrogens;
PAHs = polycyclic aromatic hydrocarbons; Ph = phenolics.
Ty-
# Compound # Compound Type
pe
55 Perillartine N 130 2,3-Dimethylphenol Ph
56 3-Methylpyrazole N 131 3,5-Dimethylphenol Ph
57 Benzyl cyanide N 132 2,5-Dimethylphenol Ph
58 3-Methylindole N 133 3-Ethylphenol Ph
Benzeneethanamine,4-ethyl-2,5-
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59 N 134 Pyrocatechol Ph
dimethoxy-a-methyl-
1,2-Benzenediol,3-
60 Pyridine, 3-methyl- N 135 Ph
methyl-
61 3-Methylpyrrole N 136 4-Methylcatechol Ph
Pyrazine, 2,3 dimethyl-5-(1-
62 N 137 4-Ethylresorcinol Ph
Propenyl)-
Benzeneethanamine, 1,4-Benzenediol,2,3,5-
63 N 138 Ph
2,5-dimethoxy- trimethyl-
64 Pyrazine, tetraethyl- N 139 Naphthalene PAHs
6-Hydroxy-1,2,3,4-
65 tetrahydroisoquinoline-1- N 140 2-Methylnaphthalene PAHs
carboxylic acid
1H-Indole, 4-(3-methyl-2-
66 N 141 2-Methylnaphthalene PAHs
butenyl)-
Naphthalene,1,2-
67 Undecane Lp 142 PAHs
dimethyl-
68 Tetradecane Lp 143 2,6-Dimethylnaphthalene PAHs
Naphthalene,1,6,7-
69 Nonadecane Lp 144 PAHs
trimethyl-
Naphthalene,1,6,7-
70 1-Hexacosene Lp 145 PAHs
trimethyl-
71 Heptadecane Lp 146 1-Methylnaphthalene PAHs
72 1-Eicosene Lp 147 Biphenyl PAHs
73 1-Hexacosene Lp 148 Naphthalene, 1-ethyl- PAHs
74 3-Eicosyne Lp 149 2-Naphthol PAHs
75 1-Docosene Lp 150 Dibenzofuran PAHs
76 1-Nonadecene Lp 151 Carbaryl PAHs
152 Fluorene PAHs
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Chapter 16
Introduction
It is well knownthat natural organic matter (NOM) is the major precursor
of disinfection by-products (DBPs) during the chlorination process in water
treatment systems (1, 2). It is estimated that NOM constitutes 50-90% of dissolved
organic carbon (DOC) in freshwater systems (3). Reducing the import of DOC
into natural waters used as drinking water sources can potentially minimize the
formation of DBP during the chlorination process. Water in forested watersheds
is a critical source of drinking water. Approximately 180 million people in
over 68,000 communities in the United States rely on forested lands to capture
and filter their drinking water (4). Large scale of natural disturbance in forest
could substantially influence water characteristics and consequently impact the
treatability downstream.
Several studies have reported negative effects of wildfire on the water quality
of forested watersheds (5–7). Prescribed fire treatment is usually implemented
as a low-cost-effective tool to reduce hazardous fuels in the forest and risks of
unwanted wildfires as well as recyclying nutrients back to the soil. Richter and
colleagues in their watershed scale study (8) indicated that periodic prescribed fire
within the Francis Marion National Forest in South Carolina is not likely to have
appreciable effects on the quality of stream rivers. Also, Arkle and Pilliod (9)
found that prescribed fire had no effects on stream habitats in Payette National
Forest, Idaho. Caldwell and colleagues (10) reported that carbon-nitrogen ratios
did not differ between streams affected by prescribed fire treatment and reference
streams within a grassland system on the Valles Caldera National Preserve, New
Mexico. It is noted that nutrients were measured quantitatively in those researches
to assess the effects of prescribed fire on the aquatic systems; however, little is
known regarding the effects of prescribed fire on the quantity and quality of DOM
exported from forest fuels.
Dead and down woody materials, litter, grasses, herbaceous plant materials,
and short shrubs are not only forest fuels but are also parts of terrestrial sources
of DOM in forested watersheds. According to Chow and colleagues (11), the
DOC extracted from California oak woodland litter is an important precursor in
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forming DBPs and the reactivity of litter and leaf leachate is dependent on types
and decomposition stages of vegetation. When prescribed fire occurs, those forest
litter materials could be chemically oxidized and transformed and consequently
alter the quantity and quality of DOM exported from the forested watersheds.
In order to study effects of prescribed fire on water quality of forested
watersheds, it is important to understand the characteristics of DOC leaching
from burned litter and duff materials. Moreover, DOM in natural water may
undergo various chemical, physical, and biological reactions during water
conveyance in streams before entering water treatment facilities. Photochemical
reactions of DOM such as solar irradiation may cause oxidative degradation of
DOM and result in smaller and more labile organic carbon moieties (12, 13).
In fact, exposure of DOM to natural sunlight could alter the characteristics of
carbon exported from foliar litters and consequently affect DBP formation in
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water disinfection processes (14, 15). The objectives of this field study were
to understand the influence of prescribed fire on DOM and DBP precursor
productions using detritus mixture burned in the field instead of using single
vegetation species burned in a temperature controlled oven, as in Part I of the
study. In addition, the leachates extracted from burned and unburned detritus
were further incubated under dark and light conditions for 15 days in order to
determine the influences of biogeochemical processes on the characteristics of
DOM and DBP precursors.
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of water extracts. The measurement of specific DBP formation represents the
reactivity of carbon in forming DBP during chlorination.
Potential changes in organic matter chemical composition due to fire effects
were assessed using a pyrolyzer (CDS5500) connected to a GC–MS system
Agilent 7890 equipped with a fused silica capillary column HP5MS (30 m×250
μm×0.25 μm inner diameter). Approximately 2 mg of unburned and burned
samples were placed in tiny platinum capsules and pyrolysis was set to 700ºC.
Pyrolysis products were identified according to GC retention times, mass spectra
with reference to the Wiley/NIST libraries and published mass spectra of pyrolysis
products (20). Major identified compounds were classified as: aromatic (Ar),
lignin (Lg), lipid (Lp), polycyclid aromatic hydrocarbon (PAH), phenolic (Ph),
polysaccharide (Ps), and nitrogen compounds (N). Individual identified organic
compounds are included in the list shown in Part I of this Chapter.
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Statistical Analysis
A paired t-test was used to determine differences in characteristics
betweenwater extracts from unburned and burned samples. The level of
significance was set to P < 0.05. All data were analyzed using SPSS.
Figure 1. Images prior to (a), during (b), and following (c) the prescribed fire in
Hobcaw Barony, SC.
Py-GCMS spectra from unburned and burned detritus materials are shown
in Figure 2. A total of 53 and 46 peaks were identified in the unburned and
burned sample respectively. Relative intensity of peaks usually decreased in
burned detritus compared to original unburned detritus pointing to the loss of a
high percentage of organic matter during burning. In addition, some of peaks
such as trimethoxybenzene (38.8 min) and dimethoxyacetophenone (43.6 min)
were missing in the burned samples (Figure 2). Meanwhile, an increase of peak
intensity for compounds such as naphthalene (27.0 min) and biphenyl (36.0
min) were observed in burned samples, although those peaks were very small
(Figure 2). Overall, Lg and Lp were decreased from 55 to 41% and 2 to < 1%
respectively, whereas Ar, Ph, and PAH increased from 12 to 18%, 24 to 30%,
and from 0.6 to 3%, respectively after fire. No obvious changes in N compounds
and Ps were observed, staying at about 3 and 4% respectively. Importantly,
the changes in relatively abundance of these fractions matched well with the
controlled laboratory burns (Part I), suggesting mixed and individual species may
not affect the results.
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Table 1. WEOC, WETN and DBPs Formation of Forest Detritus Samples
before and after Burn; Average ± Standard Deviation; n = 3
Before burn After burn P value
Water Extractable Organic Matter (1:10 litter to water extraction)
WEOC (mg/L) 1,703 ± 271 925 ± 373 0.01
WETN (mg/L) 55 ± 15 43 ± 17 0.29
C:N (mol: mol) 38 ± 17 25 ± 0 0.15
SUVA 2.03 ± 0.16 1.98 ± 0.47 0.44
Disinfection By-Product Formation
THM (mmol/mol) 6.05 ± 1.15 4.11 ± 1.57 0.16
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Figure 3. Fluroresence EEM of water extracts from (a) unburned and (b) burned
detritus materials.
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In terms of DBP formation, a lower reactivity in forming THM but a higher
reactivity in forming HANs were observed after fire although those differences
were statistically no significant. The reactivity of CHD was similar before and
after burn. Therefore all the analyses showed that low intensity prescribed fire
only reduced the quantity of WEOC but the chemistry, in terms of C:N ratio,
optical properties including both UV/VIS and fluorescence measurements, and
DBP formation, was no changed.
sunlight incubations were lower than in the original samples (Figure 4), suggesting
DOM in these extracts was highly degradable. These results were concomitant
with the results showing that WEOC and WETN in burned detritus leachate
were lower than in unburned detritus leachate (Figures 4a and 4b). Consider
burned samples as an example, there were 76 and 59% decreases in WEOC and
WETN respectively, in dark incubation, suggesting microbial processes possibly
consumed these degradable organic matters. For the sunlight treatment, decreases
of WEOC and WETN were even higher (78 and 72% respectively).
Figure 4. WEOC (a), WETN (b), C:N ratio (c), and SUVA (d) of the leachate
extracted from unburned and burned detritus under 15-days dark and sunlight
incubation; average ± standard deviation; n = 3.
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The C:N ratios of unburned and burned extracts after 15-days dark incubation
were significantly lower than the values of original samples and sunlight
incubation (Figure 4c), with an average of 22 and 14, respectively. On the other
hands, the SUVA of dark incubation were highest among other treatments (Figure
4d). The SUVA values of unburn and burned extracts increased to 3.01 and 2.73
L/mg/m, respectively. Results might suggest microbial processes dominated in
dark incubation and consumed degradable organic carbon, causing an increase
in the proportion of relatively recalcitrant aromatic carbon in water. Lower C:N
ratios and SUVA were observed after sunlight incubation when comparing to
original samples (Figures 4c and 4d). In addition, an obvious decrease of humic
acid-like fraction (Region V) in both unburned and burned extracts was observed
after 15-day sunlight exposure (Figure 5). It has been demonstrated that sunlight
could cause photobleaching of DOM is an important role in DOM characteristics
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study found that although sunlight exposure significantly decreased SUVA254
values, the reactivity of DOC in forming THM was not significantly changed.
Results also showed no significant changes on HAN formation after incubation,
which suggested that the reactivity of DOC to form HAN was not sensitive to
biogeochemical processes in such short time frame (Figure 6b). In contrast, an
increase of CHD formation ocurred after sunlight exposure as shown in Figure
6c, which is consistent with the previous studies (15).
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Figure 6. Specific formation potential of THMs (a), HANs (b), and CHD (c) of
the leachate extracted from unburned and burned detritus under 15-days dark
and sunlight incubation; average ± standard deviation; n = 3.
Implications
Quantities of forest detritus, WEOC, WETN, and DBPs expressed per unit
area in unburned and burned forest floor were summarized in Table 2. Prescribed
fire consumed and oxidized detritus materials, reducing significantly (p = 0.009)
the biomass per unit area (~ 65% reduction). In addition, WEOC and WETN
productions per unit biomass also reduced. Unburned detritus yielded 17 ± 2
g-WEOC/kg-detritus and 0.6 ± 0.2 g-WETN/kg-detritus, whereas burned detritus
produced 9 ± 4 g-WEOC/kg-detritus and 0.4 ± 0.1 g-WETN/kg-detritus. Therefore
there was a 81 and 74% reductions on WEOC and WETN per unit area, also
resulting in a significant decrease in DBP yield per unit area. As summarized
in Table 1, THM, HAN, and CHD yields were decreased in 87, 71, and 81%,
respectively.
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Table 2. Yields of Detritus, WEOC, WETN, and DBPs before and after
Prescribed Burn in the Experimental Plots
Before burn After burn Reduction (%) P value
Detritus (kg/m2) 3.5 ± 0.7 1.1 ± 0.4 65 0.009
WEOC (g/m2) 60.3 ± 20.8 11.4 ± 8.5 81 0.01
WETN (g/m2) 1.9 ± 0.6 0.5 ± 0.4 74 0.06
THM (mg/m2) 3651 ± 682 484 ± 385 87 0.001
HAN (mg/m2) 79 ± 6 23 ± 12 71 0.01
CHD (mg/m2) 238 ± 56 46 ± 36 81 0.01
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Both the controlled laboratory in Part I and controlled field studies in Part II
(this chapter) demonstrated that prescribed forest fire could reduce DOM and DBP
precursors in the detritus layers of forested watersheds in the southeastern US.
Although our controlled laboratory study suggested DOM from burned materials
could have a higher reactivity in forming N-DBPs during chlorination, significant
loss in biomass and a reduction of extractability still result an overall reduction of
DBP yield per unit area in a forested watershed. The results suggest that prescribed
fire could be an effective watershed management controlling DBP precursors in
source water.
Acknowledgments
Portions of this study were also supported by NIFA/USDA under project
number SC1700489 and SCN-2013-02784, Joint Fire Science Program
14-1-06-19, and NSF Rapid grant 1264579 as presented in technical contribution
number 6358 of the Clemson University Experiment Station.
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26. Chow, A. T.; Gao, S.; Dahlgren, R. A. Physical and chemical fraction of
dissolved organic matter and trihalomethane precursors: a review. J. Water
Supply: Res. Technol.−AQUA 2005, 54, 475–507.
27. Xie, Y. Disinfection Byproducts in Drinking Water: Formation, Analysis and
Control; Lewis Publishers: Boca Raton, FL. 2004.
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Chapter 17
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1. Introduction
Water resource shortages and growing water demands have spurred utilities to
exploit the source waters impacted by wastewater effluents and/or algal blooming.
Such source waters are typically characterized by a higher level of dissolved
organic nitrogen (DON). During chlorination or chloramination, the N-containing
organic matters in water can react with the disinfectant to form halogenated
nitrogenous disinfection by-products (N-DBPs), such as haloacetamides
(HAcAms), halonitromethanes (HNMs) and haloacetonitriles (HANs) (1), which
represent an emerging concern due to their cytotoxicity and genotoxicity (2–4).
In particular, HAcAms, an emerging class of halogenated N-DBPs that have been
found in tap waters (5), exhibited much higher genotoxicity and cytotoxicity
than many carbonaceous DBPs (C-DBPs) (e.g., trihalomethanes [THMs] and
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2. Pilot-Plant Process Flow
The water samples used was collected from Lake Taihu, the third largest
freshwater lake in China. Lake Taihu is a major potable water source of many
cities and towns in Eastern China including Shanghai, Suzhou, and Wuxi. In
recent years, the combined effects of nutrient enrichment and industrial pollution
frequently degrade the water quality of Lake Taihu, and cause a fouling smell in
the finished water from conventional treatment facilities. This pushes local WTPs
to employ pre-treatment processes and O3-BAC advanced process for further
improvement of water quality. To test the additional treatments, a pilot plant (1
m3/h) was established in a conventional drinking water treatment plant (DWTP)
near Lake Taihu. A flowchart of the pilot plant process is shown in Figure 1.
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2.1. Pretreatment
(i) PAC adsorption: 20 mg/L PAC was dosed to a raw water tank from a
hydrated PAC tank by a metering pump. The PAC was mixed in the raw water tank,
and was continuously transported to a coagulation tank (three-stage flocculation
plant). (ii) KMnO4 oxidation: 1.0 mg/L KMnO4 was added to the raw water tank.
The dosages of PAC and KMnO4 were selected based on our previous results of
jar tests and economic considerations. (iii) BCO: The BCO reactor was composed
of three flow-through columns (3.0 m length, 0.38 m diameter, 0.15 m elevation
difference and 2 h residence time), as shown in Figure 2. In these columns, the filler
vinylon silk was fixed firmly on plastic rings, and distributed evenly in the water,
providing the sites for biological films. The raw water and air were pumped into
the column bottom (gas-water ratio = 1:2), and the treated water overflowed from
the top of column. Before the BCO treatment, one month was required to allow
formation of the biomembrane by seeding Lake Taihu raw water. After biofilm
colonization, plentiful brown biological films were found in the filler, and the
removal rates of NH4+-N-N and DOC in the BCO reactors ranged within 75–85%
and 30–40%, respectively. The influent to the BCO reactor was from the raw water
tank and the effluent of the BCO reactor was transported to the ensuing coagulation
tank (three-stage flocculation plant) continuously (17).
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Figure 2. The pilot plant of BCO process (1- Influent pipe; 2- Effluent pipe; Air
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inflow pipe; 4- Discharge pipe; 5- Filler; 6- Water and air distributing device).
In most cases, disinfection was carried out by adding 5 mg/L of chlorine (as
Cl2) to the intake of a clean water tank using a metering pump. The clean water
tank was mixed intensively by mechanical agitation. The disinfectant residuals
were quenched with ascorbic acid, and glacial acetic acid was injected to achieve
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pH 5.0 ± 0.2 for the subsequent N-DBPs analysis (17–19). The DBP formation
potential (FP) test was conducted with 48 h of sample collection and involved
chlorination for a further 24 h using free chlorine, as described in detail in previous
papers (14).
3. Pretreatment Processes
3.1. Water Parameters
There were not any significant difference (p=0.42, 0.27, 0.55, corresponding
to BCO, PAC adsorption, KMnO4 oxidation, respectively) on the removal of
turbidity among the three pre-treatment processes coupled with subsequent
conventional treatment process. The removal effect of turbidity in the filtered
water by the three different pretreatment processes (<0.5 NTU) was all better
than that by conventional treatment process alone (approx 0.8 NTU). Moreover,
the algae removal by the three different pretreatment processes was also all
significantly better than the conventional treatment process alone; the PAC
adsorption, KMnO4 oxidation and BCO processes increased the average algal
removal efficiency of the subsequent conventional treatment process from 90% to
97.5%, 98.2% and 99.6%, respectively. These findings confirmed that the three
pretreatment process flows were operated as designed and expected. Additionally,
compared with the PAC adsorption (<10%) and KMnO4 oxidation (<20%), the
BCO pretreatment process achieved a dramatically higher overall removal rate
of NH4+-N (> 60%).
From Table 1, PAC adsorption and KMnO4 oxidation enhanced the average
DON removal rate of the conventional water treatment process from 34.0% to
45.6% and 42.6% (Table 1). However, the BCO pretreatment process increased
the DON concentration of the raw water by 5.1%, likely because the BCO
process produced numerous metabolic by-products in the form of nitrogenous
organic matters. It is known that a range of soluble microbial products (SMPs)
are produced by microorganisms in the BCO process and can be found in BCO
effluent (20). SMP is a pool of complex organic matters including many DON
compounds such as proteins, nucleic acids and amino acids (21–23).
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Table 1. DON Removal in Different Treatment Trains
DON SUVA
Treatment DON accumulative removal rate (%)
(mg/L) (L/(mg·m))
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trains
a b c d a b c d a b c d
A 0.53 - 0.41 0.35 0.0 - 22.6 34.0 2.46 - 2.23 2.09
B 0.57 0.49 0.37 0.31 0.0 14.0 35.1 45.6 2.45 1.75 1.45 1.59
C 0.61 0.52 0.39 0.35 0.0 14.8 36.1 42.6 2.48 1.94 1.98 1.66
D 0.59 0.62 0.53 0.51 0.0 -5.1 10.2 13.6 2.29 1.96 1.82 1.68
Sampling point: a: Original Lake Taihu raw water; b: After pretreatment; c: After coagulation-sedimentation; d: After filtration. Treatment trains: A:
Conventional water treatment process only; B: PAC adsorption + conventional water treatment process; C: KMnO4 oxidation + conventional water treatment
process; D: BCO + conventional water treatment process.
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Figure 3. Fluorescence EEM spectra of Lake Taihu water. (TLW DOC = 4.2
mg/L, pH = 7.0, T = 23 °C) A: Original raw water; B: After BCO pretreatment;
C: After coagulation-sedimentation; D: After filtration.
EEM spectra were used to characterize the Lake Taihu water natural organic
matters (NOM), as shown in Figure 3. According to the fluorescence regional
integration (FRI) method developed by Chen and colleagues (21), the EEM spectra
were operationally summarized into five regions: five regions in the EEM spectra
based on the fluorescence of model compounds: aromatic proteins (regions I and
II, λex < 250 nm, λem < 380 nm), fulvic acid-like (region III, λex < 250 nm, λem >
380 nm), SMP-like, including tyrosine-, tryptophan-, and protein-like components
(region IV, λex > 250 nm, λem < 380 nm), and humic acid-like (region V, λex >
250 nm, λem > 380 nm) regions.
As shown in Figure 3A, NOM in raw water had its intensest peak (496 mV)
and second highest peak (214 mV) in the humic region. However, when the raw
water was pretreated by the BCO process, the NOM showed the intensest peak
(804 mV) at Ex/Em of 275/320 nm, which fell within the SMP-like region (λex
> 250 nm, λem < 380 nm), and the second-highest peak (771 mV) at Ex/Em of
240/335 nm within the aromatic protein region (λex < 250 nm, λem < 380 nm)
(Figure 3B). This confirmed previous speculation that SMP containing numerous
DON compounds possibly weakens the DON removal performance of the BCO
process. Moreover, SMPs cannot be removed completely by conventional
treatment processes (coagulation-sedimentation-filtration) as shown in Figure
3(C) and (D).
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3.2. DBPs
CF and DCAN were the most abundant species in most of the water samples
(i.e. there were relatively few brominated analogues) (24). In addition, TCAN and
TCAcAm concentrations in most of the water samples were below our detection
limits. Therefore, the study mainly focused on the chlorinated DBPs (CF,
DCAN, DCAcAm, and TCNM). The concentrations of CF, DCAN, DCAcAm
and TCNM measured after different pretreatment processes (PAC adsorption,
KMnO4 oxidation and BCO) and subsequent conventional treatment processes
are summarized in Figure 4.
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The FPs of CF, DCAN, DCAcAm and TCNM in different stages of the
water treatment trains were investigated (Figure 5). From Figure 5 (A), the
mean FP removal rate of CF (65.7%) by conventional water treatment processes
alone was higher than that of DCAN (50.2%), DCAcAm (24.7%) and TCNM
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(57.0%), implying that the precursors of DCAN, DCAcAm and TCNM were
more recalcitrant than CF precursors by conventional water treatment processes
alone, especially for DCAcAm precursors.
Figure 5. The FPs of CF, DCAN, DCAcAm and TCNM in different stages of
the water treatment process (DBP FPs of original raw water were defined as
100%). A: Conventional water treatment process only; B: PAC adsorption +
conventional water treatment process; C: KMnO4 oxidation + conventional water
treatment process; D: BCO + conventional water treatment process. a: Original
raw water; b After BCO pretreatment; c: After coagulation-sedimentation; d:
After filtration. The error bars represent the standard deviation of replicate
measurements (n = 3).
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From Figure 5 (B) and (C), it can be seen that PAC adsorption can effectively
remove the precursors of CF (42.7%), DCAN (28.6%), DCAcAm (27.2%)
and TCNM (35.7%), which were greater than the mean removal rate of the
precursors of CF (14.0%), DCAN (24.5%), DCAcAm (19.8%) and TCNM
(15.6%) pre-treated by KMnO4 oxidation. As shown in Table 1, the SUVA of raw
water declined to below 2 L/mg·m after PAC adsorption and/or KMnO4 oxidation.
At SUVA < 2 L/mg·m, the organic matter was mostly comprised of non-humics
and was of low hydrophobicity (25), indicating that humics and hydrophobic
organic matter were absorbed by PAC or oxidized by KMnO4. This suggests that
these humics and hydrophobic organic matters, which probably were a significant
part of the THM precursors (26).
From Figure 5 (D), the mean FPs of N-DBPs (DCAN: 120%; DCAcAm:
116%; TCNM: 104%) of pre-treated water by the BCO process were noticeably
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higher than that (100%) of the raw water before the BCO process. As discussed
above, numerous metabolic by-products produced by the BCO process raised the
DON level, believed to be the main N-DBP precursor, which probably caused
the observed increase of N-DBP FPs. Figure 6 displays good linear relationships
between the DON concentration and the three N-DBPs (DCAN: R2 = 0.82; TCNM:
R2 = 0.69; DCAcAm: R2 = 0.83) in the DBP FP tests of BCO pretreatment and
conventional treatment processes. This suggests that DON plays an important
role in the formation of DCAN, DCAcAm and TCNM, and the presence of DON
in source waters may act as a reasonable surrogate indicator of N-DBP FPs. In
addition, from Figure 6 (B), a linear relationship was observed between SMP peak
intensity and DCAcAm (R2 = 0.94), implying that the SMP produced in the BCO
process may be an important class of HAcAm precursors and caused the higher
concentrations and FPs of DCAcAm.
Figure 6. The relationships between N-DBP FPs and DON concentration, and
DCAcAm FP and fluorescence EEM SMP peak intensity in a typical run in
November 2008 (DBP FPs of original raw water were defined as 100%).
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4. Conventional Treatment (Coagulation-IPS-Filtration versus
Coagulation-DAF-Filtration)
4.1. Precursors
(47%) in the filtered water post-IPS were lower than post-DAF (UV254: 31%;
DOC: 53%). This phenomenon was probably linked to the SUVA of the water
(25). At SUVA < 2, the organic matter in the raw water was mostly comprised of
non-humics, and had low hydrophobicity and low MW, resulting in a poor DOC
removal. When SUVA in the raw water was close to 2, the similar organic matter
characteristics (low hydrophobicity and low molecular weight) in the raw water
likely caused a poor DOC removal by the coagulation-IPS-filtration (26).
Figure 7. MW distribution of raw water and filtered water after the two different
coagulation processes (IPS and DAF).
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Table 2. DOC, DON and UV254 in the Raw Water
DOC UV SUVA DON DON/DOC
Data (mg L-1) (cm -1) (L/(mg·m)) (mg L-1) mg/mg
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28th 4.82 3.07 2.53 0.085 0.065 0.061 1.76 0.73 6.6
4.2. C-DBPs
4.3. N-DBPs
The N-DBP concentrations in the water after chlorination following the
two different processes (IPS and DAF) are summarized in Figure 9. DCAcAm,
DCAN and TCNM ranged within 1.5–2.9, 3.5–6.3 and 0.5–1.0 ug/L, respectively,
in the water treated by coagulation–IPS-filtration–chlorination. Additionally,
in the water treated by coagulation–DAF-filtration–chlorination, DCAcAm,
DCAN and TCNM varied within 0.6–1.5, 2.7–4.7 and 0.4–0.9 ug/L, respectively.
Because the better removal in the entire MW range was achieved by the
coagulation-IPS-filtration process, fewer precursors remained to form further
DCAcAm and DCAN. The TCNM concentrations after the two processes were
similar, probably because the TCNM formation was influenced by DIN (30)
instead of DON.
In addition, the average concentrations of DCAcAm (2.3 ug/L) and DCAN
(5.0 ug/L) in the water treated by coagulation–IPS-filtration–chlorination were
higher than the average levels reported in a US N-DBP occurrence study (5). A low
DOC/DON usually indicates that microorganism (e.g. algae, bacteria) products are
a major fraction of the NOM (autochthonous) (8, 31, 32). In a survey of US plants
that were impacted by algae and/or treated wastewater (33), the average DOC/
DON ratio (13 mg/mg) of the surveyed waters confirmed that these sources were
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influenced by elevated levels of DON compared to a previous US study (34), where
the average DOC/DON ratio in a broader array of surface waters was 18 mg/mg. In
the studied raw water (Table 2), DOC/DON was 4.9 to 9.5 mg/mg, with an average
value of 7.3 mg/mg, indicating the Lake Taihu raw water was relatively organic
nitrogen rich, which possibly caused relative higher DCAcAm and DCAN yields.
We also found a linear relationship (R2 = 0.83) between DCAcAm and DCAN.
This is probably because DCAcAm is a main hydrolysis product of DCAN, and
the two N-DBPs share similar precursors and/or mechanisms of formation (7, 35).
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Figure 10. Removal rates of water quality parameters (Figure 10a: turbidity,
DOC, and UV254; Figure 10b: DON and DIN) in different stages of the water
treatment process. (From Figure1, Sampling 1, 2, 3, 4 and 5 represented the
water samples collected from the raw water; after coagulation-sedimentation,
filtration, O3 and BAC processes, respectively.)
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Figure 11. Removal of DON by the BAC process with and without pre-ozonation.
(The removal rates were calculated based on the DON concentrations of
raw waters; The error bars represent the standard deviation of replicate
measurements (n = 3).)
The average removal rate of DON by the conventional process reached only
35.1%, while the post combined O3-BAC process increased its removal efficiency
to 73.7%. In addition, we compared the difference in the DON removal by
BAC with and without pre-ozonation (Figure 11). It was found that only 21.3%
of DON was removed by the BAC process without pre-ozonation, which was
lower than that achieved with pre-ozonation (28.1%). This is likely because
ozonation degrades large molecules of DON compounds into smaller ones and
hence increases the biodegradability of DON.
5.2. DBPs
From Figure 12, the removal rates of the FPs for CF and DCAN both gradually
increased throughout the treatment train. The coagulation-sedimentation-filtration
process removed 52.7% and 49.9% of the precursors for CF and DCAN,
respectively, and O3-BAC combined process further enhanced the precursor
removal efficiency of CF and DCAN to 85.0% and 80.4%, separately. The effect
of O3-BAC is in agreement with the previous observations that ozonation and
BAC substantially reduce the formation of CF and appear not to be significantly
affected by source water quality (36–38). Additionally, the conventional process
(coagulation-sedimentation-filtration) and advanced treatment process (O3-BAC)
both had higher removal rates for the FPs of CF and DCAN than of TCNM and
DCAcAm. A plausible reason is that dissolved humic material, including a major
fraction of the total organic matter in freshwaters (40), is the major precursor
of CF and DCAN but makes little contribution to the formation of TCNM and
DCAcAm (7, 41). Also, hydrophilic organic matters with low-MW trend to form
more TCNM and DCAcAm, and it is more difficult to remove these substances
than humic material with high-MW (16, 42).
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Figure 12. Removal rates of the FPs of CF, DCAN, TCNM and DCAcAm
in different stages of the water treatment process. (Sampling 1, 2, 3,
4 and 5 represented the water samples collected from raw water; after
coagulation-sedimentation, filtration, O3 and BAC processes, respectively, as
shown in Figure 1, The removal rates were calculated based on the DBP FPs
of raw waters; The error bars represent the standard deviation of replicate
measurements (n = 3).)
Figure 13. Removal of TCNMFP by the BAC process with and without
pre-ozonation. (The error bars represent the standard deviation of replicate
measurements (n = 3).)
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From Figure 13, it is would be noted that the conventional process could
not effectively remove the precursors of TCNM, and the mean removal rates of
TCNMFP decreased from 18% in filtrated water to -187.5% in ozonated water,
but increased to 49.6% after the subsequent BAC process. After ozonation, 46%
of DON was reduced relative to the raw water (Figure 10), but TCNMFP increased
from 2.7 to 7.4 ug/L. This was probably because the ozone-induced oxidation
increased the content of highly reactive specific organic compounds with high
HNMFP (43), even though the overall DON was reduced. The performance of
the BAC process in terms of controlling TCNM formation either with or without
pre-ozonation was also examined (Figure 13). The TCNMFP removal efficiency
accomplished by BAC without ozonation pre-treatment was only 38%, less than
50% achieved by the combined O3–BAC. Thus, although ozone increased the
TCNMFP, it enhanced the biodegradability of the organics responsible for HNMFP
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Figure 14. UV/vis optical spectrums of water samples in different stages of the
water treatment process. (From Figure 1, Sampling 1, 3, 4 and 5 represent the
raw water; after coagulation-sedimentation-filtration, after O3 and after the
BAC processes, respectively.)
Two O3-BAC processes were operated in parallel (Figure 16) and initially
achieved the same removal of DOC and DON and the same concentrations of
C- and N-DBPs upon subsequent chlorination. Thereafter, ozone dosing was
terminated in the second day after backwashing for one of the two O3-BAC
processes, which is represented as ‘T-O3-BAC’ in the study. And the other
O3-BAC process was operated still with continuous ozonation before BAC
filtration, which is represented as ‘C-O3-BAC’. The performance of C-O3-BAC
and T-O3-BAC was compared in terms of water quality in the effluents of sand
filtration and BAC filtration in the second, third and fourth day after BAC
backwashing. The removal rate of each parameter by C-O3-BAC or T-O3-BAC
process is presented by equation (1).
Figure 17. The removal of DOC, DON, C-DBPs and N-DBPs. (a and b Show
the removal by the C–O3–BAC and T–O3–BAC in first backwash cycle after
terminating ozone dosing, respectively; c and d show the removal by the
C–O3–BAC and T–O3–BAC in the second backwash cycle after terminating ozone
dosing, respectively; e and f show the removal by the C–O3–BAC and T–O3–BAC
in the fifth backwash cycle after terminating ozone dosing, respectively. The
removal is the average value of the samples collected three times on the second,
third and fourth day after BAC backwashing. The error bars represent the
standard deviation of three removal values.)
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Figure 18. The relationship between DOC removal and C-DBP (CF, DCAA, and
TCAA) formation potential (FP) removal by the BAC process.
Figure 19. The relationship between DON removal and N-DBP (HANs
[DCAN and TCAN], HNMs [DCNM and TCNM], and HAcAms [DCAcAm and
TCAcAm]) formation potential (FP) removal by the two BAC processes.
Figure 21. Fluorescence EEM spectra of Lake Taihu water treated by sand
filtration, ozonation, and BAC filtration in the first backwash cycle. (SF: treated
by sand filtration; O3: treated by ozonation; C-O3-BAC: treated by C-O3-BAC;
T-O3-BAC: treated by T-O3-BAC.)
EEM spectra were used to characterize the DOM in effluents of sand filtration,
C-O3-BAC filtration and T-O3-BAC filtration, as shown in Figure 21. As shown,
DOM in the sand-filtered water (Figure 21 A), ozonated water (Figure 21B), and
BAC-filtered water (Figure 21C and D) all had two intense peaks in the SMP
region (λex > 250 nm, λem < 380 nm) and aromatic protein (AP)-like region (λex <
250 nm, λem < 380 nm), and the fluorescence intensities of the two peaks (SMP
and AP) in sand-filtered water was reduced by C-O3-BAC filtration from 553
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and 362 a.u. to 246 and 77 a.u.. Previous studies (14) reported that SMP-like
and AP-like substances, containing elevated organic nitrogen, were the important
precursors of N-DBPs (HANs and HAcAms). The results for the removal of
HAN and HAcAm formation yields (Figure 17) and the variation in SMP-like
and AP-like peak intensities in EEM spectra (Figure 21 A, B and C) suggest that
the C-O3-BAC process is able to reduce the precursors of these N-DBPs, which
supports earlier evidence of this (19). However, from Figure 21D, it was noted that
the fluorescence intensities of SMP and AP peaks in the effluent of T-O3-BAC
filtration actually increased to 649 and 357 mV, which mirrored the increase of
HAN and HAcAm concentrations.
5. Conclusion
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Acknowledgments
The authors gratefully acknowledge the National Natural Science Foundation
of China (51108327, 51378366), and the National Major Science and Technology
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Abbreviations
Bromochloroacetonitrile –BCAN; Biological contact oxidation
–BCO; Carbonaceous disinfection by-products –C-DBPs; Chloroform
–CF; Dibromoacetonitrile –DBAN; Disinfection by-products –DBPs;
Dichloroacetamide –DCAcAm; Dichloroacetonitrile –DCAN; Dissolved
inorganic nitrogen –DIN; Dissolved organic carbon –DOC; Dissolved organic
nitrogen –DON; Drinking water treatment plant –DWTP; Excitation-emission
matrix –EEM; Gas chromatograph/mass spectrometry –GC/MS; Fluorescence
regional integration –FRI; Haloacetic acids –HAAs; Haloacetamides –HAcAms;
Haloacetonitriles –HANs; Halonitromethanes –HNMs; Nitrogenous disinfection
by-products –N-DBPs; N-nitrosodimethylamine –NDMA; Natural organic
matter –NOM; Powdered activated carbon –PAC; Soluble microbial product
–SMP; Specific ultraviolet absorption –SUVA; Trichloroacetamide –TCAcAm;
Trichloroacetonitrile –TCAN; Trichloronitromethane –TCNM; Trihalomethanes
–THMs; Total dissolved nitrogen –TDN; Total organic halogen –TOX.
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Chapter 18
Introduction
Disinfection by-products (DBPs) in drinking water are known to vary within
distribution systems. Several factors may influence DBP variability, such as raw
water source characteristics, the treatment applied and some distribution system
characteristics (1–3). The variability of DBP levels within systems makes it
difficult to monitor these compounds.
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Past studies have investigated the spatial variability of DBPs, but focused
mainly on two prevalent families (trihalomethanes-THMs and haloacetic
acids-HAAs) presently regulated in most industrialized countries. However,
other non-regulated DBP families occurring at low levels in drinking water
are considered as potentially of greater health concern than THMs and HAAs
(4). These include, among others, haloacetonitriles (HANs), haloacetaldehydes
(HAs), haloketones (HKs), and halonitromethanes (HNMs). A number of
studies have focused specifically on the spatial variability of these DBPs within
distribution systems where water is disinfected with chlorine (5–10). In Williams
et al. (5) and Shin et al. (6), the spatial variability of DBPs within several systems
was investigated through comparisons with the levels measured in finished water
at the water treatment plant (WTP) and at only one site located in the system (in
the middle or at the extremity according to the study). In Golfinopoulos et al.
(7), finished water and a large number (eight) of sites were characterized within
one distribution system. However, the variation of DBP levels between these
sites was not really investigated. Koudjonou et al. (8) investigated the spatial
variability of DBP levels within systems by sampling the finished water and water
from three sites spatially distributed within each system, yet only one HA species
was investigated in this study. Guilherme and Rodriguez (9) considered three
sampling sites located in systems under study to investigate the spatial variability
of three DBP families. However, the presence of DBPs in finished water was
not measured. Moreover, it is important to note that in the above studies, the
impact on DBP levels of water flowing through a distribution system storage
tank (defined in this paper as the residence time added by the storage tank) was
not investigated. Mercier-Shanks et al. (10) focused on the spatial variability of
DBPs by sampling various sites spatially dispersed in one distribution system
(which is also studied in this chapter), including two sites located after a storage
tank with re-chlorination. In this study (10), the impact of water flowing through
the storage tank was only briefly discussed, only one system was investigated and
DBP families under study were limited (HANs, HKs and one HNM species).
In this chapter, the spatial variability within systems of non-regulated DBPs
(HANs, HAs, HKs, one HNM species and cyanogen chloride) was investigated
for four distribution systems where water was disinfected with chlorine. The
focus was on the impact, on these DBPs, of water flowing through distribution
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system storage tanks (where re-chlorination was applied). The variation of this
impact according to season was also investigated. Moreover, the evolution within
distribution systems of the relationship between the levels of regulated (THMs)
and non-regulated DBPs was estimated. To conclude, strategies were discussed
to control and survey these non-regulated DBPs within distribution systems for
monitoring or exposure assessment studies.
This study was carried out in four distribution systems located in the greater
Québec City area (Province of Quebec, Canada) supplying approximately 350,000
inhabitants. The main characteristics of these systems are presented in Table 1.
These systems are supplied by surface water and all apply chlorine as their primary
or secondary disinfectant. However, the type of surface water source (e.g., lake,
river), type and efficiency of treatment applied before secondary disinfection
(e.g., presence of ozonation or not), and distribution system characteristics (e.g.,
size, hydraulic regime, pipe characteristics) differ between the systems. Each
distribution system includes at least one storage tank with a re-chlorination point.
However, the re-chlorination strategy applied (injection location, dose) and water
residence time in the storage tank vary between the systems (Table 1).
The region under study is subject to important climatic variations during the
year, with mean daily temperatures of ambient air ranging from -16.8°C to +
24.2°C (11), and different lengths of seasons (i.e., long winters and relatively short
summers). These climatic variations can result in great temporal variations in raw
water quality.
Water Sampling
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Table 1. Description of the Four Distribution Systems under Study
Systems Water source Main treatment process Storage tank characteristics
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Post-chlorination
Dc St. Charles Lake PCTa; Post-ozonation; 130,000 ~ 3 to 5 days Entrance and outlet
Post-chlorination
aComplete physical-chemical treatment including sieving, coagulation-flocculation, sedimentation and filtration; b The location of the raw water intake is
different for systems A and B; c This system was studied previously by Mercier-Shanks et al. (10)
Analytical Procedure
As presented in Table 2, seven HA species (the sum represents HA7), four
HAN species (the sum represents HAN4), two HK species (the sum represents
HK2), CP, CNCl and four THM species (the sum represents THM4) were
analyzed. The analysis of HANs, HAs, HKs, CP, CNCl and THMs was conducted
in the Health Canada laboratory and described previously (12–14). Briefly,
liquid-liquid extraction was performed with MTBE containing internal standards.
The extracts were analyzed using a Varian 3800 gas chromatograph equipped
with dual electron capture detectors. Two chromatographic columns were used: a
DB-5 column (30 m x 0.32 mm id; film thickness 1 m) as the primary column, and
a DB-1 column (30 m x 0.32 mm id; film thickness 1 m) for confirmation (15).
The method detection limit (MDL) associated with each individual DBP under
study is presented in Table 2. Measurements below the MDL were considered as
equal to zero.
Measurements of FRC were conducted using the DPD titrimetric method
(Standard method 4500-Cl-F) with a DR-890 colorimeter from Hach. Water pH
was measured with a Denver instrument AP15 pH/mV/FET meter. Turbidity
was analyzed with a Hach 2100N Turbimeter. UV254 results were obtained by
UV/visible spectrometry at 254nm (Hach DR5000) with 5 cm optical path quartz
cells.
Data Analysis
In order to investigate the spatial variability of non-regulated DBP levels in
the systems under study and, specifically, the impact of water flowing through the
storage tank with re-chlorination, sampling sites were divided into three categories
according to their location in each system. The first category included the finished
water, for which samples were taken at the WTP (noted as “FW” in the tables
and figures). The second category included the sampling sites located within
the distribution system and directly supplied by the WTP, thus not supplied by
a storage tank (noted as “Sup/WTP” in the tables and figures). The third category
included only the sites supplied by a storage tank within the distribution system
(noted as “Sup/S.tank” in the tables and figures). Depending on the system, the
second and third categories might include one or two sampling sites.
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Table 2. DBPs under Study
DBPs Abbreviations MDL (µg/L)
HA7 (sum of the 7 HAs)
Dichloroacetaldehyde DCA 0.07
Trichloroacetaldehyde TCA 0.06
Bromochloroacetaldehyde BCA 0.05
Dibromoacetaldehyde DBA 0.05
Bromodichloroacetaldehyde BDCA 0.04
Chlorodibromoacetaldehyde CDBA 0.06
Tribromoacetaldehyde TBA 0.10
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Results and Discussion
DBP Occurrence in the Area under Study
The finished water quality data (at the WTP) for the four distribution systems
during the study period are presented in Table 3.
DBP levels measured in each distribution system during the period under
study are presented in Table 4. Irrespective of the system under study, the most
abundant DBP family among those analyzed was HAs. As previously observed by
Koudjonou et al. (8), statistically significant higher HA levels (significance level
ρ<0.05) were found in the three systems using ozonation in the treatment train
(i.e., systems A, C and D). Among HAs, TCA (also known as chloral hydrate)
was found to be the main species and represented, on average, 58% of HA7. TCA
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levels up to 24.65 µg/L were found in the distribution systems under study. DCA
and BDCA were also important HA species with a mean contribution to HA7 of
26% and 11%, respectively. BCA and CDBA were detected at very low levels
(with maximum values of 0.44 µg/L and 0.66 µg/L, respectively), while TBA and
BDA were not detected in these systems.
HKs were the second major DBP family detected among those evaluated
(Table 4) with HK2 levels ranging from 0.07 to 16.10 µg/L. TCP represented
60% to 100% of HK2 with levels varying between 0.07 and 15.02 µg/L. DCP was
measured at lower levels with a maximum value of 3.41 µg/L. The same order of
magnitude for HK levels was observed in the past for system D (10).
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Table 4. Mean DBP Levels (µg/L) Found in the Four Systems during the Study Period
Systems FW HA7 Sup/ FW HAN4 Sup/ FW HK2 Sup/
Sup/ S.Tank Sup/ S.Tank Sup/ S.Tank
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found in the past for system D (10). For CNCl, levels ranging from 0.07 to 3.84
µg/L were measured during the study period.
The mean HAN4 level tended to increase within systems at sites not supplied
by the storage tank (Table 4) with levels being 1.4 and 3.8 times higher than
the level measured at the WTP. However, this increase was only statistically
significant (ρ<0.05) for system D. The increase of HAN levels related to the
water residence time was observed previously in system D (10) and in other
studies (5, 6). The water flowing through the storage tank resulted in a mean
HAN4 level of, depending on the system, 1.6 to 4.9 times higher than the level
measured at the WTP (not statistically significant at level ρ<0.05 for system
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C). Mercier-Shanks et al. (10) highlighted an increase of HAN4 levels in water
flowing through the storage tank, but found a decrease of TCAN levels during
summer for system D. Differences in the mean HAN4 levels measured at sites
not supplied by the storage tank and those located after the storage tank were
only statistically significant (ρ<0.05) for system B. The absence of ozonation at
WTP in system B could partially explain the higher mean HAN4 level compared
to the other systems (18).
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As observed in previous studies (5, 6, 10), the mean CP level increased with
the water residence time (Table 4). The spatial variability was only statistically
significant (ρ<0.05) for systems A and D. Again, the absence of ozonation in
system B might partially explain the low formation and spatial variations of CP
within this system (19). For systems A and D, the impact of water flowing through
the storage tank on CP levels was relatively high with an increase of the mean level
(compared to the measured level at the WTP) of 9.0 and 3.8 times, respectively. It
is important to remember that CP was measured at very low levels in the systems
under study.
Contrary to the other DBP families, the mean level of CNCl decreased within
systems (Table 4) due to its decomposition (20). For system B, the mean CNCl
level appeared to increase at sites not supplied by the storage tank (not statistically
significant at level ρ<0.05) and to decrease (statistically significant at level ρ<0.05)
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at site supplied by the storage tank. In the other systems, a decrease of the mean
CNCl level was observed at sites not supplied by the storage tank (not statistically
significant at level ρ<0.05 for system A). This increase was relatively important
for systems C and D. Irrespective of the system, the mean CNCl level was lowest
(statistically significant at level ρ<0.05) after the storage tank.
Figure 2. Temporal variations of spatial distribution of HA7 levels for systems A, B, C and D. Sup/WTP-1 and Sup/WTP-2 represent the
individual sampling sites directly supplied by the WTP. Sup/S.Tank-1 and Sup/S.Tank-2 represent those supplied by the storage tank.
Figure 3. Temporal variations of spatial distribution of HK2 levels for systems A, B, C and D. Sup/WTP-1 and Sup/WTP-2 represent the
individual sampling sites directly supplied by the WTP. Sup/S.Tank-1 and Sup/S.Tank-2 represent those supplied by the storage tank.
Figure 4. Temporal variations of spatial distribution of HAN4 levels for systems A, B, C and D. Sup/WTP-1 and Sup/WTP-2 represent the
individual sampling sites directly supplied by the WTP. Sup/S.Tank-1 and Sup/S.Tank-2 represent those supplied by the storage tank.
Figure 5. Temporal variations of spatial distribution of CP levels for systems A, B, C and D. Sup/WTP-1 and Sup/WTP-2 represent the
individual sampling sites directly supplied by the WTP. Sup/S.Tank-1 and Sup/S.Tank-2 represent those supplied by the storage tank.
Figure 6. Temporal variations of spatial distribution of CNCl levels for systems A, B, C and D. Sup/WTP-1 and Sup/WTP-2 represent the
individual sampling sites directly supplied by the WTP. Sup/S.Tank-1 and Sup/S.Tank-2 represent those supplied by the storage tank.
This study highlights that non-regulated DBPs varied significantly within the
investigated systems. Except for CNCl, higher levels were generally measured
at sites located after the storage tank where chlorine was added. However, the
impact of water flowing through the storage tank, with a re-chlorination step, on
the level of the investigated DBP differed during the year and between systems.
This might be explained by the fact that several factors influence the formation
and degradation of DBPs after water flowing through a storage tank. One possible
factor is the water quality supplying the storage tank which, in turn, depends
on the quality of treated water from the WTP (e.g., pH, amount and nature of
natural organic matter, residual chlorine) and on the distribution conditions (e.g.,
water residence time, age and materials of pipes, presence of biofilm). The
hydraulic characteristics of the storage tank (on which the water residence time
is dependent) and the re-chlorination factors – chlorine dose and the injection
location in the storage tank (at the entrance or/and at the outlet) – also affect DBP
formation and degradation within and downstream of the storage tank. Storage
tank management strategies may include optimization to minimize DBP levels
within the distribution system. For this, further investigations focusing more
specifically on the study of storage tank impact on DBPs should be conducted
in order to compare water quality between the storage tank entrance and points
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located immediately before and after re-chlorination at different periods of the
year and with variable hydraulic regimes. Since storage tank characteristics
and management differ from one distribution system to another, generalizing
(for all systems) the impact of water flowing through a storage tank, where
re-chlorination is done, on DBPs is not recommended.
As observed for regulated DBPs (e.g., THMs and HAAs), the high spatial
variability of non-regulated DBP levels in distribution systems results in
difficulties in selecting sampling locations for regulatory monitoring, managing
issues and exposure assessment purposes. Except for CNCl, sites located after the
storage tank may be selected for future regulatory monitoring of the DBPs studied
in this chapter. Moreover, results suggest that sites where FRC concentration is
very low (particularly in summer) do not necessarily represent the best locations
for these regulatory survey purposes. In the case of exposure assessment studies,
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results presented in this chapter demonstrate that one sampling site for a system
is probably not sufficient to estimate the public’s exposure to these DBPs. This is
exacerbated by the fact that DBP levels vary, according to the season and system,
between sites supplied by the same water infrastructure (i.e., directly by the WTP
or by the storage tank). Results also showed that THM levels could be used as
a potential indicator of some non-regulated DBPs. However, the efficiency of
THMs as indicator for other DBPs tended to decrease after water flowing through
the storage tank where re-chlorination was applied.
Acknowledgments
The authors extend their gratitude to the Drinking Water Research Chair
of Université Laval (Quebec City, Canada) and its partners (NSERC, Cities of
Québec, Levis and Saint-Jérôme, Avensys Solutions, SNC-Lavalin, Association
pour la protection de l’environnement du lac Saint-Charles et des Marais du Nord
(APEL)). The authors are also grateful to Sabrina Simard, Sylvie Leduc, Sonia
Poulin and Annick Dion-Fortier for their laboratory technical support and to all
those who participated in the collection of samples.
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Chapter 19
Introduction
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Analytical Methods
CH was detected by a GC equipped with a ECD detector (GC-9720, Fuli,
China) according to a modified EPA method 551.1, with the method detection
limit (MDL) of 0.35 µg/L. Briefly, CH extraction was carried out for a 25ml
sample by applying 5g of NaCl and 3ml of MTBE, shaking for 1 minute on a
lab-dancer (IKA, Gemany), and then letting it stand for 20 minutes. The GC
column was initially set to be 60 °C for 3 minutes and then ramped up to 150°C
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with a 20°C/min rate, and maintained the temperature for 1 minute; the flowrate of
carrier gas (99.999% nitrogen in purity) was 2ml/min, and the temperature of ECD
detector was set at 280°C. Residual chlorine was analyzed by the DPD method
using a spectrophotometer (Hach 3900, USA) according to EPA 330.5. Chloride
was analyzed by an ion chromatography instrument (IC2010, Tosoh Inc., Japan)
with a MDL of 1 µg/L. Conductivity was recorded using an electrode (SX-650,
San-Xin Instrumentation, Inc., China), and pH was analyzed using an electrode
meter (pH100, Extech Instruments Corporation, USA). Dissolved organic carbon
(DOC) was assessed by a TOC analyzer (TOC-LCPH, Shimadzu, Japan) according
to the EPA 415.3 method.
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Apparatus
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Results and Discussion
CH Treatment by Reverse Osmosis
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Figure 1. Effects of a) operating pressure, b) pH, c) initial concentration, and d)
water type on CH removal by a domestic RO cartridge (working condition: 0.6
MPa, Co=20 µg/L, pH=7, ultrapure water).
The influence of initial concentration had not been evaluated before, despite
the fact that CH may exist in a wide range of concentration in DWTPs. In this study
we compared the effect of two initial concentrations on CH removal. The results
showed that there were no noticeable CH concentration differences in permeates,
indicating that RO efficiency is independent of initial CH concentration (Figure
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1c).
The presence of interfering compounds in tap and lake water, however, may
impose an adverse effect on CH removal. Figure 1d shows that CH removal was
lowered to 83% in lake water and such efficiency is less than those in ultrapure
(95%) and tap water (94%), suggesting that a competing phenomenon from
natural organic matter (NOM) may occur in raw water and treatment of NOM,
e.g., coagulation, is necessary in practice for RO to achieve better performance.
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Figure 2. The effects of flowrate (a), adsorption material, and water type (b) on
CH removal by domestic adsorptive cartridges (normal conditions: 1.5L/min,
Co=20 µg/L, pH=7).
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Boiling water with pot or kettle has been a traditional way in many countries
to inactivate pathogens or to make coffee and tea for daily life. Its roles and
mechanisms in DBP removal, however, are not yet well-known although it has
been proven robust in eliminating many types of DBPs (19, 20). For example,
the results of Wu et al. reported non-detectable CH level after 1-min boiling of
many types of waters originating from distilled water and tap water and in the
presence of hydrophobic acid and bromide (19), indicating a complete removal of
CH by the boiling process. Additionally, the results of Krasner et al. confirmed
such efficiency in real samples, either chlorinated or chloraminated, with >97% of
CH removals. These studies, however, did not consider the automatic switch-off
function of boilers commonly used by the public. Since a boiler stops heating
immediately, which often takes seconds, a more practical evaluation of the heating
process (i.e., <1 min) appears necessary. In order to avoid the interference of
concurrent formation of DBPs (19) during the transformation process of CH, this
test evaluated the boiling effect on CH removal from both ultrapure and tap water.
Figure 4 shows the effectiveness of a boiler on the CH removals for two
types of water. Notably, the efficiency of CH removal in tap water (with residual
chlorine of 0.15 ppm) is significantly higher than that in ultrapure water (no
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chlorine residual). Such phenomena were also observed in the microwave oven
heating process (Figure 5a). Along with an increasing ratio of tap water to
ultrapure water, the CH removal increased from 21% to 99%. In contrast, because
the addition of sodium chloride (at 1000ppm) added no benefit to CH removal, the
salinity of water is invalidated as an important factor in CH removal during the
heating process (Figure 5a). Early literature suggested that residual chlorine and
chloramine may facilitate the degradation of halogenated aldehydes (24) in water;
and the presence of bromide can facilitate removal of CH (19), more in-depth
study appears necessary to clarify this issue. In this context, we evaluated the
effectiveness of free chlorine on CH degradation at ambient room temperature
(Figure 6). Enhanced degradation of CH was observed with the increase of
residual chlorine concentration. Combined with the information reported from a
recent study that free chlorine can be more rapidly consumed in hot water than in
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Figure 5. The effects of water type (a), pH (b), and initial concentration (c) on
CH treatment by a domestic microwave oven (Co=20 µg/L, headspace open).
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Figure 7. CH (a) and temperature (b) changes during microwave heating process.
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Figure 8. Effects of stirring speed (a, Co=10 mg/L, half-full volume [125ml] in
conical flask, uncapped) and ultrasonication (b, Co=20 µg/L, 40kHz, 100ml
water, uncapped) on CH removal from water.
Conclusions
Overall, RO treatment and heating are two efficient and convenient POU
methods for CH control by the public in daily life.
Acknowledgments
The study is financially supported by the National Natural Science Foundation
of China (51278144), the Shenzhen Science & Technology R&D Funding
(JCYJ20120613150442560), and the Funding for Returned Oversea Chinese from
Shenzhen (KQCX20130627094615414). Thanks to the editors for organizing
this book, and to reviewers for providing valuable comments and advice.
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Chapter 20
Introduction
Swimming, as a physical activity for people of all ages, promotes fitness
and has many advantages over land-based activities. It is generally considered
as a health-enhancing and relatively injury-free activity; it can be a good aerobic
exercise, which contributes to flexibility and muscle strength, and can have
positive social aspects. Swimming pools can be found in different kinds and sizes
in public areas, hotels and spas, or at private residential homes. In the U.S., more
than 368 million pool visits occur each year. In Germany, around 250-300 million
pool visits occur each year, averaging 3 visits per capita. In the UK, one-third of
the children and around 36% of adults (>15 years of age) visit swimming pools at
undesirable substances (e.g., skin, hair, bodily excretions such as sweat, urine,
and saliva; pathogens; and personal care products such as lotions and sunscreens)
introduced by swimmers also complicate the toxicity and expose swimmers to
potential biological and chemical health risks (2, 3).
To conserve the positive aspects of aquatic activities, it is necessary to
disinfect swimming pool water to prevent outbreaks of infectious illnesses (4,
5). To date, chlorination is still the most common measure for inactivation of
microbial pathogens. Chlorine is added to swimming pools as chlorine gas,
calcium/sodium hypochlorite, or through electrolytic generation of sodium
hypochlorite. Regardless of the method of application, once the chlorine
is in the water it forms hypochlorous acid which dissociates into hydrogen
and hypochlorite ions. The sum of the concentrations of hypochlorous acid,
hypochlorite ion and aqueous chlorine is referred as free chlorine residual.
Chlorine’s popularity is not only due to lower cost, but also to its higher
oxidizing potential, which provides a minimum level of chlorine residual to
inhibit microbial recontamination. Other disinfectants may be used, but less is
known about their ability to inactivate pathogens (6). For effective disinfection,
adequate disinfectant levels are required. In Canada, regulations in Quebec
require free chlorine in swimming pools to be between 0.8 and 2.0 mg/L, while
the required minimum level for British Columbia varies with pH: 0.5 mg/L
for pH 7.4-7.8, and 1.0 mg/L for pH of greater than 7.8 (7). In the U.S., a
survey of twenty-three indoor pools showed that the median chlorine residual
was 3 mg/L (8). In practice, chlorine residuals of 2-4 mg/L are generally
recommended for chlorinated pools (9). However, the reaction of chlorine and
chloramines with organic and inorganic precursors, such as natural organic
matter (NOM), anthropogenic inputs, bromide, etc, may cause the formation of
undesirable disinfection by-products (DBPs). The types and concentrations of
DBPs depend on several factors, including the type and amount of disinfectant
used, characteristics of the swimming pool and pool water and users’ hygiene (1).
These DBPs can be inhaled or ingested by swimmers during swimming, bathing
and showering, or absorbed dermally (10), resulting in negative effects on human
health (11, 12). DBPs were observed to produce cancer in animal models and to
have other toxic consequences, such as reproductive and developmental effects;
in particular, users of chlorinated pools may have an elevated risk for bladder
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cancer (13) and an increased frequency of micronuclei in peripheral blood cells
(a marker of DNA damage) (14). These published epidemiology studies provide
evidences that disinfected pool water might be genotoxic and carcinogenic to
humans. Given the popularity of swimming that comes with the increased risk of
exposure to pathogenic microorganisms, disinfectants and DBPs, we are only in
the early stages of understanding swimming pool chemistry, human exposures,
and potential health risks (6). Regulations must also ensure that efforts to reduce
DBPs do not result in water that is impaired due to microbial contamination:
This is the microbe-DBP balancing act of minimizing risks while maximizing
beneficial effects.
Research has specifically focused on two classes of DBPs from chlorine-based
disinfection: trihalomethanes (THMs) and haloacetic acids (HAAs) (15–19).
THMs, including chloroform, bromodichloromethane, dibromochloromethane,
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and bromoform, are the best known and most intensively investigated class of
DBPs and they are regulated in chlorinated drinking water in the U.S. with a
maximum contaminant level at 80 µg/L. Reports on THMs in swimming pools
first appeared in 1980s, and they showed a tendency of wide variations in the
reported data. Fantuzzi et al. (20) found the THM levels ranged from 18 to 71
µg/L in five indoor swimming pools in Italy. Chu and Nieuwenhuijsen (21) found
the THM levels averaged at 133 µg/L in 44 indoor swimming pools in the UK.
HAAs, commonly referred as HAA6 including monochloroacetic acid (MCAA),
monobromoacetic acid (MBAA), dichloroacetic acid (DCAA), trichloroacetic
acid (TCAA), bromochloroacetic acid (BCAA), and dibromoacetic acid (DBAA),
are also regulated for drinking water in the U.S., with a maximum contaminant
level at 60 µg/L. There is limited information on HAA levels in swimming pools.
Tang (22) reported the HAA level stabilized at approximately 1650 µg/L in an
indoor swimming pool in the U.S.. Simard et al. (23) analyzed 15 indoor and 39
outdoor municipal public pools in Canada and found the HAAs were higher in
outdoor pools (808 vs 413 µg/L). Wang et al. (24) analyzed 5 outdoor pools in
the U.S. and 9 indoor pools in China and found that the HAA levels in the pools
in the U.S. averaged at 1440 µg/L while in China the levels averaged at 117 µg/L
due to lower chlorine residuals.
Some nitrogen-containing DBPs that were previously reported in drinking
water (25) are also identified in swimming pool water (26), due to the presence of
nitrogen sources, such as urine or sweat. Haloacetonitriles (HANs) were the most
significant toxic compounds detected by Hansen et al. (27), though they were
found at much lower concentrations compared to THMs and HAAs. However, it is
not known how much the HANs contribute to the overall mixture toxicity. The pH
plays an important role on DBP classes. For decreasing pH, THM concentrations
are observed to decrease, while HAN concentrations increased. Therefore
caution is warranted if the pH level in swimming pool water is lowered for THM
control, since the the concentration of more toxic HANs appear to increase.
Besides HANs, many other DBPs, including dichloromethylamine (CH3NCl2),
cyanogen chloride (CNCl), trichloronitromethane (TCNM), chloral hydrate
(CH), haloketones (HKs), N-nitrosodimethylamine (NDMA), chloramines
and cyanogen bromide (CNBr) have also been reported in swimming pools
(28, 29), though at much lower concentrations compared to the predominant
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THM and HAA species. To date, their complete chemical and toxicological
characterizations are not available.
In this chapter, we examine three key aspects related to swimming pool water.
Formation
DBP precursors lead to the formation of DBPs upon chlorination. Research
on DBP precursors in swimming pool water is of keen interest by scientists (30,
31). One option to ensure the safety of public drinking water systems is to improve
the quality of source water through pollution prevention and precursor removal.
However, a source reduction approach is challenging for swimming pools, because
the swimmers themselves are the largest source of organic/inorganic precursors
for DBP formation. The incidental anthropogenic contaminant release as a result
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Modeling
Models for DBP levels in swimming pool water are needed, aiming at
identifying the significance of diverse operational and water quality parameters
controlling the formation of DBPs or at investigating the kinetics for their
formation. It may consist of empirical and mechanistic relationships of water
quality and operational parameters with the prevailing levels of DBPs at various
stages of a same single pool. In this section, we discussed our research on
developing predictive models for DBPs based on data obtained from field and
laboratory-scaled studies.
Control
Swimming pool water treatment in general includes flocculation, sand
filtration, and subsequent disinfection with chlorine. The continuous chlorination
and input of anthropogenic releases by bathers in combination with recirculation
of the pool water may lead to an accumulation of DBPs in the water. Better
technologies are needed to solve this issue. In this section, we discussed our
research on potential technologies on DBP control from swimming pool water.
By giving an overview of our research efforts on the three topics in this
chapter, readers can better understand the profile of DBPs and their precursors in
swimming pool water.
Analysis of HAAs
For the analysis of HAAs, a modified version of the EPA 552.3 method was
used. Sulfuric acid, sodium sulfate, surrogate standard (2-bromobutanoic acid)
and methyl-tert-butyl ether (MtBE) was added to the samples which then were
hand shaked for two minutes to extract HAAs. The MtBE phase was transferred to
a test tube and acidified methanol was added. The samples were placed in a water
bath at 50°C for 2 h to methylate the HAAs and then back-extracted with sodium
sulfate solution to remove excess methanol. The MtBE phase was transferred to
a GC vial and analyzed by a GC (HP 6890 Series GC system, Hewlett Packard)
equipped with a DB-1701 capillary column (30 m × 0.25 mm i.d., 0.25 µm film
thickness). The temperature ramping program was as follows: Initial at 35°C for
10 minutes, ramp to 75°C at 5°C/min, hold for 16 minutes, ramp to 200°C at
25°C/min and hold for 5 minutes.
Formation
The Swimming Pool under Investigation
The DBP formation in a swimming pool was investigated. The pool, with a
volume of 440 m3, was located in Capitol Union Building at The Pennsylvania
State University, Middletown, Pennsylvania, USA. The pool was completely
drained, and refilled with fresh water in the second week of June in 2009. Since
then, the pool water was periodically sampled and analyzed for DBPs during a
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1.5-yr investigation period. During the operation of the swimming pool, water
was filtered and chlorinated through recirculation of the pool water. Some water
was lost during back-washing of the filters and by evaporation, therefore fresh
water was added to maintain a constant water level at a rate of approximately 1.8
m3 weekly. Some DBPs might be adsorbed to suspended solids in the pool and
removed with the filtration; however, for this study that process and the loss of
water through evaporation were neglected, since they account for a negligible
fraction of the pool water. The pool was open year-around to students, faculty and
staff of the university, members, and guests, i.e. walk-ins of the local community.
Table 2 shows the year-around user statistics of the swimming pool. These data
show that the pool accepted 1441 users per month or 48 users per day on average.
As the typical pool hours were from 9 am to 9 pm in work days except national
holidays, the pool accepted an average of 4 users per hour.
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levels in the pool and the numbers of pool users, and the R2 value was 0.70.
Figure 1. THM and HAA levels in an indoor swimming pool after water change.
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Figure 2. Correlation between the measured HAAs and the numbers of pool users.
The predominant species of HAAs, THMs, HANs, and HKs in the swimming
pool water were DCAA and TCAA, TCM, DCAN, and TCP, respectively. Table 3
shows their concentrations in the pool water during the 1.5-yr investigation period
since water change. DCAA was found to be in a higher concentration than TCAA.
Because DCAA and TCAA are believed to be produced as a result of different
mechanistic pathways (36), the ratio of DCAA/TCAA implies that the formation
of DCAA is favoured in the swimming pool water, possibly due to the presence
of more precursors for DCAA in pool water. HANs and HKs in swimming pools
were investigated by fewer studies than those of THMs and HAAs. Lee et al. (37)
reported DCAN in the chlorinated pools as 3.9 ± 3.3 µg/L, while TCAN was not
reported. In this research, the DCAN in the swimming pool water was 1.3 ± 0.7 µg/
L. The HAN concentrations were much lower than THM and HAA concentrations,
possibly due to their decomposition to form HAAs at pH conditions higher than
7.0 (27). As the DBP formation is also attributable to precursors for DBPs, the
profiles of individual species need to be reviewed to explore the contribution from
their precursors.
Table 4 shows the DBPFPs of the anthropogenic input samples. All the
anthropogenic contaminants were found to contribute to the DBP formation,
which was consistent with the results reported by Kim et al. (39). The HAA
yields of chlorinated sweat, saliva, skin wash, hair wash, and urine samples were
300, 390, 380, 160, and 160 µg/mg C, respectively, while the THM yields of the
corresponding samples were 67, 130, 96, 50, and 74 µg/mg C, respectively. The
relative abundance of HAAs and THMs was presented by the ratio of HAA/THM.
These anthropogenic contaminants contributed to more HAAs than THMs, with
the HAA/THM ratio in the range of 2.1 and 4.5. It is noted that urine had the
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lowest HAA/THM ratio of the 5 contaminants. For the 3-day Cl2 demand per
DOC, Kanan and Karanfil (8) reported 2-8 mg/L Cl2 demand for 1 mg DOC of
filling water NOM and 17-25 mg/L Cl2 demand for 1 mg DOC of body fluid
analogue. A slight higher number, 21-40 mg/L Cl2 demand for 1 mg DOC of real
anthropogenic contaminants, was found in this research. Table 4 also presents the
yields of HAAs and THMs by normalizing HAAFP and THMFP based on DOC,
to compare different anthropogenic contaminants regardless of their dilution
ratios. Sweat was observed to have an HAA yield of 300 µg/mg C. Urine and
hair were observed to have relatively low HAA yields (160 µg/mg C) compared
to three other anthropogenic contaminants. The THM yields of sweat and urine
were 67 and 74 µg/mg C, respectively. These DBP yield data will be used in the
later modeling section.
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Swimming pool water is found to have high DBP levels, especially in forms
of HAAs. THMs, however, did not show an increase trend with water age but were
relatively constant in the pool water. We have summarized four factors that lead
to this specific DBP profile in swimming pools:
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Firstly, the long water retention time in swimming pools is special. As the
pool water is continuously exposed to disinfectants, all DBP precursors have a
potential to be driven to DBPs. This tends to result in high DBP levels.
Secondly, continuous introduction of anthropogenic contaminants leads to
high DBP levels. With an R2 of 0.70, a positive correlation between the HAA
levels and the numbers of pool users exists (Figure 2).
Thirdly, discrepancies in the chemical loss rates could lead to the high HAA
but low THM profile. Benoit and Jackson (44) observed stable THM levels in 25
whirlpool spas affected by heat, aeration, and agitation. Although these factors,
i.e. the degree of water agitation by pool users, were difficult to measure, the
THM loss rate appeared to be faster than the HAA loss rate because of much higher
Henry’s law constants for THMs. The loss rate includes the effects of evaporation,
adsorption, degradation, and other incurred processes.
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Modeling
Model Development
Where
Ni = Number of pool users at Day i, persons;
YS = DBP yield for sweat, µg DBP/mg C;
CS = Sweat carbon released per person, mg C/person;
YU = DBP yield for urine, µg DBP/mg C;
CU = Urine carbon released per person, mg C/person;
V = Volume of the swimming pool, Liter.
It is noted that CS, CU, and k were difficult to measure and show
variances from one swimming pool to another. They need to be calibrated by
computer-based regression programs. Shuffled complex evolution (SCE), a
global optimization method developed by Duan et al. (49), was used to calibrate
these difficult-to-measure parameters of the swimming pool. The calibration
process used 48 (approximately 70%) of data sets (12 months × 4 classes of
DBPs) based on statistical requirements. The CS, CU, and k were assigned an
initial value, respectively, to start the calibration. If the values were perfect, there
would be an approximate prediction but not necessarily an exact match. To take
care of small discrepancies, small adjustments were made to these parameters
until the predicted data matches the measured ones. The SCE algorithm ensured
that the root mean squared value between the predicted data and the measured
ones was the lowest. The remaining 30% of data sets were used for validation.
The coefficient of determination (R2) was used to verify the regressions between
the predicted DBP data the measured ones in the pool water.
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Model Performance
The obtained parameters of the DBP model for the swimming pool after
calibration were as follows:
the measured ones. As shown in Figure 3a, with an R2 of 0.97, the predicted
data showed a good fit to the measured ones. The validation process used the
remaining 30% of data sets, and was still able to show a good fit to the measured
data, with an R2 of 0.96 (Figure 3b). Therefore, the model calibration led to sound
results for the coefficients of the swimming pool system.
Figure 4 presents the predicted profiles of HAAs and THMs in comparison to
the actual ones. The patterns were developed as a result of a combined effect of
DBP formation and loss rates as described in the previous section. The predicted
HAA curve captured the rising trends and descending trends very well. The
predicted THM pattern also gave a quantitatively correct range. Because of the
high loss rates, THM variations with water age were not as significant as those of
HAAs. An extraordinary THM observation of 181 µg/L at the 104th day could be
attributed to a peak hourly loading of swimmers during the sampling.
Figure 3. Calibration and validation results. (a) calibration based on 70% data;
(b) validation based on 30% data.
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Figure 4. Predicted DBP profiles as a function of water age. (a) HAAs; (b) THMs.
Model Implications
Computer-based modeling is a useful tool for a number of tasks performed
by water and wastewater professionals. Because of the high R2 values of both
calibration and validation, the DBP model developed based on mass balance
and first-order kinetics is competent to predict DBPs in swimming pools. The
model basically attributes the formation of DBPs to the continuous introduction
of anthropogenic contaminants or the number of pool users.
Anthropogenic inputs represent the major cause of high DBP levels in
swimming pool water. The model suggests 1000 mg carbon from sweat per
person and 480 mg carbon from urine per person were released to the pool
every day. According to Judd and Black (46), body fluids had a carbon content
of approximately 6000 mg/L. The model implies that each pool user released
approximately 170 mL sweat and 80 mL urine to the pool. These values were
in the range reported by Gunkel and Jessen (42) and Erdinger et al. (43), who
estimated that a swimmer introduces in water 25-80 mL/h of urine and 200-1000
mL/h of sweat. The model also presents an approach to estimate the DBP loss
coefficients. It is believed that water agitation affects the DBP levels in swimming
pool water. However, the degree of water agitation is difficult to measure.
According to the model, the HAA loss coefficient was 0.035 per day while the
THM loss coefficient was 0.23 per day in the investigated pool. Lower coefficient
implies longer half life and thus higher concentration.
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Control
Control Factors
DBPs in drinking water are typically controlled by limiting both the amount
of disinfectants and the amount of NOM. In swimming pool water, the DBP
formation may be limited by three factors: disinfectant residual, the amount of
organic material in the water, and the recirculation of the pool water (50).
The amount of chlorine entering the pool water can be easily controlled, as
the chlorine, in forms of granular powder or tablets, can be added by hand or
by a mechanical dosing system. Proper dosing ensures chlorine residual kept
at a minimum and still effectively eradicate pathogenic microorganisms, in the
meanwhile keeps DBP concentrations at low levels. This is the microbe-DBP
balancing act of minimizing risks while maximizing beneficial effects.
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Filtration
Typical swimming pool water treatment includes sand filtration and
disinfection with chlorine. Hansen et al. (27) reported a few swimming pools
in Denmark use drum filters based on a weaved microsieve (cutoff 10 or 20
µm) which removes the particles from the pool water fast by washing the filter.
Although most swimming pools remove particles through a filtration unit, the
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filtration units are not designed to remove organic matter. Control of DBPs
and their organic precursors using adsorbent, i.e. GAC, could be an effective
approach.
Two types of GAC were investigated in bench-scale filters: virgin GAC
supplied by Waterlink (USA) and biologically activated carbon (BAC) collected
at a local drinking water treatment facility. The schematic setup of the GAC
filters is depicted in Figure 5. Swimming pool water was directly added to the
filter columns loaded with 40 mL of GAC and the flow rates were adjusted to 2
mL/min to have an empty bed contact time (EBCT) of 20 minutes.
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The bench-scale GAC filter was operated for 400 hours. Results showed
that TCAA was completely removed during the beginning of the experiment and
the effluent concentration of DCAA steadily increased. Before the GAC column
reached saturation, biological degradation of DCAA was observed after 128 hours
of operation. This is shown in Figure 6 at the highest peak of the curve. At this
point, the total HAA was 566 µg/L, and there was 48% reduction in total HAAs, a
9% reduction in DCAA and 99% reduction in TCAA. The results imply that GAC
was effective in removing TCAA while the adsorption capacity for DCAA was
relatively low.
The bench-scale BAC filter was initially operated for 2 hours filtering
deionized water. Then it started filtering swimming pool water for 480 hours
at the same settings with the GAC filter. Since BAC has almost no adsorption
capacity, it became saturated almost immediately for TCAA (Figure 7). There
was approximately 90% removal of DCAA throughout the entire experiment.
Opposite to what was observed in the bench-scale GAC filter, this occurred
because the bacteria capable of degrading DCAA were already established on the
BAC. The TCAA degrading bacteria, however, took approximately 30 hours to
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be established, and then the TCAA concentration in the effluent rapidly decreased
throughout the experiment. In the end of the experiment, approximately 70% of
TCAA was removed.
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Figure 6. HAA removal from swimming pool water by a bench-scale GAC filter.
Figure 7. HAA removal from swimming pool water by a bench-scale BAC filter.
These experiments show that GAC is able to adsorb TCAA and BAC can
remove DCAA efficiently at the beginning. Once TCAA degrading bacteria
become established, BAC can efficiently remove HAAs from swimming pool
water and outperforms GAC. The study also implies that, given enough time,
bacteria capable of degrading HAAs will develop on the surface of GAC,
converting it to BAC and reducing the need to replace the GAC. A disadvantage
associated with both studies is that the filter effluent had zero chlorine residual.
This may lead to problems when used on an actual swimming pool, because the
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pool water needs to be continuously chlorinated to keep a residual typically in
a range of 2-4 mg/L. Elevated costs for the use of additional chlorine could be
expected.
Besides adsorption and biodegradation during the filtration process for DBP
control in swimming pool water, other filtration technologies, i.e. membrane,
zero-valent iron, etc, are also being investigated by scientists. Cost-effective HAA
removal technologies for swimming pool water represent a promising direction of
future research.
Conclusions
In this chapter, three key aspects related to swimming pool water were
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investigated:
Formation
We measured DBP formation in a swimming pool over a 1.5-yr period since
water change. We found the HAA levels could go very high in the swimming pool,
while THM levels remained relatively constant. By exploring the DBPFPs from
anthropogenic contaminants, we found the anthropogenic inputs to swimming
pools contributed to high HAAs and significantly impacted certain DBP species
in the water.
Modeling
The DBP profile in swimming pools can be modeled and predicted. The
DBP model was developed using the DBP data of the investigated swimming
pool and a computer-based derivatization method based on mass balance and
first-order kinetics. The predictive DBP model was competent to provide
quantitatively acceptable DBP data. The model attributes the formation of DBPs
to the continuous introduction of anthropogenic contaminants and the number of
pool users, which helps the interpretation of the special DBP profile in swimming
pool water.
Control
Of the three limiting factors to DBP formation in swimming pools, reducing
the input of anthropogenic contaminants is critical. With the purpose of reducing
DBP precursors and already-formed DBPs, filtration technologies using GAC and
BAC were investigated by bench-scale experiments. GAC adsorption and BAC
biodegradation were both found to be effective options on certain HAA species
removal.
Future research efforts should be focused on three aspects: (1) monitoring
and assessment of other emerging/remerging DBPs in swimming pools; (2) the
potential health impact of swimming pool exposure to high level HAAs; and (3)
cost-effective HAA removal technologies for swimming pools.
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Frimmel, F. H. Drowning in disinfection byproducts? Assessing swimming
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2. Florentin, A.; Hautemaniere, A.; Hartemann, P. Health effects of disinfection
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3. De Laat, J.; Feng, W.; Freyfer, D. A.; Dossier-Berne, F. Concentration levels
of urea in swimming pool water and reactivity of chlorine with urea. Water
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4. Friedman, M. S.; Roels, T.; Koehler, J. E.; Feldman, L.; Bibb, W. F.;
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GSTZ1, and CYP2E1, disinfection by-products, and risk of bladder cancer
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Fernandez, P.; DeMarini, D. M.; Grimalt, J. O.; Grummt, T.; Marcos, R.
Genotoxic effects in swimmers exposed to disinfection by-products in
swimming pools. Environ. Health Perspect. 2010, 118, 1531–1537.
15. Bessonneau, V.; Derbez, M.; Clement, M.; Thomas, O. Determinants of
chlorination by-products in indoor swimming pools. Int. J. Hyg. Environ.
Health 2011, 215, 76–85.
16. Cardador, M. J.; Gallego, M. Haloacetic acids in swimming pools: swimmer
and worker exposure. Environ. Sci. Technol. 2011, 45, 5783–5790.
17. Catto, C.; Sabrina, S.; Ginette, C. T.; Manuel, R.; Robert, T. Occurrence and
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29. Chowdhury, S.; Alhooshani, K.; Karanfil, T. Disinfection byproducts in
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30. Bond, T.; Goslan, E. H.; Parsons, S. A.; Jefferson, B. A critical review of
trihalomethane and haloacetic acid formation from natural organic matter
surrogates. Environmental Technology Reviews 2012, 1, 93–113.
31. Farre, M. J.; Day, S.; Neale, P. A.; Stalter, D.; Tang, J. Y. M.; Escher, B.
I. Bioanalytical and chemical assessment of the disinfection by-product
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32. Weng, S.; Blatchley, E. R., III Disinfection by-product dynamics in a
chlorinated, indoor swimming pool under conditions of heavy use: National
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waters: A simple mass balance. Water Res. 2000, 34, 1611–1619.
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Chapter 21
Introduction
The average swimmer releases several grams of body fluids (BFs) and
excretions during an average swim (1–3). The disinfection of this organic
and inorganic matter from swimming pool water is essential for deactivating
the pathogenic microorganisms that can thrive on the released organic matter.
Swimming pool water is continuously circulated, filtered, and disinfected to
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maintain clear and biologically safe (4). Chlorine is commonly used in swimming
pools and is added continuously to maintain free available chlorine (FAC) to
prevent microbial growth (5). While deactivating microorganisms, the reaction
of chlorine with the organic (e.g., hair, sweat, dead cells, saliva, cosmetics,
dust and urine) and inorganic (e.g., urea, nitrates, nitrites and free ammonia)
matter can form a wide array of DBPs including trihalomethanes (THMs),
haloacetic acids (HAAs), haloacetonitriles (HANs), haloacids, halodiacids,
iodo-THMs, haloaldehydes, halonitriles, haloketones (HKs), halonitromethanes
(HNMs), haloamides, haloalcohols, nitrosamines, combined available chlorine,
and 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and MX
homologues, etc. (6–11). Furthermore, bromide is introduced to when the pool
is being filled and/or as impurities when chlorine is generated electrochemically
from sodium chloride. Chlorine oxidizes bromide to HOBr that can react with
organic matter to produce brominated DBPs. Although there are currently no
federal DBP regulations in swimming pool waters in the U.S., some countries are
including THMs within the swimming pool regulations (12, 13).
The overall formation of DBPs is correlated to the amount of precursors such
as organic matter. It is also well known that temperature, pH, and chlorine dose
influence the formation of DBPs. Therefore, the formation of DBPs in pool waters
would be affected by the operation of the swimming pools. The pool operational
requirements and regulations in the U.S. are variable among different states
and enforced separately by each state department of health and environment.
Generally in the U.S., FAC should be maintained in the range of 1 to 5 mg/L in
the pool water to prevent microbial growth (5, 8, 14). The pH of swimming pool
water is continuously adjusted mainly to assure an acceptable level of disinfection
efficiency, comfortable water for swimmers, and elimination of the damage to
the swimming pool structures. Typically, the pH of the pool water is maintained
between 7.2 and 7.8 range (15). Swimming pool water temperature is maintained
constant usually within the range of 26 to 40˚C depending on pool type and usage.
Finally, the turnover period for the water in swimming pools typically ranges
from 4 to 8 hours (3, 5, 16). From a DBP formation perspective, the reaction
period corresponds to the time available for chlorine to react with precursors and
form DBPs before they are removed through the pool treatment processes. It is
well-known that DBPs including THMs and HAAs have fast formation kinetics
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at the levels of chlorine dose in drinking waters (17, 18). It is postulated that
DBPs will form very rapidly in swimming pools due to much higher free chlorine
residual concentrations than in drinking waters.
Although intensive work has been devoted to investigate the formation of
regulated THMs and HAAs in drinking waters, there is relatively little known
about the formation and occurrence of DBPs in swimming pools. Moreover,
the effects of swimming pool operational parameters on the formation and
speciation of DBPs in swimming pools have not been systematically investigated.
Understanding the effect of operational parameters is essential for developing
approaches to control the formation of DBPs in pools and reduce exposure of
swimmers and swimming pool attendants to DBPs. Furthermore, to date there
is no information regarding the DBP formation kinetics under swimming pool
conditions.
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The objectives of this study were to (i) investigate the occurrence of regulated
DBPs (THMs and HAAs), as well as emerging DBPs including HNMs, HANs, and
nitrosamines in 23 indoor swimming pools, (ii) examine the effects of different
swimming pool operational parameters such as FAC in pool water, pH, organic
carbon, temperature, bromide concentration on the formation and speciation of
THMs and HAAs and (iii) determine how fast THMs and HAAs are produced
under swimming pool conditions.
THM and HAA formation potential (FP) tests were conducted in the presence
of an excess disinfectant. Chlorine stock solutions (500–2,000 mg/L) were
prepared by diluting sodium hypochlorite (~5% available free chlorine). The
chlorination FP tests were performed in 125 mL amber bottles filled headspace
free with the sample and capped with Teflon-lined PTFE caps. After mixing for
five minutes with magnetic stir bars, the bottles were stored headspace free in a
water bath for 5 days at 26 or 40°C. For the kinetic experiments an initial dose
of 100 mg/L chlorine was used. Each solution was chlorinated, and DBPs were
determined at different reaction times during 5 days (e.g., 0.5, 1, 3, 5, 7, 10, 15,
24, 48, 72, 96, 120 hours).
Analytical Methods
Analytical methods used in the study and their respective minimum reporting
levels (MRLs) are provided in Table 1. Either standard methods (SM) or USEPA
methods were used for DBP analyses with minor modifications. The detailed
information about these methods can be found elsewhere (20–23). For TOC,
TN and DBP analyses, samples were analyzed in duplicates. Error bars in all
the graphs show the variability due to multiple analysis (n=2) under the same
conditions.
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Table 1. Analytical Methods and Minimum Reporting Levels
Parameter Unit Measurement Method Instrument MRL or Accuracya
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TOCb mg/L SM 5310B TOC-VCHS & TNM-1, Shimadzu Corp., Japan 0.1
TNc mg/L High Temperature Combustion TOC-VCHS & TNM-1, Shimadzu Corp., Japan 0.1
UV Absorbanced cm-1 SM 5910 DU 640, Beckman Inst. Inc., USA ±0.005d
Bromide μg/L US EPA Method 300 ED 40, Dionex Corp., USA 10
pH - SM 4500-H+ 420A, Orion Corp., USA ±0.01e
THMs & HANsf μg/L US EPA Method 551.1 6890 GC-ECD, Agilent, USA 1.0
HAAsg μg/L SM 6251 Bg 6890 GC- ECD, Agilent, USA 1.0
HNMsh μg/L US EPA Method 551.1 6850 GC-ECD, Agilent, USA 0.7
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was used to prepare external standards. c Reagent grade potassium nitrate was used to prepare external standards. d At wavelengths of 254 nm using a
1- or 5-cm cell. Photo-metric accuracy (absorbance units). e Accuracy (pH units). f THMs and HANs were extracted by liquid-liquid extraction with
methyl-tert butyl ether (MtBE) and analyzed by GC-μECD. g HAAs were extracted by liquid-liquid extraction with MtBE, derivatized with diazomethane
and analyzed by GC-μECD. h HNM were extracted by liquid-liquid extraction with MtBE and analyzed by GC-μECD. i Nitrosamines were extracted by
solid phase extraction, eluted with dichloromethane and analyzed by GC-MS. THM (Trihalomethanes), HAN (Haloacetonitriles), HAA (Haloacetic acids),
HNM (halonitromethanes), SM (Standard Methods), EPA (Environmental Protection Agency), GC (Gas Chromatography), MS (Mass Spectrometer), FAC
(Free Available Chlorine), NA (Not Applicable).
All of the indoor swimming pools selected in this study used chlorine as
disinfectant. Some of the sampled pools used calcium hypochlorite directly,
whereas others generated chlorine in situ electrochemically using sodium
chloride. Most of the pools were operated at an approximate temperature of
26°C and some at 34°C. Except for a single pool that used groundwater from a
local well, all the pools used the local water distribution system for both fill and
make-up water. Of the 23 pools under study, sand-filter filtration was used to
treat water, and micro-filter filtration used for the other two. The water samples
characteristics of all pools under study are shown in Table 2. The FAC in the
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pools was between <0.1 and 4.0 mg/L, and the pH, TOC and TN ranged between
7.2 to 7.8, 3 to 23.6 mg/L, and 0.8 to 12.3 mg/L, respectively. The TOC was
higher than TN except for four of the swimming pools in this study.
The occurrence ranges of the five classes of DBPs in the selected twenty three
indoor pools are shown in Figure 1. The concentration of each DBP class, along
with their speciation for each swimming pool is summarized in Table 3 and Table
4. In general, carbonaceous DBPs concentrations were higher than nitrogenous
DBPs. In this survey, the HAAs were the highest measured class of DBPs,
followed by the THMs>HANs>HNMs>nitrosamines. The median, maximum,
and minimum HAAs were 960, 9005, and 172 µg/L, respectively. Trichloroacetic
acid (TCAA) and dichloroacetic acid (DCAA) were the dominant species among
the measured HAAs. Bromochloroacetic acid (BCAA) and bromodichloroacetic
acid (BDCAA) were also detected in all samples although at much lower levels
compared to DCAA and TCAA. In some of the samples dibromoacetic acid
(DBAA) and bromoacetic acid (BAA) were detected at concentrations <6 and <25
µg/L, respectively. These exceptionally (compared to drinking water samples)
high values of HAAs are attributed to (i) nonvolatile and soluble nature of these
compounds resulting in accumulate in the pool waters provided that pool water
dilution is not common in U.S., and (ii).human body fluids that have been shown
to have a high formation potential of HAAs (7, 9).
The median, maximum, and minimum THMs measured in the pools were 63,
213 and 26 µg/L, respectively, with chloroform the major THM determined in all
pools. Although the brominated THM species were at low levels in most cases,
there were relatively high in pools that use sodium chloride to generate chlorine
electrochemically and in the pool that was filled with groundwater. In 43% of the
pools, the total THMs was equal to or higher than 80 µg/L (MCL in U.S. drinking
water), while in all the pools, the measured THM was greater than 20 µg/L (the
maximum allowed in some European countries for swimming pools).
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Table 2. Water Characteristics of the Selected Indoor Swimming Pools
Tem- Dis-
FAC
Swimming per- infe- Filter TOC TN
pH (mg-
Pool Code ature cta- Type (mg C/L) (mg N/L)
/L)
(°C) nt
S1 27 7.5 3.0 Cl2 Sand 4.3 1.4
S2C 18 7.4 3.0 Cl2 Sand 4.1 1.8
S2W 31 7.4 3.0 Cl2 Sand 11.3 4.7
S3S 29 7.4 1.4 Cl2 Microfilter 10.3 4.5
S3D 28 7.3 3.1 Cl2 Microfilter 5.5 2.8
S4C 27 7.4 4.0 Cl2* Sand 7.1 9.1
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Figure 1. Box and Whisker plots of the occurrence of (A) THMs & HANs, (B)
HNMs, (C) HAAs, and (D) NDMA in indoor swimming pools (n=23).
The median, maximum and minimum HANs were 16, 53, and 5 µg/L,
respectively. The major haloacetonitrile quantified was dichloroacetonitrile
(DCAN) among the six measured HANs. In few pools, brominated acetonitriles
were detected at low levels (1-3 µg/L) except in the pool which was filled
with groundwater. In general, it was observed that the pool waters with high
levels of HAAs had high levels of HANs. Furthermore, when brominated
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HAA species were high, the brominated HANs species also increased. Since
HANs hydrolyze to HAAs, it is expected to have a positive correlation between
these two classes of DBPs (25). Among the nine HNM species, only three
HNM species [trichloronitromethane (TCNM), bromonitromethane (BNM), and
bromochloronitromethane (BCNM)] were detected in the collected swimming
pool samples. Total HNMs were between 1.4 and 13.3 µg/L.
Among the nitrosamines analyzable using the current method (22), NDMA
was the only species detected in the selected 23 indoor swimming pool water
samples, with NDMA concentrations ranging between 2 and 83 ng/L with a
median of 17 ng/L. These levels of NDMA are somewhat higher than the drinking
water levels, which was consistent with the literature (6), and also indicating
that some NDMA precursors are released with body fluids and excretions.
Nitrosamines are mainly formed during chloramination of amines (26). Although
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swimming pools are mostly chlorinated, the ammonia coming from urea would
inevitably lead to the formation of chloramines in the pools. Therefore, it is
not surprising to see some NDMA formation in swimming pools. Furthermore,
there was no correlation between NDMA and the other classes of DBPs, which
clearly indicates that their precursors differ from carbonaceous DBPs precursors,
a finding consistent with the literature (27, 28). Although the nitrogenous DBPs
(HANs, HNMs, NDMA) were detected at lower levels than carbonaceous DBPs,
they were still significant regarding their cyto- and geno-toxicity (29).
Three indoor swimming pools were further monitored for a 9-month sampling
period. The operational conditions, water quality and DBPs occurrences in these
pools are summarized in Table 5. The average FAC fell within the range of 3
mg/L, which is well within the state guidelines in place regarding adequate pool
chlorination. Although the TN varied over a narrower range, between 2.0 and 5.0
mg/L in the three pools under study, the temperature and pH remained relatively
constant and the TOC fell within a wide range of 5.3 to 25.4 mg/L.
During the nine-month monitoring period for these three pools, a narrow
variation in the DBPs occurrence was observed in each (Table 5). The THM
concentrations in all of them ranged from 29 to 259 µg/L with an average of 108
µg/L. The highest THMs measured were in the warmest pool (S17T), which also
had the highest TOC measurements. Of the THM levels measured in the three
pools, chloroform was the most predominant (data not shown). The authors also
found higher levels of measured BDCM in pools S17L and S17T because sodium
chloride was used in both to generate chlorine electrochemically. The range of the
BDCM in these three pools was 0 to 29 µg/L. The HAAs in all three pools was
also higher than the THMs, which fell within a range between 667 to 11695 µg/L,
with an average of 2820 µg/L DCAA. The TCAA were the dominant species,
and BDCAA was the major brominated HAA species. The maximum amount
of BDCAA was 151 µg/L and the minimum was 9 µg/L with an average of 57
µg/L. The levels of all of the dibrominated species were much lower (<20 µg/L),
however.
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Table 3. Carbonaceous-DBPs Occurrence in Indoor Swimming Pools Water (n=23)
TCM BDCM DBCM TBM Total BAA DCAA BCAA TCAA DBAA BDCAA DBCAA Total
S1 41 1 <MRL ND 42 <MRL 100 1 87 <MRL 8 1 198
S2C 49 1 <MRL ND 51 <MRL 314 3 224 <MRL 13 1 555
S2W 119 3 <MRL ND 122 1 896 14 718 <MRL 36 <MRL 1665
S3S 77 2 <MRL ND 80 <MRL 712 5 1537 <MRL 21 <MRL 2276
S3D 62 1 <MRL ND 63 <MRL 937 7 776 <MRL 16 1 1738
S4C 37 1 <MRL ND 38 <MRL 688 10 789 1 27 3 1518
S4W 49 3 <MRL ND 53 1 81 4 241 <MRL 60 5 392
414
Minimum 26 172
TCM (Trichloromethane), BDCM (bromodichloromethane), DBCM (dibromochloromethane), TBM (tribromomethane), CAA (chloroacetic acid), BAA
(bromoacetic acid), DCAA (dichloroacetic acid), BCAA (bromochloroacetic acid), TCAA (trichloroacetic acid), DBAA (dibromoacetic acid), DBCAA
(dibromoacetic acid), TBAA (tribromoacetic acid), MRL (Minimum Reporting Level), ND (Not Detected).
Pool Code CAN TCAN DCAN BAN BCAN DBAN Total TCNM BNM BCNM Total NDMA
S1 1 ND 8 ND ND ND 9 <MRL <MRL 2.4 2.9 30
S2C ND ND 4 ND ND ND 5 0.8 <MRL 7.5 8.3 9
S2W 1 ND 22 ND 1 ND 25 <MRL <MRL 1.3 1.9 83
S3S 1 ND 27 ND 1 ND 30 0.7 <MRL 6.3 7.0 28
S3D 1 ND 7 ND ND ND 8 0.9 <MRL 3.9 4.8 14
S4C 1 ND 15 ND 1 ND 16 <MRL <MRL 2.5 3.0 16
S4W 1 ND 21 ND 2 ND 24 <MRL <MRL 1.1 1.7 18
416
Minimum 5 1.4 2
CAN (chloroacetonitrile), TCAN (trichloroacetonitrile), DCAN (dichloroacetonitrile), BAN (bromoacetonitrile), BCAN (bromochloroacetonitrile, DBAN
(dibromoacetonitrile), TCNM (trichloronitromethane), BNM (bromonitromethane), BCNM (bromochloronitromethane), NDMA (N-nitrosodimethylamine),
MRL (Minimum Reporting Level), ND (Not Detected).
The swimming pool operational parameters that affect both the THM and
HAA formation is presented in Figure 2. An overall comparison of the results
between the filling background waters (MB and SJWD) showed that formation of
THMs and HAAs was approximately 10% higher in BFA-MB than in BFA-SJWD
water. Although both synthetic pool waters had the same TOC concentration (1
mg/L from the filling water and 5 mg TOC from BFA), there was a slightly higher
rate of THM and HAA formation in the MB than in the SJWD water, which was
due to the aromatic nature of the MB source water. Specifically, the MB water
exhibited a somewhat higher SUVA254 (~2.0 L/mg-m) compared to the SJWD
water (~1.7 L/mg-m), indicating it’s slightly higher aromatic character over SJWD.
An analysis of each parameter, except the filling waters is provided below.
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Effect of FAC
FAC levels 1, 3, and 5 mg/L were tested in this study. It was determined than
an increase in FAC concentrations resulted in a slight increase in THM formation:
5% for BFA-MB and 14% for BFA-SJWD (Figure 2). There was, however, a
distinct increase in HAA formation observed, which was caused when the chlorine
dose was increased from 1 mg/L to 5 mg/L. Specifically, the HAA formation
increased 25% and 27%, respectively for the BFA-MB and BFA-SJWD (Figure
2).
This dependence was attributed to the reaction(s) of chlorine with albumin in
BFA. An increase in dosage in turn increased the rate of albumin decomposition
(hydrolysis), which in turn generated more HAA precursors (free amino acids).
The lesser effect of the chlorine concentrations on the THM than HAA was due to
the effect of the chlorine dose on the formation of different DBPs. After satisfying
the demand, a linear relationship has been previously established between the
demand for chlorine demand and THM formation (30), and a weak correlation
between the chlorine levels and chloroform formation (31). Consistent with these
observations, the results indicate that once the chlorine demand was satisfied, there
was no effect of the chlorine dose on the THM formation.
Effect of Temperature
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be higher. The increase in DBP formation with temperature can be explained
by reaction of un-reacted DBPs precursors with chlorine and increase in the
reactivity of chlorine with precursors (35, 36).
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Effect of pH
The results show that the formation of THMs and HAAs increased with an
increase in pH (Figure 2). It is also known that THM formation increases with an
increase in pH, while the trend is the opposite for HAA formation (32). However,
in this study, an increase in pH resulted in both an increase in both THM and
HAA formation. The opposite behavior that was observed for pH dependence
of HAAs in synthetic swimming water solution was once again attributed to the
hydrolysis of albumin, one of the main components of the BFA, and its reactivity
with chlorine. The observed pH trends for HAAs also indicated that the filling
water NOM was not a major contributor to HAA formation in synthetic pool waters
because in drinking waters, the HAA concentration decreased with an increase in
pH, as mentioned above. Finally, the results clearly indicate that the reduction of
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pH from 8.0 to 6.0 would result in a decrease in both THM and HAA formation by
40-60%. This decrease in pH would also result in a corresponding decrease in the
disinfection efficiency of chlorine, particularly below the pKa of chlorine where
HOCl is a more effective disinfectant agent than OCl- (33, 34).
Effect of Bromide
Bromide was spiked at three levels in addition to the ambient fill waters
concentration. The change in THMs and HAAs speciation with the increasing
bromide concentrations is shown in Figure 3. This increase in bromide
concentrations yielded a corresponding increase in both THM and HAA
concentration, which was expected since the brominated species increased while
the chlorinated species decreased. However, bromide caused a greater increase in
THM than HAA formation. The overall mass of THM concentration increased
by 65-72%, 106-116%, and 162-167% in synthetic pool waters at 100, 300,
and 600 µg/L bromide concentrations, respectively compared to the ambient fill
waters THM formation. However, during these same experiments the increase
in HAA concentration was only within a fairly limited range of 22 and 39%.
Bromine incorporation factor (BIF) “n” is the molar amount of bromine in the
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halogenated compound (THM or HAA) divided by the molar total of that halogen
(37). That is to say when n = 0 only chlorinated compounds form whereas when
n>0 brominated species begin to appear. Subsequent BIF analysis determined
that the presence of bromide increased the formation of brominated THM over
HAA formation (data not shown).
Specifically, the incorporation factor a synthetic swimming water sample
for a bromide level of 600 µg/L was 1.3 for THMs but only 0.8 for HAAs.
This difference in bromide incorporation is also consistent with higher bromine
incorporation of THMs than HAAs in sample testing (38). These results clearly
demonstrate that the use of water with low bromide levels to either fill swimming
pools and as make up water is critical to reduce DBP formation, especially THMs.
Thus, bromide impurities should be minimized, if possible, when generating
chlorine from sodium chloride. Furthermore, the use of seawater or saline water
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as either make-up or filling water should be avoided to reduce the DBPs formation
in swimming pools.
Figure 3. The effect of bromide on the formation and speciation of THMs and
HAAs during chlorination of BFA-MB and BFA-SJWD synthetic pool water.
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DBPs Formation as Function of Time
DBP formation as function of time are presented in Figure 4 for three synthetic
pool waters: (i) a pool water at 6 mg-C/L (5 mg-C/L from BFA and 1 mg-C/L from
MB as the background filling water), (ii) 5 mg-C/L BFA, and (iii) 1 mg-C/L BFA.
The last two samples were used to investigate the formation kinetics from BFAs
alone and the formation kinetics at two Cl2/TOC ratios. Results indicate that THM
formation (within a range of 53% to 68%) occurred during the first five hours of a
five-day formation cycle in the absence and the presence of bromide for synthetic
pool water (BFA-MB) and BFA (Figure 4).
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Figure 4. THM formation fraction during five days (A) without bromide and (B)
with bromide (200 µg/L), HAA formation fraction during five days (C) without
bromide and (D) with bromide (200 µg/L). THMt (THM formed at time t), THM120
(THM formed at 120 hours), HAAt (HAA formed at time t), HAA120 (HAA formed
at 120 hours). ◆ BFA-MB (5+1 mg-C/L), □ BFA (5 mg-C/L), ▵ BFA (1 mg-C/L)
formation rate. This difference was attributed to the changes in the formation
rates of di-halogenated HAAs vs. tri-halogenated HAAs (data not shown). Since
there is always a high FAC concentration in the pool water, the HAA formation
rates in swimming pools are likely to be rapid for HAAs. This is especially true
for swimming pools in the U.S. where the dilution of pool water with the filling
water is not regularly practiced and the pool water is not replaced for long time.
Therefore, chlorine demand of filling water is exhausted at the very early period
of operation after filling the pool. Afterwards, the BF components serve as the
primary catalyst for THM and HAA formation.
The presence of NOM (i.e., BFA-MB synthetic pool water) (BFA = 5 mg-C/L)
reduced the formation rate of THMs by ~20% during the first 24 hours as compared
to the absence of NOM. This behavior is due to the higher reactivity of NOM
compared to BFA with chlorine to form THM but which occurs at a slower rate,
as compared to BFA. Concurrently, the presence of NOM (i.e., BFA-MB) did not
affect the formation rate of HAAs, indicating that while the filling water NOM can
affect the THM formation, the formation rate of HAAs remains constant.
There were small differences in the formation rates under ambient bromide
levels for both THMs and HAAs. In the presence of bromide, the difference in
the formation rates of both DBPs diminished. Since halogenation reactions are
faster with bromide than chloride (39–41), higher formation rates observed in this
study is attributed to the formation of brominated DBP species from NOM at high
bromide levels.
The overall formation rate of THMs was higher than that of HAAs in
swimming pools Figure 5. THMs were formed almost instantaneously when
chlorine reacted with BFs, whereas HAA formation occurred at a slower
rate. Practically, these results indicate that within the typical turnover time of
swimming pools most HAA precursors can be removed by the treatment system
whereas THM precursors cannot. Thus, precursors control (i.e., the release of
human BFs) will be critical in reducing the formation of THMs in swimming
pools. The precursor control requires improving the practices and behavior of
swimmers, and implementing more strict hygienic conditions by swimming
pools utilities. Better hygienic conditions include showering immediately before
swimming and not releasing urine intentionally during swimming.
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Figure 5. ◊ THMs and ▪ HAAs formation during 5-day reaction from BFA.
Conclusions
The DBPs in the 23 swimming pools that were the subject of this study were
far higher than the drinking water regulation values in the U.S., with THM levels
ranging between 26 and 213 µg/L with an average of 80 µg/L. The HAAs ranged
between 173 and 9005 µg/L with an average of 1541 µg/L. HNMs ranged between
1.4 and 13.3 µg/L with an average of 5.4 µg/L. HANs ranged between 5 and 53
µg/L with an average of 19 µg/L. The NDMA ranged between 2 and 83 ng/L with
an average of 26.5 ng/L. The electrochemically generation of chlorine increased
the brominated species of halogenated DBPs (THMs, HAAs, HNMs, HANs).
Furthermore, during the sampling period for nine months, the water quality (TOC,
TN, pH, FAC) and DBPs concentrations (THMs, HAAs) in the swimming pools
remained relatively constant. However, some fluctuation was observed likely due
to time of the year and the specific pool events/activities on the time of sampling.
The formation and speciation of THMs and HAAs were also investigated
under various disinfection and operation conditions typically used in U.S.
swimming pools. Although the increases in free available chlorine, pH, TOC,
water temperature, and bromide levels in the water increased overall DBP
formation, these factors affected the different classes of DBPs at different
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magnitudes. Higher levels of free available chlorine increased the HAA levels
more than the THMs. The temperature effect was greater on the formation of
THMs than for HAAs whereas contact time increased HAAs more than THMs.
The authors also determined that under swimming pool related conditions,
DPB formation was quite rapid, with an appreciable percentage of the increase
occurring in the first 3-6 hours, which is the typical turnover time for the pool
water. Moreover, THM formation was faster than HAA formation, with 53 to
68% of five-day THMs formed within the first 3-6 hours and 15 to 30% of five-day
HAAs formed during the first six hours. Although it is possible to reduce DBP
formation by the controlling operational parameters (pH, free available chlorine,
bather load, the number of swimmers in a pool in a 24 hour period- or dilution),
these fast formation rates imply that DBP control strategies in swimming pools
should mainly focus on control the DBP precursors at the source (i.e., swimmers).
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References
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15. Certified Pool-Spa Operator Handbook; National Swimming Pool
Foundation: Colorado Springs, CO, 2006.
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20. Method 300.0 - Determination of Inorganic Anions by Ion Chromatography;
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21. Method 551.1 - Determination of Chlorination Disinfection Byproducts,
Chlorinated Solvents, and Halogenated Pesticides/Herbicides in Drinking
Water by Liquid–Liquid Extraction and Gas Chromatography With
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Chapter 22
(United States of America, Australia and other European countries). Public pools
in Germany rely primarily on the treatment scheme, operation, and surveillance
described in DIN 19643. Despite minor differences in threshold values, applied
chemical concentrations, and the requirement for an initial flocculation step, DIN
19643 can serve as a good example of pool water treatment that is similar to that
in much of Western Europe, North America, and Australia (2).
Disinfection By-Products
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Trichloramine in Swimming Pools
gas and travel at characteristic speeds that are related to the mass, charge, size
and shape of the ions or ion clusters.
The general set-up of an IMS device is shown in Figure 1. The heart of the
IMS is the drift tube which includes an ionization chamber separated by the shutter
grit (21). The tube is built from a stack of metal guard rings which are separated
by thin isolators and attached to a voltage divider so that a smooth increase of
voltages can be applied over the whole string. A steady flow of drift gas (nitrogen
or air) at ambient pressure serves as collision and reactant gas and prevents the
tube from contamination.
Gaseous samples can be introduced directly into the ionization chamber
where an ionization source, e.g. a beta emitter (63Ni) produces reactant ions.
Analytes are ionized by proton-transfer and charge exchange reactions in a kind
of atmospheric chemical ionization mechanism. The type of ionization source
and drift gas is critical for ionization mechanisms and efficiencies, which was
demonstrated for monosubstituted toluenes and anilines for three ionization types
(63Ni beta emitter, corona discharge and photoionization (28). Corona discharge
sources often combine mixed ionization mechanisms and therefore lead to more
complicated response behavior than beta emitters. Photoionization can be used
for direct ionization without reactant ions and therefore lead to much simpler
response behavior and often large ranges of quantitative responses (27).
Ionized analytes are then transferred to the drift tube via an electronic shutter
grid which is periodically triggered. In the drift tube ions experience acceleration
by the electrical field and a number of collisions with the drift gas. This results in
a rather constant drift velocity vd which is proportional to the mobility of an ion
K and the electric field strength E (Equation 1). Analyte ions with different ion
mobilities K due to differences in size, mass and charge experience a separation.
Since the ion mobilities K depend on environmental conditions, generally
normalized mobilities K0 are given, where T is the absolute temperature of the
drift gas, T0 the standard temperature (273 K), P the atmospheric pressure during
the measurement and P0 the standard pressure (760 mm Hg) (Equation 2).
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Methods
Trichloramine Gas Generation
TCA gas standards were produced continuously in a gas generation unit
as described by Schmalz et al. (14). Shortly, ammonia chloride and sodium
hypochlorite were continuously dosed to a phosphate buffer solution (pH 3) in a
reaction bottle. Nitrogen gas with a flow rate of 100 mL/min was used to strip out
the formed TCA. The gas stream was cleaned in impingers with amidosulfonic
acid solutions and water. The TCA gas stream was splitted into two fractions.
The concentrated gas stream was trapped in cooled iso-octane and the other part
was diluted with synthetic air. The continuous TCA gas generation was controlled
by UV-absorption of the iso-octane solutions every 30 minutes. The diluted gas
stream with a flow rate of up to 7 L/min was adjusted to produce concentrations
in the range of 0.1 and 0.8 mg/m³. The concentration of the diluted gas stream
was determined by the impinger and reactive adsorption method as described
below (TCA analysis). The air humidity was varied by an impinger with water
and controlled with a hygrometer.
Trichloramine Analysis
Photometric Method
Impinger Method
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Ion Mobility Spectrometry
ions at a normalized drift time (K0) of 2.7 cm2/(Vs) and 2.5 cm2/(Vs).
Results
Trichloramine (TCA) analysis was performed by a hand-held ion mobility
spectrometer (IMS) with direct intake of gas samples from indoor air
environments, gas generation units or from Tedlar bags for spiked gas standards.
A silicone membrane at the IMS inlet protects the IMS analyzer and keeps it at a
constant humidity. A typical measurement cycle consists of the continuous intake
of gaseous sample by a built-in pump and the signal readout after constant signal
intensity was obtained. Single IMS measurements can be performed within 20
seconds and the results are stored on a storage device or can be directly viewed,
if the instrument is calibrated for the analytes. The mobility of the hand-held
instrument and the short response time allow quite flexible applications and
measurements of high spatial and temporal resolution in indoor pool settings.
In contrast to that, the conventional filter method for TCA determination
requires typically three hours of sampling time, further laboratory work for
filter extraction, sample clean-up and ion chromatographic determination of the
formed chloride. Generally, the filter method allows only the determination of
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averaged concentrations over time periods of several hours, which doesn´t allow
monitoring of the dynamic behavior of TCA concentrations in dependence of
bather activity or of the sampling location in an indoor pool hall.
in the drift tube of the IMS. This process is already known from electron capture
detectors (ECD) and described for halo- and nitro-substituted benzenes (22).
For example halogenated benzenes and alkyl halides only yielded halide ions
by a simple dissociative electron capture, whereas nitrobenzene exhibited an
associative electron capture resulting in negatively charged molecular ions.
Halogenated nitrobenzenes showed both mechanisms associative and dissociative
electron capture.
The normalized ion mobilities for chlorinated compounds are at K0 = 2.7
cm2/(Vs) (chloride ion) and for brominated compounds at K0 = 2.5 cm2/(Vs)
(bromide ion, Figure 2). For bromodichloromethane both signals could be
detected. Bromoform has only one signal for bromide. Other ions in the mobility
spectrum are from reactant gas ions which are formed from air (oxygen) and
water (signals 3 and 4 in Figure 2). The implications of the generalized signal
response of the IMS to different halogenated compounds are that the IMS signal
is not specific for individual DBPs but provides the possibility to measure all
chlorinated DBPs and all brominated DBPs in a kind of sum parameter. The
contribution of single DBPs to the sum parameter strongly depends on their
response factor and individual concentration in the gas sample.
Figure 2. IMS spectra (signal intensity vs. drift time) of a blank and volatile
DBPs (TCA, bromodichloromethane and bromoform). Signals are from chloride
(1) and bromide (2) with normalized ion mobilities of K0 = 2.7 cm2/(Vs) and K0
= 2.5 cm2/(Vs), respectively.
The response factors for the selected DBPs range over four orders of
magnitude between 3896 (arbitrary signal units m3/mg) for dichloroacetonitrile
and 0.5 (arbitrary signal units m3/mg) for chloroform (Table 1). The response
factors are mostly dependent on the ionization efficiency during dissociative
electron capture, since the detected ion is in any case chloride for chlorinated
DBPs. Therefore differences in electron capture cross sections and bond energies
of the individual compounds account for the overall response. Interestingly all
chloramines, where the halogen is bound to a nitrogen atom, show a rather high
response. However, the highest value was found for dichloroacetonitrile with
a response factor of almost 4000 (arbitrary signal units m3/mg). Due to a more
than 400fold less response, chloroform contributes to only much less than 1 %
of the chloride signal of TCA in typical indoor swimming pool environments
and can therefore be neglected. The two other THMs (bromodichloromethane,
dibromochloromethane) and dichloroaceto-nitrile also contribute to less than 1 %
to the chloride signal. Also the contribution of chlorine can be neglected due to the
low partitioning of hypochlorous acid to the gas phase and therefore the resulting
low concentrations in the air (31). Only the contribution of dichloromethylamine
is estimated to be in the range of 10 %.
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Table 1. Response Factors, Limits of Quantitation (LOQ) and Typical Air
Concentrations for Halogenated DBPs in Indoor Swimming Pools Measured
As Chloride and Bromide in Negative Ion Mobility Spectra
Ion DBP Response LOQ Typical air
mobility factor (mg/m³) concentration
K0 (m3/mg) (mg/m3)
(cm2/(Vs))
2.7 (Cl-) NCl3 221 0.1 0.1 - 0.5
2.7 CHCl3 0.5 24 0.1 - 0.5
2.7 CHBrCl2 33 0.4 < 0.02
2.7 CHBr2Cl 21 1.0 < 0.02
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Table 2. Figures of Merit for the Linear IMS Calibration Measured at Three
Days for Dry and Humid Air (65 % Relative Humidity at 25 °C)
Day/Humidity (%) Slope Standard error of Intercept
slope
1/0 200 8.6 70
2/0 235 22.1 69
3/0 259 20.2 42
1/65 246 8.8 56
2/65 209 15.0 71
3/65 211 20.2 84
The slopes of the IMS calibration for 3 different days with dry and humid air
show no significant differences, if the two means of the slopes from dry air (mean:
231.3; STD 29.7; n = 3) and from humid air (mean: 222.0; STD 20.8; n = 3)
are subjected to a t-test (Table 2). The interday statistical error is higher than that
between dry and humid gas samples and is also caused by systematic errors of the
production of TCA gas standards. TCA is a rather instable compound which has
to be produced and diluted online to suitable concentration levels for calibration,
which is a rather tedious task. The relative standard errors of the slopes of single
calibration functions are within 4.3 % and 9.4 %, which is a quite acceptable range
for this type of measurement.
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Temporal Dynamics of Trichloramine Concentrations in Indoor Pool Air
The quick response time of IMS measurements and the mobility of the
instrument allowed us to use it for the investigation of the temporal dynamics of
TCA concentrations at various locations of an indoor pool setting with a large
swimmer hall, which is connected to a non-swimmer pool with low ceiling, and a
separated, confined baby pool area (children area). The measurements were done
for defined time intervals of typically 10 to 15 min.
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Conclusions
Ion mobility spectrometry (IMS) revealed as a valuable tool to measure
trichloramine (TCA) concentrations in indoor swimming pool environments.
Since during the ionization in IMS chloramines and other chlorinated DBPs can
contribute to the chloride signal, interfering compounds and their contribution
to the chloride signal have to be considered and found to be less than 15 % in
typical indoor pool air. The short response time of about 20 s, the mobility and
stability of the IMS calibration enable to monitor the highly dynamic behavior in
time and space of TCA and therefore to determine more accurately the exposure
of swimmers and pool personnel.
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Acknowledgments
This work was supported by the German Federal Ministry of Education and
Research (BMBF 02WT1090) in the joint project “Health-Related Optimization of
Swimming Pool Water Treatment”. We further thank J. Chrapan and V. Kuemmel
for their contribution to the generation of TCA gas standards and IMS calibration.
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Subject Index
A C
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fluorescence EEM spectra of Lake dimethenamid bromination,
Taihu water, 314f pseudo-first-order rate constants,
water parameters, 312 255f
using traditional and advanced drinking excess bromide, effects on
water treatment processes, 307 pseudo-first-order rate constants,
Controlling NDMA formation, role of 258f
pre-oxidation, 151 free bromine, chemistry, 253
NDMA formation, role of free bromine speciation, more complete
oxidants/disinfectants view, 262
chlorine, 152 free chlorine concentration, influence on
chlorine dioxide, 154 pseudo-first-order rate constants, 260f
ozone, 154 model water containing bromide,
permanganate, 155 speciation of free bromine, 263f
UV irradiation, 155 natural and anthropogenic sources of
NDMA formation and effect of bromide, 252
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DBP formation potential (DBPFP) unburned, and burned detritus material,
test, 385 fluroresence EEM of water extracts,
dissolved organic carbon (DOC), 300f
analysis, 385 unburned and burned detritus, leachate
HAAs, analysis, 385 extracted, 301f
reagents, 384 specific formation potential, 303f
THMs and HANs, analysis, 385
UV absorbance, analysis, 385
modeling, 384
calibration and validation results, 394f
E
model development, 392
model implications, 395 Effect of fire on carbon quality
model performance, 394 fluorescence emission-excitation matrix,
predicted DBP profiles as function of 282f
water age, 395f fluorescence spectrometry, 278
litters before and after burns
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Formation of disinfection by-products, (UPLC/)ESI-tqMS analyses, 49
effect of prescribed burning, 282 water sampling and characterization,
before and after burn, disinfection 47
by-product yields, 284f results and discussion
dissolved organic carbon extracted from concentrations, effect of boiling, 55f
litter, chlorine reactivity, 283f ESI-tqMS PIS spectra of m/z 35, 54f
Formation of disinfection by-products from ESI-tqMS PIS spectra of m/z 79, 53f
bacterial disinfection, 235 polar brominated and chlorinated
alternative disinfectants, 246 DBPs, decomposition, 51
bacterial inactivation and DBP real tap water, detoxification by
formation, effects of pH and dosage, boiling, 56
243 TOX during boiling, reduction, 51
DBP formation during bacteria
inactivation, 240
effects of humic acid and pH on E. coli
I
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monochloramine degradation, 84 changes of differential absorbance,
NDMA formation model, 82 modelling kinetics, 66
NDMA formation from model correlations between concentration
compounds, 87 tribromoacetic acid (TBAA) and
optimized rate constant kapp, 90t differential absorbance, 70f, 71f
NDMA formation from model precursor trichloroacetic acid (TCAA) and
compound data, 88f differential absorbance, 70f, 71f
NDMA formation in NOM, 85 correlations between proportionality
rate constant and monochloramine coefficients, 73f
decomposition rate constants, 86t DBP formation in chlorinated water,
NDMA formation of amine precursors kinetics, 66
in river water, 92f differential absorbance of chlorinated
NDMA formation of pharmaceutical LK water, kinetic profiles, 67f
compounds, 90 experimental, 65
optimized rate constant kapp, 91t modelling DBPs formation and
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results and discussion, occurrence data, drinking water toxicity, forcing agents, 6
overview, 140 human biomarkers, identification, 7
MonoHAA-induced transcriptome
profile pathways, 14t
nationwide drinking water in vitro
P toxicity survey, 5
new pathway, 5, 17f
Precursors and wastewater indicators selected waters, DBP exposure, 15
analytical methods
hydraulic flow modeling, 123
nitrosamine precursors, 122
nitrosamines, 122 T
PPCPs, 122
sucralose, 123 Toxicity, 34
map of Sacramento –San Joaquin Delta, assays
120f Chinese hamster ovary cells, 35
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four distribution systems non-regulated DBP levels within
description, 344t distribution systems, spatial
finished water at WTP, average variability, 349
characteristics, 347t regulated and non-regulated DBPs
FRC concentrations, spatial within systems, relationship, 358
distribution, 350t spatial distribution, temporal variations
individual HK levels, spatial CNCl levels, 357f
distribution, 351f CP levels, 356f
material and methods HA7 levels, 353f
analytical procedure, 345 HAN4 levels, 355f
case under study, 343 HK2 levels, 354f
data analysis, 345 Spearman rank correlation coefficients,
water sampling, 343 359t
mean DBP levels (μg/L) found in four
systems during study period, 348t
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