EPA/600/R-02/068
September 2002
The Occurrence of Disinfection By-Products (DBFs)
of Health Concern in Drinking Water:
Results of a Nationwide DBF Occurrence Study
Howard S. Weinberg
The Department of Environmental Sciences and Engineering
University of North Carolina at Chapel Hill
Chapel Hill, NC
Stuart W. Krasner
Metropolitan Water District of Southern California
La Verne, CA
Susan D. Richardson and Alfred D. Thruston, Jr.
Ecosystems Research Division
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Athens, GA
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Athens, GA
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DISCLAIMER
The United States Environmental Protection Agency (EPA) through its Office of
Research and Development partially funded and collaborated in the research described here. The
information in this document has been partially funded under Cooperative Agreement No.
826697. It has been peer reviewed by the EPA and approved for publication. Mention of trade
names or commercial products does not constitute endorsement or recommendation for use.
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TABLE OF CONTENTS
Acknowledgments 4
Glossary of Terms 5
Executive Summary 8
Introduction 11
Results
EPARegion9: Plants land2 22
EPARegion6: Plants 11 and 12 65
EPARegion4: Plants7and8 121
EPARegion4: Plants 5 and 6 164
EPARegionS: Plants 3 and4 214
EPA Regions 5 and 7: Plants 9 and 10 270
Conclusions 320
Appendix 322
Experimental Methods
Chemical Standards 323
Solid Phase Extraction-Gas Chromatography/Mass Spectrometry Method 343
Liquid-Liquid Extraction-Gas Chromatography-Electron Capture Detection Method 365
Closed-Loop Stripping Analysis Method 374
Purge-and-Trap-Gas Chromatography/Mass Spectrometry Method 380
Halogenated Furanones Method 393
Carbonyl Method 429
Broadscreen Gas Chromatography/Mass Spectrometry Procedure 444
Mass Spectra for New Disinfection By-products Reported 448
Mass Spectra for MX Analogues 455
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ACKNOWLEDGMENTS
The authors would like to acknowledge the following people who contributed to this project.
University of North Carolina
Gretchen D. Onstad Ramiah Sangaiah Vanessa Pereira
Gary L. Glish Karupiah Jayaraj Katrina Jamison
Christine N. Dalton Lindsay Dubbs Zhengqi Ye
Philip C. Singer Petra Strunk
Metropolitan Water District of Southern California
Alicia Gonzalez Lely Suhady Hsiao-Chiu Wang
Salvador Pastor Jacob Nikonchuk Ching Kuo
Russell Chirm Leslie Bender Suzanne Teague
Michael J. Sclimenti Vaheh Martyr Robert Alvarez
Sylvia Barrett Tim Albrecht Jesus Vasquez, Jr.
Pat Hacker Bart Koch Eric Crofts
Sikha Kundu Tiffany Lee Himansu Mehta
U.S. EPA National Exposure Research Laboratory, Athens, GA
Terrance L. Floyd
F. Gene Crumley
We also need to express appreciation to Leif Kronberg and Angel Messegauer for providing
samples of furanone standards, as well as Bruce McKague (Can Syn Chem Co.), Francesc
Ventura (Aigues of Barcelona, Spain) and George Majetich (Majestic Research) for providing
standards for quantitative methods and new DBF identification work.
Last, but not least, we would like to gratefully acknowledge the assistance of the participating
utilities that collected the samples, provided operational and water quality data, and ensured a
successful survey. Without their generous cooperation, this study would not have been possible.
We are also extremely grateful to the U.S. EPA Office of Water and Office of Prevention,
Pesticides, and Toxic Substances scientists who undertook the initial DBF prioritization effort
that provided the focus for this study. Thank you to Vicki Dellarco, Yin-Tak Woo, David Lai,
Jennifer McLain, and Mary Ko Manibusan.
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GLOSSARY OF TERMS
AOC
BEMX
BF3/MeOH
BMX-1
BMX-2
BMX-3
CCF
CH2N2
CI
C12
CLSA
C1O2
C1O2
CT
DCAN
DIW
DBF
DCP
DOC
DS
DXAA
EBCT
BCD
El
EMX
EtAc
FE
FI
GAC
GC
H2SO4/MeOH
HAAs
HAA5
HAA9
HANs
Assimilable organic carbon
Brominated forms of EMX
Boron trifluoride methanol complex
3-Chloro-4-(bromochloromethyl)-5-hydroxy-2(5H)-furanone
3-Chloro-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone
3-Bromo-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone
Carbon contactor filtered
Diazomethane
Chemical ionization
Chlorine
Closed-loop stripping analysis
Chlorine dioxide
Chlorite
Concentration-time
Dichloroacetonitrile
Deionized water
Disinfection by-product
Dichloropropanone
Dissolved organic carbon
Distribution system
Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
Empty bed contact time
Electron capture detector
Electron ionization
(E)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid
Ethyl acetate
Filter effluent
Filter influent
Granular activated carbon
Gas chromatography or Gas chromatograph
Sulfuric acid in methanol
Haloacetic acids
Sum of 5 HAAs (monochoro-, monobromo-, dichloro-, dibromo-,
trichloroacetic acid)
Sum of 9 HAAs (HAA5 + bromochloro-, bromodichloro-,
dibromochloro-, tribromoacetic acid)
Haloacetonitriles
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HKs
HNMs
HPLC
HRMS
ICR
ID
IS
KHP
LLE
MBA
MCA
MCL
MDL
MEK
MeOH
MG
mgd
MS
MtBE
MW
MWDSC
MX
MX-analogues
MXR
MXR-analogues
NA
ND
NH2C1
NMR
NR
NS
N2
NH3
NOM
03
OE
Ox-EMX
Ox-MX
Ox-NOM
PE
PFBHA
Haloketones
Halonitromethanes
High performance liquid chromatography
High resolution mass spectrometry
Information Collection Rule
Inner diameter
Internal standard
Potassium hydrogen phosphate
Liquid-liquid extraction
Mucobromic acid
Mucochloric acid
Maximum contaminant level
Method detection limit
Methyl ethyl ketone
Methanol
Million gallons
Million gallons per day
Mass spectrometry
Methyl tertiary-butyl ether
Molecular weight
Metropolitan Water District of Southern California
3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone
MX, ZMX, EMX, ox-MX, ox-EMX, red-MX, MCA, BMX-1,2,3
Esterified form of MX
Esterified forms of MX-analogues
Not available
Not detected at or above minimum reporting level (MRL)
Chloramines
Nuclear magnetic resonance
Not reported
Not sampled
Nitrogen gas
Ammonia
Natural organic matter
Ozone
Ozone contactor effluent
Oxidized EMX, (E)-2-Chloro-3-(dichloromethyl)butenedioic acid
Oxidized MX, (Z)-2-Chloro-3-(dichloromethyl)butenedioic acid
Oxidized NOM
Plant effluent
Pentafluorobenzylhydroxylamine
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P&T
Red-MX
RDL
RM
SDS
SIR
SPE
SPME
SUVA
TCP
THMs
THM4
TIC
TLC
TOC
TT
TXAA
UNC
USEPA
uv
voc
WTP
ZMX
Purge-and-trap
Reduced MX, 3-Chloro-4-(dichloromethyl)-2(5H)-furanone
Reporting detection level
Rapid mix
Simulated distribution system
Selected ion monitoring
Solid phase extraction
Solid phase microextraction
Specific ultraviolet absorbance
Trichloropropanone
Trihalomethanes
Sum of 4 regulated THMs (chloroform, bromoform,
bromodichloromethane, dibromochloromethane)
Total ion chromatogram
Thin layer chromatography
Total organic carbon
Treatment tank effluent
Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochloro-,
tribromoacetic acid)
University of North Carolina
United States Environmental Protection Agency
Ultraviolet light
Volatile organic compound
Water treatment plant
(Z)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid
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EXECUTIVE SUMMARY
The motivation for this Nationwide Disinfection By-product (DBF) Occurrence Study
was two-fold: First, more than 500 DBFs have been reported in the literature, yet there is almost
no quantitative occurrence information for most. As a result, there is significant uncertainty over
the identity and levels of DBFs that people are exposed to in their drinking water. Second, only
a limited number of DBFs have been studied for adverse health effects. So, it is not known
whether other DBFs (besides the few that are currently regulated) pose a risk to human health.
To determine whether other DBFs pose an adverse health risk, more comprehensive quantitative
occurrence and toxicity data are needed.
Because health effects studies are very expensive, it is not possible to test all DBFs that
have been reported. It is also not feasible to measure >500 DBFs in waters across the United
States. Thus, results of a DBF prioritization effort by scientists at the U.S. Environmental
Protection Agency (USEPA) Office of Water and the USEPA Office of Prevention, Pesticides,
and Toxic Substances were used to focus this study on those DBFs that were the most
lexicologically significant. These EPA experts applied an in-depth mechanism-based structural
activity relationship analysis to the more than 500 DBFs reported in the literature, supplemented
by an extensive literature search for genotoxicity and other data, and ranked the carcinogenic
potential of these DBFs. Approximately 50 DBFs that received the highest ranking for potential
toxicity and that were not included in the USEPA's Information Collection Rule (ICR) were
selected for this occurrence study. These DBFs, denoted as 'high priority' DBFs in this report,
included such compounds as MX [3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone],
brominated forms of MX (BMXs), halonitromethanes, iodo-trihalomethanes, and many
brominated species of halomethanes, haloacetonitriles, haloketones, and haloamides.
For this Nationwide Occurrence Study, scientists from the USEPA's National Exposure
Research Laboratory (NERL) initiated a collaboration with scientists at the University of North
Carolina (UNC, Howard Weinberg, PI) and the Metropolitan Water District of Southern
California (MWDSC, Stuart Krasner, co-Pi). The 'high priority' DBFs, along with regulated and
Information Collection Rule DBFs for comparison, were quantified in drinking waters across the
United States. These waters represented diverse geographic regions with different source water
quality. Several source waters contained relatively high bromide levels (where brominated
DBFs would be expected to form). In addition, many of the waters selected for study were
relatively high in total organic carbon (TOC). Waters treated with all four major disinfectants
(chlorine, chloramines, ozone, and chlorine dioxide) were studied. In addition, the fate and
transport of these DBFs was studied in the real distribution systems and in simulated distribution
system (SDS) tests. Prior to this study, there was almost nothing known about the stability of
these DBFs in the distribution system.
Because no quantitative analytical methods existed for most of the high priority DBFs,
optimized analytical methods were initially developed at UNC and MWDSC. No one single
analytical method could be used for all DBFs, so different methods were developed and
optimized for specific groups of DBFs. Also, because there were no commercially available
standards for many of these compounds, many had to be synthesized.
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Another goal of this project was to use this opportunity to look for other DBFs that have
not been previously identified in order to provide a more complete assessment of DBFs formed
by different treatments in different regions of the United States. This work was carried out at the
USEPA NERL-Athens laboratory. For this research, a combination of advanced mass
spectrometric tools was used to identify the new DBFs.
Results revealed the presence of many of the high priority DBFs in the waters sampled.
Important observations included finding the highest levels of iodo-trihalomethanes (THMs) at a
plant that used chloramination without pre-chlorination. Levels of individual iodo-THMs ranged
from 0.2 to 15 |ig/L. Another important observation involved finding the highest concentration
of dichloroacetaldehyde at a plant that used chloramine and ozone disinfection. Therefore,
although the use of alternative disinfectants minimized the formation of the four regulated
THMs, certain dihalogenated DBFs and iodo-THMs were formed at significantly higher levels
than in waters treated with chlorine. Thus, the formation and control of the four regulated THMs
is not necessarily an indicator of the formation and control of other halogenated DBFs, and the
use of alternative disinfectants does not necessarily control the formation of all halogenated
DBFs, and can even result in increased concentrations of some. Moreover, many of these
halogenated DBFs—including certain dihalogenated and brominated species—were not studied
in the ICR.
Halogenated furanones, including MX and brominated MX (BMX) analogues, were
widely observed in these samplings. Another finding was the high levels of MX and MX-
analogues in many samples. It was previously observed that MX did not exceed a concentration
of 60 to 90 ng/L (the few measurements that had been conducted generally showed levels <60
ng/L). In this study, however, MX was often observed at levels significantly greater than 100
ng/L, with a maximum level of 310 ng/L observed in finished water from a treatment plant that
disinfected a high-TOC water with chlorine dioxide, chlorine, and chloramines. These findings
are significant because the levels of MX are much higher than previously reported. Likewise,
several other analogues of MX were identified, including BMX analogues. Results include 170
ng/L and 200 ng/L levels for BMX-1 and BEMX-3, respectively (at a treatment plant that
disinfected a high-bromide water with chlorine dioxide, chlorine, and chloramines). It is
interesting that the drinking water utilities with the highest MX and BMX levels were from
treatment plants that use chlorine dioxide for primary disinfection. MX did not form from
chlorine dioxide disinfection per se, rather chlorine dioxide oxidation appeared to not destroy
MX precursors (as ozone, another alternative disinfectant, does). Thus, MX and BMX formation
was highest at treatment plants with high levels of TOC and bromide, respectively.
Halonitromethanes, including dihalogenated and brominated species not included in the
ICR, were found in some of the samples; levels of individual species ranged from 0.1 to 3 |ig/L.
In some cases, pre-ozonation was found to increase the formation of the trihalonitromethanes
(brominated analogues of chloropicrin [trichloronitromethane]). Many brominated acids were
also identified in several finished waters that contained elevated levels of bromide in their source
waters. A number of brominated acids were identified for the first time (i.e., brominated
propanoic, propenoic, butanoic, butenoic, oxopentanoic, heptanoic, nonanoic, and butenedioic
acids), with most being observed in the finished water from a treatment plant that has significant
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bromide levels in its source water. One of the high priority DBFs, 3,3-dichloropropenoic acid,
was found in several finished waters, giving further evidence that haloacids with longer carbon
chains are prevalent DBFs (i.e., haloacetic acids are not the only haloacids formed during
disinfection).
Dihaloacetaldehydes and brominated analogues of chloral hydrate
(trichloroacetaldehyde) were detected in many samples, as were mono-, di-, tri-, and/or tetra-
species of halomethanes and haloketones. Several haloamides were also found in finished waters
at levels similar to DBFs that are commonly measured (low |ig/L levels). This is a class of DBFs
that has not been previously quantified, but the levels observed in this study indicate that their
levels in finished waters are not trivial. In addition, carbon tetrachloride was detected in some of
the waters measured, with a maximum of 0.8 jig/L observed. Although carbon tetrachloride was
present in sampled finished drinking waters, its identity as a DBF could not be proven, since
carbon tetrachloride is sometimes used to clean out chlorine cylinders before they are filled.
Thus, it could be either a DBF or a contaminant from the cleaning process.
Another finding in this study was the discovery of iodoacids for the first time. Five new
iodoacid species were tentatively identified: iodoacetic acid, iodobromoacetic acid,
iodobromopropenoic acid (2 isomers), and 2-iodo-3-methylbutenedioic acid. High resolution
mass spectrometry confirmed the presence of iodine in their structures and the overall empirical
formulas for these new DBFs. One of these—iodoacetic acid—has been confirmed through the
analysis of an authentic chemical standard (match of retention time and mass spectrum).
Additional synthetic standards are currently being prepared to confirm the other iodoacid
identifications. These iodoacids were observed as DBFs in a high-bromide water from a
treatment plant that uses only chloramine disinfection. Another iodinated DBF, tentatively
identified as iodobutanal, was found in finished waters from treatment plants on both coasts that
can be impacted by saltwater intrusion (sea water is a source of iodide in addition to a major
source of bromide in some drinking waters). This DBF has also not been reported previously.
In addition to the new iodinated DBFs and new brominated acids, another brominated
ketone was identified for the first time: 1-bromo- 1,3,3-trichloropropanone, which was found in
many of the waters sampled.
The stability of DBFs in actual distribution systems and in simulated distribution system
(SDS) tests varied. In most cases where chloramination was used, the DBFs were relatively
stable. However, when free chlorine was used, THMs and other DBFs, including haloacetic
acids, increased in concentration both in the actual distribution system and in SDS tests.
Haloacetonitriles generally were stable (at the distribution-system pH levels encountered in this
study) and increased in concentration, but many of the haloketones were found to degrade in the
distribution system and SDS tests. Halonitromethanes and dihaloacetaldehydes were found to be
stable in these systems and tests. Although controlled laboratory studies had suggested
instability of halogenated furanones, particularly MX, in water, MX and MX-analogues were
sometimes stable, and sometimes they degraded somewhat in the distribution systems and SDS
tests. When the MX analogues showed some degradation in the distribution system, they were
generally still present at detectable levels, indicating that they do not completely degrade in the
distribution system. Many times, the BMXs were stable.
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INTRODUCTION
More than 500 disinfection by-products (DBFs) have been reported in the literature for
the major disinfectants currently used (chlorine, ozone, chlorine dioxide, chloramines), as well as
their combinations (Richardson, 1998). Of these reported DBFs, only a small percentage have
been quantified in drinking waters. Thus, there is significant uncertainty over the identity and
levels of DBFs that people are actually exposed to in their drinking water. Moreover, only a
limited number of DBFs have been studied for adverse health effects. To determine whether the
other DBFs pose an adverse health risk, more comprehensive quantitative occurrence and
toxicity data are needed. To address this issue, scientists at the U.S. Environmental Protection
Agency's (USEPA's) National Exposure Research Laboratory (NERL) initiated a proposal for a
Nationwide DBF Occurrence Study.
Due to the large number of DBFs identified in drinking waters in the United States and
other countries, it is not feasible to quantify all of them, so a way of prioritizing them was
needed. Prior to this occurrence study, a multidisciplinary group of experts from the USEPA
Office of Water and the USEPA Office of Prevention, Pesticides, and Toxic Substances had
initiated a prioritization effort for the >500 DBFs reported in the literature according to their
predicted adverse health effects (Woo et al, 2002). An in-depth, mechanism-based, structural
activity relationship (SAR) analysis, supplemented by an extensive literature search for
genotoxicity and other data, was used to rank the carcinogenic potential of these DBFs.
Approximately 50 DBFs that received the highest ranking for potential toxicity, and that were
not already included in the USEPA's Information Collection Rule (ICR), were selected for this
occurrence study. Those -50 DBFs are denoted 'high priority' DBFs in this report.
The 'high priority' DBFs include brominated, chlorinated, and iodinated species of
halomethanes, brominated and chlorinated forms of haloacetonitriles, haloketones, haloacids,
and halonitromethanes, as well as analogues of MX [3-chloro-4-(dichloromethyl)-5-hydroxy-
2(5H)-furanone] (Table 1). Chemical Abstract Services (CAS) numbers are provided in Table 1
when they were available. Previously, MX had been determined to be the most mutagenic (to
Salmonella bacteria) DBF ever identified in drinking water, accounting for as much as 20-50%
of the total mutagenic activity measured in chlorinated drinking water samples (Kronberg and
Vartiainen, 1988; Backhand et al., 1988; Meier et al., 1987). MX has also been shown to be
carcinogenic in laboratory animals (Komulainen et al., 1997). Yet, very little drinking water
occurrence data has been obtained for MX, so its potential hazard to humans has not been
determined. There have also been recent reports of brominated DBF forms of MX (BMXs)
(Suzuki and Nakanishi, 1995). These brominated DBF species are of concern because
brominated species of DBFs have been shown to be significantly more carcinogenic than their
chlorinated analogues. Brominated nitromethanes have also been recently shown to be
extremely cytotoxic and genotoxic in mammalian cells (Plewa et al., 2002; Kargalioglu et al., in
press). Specifically, they have been shown to be at least an order of magnitude more genotoxic
to mammalian cells than MX and have genotoxicities greater than all of the regulated DBFs,
except for monobromoacetic acid. It is interesting that dibromonitromethane and
11
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bromonitromethane received the highest priority ranking of all DBFs in the SAR toxicity
analysis effort.
It should be noted that Table 1 lists the identity of more than 50 high priority target
species. During method development, additional species in the same analyte group were
included for some of the drinking water plant surveys.
Because most of the high priority DBFs were from chlorine or chloramine disinfection, a
few additional ozone and chlorine dioxide DBFs that were not ranked as a high priority were also
included for completeness (i.e., to provide more information on those alternative disinfectants).
In addition, methyl tert-buty\ ether (MtBE) and methyl bromide, which are volatile organic
compounds (VOCs) but not DBFs, were included in the list of target analytes because they are
important source water pollutants, and their measurement would provide valuable occurrence
information. Regulated and some ICR DBFs were also included in this study for comparison
purposes (Table 2). In addition, routine water quality measurements, such as total organic
carbon (TOC), total organic halide (TOX), assimilable organic carbon (AOC), and bromide were
determined.
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Table 1. Priority DBFs selected for Nationwide Occurrence Study a
1 MX and MX-Analogues:
I 3-Chloro-4-(dicMoromemyl)-5-hydroxy-2(5H)-furanone (MX)
I 3-Chloro-4-(dichloromethyl)-2-(5H)-furanone (red-MX)
I (E)-2-Chloro-3-(dichloromethyl)-butenedioic acid (ox-MX)
I (E)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid (EMX)
I 2,3-Dichloro-4-oxobutenoic acid (Mucochloric acid) [87-56-9]
! 3-Chloro-4-(bromocMorometnyl)-5-hydroxy-2(5H)-furanone(BMX-l) [132059-51-9]
| 3-Chloro-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone(BMX-2) [132059-52-0]
| 3-Bromo-4-(dibromome1hyl)-5-hydroxy-2(5H)-furanone(BMX-3) [132059-53-1]
| (E)-2-Chloro-3-(bromochloromethyl)-4-oxobutenoic acid (BEMX-1) °
! (E)-2-Chloro-3-(dibromomethyl)-4-oxobutenoic acid (BEMX-2) °
| (E)-2-Bromo-3-(dibromomethyl)-4-oxobutenoic acid (BEMX-3) °
I Haloacids:
I 3,3-Dichloropropenoic acid
j Halomethanes:
I Chloromethane [74-87-3]
I Bromomethane (methyl bromide) [74-83-9] b
I Dibromomethane [74-95-3]
I Bromochloromethane [74-97-5]
I Bromochloroiodomethane [34970-00-8]
! Dichloroiodomethane [594-04-7]
! Dibromoiodomethane ° [593-94-2]
I Chlorodiiodomethane ° [638-73-3]
I Bromodiiodomethane ° [557-95-9]
I lodofbrm [75-47-8]c
I Chlorotribromomethane [594-15-0]
I Carbon tetrachloride [56-23-5]
I Halonitromethanes:
| Bromonitromethane [563-70-2]
I Chloronitromethane ° [1794-84-9]
I Dibromonitromethane [598-91-4]
I Dichloronitromethane ° [7119-89-3]
I Bromochloronitromethane ° [135531-25-8]
| Bromodichloronitromethane ° [918-01-4]
I Dibromochloronitromethane ° [1184-89-0]
I Tribomnifromethane
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Table! (Continued)
Haloacetonitriles:
Bromoacetonitrile [590-17-0]
Chloroacetonitrile [107-14-2]
Tribromoacetonitrile [75519-19-6]
Bromodichloroacetonitrile [60523-73-1]
Dibromochloroacetonitrile [ 144772-39-4]
Haloketones:
Chloropropanone [78-95-5]
1,3-Dichloropropanone [534-07-6]
1,1 -Dibromopropanone
1,1,3-Trichloropropanone [921-03-9]
1 -Bromo-1,1 -dichloropropanone
1,1,1,3-Tetrachloropropanone [16995-35-0]
1,1,3,3-Tetrachloropropanone [632-21-3]
1,1,3,3-Tetrabromopropanone ° [22612-89-1]
1,1,1,3,3-Pentachloropropanone [1768-31-6]
Hexachloropropanone [116-16-5]
Haloaldehydes:
Chloroacetaldehyde [107-20-0]
Dichloroacetaldehyde [70-02-7]
BromocMoroacetaldehyde° [98136-99-3]
Tribromoacetaldehyde [115-17-3] °
Haloacetates:
Bromochloromethyl acetate [247943-54-0]
Haloamides:
Monochloroacetamide [79-07-2] °
Monobromoacetamide [683-57-8] °
Dichloroacetamide [683-72-7]
Dibromoacetamide ° [598-70-9]
Trichloroacetamide [594-65-0] °
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Table! (Continued)
Non-Halogenated Aldehydes and Ketones:
2-Hexenal [505-57-7]; [6728-26-3]
5-Keto-l-hexanald
Cyanoformaldehyde [4471-47-0]
Methylethyl ketone (2-butanone) [78-93-3] d
6-Hydroxy-2-hexanone d
Dimethylglyoxal (2,3-butanedione) [431-03-8]
Volatile organic compounds (VOCs) and Miscellaneous DBFs:
1,1,1,2-Tetrabromo-2-chloroethane
l,l,2,2-Tetrabromo-2-chloroethane °
Methyl-fert-butyl ether [1634-04-4] b
Benzyl chloride [100-44-7]
a Chemical Abstracts Services (CAS) numbers provided in brackets when available.
b Not a DBF, but included because it is an important source water contaminant.
0 DBF not originally prioritized (identified in drinking water after initial prioritization), but
included due to similarity to other priority compounds.
d DBF not given a high priority, but included for completeness sake to provide more
representation to ozone DBFs for occurrence.
Table 2. Information Collection Rule and regulated DBFs included for comparison a
Halomethanes
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Trichloroacetonitrile
Haloketones
1,1 -Dichloropropanone
1,1,1 -Trichloropropanone
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Haloacetic acids (cont).
Dibromoacetic acid
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
Halonitromethanes
Chloropicrin (trichloronitromethane)
Haloaldehydes
Chloral hydrate
(trichloroacetaldehyde)
Oxyhalides
Bromate
Chlorate
Chlorite
a Five HAAs are regulated; six HAAs were required in the ICR, however some utilities reported
data on the complete set of 9 HAAs.
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The design of this study involved the study of drinking waters disinfected with the four
common disinfectants: chlorine, chloramines, ozone, and chlorine dioxide. Because many of the
high priority DBFs were brominated, it was important to include drinking waters that contained
relatively high bromide levels. In addition, many of the waters selected for study were relatively
high in TOC. Drinking water samples were selected from across the United States to assess the
distribution and speciation of by-products in a variety of different waters from geographically
diverse regions, with differing water quality, treatment, and distribution system characteristics
(Figure 1). Moreover, pairs of treatment plants were chosen that used source waters from the
same (or similar) watersheds but employed different treatment technologies and disinfection
scenarios. This permitted an evaluation of the impact of technology and disinfectant
combinations on by-product formation, while minimizing confounding factors related to
differing source water quality. Each of the plants provided operational information and
complementary water quality analyses. Drinking water was also sampled at typically two points
in each distribution system to determine the fate and transport of DBFs—as well as actual
occurrence in the distribution system—and simulated distribution system (SDS) tests were
conducted to determine the formation and stability of DBFs in the presence of chlorine or
chloramines. Previously, most of the newly identified DBFs were detected in drinking waters
that had been sampled only at the treatment plant; very little was known about the fate and
transport (and stability) of most of the newly identified DBFs in the distribution system. To this
end, the influence of water quality parameters, treatment, and distribution system conditions on
DBF concentrations and persistence (stability) was a major objective of this work. The drinking
water utilities that were sampled are shown in Table 3.
16
-------
Sampling Survey: 12 plants sampled quarterly
2 plants - same watershed - different treatment/disinfection
Plants sampled in EPA Regions 3, 4, 5, 6, 7, and 9
...crtior RvtftQH ssi:es
•* Quart
•» American Same a
•* Trust Territnries
...Of/KV RfOiCn't 2 Siti-S
| •* Puerto Rico
| •» Virgin Islanrts
oftho
Northern Mariana Islands
Figure 1. Sampling survey.
Table 3. Drinking water utilities sampled
Utility81 (EPA Region13)
Plant 1 (EPA Region 9)
Plant 2 (EPA Region 9)
Plant 12 (EPA Region 6)
Plant 1 1 (EPA Region 6)
Plant 8 (EPA Region 4)
Plant 7 (EPA Region 4)
Plant 6 (EPA Region 4)
Plant 5 (EPA Region 4)
Plant 3 (EPA Region 3)
Plant 4 (EPA Region 3)
Plant 10 (EPA Region 5)
Plant 9 (EPA Region 7)
Disinfection Used
Ozone - chlorine - chloramines
Chlorine- chloramines
(Chlorine dioxide- )Chloramines
Chlorine dioxide-chlorine-chloramines
Chlorine- chloramines
Chloramines- ozone
Chlorine dioxide-chlorine-chloramines
Ozone -chlorine
Chlorine- chloramines
Chlorine
Chlorine- chloramines
Chlorine- chloramines
17
-------
aThe following pairs of plants treated water from the same or similar watersheds: plants land 2;
3 and 4; 5 and 6; 7 and 8; 9 and 10; and 11 and 12.
bThe 12 plants in this survey were located in six of the nine regions defined by the EPA. The
states included in each of these six regions are as follows:
EPA Region 9—Arizona, California Hawaii, Nevada
EPA Region 6—Arkansas, Louisiana, New Mexico, Oklahoma, Texas
EPA Region 4—Alabama, Florida, Georgia, Kentucky, Mississippi, North Carolina, South
Carolina, Tennessee
EPA Region 3—Delaware, Maryland, Pennsylvania, Virginia, West Virginia, Washington
D.C.
EPA Region 5—Illinois, Indiana, Michigan, Minnesota, Ohio, Wisconsin
EPA Region 7—Iowa, Kansas, Missouri, Nebraska
Because there were no existing quantitative analytical methods for most of the high
priority DBFs, methods were initially developed at UNC and MWDSC. The high priority DBFs
were divided between UNC and MWDSC for method development and quantitative analyses
(UNC measured the MX analogues, carbonyls, 3,3-dichloropropenoic acid, haloacetates,
haloamides, and some haloaldehydes; MWDSC measured bromate, chlorate, chlorite,
halomethanes, haloacetic acids, haloacetonitriles, haloacetaldehydes, haloketones,
halonitromethanes, methyl ethyl ketone, methyl tertiary butyl ether (MTBE),
tetrabromochloroethane, and benzyl chloride). In addition, a method was used at UNC for
differentiating the total organic chlorine and bromine. No one single analytical method could be
used for all DBFs, so different methods were developed and optimized for specific groups of
DBFs. Also, because there were no commercially available standards for many of these
compounds, a significant number had to be synthesized. A combination of extraction and
derivatization techniques were utilized that minimized artifact formation and maximized
recovery of the target analytes from the aquatic matrix. Positive identification was achieved
through use of a combination of complementary spectroscopic tools, some of which were
designed to target a broader range of by-products than those listed, and/or dual-column gas
chromatography. Once methods for the target by-products were established, studies of their
formation and stability were conducted at full-scale treatment plants and their respective
distribution systems.
Another goal of this project was to use this opportunity to look for other DBFs that had
not been previously identified in order to provide a more complete assessment of DBFs formed
by different treatments in different regions of the U.S. This work was carried out at the USEPA
NERL-Athens laboratory. For this research, a combination of mass spectrometric techniques
(gas chromatography with high and low resolution electron ionization mass spectrometry, and
with chemical ionization mass spectrometry) was used to aid in the identification of these new
DBFs. Mass spectra for those DBFs that had not been previously reported (i.e., those identified
in this study for the first time) are provided in the Appendix of this report.
Presentations of preliminary results from this Nationwide DBF Occurrence Study have
been given at several scientific meetings over the last three years. Citations of the more
comprehensive proceedings articles appear below for reference (Krasner et al., 2002; Sclimenti
18
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et al., 2002; Krasner et al, 2001; Weinberg et al., 2001; Gonzalez et al., 2000; Onstad et al,
2000, Onstad and Weinberg, 2001).
This report is presented in multiple chapters, each of which represents a specific
component of the research, method development, and DBF analysis in the treatment plants after
different unit processes and/or disinfectant addition and in the distribution systems.
19
-------
REFERENCES
Backhand, P., L. Kronberg, and L. Tikkanen. Formation of Ames mutagenicity and of the strong
bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone and other halogenated
compounds during disinfection of drinking water. Chemosphere 17(7): 1329(1988).
Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly
identified disinfection by-products in drinking water. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2000.
Kargalioglu, Y., E. D. Wagner, S. D. Richardson, and M. J. Plewa. DNA damage in the
CHO/Comet assay induced by nitrohalomethanes, a novel class of drinking water disinfection
by-products. Environmental Science & Technology (in press).
Komulainen, H., V.-M. Kosma, S.-L. Vaittinen, T. Vartiainen, E. Kaliste-Korhonen, S. Lotionen,
R. K. Tuominen, and J. Tuomisto. Carcinogenicity of the drinking water mutagen 3-chloro-4-
(dichloromethyl)-5-hydroxy-2(5H)-furanone in the rat. Journal of the National Cancer Institute
89(12): 848 (1997).
Krasner, S. W., R. Chinn, S. Pastor, M. J. Sclimenti, S. D. Richardson, A. D. Thruston, Jr., and
H. S. Weinberg. Relationships between the different classes of DBFs: formation, speciation, and
control. Proceedings of the American Water Works Association Water Quality Technology
Conference., American Water Works Association: Denver, CO, 2002.
Krasner, S. W., S. Pastor, R. Chinn, M. J. Sclimenti, H S. Weinberg, and S. D. Richardson. The
occurrence of a new generation of DBFs (beyond the ICR). Proceedings of the American Water
Works Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2001.
Kronberg, L., and T. Vartiainen. Ames mutagenicity and concentration of the strong mutagen 3-
chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone and of its geometric isomer E-2-chloro-3-
(dichloromethyl)-4-oxo-butenoic acid in chorine-treated tap waters. Mutation Research 206:177
(1988).
Meier, J. R., R. B. Knohl, W. E. Coleman, H. P. Ringhand, J. W. Munch, W. H. Kaylor, R. P.
Streicher, and F. C. Kopfler. Studies on the potent bacterial mutagen, 3-chloro-4-
(dichloromethyl)-5-hydroxy-2(5H)-furanone: aqueous stability, XAD recovery and analytical
determination in drinking water and in chlorinated humic acid solutions. Mutation Research
189:363 (1987).
Onstad, G. D., H. S. Weinberg, S. W. Krasner, and S. D. Richardson. Evolution of analytical
methods for halogenated furanones in drinking water. Proceedings of the American Water
20
-------
Works Association Water Quality Technology Conference., American Water Works Association:
Denver, CO, 2000.
Onstad, G. D., and H. S. Weinberg. Improvements in extraction of MX-analogues from drinking
water. Proceedings of the American Water Works Association Water Quality Technology
Conference, American Water Works Association: Denver, CO, 2001.
Plewa, M. L, E. D. Wagner, and S. D. Richardson. Quantitative comparative mammalian cell
cytotoxicity and genomic genotoxicity of drinking water disinfection by-products. Paper
presented at the International Society of Exposure Analysis (ISEA)-International Society for
Environmental Epidemiology (ISEE) Conference, Vancouver, Canada, August 11-15, 2002.
Richardson, S. D. Drinking water disinfection by-products. In The Encyclopedia of
Environmental Analysis and Remediation (R.A. Meyers, ed.), Vol. 3, John Wiley & Sons: New
York, 1998, pp.1398-1421.
Sclimenti, M. J., S. W. Krasner, and S. D. Richardson. The determination of DBFs using a solid
phase microextraction (SPME)-GC/ECD technique. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2002.
Suzuki, N., and J. Nakanishi. Brominated analogues of MX (3-chloro-4-(dichloromethyl)-5-
hydroxy-2(5H)-furanone in chlorinated drinking water. Chemosphere 30(8): 1557 (1995).
Weinberg, H. S., S. W. Krasner, and S. D. Richardson. Determination of new carbonyl-
containing disinfection by-products in drinking water. Proceedings of the American Water
Works Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2001.
Woo, Y.-T., D. Lai, J. L. McLain, M. K. Manibusan, and V. Dellarco. Use of mechanism-based
structure-activity relationships analysis in carcinogenic potential ranking for drinking water
disinfection by-products. Environmental Health Perspectives 110(Suppl. 1):75 (2002).
21
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RESULTS
EPA REGION 9: PLANTS 1 AND 2
Plant Operations and Sampling
On October 30, 2000, January 23, 2001, July 17, 2001, and March 19, 2002, two
treatment plants in EPA Region 9 were sampled.
The treatment processes at plant 1 (Figure 1) included ozonation, flocculation,
coagulation, sedimentation, and filtration. A secondary disinfectant was not applied until after
the filters, so the filters were operated biologically. After the filters, the water was chlorinated
with a short, free chlorine contact time, and then ammonia was added to form chloramines.
Note, the basins at plant 1 were chlorinated (using sodium hypochlorite) on average twice per
week for approximately four hours. This chlorine was applied to the effluent of the ozone
contactors to help control algae and other growths in the basins.
Plant 1 was sampled at the following locations:
(1) raw water before the ozone contactor
(2) the ozone (Os) contactor effluent
(3) the filter influent
(4) the filter effluent
(5) the clearwell effluent
(6) the finished water
The treatment processes at plant 2 (Figure 2) included coagulation and filtration.
Chlorine was applied to the raw, settled, and filtered waters. Ammonia was added to the finished
water to form chloramines.
Plant 2 was sampled at the following locations:
(1) filter influent (settled water) or filter effluent
(2) the effluent of the treated water tank
(3) the finished water
In addition, finished water was collected from both plants, and simulated distribution system
(SDS) testing conducted for average and maximum detention times for that time of the year
(Table 1). Furthermore, the distribution system was sampled at two locations, one representing
an average detention time and the other representing a maximum detention time. (Raw water
was not sampled at plant 2, as it was the same as was used at plant 1.)
Table 1. SDS holding times (hr) at the EPA Region 9 treatment plants
Sample
Plant 1 average detention time
Plant 1 maximum detention time
Plant 2 average detention time
Plant 2 maximum detention time
10/30/00
18
NSa
18
NS
1/23/01
23
48
22
38
7/17/01
6
28
4
5
3/19/02
65
70
5
10
aNS = Not sampled
22
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Figure 1
RAW -
WATER
O/jone
V
Plant 1 Schematic
Ah
J
Alum/ Ferric Chloride
Cationic Polymer
Ozone Contact Basin
Flash Mixer
Aqua Ammonium Sodium Hypochlorite
Sodium Hydroxide
Clearwell
Filters
Flocculator
Sedimentation Basin
DISTRIBUTION SYSTEM
Reservoir
Figure 2
Plant 2 Schematic
Chlorine
Alum
Cationic Polymer
RAW
WATER
Aqua Ammonia
Sodium Hydroxide
FINISHED^ V
WATER
Chlorine
Nonionic Polymer
Chlorine
23
Clearwell
-------
On the day of sampling, information was collected on the operations at each plant
(Tables 2-3).
Table 2. Operational information at plant 1
Parameter
Plant flow (mgd)
Ozone dose (mg/L)
HRTa in ozone contactor (min)
CT achieved from ozonation (mg/L- min)
Giardia inactivation achieved from ozonation (logs)
Coagulant6 dose (mg/L)
Filter loading rate (gpm/sq ft)
Filter EBCT1 (min)
Chlorine dose at ozone contactor effluent (mg/L)
Chlorine dose at filter effluent (mg/L)
Ammonia dose at clearwell effluent (mg/L as N)
10/30/00
11.0
1.84
4.9
1.67
0.75
14
2.8
6.7
0
2.93
0.56
1/23/01
16.2
2.53
9.5
1.24
2.82
13
3.4
7.7
0
4.65
0.72
7/17/01
22.0
2.43
6
0.20
1.31
18
4.7
5.5
0
2.15
0.48
3/19/02
15.8
2.33
9.8
3.6
NAC
16
4.8
9
0
3.6
0.55
aHydraulic retention time in cells 1 and 2 only
bFerric chloride (FeCls)
°NA = Not available
dEmpty bed contact time through both media layers
Table 3. Operational information at plant 2
Parameter
Plant flow (mgd)
Coagulant3 dose (mg/L)
Chlorine dose at plant influent (mg/L)
Chlorine dose at filter influent (mg/L)
Chlorine dose at filter effluent (mg/L)
Ammonia dose at effluent of treated water tank
(mg/L as N)
10/30/00
6.8
20
1.11
0.65
1.93
0.46
1/23/01
5.6
19
1.3
0.60
2.31
0.44
7/17/01
7.7
25
1.5
0.8
1.95
0.5
3/19/02
4.4
12
1.2
0.75
3.7
0.62
aAlum [A12(SO4)3 14H2O] on 10/30/00 and 1/23/01, ferric chloride (FeCl3) on 7/17/01 and
3/19/02
Water Quality
On the day of sampling, information was also collected on the water quality at each plant
(Tables 4- 5).
24
-------
Table 4. Water quality information at plant 1
Location
Raw
O3 eff.
Filt. inf.
Filt. eff.
Clear, eff.
Fin. water
DS7ave.
DS/max
SDS/ave.
SDS/max
PH
10/30/00
8.16
8.13
7.73
7.84
7.59
8.20
8.1
8.35
8.19
NS
1/23/01
8.3
7.89
7.20
6.90
9.0
8.63
8.74
8.65
8.09
8.57
7/17/01
7.7
7.4
6.8
6.7
6.7
8.7
8.2
8.3
8.6
8.2
3/19/02
9.07
7.14
6.78
6.82
6.73
8.22
8.54
8.61
8.43
8.34
Temperature (°C)
10/30/00
17.3
17
17.3
17.1
17
16
17.1
17.9
15.6
NS
1/23/01
10.6
10.4
10.9
10.6
10.5
9.7
11.9
11.8
12.4
10.2
7/17/01
20.7
22.3
21.5
21.0
21.4
20.7
22.3
21.8
21.3
20.8
3/19/02
13.6
13.4
13.8
13.9
13.7
13.2
14.7
14.4
14.2
14.9
Disinfectant Residual3 (mg/L)
10/30/00
—
0.34
—
—
2.26
1.81
1.61
1.14
1.67
NS
1/23/01
—
0.26
—
—
3.61
3.65
1.62
0.26
1.59
1.21
7/17/01
—
0.20
—
—
2.05
1.86
1.81
1.78
1.86
1.80
3/19/02
—
0.37
—
—
2.64
2.81
>2.20
>2.20
2.11
2.08
3Ozone residuals (values shown in bold) in effluent of cell 2 of ozone contactor; chlorine residuals (values shown in italics) at clearwell effluent;
chloramine residuals at other locations.
bDS = Distribution system
Table 5. Water quality information at plant 2
Location
Filt. eff.D
Treat, tank0
Fin. water
DS/ave.
DS/max
SDS/ave.
SDS/max
PH
10/30/00
7.5
7.5
7.88
8.23
8.35
8.16
NS
1/23/01
7.4
7.3
8.3
8.95
8.69
8.51
8.51
7/17/01
6.7
6.6
8.6
8.5
8.5
8.14
8.10
3/19/02
7.35
7.21
8.74
8.98
8.72
8.56
8.67
Temperature (°C)
10/30/00
17.8
16.4
16.3
14.6
19.6
17.6
NS
1/23/01
10.7
11.5
11.6
10.9
12.4
11.4
10.1
7/17/01
21.5
21.8
21.7
21.4
21.8
21.2
20.9
3/19/02
13.0
13.2
13.4
13.5
14.0
14.3
16.1
Disinfectant Residual3 (mg/L)
10/30/00
0.72
1.69
1.85
1.38
0.96
1.55
NS
1/23/01
0.33
1.83
1.88
1.35
0.97
1.46
1.50
7/17/01
0.22
1.91
1.84
2.00
1.78
1.93
2.05
3/19/02
0.26
2.71
2.43
1.83
1.92
2.13
2.20
3Chlorine residuals (values shown in italics) at filter effluent and at effluent of treated water tank; chloramine residuals at other locations.
bSampled settled water (filter influent) rather than filter effluent on 10/30/00
GEffluent of treated water tank
25
-------
Other data collected included total organic carbon (TOC) and ultraviolet (UV)
absorbance (Table 6). The TOC ranged from 3.0 to 4.5 mg/L and the UV was 0.076 to 0.136
cm"1. Typically, ozonation had little effect on TOC. In July 2001, ozonation resulted in a slight
increase in the value of the TOC. This phenomenon is due to the conversion of "recalcitrant"
TOC by ozone to a form that can be more readily measured by a TOC analyzer. On the other
hand, a significant portion of the UV absorbance was reduced by ozone. At plant 1, coagulation
removed 27-47 % of the TOC and biofiltration removed another 14-21 %. In addition,
coagulation reduced the UV by 38-63 %. The overall (cumulative) removal of TOC at plant 1
was 37-53 % and the UV reduction was 70-81 %. At plant 2, 8-47 % of the TOC was removed
and UV reduced by 51-80 % by the coagulation/filtration process.
Table 6. TOC and UV removal at the EPA Region 9 treatment plants
Location
10/30/2000
Plant 1 Raw
Plant 1 03 Eff.
Plant 1 Filter Inf.
Plant 1 Filter Eff.
Plant 2 Filt. Eff.
1/23/2001
Plant 1 Raw
Plant 1 O3 Eff.
Plant 1 Filter Inf.
Plant 1 Filter Eff.
Plant 2 Filt. Eff.
7/17/2001
Plant 1 Raw
Plant 1 O3 Eff.
Plant 1 Filter Inf.
Plant 1 Filter Eff.
Plant 2 Filt. Eff.
3/19/2002
Plant 1 Raw
Plant 1 O3 Eff.
Plant 1 Filter Inf.
Plant 1 Filter Eff.
Plant 2 Filt. Eff.
TOC
(mg/L)
3.1
3.1
2.3
2.0
2.9
4.48
4.34
3.11
2.47
3.00
2.99
3.11
1.64
1.4
1.57
4.5
4.4
2.69
2.2
3.02
UV
(cm'1)
0.076
0.039
0.024
0.023
0.037
0.136
0.070
0.031
0.031
0.055
0.093
0.048
0.018
0.018
0.019
0.132
0.069
0.030
0.029
0.060
SUVA3
(L/mg-m)
2.4
1.3
1.1
1.2
1.3
3.0
1.6
1.0
1.3
1.8
3.1
1.5
1.1
1.3
1.2
2.9
1.6
1.1
1.3
2.0
Removal/Unit (%)
TOC
___
1.3%
27%
14%
7.7%
—
3.1%
28%
21%
33%
___
-4.0%
47%
15%
47%
___
2.2%
39%
18%
33%
UV
—
49%
38%
4.2%
51%
—
49%
56%
0%
60%
—
48%
63%
0%
80%
—
48%
57%
3.3%
55%
Removal/Cumulative (%)
TOC
—
1.3%
27%
37%
7.7%
—
3.1%
31%
45%
33%
—
-4.0%
45%
53%
47%
—
2.2%
40%
51%
33%
UV
—
49%
68%
70%
51%
—
49%
77%
77%
60%
—
48%
81%
81%
80%
—
48%
77%
78%
55%
aSUVA = Specific ultraviolet absorbance
where DOC = dissolved organic carbon,
(used TOC values in calculating SUVA)
= 100*UV/DOC,
which typically = 90-95% TOC
Table 7 shows the values of miscellaneous other water quality parameters in the EPA
Region 9 treatment plants' raw source water. Bromide ranged from 0.12 to 0.40 mg/L. At both
plant 1 and plant 2, they treated surface water impacted by saltwater intrusion.
26
-------
Table 7. Miscellaneous water quality parameters in plant 1 and 2's raw water
Date
10/30/2000
01/23/2001
07/17/2001
03/19/2002
Bromide
(mg/L)
0.16
0.40
0.14
0.12
Alkalinity
(mg/L)
106
66
72
82
Ammonia
(mg/L as N)
NDa
0.04
0.04
ND
aND= Not detected
The source water was moderate in alkalinity. The raw-water pH varied from 7.7 to 9.1
(Table 4). The source water can have significant variability in these inorganic parameters.
DBFs
Oxyhalides. Ozonation resulted in the formation of <3 to 26 |ig/L of bromate (Table 8).
Bromate formation was highest in January 2001 when the bromide concentration in the raw
water was highest (Table 7).
Table 8. Oxyhalide formation at the EPA Region 9 treatment plants
Location
10/30/2000
Plant 1 O3 eff.
Plant 1 clear, eff.
1/23/2001
Plant 1 O3 eff.
Plant 1 clear, eff.
Plant 2 fin. water
7/17/2001
Plant 1 03 eff.
Plant 1 clear, eff.
Plant 2 fin. water
3/19/2002
Plant 1 03 eff.
Plant 1 clear, eff.
Plant 2 fin. water
Bromate
(Ufl/D
5.7
5.2
26
22
ND
4.9
5.5
ND
NDa (2)
4
ND(1)
Chlorate
ftjQ/L)
10
157
5.9
121
114
9.8
133
93
10
80
127
Bro mate/Bromide
(|jmol/|jmol)
2.2%
4.0%
2.2%
1 .0%
2.1%
aND = Not detected
(bromate minimum reporting level [MRL] = 3 |jg/L;
value in parenthesis is < MRL)
The conversion of bromide to bromate was 1-4 % (on a molar basis), which is a typical
conversion rate for an ozone plant operating for Giardia inactivation (Douville and Amy, 2000).
In addition, sodium hypochlorite can be contaminated with low or sub-|ig/L levels of bromate
(Delcomyn et al, 2000). In March 2002, there was an increase in the concentration of bromate
in the treated water at plant 1 after secondary disinfection (4 versus <3 |ig/L). Bromate was not
detected (minimum reporting level of 3 |ig/L) at plant 2. However, some chlorate was
27
-------
introduced into the finished waters at both plants from secondary disinfection (Table 8) (chlorate
is a by-product formed during the decomposition of the hypochlorite stock solution [Bolyard et
al. [1992]).
Biodegradable Organic Matter. Ozone can convert natural organic matter in water to
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Kooij et
al., 1982). Table 9 shows the carboxylic acid and AOC data for plant 1. Because AOC data are
expressed in units of micrograms of carbon per liter (jig C/L), the carboxylic acid data were
converted to the same units. A portion of the molecular weight (MW) of each carboxylic acid is
due to carbon atoms (i.e., 27-49 %) and the remainder is due to oxygen and hydrogen atoms.
The sums of the five carboxylic acids (on a jig C/L basis) were compared to the AOC data. On a
median basis for each sample date, 19 to 30 % of the AOC was accounted for by the carboxylic
acids.
Figures 3 and 4 show the AOC and the carboxylic acid results, respectively, for the July
2001 sample date. Ozonation resulted in a significant increase in AOC and the concentration of
the carboxylic acids, especially oxalate. (Note, one of the bacterial strains used in the AOC
method [i.e., Spirillum NOX\ is used to estimate oxalate-carbon equivalents of the AOC [van der
Kooij and Hijnen, 1984].) The carboxylic acids and AOC were both significantly reduced in
concentration in the downstream treatment processes (coagulation/sedimentation) prior to
biological filtration. Because chlorine was not applied until after the filters, there may have been
biological activity in the basins that degraded the AOC. Also, some of the AOC may have been
removed by the coagulation process (Volk and LeChevallier, 2002) along with the TOC
(Table 6).
Figures 5 and 6 show the formation and removal of AOC and oxalate, respectively, for all
of the sample dates. AOC increased from 16-83 jog C/L in the raw water to 504-707 jig C/L in
the ozonated water. AOC decreased to 148-333 jig C/L in the settled water and to 131-
224 jjg C/L in the filtered water. Oxalate increased from 14-18 |ig/L in the raw water to 314-
409 |ig/L in the ozonated water. Oxalate decreased to 56-223 jig/L in the settled water and to 9-
33 |ig/L in the filtered water. The formation and removal of carboxylic acids—in particular that
of oxalate—and AOC tended to follow the same trends through the different treatment processes.
Halogenated Organic and Other Non-halogenated Organic DBFs. Tables 10 and 11
(10/30/00), Tables 13 and 14 (1/23/01), Tables 16 and 17 (7/17/01), and Tables 20 and 21
(3/19/02) show results for the halogenated organic DBFs that were analyzed by MWDSC.
28
-------
Table 9. Formation and removal of carboxylic acids and AOC at plant 1
Location
10/30/2000
Raw water
Ozone effluent
Filter influent
Filter effluent
1/23/2001
Raw water
Ozone effluent
Filter influent
Filter effluent
7/17/2001
Raw water
Ozone effluent
Filter influent
Filter effluent
3/19/2002
Raw water
Ozone effluent
Filter influent
Filter effluent
Formula
MW (am/molel
C oortion (am/mole)
C% of MW
Concentration3 (|jg/L)
Acetate
ND
ND
ND
ND
N/A
N/A
N/A
N/A
13
80
16
45
11
77
40
ND
CH3COO"
59
24
41%
Propionate
ND
ND
ND
ND
N/A
N/A
N/A
N/A
ND
8.8
5.5
ND
ND
ND
ND
ND
CH3CH2COO"
73
36
49%
Formate
ND
ND
32
25
N/A
N/A
N/A
N/A
15
223
43
43
12
206
125
ND
HCOO"
45
12
27%
Pyruvate
ND
ND
19
25
N/A
N/A
N/A
N/A
13
50
19
14
7.1
31
23
4.0
CHsCOCOO"
87
36
41%
Oxalate
17
314
70
33
N/A
N/A
N/A
N/A
14
378
56
22
18
409
223
8.7
c2o42"
88
24
27%
Concentration (|jg C/L)
Acetate
ND
ND
ND
ND
5.3
32
6.4
18
4.3
31
16
ND
Propionate
ND
ND
ND
ND
ND
4.4
2.7
ND
ND
ND
ND
ND
Formate
ND
ND
8.6
6.6
3.9
60
11
12
3.2
55
33
ND
Pyruvate
ND
ND
7.8
10
5.5
21
7.9
57
2.9
13
9.5
1.7
Oxalate
4.6
86
19
9.0
3.9
103
15
59
5.0
112
61
2.4
Sum
4.6
86
36
26
19
220
44
41
15
211
120
4.0
AOC-P17
N/Ab
168
N/A
72
13
191
54
50
54
186
41
43
48
266
38
51
AOC-NOX
N/A
336
N/A
101
AOC
504
173
median
3.4
386
279
91
29
516
107
89
16
578
333
141
83
703
148
131
median
4.7
441
205
173
53
707
243
224
median
Sum/
AOC
17%
21%
19%
22%
31%
30%
33%
30%
29%
30%
49%
2%
29%
Method detection limit (MDL) = 3 |jg/L; reporting detection level (RDL) = 15 |jg/L; value in italics < RDL
29
-------
800
Figure 3
Formation and Removal of AOC at Plant 1: 7/17/01
IAOC-P17 DAOC-NOX
700
600
O 500
D)
O 400
O
S 300
O
200
100
800
700
Raw water
Ozone effluent
Filter influent
Filter effluent
Figure 4
Formation and Removal of Carboxylic Acids at Plant 1: 7/17/01
• Acetate DPropionate El Formate HPyruvate HOxalate
Raw water
Ozone effluent
Filter influent
Filter effluent
30
-------
Figure 5
Formation and Removal of AOC at Plant 1
800
700
110/30/2000 • 1/23/2001 • 7/17/2001 D3/19/2002
N/A = Not available, samples lost
Raw water
Ozone effluent
Filter influent
Filter effluent
Figure 6
Formation and Removal of Oxalate at Plant 1
110/30/2000 • 7/17/2001 D3/19/2002
450
1/23/01: Not available, samples lost
Raw water
Filter effluent
-------
Table 10. DBF results at plant 1 (10/30/00)
10/30/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroaceticacid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAAj
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Haloacetaldehvdes
Dichloroacetaldehvde
Bromochloroacetaldehyde1
Chloral hydrate6
Tribromoacetaldehyde
MRLa
ljg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.19
0.14
0.5
0.5
0.5
0.59
0.53
0.22
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.11
0.1
0.16
0.2
0.1
Plant 1b
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
03Eff
ND
ND
ND
ND
0.7
0.7
1
0.2
3
ND
NR
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clear. Eff
ND
ND
ND
ND
1
1
4
2
8
NR9
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.3
ND
ND
ND
0.2
Fin. Water
ND
ND
ND
ND
1
3
8
4
16
NR
NR
NR
ND
ND
ND
ND
0.1
ND
ND
1.3
1.6
2.1
ND
ND
ND
ND
3.4
5.0
5.0
ND
ND
ND
0.2
0.4
0.6
ND
0.4
1
0.1
SDS
ND
ND
ND
ND
2
3
8
4
17
1
NR
NR
ND
ND
ND
ND
0.1
ND
ND
1.8
2.0
2.9
ND
ND
ND
ND
4.7
6.7
6.7
ND
ND
ND
0.2
0.4
0.6
ND
0.7
2
ND
DS/Ave.
ND
ND
ND
ND
8
3
7
3
21
1
NR
NR
ND
ND
ND
ND
ND
ND
ND
5.8
2.2
2.1
1.8
ND
ND
ND
10
12
10
1.8
ND
ND
0.4
0.4
0.4
ND
0.4
2
ND
DS/Max.
4
4
11
5
24
NR
NR
NR
ND
ND
ND
0.1
ND
ND
0.3
0.6
0.7
ND
0.7
0.6
0.2
32
-------
Table 10 (continued)
10/30/2000
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1-Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Corrmounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
ug/L
0.1
0.1
0.1
3
0.1
0.1
3
3
3
0.1
0.1
0.1
3
0.11
0.1
1.9
0.16
0.5-3
Plant 1b
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.9
ND
03Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
Clear. Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
ND
ND
0.6
ND
Fin. Water
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.8
NR
SDS
0.3
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
0.7
NR
DS/Ave.
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.4
NR
DS/Max.
0.2
0.2
ND
0.1
0.1
ND
ND
ND
ND
0.2
NR
aMRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
bPlant 1 sampled at (1) raw water, (2) ozone contactor effluent, (3) clean/veil effluent,
(4) finished water, (5) SDS testing of finished water,
(6) distribution system at average detention time and (7) at maximum detention time.
cPlant 2 sampled at (1) filter influent, (2) effluent of treated water tank,
(3) finished water, (4) SDS testing of finished water,
(5) distribution system at average detention time and (6) at maximum detention time.
dND = Not detected at or above MRL
eDBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
fTHM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
9NR = Not reported, due to interference problem on gas chromatograph or
to problem with quality assurance
hHAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-,
trichloroacetic acid)
'HAA9 = Sum of 9 haloacetic acids
JDXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
kTXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
'Bromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs
m<3: Concentration less than MRL of 3 |jg/L
33
-------
Table 11. DBF results at plant 2 (10/30/00)
10/30/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloro methane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroaceticacid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde'
Chloral hydrate6
Tribromoacetaldehyde
MRLa
M9/L
0.15
0.20
0.14
0.11
0.1
0.1
0.19
0.14
0.5
0.5
0.5
0.59
0.53
0.22
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.11
0.1
0.16
0.2
0.1
Plant 2C
Filt. Inf
10
8
16
4
38
NR
NR
NR
ND
ND
NR
ND
ND
ND
1
1
0.8
ND
0.6
3
0.5
Treat. Tank
ND
ND
ND
ND
11
15
25
5
56
NR
1
NR
ND
ND
ND
ND
ND
ND
ND
9.9
9.4
6.9
8.4
6.0
2.5
ND
25
43
26
17
ND
ND
2
2
1
ND
0.9
4
0.6
Fin. Water
ND
ND
ND
ND
14
14
25
5
58
NR
1
NR
ND
ND
ND
ND
ND
ND
ND
9.5
9.1
6.6
7.9
5.6
2.4
ND
24
41
25
16
ND
ND
2
2
1
ND
1
4
0.4
SDS
ND
ND
ND
ND
15
17
26
5
63
3
1
NR
ND
ND
ND
ND
ND
ND
ND
11
10
7.1
8.6
3.4
1.6
ND
27
42
28
14
ND
ND
2
2
1
ND
2
4
ND
DS/Ave.
ND
ND
ND
ND
14
23
35
6
78
4
1
1
0.7
ND
ND
ND
ND
ND
ND
11
11
8.1
8.4
ND
ND
ND
28
39
30
8.4
ND
ND
2
2
2
ND
1
4
0.3
DS/Max.
17
20
31
6
74
NR
NR
NR
ND
ND
ND
ND
ND
ND
2
2
1
ND
2
5
ND
34
-------
Table 11 (continued)
10/30/2000
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1 , 1 , 1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
ug/L
0.1
0.1
0.1
3
0.1
0.1
3
3
3
0.1
0.1
0.1
3
0.11
0.1
1.9
0.16
0.5-3
Plant 2C
Filt. Inf
ND
0.4
ND
0.9
0.1
0.2
ND
ND
ND
ND
NR
Treat. Tank
ND
0.3
ND
ND
2
ND
<3m
ND
ND
0.2
ND
ND
ND
ND
ND
ND
0.9
NR
Fin. Water
ND
0.3
ND
ND
1
ND
<3
ND
ND
0.2
ND
ND
ND
ND
ND
ND
0.9
NR
SDS
0.1
0.4
ND
ND
0.7
ND
ND
ND
ND
0.1
ND
ND
ND
ND
0.2
ND
0.9
NR
DS/Ave.
0.2
0.4
ND
ND
1
ND
ND
ND
ND
0.2
ND
ND
ND
ND
0.2
ND
0.9
NR
DS/Max.
0.2
0.4
ND
0.3
ND
ND
ND
ND
ND
0.3
NR
35
-------
Table 12. Additional target DBF results (ug/L) at the EPA Region 9 treatment plants
(10/30/00)
10/30/00
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (ug/L as CO
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
trans -2-Hexenal
Plant la
Raw
0
0
0
0
0.5
0
NAC
<0.1
<0.4
<0.4
<0.4
<0.5
OE
0
0
0
0
0.1
0
NA
<0.1
<0.4
<0.4
1.3
<0.5
FE
0
0
0
0
0.1
0
10.2
<0.1
<0.4
<0.4
1.1
<0.5
PE
0
0.6
1.0
0.1
0.1
0.2
75.5
0.2
<0.4
<0.4
<0.4
<0.5
DS
0
0.7
1.3
0.1
0.1
0.3
109
0.2
<0.4
<0.4
<0.4
<0.5
Plant 2b
Raw
0
0
0
FI
0.1
0.9
1.7
0.3
0
0
NA
0.1
<0.4
<0.4
<0.4
<0.5
TT
0.1
1.1
1.9
0.4
0
0
NA
<0.1
<0.4
<0.4
<0.4
<0.5
PE
0.1
1.4
1.3
0.7
0
0.8
199
0.3
<0.4
<0.4
<0.4
<0.5
DS
0.2
1.7
1.1
0.2
0
1.4
135
0.3
<0.4
<0.4
<0.4
<0.5
aPlant 1 sampled at (1) raw water, (2) ozone contactor effluent (OE), (3) filter effluent (FE), (4)
finished water at plant effluent (PE), and (5) distribution system (DS) at average detention time.
bPlant 2 sampled at (1) filter influent (FI), (2) effluent of treated water tank (TT), (3) finished
water at PE, and (4) DS at average detention time.
°NA = Not available
36
-------
Table 13. DBF results at plant 1 (1/23/01)
1/23/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Halnaretir acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoaceticacid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAk
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRLa
ug/L
0.15
0.20
0.14
0.11
0.1
0.1
0.12
0.12
0.25
0.20
0.64
0.52
0.60
0.70
0.06
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.10
0.1
0.16
0.1
0.1
0.1
Plant 1"
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
03Eff
ND
ND
ND
ND
0.2
1
1
0.5
3
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
0.3
0.6
0.2
0.1
Clear. Eff
ND
ND
ND
ND
0.5
2
4
3
10
ND
ND
ND
ND
ND
ND
ND
ND
1.1
2.1
3.0
14
ND
1.0
2.2
ND
17
23
19
3.2
ND
ND
0.1
0.3
0.6
ND
0.8
3
0.1
1
Fin. Water
ND
ND
ND
ND
NRg
NR
NR
NR
NR
0.2
ND
ND
ND
ND
ND
ND
ND
1.4
2.0
3.0
13
ND
ND
1.4
ND
16
21
18
1.4
ND
ND
0.1
0.3
0.7
ND
NR
3
NR
NR
DS/Ave
ND
ND
ND
ND
2
7
16
20
45
0.3
0.2
ND
ND
ND
ND
ND
ND
1.2
3.6
7.0
13
1.0
1.4
2.1
ND
19
29
24
4.5
ND
ND
0.2
0.3
0.7
ND
0.8
3
0.2
0.5
DS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.4
1
2
ND
1
6
0.3
0.4
SDS/Ave
ND
ND
ND
ND
1
6
20
30
57
0.2
ND
ND
ND
ND
ND
ND
ND
1.4
2.4
4.9
11
ND
ND
1.4
ND
15
21
18
1.4
ND
ND
0.2
0.9
2
ND
2
7
0.2
0.2
SDS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.2
0.9
2
ND
2
6
0.2
ND
37
-------
Table 13 (continued)
1/23/2001
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanonee
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 . 1 . 1-Trichloropropanonee
1 . 1 ,3-Trichloropropanone
1 -Bromo-1 , 1-dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1.1. 1 .3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrirf
Miscellaneous Compounds
Methvl ethvl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL
ug/L
0.5
0.10
0.1
N/AP
0.10
0.5
N/A
N/A
N/A
0.10
N/A
0.5
0.1
N/A
N/A
0.10
0.1
1.9
0.16
2
Plant 1
Raw
ND
ND
ND
NR
ND
ND
NR
NR
NR
ND
NR
ND
ND
NR
NR
ND
ND
ND
0.3
ND
03Eff
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
Clear. Eff
ND
0.3
ND
NR
0.2
ND
NR
NR
NR
ND
NR
0.2-0.6q
0.1
NR
NR
0.1-0.2q
ND
ND
0.2
ND
Fin. Water
ND
0.2
ND
NR
0.3
ND
NR
NR
NR
ND
NR
ND
0.1
NR
NR
0.1-0.2
ND
ND
0.2
ND
DS/Ave
ND
0.3
ND
NR
0.2
ND
NR
NR
NR
ND
NR
ND
0.1
NR
NR
0.1-0.2
ND
ND
0.2
ND
DS/Max
ND
0.2
ND
0.2
ND
ND
ND
0.2
0.2-0.3
0.2
ND
SDS/Ave
ND
0.1
ND
NR
0.2
ND
NR
NR
NR
ND
NR
ND
0.2
NR
NR
0.1-0.2
0.2
ND
0.2
ND
SDS/Max
ND
0.2
ND
ND
ND
ND
ND
0.2
ND
0.4
ND
"Plant 1 sampled at (1) raw water, (2) ozone contactor effluent, (3) clearwell effluent, (4) finished water,
(5) SDS testing of finished water at average detention time and (6) at maximum detention time, and
(7) distribution system at average detention time and (8) at maximum detention time.
°Plant 2 sampled at (1) filter effluent, (2) effluent of treated water tank, (3) finished water,
(4) SDS testing of finished water at average detention time and (5) at maximum detention time, and
(6) distribution system at average detention time and (7) at maximum detention time.
PN/A = Not applicable
qSpike recovery »100%; range of values represents reported values and values corrected for recovery
38
-------
Table 14. DBF results at plant 2 (1/23/01)
1/23/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloro methane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoaceticacid
HAA5h
HAA91
DXAAJ
TXAA*
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL
Mg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.12
0.12
0.25
0.20
0.64
0.52
0.60
0.70
0.06
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.10
0.1
0.16
0.1
0.1
0.1
Plant 2°
Filt. Eff
NR
NR
NR
NR
NR
NR
NR
ND
ND
0.6
ND
ND
ND
2
2
2
ND
1
4
0.6
1
Treat. Tank
ND
ND
ND
ND
8
20
30
18
76
0.5
0.6
ND
ND
ND
ND
ND
ND
1.2
14
19
18
9.7
16
15
3.9
43
97
51
45
ND
ND
2
3
3
ND
2
4
1
3
Fin. Water
ND
ND
ND
ND
11
30
40
18
99
0.6
0.8
0.6
ND
ND
ND
ND
ND
1.2
14
18
18
8.6
15
15
3.6
42
93
50
42
ND
ND
2
3
2
ND
2
4
1
3
DS/Ave
ND
ND
ND
ND
18
40
50
19
127
0.4
0.4
0.8
ND
ND
ND
ND
ND
1.3
15
19
20
8.6
15
14
3.3
45
96
54
41
ND
ND
2
3
3
ND
3
4
2
1
DS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
2
3
3
ND
4
3
2
0.2
S DS/Ave
ND
ND
ND
ND
17
40
50
20
127
0.5
0.5
ND
ND
ND
ND
ND
ND
1.4
15
19
20
9.1
15
15
3.5
46
98
54
43
ND
ND
2
3
3
ND
3
4
2
1
SDS/Max
NR
NR
NR
NR
NR
NR
NR
0.8
ND
ND
ND
ND
ND
2
3
3
ND
3
4
2
0.5
39
-------
Table 14 (continued)
1/23/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1-Trichloropropanone8
1,1,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitro methane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL
ug/L
0.5
0.10
0.1
N/A
0.10
0.5
N/A
N/A
N/A
0.10
N/A
0.5
0.1
N/A
N/A
0.10
0.1
1.9
0.16
2
Plant 2
Filt. Eff
ND
0.4
ND
1
ND
ND
0.7-2
0.2
0.2-0.4
0.2
ND
Treat. Tank
ND
0.4
ND
NR
1
ND
NR
NR
NR
ND
NR
0.5-2
0.2
NR
NR
0.2-0.5
0.3
ND
0.3
ND
Fin. Water
ND
0.4
ND
NR
1
ND
NR
NR
NR
ND
NR
0.6-2
0.1
NR
NR
0.2-0.4
ND
ND
0.3
ND
DS/Ave
ND
0.4
ND
NR
1
ND
NR
NR
NR
ND
NR
0.3-0.9
ND
NR
NR
0.2-0.3
0.5
ND
0.3
ND
DS/Max
ND
0.5
ND
0.7
ND
ND
ND
ND
<0. 1-0.1
0.8
ND
S DS/Ave
ND
0.6
ND
NR
1
ND
NR
NR
NR
ND
NR
ND
ND
NR
NR
ND
1
ND
0.3
ND
SDS/Max
ND
0.6
ND
1
ND
ND
ND
ND
ND
2
ND
40
-------
Table 15. Occurrence of other DBPsa at plant 1 (1/23/01)
Compound
Halomethanes
Bromochloromethane
Dibromomethane
Bromodichloromethaneb
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Haloacids
Bromoacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
2, 2-Dibromopropanoic acid
3, 3-Dibromopropenoic acid
cis -2, 3-Dibromopropenoic acid
Tribromopropenoic acid
2-Bromobutanoic acid
?ra«s-4-Bromo-2-butenoic acid
c/s-4-Bromo-2-butenoic acid
2,3-Dibromo-2-butenoic acid
Bromodichloro-butenoic acid0
Bromochloro-4-oxopentanoic acid
3, 3-Dibromo-4-oxopentanoic acid
cis-2-Bromo-butenedioic acid
trans-2, 3-Dibromo-butenedioic acid
cis-2-Bromo-3-methylbutenedioic
acid
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
OE
X
X
X
X
X
-
-
-
X
X
-
-
-
-
-
-
-
-
_
-
-
PE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Compound
Haloaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Trichloroacetaldehyde
Tribromoacetaldehyde
2-Bromo-2-methylpropanal
Haloketones
1 , 1 -Dichloropropanone
1 -Bromo- 1 -chloropropanone
1, 1-Dibromopropanone
1,1,1 -Trichloropropanone
1 , 1 ,3-Trichloropropanone
1 -Bromo- 1 , 1 -dichloropropanone
1, 1, 1-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1, 1, 3 -Tribromo -3 -chloropropanone
1, 1, 3, 3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dibromonitromethane
Miscellaneous Halogenated DBFs
Chlorobenzene
Tribromophenol
Non-halogenated DBFs
Glyoxal
Pentanoic acid
Hexanoic acid
Heptanoic acid
Octanoic acid
Nonanoic acid
Decanoic acid
Undecanoic acid
Dodecanoic acid
Tetradecanoic acid
Pentadecanoic acid
Hexadecanoic acid
Octadecanoic acid
Ethanedioic acid
Octanedioic acid
Nonanedioic acid
OE
X
X
X
X
-
X
-
X
X
-
-
-
X
-
X
-
-
X
-
X
X
X
X
X
X
X
-
-
X
X
X
X
-
-
X
PE
-
X
-
-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
"DBFs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique
bCompounds listed in italics were confirmed through the analysis of authentic standards; haloacids
and non-halogenated carboxylic acids identified as their methyl esters.
°Exact isomer not known
41
-------
Table 16. DBF results at plant 1 (7/17/01)
07/17/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAAJ
TXAAk
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehvde
Chloral hydrate6
Tribromoacetaldehvde
MRLa
Mg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.25
0.5
0.1-0.5
0.5
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.22
0.1
0.1
0.1
Plant 1 "
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
O3Eff
ND
ND
ND
ND
0.1
0.1
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clear. Eff
ND
ND
ND
ND
0.2
0.7
1
0.8
3
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
1.1
2.4
4.2
ND
ND
ND
ND
5.3
7.7
7.7
ND
ND
ND
ND
ND
0.6
ND
2
1
2
2
Fin. Water
ND
ND
ND
ND
0.4
2
4
3
9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.2
2.2
3.6
ND
ND
ND
ND
5.8
8.0
8.0
ND
ND
ND
0.1
0.3
0.6
ND
ND
ND
ND
0.2
0.4
ND
0.1
DS/Ave
ND
ND
ND
ND
1
3
4
3
11
ND
ND
ND
0.3
ND
ND
ND
ND
ND
ND
4.8
3.6
4.3
1.2
1.1
ND
ND
10
15
13
2.3
ND
ND
0.2
0.1
0.6
ND
1
ND
ND
ND
DS/Max
1
3
NR9
3
NR
ND
NR
ND
ND
ND
ND
ND
ND
ND
0.2
0.3
0.6
ND
2
ND
ND
ND
SDS/Ave
ND
ND
ND
ND
0.3
2
3
3
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.2
3.8
6.4
ND
ND
ND
ND
9
12
12
ND
ND
ND
0.1
0.3
0.6
ND
0.7
ND
ND
ND
SDS/Max
0.4
2
NR
3
NR
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.4
ND
ND
ND
ND
2
0.1
ND
ND
42
-------
Table 16 (continued)
07/17/2001
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 .3-Dichloropropanone
1 .1-Dibromopropanone
1.1.1 -Trichloroorooanone6
1 . 1 .3-Trichloropropanone
1 -Bromo-1 . 1 -dichloropropanone
1,1,1 -Tribromopropanone
1.1.3-Tribromopropanone
1.1.3.3-Tetrachloropropanone
1.1.1 .3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
ug/L
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.10
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.1
0.25
Plant 1"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
O3Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
1
ND
ND
NR
Clear. Eff
0.1
0.2
0.5
0.3
0.5
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
ND
ND
ND
Fin. Water
0.1
0.2
ND
0.1
0.1
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
0.2
0.5
ND
0.7
1.5
2.5
ND
ND
ND
ND
DS/Ave
0.1
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
0.2
0.2
ND
ND
ND
ND
DS/Max
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
0.1
0.2
0.1
ND
NR
SDS/Ave
0.1
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
0.2
0.4
0.1
ND
ND
ND
ND
SDS/Max
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
0.1
0.2
0.2
0.9
1.7
2.8
ND
NR
r<0.5 = Detected by GC/MS below its MRL of 0.5 ug/L; interference problem with GC/ECD analysis
43
-------
Table 17. DBF results at plant 2 (7/17/01)
07/17/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoaceticacid
HAA5h
HAA9'
DXAAJ
TXAAk
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL
^g/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.25
0.5
0.1-0.5
0.5
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.22
0.1
0.1
0.1
Plant 2°
Filt. Eff
5
9
NR
2
NR
5
NR
NR
0.4
ND
ND
ND
ND
ND
1
1
1
ND
2
2
1
0.3
Treat. Tank
ND
ND
ND
ND
6
11
7
2
26
4
1
<0.5r
<0.5
ND
ND
ND
ND
ND
ND
12
12
6.2
9.2
7.9
3.7
ND
27
51
30
21
0.1
ND
2
2
2
ND
1
1
2
0.2
Fin. Water
ND
ND
ND
ND
7
13
10
2
32
4
1
<0.5
<0.5
ND
ND
ND
ND
ND
ND
12
11
6.2
9.0
7.8
3.6
ND
27
50
29
20
0.1
ND
2
2
2
ND
ND
ND
ND
1
1
2
0.2
DS/Ave
ND
ND
ND
ND
7
15
11
2
35
3
1
<0.5
<0.5
ND
ND
ND
ND
ND
ND
12
11
6.2
7.5
7.0
3.0
ND
26
47
29
18
0.1
ND
2
2
2
ND
ND
ND
ND
0.9
1
2
0.1
DS/Max
9
16
NR
2
NR
0.6
NR
ND
ND
ND
ND
ND
0.1
ND
2
2
2
ND
1
0.6
1
ND
SDS/Ave
ND
ND
ND
ND
8
16
11
2
37
3
1
0.7
0.5
ND
ND
ND
ND
ND
ND
13
12
6.6
9.3
8.3
3.8
ND
29
53
32
21
0.1
ND
2
2
1
ND
1
1
2
0.1
SDS/Max
8
16
NR
2
NR
2
NR
NR
NR
ND
ND
ND
0.1
ND
2
2
2
ND
ND
ND
ND
2
1
2
0.1
44
-------
Table 17 (continued)
07/17/2001
Compound
Halnketnnes
Chloropropanone
1,1-Dichloropropanonee
1 .3-Dichloropropanone
1,1-Dibromopropanone
1 , 1 , 1-Trichloropropanonee
1,1,3-Trichloropropanone
1 -Bromo-1 , 1-dichloropropanone
1,1,1 -Tribromopropanone
1 .1 .3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL
ug/L
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.10
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.1
0.25
Plant 2°
Filt. Eff
ND
0.7
ND
0.6
0.7
ND
NR
ND
ND
ND
ND
ND
ND
0.2
0.1
0.1
0.1
ND
NR
Treat. Tank
ND
0.8
ND
0.3
1
ND
1
ND
ND
ND
ND
ND
ND
0.2
0.1
0.1
0.2
ND
ND
ND
ND
Fin. Water
0.1
0.7
ND
0.3
1
ND
1
ND
ND
ND
ND
ND
ND
0.2
0.1
0.1
0.2
0.8
1.0
ND
ND
ND
ND
ND
DS/Ave
0.1
0.5
ND
0.2
0.9
ND
0.3
ND
ND
ND
ND
ND
ND
0.2
0.1
0.1
0.2
0.6
0.8
ND
ND
ND
ND
ND
DS/Max
0.1
0.5
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
0.1
ND
NR
SDS/Ave
0.1
0.6
ND
0.2
0.8
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
ND
0.1
ND
ND
ND
ND
SDS/Max
0.1
0.7
ND
0.1
0.7
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
0.2
0.8
0.9
ND
ND
NR
45
-------
Table 18. Additional target DBF results (ug/L) at the EPA Region 9 treatment plants
(7/17/01)
7/17/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromo chloromethylacetate
2,2-Dichloroacetamide
TOX (ng/L as Cl")
Cy anof ormaldehy de
5-Keto-l-hexanal
6-Hydroxy -2-hexanone
Dimethylglyoxal
trans-2-Hexena\
Plant la
Raw
0
0
0
NA
O.I
O.4
O.4
0.4
0.4
OE
0
0
0
NA
O.I
O.4
O.4
0.8
O.4
FE
0
0
0
10.2
O.I
O.4
O.4
O.4
O.4
PE
0
0
0
21.1
O.I
O.4
O.4
0.4
0.4
DS
0
0
0
25.3
O.I
O.4
O.4
O.4
O.4
SDS
0
0
0
43.2
O.I
O.4
O.4
0.4
0.4
Plant T
FI
0
0
0
75.6
O.I
O.4
O.4
0.4
0.4
TT
0
0
0
84.5
O.I
O.4
O.4
O.4
O.4
PE
0
0
0
91.3
O.I
O.4
O.4
0.4
0.4
DS
0
0
0
106
O.I
O.4
O.4
O.4
O.4
SDS
0
0
0
114
O.I
O.4
O.4
O.4
O.4
3SDS testing of finished water at maximum detention time
Table 19. Halogenated furanone results (ug/L) at the EPA Region 9 treatment plants
(7/17/01)
7/17/01
Compound
Mucochloric acid (ring)
Mucochloric acid (open)
MX
ZMX
EMX
Plant 1
FE
<0.04
<0.04
<0.04
<0.04
<0.04
PE
<0.04
<0.04
<0.04
<0.04
<0.04
Plant 2
FE
<0.04
0.07
0.12
0.05
<0.04
DS
<0.04
<0.04
0.07
<0.04
<0.04
46
-------
Table 20. DBF results at plant 1 (3/19/02)
03/19/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid9
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAk
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehvde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehvde
MRLa
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.2
0.25
0.25
0.5
0.1
0.52
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.2
0.5
0.1
0.1
0.5
0.5
0.96
0.98
0.5
0.1
0.1
Plant 1"
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
03Eff
ND
ND
ND
ND
1
1
0.4
ND
2
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
ND
Clear. Eff
ND
ND
ND
ND
2
2
2
0.6
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.9
2.3
2.7
1.5
2.0
ND
ND
6.1
10
6.9
3.5
ND
ND
ND
<0.5
0.5
ND
1
0.9
0.7
0.8
Fin. Water
ND
ND
ND
ND
2
3
3
0.8
9
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.1
1.3
2.1
1.6
1.0
ND
ND
5.8
8.1
5.5
2.6
ND
ND
0.2
0.8
0.6
ND
ND
ND
ND
1
1
0.6
0.5
DS/Ave
ND
ND
ND
ND
3
4
4
2
13
ND
<0.25S
ND
ND
ND
ND
ND
ND
ND
ND
4.2
3.9
5.4
1.6
1.6
1.8
ND
11
19
14
5.0
ND
ND
ND
1
0.8
ND
2
2
0.5
ND
DS/Max
NR9
NR
NR
NR
NR
NR
0.6
ND
ND
ND
ND
ND
ND
ND
NR
2
0.8
ND
2
2
0.8
ND
S DS/Ave
ND
ND
ND
ND
2
4
4
2
12
ND
<0.25
ND
ND
ND
ND
ND
ND
ND
ND
3.9
3.6
5.9
2.0
2.3
2.0
ND
12
20
13
6.3
ND
ND
ND
1
0.3
ND
2
2
1
ND
SDS/Max
2
5
7
1
15
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
2
0.8
ND
2
2
1
ND
47
-------
Table 20 (continued)
03/19/2002
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 .3-Dichloropropanone
1 .1-Dibromopropanone
1.1.1 -Trichloropropanone6
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 . 1 -dichloropropanone
1.1.1 -Tribromopropanone
1.1.3-Tribromopropanone
1.1.3.3-Tetrachloropropanone
1.1.1 .3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methvl ethvl ketone
Methyl tertian/ butvl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
NA'
0.1
0.5
0.10
0.1
NA
0.1
0.1
0.1
0.10
0.5
0.5
2
0.5
0.5
0.2
0.54
0.5
Plant 1"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
O3Eff
ND
0.4
ND
ND
0.5
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
Clear. Eff
ND
NR
0.2
ND
<0.5
ND
0.1
NR
0.5
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fin. Water
ND
0.8
ND
ND
0.5
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
NR
ND
ND
0.6
ND
ND
NR
ND
ND
ND
ND
ND
ND
0.2
0.2
ND
<0.5
ND
ND
ND
ND
DS/Max
ND
NR
ND
ND
0.6
ND
ND
NR
ND
ND
ND
ND
ND
0.2
ND
ND
NR
ND
NR
SDS/Ave
ND
1
ND
ND
0.3
ND
ND
NR
ND
ND
ND
ND
ND
ND
0.3
ND
ND
<0.5
ND
ND
ND
ND
SDS/Max
ND
2
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
NR
ND
ND
<0.25 or <0.5 or <1 = Detected by GC/MS below its
quality assurance problem with gas chromatograph
*NA = Not available.
MRL of 0.25 or 0.5 or 1 ug/L;
method
48
-------
Table 21. DBF results at plant 2 (3/19/02)
03/19/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoaceticacid
HAA5h
HAA9'
DXAAJ
TXAA*
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL
^g/L
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.2
0
0.25
0.25
0.5
0.1
0.52
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0
0
0
0
0.1
0.1
0.2
0.5
0.1
0.1
0.5
0.5
0.96
0.98
0.5
0.1
0.1
Plant 2°
Filt. Eff
NR
NR
NR
NR
NR
NR
1
0.7
NR
ND
ND
ND
ND
ND
NR
2
0.8
ND
2
0.6
2
ND
Treat. Tank
ND
ND
ND
ND
15
17
6
0.7
39
2
1
0.5
<0.5
ND
ND
ND
ND
ND
ND
18
9.6
3.5
14
9.7
2.7
ND
36
58
31
26
0.1
ND
1
1
0.5
ND
2
0.7
4
0.4
Fin. Water
ND
ND
ND
ND
16
19
7
0.6
43
2
1
0.6
<0.5
ND
ND
ND
ND
2.1
ND
19
6.1
3.4
13
9.2
2.4
ND
38
55
29
25
0.1
ND
2
2
0.9
ND
ND
ND
ND
2
0.5
3
0.1
DS/Ave
ND
ND
ND
ND
28
23
8
0.7
60
2
1
<0.5
<0.5
ND
ND
ND
ND
ND
ND
20
6.2
3.7
13
9.5
2.4
ND
37
55
30
25
0.1
ND
2
2
0.5
ND
ND
ND
ND
2
ND
4
ND
DS/Max
NR
NR
NR
NR
NR
2
2
ND
NR
ND
ND
ND
0.2
ND
NR
1
0.7
ND
2
ND
4
ND
SDS/Ave
ND
ND
ND
ND
25
25
8
0.9
59
3
1
0.5
<0.5
ND
ND
ND
ND
2.2
ND
22
10
4.0
16
11
3.0
ND
44
68
36
30
0.2
ND
2
1
0.6
ND
2
ND
4
ND
SDS/Max
34
27
11
0.4
72
2
2
ND
NR
ND
ND
ND
ND
0.2
ND
3
2
1
ND
ND
ND
ND
3
ND
4
ND
49
-------
Table 21 (continued)
03/19/2002
Compound
Halnketnnes
Chloropropanone
1.1-Dichloroorooanonee
1 .3-Dichloroorooanone
1,1-Dibromopropanone
1 . 1 . 1-Trichloropropanonee
1.1.3-Trichloropropanone
1 -Bromo-1 , 1-dichloropropanone
1.1.1 -Tribromopropanone
1 .1 .3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 . 1 ,2.2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
NA
0.1
0.5
0.10
0.1
NA
0.1
0.1
0.1
0.10
0.5
0.5
2
0.5
0.5
0.2
0.54
0.5
Plant 2°
Filt. Eff
ND
NR
ND
ND
NR
ND
0.4
NR
0.2
ND
ND
ND
ND
0.2
0.2
ND
NR
ND
NR
Treat. Tank
ND
2
ND
ND
3
ND
<1
NR
ND
ND
ND
ND
ND
ND
0.3
ND
ND
<0.5
ND
ND
ND
ND
Fin. Water
ND
1
ND
ND
3
ND
0.9
ND
0.1
ND
ND
ND
ND
ND
0.2
0.3
ND
<0.5
1
ND
ND
ND
ND
ND
ND
DS/Ave
ND
1
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
<0.5
0.8
ND
ND
ND
ND
ND
ND
DS/Max
ND
NR
ND
ND
NR
ND
ND
NR
ND
ND
ND
ND
ND
0.3
0.1
ND
NR
ND
NR
SDS/Ave
ND
1
ND
ND
2
ND
ND
NR
ND
ND
ND
ND
ND
ND
0.3
ND
ND
0.5
ND
ND
ND
ND
SDS/Max
ND
1
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
NR
1
ND
ND
ND
NR
50
-------
Table 22. Additional Target DBF Results (ug/L) at the EPA Region 9 treatment plants
(3/19/02)
3/19/02
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Monochloroacetamide
Monobromoacetamide
2,2-Dichloroacetamide
Dibromoacetamide
Trichloroacetamide
TOX (ng/L as Cl")
TOBr (ng/L as Br")
TOC1 (ng/L as Cl")
Cy anof ormaldehy de
5-Keto-l-hexanal
6-Hydroxy -2-hexanone
Dimethylglyoxal
trans-2-Hexena\
Plant r
Raw
0
0
0
0
0
0
0
0
0
0
11.3
4.6
9.3
O.I
O.I
O.I
0.1
0.1
OE
1.8
0
0
O.I
O.I
O.I
0.4
0.1
FE
2.2
0
0
0
0
0
0
0
0.1
0.1
18.3
2.0
20.5
O.I
O.I
O.I
0.1
0.1
PE
2.4
3.5
1.8
0
0
0
0
0.6
1.6
0.1
145
79.7
87.2
O.I
O.I
O.I
0.1
0.1
DS
0
1.5
3.0
0
0
0
0
1.1
1.6
0.2
164
50.0
142
O.I
O.I
O.I
0.1
1.0
Plant 2b
FE
0.2
2.9
1.3
0
0
0
0
1.2
0.4
0.3
191
67.0
116
O.I
O.I
O.I
0.1
0.1
TT
234
72.0
202
O.I
O.I
O.I
0.1
0.1
PE
0
4.2
1.1
0
0
0
0
3.9
0.8
0.3
200
76
185
O.I
O.I
O.I
0.1
0.1
DS/a
164
76
155
O.I
O.I
O.I
0.1
0.1
DS/m
0.3
5.8
1.2
0
0
0
0
4.5
0.7
0.3
243
84
195
O.I
O.I
O.I
0.1
0.1
SDS
246
86
204
O.I
O.I
O.I
0.1
0.1
3Plant 1 DS sampled at maximum detention time
bPlant 2 DS sampled at average (a) and maximum (m) detention times
Table 23. Halogenated furanone results (ug/L) at the EPA Region 9 treatment plants
(3/19/02)
3/19/02
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
Plant 1
FE
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
PE
<0.02
0.02
<0.02
<0.02
<0.02
<0.02 (0.01)
<0.02
<0.02
<0.02
<0.02
<0.02
0.03
Plant 2
FE
<0.02
<0.02 (0.01)
<0.02 (0.01)
<0.02 (0.01)
<0.02
0.04
<0.02
<0.02
<0.02
<0.02
<0.02
0.09
PE
<0.02
0.29
0.02
0.03
<0.02
0.17
<0.02
<0.02
<0.02
<0.02
<0.02
0.10
DS/max
<0.02
0.18
<0.02 (0.01)
0.04
<0.02
0.06
<0.02
<0.02
<0.02
<0.02
<0.02
0.11
51
-------
Table 12 (10/30/00), Table 18 (7/17/01), and Table 22 (3/19/02) show results for additional
target DBFs that were analyzed at the University of North Carolina (UNC). Table 15 (1/23/01)
shows results from broadscreen DBF analyses conducted at the U.S. Environmental Protection
Agency (USEPA). Table 19 (7/17/01) and Table 23 (3/19/02) show results for halogenated
furanones that were analyzed at UNC.
Summary of tables for halogenated or
DBF Analyses (Laboratory)
Halogenated organic DBFs (MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
janic and other nonhalogenated organic DBFs
10/30/00
Tables 10-11
Table 12
1/23/01
Tables 13-14
Table 15
7/17/01
Tables 16-17
Table 18
Table 19
3/19/02
Tables 20-21
Table 22
Table 23
Halomethanes. Figure 7 shows the effect of the different treatment/disinfection scenarios
at plant 1 and at plant 2 (for July 2001) on tribalomethane (THM) formation and speciation. The
use of ozonation/chloramination significantly reduced THM formation. However, at plant 1,
there was a shift to the formation of the more brominated species. Jacangelo and colleagues
(1989) also observed that pre-ozonation in bromide-containing waters could result in a shift in
speciation upon post-chlorination. In addition, because chlorine was not added until after
coagulation at plant 1, the bromide-to-TOC ratio was higher (since coagulation removes TOC,
but not bromide), which can also result in a shift in THM speciation (Symons et al., 1993).
Figure 7
Effect of Ozone/Chlorine/Chloramines at Plant 1 and
Chlorine/Chloramines at Plant 2 on Trihalomethane Formation
and Speciation in Finished Waters (July 17, 2001)
Plant 2
Plant 1
52
-------
Figure 8 shows the effect of bromide on THM formation and speciation in the finished
water at plant 2 for the January 2001, July 2001, and March 2002 samplings. The increase in
bromide resulted in more THM formation, as well as a shift in speciation. For example,
dibromochloromethane and bromoform formation were significantly higher when the bromide
level in the source water increased.
Figure 8
Impact of Bromide on Trihalomethane Speciation
in Plant 2 Effluent: January 2001 - March 2002
0.40
0-14 Bromide
0.12 (mg/L)
In addition, low or sub-ug/L levels of iodinated THMs were detected, primarily at plant
2. (At plant 1 and plant 2, saltwater intrusion is the source of bromide and, thus, should also be a
source of iodide). For example, in January 2001 (bromide = 0.40 mg/L), 1 ug/L of iodoform was
detected in the ozone contactor effluent at plant 1, but was not detected (with a minimum
reporting level [MRL] of 0.7 ug/L) in downstream locations. However, 0.3 and 0.2 ug/L of
dichloroiodo- and bromochloroiodomethane, respectively, were detected in the chloraminated,
distributed water. Broadscreen GC/MS analyses also revealed the presence of
dichloroiodomethane and bromochloroiodomethane, as well as dibromoiodomethane in finished
water from plant 1 (January 2001) (Table 15). At plant 2, 0.5 and 0.6 ug/L of dichloroiodo- and
bromochloroiodomethane, respectively, were detected in the plant after chlorination, and 0.6
ug/L of dibromoiodomethane was detected after chloramination.
Iodide is oxidized to hypoiodous acid in the presence of ozone, chlorine, or chloramines.
Bichsel and von Gunten (2000) found that when ozone (Os, 1.0 mg/L) was used on a low-TOC
(1.3 mg/L) water (O3:TOC = 0.77 mg/mg), no iodinated THMs were detected and >90 % of the
iodide was transformed to iodate, whereas chlorine led to the formation of iodate and iodinated
THMs. At plant 1 in January 2001, 2.5 mg/L ozone was used on a moderate-TOC (4.5 mg/L)
53
-------
water (OsiTOC = 0.56 mg/mg). Although iodate was not measured in this study, the formation
of iodoform after ozonation and other iodinated THMs after chloramination suggests that the
lower OsiTOC ratio did not result in a quantitative conversion of iodide to iodate. However, the
use of ozone at plant 1 did result in the formation of less iodinated THMs in the finished water
than at plant 2.
Figure 9 shows the THM speciation—including the iodomethanes—at plant 2 in July
2001 (bromide = 0.14 mg/L). Bromodichloromethane was the major species of the four
regulated THMs, and dichloroiodomethane was the major iodomethane. In both cases, the major
THM formed for each group of halomethanes was dichlorinated, with either a bromine or iodine
atom as the third halogen.
Figure 9
DibromoiodomethaneD
2%D
BromochloroiodomethaneD
2%D
ChlorodiiodomShane
1%
Dichloroiodomethane
7%
Bromodiiodomethane
0%
Chloroform
Dibromochloromethane
26%
romodichloromethanen
38% D
Trihalomethane Speciation at Plant 2
SDS (Average Detention Time) Sample (July 17, 2001)
Haloacids. Figure 10 shows the effect of bromide (Br") on haloacetic acid (HAA)
formation and speciation in the finished water at plant 2 for the October 2000 and the January
2001 samplings. For example, tribromoacetic acid was detected when the bromide level in the
source water increased, whereas it was not detected when the bromide level was lower. In
addition, there was a shift to the formation of the other bromine-containing HAAs.
At plant 2, the sum of the dihalogenated HAAs (DXAAs) was somewhat higher than the
sum of the trihalogenated HAAs (TXAAs), whereas at plant 1 the formation of HAAs was
almost due only to the DXAAs. In other research, ozonation had been shown to be able to
destroy THM and TXAA precursors better than DXAA precursors (Reckhow and Singer, 1984).
54
-------
Figure 10
Effect of Bromide on HAA Formation and Speciation in Finished Water
at Plant 2: 10/30/00 Br' = 0.16 mg/L; 1/23/01 Br' = 0.40 mg/L
„»"
.*
^
^
&
^
&
^
'//////*
•* .* i« t
1/23/2001
10/30/2000
Similarly, chloramination has been shown to be more effective at controlling the formation of
THMs and TXAAs than the formation of DXAAs (Krasner et al., 1996).
In addition to the target HAAs, other haloacids were detected in selected drinking water
samples by the broadscreen GC/MS methods (Table 15). Plant 1—whose source water had 0.40
mg/L bromide in January 2001—had numerous brominated acids. Fourteen brominated acids
(2,2-dibromopropanoic acid, 3,3-dibromopropenoic acid, c/'s-2,3-dibromopropenoic acid,
tribromopropenoic acid, 2-bromobutanoic acid, rram--4-bromo-2-butenoic acid, c/'s-4-bromo-2-
butenoic acid, 2,3-dibromo-2-butenoic acid, bromodichlorobutenoic acid, bromochloro-4-
oxopentanoic acid, 3,3-dibromo-4-oxopentanoic acid, 2-bromobutenedioic acid, trans-2,3-
dibromobutenedioic acid, c/5-2-bromo-3-methylbutenedioic acid) had not been previously
reported in drinking water. Several of these bromo-acids were also seen in finished waters from
plant 11 (EPA Region 6), and also in drinking waters from Israel that had been treated with
chlorine or chlorine dioxide-chloramine (Richardson et al., submitted).
October 2000 results from UNC indicated the presence of another target halo-acid, 3,3-
dichloropropenoic acid, at levels of 0.1 and 0.7 |ig/L, respectively, in finished waters from the
plant 1 and plant 2 (Table 12).
Haloacetonitriles. In other DBF research, haloacetonitriles (HANs) were found to be
produced at approximately one-tenth the level of the THMs (Krasner et al., 1989). This was also
observed in the plant 1 and plant 2 samples. Dichloro-, bromochloro-, and dibromoacetonitrile—
55
-------
Information Collection Rule (ICR) DBFs—were detected at both treatment plants.
Trichloroacetonitrile—another ICR DBF—was not detected; likewise, the brominated analogues
of trichloroacetonitrile were not detected. Sub-|ig/L levels of chloroacetonitrile were detected at
plant 2 in July 2001 and March 2002.
Haloketones. In addition to the formation of low levels of haloketone (HK) compounds
from the ICR, low levels of 1,1,3,3-tetrabromopropanone were detected in January 2001,
primarily at plant 2. The concentration of this HK at plant 2 decreased in the distribution system,
and was not detected in the SDS samples. The distribution-system and SDS samples were at a
pH of 8.5 to 9.0, thus the disappearance of this HK was probably due to base-catalyzed
hydrolysis. (For example, Croue and Reckhow (1989) found that 1,1,1-trichloropropanone—
another HK—undergoes base-catalyzed hydrolysis at pH 8.5.) During the October 2000
sampling, this brominated HK was not detected, instead its chlorinated analogue, 1,1,3,3-
tetrachloropropanone, was detected. Thus, the higher bromide level in the source water in
January 2001 also changed the speciation of this HK.
Low levels of other HKs were also detected in July 2001 (Figure 11). These included a
monohalogenated HK (i.e., chloropropanone) and other di- and trihalogenated HKs in which the
halogens were not all on the same carbon atom and/or there was bromine substitution.
Figure 11
Haloketone Speciation at Plant 1
Clean/veil Effluent Sample (July 17, 2001)
Tetrahalogenated species not detected ._1 •1 •1 -Tribromopropanone
0%
1,1,3-Tribromopropanone
0%
Chloropropanone
1-Bromo-1,1-
dichloropropanone
20% ^^"^ _ 1,1-Dichloropropanone
"~ 10%
1,1,3-Trichloropropanone
0%
1,3-Dichloropropanone
25%
1,1,1-Trichloropropanon
25%
1,1-Dibromopropanone
15%
In addition to the target HKs, other HKs were detected by the broadscreen GC/MS
methods (Table 15). A number of these HKs were analogous to the di-, tri-, and tetrahalogenated
56
-------
HKs quantified by MWDSC, except that these were brominated or mixed bromochloro species.
For example, in January 2001, when the raw-water bromide was at 0.40 mg/L, MWDSC detected
1,1-dichloro-, 1,1,1-trichloro-, and 1,1,3,3-tetrabromopropanone after chloramination and
ozonation at plant 1. Broadscreen GC/MS analysis of this same water also detected two
brominated analogues of 1,1-dichloropropanone, two brominated analogues of 1,1,1-
trichloropropanone, and a bromochloro analogue of 1,1,3,3-tetrabromopropanone. Most were
observed in the finished water that had been treated with secondary chlorine and chloramine, but
some were also seen in waters from the ozone contactor effluent. The chlorinated species were
likely formed by the twice-a-week treatment of the flocculation and sedimentation basins with
chlorine (which was applied at the ozone contactor effluent) to control algal growth, and not by
the treatment with ozone. Alternatively, the brominated species may have been formed by
ozone, as ozone can oxidize bromide to hypobromous acid, which can react with TOC to form
brominated DBFs.
Haloaldehydes. Figure 12 shows the impact of bromide on haloacetaldehyde speciation
in the plant effluent of plant 2. When the bromide level was the highest (0.40 mg/L), there was a
significant formation of bromochloro- and tribromoacetaldehyde. When the bromide
Figure 12
Impact of Bromide on Haloacetaldehyde Speciation
in Plant 2 Effluent: January 2001 - March 2002
0.40
'•14 Bromide
12 (mg/L)
concentration was lower (0.12-0.14 mg/L), both of these brominated species were formed at
lower levels and the formation of the chlorinated species (dichloroacetaldehyde and chloral
hydrate) were the major haloacetaldehydes produced.
57
-------
Likewise, when the bromide level was the highest, there was a significant formation of
the bromine-containing THMs (bromodichloromethane, dibromochloromethane, and
bromoform) (Figure 8). When the bromide concentration was lower, bromoform was formed at
lower levels, and the formation of the chlorine-containing species (chloroform and
bromodichloromethane) were typically the major THMs produced.
In January 2001, tribromoacetaldehyde decreased in concentration in both sets of
distribution-system and SDS samples, whereas the dihalogenated acetaldehydes increased in
concentration in the distribution-system and SDS samples for plant 1. Moreover, the
concentration of bromochloroacetaldehyde was higher in the distribution-system and SDS
samples at plant 1 than at MSWTP. The results for tribromoacetaldehyde are consistent with the
research of Xie and Reckhow (1996), who found that tribromoacetaldehyde degraded quickly at
pH 9.0. In other research, acetaldehyde (an ozone by-product) was found to react with chlorine
to form chloroacetaldehyde, which in the presence of free chlorine rapidly reacted to form
chloral hydrate (McKnight and Reckhow, 1992). At plant 1, chlorine (in the presence of
ammonia and bromide) may have reacted with acetaldehyde formed by the ozonation process to
produce dichloro- and bromochloroacetaldehyde.
In addition to the target haloacetaldehydes, another brominated aldehyde (2-bromo-
2-methylpropanal) was detected by the broadscreen GC/MS methods (Table 15).
Halonitromethanes. In addition to low levels of chloropicrin (trichloronitromethane) (an
ICR DBF), low or sub-|ig/L levels of other halonitromethanes (HNMs) were detected in the
selected samples (Figure 13). Although ozone/chlorine/chloramines at plant 1 produced less
THMs than chlorine/chloramines produced at plant 2 (Figure 7), a higher concentration of the
trihalogenated HNMs was detected at plant 1 in July 2001 (Figure 13) (this was not the situation
in March 2002). In other research, pre-ozonation was found to increase chloropicrin formation
upon post-chlorination (Hoigne and Bader, 1988). In addition, the speciation of the
trihalogenated HNMs was similar to the speciation of the THMs. At plant 2, the bromochloro
species predominated, whereas at plant 1 there was more of a shift to the formation of the more
fully brominated species.
58
-------
Figure 13
Effect of Ozone/Chlorine/Chloramines at Plant 1 and
Chlorine/Chloramines at Plant 2 on Halonitromethane Formation and
Speciation in Finished Waters (July 17, 2001)
2.5
D)
Halogenatedfuranones. Tables 19 and 23 show results for halogenated furanones in the
July 2001 and March 2002 samplings for the EPA Region 9 treatment plants. Data are included
for 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-
chloro-3-(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found
as a closed ring or in an open form. Results are displayed graphically in Figure 14.
In July 2001, 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known
as MX, was detected at plant 2 but not at plant 1 (with an MRL of 0.04 |ig/L) (Table 19;
Figure 14). This is probably because ozone in the plant 1 treatment scheme removes MX
precursors from the raw TOC, while chlorine in the plant 2 treatment scheme reacts with the raw
TOC to form MX . Likewise, plant 1 produced less TFIMs than plant 2 (Figure 7). The filter
effluent sample from plant 2 contained a higher concentration of MX (120 ng/L) than reported in
a survey of Australian waters (<90 ng/L) (Simpson and Hayes, 1998). However, water quality
and treatment/disinfection schemes may be different in Australia than in the United States. In
particular, regulatory requirements in Australia are significantly different than in the United
States. MX appears to degrade between the filter effluent and the distribution system (DS)/
average sample of plant 2. However, water in the distribution system may represent a blend of
water from more than one treatment plant. In addition, water in the distribution system may
represent water produced at plant 2 on a previous day, as the survey was not set up to follow a
"plug" of waterier se. The second sampling of plant 1 and plant 2 (March 2002) for
59
-------
halogenated furanones showed similar trends, such as removal of MX-analogue precursors by
ozonation in plant 1, when compared to plant 2 (Table 23, Figure 15). Overall, plant 2 exhibited
higher concentrations of mucochloric acid (MCA open) and brominated MX-analogues than
plant 1. Within the distribution system of plant 2, BEMX-1 appeared to decrease (from 290 ng/L
in the plant effluent to 180 ng/L in the DS/maximum sample) and BEMX-3 appeared to decrease
(from 170 ng/L in the plant effluent to 60 ng/L in the DS/maximum sample). Because TOC and
bromide levels in the source water of this treatment plant can vary frequently (Krasner et al.,
1994)—as well as the pH of the water (which can significantly vary on a diurnal basis)—
differences between the plant effluent and the distribution system (particularly at a maximum
detention time) may be due (in part) to a comparison of different "packets" of water treated at
different points in time. Alternatively, analysis of SDS samples for halogenated furanones
would have allowed for a more direct assessment of the impact of distribution system detention
time, etc., on the formation and stability of these DBFs.
Figure 14
Plant 1 and Plant 2 (7/17/01)
I MX • ZMX D EMX D MCA ring D MCA open
0.30
ro
J= 0.25
9)
O
0.20 1
0.15 -
•O 0.10
&
us
| 0.05
.O
ro
0.00
FE
O3+Filter
Plant 1
PE
NaOCI+NH3
Plant 1
FE
NaOCI+Filter
Plant 2
DS/ave
NaOCI+NH3
Plant 2
Sampling Point
60
-------
Figure 15
Plant 1 and Plant 2 (3/19/02)
DBMX-1 DBEMX-1 I
• MX • EMX I
c n ?n
o
5
ra
fa n fin
M U.DU
0)
o
c n f^n
0 U'bU
J
2 — » n 4n
C T u.^u
o d
c o
£ 3r n ?n
~ ^~"^ u.ou
J_
S n 9n
i->
re
c
® n m
0) U' IU
0
re
Onn
.UU
FE
O3+Filter
Pla
H BMX-2 D
• ZMX D
PE
NaOCI+NH3
it 1
B E MX-2 D B MX-3 D B E MX-3
MCA (ring) D MCA (open) D Ox-MX
FE
NaOCI+Filter
PE
NaOCI+NH3
Plant 2
DS/max
NaOCI+NH3
Sample Sites
61
-------
VOCs. Although methyl tertiary butyl ether (MtBE) is not a DBF, it is a VOC that was
included in this study. In January 2001, 0.3 |ig/L of MtBE was detected in the raw water sample.
The same level of MtBE was detected in the treated waters at plant 2, whereas a somewhat lower
level (i.e., 0.2 |ig/L) was detected at plant 1. In other research, ozone has been shown to destroy
(at least in part) MtBE (Liang et al., 1999). If the decrease in MtBE at plant 1 was real, this
could have been due to ozonation.
Methyl ethyl ketone (MEK) is also a VOC. In addition, it was detected after ozonation at
plant 1 in July 2001. Non-halogenated ketones can be formed by ozone (Glaze et al., 1989).
MEK was not detected downstream of the ozone contactor effluent (with an MRL of 0.5 |ig/L),
perhaps due to biodegradation through the downstream treatment processes.
Other HalogenatedDBPs. A few additional, miscellaneous halogenated DBFs were also
detected. UNC methods detected dichloroacetamide at 0.2 and 0.8 jig/L in finished water,
respectively, from plant 1 and plant 2 in October 2000 (Table 12). Bromochloromethylacetate
was also detected in finished waters from plant 1 at 0.1 jig/L (Table 12). In addition,
broadscreen GC/MS analyses revealed the presence of chlorobenzene and tribromophenol (Table
15) in finished waters from plant 1 (January 2001). None of these compounds were observed in
the corresponding raw, untreated water.
Non-HalogenatedDBPs. The plant 1 ozonated drinking water offered one of the few
times that cyanoformaldehyde was detected in the Nationwide DBF Occurrence Study.
Cyanoformaldehyde had been first identified in a DBF study published in 1999 on ozonated
drinking waters from a pilot plant (Richardson et al, 1999). Cyanoformaldehyde was found in
the finished water at plant 1 in October 2000 at 0.2 jig/L, and its concentration remained steady
at 0.2 |ig/L in the distribution system (Table 12). Cyanoformaldehyde was also found in
finished waters from plant 2 (which used chlorine disinfection) at 0.3 |ig/L (October 2000).
Dimethylglyoxal was also seen in ozone contactor effluent samples from plant 1 in both October
2000 and July 2001, but was below detection in the finished water (plant effluent). In the July
2001 sampling, it appeared to be removed by biological filtration, but in the October 2000
sampling, its levels decreased between the filter effluent sampling and the plant effluent,
indicating a possible reaction with the secondary chlorine-chloramine that was added following
filtration. Broadscreen GC/MS analysis also revealed the presence of glyoxal and several non-
halogenated carboxylic acids in samples from plant 1 in January 2001 (Table 15). Several of
these carboxylic acids were also seen in the raw, untreated water, but those listed as DBFs in
Table 15 represent those whose levels increased substantially (2-3X) in the treated waters vs. the
raw, untreated waters.
REFERENCES
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
62
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Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomelhanes during disinfection and
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784
(2000).
Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992).
Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite.
Environmental Science & Technology 23(11): 1412 (1989).
Douville, C. J., and G. L. Amy. Influence of natural organic matter on bromate formation during
ozonation of low-bromide drinking waters: a multi-level assessment of bromate. In Natural
Organic Matter and Disinfection By-Products: Characterization and Control in Drinking Water
(S.E. Barrett, S.W. Krasner, & G.L. Amy, eds.), pp. 282-298, American Chemical Society:
Washington, D.C., 2000.
Delcomyn, C. A., H. S. Weinberg, and P. C. Singer. Measurement of sub-|ig/L levels of bromate
in chlorinated drinking waters. Proceedings of the American Water Works Association Water
Quality Technology Conference, American Water Works Association: Denver, CO, 2000.
Glaze, W. H., M. Koga, D. Cancilla, K. Wang, M. J. McGuire, S. Liang, M. K. Davis, C. H.
Tate, and E. M. Aieta. Evaluation of ozonation by-products from two California surface waters.
Journal of the American Water Works Association 81(8):66 (1989).
Hoigne, J., and H. Bader. The formation of trichloronitromethane (chloropicrin) and chloroform
in a combined ozonation/chlorination treatment of drinking water. Water Research 22(3): 313
(1988).
Jacangelo, J. G., N. L. Patania, K. M. Reagan, E. M. Aieta, S. W. Krasner, and M. J. McGuire.
Ozonation: assessing its role in the formation and control of disinfection by-products. Journal
of the American Water Works Association 81(8):74 (1989).
Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta.
The occurrence of disinfection by-products in U.S. drinking water. Journal of the American
Water Works Association 81(8):41 (1989).
Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R Xia, and S. E.
Barrett. Effects of water quality parameters on DBF formation during chloramination.
Proceedings of the American Water Works Association Annual Conference, Vol. D, American
Waterworks Association: Denver, CO, 1996.
Kuo, C.-Y., H.-C. Wang, S. W. Krasner, and M. K. Davis. lon-chromatographic determination
of three short-chain carboxylic acids in ozonated drinking water. In Water Disinfection and
Natural Organic Matter: Characterization and Control (R.A. Minear & G.L. Amy, eds.), pp.
350-365, American Chemical Society: Washington, D.C., 1996.
63
-------
Liang, S., L. S. Palencia, R. S. Yates, M. K. Davis, J.-M. Bruno, and R. L. Wolfe. Oxidation of
MTBE by ozone and PEROXONE processes. Journal of the American Water Works Association
91(6): 104 (1999).
McKnight, A., and D. A. Reckhow. Reactions of ozonation by-products with chlorine and
chloramines. Proceedings of the American Water Works Association Annual Conference (Water
Research), American Waterworks Association: Denver, CO, pp. 399-409, 1992.
Reckhow, D. A., and P. C. Singer. The removal of organic halide precursors by preozonation
and alum coagulation. Journal of the American Water Works Association 76(4): 151 (1984).
Richardson, S. D., A. D. Thruston, Jr., T. V. Caughran, P. H. Chen, T. W. Collette, T. L. Floyd,
K. M. Schenck, B. W. Lykins, Jr., G.-R. Sun, and G. Majetich. Identification of ozone
disinfection byproducts in drinking water. Environmental Science & Technology 33:368 (1999).
Richardson, S. D., A. D. Thruston, Jr., C. Rav-Acha, L. Groisman, I. Popilevsky, O. Juraev, V.
Glezer, A. B. McKague, M. J. Plewa, and E. J. Wagner. Tribromopyrrole, brominated acids, and
other disinfection byproducts produced by disinfection of drinking water rich in bromide.
Environmental Science & Technology (submitted).
Simpson, K.L. and K. P. Hayes. Drinking water disinfection by-products: an Australian
perspective. Water Research 32(5): 1522 (1998).
Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water
Works Association 85(1):51 (1993).
van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily
assimilable organic carbon in drinking water. Journal of the American Water Works Association
74(10):540 (1982).
van der Kooij, D., and W. A. M. Hijnen. Substrate utilization by an oxalate consuming Spirillum
species in relation to its growth in ozonated water. Applied Environmental Microbiology 47:551
(1984).
Volk, C. J., and M. W. LeChevallier. Effects of conventional treatment on AOC and BDOC
levels. Journal of the American Water Works Association 94(6): 112 (2002).
Xie, Y., and D. A. Reckhow. Hydrolysis and dehalogenation of trihaloacetaldehydes. In
Disinfection By-Products in Water Treatment: The Chemistry of Their Formation and Control
(RA. Minear & GL. Amy, eds.), pp. 283-291, CRC Lewis Publishers: Boca Raton, FL, 1996.
64
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EPA REGION 6: PLANTS 11 AND 12
Plant Operations and Sampling
Plant 11 treated water from a river in EPA Region 6 (Figure 1) and plant 12 treated water
from another river basin and lake in EPA Region 6. On March 26, 2001, September 10, 2001,
November 5 or 15, 2001, and February 11 or 12, 2002, plants 11 and 12 were sampled.
Plant 11 operated a chlorine dioxide plant (Figure 2):
• Ferric sulfate ^62(804)3] and cationic polymer were used for coagulation.
• There was up-flow solids contact flocculation/clarification and
dual-media filtration.
• The disinfection strategy used a combination of free chlorine and chlorine dioxide to achieve
disinfection requirements through the plant clearwell.
• In March 2001, chlorine dioxide was only added post-filtration, in September 2001 and
February 2002 chlorine dioxide was added to the clarified water and post-filtration, and in
November 2001 chlorine dioxide was added before the clarifier and after the filters (after the
sampling point for the clearwell influent).
• The free chlorine residual was quenched with ammonia to form a chloramine residual prior to
the storage tank and distribution.
At plant 12 (Figure 3):
• Alum was used for coagulation.
• There was dual-media filtration. (They were in the process of scrapping the granular
activated carbon [GAC] filter media and going back to dual media.)
• The disinfection strategy used a combination of chlorine and ammonia to form chloramines.
In February 2002, they used chlorine dioxide during pre-treatment. (They did not use
chlorine dioxide as part of their treatment process in March, September, and November
2001.)
Plant 11 was sampled at the following locations:
(1) raw water
(2) filter influent
(3) filter effluent or clearwell influent
(4) clearwell effluent (not sampled in November 2001 and February 2002)
(5) the plant effluent
In addition, the distribution system was sampled at two locations, one representing an average
detention time and the other representing a maximum detention time. Furthermore, plant
effluent was collected, and simulated distribution system (SDS) testing conducted with a 24- and
a 48-hr holding time to represent the average and maximum detention times, respectively, in
March 2001, September 2001, and February 2002. In November 2001, the SDS tests were
conducted with holding times of 36 and 72 hr, respectively.
However, the plant 11 SDS samples that were shipped on September 12, 2001 were not
delivered to Metropolitan Water District of Southern California (MWDSC) until September 17,
2001, since Federal Express could not use air delivery at that time. Because the samples were
65
-------
not kept cold for that entire period of time, the SDS samples for the September 2001 sampling
represent a test of the long-term stability of the DBFs when held at room temperature.
Figure 1. EPA Region 6
- - - - Texas
66
-------
Figure 2. Plant 11 schematic
Cationic Polymer
Low Lift Pumps
Activated Carbon
Nonlonic Polymer
Ferric Sulfate
~.~r~ al
Filter Aid Polymer/
Carbon Dioxide (Suspended)
Chlorine (Suspended)
Chlorine Dioxide (Suspended)
Olclllliei ^ ^
O I. ._! ^^^^ f
Zinc Polyphosphate-
Sodium Fluoride
Chlorine Dioxide —
Chlorine
Backwash
Water
-Chlorine
Clearwell
Ammonia
Distribution Pumps
/ Ground \
( Sorage )
V Tank J
^ To Distribution
67
-------
Figure 3. Plant 12 schematic
(Chlorine
Dioxide)
Alum
Dual Media
(or GAC)
Pre-
sedimentation
Chlorine (gas)
+ Ammonia
Coagulation
Sedimentation
•> Filtration
Chlorine (gas)
+ Ammonia
Distribution
Plant 12 was sampled at the following locations:
(1) raw water,
(2) after pre-treatment,
(3) filter influent,
(4) filter effluent,
(5) and the plant effluent.
In addition, the distribution system was sampled at two locations, one representing an average
detention time and the other representing a maximum detention time. In March 2001, plant
effluent was collected and SDS testing was conducted with a 18- and a 30-hr holding time to
represent the average and maximum detention times, respectively. SDS testing was not
performed in September 2001. In November 2001, the SDS tests were conducted with holding
times of 24 and 48 hr, respectively. In February 2002, the SDS samples were held for less than
one day (holding times are not available). On the day of sampling, information was collected on
the operations at each plant (Tables 1-2).
-------
Table 1. Operational information at plant 11
Parameter
Plant flow (mgd)
F 62(804)3 dose (mg/L)
Polymer (coagulant aid) dose (mg/L)
Polymer (filter aid) dose (mg/L)
Chlorine dioxide dose before clarifier (mg/L as CIO 2)
Chlorine dioxide dose at clarifier (mg/L as CIO 2)
Chlorine dioxide dose post- filtration (mg/L as CIO 2)
Chlorine dose at filter effluent (mg/L as Cb)
Ammonia dose at clearwell effluent (mg/L as NFfe-N)
3/26/01
12.96
18.7
3.9
0.024
0
0
0.75
4.5
1.25
9/10/01
37.4
7.6
2.7
0.048
0
0.35
0.5
4.1
1.15
11/5/01
31.7
8.5
2.4
0.048
0.35
0
0.5
4.1
1.15
2/11/02
28.8
10.4
7.1
0.048
0
0.25
0.5
4.0
0.86
Table 2. Operational information at plant 12
Parameter
Plant flow (mgd)
Coagulant dose used for pre- treatment (mg/L)
Chlorine dioxide dose (mg/L as CIO 2)
Potassium permanganate (KMnO/j) dose used for pre-
treatment (mg/L)
Chlorine dose after pre- treatment (mg/L as Cb)
Ammonia dose after pre- treatment (mg/L as NHs-N)
Aluminum sulfate dose used in sed. basins (mg/L)
No. filters contained GAC, contained dual media
Chlorine dose at filter effluent (mg/L as Cb)
Ammonia dose at filter effluent (mg/L as NFfe-N)
3/26/01
72
0
0
NAa
4.6
0.72
80
8,9
5.5
0.71
9/10/01
64
0
0
1
6.0
1.5
95
0,all
4.8
1.2
11/15/01
60
0
0
1.0
6.5
1.2
80
0,22
3.3
0.61
2/12/02
60
0
1.0
1.0
5.0
0.82
80
0,22
2.4
0.44
aNA = Not available
Water Quality
On the day of sampling, information was collected on water quality at each plant
(Tables 3-4). Additional data were collected for total organic carbon (TOC) and ultraviolet (UV)
absorbance (Tables 5-6). At plant 12, the raw water equaled a blend from two lakes. The blend
ratio changed from day to day. Water after pre-treatment equaled a blend of raw and pre-treated
(KMnO/t) water. The detention time in the pre-sedimentation basin lead to a mixture of current
and previous blends. Thus, the difference in water quality between the raw and pre-treated water
at plant 12 represented, in part, changes in the blend ratio.
At plant 12 in March 2001, September 2001, November 2001, and February 2002, the
water after pre-treatment had 2-19 % less TOC than the raw water, and coagulation subsequently
removed 21-40 % of the remaining TOC in the pre-treated water. The water after pre-treatment
had a 13-28 % reduction in UV, and coagulation reduced the UV of the pre-treated water by an
additional 38-54 %. At plant 11 in March 2001, September 2001, November 2001, and February
2002, coagulation and filtration cumulatively removed 17-30 % of the TOC and reduced the UV
by 23-65 %.
69
-------
Table 3. Water quality information at plant 11
Location
Raw water
Filter influent
Filter eff. or clear, inf.
Clearwell effluent
Plant effluent
Dist. system/average
Dist. system/maximum
SDS/average
SDS/maximum
PH
3/26/01
8.14
7.54
7.65
7.30
7.40
7.52
7.44
7.63
7.52
9/10/01
8.12
7.86
7.38
7.48
7.52
7.62
7.58
7.53
7.57
11/5/01
8.33
8.13
7.47
NSD
7.52
7.62
7.68
7.52
7.56
2/11/02
NA
7.98
7.49
NS
7.47
7.62
7.68
7.53
7.52
Temperature (°C)
3/26/01
19.2
19.0
19.0
18.0
18.2
19.3
20.2
20.0
18.1
9/10/01
26.2
26.8
26.4
27.8
24.8
27.6
27.8
26.0
25.8
11/5/01
21.2
21.3
22.3
NS
21.9
23.3
22.9
21.4
21.6
2/11/02
11.2
11.6
11.4
NS
11.4
12.1
12.3
13.9
14.1
Disinfectant Residual3 (mg/L)
3/26/01
—
—
—
0.31/
2.5
0.02/
2.7
2.6
2.5
2.7
2.5
9/10/01
—
0.31
3.3
2.6
3.0
2.6
2.5
2.4
2.3
11/5/01
—
—
—
NS
0.10/
2.9
2.7
2.4
2.5
2.2
2/11/02
—
—
0.17/
3.7
NS
0.13/
3.2
2.7
2.5
2.8
2.7
3Chlorine dioxide residuals (values shown in bold) in clearwell effluent and plant effluent in March 2001, in filter influent in September 2001, in
plant effluent in November 2001, and in clearwell influent and in plant effluent in February 2002; chlorine residuals (values shown in italics) in
clearwell influent in September 2001 and in February 2002; chloramine residuals at other locations.
bNS= Not sampled
Table 4. Water quality information at plant 12
Location
Raw water
After pre-treatment
Filter influent
Filter effluent
Plant effluent
Dist. system/average
Dist. system/maximum
SDS/average
SDS/maximum
pH
3/26/01
8.3
8.4
8.8
8.2
8.1
7.8
7.7
NA
NA
9/10/01
7.7
7.8
8.3
7.6
7.6
7.7
7.7
NSD
NS
11/15/01
7.6
8.0
8.1
NA
8.3
NA
NA
7.3
7.3
2/12/02
7.8
7.8
8.4
8.1
7.6
7.4
7.4
7.4
7.4
Temperature (°C)
3/26/01
20.9
19.9
19.0
20.8
20.8
15.4
21.3
NA
NA
9/10/01
28
28
27
27
27
26
25
NS
NS
11/15/01
23.6
23.4
24.1
23.1
23.4
NA
NA
25
25
2/12/02
16
14
17
16
14
16
18
16
18
Disinfectant Residuaf (mg/L)
3/26/01
—
—
2.1
1.6
4.9
3.6
2.2
NA
NA
9/10/01
—
—
1.6
4.8
4.7
3.2
2.6
NS
NS
11/15/01
—
—
2.3
2.1
4.3
NA
NA
3.4
2.8
2/12/02
—
0.15
1.7
1.4
4.6
NA
NA
2.7
2.4
aChlorine dioxide residual (value shown in bold) at pre-treatment sample location in February 2002; chloramine residuals at other locations.
bNS = Not sampled
70
-------
Table 5. TOC and UV removal at plant 11
Location
03/26/2001
Raw
Filter Inf.
Filter Eff.
09/10/2001
Raw
Filter Inf.
Clearwell Inf.
11/5/2001
Raw
Filter Inf.
Clearwell Inf.
02/11/2002
Raw
Filter Inf.
Clearwell Inf.
TOC
(mg/L)
5.66
4.08
4.24
3.51
3.24
2.89
4.68
4.0
3.87
4.26
3.25
3.0
uva
(cm'1)
0.137
0.083
0.089
0.079
0.069
0.044
0.115
0.094
0.088
0.108
0.055
0.038
SUVAb
(L/mg-m)
2.42
2.03
2.10
2.25
2.13
1.52
2.46
2.35
2.27
2.54
1.69
1.27
Remova
TOC
—
28%
-3.9%
—
7.7%
11%
15%
3.3%
—
24%
7.7%
/Unit (%)
UV
—
39%
-7.2%
—
13%
36%
18%
6.4%
—
49%
31%
Removal/Cu
TOC
—
28%
25%
—
7.7%
18%
15%
17%
—
24%
30%
mulative (%)
UV
—
39%
35%
—
13%
44%
18%
23%
—
49%
65%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm^/DOC (mg/L) or UV (m-1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.137/cm = 0.137/(0.01 m) = 13.7/m, DOC = 5.66 mg/L, SUVA = (13.7 rrf1)/(5.66 mg/L) = 2.42 L/mg-m)
Table 6. TOC and UV removal at plant 12
Location
03/26/2001
Raw
After Pre-Treat.
Filter Inf.
Filter Eff.
09/10/2001
Raw
After Pre-Treat.
Filter Inf.
Filter Eff.
11/15/2001
Raw
After Pre-Treat.
Filter Inf.
Filter Eff.
02/12/2002
Raw
After Pre-Treat.
Filter Inf.
Filter Eff.
TOC
(mq/L)
6.72
6.12
4.48
4.52
7.52
6.20
3.70
3.80
7.01
5.71
4.51
4.42
5.33
5.24
3.30
3.21
UV3
(cm'1)
0.184
0.160
0.095
0.086
0.273
0.196
0.091
0.089
0.233
0.188
0.117
0.115
0.176
0.129
0.070
0.069
SUVAb
(L/mg-m)
2.74
2.61
2.12
1.90
3.63
3.16
2.46
2.34
3.32
3.29
2.59
2.60
3.30
2.46
2.12
2.15
Remova
TOC
8.9%
27%
-0.9%
—
18%
40%
-2.7%
19%
21%
2.0%
—
1 .7%
37%
2.7%
/Unit (%)
UV
13%
41%
9.5%
—
28%
54%
2.2%
19%
38%
1 .7%
—
27%
46%
1 .4%
Removal/Cu
TOC
8.9%
33%
33%
—
18%
51%
49%
19%
36%
37%
—
1 .7%
38%
40%
mulative (%)
UV
13%
48%
53%
—
28%
67%
67%
19%
50%
51%
—
27%
60%
61%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (crrf1)/DOC (mg/L) or UV (m-1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.184/cm = 0.184/(0.01 m) = 18.4/m, DOC = 6.72 mg/L, SUVA = (18.4 rrf1)/(6.72 mg/L) = 2.74 L/mg-m)
71
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Table 7 shows the values of miscellaneous other water quality parameters in the raw
waters at the two EPA Region 6 plants.
Table 7. Miscellaneous water quality parameters in raw water at the EPA Region 6 plants
Plant 11
Plant 12
Date
03/26/2001
09/10/2001
11/5/2001
02/11/2002
Bromide
(mg/L)
0.18
0.21
0.16
0.18
Alkalinity
(mg/L)
121
117
133
153
Ammonia
(mg/L as N)
ND
0.15
ND
ND
Date
03/26/2001
09/10/2001
11/15/2001
02/12/2002d
Bromide
(mg/L)
0.25
0.02
0.15
0.33
Alkalinity
(mg/L)
123
54
70
111
Ammonia
(mg/L as N)
ND
0.04
ND
ND
aBromide sampled at pre-treatment sample
location in February 2002
Both EPA Region 6 plants treated waters high in TOC, bromide, and alkalinity in March
2001, November 2001, and February 2002 (Tables 5-7, Figure 4). However, in September 2001,
the water qualities were quite different (Table 5-7, Figure 5): the TOC at plant 11 was lower,
whereas the bromide and alkalinity at plant 12 was lower.
Figure 4
Figure 5
Comparison of Raw Water Quality at
Plants 11 and 12: 3/26/01
Comparison of Raw Water Quality at
Plants 11 and 12: 9/10/01
10*TOC(mg/L)
Bromide (Mg/L)
Alkalinity (mg/L)
10*TOC(mg/L)
Bromide (Mg/L)
Alkalinity (mg/L)
At plant 12, the bromide and alkalinity on September 10, 2001 were significantly lower
than on March 26, 2001, whereas the TOC was only slightly higher. This could either reflect a
different blend of source waters on the two sampling dates or some seasonal variation in water
quality. For example, a storm event can result in an increase in TOC due to runoff and a dilution
of inorganic parameters such as bromide and alkalinity.
DBFs
Oxyhalides. Tables 8-9 show the formation of oxyhalides at the two plants. Chlorine
dioxide will typically not react with bromide to form bromate, as was observed at plant 11 (Table
8) and plant 12 in February 2002 (Table 9).
72
-------
Table 8. Oxyhalide formation at plant 11
Location
03/26/2001
Filter Eff.
Clearwell Eff.
09/10/2001
Clearwell Inf.
Clearwell Eff.
11/5/2001
Filter Inf.
Clearwell Inf.
Plant Eff.
02/11/2002
Filter Inf.
Clearwell Inf.
Plant Eff.
Bromate3
(M9/L)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Chlorite3
(M9/L)
ND
639
399
406
238
202
478
135
212
420
Chlorate3
(M9/L)
ND
244
94
160
47
47
159
36
289
167
CI02VCI02b
%
—
85%
47%
48%
68%
58%
56%
54%
28%
56%
3Reporting detection level for bromate = 3 |jg/L and for chlorate and chlorite = 5 |jg/L
bChlorine dioxide dose in March 2001 = 0.75 mg/L
Chlorine dioxide dose in September 2001 = 0.35 mg/L at clarifier and 0.5 mg/L at post
Chlorine dioxide dose in November 2001 = 0.35 mg/L before clarifier and 0.5 mg/L at post
Chlorine dioxide dose in February 2002 = 0.25 mg/L at clarifier and 0.5 mg/L at post
Table 9. Oxyhalide formation at plant 12
Location
03/26/2001
After Pre-Treat.
Filter Inf.
Filter Eff.
09/10/2001
After Pre-Treat.
Filter Inf.
Filter Eff.
11/15/2001
After Pre-Treat.
Filter Inf.
Filter Eff.
02/12/2002
After Pre-Treat.
Filter Inf.
Filter Eff.
Bromate
(M9/L)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Chlorite
(M9/L)
ND
ND
ND
ND
ND
ND
ND
ND
ND
900
648
634
Chlorate
(M9/L)
8.6
30
32
ND
ND
ND
ND
ND
ND
94
182
169
CIO27CIO23
%
—
—
—
—
—
...
...
—
—
90%
65%
63%
Chlorine dioxide dose in February 2002 = 1.0 mg/L
73
-------
It has been reported that during water treatment, approximately 50-70 % of the chlorine
dioxide (CIO 2) reacted will immediately appear as chlorite (CIO 2") and the remainder as chloride
(Aieta and Berg, 1986). At plant 11, a similar percentage was observed in November 2001 and
for most of the samples collected in February 2002, whereas a somewhat higher amount of
chlorite was detected in March 2001 and a somewhat lower level was detected in September
2001 (Table 8). Likewise, a similar percentage to that reported by Aieta and Berg (1986) was
observed for most of the samples collected in February 2002 at plant 12 (Table 9).
Because chlorine dioxide was not used at plant 12 on March 26, 2001, September 10,
2001, or November 15, 2001, no chlorite was detected (Table 9). However, a very low amount
of chlorate was found in the water in March 2001, even before the addition of chlorine (Table 9).
In other research, low levels of chlorate have been detected in raw water samples (Bolyard et al.,
1992).
Organic DBFs. Tables 10 and 11 (3/26/01), Tables 13 and 14 (9/10/01), Tables 19 and
20 (11/5/01 and 11/15/01), and Tables 22 and 23 (2/11/02 and 2/12/02) show results for the
halogenated organic DBFs that were analyzed by MWDSC. Table 12 (3/26/01 [plant 11] and
Table 21 (11/15/01 [plant 12]) shows results from broadscreen DBF analyses conducted at the
U.S. Environmental Protection Agency (USEPA). Tables 15 and 16 (9/10/01), and Tables 24
and 25 (2/11/02 and 2/12/02) show results for additional target DBFs that were analyzed for at
the University of North Carolina (UNC). Tables 17 and 18 (9/10/01), and Tables 26 and 27
(2/11/02 and 2/12/02) show results for halogenated furanones that were analyzed at UNC.
Summary of tables for organic DBFs
DBF Analyses (Laboratory)
Halogenated organic DBFs
(MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
3/26/01
Tables 10-
11
Table 12a
9/10/01
Tables 13-14
Tables 15-16
Tables 17-18
11/5/01 and
11/15/01
Tables 19-20
Table 21°
2/1 1/02 and
2/12/02
Tables 22-23
Tables 24-25
Table 26-27
"Plant 11
bPlant 12
74
-------
Table 10. DBF results at plant 11 (3/26/01)
03/26/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethane
Dibromochloromethaned
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acicf1
Monobromoacetic acidd
Dichloroacetic acid
Bromochloroacetic acidd
Dibromoacetic acicf1
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA9g
DXAAh
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitrile
Dibromoacetonitriled
Trichloroacetonitriled
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
MRLa
UJJ/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.2
0.20
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
Plant 11b
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
ND
Filt Eff
0.2
0.4
0.4
ND
1.0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clearwell
ND
ND
ND
ND
8
19
23
7
57
0.3
0.3
ND
ND
ND
ND
0.2
ND
ND
ND
10
12
8.7
4.5
10
8.8
ND
23
54
31
23
ND
ND
0.3
0.4
0.6
ND
1
0.6
0.3
ND
Plant Eff
ND
ND
ND
ND
6
15
19
6
46
ND
ND
ND
ND
ND
ND
0.15
ND
ND
ND
9.7
11
8.1
3.8
9.0
7.5
ND
22
49
29
20
ND
ND
2
3
3
ND
0.4
0.3
0.5
ND
DS/Ave
ND
ND
ND
ND
6
15
18
6
45
0.2
0.2
ND
ND
ND
ND
ND
ND
ND
ND
11
13
8.9
5.1
11
8.9
ND
25
58
33
25
ND
ND
2
3
4
ND
0.8
0.4
0.6
ND
DS/Max
6
17
21
5
49
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
3
4
ND
1
0.8
1
0.5
SDS/Ave
0.35
ND
ND
ND
7
17
20
6
50
ND
0.2
ND
ND
ND
ND
ND
ND
2.7
ND
12
13
9.2
5.4
11
9.2
ND
29
63
34
26
ND
ND
2
3
4
ND
0.8
0.4
0.7
ND
SDS/Max
7
17
20
6
50
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
3
4
ND
1
0.4
0.6
ND
75
-------
Table 10 (continued)
03/26/2001
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanone
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,3-Dibromopropanone
1,1,1-Trichloropropanoned
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1 . 1 .1 .3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
uq/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.5
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 11 b
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clean/veil
ND
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
Plant Eff
ND
0.3
ND
ND
ND
0.8
ND
<1J
ND
ND
ND
ND
ND
ND
<1
<1
0.4
ND
ND
ND
ND
DS/Ave
ND
0.4
ND
ND
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
<1
<1
ND
0.4
ND
ND
ND
DS/Max
ND
0.3
0.5
1
ND
ND
ND
ND
0.2
0.1
ND
SDS/Ave
ND
0.4
ND
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
ND
<1
<1
ND
0.2
ND
ND
ND
SDS/Max
ND
0.5
ND
0.4
ND
ND
ND
ND
ND
0.4
ND
MRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
bPlant 11 sampled at (1) raw water, (2) filter effluent, (3) clearwell effluent, (4) plant effluent,
distribution system (DS) at (5) average and (6) maximum detention times, and
SDS testing of plant effluent at (7) average and (8) maximum detention times
CND = Not detected at or above MRL
dDBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
eTHM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
fHAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid)
9HAA9 = Sum of 9 haloacetic acids
hDXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
'TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
J<1: Concentration less than lowest calibration standard (i.e., 1 ug/L)
76
-------
Table 11. DBF results at
03/26/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethane
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acid
Dichloroacetic acid
Bromochloroacetic acidd
Dibromoacetic acid
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitriled
Trichloroacetonitrile
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
plant 12 (3/26/01)
MRL*
Hp/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.2
0.20
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
Plant 12K
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
Pre-Treat
0.2
ND
0.4
ND
0.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
ND
ND
ND
ND
6
11
8
5
30
3
3
2
2
ND
ND
ND
ND
ND
ND
11
10
6.9
2.4
2.1
1.5
ND
20
34
28
6.0
ND
ND
0.8
1
0.6
ND
1
0.9
0.8
0.6
Filt Eff
5
10
8
7
30
NR'
NR
2
1
ND
ND
ND
ND
ND
12
12
7.7
4.1
4.8
3.4
ND
24
44
32
12
ND
ND
0.7
1
0.6
ND
0.5
0.4
0.2
ND
Plant Eff
ND
ND
ND
ND
5
11
10
8
34
4
3
3
2
0.3
ND
ND
ND
ND
ND
14
15
12
5.1
6.0
3.9
ND
31
56
41
15
ND
ND
1
2
1
ND
0.6
0.6
0.2
0.2
DS/Ave
ND
ND
ND
ND
6
14
18
14
52
4
6
7
3
1
ND
ND
ND
ND
ND
12
15
14
3.5
5.2
4.1
ND
30
54
41
13
ND
ND
2
2
3
ND
0.6
0.9
0.4
0.2
DS/Max
6
17
30
31
84
NR
NR
0.8
ND
ND
ND
ND
ND
ND
1
3
4
ND
0.3
0.6
0.2
0.2
S DS/Ave
ND
ND
ND
ND
5
12
12
9
38
4
3
4
3
0.4
ND
ND
ND
2.0
ND
14
14
12
5.1
5.8
3.7
ND
33
57
40
15
ND
ND
2
2
2
ND
0.7
0.8
0.3
0.3
SDS/Max
7
15
16
11
49
NR
2
4
2
ND
ND
ND
ND
ND
2
2
2
ND
0.8
0.9
0.3
0.2
77
-------
Table 11 (continued)
03/26/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 .1-Dibromopropanone
1 .3-Dibromopropanone
1 ,1 ,1-Trichloropropanone
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
Ho/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.5
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 12°
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Pre-Treat
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
ND
0.4
0.3
ND
ND
0.3
ND
<1'
ND
ND
ND
ND
ND
ND
<1
<1
0.1
0.1
ND
ND
ND
Filt Eff
ND
0.3
ND
0.2
ND
ND
ND
ND
ND
0.1
ND
Plant Eff
ND
0.3
ND
ND
ND
0.3
ND
<1
ND
ND
ND
ND
ND
ND
<1
<1
0.3
0.2
ND
ND
ND
DS/Ave
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
<1
<1
0.4
0.2
ND
ND
ND
DS/Max
ND
ND
ND
ND
ND
ND
ND
ND
0.8
0.1
ND
SDS/Ave
ND
0.3
ND
ND
ND
0.3
ND
<1
ND
ND
ND
ND
ND
ND
<1
<1
0.3
0.2
ND
ND
ND
SDS/Max
ND
0.3
ND
0.3
ND
ND
ND
ND
0.2
0.4
ND
Plant 12 sampled at (1) raw water, (2) after pre-treatment, (3) filter influent, (4) filter effluent,
(5) plant effluent, DS at (6) average and (7) maximum detention times, and
SDS testing of plant effluent at (8) average and (9) maximum detention times
NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance
78
-------
Table 12. Occurrence of other DBFs3 at plant 11: plant effluent (3/26/01)
Halomethanes
Dibromochloromethaneb
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Haloacids
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Bromodichloroacetic acid
Tribromoacetic acid
2,2-Dibromopropanoic acid
Dibromochloropropanoic acid0
3,3-Dibromopropenoic acid
Bromochloro-4-oxopentanoic acid0
3,3-Dibromo-4-oxopentanoic acid
Bromoheptanoic acid0
Bromochloroheptanoic acid0 (2
isomers)
Dibromoheptanoic acid0
Bromochlorononanoic acid0
2-(4-Chloro-2-methylphenoxy)-
propanoic acid
cis-2-Bromo-3-methylbutenedioic acid
Haloketones
1,1 -Dichloropropanone
1,1,1 -Trichloropropanone
1,1,3-Trichloropropanone
1 -Bromo-1,1 -dichloropropanone
1, l-Dibromo-3-chloropropanone
1,1,3-Tribromopropanone
1 -Bromo-1,3,3 -trichloropropanone
1,3-Dibromo-l, 3-dichloropropanone
1,1,3-Tribromo-3-chloropropanone
1,1,3,3-Tetrabromopropanone
Haloacetonitriles
Bromochloroacetonitrile
Dibromoacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloaldehydes
Bromochloroacetaldehyde
Dibromoacetaldehyde
Bromodichloroacetaldehyde
2-Bromo-2-methylpropanal
Halonitromethanes
Dichloronitromethane
Non-halogenated DBFs
Octadecanoic acid
"DBFs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique.
bCompounds listed in italics were confirmed through the analysis of authentic standards;
haloacids and non-halogenated carboxylic acids identified as their methyl esters.
°Exact isomer not known
79
-------
Table 13. DBF results at plant 11 (9/10/01)
09/10/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitrile
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehvde
Chloral hydrated
Tribromoacetaldehvde
MRLa
ug/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.25
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.22
0.5
0.1
0.1
Plant 1 1 b
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Eff
1
6
10
2
19
2
ND
ND
ND
ND
ND
ND
ND
ND
3.2
5.1
8.2
ND
3.1
3.2
ND
11
23
17
6.3
ND
ND
0.4
0.6
0.6
ND
0.7
0.6
ND
0.2
Clean/veil
ND
ND
ND
ND
3
16
24
6
49
1
0.8
0.4
ND
ND
ND
ND
ND
ND
1.4
4.8
8.0
9.1
2.2
8.1
7.6
2.2
18
43
22
20
0.2
ND
0.6
1
2
ND
ND
0.6
ND
1
1
1
0.8
Plant Eff
ND
ND
ND
ND
2
17
24
6
49
2
0.7
0.4
0.3
ND
ND
ND
ND
ND
1.4
4.7
7.8
9.4
2.0
7.6
7.2
2.0
18
42
22
19
ND
ND
0.6
1
2
ND
ND
ND
ND
2
0.8
NR
0.4
DS/Ave
ND
ND
ND
ND
4
21
26
8
59
0.9
ND
ND
ND
ND
ND
ND
ND
ND
1.2
5.1
9.4
8.8
2.3
7.8
7.1
2.2
17
44
23
19
ND
ND
0.7
1
2
ND
0.9
0.9
0.9
ND
DS/Max
4
22
27
9
62
0.7
ND
ND
ND
ND
ND
ND
ND
0.2
0.8
1
2
ND
0.9
0.9
0.8
ND
SDS/Ave
ND
ND
ND
ND
1
16
24
5
46
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
2
NR1
ND
0.4
0.3
0.2
ND
SDS/Max
1
44
16
8
69
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
2
NR
ND
ND
ND
ND
0.9
0.4
0.3
ND
-------
Table 13 (continued)
09/10/2001
Compound
Haloketones
Chloropropanone
1 .1-DichloroDrooanone
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanone d
1.1.3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1-Tribromopropanone
1,1,3-Tribromopropanone
1.1.3.3-TetrachloroDrooanone
1.1.1 .3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chlorooicrin
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methvl tertiary butvl ether
Benzyl chloride
1.1.2.2-Tetrabromo-2-chloroethane
MRLa
uo/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
2.5
0.1
0.1
0.10
0.5
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.25
0.5
Plant 1 1 b
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
Filt Eff
0.1
0.4
ND
0.4
0.3
ND
0.2
NR
ND
0.6
ND
ND
ND
ND
ND
ND
ND
NR
ND
Clean/veil
ND
0.2
ND
0.2
0.5
ND
0.4
ND
ND
0.3
0.5
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
0.1
0.3
ND
0.2
0.5
ND
0.4
ND
ND
0.1
0.1
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
0.2
ND
0.2
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
0.6
ND
ND
ND
DS/Max
0.1
0.3
ND
0.2
0.2
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.1
NR
ND
SDS/Ave
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
ND
SDS/Max
ND
0.1
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
0.5
ND
NR
ND
81
-------
Table 14. DBF results at plant 12 (9/10/01)
09/10/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoaceticacidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehvde
Chloral hydrated
Tribromoacetaldehyde
MRLa
M9/L
0.2
0.2
0.5
0.5
0.1
0.2
0.25
0.5
0.5
0.5
0.52
0.25
0.25
0.25
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.22
0.5
0.1
0.1
Plant 12k
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
0.5
0.7
Pre-Treat
0.4
NR1
NR
ND
NR
NR
ND
ND
NR
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
0.1
Filt Inf
ND
ND
ND
ND
9
9
4
1
23
6
1
0.6
0.4
ND
ND
ND
ND
2.8
1.0
26
15
4.8
8.0
4.9
1.1
ND
43
64
46
14
ND
ND
1
0.6
0.2
ND
ND
ND
ND
3
1
2
0.7
Filt Eff
14
NR
NR
NR
NR
NR
2
0.8
NR
ND
NR
ND
2.8
1.2
26
16
4.9
9.8
5.9
1.3
ND
45
68
47
17
0.1
0.2
2
0.9
0.4
ND
5
2
2
0.9
Plant Eff
ND
ND
ND
ND
14
13
6
1
34
7
2
1
0.5
0.3
ND
ND
ND
3.0
1.3
29
19
6.7
11
6.9
1.8
ND
51
79
55
20
0.1
ND
3
1
0.6
ND
ND
ND
ND
4
2
2
0.3
DS/Ave
ND
ND
ND
ND
17
15
7
2
41
10
2
1
2
0.6
0.3
ND
ND
2.1
ND
26
14
5.9
9.0
5.6
1.3
ND
43
64
46
16
0.1
ND
2
1
0.9
ND
6
1
2
0.1
DS/Max
19
NR
NR
NR
NR
NR
2
ND
NR
ND
NR
ND
ND
ND
3
1
1
ND
6
1
2
ND
82
-------
Table 14 (continued)
09/10/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1-Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1,1,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
2
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.25
0.5
Plant 12k
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Pre-Treat
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
NR
NR
Filt Inf
0.1
0.8
0.2
ND
0.1
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
0.4
1
2
2
0.6
ND
ND
ND
Filt Eff
0.1
1
ND
ND
0.3
ND
ND
ND
ND
ND
0.5
ND
0.4
ND
ND
ND
0.6
NR
NR
Plant Eff
0.1
1
ND
ND
0.4
ND
ND
ND
ND
ND
0.5
ND
ND
ND
0.2
ND
0.9
2
2
ND
ND
ND
ND
ND
DS/Ave
0.2
0.8
ND
ND
ND
ND
ND
ND
ND
ND
0.4
ND
ND
ND
ND
ND
1
0.6
ND
ND
ND
DS/Max
0.3
0.9
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
ND
ND
2
NR
NR
83
-------
Table 15. Additional target DBF results (ug/L) at plant 11 (9/10/01)
9/10/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (|ig/L as Cr)
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
tmns-2-Hexenal
Plant lla
Raw
0
0
0
0
0
0
33.5
<0.1
<0.1
<0.1
<0.1
<0.1
FI
0
0
0
0
0
0
48.1
<0.1
<0.1
0.8
<0.1
<0.1
CWI
0.2
1.4
1.0
0.8
0
0
299
<0.1
<0.1
<0.1
1.1
<0.1
CWE
0
1.2
1.5
0.9
0
2.5
129
<0.1
<0.1
<0.1
1.5
<0.1
PE
0
3.2
2.8
0.7
0
2.8
126
<0.1
<0.1
<0.1
1.2
<0.1
DS
0
2.8
2.6
0.6
0
2.7
118
<0.1
<0.1
<0.1
0.8
<0.1
SDS
0
3.5
1.8
0.6
0
2.4
121
<0.1
<0.1
<0.1
1.5
<0.1
aPlant 11 sampled at (1) raw water, (2) filter influent (FI), (3) clearwell influent (CWI), (4)
clearwell effluent (CWE), (5) finished water at plant effluent (PE), (6) distribution system (DS)
at average detention time, and (6) SDS at maximum detection time.
Table 16. Additional target DBF results (ug/L) at plant 12 (9/10/01)
9/10/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (|ig/L as Cl')
Cyanoformaldehyde
5-Keto- 1 -hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
Trans -2-HQxena\
Plant 12b
Raw
0
0
0
0
0
0
6.6
<0.1
<0.1
<0.1
<0.1
<0.1
PT
0.3
0.4
2.1
0
0
0
35.0
<0.1
<0.1
<0.1
<0.1
<0.1
FI
4.2
2.4
0.5
0
4.5
196
<0.1
<0.1
<0.1
2.4
<0.1
FE
6.2
3.1
0
0
4.4
223
<0.1
<0.1
<0.1
3.1
<0.1
PE
1.2
5.8
3.0
0
0
5.6
260
<0.1
<0.1
<0.1
2.5
<0.1
DS
6.5
2.5
0
0
5.1
245
<0.1
<0.1
<0.1
2.0
<0.1
SDS
1.8
6.8
2.1
0
0
5.5
165
<0.1
<0.1
<0.1
2.9
<0.1
"Plant 12 sampled at (1) raw water, (2) pre-treated water (PT), (3) filter influent (FI), (4) filter
effluent (FE), (5) finished water at plant effluent (PE), (6) distribution system (DS) at average
detention time, and (7) SDS at maximum detection time.
84
-------
Table 17. Halogenated furanone results (iig/L) at plant 11 (9/10/01)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Mucochloric acid (ring)
Mucochloric acid (open)
FI
<0.02
0.02
<0.02
O.02
<0.02
<0.02
<0.02
<0.02
O.02
<0.02
<0.02
FE
0.05
0.02
0.02
(0.011)
O.02
0.02
0.37
O.02
O.02
O.02
0.02
0.02
CWE
0.12
0.02
(0.01)
0.02
(0.011)
O.02
0.02
0.31
0.02
O.02
0.09
0.02
0.02
PE
0.17
0.02
0.02
(0.016)
O.02
0.02
0.20
0.02
O.02
O.02
0.02
0.02
DS/ave
0.14
0.02
(0.01)
0.02
(0.015)
O.02
0.02
0.02
0.85
O.02
O.02
0.02
0.02
SDS/max
0.21
0.02
0.02
(0.013)
O.02
0.02
0.49
NA
NA
NA
NA
NA
Table 18. Halogenated furanone results (iig/L) at plant 12 (9/10/01)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Mucochloric acid (ring)
Mucochloric acid (open)
Raw
O.02
0.03
0.02
O.02
O.02
0.02
O.02
O.02
O.02
0.02
0.02
PT
O.02
0.02
0.02
O.02
O.02
0.02
O.02
O.02
O.02
0.02
0.02
FI
O.02
0.02
0.02
O.02
O.02
0.02
O.02
O.02
O.02
0.02
0.02
FE
O.02
0.02
0.02
O.02
O.02
0.02
0.08
O.02
O.02
0.02
0.02
PE
0.09
0.02
0.03
O.02
O.02
0.02
O.02
(0.014)
O.02
O.02
0.02
0.02
DS/ave
0.08
0.02
0.02
O.02
O.02
0.04
NA
NA
NA
NA
NA
SDS/max
0.03
0.02
0.02
(0.017)
O.02
O.02
0.02
NA
NA
NA
NA
NA
85
-------
Table 19. DBF results at plant 11 (11/5/01)
11/05/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acicf
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehvde
Chloral hydrated
Tribromoacetaldehyde
MRLa
ug/L
0.2
0.2
0.5
0.5
0.5
0.1
0.1
0.11
0.5
0.25
0.52
0.5
0.5
2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.90
1.1
0.5
0.1
0.5
Plant 1 1 m
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
ND
0.1
ND
ND
0.1
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clean/veil
ND
ND
ND
ND
ND
0.4
0.3
ND
0.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
Plant Eff
ND
ND
ND
ND
5
14
15
3
37
1
0.4
ND
ND
ND
ND
ND
ND
ND
1.1
8.8
10
7.9
4.7
9.6
6.2
ND
23
48
27
21
ND
ND
1
NR
2
ND
ND
0.6
ND
1
1
1
<0.5"
DS/Ave
ND
ND
ND
ND
7
17
16
3
43
2
0.3
ND
ND
ND
ND
ND
ND
ND
1.1
11
11
8.0
5.3
11
6.9
ND
25
54
30
23
0.3
ND
1
NR
2
ND
2
1
1
ND
DS/Max
8
17
18
4
47
NR1
ND
NR
ND
ND
ND
ND
ND
2
2
1
ND
3
1
1
ND
SDS/Ave
ND
ND
ND
ND
8
18
18
3
47
2
0.4
ND
ND
ND
ND
ND
ND
ND
1.1
11
11
8.0
4.5
10
5.9
ND
25
52
30
20
0.4
ND
2
2
2
ND
3
1
2
ND
SDS/Max
9
20
19
3
51
NR
ND
NR
ND
ND
ND
ND
ND
2
2
2
ND
ND
0.5
ND
3
1
2
ND
86
-------
Table 19 (continued)
11/05/2001
Compound
Haloketones
Chloropropanone
1 .1-DichloroDroDanoned
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanone d
1.1.3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1-Tribromopropanone
1,1,3-Tribromopropanone
1.1.3.3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methvl tertiary butvl ether
Benzyl chloride
1.1.2.2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
1.0
0.29
0.14
0.10
0.10
0.5
0.1
0.1
0.1
0.10
0.1
0.5
2
2
0.5
0.2
0.5
0.5
Plant 11 m
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
Filtlnf
ND
0.2
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clean/veil
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
0.2
0.5
ND
ND
0.8
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
0.1
0.7
ND
ND
0.8
ND
ND
ND
DS/Ave
0.1
0.6
ND
ND
0.7
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
0.2
0.7
ND
ND
ND
DS/Max
0.3
0.7
ND
ND
0.7
ND
NR
ND
ND
ND
ND
ND
ND
0.3
ND
ND
0.5
ND
ND
SDS/Ave
ND
0.8
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
0.4
ND
ND
1
0.9
ND
ND
ND
SDS/Max
ND
0.8
ND
ND
0.4
ND
ND
NR
ND
ND
ND
ND
ND
0.4
ND
ND
1
1
ND
ND
ND
ND
Plant 11 sampled at (1) raw water, (2) filter influent, (3) clean/veil influent, (4) plant effluent,
DS at (5) average and (6) maximum detention times, and
SDS testing of plant effluent at (7) average and (8) maximum detention times
"<0.5: Concentration less than MRL (i.e., 0.5 ug/L)
87
-------
Table 20. DBF results at plant 12 (11/15/01)
11/15/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethane
Dibromochloromethane
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acid
Dichloroacetic acid
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehyde
Chloral hydrate
Tribromoacetaldehyde
MRLa
^g/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.25
0.52
0.5
0.5
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.90
0.22
0.5
0.1
0.5
Plant 12K
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Pre-Treat
0.3
0.3
ND
ND
0.6
NR'
ND
NR
ND
ND
ND
ND
ND
1.1
ND
ND
ND
ND
ND
ND
1.1
1.1
1.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
Filtlnf
ND
ND
ND
ND
7
11
6
2
26
11
3
1
0.6
ND
ND
ND
ND
3.7
ND
19
21
8.6
4.5
3.8
1.8
ND
36
62
49
10
ND
ND
1
0.7
0.5
ND
ND
ND
ND
3
1
1
ND
Filt Eff
5
8
5
1
19
NR
2
NR
NR
ND
ND
ND
3.3
ND
18
21
8.6
4.2
3.9
1.7
ND
34
61
48
10
ND
ND
0.7
0.4
0.2
ND
2
0.5
1
ND
Plant Eff
ND
ND
ND
ND
5
10
6
2
23
11
3
2
2
0.7
ND
ND
ND
5.5
ND
22
18
11
5.7
5.7
2.8
ND
44
71
51
14
0.4
ND
2
1
0.9
ND
ND
ND
ND
3
2
1
ND
DS/Ave
ND
ND
ND
ND
11
21
15
9
56
15
5
3
1
0.7
ND
ND
ND
2.1
1.0
17
18
8.2
7.2
5.4
2.2
ND
36
61
43
15
ND
ND
2
3
2
ND
4
4
2
ND
DS/Max
13
25
18
9
65
NR
4
3
NR
0.7
ND
ND
ND
ND
2
2
0.9
ND
4
4
2
ND
S DS/Ave
ND
ND
ND
ND
11
20
14
7
52
14
4
3
1
ND
ND
ND
ND
2.8
2.7
27
21
15
7.1
6.7
2.8
ND
55
85
63
17
ND
ND
2
3
2
ND
5
3
1
ND
SDS/Max
11
19
14
8
52
NR
3
NR
NR
ND
ND
ND
ND
ND
2
2
1
ND
ND
ND
ND
5
4
2
ND
-------
Table 20 (continued)
11/15/2001
Compound
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1 ,1,1-Tribromopropanone
1 .1 .3-Tribromopropanone
1 .1 ,3.3-Tetrachloropropanone
1 .1 .1 .3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methvl ethvl ketone
Methyl tertiary butyl ether
Benzvl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRLa
Mg/L
0.1
0.10
0.1
0.10
0.1
0.1
0.1
2.5
0.14
0.10
0.10
0.5
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.2
0.5
0.5
Plant 12K
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
Pre-Treat
ND
0.2
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
ND
0.7
ND
ND
0.2
ND
ND
ND
ND
ND
0.1
ND
ND
0.3
ND
ND
0.3
1
2
2
ND
ND
ND
ND
Filt Eff
ND
0.8
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
0.3
ND
ND
0.2
ND
ND
Plant Eff
ND
0.8
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
0.4
ND
ND
0.7
1
1
2
0.7
ND
ND
ND
DS/Ave
ND
0.8
ND
0.1
0.4
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
1
0.8
ND
ND
ND
DS/Max
ND
0.8
ND
0.1
0.3
ND
ND
NR
ND
ND
ND
ND
ND
0.9
ND
ND
0.9
ND
ND
S DS/Ave
0.6
0.9
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
1
0.3
ND
ND
SDS/Max
ND
0.7
ND
ND
0.1
ND
ND
NR
ND
ND
ND
ND
ND
0.4
ND
ND
1
ND
1
0.7
NR
ND
-------
Table 21. Occurrence of other DBFs a at plant 12: plant effluent (11/15/01)
Halomethanes
Bromodichloromethaneb
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
Haloacids
lodoacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
lodobromoacetic acid
Tribromoacetic acid
3,3-Dichloropropenoic acid
3,3-Dibromopropenoic acid
lodobromopropenoic acid0 (2 isomers)
cis-2-Bromo-butenedioic acid
2-Iodo-3-methylbutenedioic acid
Haloacetonitriles
Bromochloroacetonitrile
Dibromoacetonitrile
Haloaldehydes
2-Bromo-2-methylpropanal
Haloketones
1, l-Dibromo-3,3-dichloropropanone
1,3-Dibromo-l, 3-dichloropropanone
1,1,3-Tribromo-3-chloropropanone
1,1,3,3-Tetrabromopropanone
Pentachloropropanone
Miscellaneous Halogenated DBFs
Dibromoaniline
Dibromodichloroaniline
Tribromochloroaniline
Non-halogenated DBFs
Acetone
Glyoxal
Hexanoic acid
Heptanoic acid
Octanoic acid
Nonanoic acid
Decanoic acid
Dodecanoic acid
Tetradecanoic acid
Hexanedioic acid
Decanedioic acid
Undecanedioic acid
3DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique.
bCompounds listed in italics were confirmed through the analysis of authentic standards; haloacids and
non-halogenated carboxylic acids identified as their methyl esters.
°Exact isomer not known
90
-------
Table 22. DBF results at plant 11 (2/11/02)
02/11/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoform d
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acid
Dibromoacetic acid
Trichloroacetic acicf
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehvde
Chloral hvdrated
Tribromoacetaldehyde
MRLa
ug/L
0.2
0.2
0.5
0.5
0.2
0.5
0.25
0.5
1.0
0.5
0.53
0.1
0.52
2.2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
2.5
0.5
1.0
0.1
0.5
0.5
0.90
0.98
0.5
0.1
0.1
Plant 11m
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
Filtlnf
NR1
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
4.8
ND
ND
2.0
ND
ND
ND
6.8
6.8
4.8
2.0
ND
ND
NR
ND
ND
ND
ND
ND
0.2
ND
Clean/veil
ND
ND
ND
ND
4
4
5
2
15
<1°
0.5"
ND
ND
ND
ND
ND
ND
3.0
1.0
6.6
5.0
5.7
3.4
6.6
6.2
ND
20
38
17
16
ND
ND
<1
0.5
<1
ND
ND
ND
ND
ND
ND
0.2
ND
Plant Eff
ND
ND
ND
ND
5
9
10
4
28
<1
<0.5
ND
ND
ND
ND
ND
ND
2.8
1.4
6.7
6.3
6.1
4.4
9.0
9.1
ND
21
46
19
23
ND
ND
<1
2
2
ND
ND
ND
ND
ND
0.6
0.3
ND
DS/Ave
ND
ND
ND
ND
7
10
11
4
32
<1
<0.5
0.6
ND
ND
ND
ND
ND
2.8
1.5
9.2
6.3
5.5
4.7
8.8
8.7
4.6
24
52
21
27
ND
ND
<1
2
2
ND
ND
0.7
0.3
ND
DS/Max
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
NR
NR
NR
ND
ND
0.7
0.3
ND
SDS/Ave
ND
ND
ND
ND
6
11
12
4
33
<1
0.7
ND
ND
ND
ND
ND
ND
3.2
1.6
8.0
6.2
5.3
4.0
8.6
8.5
ND
22
45
20
21
ND
ND
<1
2
2
ND
ND
0.8
0.5
ND
SDS/Max
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
NR
NR
NR
ND
ND
ND
ND
ND
0.8
0.4
ND
91
-------
Table 22 (continued)
02/11/2002
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanone
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanone d
1.1.3-Trichloropropanone
1 -Bromo-1 . 1 -dichloropropanone
1,1,1-Tribromopropanone
1,1,3-Tribromopropanone
1.1.3.3-TetrachloroDrooanone
1.1.1 .3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chlorooicrin
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methvl tertiary butvl ether
Benzvl chloride
1,1,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.1
1.0
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.10
0.10
0.5
NA
0.1
0.10
0.1
0.10
0.1
2
2
0.5
0.5
0.2
0.5
0.5
Plant 11 m
Raw
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filtlnf
0.1
1
ND
ND
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Clean/veil
1
1
ND
0.4
0.9
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
0.3
ND
ND
ND
ND
ND
ND
ND
Plant Eff
1
<1
ND
0.3
0.8
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
0.4
ND
ND
1
ND
ND
ND
ND
DS/Ave
1
<1
ND
0.4
0.8
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
0.1
0.1
0.2
ND
ND
ND
ND
DS/Max
0.5
<1
ND
0.2
0.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.4
NR
ND
SDS/Ave
1
<1
ND
0.2
0.7
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
0.4
ND
ND
ND
ND
SDS/Max
1
<1
ND
0.2
0.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.7
ND
ND
ND
NR
ND
°<1.0: Concentration less than MRL(e.g., 1.0 ug/L)
92
-------
Table 23. DBF results at plant 12 (2/12/02)
02/12/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoformd
THM4e
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acid
Dichloroacetic acidd
Bromochloroacetic acid
Dibromoacetic acidd
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5f
HAA99
DXAAh
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitrile
Dibromoacetonitriled
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
MRLa
pfl/L
0.2
0.2
0.5
0.5
0.2
0.5
0.25
0.5
1.0
0.5
0.53
0.1
0.52
2.2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
2.5
0.5
1.0
0.1
0.5
0.5
0.90
0.98
0.5
0.1
0.1
Plant 12K
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
Pre-Treat
NDC
ND
ND
ND
0.4
0.8
1
0.5
3
NR
ND
ND
ND
ND
ND
ND
ND
3.9
1.3
7.8
6.9
6.6
ND
4.7
1.2
ND
20
32
21
5.9
ND
ND
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
ND
ND
ND
ND
3
12
19
17
51
<1°
2
3
ND
ND
ND
ND
ND
3.2
2.2
11
14
16
2.4
6.5
6.3
ND
35
62
41
15
ND
ND
<1
1
1
ND
ND
ND
ND
ND
2
0.7
2
Filt Eff
NR'
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
3.2
2.2
11
13
14
2.2
8.0
5.9
ND
33
60
38
16
ND
ND
NR
NR
NR
ND
ND
2
0.5
1
Plant Eff
ND
ND
ND
ND
3
14
21
19
57
<1
2
4
ND
<0.5"
ND
ND
ND
3.0
2.1
10
14
18
3.1
9.0
8.1
ND
36
67
42
20
ND
ND
<1
2
2
ND
ND
ND
ND
ND
2
0.7
2
DS/Ave
ND
ND
ND
ND
3
15
23
19
60
<1
3
4
ND
<0.5
ND
ND
ND
2.1
2.5
18
22
22
3.8
9.7
8.8
ND
48
89
62
22
ND
ND
<1
2
2
ND
ND
2
0.9
1
DS/Max
NR
NR
NR
NR
NR
NR
NR
NR
ND
<0.5
ND
ND
ND
ND
NR
NR
NR
ND
ND
2
1
0.6
S DS/Ave
ND
ND
ND
ND
3
12
19
16
50
<1
2
3
ND
ND
ND
ND
ND
2.6
2.0
9.6
14
16
2.7
9.1
7.5
ND
33
64
40
19
ND
ND
<1
2
2
ND
ND
2
0.8
2
SDS/Max
NR
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
<1
NR
NR
ND
ND
ND
ND
ND
2
0.7
2
93
-------
Table 23 (continued)
02/12/2002
Compound
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanone
1 .1 ,3-Trichloropropanone
1-Bromo-1.1-dichloropropanone
1 .1.1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRLa
pfl/L
0.1
1.0
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.10
0.10
0.5
NA
0.1
0.10
0.1
0.10
0.1
2
2
0.5
0.5
0.2
1.0
0.5
Plant 12K
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Pre-Treat
ND
<1
ND
0.3
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
NR
ND
Filt Inf
ND
<1
ND
0.4
0.6
ND
0.5
ND
ND
ND
ND
ND
ND
ND
0.3
0.7
0.5
0.4
ND
3
4
ND
ND
ND
ND
Filt Eff
ND
<1
ND
0.3
<0.5
ND
0.1
ND
ND
ND
ND
ND
0.1
0.2
0.7
0.4
0.4
NR
ND
Plant Eff
ND
<1
ND
0.4
0.6
ND
0.5
ND
ND
ND
ND
ND
ND
0.2
0.3
0.7
0.5
0.4
ND
3
5
ND
ND
ND
ND
DS/Ave
ND
<1
ND
0.2
<0.5
ND
0.1
ND
ND
ND
ND
ND
ND
ND
0.3
0.9
0.4
0.7
ND
ND
ND
ND
DS/Max
ND
<1
ND
0.2
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
0.3
0.9
0.4
1
NR
ND
S DS/Ave
ND
<1
ND
0.4
0.6
ND
0.6
ND
ND
ND
ND
ND
ND
ND
0.2
0.8
0.5
0.4
ND
ND
ND
ND
SDS/Max
ND
<1
ND
0.4
0.6
ND
0.2
ND
ND
ND
ND
ND
ND
0.2
0.8
0.6
0.4
ND
3
5
NR
ND
94
-------
Table 24. Additional target DBF results (iig/L) at plant 11 (2/11/02)
2/11/02
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Monochloroacetamide
Monobromoacetamide
2,2-Dichloroacetamide
Dibromoacetamide
Trichloroacetamide
TOX (ng/L as Cr)
TOBr (\ig/L as Br")
TOC1 (ng/L as CO
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
trans -2-Hexenal
Plant llc
FI
0
0
0
0
0
0
0
0
0
0
57.0
59.3
14.6
<0.1
O.I
O.I
O.I
O.I
PE
0.2
1.8
2.0
0
0
0.4
0.8
1.4
1.8
1.1
151
79.0
105
O.I
O.I
O.I
1.4
O.I
DS
1.6
6.7
3.1
0
0
0.6
1.0
1.0
1.5
0.8
139
83.0
102
O.I
O.I
O.I
1.1
O.I
°Plant 11 sampled at (1) FI, (2) PE, and (3) DS at maximum detention time.
Table 25. Additional target DBF results (iig/L) at plant 12 (2/12/02)
2/12/02
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Monochloroacetamide
Monobromoacetamide
2,2-Dichloroacetamide
Dibromoacetamide
Trichloroacetamide
TOX (ug/L as Cl")
TOBr (ug/L as Br")
TOC1 (ug/L as Cl")
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
trans -2-Hexenal
Plant 12d
FI
0.5
2.1
2.1
0
0
1.0
1.5
2.4
2.5
0.9
236
250
108
O.I
O.I
O.I
3.2
O.I
FE
0.5
2.1
2.1
PE
0.1
1.3
4.0
0
0
0.5
1.1
2.0
2.8
1.0
211
229
145
O.I
O.I
O.I
1.5
O.I
DS
0.4
2.4
4.0
0
0
0.8
1.0
1.5
2.2
1.1
212
212
139
O.I
O.I
O.I
1.9
O.I
dPlant 12 sampled at (1) FI, (2) FE, (3) PE, and (4) DS at maximum detention time.
95
-------
Table 26. Halogenated furanone results (iig/L) at plant 11 (2/11/02)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
FI
O.02
O.02
O.02
O.02
0.02
O.02
0.02
O.02
0.02
0.02
0.02
O.02 (0.01)
PE
0.08
O.02
O.02
O.02
0.02
O.02
0.02
O.02
0.02
0.02
0.04
0.02
DS/max
O.02
O.02
O.02
O.02
0.02
O.02
0.03
O.02
0.02
0.02
0.06
0.02
Table 27. Halogenated furanone results (iig/L) at plant 12 (2/12/02)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
FI
0.02
O.02
O.02
O.02
O.02
O.02
O.02 (0.01)
0.02
0.02
0.02
0.13
0.02
PE
0.06
O.02
O.02
O.02
O.02
O.02
0.03
0.02
0.02
0.02
0.08
0.02
DS/max
0.02
O.02
O.02
O.02
O.02
O.02
O.02 (0.01)
0.02
0.02
0.02
0.06
0.02
96
-------
Figure 6. March 26, 2001
Effect of Bromide and Iodide and Disinfection Scheme on
THM Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/
Chlorine/Chloramines) and Plant 12 (Chloramines Only)
Halomethanes. Chlorine dioxide/chlorine/chloramine disinfection at plant 11 resulted in
the formation of 28-49 |ig/L of the four regulated trihalomethanes (THM4) in the plant effluent
in March 2001, September 2001, November 2001, and February 2002. Chloramine disinfection
at plant 12 resulted in the formation of 23-57 |ig/L of THM4 in the plant effluent in March 2001,
September 2001, November 2001, and February 2002. Even with chloramines only, a fair
amount of THMs was formed at plant 12. Because of the relatively high amount of TOC and/or
bromide in these EPA Region 6 waters, TFDVI formation potentials were probably high; thus,
alternative disinfectants were used to minimize TFDVI formation.
In March 2001, because of the high level of bromide in these waters, the major THMs
formed were mixed bromochloro species (Figure 6). In addition, sub-|ig/L levels of two
iodinated THMs were detected in selected samples at plant 11, whereas |ig/L levels of five
iodinated THMs were detected at plant 12 (Figure 6). In addition to bromide in the source water,
there was iodide as well. In other research, the formation of iodinated THMs was favored by
chloramination, especially if the ammonia was added first, whereas the addition of chlorine first
was found to favor the formation of the bromochloro species (Bichsel and von Gunten, 2000).
Although the source water concentration of iodide was not measured in this study, the level of
bromide in both source waters was comparable in March 2001. The difference in the formation
of iodinated THMs at these two utilities may have been due to the order of addition of the
chlorine and ammonia (chlorine first at plant 11, chlorine and ammonia together at plant 12).
At plant 11, there was no significant seasonal variation in THM speciation (Figure 7).
However, the formation of THM4 was highest in September 2001 when the water temperature
97
-------
was the warmest (25°C) and was the lowest in February 2002 when the water temperature was
the coldest (11°C). Likewise, there was a similar seasonal variation in iodinated THM formation
(Figure 8), with more formation in September 2001 and less in March 2001 (18°C) and in
February 2002.
Figure 7. Seasonal formation and speciation Figure 8. Seasonal variations in iodinated
of THMs at plant 11 effluent THM formation at plant 11 clearwell or
plant effluent
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
03/26/2001
09/10/2001 Chlorodiiodomethane
11/05/2001
02/11/2001
Bromodiiodomethane
lodoform
<0.5 or <1: Less than MRL (0.5 or 1.0 M9/L)
m 02/11/2001 H11/05/2001 M 09/10/2001 D 03/26/2001
0.4 0.6 0.8
Trihalomethane (\iglL)
At plant 12, because of the high level of bromide in this water in March 2001 (0.25
mg/L) and February 2002 (0.33 mg/L), the major TFDVIs formed were brominated species
(Figure 9). Alternatively, in September 2001 the low level of bromide (0.02 mg/L) resulted in a
shift to more highly chlorinated TFDVIs (Figure 9). In addition, |ig/L levels of five of the
iodinated THMs were detected in these samples (Figure 10). The sixth iodinated THM,
iodoform, was detected in only one sample (in the distribution system) in September 2001. The
iodinated THMs formed included various combinations of chlorine, bromine, and iodide atoms.
Similar to the THM4 speciation (Figure 9), as the level of bromide increased, the formation of
dibromoiodomethane increased (from 1 to 4 |ig/L), whereas the formation of
dichloroiodomethane decreased (from 7-11 down to <1 |ig/L) (Figure 10).
98
-------
Figure 9. Impact of bromide on THM
speciation at plant 12 effluent
Figure 10. Seasonal variations in iodinated
THM speciation at plant 12 effluent
<0.5 or <1: Less than MRL (0.5 or 1.0 Mg/L)
Bromide (mg/L) ^0.02 ^0.15 S0.25 D0.33
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
3
Bromodiiodomethane
Bromide
(mg/L)
lodoform
I <1
-
N=
j <0.5
I
Trihalomethane (pg/L)
Haloacids. Chlorine dioxide/chlorine/chloramine disinfection at plant 11 resulted in the
formation of 18-23 |ig/L of the five regulated haloacetic acids (HAAS) in the plant effluent in
March 2001, September 2001, November 2001, and February 2002. In addition, all nine HAAs
(HAA9) were measured, which included all of the brominated HAA species. The levels of
HAA9 in the plant effluents in March 2001, September 2001, November 2001, and February
2002 at plant 11 were 42-49 |ig/L. In March 2001, September 2001, November 2001, and
February 2002, (chlorine dioxide and) chloramine disinfection at plant 12 resulted in the
formation of 31-51 and 56-79 |ig/L of HAAS and HAA9, respectively, in the plant effluents. At
these two plants, variations in bromide and disinfection practices impacted HAA formation and
speciation (see discussion below).
Because of the high level of bromide in these waters in March 2001, a major portion of
the HAAs formed in the plant effluent and distribution system were the mixed bromochloro
species (i.e., bromochloro-, bromodichloro-, and dibromochloroacetic acid) (Figure 11). At plant
11 in March 2001, the formation of dihalogenated HAAs (DXAAs) was somewhat higher than
the formation of the trihalogenated species (TXAAs) (Figure 12). The monohalogenated HAAs
(MXAAs) were formed to a very low extent (as is found in other waters [Krasner et al., 1989]).
A different pattern was observed at plant 12 in March 2001. At plant 12, the formation of
DXAAs was significantly higher than the formation of TXAAs (Figure 12).
99
-------
Figure 11. March 26, 2001
Effect of Bromide on HAA Speciation at Plants 11 and 12 in Simulated
Distribution System Samples/Average Detention Time
Figure 12. March 26, 2001
Effect of Disinfection Scheme on HAA Speciation in Plant Effluents at
Plant 11 (Chlorine Dioxide/Chlorine/Chloramines)
and Plant 12 (Chloramines Only)
Plant 11
MXAAs
Plant 12
DXAAs
TXAAs
100
-------
In other research, chlorine dioxide (Zhang et al., 2000) and chloramines (Krasner et al.,
1996) have both been shown to produce little or no TXAAs, whereas DXAAs have been formed.
The use of chloramines only at plant 12 did minimize TXAA formation much more than DXAA
formation, whereas the formation of both types of HAAs at plant 11 was probably due to the
presence of free chlorine in the clearwell. Because of the presence of a significant amount of
THMs at plant 11, it is likely that most of the THMs and HAAs formed at this plant is due to the
free chlorine usage. In other research, waters with relatively low levels of specific UV
absorbance (SUVA) have formed more DXAAs than TXAAs (Hwang et al., 2000). The SUVA
of the water at plant 11, especially at the point of disinfectant addition (i.e., 2.1 L/mg-m in March
2001), was relatively low. It is likely that a combination of the disinfection scheme and natural
organic matter of the water resulted in a higher formation of DXAAs than TXAAs at plant 11.
Because of the higher level of bromide at plant 11 as compared to plant 12 in September
2001, there was a greater shift to the formation of brominated HAAs at plant 11 than at plant 12
(Figure 13). At both plants, there was 19-20 |ig/L of TXAAs in the plant effluent (Figure 14),
with the major difference for this DBF subclass being the bromine speciation (Figure 13).
Alternatively, there was much more formation of DXAAs in the plant effluent at plant 12 than at
plant 11 (55 versus 23 |ig/L) (Figure 14). The change in bromide levels at plant 12—between
March and September 2001—resulted in a shift in HAA speciation between chlorinated and
brominated species (Figures 11 and 13). However, the relative formation of DXAAs and
TXAAs was comparable in March and September 2001 at plant 12 (Figures 12 and 14), which
was due to the use of chloramines only.
Figure 13. 9/10/01 (plant 11 Br = 0.21 mg/L, plant 12 Br = 0.02 mg/L)
Effect of Bromide and Disinfection Scheme on HAA Formation and
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/
Chlorine/Chloramines) and Plant 12 (Chloramines Only)
D)
101
-------
Figure 14. September 10, 2001
Effect of Disinfection Scheme on THM and HAA Formation and
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/
Chlorine/Chloramines) and Plant 12 (Chloramines Only)
60
Plant 12
THM4
Plant 11
DXAAs
TXAAs
At plant 11 in November 2001, chlorine dioxide was initially dosed before the clarifier.
No HAAs and essentially no THMs were detected from pre-disinfection with chlorine dioxide.
At plant 11 in February 2002, chlorine dioxide was initially dosed at the clarifier. HAAs (5 and
2 |ig/L of dichloro- and trichloroacetic acid, respectively) were detected from pre-disinfection
with chlorine dioxide. THM data for the filter influent sample were not reported due to quality
control problems. However, the primary THM detected at that sample site was chloroform. At
plant 11 in February 2002, after the addition of chlorine, significantly more THMs and HAAs
were detected, which included the brominated species. It is possible that there was some DBF
formation during the preparation of the chlorine dioxide solution, when the chlorine dioxide gas
was dissolved in water.
At plant 12 in February 2002, a significant level of HAA9 (32 |ig/L) was produced
during pre-treatment with chlorine dioxide disinfection, whereas very little THMs (3 |ig/L) were
formed. The majority of the HAAs produced were DXAAs (21 |ig/L). These results are
consistent with that of Zhang and colleagues (2000), in which chlorine dioxide was found to
form very little THMs or TXAAs, but did form a significant amount of DXAAs.
In addition to the target HAAs, several new brominated acids were identified by the
broadscreen gas chromatography/mass spectrometry (GC/MS) methods (Tables 12 and 21). For
example, 2,2-dibromopropanoic acid, dibromochloropropanoic acid, 3,3-dibromopropenoic acid,
bromochloro-4-oxo-pentanoic acid, 3,3-dibromo-4-oxopentanoic acid, bromoheptanoic acid,
bromochloroheptanoic acid, bromochlorononanoic acid, dibromoheptanoic acid, and cis-2-
bromo-3-methylbutenedioic acid were identified (Table 12). Several of these bromo-acids were
102
-------
also seen in finished waters from plant 1 (EPA Region 9), and also in drinking waters from Israel
that had been treated with chlorine or chlorine dioxide-chloramine (Richardson et al., submitted).
At plant 12, in addition to the detection of brominated acids, five iodinated acids were
detected (Table 21; mass spectra included in the Appendix). This represents the first time an
iodo-acid has been identified as a DBF in drinking water. The identification of iodoacetic acid
was confirmed through the analysis of an authentic standard (match of retention time and mass
spectrum). Other identifications should be considered tentative until authentic chemical
standards can be obtained to confirm them. However, high resolution mass spectrometry
confirmed the presence of iodine in their structures, as well as their overall empirical formulas.
In the case of iodobromoacetic acid, this assignment is very confident, due to only one isomer
being possible. An attempt is currently being made to synthesize chemical standards for the
remaining compounds to confirm their identities.
Finally, target analysis carried out by UNC revealed the presence of 3,3-
dichloropropenoic acid in finished water from plant 11 in September 2001 (Table 15). It was
present at 0.7 |ig/L in the finished water and remained stable in the distribution system. 3,3-
Dichloropropenoic acid was also formed at plant 12 in September 2001 but was not detected in
downstream locations (Table 16).
Haloacetonitriles. In other DBF research, haloacetonitriles (HANs) have been found to
be produced at approximately one-tenth the level (10 %) of the THMs (Oliver, 1983). A
somewhat higher amount (on a relative basis) was detected in the plant 11 samples in March
2001, and a somewhat lower amount was detected in September 2001. A somewhat higher
amount (12 and 14 % in March and September 2001, respectively) was detected in the plant 12
samples.
Because of the high level of bromide in these waters in March 2001, brominated HANs
predominated (Figure 15). Although plant 12 had somewhat more raw-water bromide than plant
11 in March 2001, the shift in speciation to the more brominated HANs was greater in the plant
11 samples. This may have been due, in part, to differences in the formation of brominated
DBFs in the presence of chlorine (i.e., at plant 11) and in the presence of chloramines (i.e., at
plant 12). In the presence of chlorine, bromide is oxidized to hypobromous acid, which is a very
powerful halogenation agent. In the presence of chloramines, bromide can be converted to
bromamines, which will not produce as much brominated DBFs as hypobromous acid.
103
-------
Figure 15. March 26, 2001
Effect of Bromide and Disinfection Scheme on HAN Speciation in
Plants Effluents at Plant 11 (Chlorine Dioxide/Chlorine/Chloramines)
and Plant 12 (Chloramines Only)
D)
Plant 11
Plant 12
Because of the higher level of bromide at plant 11 than plant 12 in September 2001, there
was a significantly greater shift to the formation of brominated HANs at plant 11 than at plant 12
that month (Figure 16). In addition to the formation of more of the brominated HANs in the
Information Collection Rule (ICR) (e.g., dibromoacetonitrile) at plant 11, the target HAN
dibromochloroacetonitrile was detected at plant 11 but not at plant 12 in September and
November 2001.
Chloroacetonitrile, another target HAN, was detected at both plants in September 2001
(Figure 16) and November 2001. In addition, bromoacetonitrile was detected in one sample site
per plant in September 2001. Dibromochloro- and tribromoacetonitrile—both brominated
analogues of the ICR HAN trichloroacetonitrile—were detected at plant 11 in March 2001 by the
broadscreen GC/MS methods (Table 12).
Haloketones. In addition to the formation of low levels of haloketone (HK) compounds
from the ICR (i.e., 1,1-dichloro- and 1,1,1-trichloropropanone), low levels of some of the target
study HKs were detected in selected samples from plant 11 and plant 12 (Figure 17). In addition
to the formation of the two chlorinated HKs in the ICR, brominated analogues of these two HKs
(i.e., 1,1-dibromo- and l-bromo-l,l-dichloropropanone, respectively) were detected in
September 2001 at plant 11, but were not detected at plant 12. In contrast, more of the 1,1,1,3-
tetrachloropropanone was formed in September 2001 at plant 12.
104
-------
Figure 16. September 10, 2001
Effect of Bromide on HAN Speciation at
Plant 11 (Br~ = 0.21 mg/L) and Plant 12 (Br~ = 0.02 mg/L)
Plant 12 Eff
Plant 11 Clean/veil Eff
Figure 17. September 10, 2001
Effect of Bromide on HK Speciation in Plant Effluents at
Plant 11 (Br~ = 0.21 mg/L) and Plant 12 (Br~ = 0.02 mg/L)
1.0
>^vV
-• •>• ^
105
-------
Figure 18 shows the impact of bromide on HK speciation at plant 12. In September
2001, when the bromide level was low (0.02 mg/L), two chlorinated HKs (chloro- and 1,1,1,3-
tetrachloropropanone) were detected that were not found in March 2001, November 2001, or
February 2002. In March 2001 and February 2002, when the bromide level was high (0.25 and
0.3 mg/L, respectively), two brominated HKs (1,1-bromopropanone [February 2002 only] and 1-
bromo-l,l-dichloropropanone) were detected that were not found in September and November
2001 (November bromide = 0.15 mg/L).
Figure 18. Impact of bromide on HK speciation at plant 12 effluent
<1: Less than MRL(1.0|jg/L)
1.0
D)
*• o" e,
-•*• y y „/•
0.33
0.25
0.15
002 (mg/L)
Bromide
\'
In addition to the target HKs, other HKs were detected by the broadscreen GC/MS
methods (Tables 12 and 21). Some of these HKs were analogous to the tri- and tetrahalogenated
HKs analyzed by MWDSC, except they were mixed bromochloro species. In addition, another
HK that was detected by the broadscreen GC/MS methods at plant 12 was pentachloropropanone
(PCP). MWDSC analysts had attempted to include PCP in its target compound list, but it
degraded immediately and completely in water under all conditions they evaluated (Gonzalez et
al., 2000).
Haloaldehydes. In addition to the formation of low levels of chloral hydrate
(trichloroacetaldehyde), low levels of target haloacetaldehydes were detected (Figure 19). Both
chlorinated and brominated species were formed. In March 2001, the level of chloral hydrate
was higher at plant 11. In other research, chloramines were found to minimize the formation of
chloral hydrate, whereas certain dihalogenated DBFs were formed to greater extents (Young et
al., 1995). Consistent with that research, the formation of dihalogenated acetaldehydes was
favored over trihalogenated species at plant 12. Moreover, the relative formation of di- versus
106
-------
trihalogenated acetaldehydes at both utilities was consistent with the DXAA versus TXAA data
at these plants (Figure 20).
Figure 19. March 26, 2001
Effect of Bromide and Disinfection Scheme on Haloacetaldehyde
Speciation at Plant 11 (Chlorine Dioxide/Chlorine/Chloramines) and
Plant 12 (Chloramines Only) in Distribution System Sample/Maximum
Detention Time
Plant 11
Plant 12
Figure 20. March 26, 2001
Effect of Disinfection Scheme on HAA and Haloacetaldehyde
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/
Chlorine/Chloramines) and Plant 12 (Chloramines Only)
• Dihalogenated species DTrihalogenated species
100%
Haloacetaldehydes
•« Plant 11-
HAAs
>•
107
Haloacetaldehydes HAAs
•4 Plant 12 >•
-------
Figure 21 shows seasonal variations in the formation and speciation of haloacetaldehydes
at plant 11. In September 2001, there was more of a shift to the brominated species. Also,
because of the warmer water temperature in September 2001, there was the greatest
haloacetaldehyde formation that month. Because of the colder water temperature in February
2002, there was the lowest halaocetaldehyde formation that month.
Figure 21. Seasonal formation and speciation of haloacetaldehydes at plant 11 clearwell or
plant effluent
<0.5: Less than MRL (0.5 ug/L)
• 02/11/2002 IH11705/2001 • 09/10/2001 D03/26/2001
Tribromoacetaldehyde
Chloral hydrate
Bromochloroacetaldehyde
Dichloroacetaldehyde
0.2 0.4 0.6 0.8
Haloacetaldehyde (H9/L)
1.2
Figure 22 shows the impact of bromide on the formation and speciation of
haloacetaldehydes at plant 12. In February 2002, when the level of bromide was the highest
(0.33 mg/L), no dichloroacetaldehyde was detected, whereas there was bromochloroacetaldehyde
formation. In addition, the formation of chloral hydrate (trichloroacetaldehyde) was low,
whereas the formation of tribromoacetaldehyde was high. In March 2001 when the level of
bromide was also high (0.25 mg/L), the formation of dichloro- and bromochloroacetaldehyde
(both dihalogenated species) were similar and the amounts of the chloral hydrate and
tribromoacetaldehyde (both trihalogenated species) were the same. Alternatively, in September
2001 when the level of bromide was low (0.02) or in November 2001 when the level of bromide
was moderate (0.15 mg/L), the formation of dichloroacetaldehyde was higher than that of
bromochloroacetaldehyde and the formation of chloral hydrate was higher than that of
tribromoacetaldehyde. Regardless of the level of bromide, the formation of dihalogenated
species was typically favored over trihalogenated species (e.g., dichloroacetaldehyde versus
chloral hydrate) at plant 12 (Figure 22). In February 2002 (bromide = 0.33 mg/L),
108
-------
dichloroacetaldehyde was not detected with an minimum reporting level (MRL) of 0.98 |ig/L.
As a result, the sum of the dihalogenated species was relatively low that month. In addition, that
was the only month in which chlorine dioxide was used during pre-treatment.
In addition to the target haloacetaldehydes, other haloaldehydes were detected by the
broadscreen GC/MS methods (Tables 12 and 21). At plant 11, dibromo- and
bromodichloroacetaldehyde—which are brominated analogues of dichloroacetaldehyde and
chloral hydrate, respectively—were detected. In addition, another brominated aldehyde
(2-bromo-2-methylpropanal) was detected at both plants.
Halonitromethanes. In March 2001, September 2001, November 2001, and February
2002, sub-|ig/L levels of chloropicrin (trichloronitromethane) and other halonitromethanes were
detected in selected samples at plant 11 (bromopicrin was detected at 1 |ig/L in one sample in
February 2002). This included mono-, di-, and trihalogenated species, with and without
bromine. Sub-|ig/L to low |ig/L levels of halonitromethanes were detected at plant 12 in March
2001, September 2001, November 2001, and February 2002.
109
-------
Figure 22. Impact of bromide on haloacetaldehyde speciation at plant 12 effluent
Bromide (mg/L) • 0.02 • 0.15 • 0.25 D 0.33
Tribromoacetaldehyde
Chloral hydrate
Bromochloroacetaldehyde
Dichloroacetaldehyde
1.5 2 2.5
Haloacetaldehyde
Figure 23. Haloacetaldehyde speciation at plant 12 effluent
*Dichloroacetaldehyde not detected with MRL of 0.98 |jg/L
Dihalogenated
% of Halo- Trihalogenated
acetaldehydes % °f Halo-
acetaldehydes
0.33
0.25
Bromide
(mg/L)
110
-------
Figure 24 shows the impact of bromide on the speciation of the halonitromethanes at
plant 12. As bromide increased, the formation of chloropicrin decreased (from 0.9 down to 0.2-
0.4 |ig/L), whereas the formation of the brominated species increased (e.g.,
bromochloronitromethane formation increased from not detected or 0.2 to 0.7 or <1 |ig/L). In
February 2002, when the level of bromide was the highest (0.33 mg/L), bromonitromethane was
detected, but not in other months. In addition, dibromonitromethane was only detected in
February 2002 and in March 2001 (bromide = 0.25 mg/L). In addition to the formation of
chloropicrin, brominated analogues of this trihalogenated nitromethane were detected in the
September 2001, November 2001, and February 2002 samples. Data for the brominated
trihalogenated nitromethanes were not available (N/A) in the March 2001 samples. Bromopicrin
was detected in September 2001 (bromide = 0.02 mg/L) in the filter influent sample, but was not
detected in the plant effluent sample, whereas the two mixed bromochloro trihalogenated species
were detected in the plant effluent. Alternatively, when bromide was higher (in November 2001
[0.15 mg/L) and February 2002), bromopicrin formation was the highest (2 and 5 |ig/L,
respectively).
Figure 24. Impact of bromide on halonitromethane speciation at plant 12 effluent
<1: Less than MRL (1.0 |jg/L); N/A= Not analyzed in March 2001 when bromide = 0.25 mg/L;
*Bromodichloronitromethane not detected in Feb. 2002 (Br" = 0.33 mg/L) with MRL of 2.0 |jg/L
Bromide (mg/L)
I0.02 HO.15 B0.25 DO.33
Bromopicrin
Di bromochloronitromethane
Bromodichloronitromethane
Chloropicrin
Dibromonitromethane
Bromochloronitromethane
Dichloronitromethane
Bromonitromethane
N/A
0.5 1 1.5 2 2.5 3 3.5
Halonitromethane (M9/L)
4.5
At plant 11 in September 2001, bromodichloro- and dibromochloronitromethane were
detected at or above the MRL of 0.5 |ig/L in the SDS sample held for maximum detention time.
Although the SDS samples were not kept cold during the prolonged shipping period in
September 2001, these results suggest that these compounds may have been present in other
plant 11 samples, but at concentrations below the MRL.
ill
-------
Halogenatedfuranones. Tables 17 and 18 show the results for halogenated furanones in
the September 2001 samplings for plants 11 and 12; Tables 26 and 27 show the results for the
February 2002 samplings. Data are included for 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-
furanone, otherwise known as MX; (E)-2-chloro-3-(dichloromethyl)-4-oxobutenoic acid,
otherwise known as EMX; (Z)-2-chloro-3-(dichloromethyl)-4-oxobutenoic acid (ZMX); the
oxidized form of MX (Ox-MX); brominated forms of MX and EMX (BMXs and BEMXs); and
mucochloric acid (MCA), which can be found as a closed ring or in an open form. Results are
displayed graphically in Figures 25 and 26.
Many sample points were analyzed in the EPA Region 6 plants (9/10/01), clearly
showing that C1O2 at plant 11 did not produce MX and MX-analogues at the filter influent except
for 20 ng/L of BEMX-1, and that intermediate chlorination/post-chloramination at plant 11
produced more MX-analogues than chloramines at plant 12. ZMX was detected (90 ng/L) in the
plant 11 clearwell effluent, but was not detected in the plant effluent, whereas MX was the same
at both sample sites (20 ng/L). Predisinfection with C1O2 at plant 11 did not appear to effectively
remove precursors of MX-analogues as has been observed for predisinfection with ozone for
other treatment plants in this study. A significant higher concentration of MX (853 ng/L) was
detected in the plant 11 DS/average sample compared to the PE sample (20 ng/L), whereas the
BEMX-3 was detected in the PE (200 ng/L) and not in the DS/average sample. The plant 11
SDS/maximum sample (490 ng/L BEMX-3) shows that BEMX-3 was stable under the
conditions employed in the SDS test. These results suggest that the DS/average sample may
represent a different water than the PE sample, as these samples were not collected to follow a
"plug" of water over time (as the SDS test was set up to do). With a bromide concentration of
0.21 mg/L and TOC concentration of 3.5 mg/L, the raw water for plant 11 produced BMX
compounds during intermediate chlorination/post-chloramination, as found in the majority of
samples (11-490 ng/L) from plant 11. Due to the difference in water quality of the river basin in
September 2001 (0.02 mg/L Br- and 7.5 mg/L TOC), which fed plant 12, and the difference in
disinfection (chloramines only), substantially less brominated MX-analogues (17-90 ng/L) were
produced relative to plant 11. At plant 11, the major production of BMX-analogues occurred in
the clearwell influent after intermediate chlorination, whereas at plant 12, it occurred between
the filter effluent and plant effluent samples.
In the second sampling of the EPA Region 6 plants (2/11/02 or 2/12/02) for halogenated
furanones, MX and a chlorinated MX-analogue, MCA, were more predominant at plants 11 and
12 than in the earlier sampling (September 2001). One BMX analogue, BMX-1, was also
formed at 80 and 60 ng/L in finished waters from plants 11 and 12, respectively, but was not
detectable in the DS/maximum samples. The raw water quality of plant 11 was not that different
in February 2002 (0.18 mg/L of bromide and 4.3 mg/L of TOC), whereas plant 12's was
significantly different (0.33 mg/L bromide and 5.3 mg/L of TOC). In addition, plant 12 used
chlorine dioxide during pretreatment in February 2002. These changes in the distribution and
occurrence levels of the MX-analogues may be due to changes in raw water quality and
operational (treatment/disinfection) parameters from Fall 2001 to Winter 2002.
112
-------
Figure 25. Halofuranone data at EPA Region 6 plants (9/10/01)
EPA Region 6 (9/10/01)
DBMX-1 1BEMX-1 1BMX-2 DBEMX-2 1BMX-3 HBEMX-3
• MX 1EMX 1ZMX • MCA (ring) DMCA (open)
1 °n
•^
j
5)
"T -I nn
0
3
V
3
— n RO
fl) U.OU
u
c
o
J
a) nfin -
5
c
Q
^ n /in
D
2
5
i> 090
D)
O
ro
E
0 00
Fl
CI02
| .
FE
002 + CI2 +
Dual Media
Filters
iwiwiiti
Clearwsll Eff
Plant 1 1
f
PE
012 +
DS/ave
NH3
I
1
1
n
SDS/max
1 1
Raw
Pre-treat
Fl
CI2+NH3
m
FE
Filter
Plant 12
n
PE
|
DS/ave
CI2+NH3
SDS/max
Sampling Sites
113
-------
Figure 26. Halofuranone data at EPA Region 6 plants (2/11/02 or 2/12/02)
EPA Region 6 (2/11/02 or 2/12/02)
• BMX-1
• MX
5
n
5 n , .
T!
Jj 0. 12 -
1
Lj
5
- 0 06 -
L
3
3) U'U^
3
c ooo
• BEMX-1 BBMX-2 BBEMX-2 HBMX-3 DBEMX-3
• EMX BZMX DMCA (ring) • MCA (open) BOx-MX
Fl
CIO2
Plant 11
PE
Dual Media Filters
+CIO2+CI2+NH3
•
DS/max
t
_
Fl
CIO2+CI2+NH3
Plant 12
=
•
PE
Filter+CI2+NH3
u
DS/max
Sampling Points
Other HalogenatedDBFs. In target analyses conducted at UNC, haloamides were
frequently identified in finished waters from plants 11 and 12 (Tables 15-16, 24-25). In samples
taken in February 2002, all five target haloamides were identified: monochloroacetamide,
monobromoacetamide, dichloroacetamide, dibromoacetamide, and trichloroacetamide.
Concentrations of individual species ranged from 0.4 to 2.8 |ig/L in the plant effluent and were
comparable in the distribution system. In September 2001, only one haloacetamide was
targeted—dichloroacetamide, which was found at 2.8 and 5.6 |ig/L in finished waters from
plants 11 and 12, respectively. Haloamides have not been a class of DBFs quantified in potable
waters previously. Because the levels observed in these samples are similar to other DBFs that
are commonly measured, this may be an important class of DBF that warrants further study.
A few additional halogenated DBFs were identified by broadscreen GC/MS analysis,
including dibromoaniline, dibromodichloroaniline, and tribromochloroaniline (plant 12 finished
water, November 2001). These compounds were not present in the raw, untreated water.
Volatile Organic Compounds. Carbon tetrachloride was detected in two samples at plant
11 (clearwell and plant effluent) in March 2001 at sub-|ig/L levels. Carbon tetrachloride is a
volatile organic compound (VOC) and a possible DBF. Carbon tetrachloride has been detected
by some utilities in gaseous chlorine cylinders (EE&T, 2000). Incidents of carbon tetrachloride
contamination of chlorine cylinders have been traced to either imperfections in the
manufacturing process or improper cleaning procedures. Carbon tetrachloride is used to clean
114
-------
out cylinders before filling with chlorine. If carbon tetrachloride is not allowed sufficient time to
evaporate, it can contaminate the chlorine.
Methyl ethyl ketone (MEK) was detected in the raw water, in the distribution system, and
in SDS testing at plant 11 on September 10, 2001 at a concentration of 0.6-0.7 |ig/L. MEK was
not detected at or above the MRL of 0.5 |ig/L in the clearwell effluent or the plant effluent.
MEK was detected at the filter influent and in the distribution system of plant 12 on September
10, 2001 at a concentration of 0.6 |ig/L. MEK was not detected at or above the MRL in the raw
water or the plant effluent. MEK is an industrial solvent and a possible DBF. At plant 11, its
presence in the distribution system was most likely due to its low-level occurrence in the raw
water. At plant 12, its occurrence in some samples slightly above the MRL does not allow for a
determination as to its origin.
Non-Halogenated DBFs. A few non-halogenated DBFs were detected in treated waters
from plants 11 and 12 (Tables 15-16, 24-25). The finding of 6-hydroxy-2-hexanone in the filter
influent (at 0.8 |ig/L) of plant 11 represented one of the few times this DBF was identified in this
study (September 2001, Table 15). This compound was likely formed by the initial treatment
with chlorine dioxide. 6-Hydroxy-2-hexanone has also been previously reported as an ozone
DBF (Richardson et al., 1999). However, although it was initially formed, it was not present in
the plant effluent (finished water). Because plant 11 did not use GAC or biofiltration, it was
probably not removed by the filtration process. Many ketones can undergo base-catalyzed
hydrolysis or can react with chlorine to form secondary by-products. Either phenomenon may be
responsible for the loss of this DBF. Another DBF that is typically an ozone DBF—
dimethylglyoxal—was also found in the finished water from both plants 11 and 12, generally at
levels between 1 and 3 jig/L in the plant effluent. Zhang and colleagues (2000) demonstrated
that other disinfectants/oxidants can form carbonyl containing compounds. Broadscreen GC/MS
analysis also revealed the presence of acetone and glyoxal in finished water from plant 12
(November 2001), as well as several non-halogenated carboxylic acids in the finished waters,
which were at significantly higher concentrations than in the raw, untreated water.
Distribution System Issues. Because plant 11 used chloramines in the distribution
system, most of the DBFs were found to not increase significantly in concentration in SDS
testing (Figure 27) or in the distribution system. Many non-THM DBFs (e.g.,
dichloroacetonitrile, 1,1,1-trichloropropanone, chloral hydrate) are known to degrade at high pH
(Stevens et al., 1989; Croue and Reckhow, 1989). Because the distribution system and SDS
testing in March 2001 was only at a pH of 7.4-7.6, most non-THM DBFs were found to be
relatively stable (Figure 27).
115
-------
Figure 27: March 26, 2001
Effect of Simulated Distribution System Testing at Plant 11 on
Formation and Stability of DBFs in Chloraminated Water at pH 7.4-7.6
• Plant Eff BSDS/Ave USDs/Max
100
O)
HAA analysis not done for SDS/max
Figure 28 shows a comparison of SDS testing and distribution-systems samples to the
plant effluent for the THMs for plant 12 for March 2001. Because plant 12 used chloramines,
THMs would not be expected to increase significantly in concentration in the distribution system
or in SDS testing. THM4 concentration did increase in the plant 12 SDS testing (from 34 |ig/L
in the plant effluent to 38 and 49 ug/L in the SDS samples held for average and maximum
detention times, respectively). The increase in concentration in the SDS samples (especially at
maximum detention time) was primarily due to the formation of the brominated THMs (Figure
28). Other research has shown that TFDVI formation can increase in chloraminated water when
an elevated level of bromide is present (Diehl et al., 2000).
116
-------
Figure 28. March 26, 2001
35
30
25
Comparison of SDS Testing and Distribution-System Samples
to Plant 12 Effluent for the THMs
O Plant Eff IISDS/Ave BSDS/Max HDS/Ave HDS/Max
Dichloroiodomethane Not Reported (NR) for SDS/Max and DS/Max
and Bromochloroiodomethane NR for DS/Max
Alternatively, THM4 was significantly higher in concentration in the plant 12
distribution-system samples in March 2001 (34 ug/L in the plant effluent versus 52 and 84 ug/L
in the distribution-system samples collected at average and maximum detention times,
respectively). The increase in concentration in the distribution-system samples (especially at
maximum detention time) was primarily due to the formation of dibromochloromethane and
bromoform (Figure 28). Distribution-system samples can be significantly different than the plant
effluent for two reasons:
* One, grab samples for the plant and distribution system were collected on the same day
(as requested) rather than following a plug of water over time—i.e., collecting the plant effluent
on one day and collecting the distribution-system samples a period of time (e.g., days) later that
matched the expected detention time in the system. Thus, the distribution-system samples
(especially at maximum detention time) represented water produced at the plant on a different
day in which the source-water quality and/or plant operations may have been different.
* Second, distribution-system samples may not always contain water only from the plant
effluent if there are other sources of water that may feed the distribution system (e.g., well
water).
* Thus, distribution-system samples represented the actual occurrence of DBFs, whereas
SDS testing allowed for an examination of the effect of detention time on DBF formation
without any of the confounding issues associated with distributed water.
In terms of the iodinated THMs at plant 12 in March 2001, SDS results were comparable
to the plant effluent data. Alternatively, some of the iodinated THMs (i.e.,
117
-------
bromochloroiodomethane, dibromoiodomethane, and bromodiiodomethane) were significantly
higher in the distribution system at average detention time as compared to the plant effluent and
one of the iodinated THMs (i.e., dibromoiodomethane) was significantly lower in the distribution
system at maximum detention time (Figure 28). Because a similar increase or decrease in
formation was not observed in the SDS testing, this suggests that the distribution-system samples
represented a somewhat different source of water than the plant effluent collected on the same
day.
Figure 29 shows the effect of SDS testing at plant 12 in March 2001 on the formation and
stability of a range of DBFs. Because the SDS testing was only at a pH of ~8, most non-THM
DBFs were found to be relatively stable (Figure 29).
Figure 29. March 26, 2001
Effect of Simulated Distribution System Testing at Plant 12 on
Formation and Stability of DBFs in Chloraminated Water at pH ~8
• Plant Eff BSDS/Ave BSDS/Max
100
HAA analysis not done for SDS/max
0.1
/ y
<
118
-------
REFERENCES
Aieta, E. M., and J. D. Berg. A review of chlorine dioxide in drinking water treatment. Journal
of the American Water Works Association 78(6):62 (1986).
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomethanes during disinfection and
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784
(2000).
Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992).
Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite.
Environmental Science & Technology, 23(11): 1412 (1989).
Diehl, A. C., G. E. Speitel Jr., J. M. Symons, S. W. Krasner, C. J. Hwang, and S. E. Barrett.
DBF formation during chloramination. Journal of the American Water Works Association,
92(6):76 (2000).
Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to
AWWA Research Foundation, Denver, CO, 2000.
Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly
identified disinfection by-products in drinking water. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2000.
Hwang, C. J., M. J. Sclimenti, and S. W. Krasner. Disinfection by-product formation reactivities
of natural organic matter fractions of a low-humic water. In Natural Organic Matter and
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W.
Krasner, and G. L. Amy, eds.), American Chemical Society: Washington, D.C., pp. 173-187,
2000.
Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta.
The occurrence of disinfection by-products in U.S. drinking water. Journal of the American
Water Works Association 81(8):41 (1989).
Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E.
Barrett. Effects of water quality parameters on DBF formation during chloramination.
119
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Proceedings of the American Water Works Association Annual Conference, Vol. D, pp. 601-628,
American Water Works Association: Denver, CO, 1996.
Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors.
Environmental Science & Technology 17(2):80 (1983).
Richardson, S. D., A. D. Thruston, Jr., T. V. Caughran, P. H. Chen, T. W. Collette, T. L. Floyd,
K. M. Schenck, and B. W. Lykins, Jr. Identification of new ozone disinfection by-products in
drinking water. Environmental Science & Technology 33:3368 (1999).
Richardson, S. D., A. D. Thruston, Jr., C. Rav-Acha, L. Groisman, I. Popilevsky, O. Juraev, V.
Glezer, A. B. McKague, M. J. Plewa, and E. J. Wagner. Tribromopyrrole, brominated acids, and
other disinfection byproducts produced by disinfection of drinking water rich in bromide.
Environmental Science & Technology (submitted).
Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and
related halogenated disinfection by-products in chlorinated and chloraminated water; application
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical
Society (ACS) National Meeting, Chicago, IL, American Chemical Society: Washington, D.C.,
pp. 748-751, 1995.
Stevens, A. A., L. A. Moore, and R. J. Miltner. 1989. Formation and control of non-
trihalomethane disinfection by-products. Journal of the American Water Works Association,
81(8):54(1989).
Zhang, X., S. Echigo, R. A. Minear, and M. J. Plewa. Characterization and comparison of
disinfection by-products of four maj or disinfectants. In Natural Organic Matter and
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W.
Krasner, and G. L. Amy, eds.), pp. 299-314, American Chemical Society: Washington, D.C.,
2000.
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EPA REGION 4: PLANTS 7 AND 8
Plant Operations and Sampling
On December 11, 2000, March 12, 2001, September 24, 2001, and January 14-16, 2002,
plants 7 and 8 (in EPA Region 4) were sampled.
Plant 7 is an ozone plant (Figure 1). The raw water was first treated with chloramines.
The water was then lime-softened and filtered. The filtered water was ozonated. The ozonated
water was chlorinated, stored, and distributed.
Figure 1
Plant 7 Schematic
03
111
C O t^-> 1>
a a -s |
Raw
Water
1111
Coagulation and
Floculation
CO
Ozonation
Filtration
chlorine
Ground
Storage
-> Distribution
Plant 8 is a membrane plant (Figure 2). This plant consisted of two facilities operating
simultaneously and parallel to one another; a portion of the water was treated with membranes:
• In the lime softening portion of the plant, the raw water was treated with chlorine. The water
was then lime-softened. The softened water was chloraminated, filtered, and stored.
• In the membrane-softening portion of the plant, the pH of the raw water was adjusted with
sulfuric acid. The acidified water was filtered and treated with membranes (TFC®-S
polyamide, Koch Membrane Systems; softening, low pressure for brackish water treatment
membrane elements). The membrane-treated water was chlorinated and passed through an
adsorber and stripper towers. The pH of the water was adjusted with sodium hydroxide and
mixed with the lime-softened water.
The combined treated waters were chloraminated, stored, and distributed.
121
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Lime Softening
Train
Coagulation and
Floculation
Filtration
Figure 2
Plant 8 Schematic
Raw Water
chlorine
polymer
lime
chlorine
"ammonia
Membrane
Softening Train
H2S04
Cartridge
Filters
Membranes
chlorine-
Clearwell
chlorine
i
Clearwell
Adsorber/
Stripper Towers
ammonia
Distribution <-
Ground
Storage
Plant 7 was sampled at the following locations:
(1) raw water
(2) settled water
(3) filter effluent
(4) effluent of the ozone contactor
(5) the plant effluent
In addition, plant effluent was collected and simulated distribution system (SDS) testing was
conducted (a 24-hr holding time was typically used [27-hr in January 2002]). Furthermore, the
distribution system was sampled at a location that receives water from plant 7 and from another
treatment plant.
Plant 8 was sampled at the following locations:
(1) raw water
Lime Softening
(2) settled water
(3) filter effluent
Membrane Softening
(4) membrane effluent
(5) effluent of the stripper towers
Combined Treated Waters
122
-------
(6) the plant effluent
In addition, plant effluent at plant 8 was collected and SDS testing was conducted (a 24-hr
holding time was typically used [22.5 h in September 2001]. Furthermore, the distribution
system of plant 8 was sampled at one location.
On the day of sampling, information was collected on the operations at each plant
(Tables 1-2).
Table 1. Operational information at plant 7
Parameter
Plant flow (mgd)
Total chlorine dose at plant influent (mg/L as C12)
Chlorine dose at influent pipe or raw standpipe
(mg/L as C12)
Chlorine dose at treatment unit collector ring or
basin effluent (mg/L as C12)
Ammonia dose at plant influent (mg/L as NH3-N)
Lime dosage (mg/L)
Polymer dosage (mg/L)
CO2 dosage (mg/L)
Ozone dose (mg/L)
Hydraulic retention time in ozone contactor (min)
CT achieved from ozonation (mg/L-min)
Chlorine dose at ozone contactor eff. (mg/L as C12)
12/11/00
8.7
13
3.0
7.0
1.1
219
0.2
8.3
6.4
25
NAa
3.1
3/12/01
9.0
10
7.0
3.0
1.1
225
0.2
4.0
5.0
20
NA
3.0
9/24/01
9.6
5
2
3
0.94
230
0.2
10
4
30
NA
6.0
1/14/02
13.6
5.3
2
3.3
1.3
243
0.2
3.6
7.4
20
0.37
6.7
aNA = Not available
Table 2. Operational information at plant 8
Parameter
Overall plant flow (mgd)
Plant flow for lime softening (mgd)
Plant flow for membrane softening (mgd)
Lime Softening
Chlorine dose at lime softening inf. (mg/L as C12)
Lime dosage (mg/L)
Polymer dosage (mg/L)
Chlorine dose at filter influent (mg/L as C12)
Ammonia dose at filter influent (mg/L as NHs-N)
Membrane Softening
H2SO4 dose at membrane softening inf. (mg/L)
Operating pressure (psi)
Chlorine dose at membrane effluent (mg/L as C12)
NaOH dose at stripper tower effluent (mg/L)
Chlorine dose at stripper tower eff. (mg/L as C12)
Combined Treated Waters
Ammonia dose at plant effluent (mg/L as NH3-N)
12/11/00
11.05
4.5
6.55
6.0
205
0.05
12
1.0
180
118
2.6
16.6
7.1
1.0
3/12/01
11.41
3.0
8.41
6.0
225
0.05
12
1.0
180
118
2.6
62
7.1
1.0
9/24/01
10.1
o o
J.J
6.8
8.0
215
0.025
12
1.0
134
118
2.6
16
7.5
1.0
1/16/02
11.64
3.00
8.64
8
225
0.025
12
1
182
118
1.8
26
6.5
NA
123
-------
Water Quality
On the day of sampling, information was also collected on water quality at each plant
(Tables 3-4). Data were collected for total organic carbon (TOC) and ultraviolet (UV)
absorbance for plant 7 and plant 8 (Table 5). Plants 7 and 8 treated a groundwater that was high
in TOC (12-13 mg/L) and in color. Lime softening at plant 7 and plant 8 removed 21-35 % of
the TOC and reduced the UV by 38-48 %. Filtration removed another 3-9 % of the TOC. At
plant 7, ozonation did not significantly effect the level of TOC, whereas the UV was reduced by
another 13-37 %. The overall (cumulative) removal of TOC at plant 7 (due to lime softening,
filtration, and ozonation) was 27-33 % and the UV was reduced by 52-61 %. The overall
(cumulative) removal of TOC at plant 8 in the lime-softening portion of the plant was 29-39 %
and the UV was reduced by 43-54 %. At plant 8, the membrane process reduced both the TOC
and the UV by 97-98 %. At plant 8, the plant effluent TOC was 2.5-3.6 mg/L, which
approximately matched the relative contributions of TOC from each of the two portions of the
plant. The concentration of TOC (2.6-3.5 mg/L) in the distribution system of plant 8 confirmed
that this location was receiving membrane treated water.
Table 6 shows the values of miscellaneous other water quality parameters in the raw
water of plants 7 and 8. The raw water at each plant contained a moderate or high amount of
bromide (the bromide concentrations at plant 7 and plant 8 were 0.12-0.14 and 0.25-0.33 mg/L,
respectively). At plant 8, a significant percentage (60-67 %) of the raw-water bromide was
rejected by the membrane process.
The raw water also contained a moderate amount of ammonia (0.5-0.7 mg/L as N). It
takes 7.6 mg/L of chlorine to breakpoint chlorinate 1.0 mg/L of ammonia-nitrogen. Ground-
waters that are high in ammonia are often high in hydrogen sulfide (Krasner et al., 1996), which
also exerts a high chlorine demand. When chlorine is added to such groundwaters, typically
chloramines are formed, since not all of the ammonia will be breakpoint chlorinated. At plant 8,
chloramines were formed during the chlorination of the raw water at the lime-softening portion
of the plant and during the chlorination of the membrane effluent (Table 4).
DBFs
Oxyhalides. At plant 7, ozonation did not result in the formation of bromate at or above
the minimum reporting level (MRL) of 3 |ig/L. Ammonia addition is a method of controlling
bromate formation, because the ammonia may be able to tie up the bromide as bromamines
(Krasner et al., 1993). At plant 7, 0.9-1.3 mg/L of ammonia-nitrogen was added to the raw water
in addition to the 0.6-0.7 mg/L that was naturally present. Ozonation of a water with a free
chlorine residual can result in the formation of chlorate. Chlorate was not detected at plant 7,
since the free chlorine was converted to chloramines by the ammonia present prior to the
addition of ozone.
124
-------
Table 3. Water quality information at plant 7
Location
Raw water
Settled
Filter eff.
Ozone eff.
Plant eff.
Dist. syst.
SDS
pH
12/11/00
7.1
9.75
9.60
9.23
8.95
8.98
NA
3/12/01
7.35
9.59
9.51
9.24
8.91
8.95
NA
9/24/01
7.3
10.1
9.8
9.4
9.0
9.0
NA
1/14/02
7.30
10.09
9.96
9.55
9.07
9.08
9.07
Temperature (°C)
12/11/00
25
25
25
25
25
25
NA
3/12/01
25
25
25
25
25
25
NA
9/24/01
25
25
25
25
25
25
NA
1/14/02
25
25
25
25
25
25
25
Disinfectant Residual" (mg/L)
12/11/00
—
2.5
1.4
>0.9
5.0
4.4
NA
3/12/01
—
—
3.6
2.7
4.8
3.6
NA
9/24/01
—
0.6
0.4
trace
4.9
4.6
NA
1/14/02
—
NDb
0.9
1.0
4.7
4.1
4.7
aChloramine residuals
bND = Not detected
Table 4. Water quality information at plant 8
Location
Raw water
pH
12/11/00
7.05
3/12/01
7.02
9/24/01
7.2
1/14/02
7.19
Temperature (°C)
12/11/00
24.8
3/12/01
24.8
9/24/01
24.6
1/14/02
24.2
Disinfectant Residual3 (mg/L)
12/11/00
—
3/12/01
—
9/24/01
—
1/14/02
—
Lime Softening
Settled
Filter eff.
9.7
9.2
10.4
10.0
NA
10.2
10.52
10.16
24.4
25.6
25.0
25.3
NA
24.8
23.9
23.9
1.1
5.0
0.4
3.5+
NA
5.9
1.6
3.5+
Membrane Softening
Memb. eff
Stripper
tower eff.
5.5
8.1
5.38
7.30
5.4
9.1
5.55
6.81
25.0
25.0
25.4
25.2
23.8
24.2
24.4
25.1
—
5.5
—
3.5+
—
4.7
—
3.5+
Combined Treated Waters
Plant eff.
Dist. syst.
SDS
8.8
8.8
8.7
8.93
8.90
NA
9.0
9.0
8.8
8.75
8.95
8.8
25.0
25.0
23.5
26.7
25.5
NA
24.3
24.9
23.0
25.1
25.0
24.2
4.1
4.1
3.7
3.5+
4.0
NA
4.6
4.5
4.3
3.5+
4.2
4.0
aChloramine residuals
125
-------
Table 5. TOC and UV removal at plants 7 and 8
Location
12/11/2000
Plant 7 Raw
Plant 7 Settled
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
Plant 7 Dist. Syst.
Plant 8 Raw
Plant 8 Settled
Plant 8 Filter Eff.
Plants Membrane Eff.
Plant 8 Plant Eff./Measured
Plant 8 Plant Eff ./Predicted0
Plant 8 Dist. Syst.
3/12/2001
Plant 7 Raw
Plant 7 Settled
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
Plant 7 Dist. Syst.
Plant 8 Raw
Plant 8 Settled
Plant 8 Filter Eff.
Plants Membrane Eff.
Plant 8 Plant Eff./Measured
Plant 8 Plant Eff./Predicted
Plant 8 Dist. Syst.
9/24/2001
Plant 7 Raw
Plant 7 Settled
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
Plant 8 Raw
Plant 8 Settled
Plant 8 Filter Eff.
Plants Membrane Eff.
Plant 8 Plant Eff./Measured
Plant 8 Plant Eff./Predicted
Plant 8 Dist. Syst.
01/14-16/2002
Plant 7 Raw
Plant 7 Settled
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
Plant 7 Dist. Syst.
Plant 8 Raw
Plant 8 Settled
Plant 8 Filter Eff.
Plants Membrane Eff.
Plant 8 Plant Eff./Measured
Plant 8 Plant Eff./Predicted
Plant 8 Dist. Syst.
TOC
(mg/L)
12.7
9.21
8.85
8.55
7.87
13.4
8.7
8.13
0.42
3.55
3.56
3.47
12.3
9.28
8.96
8.52
8.42
12.8
8.84
8.44
0.3
2.9
2.44
2.82
12.7
10.0
9.3
9.2
12.4
9.4
8.7
0.39
3.5
3.1
3.3
12.6
9.5
9.3
9.2
8.8
11.3
8.8
8.0
0.28
2.5
2.3
2.6
uva
(cm'1)
0.470
0.277
0.282
0.211
0.505
0.262
0.233
0.01
0.458
0.283
0.283
0.179
0.494
0.267
0.248
0.013
0.465
0.287
0.277
0.224
0.454
0.268
0.257
0.012
0.454
0.262
0.248
0.213
0.414
0.248
0.233
0.01
SUVA"
(L/mg-m)
3.70
3.01
3.19
2.47
3.77
3.01
2.87
2.38
3.72
3.05
3.16
2.10
3.86
3.02
2.94
4.33
3.66
2.86
2.97
2.44
3.67
2.85
2.96
3.08
3.60
2.76
2.68
2.32
3.66
2.82
2.90
3.57
Removal/Unit (%)
TOC
—
27%
3.9%
3.4%
—
35%
6.6%
97%
—
25%
3.4%
4.9%
—
31%
4.5%
98%
—
21%
6.9%
1 .6%
—
24%
7.7%
97%
—
25%
2.2%
0.9%
—
22%
8.6%
98%
UV
—
41%
-1 .8%
25%
—
48%
11%
98%
—
38%
0%
37%
—
46%
7.1%
97%
—
38%
3.5%
19%
—
41%
4.1%
97%
—
42%
5.3%
13%
—
40%
6.0%
98%
Removal/Cumulative (%)
TOC
—
27%
30%
33%
—
35%
39%
97%
—
25%
27%
31%
—
31%
34%
98%
—
21%
27%
28%
—
24%
30%
97%
—
25%
26%
27%
—
22%
29%
98%
UV
—
41%
40%
55%
—
48%
54%
98%
—
38%
38%
61%
—
46%
50%
97%
—
38%
40%
52%
—
41%
43%
97%
—
42%
45%
53%
—
40%
44%
98%
Flow
(mgd)
4.5
6.55
11.05
3.00
8.41
11.41
3.3
6.8
10.1
3.0
8.6
11.6
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
"SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm-1)/DOC (mg/L) or UV (m-1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.470/cm = 0.470/(0.01 m) = 47.0/m, DOC = 12.7 mg/L, SUVA = (47.0 rr|-1)/(12.7 mg/L) = 3.70 L/mg-m)
c(lime softening flow)*(filter effluent TOC) + (membrane softening flow)*(membrane effluent TOC) = plant effluent TOC
126
-------
Table 6. Miscellaneous water quality parameters at plants 7 and 8
Location
12/11/2000
Plant 7 Raw
Plant 8 Raw
Plant 8 Membrane Eff.
Plant 8 Bromide Rejection (%)
3/12/2001
Plant 7 raw water
Plant 8 raw water
Plant 8 membrane effluent
Plant 8 bromide rejection (%)
9/24/2001
Plant 7 Raw
Plant 8 Raw
Plant 8 Membrane Eff.
Plant 8 Bromide Rejection (%)
01/14-16/2002
Plant 7 Raw
Plant 8 Raw
Plant 8 Membrane Eff.
Plant 8 Bromide Rejection (%)
Bromide
(mg/L)
0.12
0.33
0.11
66%
0.14
0.3
0.1
67%
0.14
0.25
0.1
60%
0.14
0.27
0.1
63%
Alkalinity
(mg/L)
265
249
265
250
264
236
130
236
Ammonia
(mg/L as N)
0.73
0.62
0.69
0.62
0.62
0.48
0.67
0.46
Chlorine
Demand3 (mg/L)
5.5
4.7
5.2
4.7
4.7
3.6
5.1
3.5
Chlorine demand from ammonia = 7.6 x ammonia (mg/L as N)
Biodegradable Organic Matter. Ozone can convert natural organic matter in water to
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Koiij et
al., 1982). Table 7 shows the carboxylic acid and AOC data for all four sampling dates at plant
7. In addition, Figure 3 shows the AOC results for the December 2000, March 2001, and
September 2001 samplings. Low concentrations of AOC and certain carboxylic acids were
detected in the raw water at plant 7. Those levels increased somewhat after chloramination and
increased significantly after ozonation (except for the AOC in September 2001).
Because AOC data are expressed in units of micrograms of carbon per liter (jig C/L), the
carboxylic acid data were converted to the same units. A portion of the molecular weight (MW)
of each carboxylic acid is due to carbon atoms (i.e., 27-49 %) and the remainder is due to oxygen
and hydrogen atoms. The sums of the five carboxylic acids (on a jig C/L basis) were compared
to the AOC data. On a median basis for each sample date, 23-30 % of the AOC was accounted
for by the carboxylic acids. The amount of AOC that was accounted for by carboxylic acids in
the ozone contactor effluent was typically greater than the percentage accounted for in the
chloraminated water. Although carboxylic acids have been shown to be ozone by-products, they
have not been shown to be by-products of chloramines. However, in other research (Jacangelo et
127
-------
Table 7. Formation and removal of carboxylic acids and AOC at plant 7
Location
12/11/2000
Plant 7 Raw
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
3/12/2001
Plant 7 Raw
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
9/24/2001
Plant 7 Raw
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
1/14/2002
Plant 7 Raw
Plant 7 Filter Eff.
Plant 7 Ozone Eff.
Formula
MW (gm/mole)
C portion (gm/mole)
C% of MW
Concentration3 (ug/L)
Acetate
35
50
150
ND
41
223
7.1
37
102
11
28
102
CH3COO"
59
24
41%
Propionate
NDb
ND
ND
ND
ND
ND
ND
ND
5.2
ND
ND
ND
CH3CH2COO"
73
36
49%
Formate
37
50
247
23
59
369
8.5
37
177
73
122
223
HCOO"
45
12
27%
Pyruvate
NRC
NR
NR
ND
44
52
ND
17
24
ND
27
40
CH3COCOO"
87
36
41%
Oxalate
21
54
324
ND
60
657
5.7
35
235
19
37
279
c2o42-
88
24
27%
Concentration (ug C/L)
Acetate
14
20
61
ND
17
91
2.9
15
41
4.6
11
41
Propionate
ND
ND
ND
ND
ND
ND
ND
ND
2.6
ND
ND
ND
Formate
9.8
13
66
6.1
16
98
2.3
10
47
19
33
59
Pyruvate
NR
NR
NR
ND
18
22
ND
7.0
10
ND
11
16
Oxalate
5.8
15
88
ND
16
179
1.6
10
64
5.1
10
76
Sum
30
48
215
6.1
67
390
6.7
41
165
29
65
194
AOC
111
269
577
median
112
277
1031
median
102
197
203
median
98
147
657
median
Sum/
AOC
27%
18%
37%
27%
5%
24%
38%
24%
7%
21%
81%
23%
30%
44%
29%
30%
Method detection limit (MDL) = 3 ug/L; reporting detection level (RDL) = 15 ug/L
Values > MDL but < RDL shown in italics
bND = Not detected, value is < RDL
CNR = Not reported, quality control problem
128
-------
Figure 3
AOC Results: Plant 7
1200
Raw Water
Filter
Effluent
Ozone
Effluent
Raw Water
Filter
Effluent
Ozone
Effluent
Raw Water
Filter
Effluent
Ozone
Effluent
• December 11, 2000 -
September 24, 2001
•4— March 12, 2001 *•
Sample Site
*AOC evaluated with two test bacteria: Pseudomonas fluorescens P-17 and Spirillum NOX
al., 1989), chloramines have been shown to be capable of producing aldehydes—other ozone by-
products—at lower levels than that produced during ozonation.
Halogenated Organic and Other Nonhalogenated Organic DBFs. Tables 8 and 9
(12/11/00), Tables 11 and 12 (3/12/01), Tables 14 and 15 (9/24/01), and Tables 17 and 18 (1/14-
16/02) show results for the halogenated organic DBFs that were analyzed at Metropolitan Water
District of Southern California (MWDSC). Table 10 (12/11/00 [plant 7] and Table 16 (9/24/01
[plant 8]) show results from broadscreen DBF analyses conducted at the U.S. Environmental
Protection Agency (USEPA). Table 13 (3/12/01) and Table 19 (1/14-16/02) show results for
additional target DBFs that were analyzed for at the University of North Carolina (UNC). Tables
20-21 (1/14-16/02) show results for halogenated furanones that were analyzed at UNC.
Summary of tables for halogenated organic and other nonhalogenated organic DBFs
DBF Analyses (Laboratory)
Halogenated organic DBFs (MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
12/11/00
Tables 8-9
Table 10a
3/12/01
Tables 11-12
Table 13
9/24/01
Tables 14-15
Table 16b
1/14-16/02
Tables 17-18
Table 19
Tables 20-21
"Plant 7
bPlant 8
129
-------
Table 8. DBF results at plant 7 (12/11/00)
12/11/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM49
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA91
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehydem
Chloral hydrate8
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.12
0.10
3
0.64
0.10
0.12
0.14
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.16
0.20
0.10
Plant 7°
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
10
1
ND
ND
11
ND
NR
ND
ND
ND
ND
ND
1.2
6.5
ND
ND
1.1
ND
ND
ND
8.8
8.8
6.5
1.1
ND
ND
ND
ND
ND
ND
1
ND
ND
Filt Eff
ND
ND
ND
ND
17
1
0.1
ND
18
ND
ND
ND
0.2
ND
ND
ND
ND
1.3
12
1.1
ND
3.2
ND
ND
ND
16
17
13
3.2
ND
ND
ND
ND
ND
ND
3
ND
ND
03 Eff
16
NR'
NR
ND
NR
ND
NR
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
12
0.3
ND
Plant Eff
ND
ND
ND
ND
17
1
0.1
ND
18
0.3
ND
ND
ND
ND
ND
ND
2.2
1.6
20
1.7
ND
3.4
ND
ND
ND
27
29
22
3.4
ND
ND
0.3
ND
ND
ND
14
0.5
ND
DS
ND
ND
ND
ND
16
1
0.1
ND
17
ND
ND
ND
ND
ND
ND
0.07
ND
1.4
22
1.7
1.0
3.0
ND
ND
ND
27
29
24
3.0
ND
ND
ND
ND
ND
ND
15
0.5
ND
SDS
ND
ND
ND
ND
17
1
0.1
0.3
18
0.2
<1h
ND
0.2
ND
ND
ND
2.6
1.5
27
2.0
ND
3.3
ND
ND
ND
34
36
29
3.3
ND
ND
ND
ND
ND
ND
16
0.5
ND
130
-------
Table 8 (continued)
12/11/2000
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone8
1,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin8
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 7D
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
Settled
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
NR
Filt Eff
0.3
0.3
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
ND
NR
ND
ND
ND
ND
ND
03 Eff
0.6
0.5
ND
ND
ND
ND
0.1
ND
ND
ND
NR
Plant Eff
2
2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
NR
ND
ND
ND
ND
ND
DS
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
SDS
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
NR
ND
ND
ND
ND
ND
MRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
bPlant 7 sampled at (1) raw water, (2) settled water, (3) filter effluent (FE), (4) effluent of ozone contactor,
(5) plant effluent (PE), (6) distribution system (DS), and (7) SDS testing of plant effluent
cPlant 8 sampled at (1) raw water; lime softening portion of plant at (2) settled water, (3) filter effluent;
membrane softening portion of plant at (4) effluent of stripper towers; combined treated waters at
(5) plant effluent, (6) DS, and (7) SDS testing of plant effluent
dND = Not detected at or above MRL
8DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
fNR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance
9THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
h<1: Concentration less than lowest calibration standard (i.e., 1 ug/L)
'HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid)
JHAA9 = Sum of 9 haloacetic acids
kDXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
'iXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
mBromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs
131
-------
Table 9. DBF results at plant 8 (12/11/00)
12/11/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM49
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA91
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehydem
Chloral hydrate8
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.12
0.10
3
0.64
0.10
0.12
0.14
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.16
0.20
0.10
Plant 8C
Raw
0.6
ND
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
15
NR
NR
ND
NR
ND
NR
ND
ND
ND
ND
ND
1.3
7.6
1.0
ND
1.8
ND
ND
ND
11
12
8.6
1.8
ND
ND
ND
ND
ND
ND
1
ND
ND
Filt Eff
0.2
ND
ND
ND
90
22
3
0.4
115
2
<1
<1
ND
ND
ND
ND
ND
1.7
35
6.3
1.0
15
3.2
1.0
ND
53
64
42
19
ND
ND
8
2
0.2
ND
3
13
ND
Tower Eff
ND
ND
ND
ND
1
1
0.5
0.5
3
0.8
<1
<1
ND
ND
ND
ND
ND
1.3
1.7
ND
1.1
ND
ND
ND
ND
4.1
4.1
2.8
ND
ND
ND
0.2
0.2
0.2
ND
ND
0.2
ND
Plant Eff
ND
ND
ND
ND
57
9
1
0.8
68
1
<1
<1
ND
ND
ND
ND
ND
1.5
21
3.2
ND
5.8
1.1
ND
ND
28
33
24
6.9
ND
ND
0.6
0.4
0.2
ND
2
1.6
ND
DS
ND
ND
ND
ND
61
9
1
0.9
72
1
<1
<1
ND
ND
ND
ND
ND
1.4
20
2.7
1.0
5.0
1.1
ND
ND
27
31
23
6.1
ND
ND
0.6
0.4
0.2
ND
1
1.5
ND
SDS
ND
ND
ND
ND
61
9
1
0.8
72
1
<1
<1
ND
ND
ND
ND
ND
1.4
24
4.4
1.2
6.4
1.3
ND
ND
33
38
29
7.7
ND
ND
0.2
0.2
0.1
ND
3
0.2
ND
132
-------
Table 9 (continued)
12/11/2000
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1 -Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 8°
Raw
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
Settled
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
NR
Filt Eff
0.3
0.4
ND
ND
0.9
0.2
ND
ND
ND
ND
0.1
ND
NR
ND
0.4
ND
ND
ND
Tower Eff
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
Plant Eff
0.3
0.2
ND
ND
ND
0.1
ND
ND
ND
ND
0.1
ND
NR
ND
0.4
ND
ND
ND
DS
0.2
0.2
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
NR
ND
0.4
ND
ND
ND
SDS
0.3
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
NR
ND
0.4
ND
ND
ND
Table 10. Occurrence of other DBFs" at plant 7 (12/11/00)
Compound
Halomethanes
Bromodichloromethaneb
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Diiodochloromethane
Haloacids
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Trichloroacetic acid
Haloacetonitriles
Bromochloroacetonitrile
Dibromoacetonitrile
Haloaldehvdes
Dibromoacetaldehyde
2-Bromo-2-methylpropanal
Halonitromethane s
Dichloronitromethane
Bromochloronitromethane
FE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
PE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Compound
Haloketones
, 1 -Dichloropropanone
-Bromo- 1 -chloropropanone
,1,1 -Trichloropropanone
,1,3 -Trichloropropanone
-Bromo- 1 , 1 -dichloropropanone
1,1, 3-Tribromopropanone
, 1 , 3 ,3 -Tetrachloropropanone
-Bromo- 1 ,3 ,3 -trichloropropanone
l,l-Dibromo-3, 3 -dichloropropanone
1, 3-Dibromo-l, 3 -dichloropropanone
1,1, 3-Tribromo-3-chloropropanone
1,1,3, 3-Tetrabromopropanone
Pentachloropropanone
Miscellaneous Halogenated DBFs
Hexachlorocyclopentadiene
Bromopentachlorocyclopentadiene
Non-haloaenated DBFs
Formaldehyde
Acetone
Glyoxal
Methyl glyoxal
FE
X
X
X
X
X
X
X
X
X
X
X
X
-
PE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
aDBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique
bCompounds listed in italics were confirmed through the analysis of authentic standards; haloacids
non-halogenated carboxylic acids identified as their methyl esters.
and
133
-------
Table 11. DBF results at plant 7 (
03/12/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM49
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
3
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
3/12/01)
Plant 7°
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
8
0.8
ND
ND
9
NR'
NR
ND
ND
ND
ND
ND
ND
ND
7.4
ND
ND
1.2
ND
ND
ND
8.6
8.6
7.4
1.2
ND
ND
ND
ND
ND
ND
0.8
ND
ND
ND
Filt Eff
ND
ND
ND
ND
15
3
ND
ND
18
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
12
1.0
ND
4.0
ND
ND
ND
16
17
13
4.0
ND
ND
0.2
ND
ND
ND
3
0.2
0.1
ND
OSEff
14
3
ND
ND
17
NR
NR
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
6
ND
ND
ND
Plant Eff
ND
ND
ND
ND
13
2
ND
ND
15
ND
ND
ND
ND
ND
ND
0.4
ND
2.8
ND
22
1.7
ND
5.1
ND
ND
ND
30
32
24
5.1
ND
ND
0.5
ND
ND
ND
9
0.1
0.7
ND
DS
ND
ND
ND
ND
21
3
ND
ND
24
ND
ND
ND
ND
ND
ND
0.5
ND
2.6
ND
20
1.5
ND
3.5
ND
ND
ND
26
28
22
3.5
ND
ND
0.2
ND
ND
ND
9
ND
0.5
ND
SDS
ND
ND
ND
ND
24
4
0.2
ND
27
ND
ND
ND
ND
ND
ND
0.4
ND
3.6
ND
32
2.1
ND
5.6
ND
ND
ND
41
43
34
5.6
ND
ND
0.3
ND
ND
ND
10
ND
0.6
ND
134
-------
Table 11 (continued)
03/12/2001
Compound
Haloketones
Chloropropanone
1 , 1-Dichloropropanonee
1,3-Dichloropropanone
1 , 1-Dibromopropanone
1,3-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
M9/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.5
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 7°
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
OSEff
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
0.7
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SDS
ND
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
135
-------
Table 12. DBF results at plant 8 (
03/12/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM49
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
3
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
3/12/01)
Plant 8C
Raw
ND
ND
ND
ND
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
Settled
14
3
0.2
ND
17
NR
NR
ND
ND
ND
ND
ND
ND
ND
6.3
1.0
ND
1.3
ND
ND
ND
7.6
8.6
7.3
1.3
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
Filt Eff
ND
ND
ND
ND
81
15
2
ND
98
2
<1h
ND
ND
ND
ND
0.7
ND
ND
ND
36
3.8
ND
9.1
1.6
ND
ND
45
51
40
11
ND
ND
3
ND
ND
ND
0.8
ND
5.7
ND
Tower Eff
ND
ND
ND
ND
1
0.6
0.2
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
2.4
ND
1.0
ND
ND
ND
ND
ND
ND
3.4
3.4
1.0
ND
ND
ND
0.1
ND
ND
ND
ND
ND
0.5
ND
Plant Eff
ND
ND
ND
ND
41
7
2
ND
50
0.7
<1
ND
ND
ND
ND
0.5
ND
ND
ND
14
2.0
ND
2.5
ND
ND
ND
17
19
16
2.5
ND
ND
0.5
ND
ND
ND
0.7
ND
0.4
ND
DS
ND
ND
ND
ND
42
7
2
ND
51
0.6
<1
ND
ND
ND
ND
0.5
ND
2.2
ND
14
2.2
ND
2.4
ND
ND
ND
19
21
16
2.4
ND
ND
0.5
ND
ND
ND
0.7
ND
0.4
ND
SDS
ND
ND
ND
ND
42
7
2
ND
50
0.7
<1
ND
ND
ND
ND
0.4
ND
ND
ND
15
2.3
ND
2.5
ND
ND
ND
18
20
17
2.5
ND
ND
0.2
ND
ND
ND
1
ND
0.3
ND
136
-------
Table 12 (continued)
03/12/2001
Compound
Haloketones
Chloropropanone
1 , 1-Dichloropropanonee
1,3-Dichloropropanone
1 , 1-Dibromopropanone
1,3-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.5
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 8C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
0.3
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.9
ND
Tower Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
0.1
ND
ND
ND
DS
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
0.1
ND
ND
ND
SDS
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
0.2
ND
ND
ND
137
-------
Table 13. Additional target DBF results (iig/L) at plants 7 and 8 (3/12/01)
3/12/01
Compound
Monochloroacetaldehyde
Di chl oroacetal dehy de
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (|ig/L as Cr)
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
trans -2-Hexenal
Plant T
Raw
0
0
0.6
0
0
24.2
<0.1
<0.1
<0.1
0.4
<0.1
FE
0.2
2.4
0.2
205
<0.1
<0.1
<0.1
0.2
<0.1
OE
1.2
4.4
0.1
127
<0.1
<0.1
<0.1
4.0
<0.1
PE
0.7
6.8
1.8
203
<0.1
<0.1
<0.1
3.5
<0.1
DS
0.5
7.6
0.4
0
2.5
121
<0.1
<0.1
<0.1
1.4
<0.1
SDS
0.5
8.6
3.0
207
<0.1
<0.1
<0.1
1.9
<0.1
Plant 8a
Raw
0
0.1
0
0
0
33.0
<0.1
<0.1
<0.1
0.3
<0.1
FE
0
0.7
4.0
459
<0.1
<0.1
<0.1
<0.1
<0.1
STE
0
0
0
41
<0.1
<0.1
<0.1
<0.1
<0.1
PE
0
0.5
2.1
142
<0.1
<0.1
<0.1
<0.1
<0.1
DS
0
0.6
0
0
2.2
157
<0.1
<0.1
<0.1
<0.1
<0.1
SDS
0
0.6
3.4
130
<0.1
<0.1
<0.1
<0.1
<0.1
aPlant 7 or plant 8 sampled at (1) raw water, (2) filter effluent (FE), (3) ozone contactor effluent (OE) or stripper tower
effluent (STE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention time, and
(6) SDS sample.
138
-------
Table 14. DBF results at plant 7
09/24/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM49
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tri brom oacetaldehyde
MRL"
^g/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.25
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.90
0.22
0.5
0.1
0.1
9/24/01)
Plant 7b
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
Settled
3
0.3
ND
ND
3
NRf
NR
ND
ND
ND
ND
ND
ND
ND
4.7
ND
ND
1.1
ND
ND
ND
5.8
5.8
4.7
1.1
ND
ND
0.3
ND
ND
ND
0.9
ND
0.6
ND
Filt Eff
ND
ND
ND
ND
3
0.3
ND
ND
3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.2
ND
ND
1.1
ND
ND
ND
5.3
5.3
4.2
1.1
ND
ND
0.1
ND
ND
ND
ND
ND
ND
1
ND
0.6
ND
OSEff
3
0.4
ND
ND
3
NR
NR
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
2
ND
0.4
ND
Plant Eff
ND
ND
ND
ND
7
1
0.1
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
4.2
ND
16
1.9
ND
2.0
ND
ND
ND
22
24
18
2.0
ND
ND
0.6
ND
ND
ND
ND
ND
ND
14
ND
0.6
ND
DS
0.2
ND
ND
ND
11
1
0.1
ND
12
0.6
ND
ND
ND
ND
ND
ND
ND
3.7
ND
16
1.6
ND
2.5
ND
ND
ND
22
24
18
2.5
ND
ND
0.6
ND
ND
ND
14
ND
0.4
ND
SDS
ND
ND
ND
ND
12
1
0.2
ND
13
0.6
ND
ND
ND
ND
ND
ND
ND
4.4
ND
20
1.8
ND
2.3
ND
ND
ND
27
29
22
2.3
ND
ND
0.3
ND
ND
ND
15
ND
0.3
ND
139
-------
Table 14 (continued)
09/24/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanone8
1,1,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1,1,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 , 1 ,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.1
0.10
0.5
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.25
0.5
Plant 7b
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
0.1
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Filt Eff
0.1
0.2
ND
ND
ND
0.4
ND
ND
0.6
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
OSEff
0.4
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Plant Eff
0.8
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
1
0.8
ND
1
ND
ND
ND
DS
0.8
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
SDS
0.8
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
0.9
ND
ND
ND
140
-------
Table 15. DBF results at plant 8 (9/24/01)
09/24/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4g
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRL"
^g/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.25
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.90
0.22
0.5
0.1
0.1
Plant 8C
Raw
1
0.2
ND
ND
1
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.7
ND
Settled
16
2
0.2
ND
18
NR
NR
ND
ND
ND
ND
ND
ND
ND
7.0
ND
ND
2.0
ND
ND
ND
9.0
9.0
7.0
2.0
ND
ND
ND
ND
ND
ND
ND
ND
ND
4
0.6
0.9
ND
Filt Eff
ND
ND
ND
ND
63
10
1
ND
74
7
ND
ND
ND
ND
ND
ND
ND
4.1
ND
28
3.0
ND
7.3
1.6
ND
ND
39
44
31
8.9
ND
ND
2
0.3
ND
ND
ND
ND
ND
2
ND
3
ND
Tower Eff
ND
ND
ND
ND
0.5
0.4
0.2
ND
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.5
ND
ND
ND
ND
ND
ND
1.5
1.5
1.5
ND
ND
ND
0.2
0.1
ND
ND
ND
ND
ND
ND
ND
0.2
ND
Plant Eff
ND
ND
ND
ND
35
5
0.9
0.1
41
3
ND
ND
ND
ND
ND
ND
ND
2.4
ND
18
2.5
ND
3.2
ND
ND
ND
24
26
21
3.2
ND
ND
0.5
0.4
0.2
ND
ND
ND
ND
0.9
ND
0.3
ND
DS
ND
ND
ND
ND
27
5
1
0.2
33
2
0.3
ND
ND
ND
ND
ND
ND
ND
ND
19
2.6
1.0
3.3
ND
ND
ND
23
26
23
3.3
ND
ND
0.8
0.6
0.2
ND
2
ND
0.7
ND
SDS
ND
ND
ND
ND
26
5
1
0.2
32
4
0.3
ND
ND
ND
ND
ND
ND
2.3
ND
19
3.4
1.0
3.0
ND
ND
ND
25
29
23
3.0
0.1
ND
0.3
0.3
0.1
ND
2
ND
0.3
ND
141
-------
Table 15 (continued)
09/24/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 , 1 ,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.1
0.10
0.5
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.25
0.5
Plant 8C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Settled
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Filt Eff
0.2
0.5
ND
ND
0.2
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
0.2
0.5
ND
ND
ND
ND
ND
ND
Tower Eff
0.5
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
ND
Plant Eff
0.1
0.3
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
0.6
0.6
ND
ND
ND
ND
DS
0.2
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
SDS
0.4
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.9
ND
ND
ND
142
-------
Table 16. Occurrence of other DBFs" at plant 8 (9/24/01)
Compound
Halomethanes
Dibromomethane
Bromodichloromethaneb
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Diiodochloromethane
Haloacids
Bromoacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Bromodichloroacetic acid
Trichloroacetic acid
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Haloaldehydes
Dichloroacetaldehyde
Dibromoacetaldehyde
Trichloroacetaldehyde
2-Bromo-2-methylpropanal
Haloketones
Chloropropanone
, 1 -Dichloropropanone
-Bromo- 1 -chloropropanone
,1,3 -Trichloropropanone
-Bromo- 1 , 1 -dichloropropanone
, 1 , 3 ,3 -Tetrachloropropanone
-Bromo- 1 ,3 ,3 -trichloropropanone
l,l-Dibromo-3, 3 -dichloropropanone
1, 3-Dibromo-l, 3 -dichloropropanone
1,1, 3-Tribromo-3-chloropropanone
1,1,3, 3-Tetrabromopropanone
Halonitromethane s
Dichloronitromethane
Bromochloronitromethane
FE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
PE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Compound
Miscellaneous Halogenated DBFs
Hexachlorocyclopentadiene
Bromopentachlorocyclopentadiene
Non-haloeenated DBFs
Acetone
Propanal
2-Butanone
3-Hexanone
2-Hexanone
Glyoxal
Methyl glyoxal
Heptanoic acid
Octanoic acid
Nonanoic acid
Decanoic acid
Undecanoic acid
Dodecanoic acid
Tetradecanoic acid
Pentadecanoic acid
Hexadecanoic acid
Heptadecanoic acid
Octadecanoic acid
Butanedioic acid
Pentanedioic acid
Octanedioic acid
Nonanedioic acid
Decanedioic acid
Benzene-l,3-dicarboxylic acid
FE
X
X
X
X
X
X
X
X
X
-
-
-
-
-
-
-
-
-
-
-
-
-
-
PE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
aDBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique
bCompounds listed in italics were confirmed through the analysis of authentic standards; haloacids
non-halogenated carboxylic acids identified as their methyl esters.
and
143
-------
Table 17. DBF results at plant 7 (1/14/02)
1/14/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4g
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRLa
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.5
0.1
2.5
0.5
0.53
0.1
0.52
0.22
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
NA
0.5
0.25
0.1
NA
NA
NA
0.98
0.5
0.1
0.1
Plant 7b
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
Settled
NRf
NR
ND
ND
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
Filt Eff
ND
ND
ND
ND
3
0.3
0.5
ND
4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.9
ND
ND
ND
ND
ND
ND
3.9
3.9
3.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
OSEff
4
0.6
0.5"
ND
5
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
Plant Eff
ND
ND
ND
ND
6
2
<0.5
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
3.7
ND
15
1.6
ND
1.8
ND
ND
ND
21
22
17
1.8
ND
ND
0.6
ND
ND
ND
ND
ND
ND
8
ND
0.5
ND
DS
ND
ND
ND
ND
8
1
ND
ND
9
ND
ND
ND
ND
ND
ND
0.2
ND
4.1
ND
15
1.6
ND
1.7
ND
ND
ND
21
22
17
1.7
ND
ND
NR
ND
ND
ND
9
ND
0.3
ND
SDS
ND
ND
ND
ND
8
1
ND
ND
9
ND
ND
ND
ND
ND
ND
ND
ND
5.4
ND
22
2.0
ND
2.0
ND
ND
ND
29
31
24
2.0
ND
ND
NR
ND
ND
ND
11
ND
0.7
ND
"<0.5: Concentration less than MRL of 0.5 pg/L
144
-------
Table 17 (continued)
1/14/2002
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 , 1 ,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.5
NA
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.10
0.5
0.5
0.1
NA
0.1
0.10
0.1
NA
NA
NA
0.5
0.2
0.2
0.5
Plant 7b
Raw
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
Filt Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
OSEff
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
0.5
ND
ND
0.1
ND
ND
ND
ND
ND
Plant Eff
1
1
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
0.5
ND
0.7
ND
ND
0.4
3
ND
ND
0.6
ND
ND
ND
DS
1
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
0.2
0.8
ND
ND
ND
SDS
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
0.4
0.9
ND
ND
ND
145
-------
Table 18. DBF results at plant 8 (1/16/02)
1/16/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4g
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
MRLa
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.5
0.1
2.5
0.5
0.53
0.1
0.52
0.22
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
NA
0.5
0.25
0.1
NA
NA
NA
0.98
0.5
0.1
0.1
Plant 8C
Raw
ND
ND
ND
ND
ND
NRf
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
0.3
ND
Settled
14
2
0.8
ND
17
NR
ND
ND
ND
ND
ND
0.2
ND
ND
ND
9.9
ND
ND
2.1
ND
ND
ND
12
12
10
2.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
Filt Eff
NDd
ND
ND
ND
59
6
0.9
ND
66
3
ND
ND
ND
ND
ND
0.3
ND
2.7
ND
28
2.6
ND
6.8
1.3
ND
ND
38
41
31
8.1
ND
ND
0.9
<0.5n
ND
ND
ND
ND
ND
1
ND
2
ND
Tower Eff
ND
ND
ND
ND
0.3
0.9
0.8
ND
2
ND
ND
ND
ND
ND
ND
0.6
ND
3.4
ND
1.2
ND
ND
ND
ND
ND
ND
4.6
4.6
1.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
Plant Eff
ND
ND
ND
ND
25
3
0.7
ND
29
<2.5°
ND
ND
ND
ND
ND
ND
ND
ND
ND
17
1.5
ND
2.6
ND
ND
ND
20
21
19
2.6
ND
ND
ND
<0.5
ND
ND
ND
ND
ND
ND
ND
0.2
ND
DS
ND
ND
ND
ND
32
3
0.7
ND
36
<2.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
16
1.4
ND
2.4
ND
ND
ND
18
20
17
2.4
ND
ND
NR
<0.5
ND
ND
ND
ND
0.2
ND
SDS
ND
ND
ND
ND
28
3
0.5
ND
32
ND
ND
ND
ND
ND
ND
ND
ND
2.7
ND
16
1.9
ND
2.4
2.5
ND
ND
21
26
18
4.9
ND
ND
NR
<0.5
ND
ND
1
ND
0.1
ND
<2.5: Concentration less than MRL of 2.5 pg/L
146
-------
Table 18 (continued)
1/16/2002
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanonee
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 , 1 ,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.5
NA
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.10
0.5
0.5
0.1
NA
0.1
0.10
0.1
NA
NA
NA
0.5
0.2
0.2
0.5
Plant 8C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
0.9
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
<0.5
ND
0.5
ND
ND
0.6
1
ND
ND
ND
ND
ND
ND
Tower Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.5
ND
ND
ND
ND
ND
1
ND
1
1
0.3
ND
ND
Plant Eff
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.4
0.9
ND
ND
ND
ND
ND
ND
DS
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
0.3
<0.5
ND
ND
ND
SDS
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
0.3
ND
ND
ND
ND
147
-------
Table 19. Additional target DBF results (iig/L) at plants 7 and 8 (1/14-16/02)
1/14-16/02
Compound
Monochloroacetaldehyde
Di chl oroacetal dehy de
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Monochl oroacetami de
Monobromoacetamide
Di chl oroacetami de
Dibromoacetamide
Tri chl oroacetami de
TOX (|ig/L as CO
TOBr (|ig/L as Br )
TOC1 (|ig/L as Cr)
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
trans -2-HQXQna\
Plant T
Raw
0
0
0
0
0
0
0
0
0
0
0
<0.1
<0.1
<0.1
<0.1
<0.1
FE
0
1.6
0.1
0
0
0
0
0.1
0
0
94.9
17.0
83.5
<0.1
<0.1
<0.1
<0.1
<0.1
OE
3.1
7.5
0.2
0
0
0
0
0.2
0
0
94.2
12.0
85.0
<0.1
<0.1
<0.1
2.4
<0.1
PE
1.9
12.2
0.6
0
0
0
0
1.8
0.2
0.1
200
36.5
206
<0.1
<0.1
<0.1
2.8
<0.1
DS
1.5
9.2
0.4
0
0
0
0
2.5
0.4
0.2
154
23.2
121
<0.1
<0.1
<0.1
1.9
<0.1
SDS
2.2
13.1
0.6
0.6
0
0
0
3.0
0.5
0.3
212
42.1
185
<0.1
<0.1
<0.1
2.5
<0.1
Plant 8a
Raw
0
0
0
0
0
0
0
0
0
0
0
0
0
<0.1
<0.1
<0.1
<0.1
<0.1
FE
0.2
1.3
0.3
0.1
0
486
137
450
<0.1
<0.1
<0.1
0.8
<0.1
STE
0
0
0
0
0
40.4
24.0
29.7
<0.1
<0.1
<0.1
<0.1
<0.1
PE
0
0
0
0
1.5
0.3
0.1
179
80.9
203
<0.1
<0.1
<0.1
<0.1
<0.1
DS
0
0.9
0.1
0
0
0
0
1.4
0.2
0.6
161
64.0
189
<0.1
<0.1
<0.1
<0.1
<0.1
SDS
0
1.0
0.1
0
0
0
0
1.2
0.2
0.5
133
68.0
190
<0.1
<0.1
<0.1
<0.1
<0.1
148
-------
Table 20. Halogenated furanone results (iig/L) at plant 7 (1/14/02)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
Raw
<0.02
<0.02
<0.02
<0.02
<0.02
0.10
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
FE
<0.02
<0.02
<0.02
<0.02
<0.02
0.10
<0.02
<0.02
<0.02
<0.02
<0.02
0.03
OE
<0.02
0.03
<0.02
<0.02
<0.02
0.15
<0.02
<0.02
<0.02
<0.02
<0.02
(0.015)
0.08
PE
0.03
<0.02
<0.02
0.06
<0.02
0.28
0.17
0.05
<0.02
<0.02
0.02
0.20
DS
<0.02
<0.02
<0.02
0.06
<0.02
0.18
<0.02
<0.02
<0.02
<0.02
0.05
0.21
SDS
0.02
<0.02
<0.02
0.03
<0.02
0.18
0.04
<0.02
<0.02
(0.013)
<0.02
0.02
0.22
Table 21. Halogenated furanone results (iig/L) at plant 8 (1/16/02)
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
Raw
<0.02
0.08
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
FE
<0.02
<0.02 (0.011)
<0.02
0.12
<0.02
0.43
<0.02 (0.015)
<0.02
0.09
<0.02
0.02
0.30
PE
0.11
0.72
<0.02 (0.014)
0.81
0.04
0.41
0.10
<0.02
<0.02
<0.02
0.02
0.16
DS
0.03
<0.02
0.03
0.11
<0.02
0.37
0.12
<0.02
<0.02
<0.02
0.02
0.17
SDS
0.05
<0.02
0.02
0.10
<0.02
1.28
0.10
<0.02
<0.02
<0.02
0.02
0.18
149
-------
Halomethanes. Pre-chloramination at plant 7 resulted in the formation of 3-18 |ig/L of
the four regulated trihalomethanes (THM4) by the filter effluent sampling point. Post-ozonation
did not change the concentration of the THMs. Post-chlorination at plant 7 resulted in 7-18 |ig/L
of THM4. Pre-chlorination and intermediate chloramination in the lime softening portion of
plant 8 resulted in the formation of 66-1 15 |ig/L of THM4, whereas only 1-3 |ig/L was produced
in the membrane softening portion of the plant. The combined treated waters at plant 8 after
final chloramination contained 29-68 |ig/L of THM4. Figure 4 shows the seasonal variation in
THM4 at plant 7 and plant 8 in 2000-2001. THM formation did not vary significantly from
season to season.
Figure 4
Seasonal Variation in Trihalomethanes at Plants 7 and 8
120
Plant 8 filter
effluent Plant 8
stripper
tower eff.
9/24/2001
3/12/2001
12/11/2000
Plant 8
plant
effluent
Plant7
P|ant
effluent
Even though the source groundwaters contained moderate to high levels of bromide (0.12
to 0.33 mg/L), chloroform was the dominant THM (e.g., 91 and 81 % of THM4 in SDS testing in
September 2001 at plant 7 and plant 8, respectively) (Figure 5). In other DBF research, it has
been shown that bromine speciation is effected by the bromide-to-TOC ratio and the chlorine-to-
bromide ratio (Symons et al., 1993). In these samples, both the TOC (11-13 mg/L in raw water)
and chlorine dosages (5-13 mg/L at plant 7 influent; 6-8 mg/L at influent to lime softening
portion of plant 8) were relatively high. As a result, chlorine was able to effectively compete
with bromine in forming halogenated DBFs. In addition, low levels of some of the iodinated
THMs were detected (Figure 5; Tables 10, 16, and 18). Because the concentration of bromide
was higher at plant 8, this resulted in somewhat more bromine incorporation in the THMs,
including the formation of a bromine-containing iodinated THM (Figure 5).
150
-------
Figure 5
Effect of Bromide and Treatment/Disinfection Process on Trihalomethane
Formation and Speciation in Simulated Distribution System Testing
(September 24, 2001): Plant 7 Br' = 0.14 mg/L, Plant 8 Br' = 0.25 mg/L
Haloacids. Chloramination and ozonation at plant 7 resulted in the formation of 21-
30 |ig/L of the five regulated haloacetic acids (HAAS). Pre-chlorination and intermediate
chloramination in the lime softening portion of plant 8 resulted in the formation of 38-53 |ig/L of
HAAS, whereas only 2-5 |ig/L were produced in the membrane softening portion of the plant.
The combined treated waters at plant 8 after final chloramination contained 17-28 jig/L of
HAAS.
In addition, all nine HAAs (HAA9) were measured, which includes all of the brominated
HAA species. However, HAA9 values were not significantly higher than the levels of HAAS.
This reflects the relatively low bromine substitution that occurred in these waters. Figure 6
shows the seasonal variation in HAA9 at plant 7 and plant 8 in 2000-2001. HAA formation did
not vary significantly from season to season.
At both plants, the sum of the dihalogenated HAAs (DXAAs) was much higher than the
sum of the trihalogenated HAAs (TXAAs) (Figure 7). In other DBF research, chloramination
has been shown to control TXAA formation much better than DXAA formation (Krasner et al.,
1996). In addition, ozonation has been shown to be able to destroy trichloroacetic acid (TCAA)
precursors better than dichloroacetic acid (DCAA) precursors (Reckhow and Singer, 1984).
Furthermore, other research has shown that THM formation—in the presence of free chlorine—
was higher with increasing pH (Stevens et al., 1989). In this same research, pH (in the range of 5
to 9.4) had no significant effect on DCAA formation, whereas TCAA formation was lower at pH
9.4 than at the lower pH levels (Stevens et al., 1989). Because chlorine (and chloramines) was
applied to lime-softened water at plants 7 and 8, pH was a factor in determining which DBFs
151
-------
Figure 6
Seasonal Variation in Haloacetic Acids at Plants 7 and 8
Plant 8 filter
effluent
Plant 8
stripper
tower eff.
Plant 8
plant Plant7
effluent P|ant
effluent
9/24/2001
3/12/2001
12/11/2000
Figure 7
Effect of Treatment/Disinfection Process on Trihalomethane and
Haloacetic Acid Formation at Plants 7 and 8 (September 24, 2001)
THM4
Plant 8 Filter Eff.
Plant 7 Plant Eff.
DXAAs
TXAAs
152
-------
formed. Because DXAA formation was higher than THM4 formation at plant 7 in September
2001, the use of pre-chloramination was probably the major determinant of the relative
proportion of these DBFs during that sampling date. Because THM4 formation was higher than
DXAA formation in the softened water at plant 8, the effect of pH was probably the major
determinant of the relative proportion of these DBFs.
For example, Figure 8 shows the effect of the disinfection scheme on DBF formation in
lime-softened waters at plants 7 and 8 for March 12, 2001. At plant 7, chlorine (10 mg/L) and
ammonia (1.1 mg/L) were added to the raw water that contained 0.69 mg/L of ammonia to begin
with. At plant 8, on the lime-softening train, chlorine (6.0 mg/L) was added to the raw water.
Although ammonia was not added at plant 8, the raw water contained 0.62 mg/L of ammonia.
Therefore, both plants were operating with chloramines, which helped minimized DBF
formation in this high-TOC groundwater. At plant 8, in the lime-softening portion of the plant,
additional chlorine (12 mg/L) and ammonia (1.0 mg/L) were added to the softened water.
Although chloramines were still present, it is possible that the "effective" chlorine-to-nitrogen
ratio was much higher than in the raw water. At higher chlorine-to-nitrogen ratios, TFDVI
formation is more likely to occur (Diehl et al., 2000), as evidenced by the relatively high level of
TFDVIs (98 |ig/L) in the filter influent sample at plant 8.
Figure 8
Effect of Disinfection Scheme on DBF Formation on
Lime-Softened Waters at Plants 7 and 8: 3/12/01
100
D)
Plant 8/Raw water:
chlorine dose = 6 mg/L
total ammonia (raw +
dose) = 0.6 mg/L
Filter influent:
chlorine dose = 12 mg/L
total ammonia (raw +
dose) = 1.6 mg/L
THM4
DXAAS TXAAs
• Settled Water *
TTHMs
DXAAs
• Filtered Water
TXAAs
Haloacetonitriles. In other DBF research, haloacetonitriles (HANs) have been found to
be produced at approximately one-tenth the level of the TFDVIs (Oliver, 1983). HANs were only
observed at plant 8 in the filter effluent sample in December 2000 and in selected samples at
both plants in January 2002. HANs can undergo base-catalyzed hydrolysis (Croue and
153
-------
Reckhow, 1989). Because of the high pH of the treated waters at these two plants, most of the
HANs formed were degraded. None of the target HANs—that were not included in the
Information Collection Rule (ICR)—were detected in these high-pH samples, except for
chloroacetonitrile in the SDS sample at plant 8 in September 2001.
Haloketones. One of the haloketones (HKs) from the ICR—1,1-dichloropropanone
(1,1-DCP)—was detected at both plant 7 and plant 8, whereas the other ICR HK (1,1,1-
trichloropropanone) was detected in selected samples at plant 8 and in January 2002 at one
sample location at plant 7. The latter HK also can undergo base-catalyzed hydrolysis at high pH
(Croue and Reckhow, 1989). In addition, some of the other target HKs were detected in selected
samples (Figure 9).
Figure 9
Formation of Haloketones at Filter Effluents at Plants 7 and 8
(September 24, 2001)
0.6-r
0.5-
D)
-------
Figure 10
Effect of Disinfection/Treatment Scheme and pH (9-10) on
Haloacetaldehyde Formation and Stability at Plants 7 and 8: 3/12/01
ra 7-
Plant 7/Chlorine and
ammonia addition to raw water;
ozone addition to filtered water
Plant 8/Lime softening train:
Chlorine addition to raw water,
chlorine and addition addition to
softened water; plant effluent =
blend of lime and membrane
softened waters
Plant 7
Plant 8
• Filtered Water>
. Plant Effluent.
Haloaldehydes. Chloral hydrate (trichloroacetaldehyde) (an ICR DBF) was detected (2-
13 |ig/L) in the filter effluent sample at plant 8 (Figure 10). Chloral hydrate also undergoes
base-catalyzed hydrolysis (Stevens et al., 1989) (it is converted to chloroform). Thus, its low
concentration (0.2-2 |ig/L) in the combined treated waters at plant 8 was a result of degradation,
not only because of dilution with membrane-treated water. In addition, a low level (<3 |ig/L) of
dichloroacetaldehyde (a target DBF) was found at plant 8.
In contrast, at plant 7, very little chloral hydrate was detected (<1 |ig/L), whereas a high
amount of dichloroacetaldehyde (8-14 |ig/L) was detected in the finished water (Figure 10). In
other DBF research, acetaldehyde (an ozone by-product) was found to react with chlorine to
form chloroacetaldehyde, which in the presence of free chlorine rapidly reacted to form chloral
hydrate (McKnight and Reckhow, 1992). At plant 7, chlorine (in the presence of ammonia) may
have reacted with acetaldehyde formed by the ozonation process to produce dichloro-
acetaldehyde.
In addition, bromochloroacetaldehyde—a brominated analogue of dichloroacetaldehyde
—was detected at sub-|ig/L levels at two locations at plant 7 in March 2001. The results for
chloral hydrate in December 2000 represented the sum of the concentrations of chloral hydrate
and bromochloroacetaldehyde, since these two DBFs co-eluted in the original GC method
(Krasner et al., 2001). However, based on the March 2001 results, bromochloro-acetaldehyde
probably did not contribute that much to the December 2000 chloral hydrate results.
155
-------
In addition to the target haloaldehydes, two other haloaldehydes were detected in selected
samples by the broadscreen GC/MS methods (Tables 10 and 16). Dibromoacetaldehyde, the
fully bromine-substituted analogue of dichloro- and bromochloroacetaldehyde, was detected at
both plants. Another brominated aldehyde (2-bromo-2-methylpropanal) also was detected at
both plants.
Halonitromethanes. Sub-|ig/L levels of chloropicrin (trichloronitromethane) (an ICR
DBF) were detected at selected sites at plant 8 and in January 2002 at plant 7. In addition, some
of the target halonitromethanes were detected at both plant 7 and plant 8 (Figure 11; Tables 10,
16, 17, and 18).
Figure 11
Formation of Halonitromethanes in Plant Effluents at Plants 7 and 8
(September 24, 2001)
B>
HalogenatedFuranones. Tables 20 and 21 show results for halogenated furanones in the
January 2002 sampling for plant 7 and plant 8. Data are included for 3-chloro-4-
(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found
as a closed ring or in an open form. Results are displayed graphically in Figure 12.
At plant 7 (1/14/02), pre-chloramination and post-ozonation controlled (in part) the
formation of MX and MX-analogues in a high-TOC (12.6 mg/L) groundwater, as compared
156
-------
Figure 12
Plants 7 and 8 (1/14-16/02)
BMX-1
MX
BEMX-1
EIVIX
BMX-2
ZIVIX
BEMX-2
MCA (ring)
BMX-3
MCA (open)
IBEMX-3
lOx-MX
0.00
Plant 7
CI2+NH3
Sampling
157
-------
to plant 8 (1/16/02) (TOC = 11.3 mg/L) that used lime softening with pre-chlorination in one
portion of the plant and membranes in the other portion of the plant to control DBF formation
and remove TOC. Likewise, pre-chlorination in the lime softening portion of plant 8 produced
more THMs and HAAs than chloramination/ozonation at plant 7 (Figure 7-8). These are the
results of only one sample event. Additional measurements of membrane-treated water should
be conducted in the future to determine whether these results are repeatable. However, the
significant brominated MX-analogue production in plant 8 is consistent with the high-bromide,
source-water quality (0.27 mg/L in the raw water and 0.1 mg/L in the membrane effluent).
Volatile Organic Compounds (VOCs). In December 2000, carbon tetrachloride was
detected in one sample (distribution system of plant 7) just above its MRL (0.06 |ig/L). In
March 2001, this compound was found in all of the samples (0.2-0.7 |ig/L) except for the raw
waters and the effluent of the stripping towers (i.e., membrane-softened water). In September
2001, it was not detected in any of the samples with an MRL of 0.2 |ig/L. In January 2002,
carbon tetrachloride was detected in one sample (distribution system) of plant 7 at the revised
MRL (0.2 |ig/L) and in several samples at plant 8 (0.2-0.6 |ig/L). Carbon tetrachloride is a VOC
and a possible DBF. Carbon tetrachloride has been detected by some utilities in gaseous chlorine
cylinders (EE&T, 2000). Incidents of carbon tetrachloride contamination have been traced to
either imperfections in the manufacturing process or improper cleaning procedures. Carbon
tetrachloride is used to clean out cylinders before filling with chlorine. If carbon tetrachloride is
not allowed sufficient time to evaporate, it can contaminate the chlorine.
In September 2001, methyl ethyl ketone (MEK) was detected in selected samples at 0.9-
1 ng/L. In January 2002, MEK was detected after ozonation at plant 7 (0.6-0.9 |ig/L) and in two
samples at plant 8 (<0.5-1 |ig/L). MEK is a VOC and a possible DBF. Also in January 2002,
methyl tertiary butyl ether (MTBE) was detected (0.3 |ig/L) in one sample (stripper tower
effluent) of plant 8 just above its MRL (0.2 |ig/L). MTBE is a VOC, not a DBF.
Other HalogenatedDBPs. A few additional, miscellaneous halogenated DBFs were also
detected. UNC methods detected dichloroacetamide at 1.8 and 2.1 |ig/L in finished waters from
plant 7 and plant 8, respectively, in March 2001 (Table 13). In addition, the concentration of
dichloroacetamide increased in SDS testing. In samples collected in January 2002,
dichloroacetamide, dibromoacetamide, and trichloroacetamide were found in finished waters
from both treatment plants at levels for individual species ranging from 0.1 to 3.0 |ig/L (Table
19). The concentrations of these latter compounds either increased or remained steady in the
distribution system. Broadscreen GC/MS analyses revealed the presence of
hexachlorocyclopentadiene and bromopentachlorocyclopentadiene in finished water from plant 7
in December 2000 (Table 10) and plant 8 in September 2001 (Table 16). These compounds were
not observed in the corresponding raw, untreated water.
Non-HalogenatedDBFs. A few non-halogenated DBFs were also detected in finished
waters from plants 7 and 8. Dimethylglyoxal was identified at 3.5 |ig/L in finished waters from
plant 7 in March 2001 (Table 13) and in finished waters at 2.8 |ig/L from plant 7 in January 2002
(Table 19). Broadscreen GC/MS analysis also revealed the presence of formaldehyde, acetone,
glyoxal, and methyl glyoxal in plant 7 finished waters in December 2002, and acetone, propanal,
2-butanone, 3-hexanone, 2-hexanone, glyoxal, and methyl glyoxal in finished waters from plant
158
-------
8 in September 2001 (Table 16). Several non-halogenated carboxylic acids were also observed
in the finished waters at significantly higher levels than found in the raw, untreated water (Table
16).
Other DBF Formation and Stability Issues. Figures 13-14 show the effect of seasonal
variations on DBF formation at plant 7 (plant effluent) and at plant 8 (filter effluent).
Essentially, there did not appear to be any significant seasonal variations in water quality,
operations or DBF formation at either of these two treatment plants.
Figure 13
Effect of Seasonal Variations on DBF Formation at Plant 7:
Plant Effluent
3/12/2001
12/11/2000
159
-------
Figure 14
Effect of Seasonal Variations on DBF Formation at Plant 8:
Filter Effluent
3/12/2001
12/11/2000
At plant 7, HAA formation (the sum of all nine species) was greater than THM formation
(on a weight basis). The haloacetaldehydes were the third largest fraction (by weight) of
halogenated DBFs. At plant 7, most of the haloacetaldehyde formation was due to dichloro-
acetaldehyde (a target DBF) and not due to chloral hydrate (an ICR DBF). HAN formation was
quite small.
Alternatively, at plant 8, THM formation was greater than HAA formation. The
haloacetaldehydes and HANs were the third and fourth largest fractions of halogenated DBFs.
The formation of the latter two fractions was higher in December 2000 than in March 2001.
During the December 2000 sampling, the pH of the settled water and filter effluent were 9.7 and
9.2, respectively, whereas during the March 2001 sampling, the pH of the settled water and filter
effluent were 10.4 and 10.0, respectively. Because chloral hydrate and dichloroacetonitrile (the
major components of the latter two fractions at plant 8, respectively) both undergo base-
catalyzed hydrolysis, their formation may have been lower in March 2001 because of the
somewhat higher pH.
Figure 15 shows the effect of blending lime-softened water (filter effluent) with
membrane-softened water (effluent of stripper towers) and base-catalyzed hydrolysis on DBF
concentrations in the plant effluent of plant 8 on September 24, 2001. The flows of the lime-
softening and membrane-softening portions of the plant were 3.3 and 6.8 mgd, respectively. For
the TXAAs, 8.9 |ig/L was detected in the lime-softened water, whereas none was detected in the
membrane-softened water. Based on blending, using the flows of each portion of the treatment
plant, one would expect the TXAAs to be diluted down to 2.9 |ig/L. In the actual plant effluent,
there was 3.2 |ig/L of TXAAs. In contrast, the theoretical levels of dichloroacetonitrile
160
-------
(0.8 |ig/L) and of chloral hydrate (1.1 |ig/L) were greater than the measured values (i.e., 0.5 and
0.3 |ig/L, respectively). As discussed previously, the lower measured values—especially for
chloral hydrate—were due to base-catalyzed hydrolysis. On the other hand, the theoretical levels
of DXAAs (11 |ig/L) and of THM4 (25 |ig/L) were significantly less than the measured values
(i.e., 21 and 41 |ig/L, respectively). These latter DBFs continued to form downstream of
blending (and after additional chlorine addition). In addition, when chloral hydrate is
hydrolyzed, chloroform (one of the THMs) is formed. Thus, some of the formation may also be
due to the breakdown of other unstable DBFs (at least unstable at pH 9). Finally,
dichloroacetaldehyde was relatively conservative (theoretical and measured values of 0.7 and
0.9 |ig/L, respectively). Therefore, it did not undergo base-catalyzed hydrolysis as the chloral
hydrate (trichloroacetaldehyde) did.
Figure 15
Effect of Blending and pH on Formation and Stability of DBFs at
Plant 8 (September 24, 2001)
100
J>/ DXAAs
ATXAAs
Dichloroacetonitrile
Chloral hydrate
Dichloroacetaldehyde
161
-------
REFERENCES
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite.
Environmental Science & Technology 23(11): 1412 (1989).
Diehl, A. C., G. E. Speitel Jr., J. M. Symons, S. W. Krasner, C. J. Hwang, and S. E. Barrett.
DBF formation during chloramination. Journal of the American Water Works Association
92(6):76 (2000).
Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to
AWWA Research Foundation, Denver, CO, 2000.
Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly
identified disinfection by-products in drinking water. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2000.
Jacangelo, J. G., N. L. Patania, K. M. Reagan, E. M. Aieta, S. W. Krasner, and M. J. McGuire.
Ozonation: assessing its role in the formation and control of disinfection by-products. Journal
of the American Water Works Association 81(8):74 (1989).
Krasner, S. W., W. H. Glaze, H. S. Weinberg, P. A. Daniel, and I. N. Najm. Formation and
control of bromate during ozonation of waters containing bromide. Journal of the American
Water Works Association 85(1):73 (1993).
Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E.
Barrett. Effects of water quality parameters on DBF formation during chloramination.
Proceedings of the American Water Works Association Annual Conference (Water Quality)., Vol.
D, American Waterworks Association: Denver, CO, pp. 601-628, 1996.
Krasner, S. W., S. Pastor, R. Chinn, M. J. Sclimenti, H. S. Weinberg, and S. D. Richardson. The
occurrence of a new generation of DBFs (beyond the ICR). Proceedings of the American Water
Works Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2001.
Kuo, C.-Y., H.-C. Wang, S. W. Krasner, and M. K. Davis. lon-chromatographic determination
of three short-chain carboxylic acids in ozonated drinking water. In Water Disinfection and
Natural Organic Matter: Characterization and Control (R. A. Minear and G. L. Amy, eds.), pp.
350-365, American Chemical Society: Washington, D.C., 1996.
162
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McKnight, A., and D.A. Reckhow. Reactions of ozonation by-products with chlorine and
chloramines. Proceedings of the American Water Works Association Annual Conference (Water
Research), American Waterworks Association: Denver, CO, pp. 399-409, 1992.
Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors.
Environmental Science & Technology 17(2):80 (1983).
Reckhow, D. A., and P. C. Singer. The removal of organic halide precursors by preozonation
and alum coagulation. Journal of the American Water Works Association 76(4):151 (1984).
Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane
disinfection by-products. Journal of the American Water Works Association 81(8):54 (1989).
Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water
Works Association 8 5 (1): 51 (1993 ).
van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily
assimilable organic carbon in drinking water. Journal of the American Water Works Association
74(10):540 (1982).
163
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EPA REGION 4: PLANTS 5 AND 6
Plant Operations and Sampling
Plant 5 and plant 6 in EPA Region 4 treated water from the same river. On November
27, 2000, February 26, 2001, August 13, 2001, October 22, 2001, and April 15, 2002, these two
plants were sampled
Plant 5 was an ozone plant (Figure 1). This plant consisted of two facilities operating
simultaneously and parallel to one another:
• One was a conventional facility. After raw-water ozonation, the water underwent
flocculation, coagulation, and sedimentation. The settled water then underwent intermediate
ozonation. Ozonated settled water then entered biologically-activated filters, composed of
granulated activated carbon (GAC) over sand.
• The other facility utilized solids contact - upflow clarification of coagulated water (Super
Pulsator technology) following ozonation of the raw water. After clarification, the settled
water underewent intermediate ozonation. Ozonated settled water then entered biologically
activate filters, composed of deep-bed GAC filters.
Effluents from all of the filters were combined and final chemical adjustments were made. This
included the addition of sodium hypochlorite for secondary disinfection and residual
maintenance. Finished water then flowed first into one and then another closed reservoir for
storage prior to being pumped into the distribution system.
Figure 1
Plant 5 Schematic
Ozonation
River
Flocculation
Sedimentation
Super
Pulsator
Ozonation
chlorine
Distribution < j
System
164
-------
Plant 5 was sampled at the following locations:
(1) raw water
(2) the effluent of the raw-water ozone contactor
(3) the GAC/sand influent on the conventional train
(4) the GAC/sand effluent on the conventional train
(5) the GAC influent on the Super Pulsator train
(6) the GAC effluent on the Super Pulsator train
(7) the composite filter effluent (on selected dates)
(8) the plant effluent
In addition, plant effluent was collected and simulated distribution system (SDS) testing was
conducted for average and maximum detention times (Table 1). Furthermore, the distribution
system was sampled at two locations, one representing an average detention time and the other
representing a maximum detention time.
Plant 6 was a chlorine dioxide plant (Figure 2):
• After disinfection of the raw water with chlorine dioxide, the water underwent coagulation
and clarification. The settled water was then chlorinated and filtered. Filtered water was
then chloraminated and distributed.
• Starting with the August 2001 sampling, plant 6 moved their chlorine dioxide feed point up-
stream of the plant. In November 2000 and February 2001, chlorine dioxide had been fed at
the flash mixers. Plant 6 gained approximately 7-10 minutes of contact time (depending on
flow) by adding the new feed point.
Figure 2
Plant 6 Schematic
River
chlorine
dioxide
chlorine
Pulsator Clarifier
Filters
o
s
1
Clearwell
i
' i
' ^
Distribution
System
165
-------
Plant 6 was sampled at the following locations:
(1) raw water
(2) settled water
(3) filter effluent
(4) clearwell effluent
(5) the plant effluent
In addition, plant effluent was collected and SDS testing was conducted for average and
maximum detention times for that time of the year. Furthermore, the distribution system was
sampled at two locations, one representing an average detention time and the other representing a
maximum detention time.
Table 1. SDS holding times (days) at plants 5 and 6
Sample
Plant 5 average detention time
Plant 5 maximum detention time
Plant 6 average detention time
Plant 6 maximum detention time
1 1/27/00
2.9
6
4
7
2/26/01
2.9
6
4
7
8/13/01
3.1
7
4
7
10/22/01
4
8
4
7
4/15/02
5.3
7
3
7
On the day of sampling, information was collected on the operations at each plant
(Tables 2-3).
Table 2. Operational information at plant 5
Parameter
Overall plant flow (mgd)
Plant flow for conventional coag. train (mgd)
Plant flow for Super Pulsator train (mgd)
Raw-Water Ozone Contactor
Ozone dose (mg/L)
CT (mg/L-min) achieved from ozonation
Conventional Train
Coagulant0 (mg/L)
Ozone dose (mg/L)
Hydraulic retention time (tio) in ozone contactor
(min)
CT (mg/L-min) achieved from ozonation
GAC/sand filter loading rate (gpm/sq ft)
Super Pulsator Train
Coagulant (mg/L)
Ozone dose (mg/L)
tio in ozone contactor (min)
CT (mg/L-min) achieved from ozonation
GAC filter loading rate (gpm/sq ft)
Composite Filter Effluent
Chlorine dose at filter effluent (mg/L as C12)
Chlorine dose at clearwell effluent (mg/L as C12)
1 1/27/00
25a
15a
10a
4.33
NAb
29.5
3.98
-20
NA
1.18
38.4
2.03
-20
NA
1.29
1.7
-2.0
2/26/01
12.3
6.0
6.3
3.4
NA
31
1.0
-20
NA
0.96
29
0.5
-20
NA
1.9
1.8
1.6
8/13/01
19.35
9.97
9.38
3.90
NA
41.6
2.30
-20
NA
1.63
46.7
1.50
20
NA
3.13
4.0
1.5
10/22/01
17.26
9.41
7.85
2.80
NA
40.5
2.20
-20
7.0
1.47
45.7
0.90
20
7.0
2.65
4.1
1.9
4/15/02
17.4
7.59
9.81
4.50
9.0
40.32
2.52
-20
7.0
1.25
45.4
2.52
20
7.0
3.38
2.53
1.02
aDesign flows
bNA = Not available
cAlum [A12(SO4)3 14H2O]
166
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Table 3. Operational information at plant 6
Parameter
Plant flow (mgd)
Coagulant21 (mg/L wet;
mg/L dry)
Chlorine dioxide dose (mg/L as C1O2)
Chlorine dose at filter influent (mg/L as Cb)
Chlorine dose at clearwell eff. (mg/L as C12)
Ammonia dose at plant eff. (mg/L as NHs-N)
1 1/27/00
8
16
1.95
0.60
3.2
1.0
2/26/01
8.2
18
1.5
0.66
2.5
0.76
8/13/01
9
38;
-19
1.98
2.5
2.7
0.87
10/22/01
8
32;
16
2.1
1.5
3.0
1.0
4/15/02
7
53;
26.5
1.5
1.11
3.0
1.0
aPAX 18 polyaluminum chloride [A1(OH)C1] (17 % as A12O3)
Water Quality
On the day of sampling, information was also collected on the water quality at each plant
(Tables 4-5).
Data were collected for total organic carbon (TOC) and ultraviolet (UV) absorbance
(Tables 6-7). The TOC ranged from 6.2 to 10 mg/L at plant 5 and from 6.4 to 10 mg/L at plant
6. The UV was 0.19 to 0.35 cm"1 at plant 5 and was 0.19 to 0.30 cm"1 at plant 6.
At plant 5, pre-ozonation reduced the level of TOC by 0-29 %, whereas the UV was
reduced by 20-67 %. In the Super Pulsator treatment train, coagulation removed 43-54 % of the
TOC and GAC filtration removed another 5-23 %. Coagulation reduced the UV by 63-83 %.
The overall (cumulative) removal of TOC at the Super Pulsator treatment train—including from
pre-ozonation—was 58-65 %, and the UV reduction was 85-93 %. The overall (cumulative)
removal of TOC at the conventional train—including from pre-ozonation—was 62-69 %, and the
UV reduction was 85-95 %.
At plant 6, coagulation removed 38-57 % of the TOC and filtration removed another 4-7
%. Coagulation reduced the UV by 68-77 %.
Table 8 shows the values of miscellaneous other water quality parameters in raw water at
the two plants. Bromide ranged from 0.05 to 0.08 mg/L at plant 5 and from 0.04 to 0.08 mg/L at
plant 6. For plant 5, the raw water was collected 23 miles upstream to eliminate the intake of
salty water due to tidal changes. However, the presence of bromide in the raw water, which was
higher in concentration in the fall, may indicate some saltwater intrusion.
The source water was low in alkalinity. Because of the low alkalinity, settled water (after
the addition of coagulant) was acidic (Tables 4-5).
167
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Table 4. Water quality information at plant 5
Location13
Raw water
Pre-O3 eff.
PH
11/27/00
6.8
6.8
2/26/01
6.5
6.6
8/13/01
6.4
6.4
10/22/01
6.6
6.5
4/15/02
6.2
6.2
Temperature (°C)
11/27/00
13.8
13.0
2/26/01
16
16
8/13/01
29
29
10/22/01
21
22
4/15/02
21
21
Disinfectant Residual3 (mg/L)
11/27/00
—
NDC
2/26/01
—
ND
8/13/01
—
ND
10/22/01
—
ND
4/15/02
—
ND
Conventional Train
GAC/s inf.
GAC/s eff.
5.8
5.9
5.6
5.6
5.7
5.7
5.8
5.9
5.6
5.7
11.9
12.0
13
13
29
29
21
22
21
20
NDd
—
0.05
—
0.08
—
0.1
—
0.09
—
Super Pulsator Train
GAC inf.
GAC eff.
5.9
5.9
5.7
5.6
5.7
5.7
5.7
5.7
5.6
5.6
11.9
12.0
12
13
29
29
21
22
21
21
NDd
—
0.04
—
0.09
—
0.08
—
0.1
—
Composite Filter Effluent
Filter eff.
Plant eff.
DS/ave.
DS/max.
SDS/ave.
SDS/max.
5.9
7.0
7.0
7.5
7.2
7.2
NSe
7.0
7.5
7.5
6.8
6.7
NS
7.0
7.0
7.0
7.0
7.0
NS
7.1
7.5
7.5
7.0
7.1
NS
7.0
7.0
7.5
6.8
7.2
13.4
15.8
15
15
18
18
NS
16
12
11
19
20
NS
29
28
28
23.5
25.0
NS
22
24.9
23.2
23
23
NS
20
18
18
23
24
—
2.0
1.8
0.2
1.8
0.3
NS
1.6
0.8
0.8
0.5
0.04
NS
1.7
1.2
0.1
1.0
0.6
NS
1.5
0.4
0.3
0.9
0.5
NS
1.6
1.0
0.1
0.1
0.1
aOzone residuals (values shown in bold) in effluent of raw-water ozone contactor and in effluents of intermediate ozone contactors at GAC/sand and GAC influents;
chlorine residuals at plant effluent, in distribution system, and in SDS testing.
bPre-O3 = raw-water ozone contactor, GAC/s = GAC/sand, DS = distribution system.
CND = Not detected.
dOzone sequestered with hydrogen peroxide prior to filtration.
eNS = Not sampled.
Table 5. Water quality information at plant 6
Location13
Raw water
Settled
Filter eff.
Clearwell
Plant eff.
DS/ave.
DS/max.
SDS/ave.
SDS/max.
PH
11/27/00
7.0
6.6
6.5
7.0
7.1
7.3
7.7
7.3
7.1
2/26/01
6.9
6.4
6.7
6.8
6.8
7.2
7.4
NA
NA
8/13/01
6.5
6.2
7.4
6.9
7.2
7.1
7.5
7.3
7.2
10/22/01
7.0
6.7
7.5
7.1
7.2
7.9
8.1
7.0
7.0
4/15/02
6.7
6.2
8.0
6.9
7.1
6.8
7.4
7.2
6.9
Temperature (°C)
11/27/00
13.0
13.4
13.0
12.8
13.9
12.0
13.0
5.0
5.0
2/26/01
13.6
13.8
12.6
12.4
12.5
12.0
12.0
NA
NA
8/13/01
28.4
27.3
28.1
28.5
27.4
27
26
28.5
27.9
10/22/01
19.9
19.8
20.3
20.1
20.5
21.0
21.0
20.3
19.4
4/15/02
18
20.2
19.9
19.0
20.9
18.4
18.3
21.8
22.6
Disinfectant Residual3 (mg/L)
11/27/00
—
ND/0.2
ND/0.4
0.03/2.2
2.2-2.6
2.0
0.9
2.1
1.7
2/26/01
0.2
0.04
0.3
1.7
2.2
1.7
1.2
NA
NA
8/13/01
—
0.02
o.sim
2.61 SSI
2.9/.05
2.2
1.5
1.3
1.1
10/22/01
—
.05/0.2
2.0
2.2
2.6
1.4
1.3
1.9
1.4
4/15/02
—
ND
0.2
2.9
3.2
3.2
1.8
>2.2
2.0
aChlorine dioxide residuals (values shown in bold) and chlorine residuals (values shown in italics) in raw water, settled water, filter effluent, clearwell effluent, and plant
effluent; chloramine residuals (total chlorine residual as C12) at plant effluent, in distribution system, and in SDS testing.
bDS = Distribution system
168
-------
Table 6. TOC and UV removal at plant 5
Location
11/27/2000
Raw
P re-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
02/26/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
08/13/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
10/22/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
04/15/2002
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
TOC
(mg/L)
6.23
6.07
3.22
2.24
2.88
2.22
7.44
7.45
NR"
2.81
3.41
3.14
7.26
5.18
4.46
2.26
2.94
2.8
6.74
5.26
3.22
2.45
2.87
2.66
10.28
8.66
4.44
3.36
3.95
3.64
uva
(cm'1)
0.204
0.157
0.024
0.019
0.026
0.019
0.244
0.196
0.036
0.030
0.035
0.033
0.251
0.082
0.020
0.013
0.023
0.018
0.192
0.082
0.029
0.028
0.030
0.029
0.351
0.133
0.036
0.030
0.039
0.036
SUVA"
(L/mg-m)
3.27
2.59
0.75
0.85
0.90
0.86
3.28
2.63
NA
1.07
1.03
1.05
3.46
1.58
0.45
0.58
0.78
0.64
2.85
1.56
0.90
1.14
1.05
1.09
3.41
1.54
0.81
0.89
0.99
0.99
Removal/Unit (%)
TOC
—
2.6%
47%
30%
53%
23%
—
-0.1%
NA
NA
54%
7.9%
—
29%
14%
49%
43%
4.8%
—
22%
39%
24%
45%
7.3%
—
16%
49%
24%
54%
7.8%
UV
—
23%
85%
21%
83%
27%
—
20%
82%
17%
82%
5.7%
—
67%
76%
35%
72%
22%
—
57%
65%
3.4%
63%
3.3%
—
62%
73%
17%
71%
7.7%
Removal/Cumulative (%)
TOC
—
2.6%
48%
64%
54%
64%
—
-0.1%
NA
62%
54%
58%
—
29%
39%
69%
60%
61%
—
22%
52%
64%
57%
61%
—
16%
57%
67%
62%
65%
UV
—
23%
88%
91%
87%
91%
—
20%
85%
88%
86%
86%
—
67%
92%
95%
91%
93%
—
57%
85%
85%
84%
85%
—
62%
90%
91%
89%
90%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm-1)/DOC (mg/L) or UV (m-1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.204/cm = 0.204/(0.01 m) = 20.4/m, DOC = 6.23 mg/L, SUVA = (20.4 m"1)/(6.23 mg/L) = 3.27 L/mg-m)
bNR = Not reported; sample very turbid (white cloudy material that stayed in suspension)
169
-------
Table 7. TOC and UV removal at
Location
11/27/2000
Raw
Settled Water
Filter Eff.
02/26/2001
Raw
Settled Water
Filter Eff.
08/13/2001
Raw
Settled Water
Filter Eff.
10/22/2001
Raw
Settled Water
Filter Effluent
04/15/2002
Raw
Settled Water
Filter Effluent
TOC
(mg/L)
6.36
3.76
3.51
8.09
4.24
3.99
7.86
4.7
4.53
6.66
4.16
3.93
9.5
4.07
3.88
uva
(cm'1)
0.210
0.062
0.058
0.261
0.070
0.069
0.264
0.085
0.070
0.189
0.071
0.066
0.305
0.070
0.062
plant 6
SUVAb
(L/mg-m)
3.30
1.65
1.65
3.23
1.65
1.73
3.36
1.81
1.55
2.84
1.71
1.68
3.21
1.72
1.60
Removal/Unit (%)
TOC
—
41%
6.6%
—
48%
5.9%
—
40%
3.6%
—
38%
5.5%
—
57%
4.7%
UV
—
70%
6.5%
—
73%
1 .4%
—
68%
18%
—
62%
7.0%
—
77%
11%
Removal/Cumulative (%)
TOC
—
41%
45%
—
48%
51%
—
40%
42%
—
38%
41%
—
57%
59%
UV
—
70%
72%
—
73%
74%
—
68%
73%
—
62%
65%
—
77%
80%
Table 8. Miscellaneous water quality parameters in raw water at plant 5 and plant 6
Plant 5 Plant 6
Date
11/27/2000
02/26/2001
08/13/2001
10/22/2001
04/15/2002
Bromide
(mg/L)
0.08
0.047
0.06
0.08
0.06
Alkalinity
(mg/L)
26
22
19
28
20
Ammonia
(mg/L as N)
ND
ND
ND
0.04
0.08
Date
11/27/2000
02/26/2001
08/13/2001
10/22/2001
04/15/2002
Bromide
(mg/L)
0.08
0.039
0.05
0.08
0.06
Alkalinity
(mg/L)
25
21
20
27
20
Ammonia
(mg/L as N)
ND
0.08
ND
ND
0.05
DBFs
Oxyhalides. Tables 9-10 show the formation of oxyhalides at the two plants. At plant 5,
ozonation resulted in the formation of from <3 to 6 jig/L of bromate when bromate was detected
(Table 9). The conversion of bromide to bromate—when bromate was detected—was 2-5 % (on
a molar basis), which is a typical conversion rate for an ozone plant operating for Giardia
inactivation (Douville and Amy, 2000). Because the pH of ozonation was acidic (Table 4),
bromate was often not detected, since low-pH ozonation minimizes bromate formation (Krasner
170
-------
Table 9. Oxyhalide formation at Plant 5
Location
11/27/2000
Pre-Ozone Eff.
Plant Eff.
02/26/2001
Pre-Ozone Effl.
GAC/Sand Inf.
GAG Inf.
Plant Eff.
08/13/2001
Pre-Ozone Effl.
GAC/Sand Inf.
GAG Inf.
Plant Eff.
10/22/2001
Pre-Ozone Effl.
GAC/Sand Inf.
GAG Inf.
Plant Eff.
04/15/2002
Pre-Ozone Effl.
GAC/Sand Inf.
GAG Inf.
Plant Eff.
Bromate3
(|jg/i-)
ND
3.8
ND
ND
ND
ND
5
ND
ND
ND
5.6
2.1
ND
1.9
3.5
2.2
ND
2.98
Chlorate
(|jg/i-)
5.8
79
4.6
8.4
5.7
45
5
12
14
245
ND
ND
ND
162
ND
ND
ND
184
Bromate/Bromide
(|jmol/|jmol)
—
3.0%
—
—
—
—
5.2%
—
—
—
4.4%
1 .6%
—
1 .5%
3.6%
2.3%
—
3.1%
Reporting detection level (RDL) for bromate = 3 |jg/L;
value in italics < RDL
Table 10. Oxyhalide formation at Plant 6
Location
11/27/2000
Settled Water
Plant Eff.
02/26/2001
Settled Water
Plant Eff.
08/13/2001
Settled Water
Clearwell Eff.
10/22/2001
Settled Water
Plant Eff.
04/15/2002
Settled Water
Plant Eff.
Chlorite
(M9/L)
1180
1300
783
651
772
697
1300
1040
765
694
Chlorate
(M9/L)
106
146
69
77
137
283
90
184
100
139
CIO27CIO2
%
61%
67%
51%
43%
39%
35%
62%
50%
51%
46%
171
-------
et al., 1993). In addition, sodium hypochlorite can be contaminated with low or sub-|ig/L levels
of bromate (Delcomyn et al., 2000). Because the reporting detection level for bromate was 3
|ig/L, it was not possible to determine if there was a significant increase in the concentration of
bromate in the treated water after secondary disinfection. Low levels (<15 |ig/L) of chlorate
were detected at plant 5 until the plant effluent (Table 9). Chlorate was primarily introduced into
the finished water after the secondary disinfection (chlorate is a by-product formed during the
decomposition of the hypochlorite stock solution [Bolyard et al. [1992]).
It has been reported that during water treatment, approximately 50-70 % of the chlorine
dioxide (C1O2) reacted will immediately appear as chlorite (CICV) and the remainder as chloride
(Aieta and Berg, 1986). An amount of chlorite consistent with this report was detected at plant 6
in the settled water (Table 10). The residual chlorite can continue to degrade in the water
system. At plant 6, the concentration of chlorite was typically somewhat lower in the plant
effluent, whereas the level of chlorate was somewhat higher.
Biodegradable Organic Matter. Ozone can convert natural organic matter in water to
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Kooij et
al., 1982). Table 11 shows the carboxylic acid and AOC data for plant 5. Because AOC data are
expressed in units of micrograms of carbon per liter (jig C/L), the carboxylic acid data were
converted to the same units. A portion of the molecular weight (MW) of each carboxylic acid is
due to carbon atoms (i.e., 27-49 %), and the remainder due to oxygen and hydrogen atoms. The
sums of the five carboxylic acids (on a jig C/L basis) were compared to the AOC data. On a
median basis for each sample date, 29 to 70 % of the AOC was accounted for by the carboxylic
acids. For the raw-water sample in February 2001, »100 % of the AOC was accounted for by
the carboxylic acids. Because the amount of AOC in the raw water was low, this comparison
was not as accurate as for the other samples in the plant.
Pre-ozonation significantly increased the concentration of the carboxylic acids (Table 11,
Figure 3). In August 2001 (and in October 2001 and April 2002), formation of carboxylic acids
(e.g., oxalate) was much higher during pre-ozonation (Table 11, Figure 4). The concentrations
of the carboxylic acids were significantly decreased in both trains prior to the filters in August
2001 (Figure 3) (and in October 2001 and April 2002 [Table 11]). In the previous two
samplings, the concentration of most of the carboxylic acids (e.g., oxalate) increased after
intermediate ozonation (e.g., see GAC/sand influent data) (Figure 4). In the August 2001,
October 2001, and April 2002 samplings, some of the carboxylic acids may have been removed
during the coagulation process and/or biodegraded in the basins (Volk and LeChevallier, 2002).
Biological filtration on the GAC/sand filters in the conventional treatment train and the GAC
filters in the Super Pulsator treatment train resulted in further removal of the carboxylic acids
that were present in the filter influent (Table 11, Figures 3-4). Moreover, the residual amount of
carboxylic acids (e.g., oxalate) in the filtered water was somewhat similar in each season
regardless of the level produced by the ozonation process (Table 11, Figure 3).
172
-------
Table 11. Formation and removal of carboxylic acids and AOC at plant 5
Location
11/27/2000
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
02/26/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
08/13/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
10/22/2001
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
04/15/2002
Raw
Pre-Ozone Eff.
GAC/Sand Inf.
GAC/Sand Eff.
GAC Inf.
GAC Eff.
Formula
MW (gm/mole)
C portion (gm/mole)
C% of MW
Concentration3 (|jg/l-)
Acetate
5.0
37
127
19
98
18
20
28
136
31
NRC
15
17
600
156
37
54
32
9.6
174
111
21
25
37
7.4
343
159
37
71
31
CH3COO"
59
24
41%
Propionate
6.5
ND
9.4
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
3.1
ND
ND
ND
ND
ND
5.2
4.8
ND
ND
ND
CH3CH2COO"
73
36
49%
Formate
8.3
120
244
50
202
38
42
34
313
66
NR
22
11
880
264
57
78
44
8.1
367
193
40
52
36
17
618
235
72
137
82
HCOO"
45
12
27%
Pyruvate
NDb
38
20
19
ND
17
22
27
79
26
NR
ND
ND
94
53
8.5
19
13
ND
82
37
8.4
9.7
7.1
9.0
88
69
22
36
23
CH3COCOO"
87
36
41%
Oxalate
17
185
328
52
220
51
43
398
468
67
NR
72
24
1800
472
49
159
58
16
857
312
45
66
33
30
2021
713
101
286
88
c2o42-
88
24
27%
Concentration (|jg C/L)
Acetate
2.0
15
52
7.6
40
7.4
8.1
11
55
13
NR
6.1
6.9
244
63
15
22
13
3.9
71
45
8.5
10
15
3.0
140
65
15
29
13
Propionate
3.2
ND
4.6
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
1.5
ND
ND
ND
ND
ND
2.6
2.4
ND
ND
ND
Formate
2.2
32
65
13
54
10
11
9.1
83
18
NR
5.9
2.9
235
70
15
21
12
2.2
98
51
11
14
9.6
4.5
165
63
19
37
22
Pyruvate
ND
16
8.3
8.0
ND
7.2
9.1
11
33
11
NR
ND
ND
39
22
3.5
7.9
5.4
ND
34
15
3.5
4.0
2.9
3.7
36
29
9.1
15
9.5
Oxalate
4.7
50
89
14
60
14
12
109
128
18
NR
20
6.5
491
129
13
43
16
4.4
234
85
12
18
9.0
8.2
551
194
28
78
24
Sum
12
113
219
43
154
38
40
140
299
59
NR
32
16
1009
285
47
94
46
10
438
197
35
46
37
19
894
353
71
158
68
AOC
18
420
428
349
median
13
430
331
237
median
38
329
218
87
median
31
759
161
128
median
46
317
553
315
median
Sum/
AOC
68%
52%
36%
11%
44%
310%
70%
13%
70%
44%
87%
43%
53%
48%
34%
26%
29%
29%
29%
42%
1 1 1 %
29%
22%
35%
Method detection limit (MDL) = 3 |jg/L; reporting detection level (RDL) = 15 |jg/L; value in italics is < RDL
bND = Not detected, value is < MDL
°NR = Not reported; apparent problems with the results of this sample
173
-------
Figure 3
Formation and Removal of Carboxylic Acids at Plant 5
(August 13, 2001)
• Acetate DPropionate •Formate HPyruvate DOxalate
4000 -i
3500
3- 3000
"3)
~ 2500
~o
o
y 2000
| 1500
ro
O 1000
500
n
^^^^a.
Conventional Train
Super Pulsator Train
Raw Pre-Ozone GAC/Sand GAC/Sand GAC Influent GAC Effluent
Effluent Influent Effluent
Figure 4
Seasonal Variation in Formation and Degradation
of Oxalate at Plant 5
Raw
Pre-Ozone
Effluent
8/13/2001
2/26/2001
11/27/2000
GAC/Sand
Influent
GAC/Sand
Effluent
174
-------
Ozonation resulted in a significant increase in the concentration of AOC (Table 11,
Figure 5). (Note, one of the bacterial strains used in the AOC method [i.e., Spirillum NOX\ is
used to estimate oxalate-carbon equivalents of the AOC [van der Kooij and Hijnen, 1984].) In
August 2001, there was a significant reduction in the AOC on the GAC filter in the Super
Pulsator train. (AOC was not sampled at the GAC/sand filter effluent in the conventional train,
but based on carboxylic acid data [Figure 3], AOC should have been reduced in concentration.)
In the other seasons, there was less AOC removal. The higher removal in August 2001 may
have been due, in part, to the higher water temperature in the summer, which would have
supported more biological activity.
Figure 5
Formation and Removal of AOC at Plant 5 (August 13, 2001)
IAOC-P17 lUAOC-NOX
350
300
250
O
g 200
O
< 150
100 -
50
Raw GAC/Sand Influent GAC Influent GAC Effluent
*AOC evaluated with two test bacteria: Pseudomonas fluorescens P-17 and Spirillum NOX
Halogenated Organic and Other Nonhalogenated Organic DBFs. Tables 12 and 13
(11/27/00), Tables 15 and 16 (2/26/01), Tables 18 and 19 (8/13/01), Tables 22 and 23 (10/22/01),
and Tables 24 and 25 (4/15/02) show results for the halogenated organic DBFs that were
analyzed at Metropolitan Water District of Southern California (MWDSC). Table 14 (11/27/00),
Table 20 (8/13/01), and Table 26 (4/15/02) show results for additional target DBFs that were
analyzed for at the University of North Carolina (UNC). Table 17 (2/26/01 [plant 6] and
10/22/01 [plant 5]) shows results from broadscreen DBF analyses conducted at the U.S.
Environmental Protection Agency (USEPA). Table 21 (8/13/01) and Table 27 (4/15/02) show
results for halogenated furanones that were analyzed at UNC.
175
-------
Table 12. DBF results at Plant 5 (11/27/00)
11/27/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA51
HAA9J
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehydem
Chloral hydrated
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.12
0.25
3
0.64
0.10
0.12
3
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.16
0.20
0.10
Plant 5C
Raw
NDC
ND
ND
ND
0.8
0.3
0.2
ND
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC/Sand Inf
NRe
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
GAG Inf
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
ND
ND
ND
ND
12
14
13
2
41
ND
<39
ND
ND
ND
ND
ND
3.5
ND
8.7
7.0
2.2
3.8
5.7
2.9
ND
18
34
18
12
0.1
0.1
1
1
0.7
ND
1
6
0.1
DS/Ave
ND
ND
ND
ND
15
16
15
2
48
ND
<3
ND
ND
ND
ND
ND
3.5
ND
9.8
7.7
2.5
5.3
7.0
3.4
ND
21
39
20
16
0.2
ND
1
1
0.7
ND
1
7
0.1
DS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
NR
ND
ND
2
2
0.9
ND
1
21
ND
SDS/Ave
ND
ND
ND
ND
48
30
16
2
96
ND
<1h
ND
ND
ND
ND
ND
3.4
ND
22
12
4.9
9.0
8.1
4.2
ND
39
64
39
21
ND
ND
2
2
0.9
ND
1
27
ND
SDS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
NR
ND
ND
2
2
0.8
ND
1
29
ND
176
-------
Table 12 (continued)
11/27/2000
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1 , 1 ,1 -Trichloropropanoned
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1,1,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin0
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 5C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC/Sand Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAG Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
0.3
0.5
ND
ND
4
ND
<3
ND
ND
ND
0.1
ND
ND
ND
0.4
ND
ND
ND
DS/Ave
0.2
0.4
ND
ND
4
ND
3
ND
ND
ND
0.1
ND
ND
ND
0.4
ND
ND
ND
DS/Max
0.3
0.2
ND
8
ND
ND
ND
ND
0.1
3
NR
SDS/Ave
0.2
0.2
ND
ND
9
ND
<1
ND
ND
ND
ND
ND
<3
ND
2
ND
ND
ND
SDS/Max
0.3
ND
ND
8
ND
ND
ND
ND
ND
3
NR
MRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
treatment plant sampled at (1) raw water, conventional train sampled at (2) GAC/sand influent,
Super Pulsator train sampled at (3) GAC influent, (4) plant effluent,
(5) DS at average detention time and (6) at maximum detention time, and
(7) SDS testing of plant effluent held for average detention time and (8) held for maximum detention time.
CND = Not detected at or above MRL
dDBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
eNR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance
fTHM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
9<3: Concentration less than MRL of 3 ug/L
h<1: Concentration less than lowest calibration standard (i.e., 1 ug/L)
'HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid)
JHAA9 = Sum of 9 haloacetic acids
kDXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
'iXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
mBromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs
177
-------
Table 13. DBF results at Plant 6 (11/27/00)
11/27/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform
Bromodichloromethaned
Dibromochloromethaned
Bromoform
THM4f
Dichloroiodom ethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acid
Dichloroacetic acid"
Bromochloroacetic acid
Dibromoacetic acid0
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9'
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitrile0
Dibromoacetonitrile0
Trichloroacetonitriled
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde"1
Chloral hydrate"
Tribromoacetaldehyde
MRL"
ug/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.12
0.25
3
0.64
0.10
0.12
3
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.16
0.20
0.10
Plant 6"
Raw
NDC
ND
ND
ND
0.3
0.3
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
0.8
1
0.5
ND
2
NR
NR
ND
ND
ND
NR
2.0
ND
11
5.2
ND
ND
ND
ND
ND
13
18
16
ND
ND
ND
0.2
0.1
ND
ND
0.6
ND
ND
Filter Eff
ND
ND
ND
ND
4
4
2
0.5
11
ND
ND
ND
ND
ND
ND
ND
2.4
ND
14
7.8
1.5
2.7
1.7
1.0
ND
20
31
23
5.4
ND
ND
0.5
0.3
ND
ND
1
1
0.1
Clean/veil Eff
NRe
NR
NR
NR
NR
NR
NR
ND
ND
ND
NR
2.6
1.0
16
9.1
2.0
3.7
2.1
1.1
ND
25
38
27
6.9
ND
ND
0.7
0.4
0.1
ND
1
2
ND
Plant Eff
ND
ND
ND
ND
8
8
5
1
22
0.3
<39
ND
ND
ND
ND
ND
ND
ND
16
9.3
2.0
3.5
2.0
1.0
ND
22
34
28
6.5
ND
ND
0.7
0.4
0.1
ND
2
2
ND
DS/Ave
ND
ND
ND
ND
8
8
5
1
22
0.3
<3
ND
ND
ND
ND
ND
2.3
ND
17
9.5
2.1
3.2
1.9
1.1
ND
25
37
29
6.2
ND
ND
0.8
0.4
0.1
ND
2
2
ND
DS/Max
NR
NR
NR
NR
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.9
0.6
0.1
ND
5
3
ND
SDS/Ave
ND
ND
ND
ND
10
9
5
1
25
0.4
<1n
ND
0.1
ND
ND
ND
2.2
ND
16
9.4
2.0
3.6
2.0
1.1
ND
24
37
28
6.7
ND
ND
0.8
0.5
0.1
ND
2
2
0.1
SDS/Max
NR
NR
NR
NR
NR
NR
NR
ND
0.2
ND
ND
ND
ND
1
0.5
0.1
ND
2
2
0.1
178
-------
Table 13 (continued)
11/27/2000
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanoned
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1-Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin d
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
Mg/L
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 6"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
0.4
0.5
ND
0.1
ND
ND
ND
ND
ND
ND
NR
Filter Eff
0.5
0.9
ND
ND
0.5
ND
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clean/veil Eff
0.6
1
ND
0.5
ND
ND
ND
ND
ND
0.2
NR
Plant Eff
0.6
1
ND
ND
0.5
ND
<1
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
DS/Ave
0.6
1
ND
ND
0.4
ND
<1
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
ND
DS/Max
1
2
ND
0.1
ND
ND
ND
ND
ND
0.7
NR
SDS/Ave
0.8
1
ND
ND
0.4
ND
<1
ND
ND
ND
ND
ND
<1
ND
0.4
ND
ND
ND
S DS/Max
0.9
2
ND
0.5
ND
ND
ND
ND
ND
0.8
NR
"Treatment plant sampled at (1) raw water, (2) settled water, (3) filter effluent, (4) clearwell effluent,
(5) plant effluent, (6) DS at average detention time and (7) at maximum detention time, and
SDS testing of plant effluent (8) held for average detention time and (9) held for maximum detention time.
Table 14. Additional target DBF results (ug/L) at plants 5 and 6 (11/27/00)
11/27/2000
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (ng/L as Cl")
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethyglyoxal
trans -2-Hexenal
Plant 5a
Raw
0
0
0
0.2
0
0
36.9
<0.1
0.1
<0.1
<0.4
<0.1
OE1
0
0
0
0.1
0
0
<0.1
<0.1
<0.1
0.7
0.3
Comb FE
0
0
0
0.1
0
0
16.1
<0.1
<0.1
<0.1
3.2
<0.1
PE
0.2
2.0
2.2
0.9
0
0
205
0.1
0.1
O.I
2.1
O.I
DS/ave
0.1
1.9
2.0
1.3
0
0
227
0.1
0.1
O.I
2.1
O.I
SDS/max
0.6
2.6
2.3
0.6
0
0
245
0.1
0.1
O.I
2.1
O.I
Plant 6b
Raw
0
0
0
0.1
0
0
15.2
0.1
0.1
O.I
0.4
O.I
Settled
0.6
0.6
0.7
0.4
0
0
88.8
0.1
0.1
O.I
1.1
O.I
FE
0.7
1.0
1.2
0.5
0
0
120
0.1
0.1
O.I
0.6
O.I
PE
0.3
1.3
1.8
0.7
1.1
1.5
146
O.I
0.1
O.I
1.7
O.I
DS/ave
0.4
1.8
2.3
0.9
0
1.2
124
0.1
0.1
O.I
1.3
O.I
SDS/max
0.3
1.3
1.8
1.4
0
2.5
148
0.1
0.1
O.I
1.8
O.I
aOEl= Raw-water ozone contactor effluent, Comb FE = combined filter effluent, PE = plant effluent
bFE = Filter effluent, PE = plant effluent
179
-------
Table 15. DBF results at plant 5 (2/26/01)
2/26/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA51
HAA9J
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
MRL"
Mg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
0.20
0.48
0.51
0.56
0.54
0.06
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
Plant 5C
Raw
NDC
ND
ND
ND
0.1
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC/Sand Inf
ND
ND
ND
ND
ND
NRe
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAG Inf
0.1
ND
ND
ND
0.1
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
Plant Eff
ND
ND
ND
ND
3
8
6
0.6
18
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
9.8
5.0
1.2
4.8
4.8
2.2
ND
16
28
16
12
0.1
ND
1
0.8
ND
ND
0.7
0.4
3
ND
DS/Ave
ND
ND
ND
ND
17
12
7
1
37
0.3
ND
ND
ND
ND
ND
ND
ND
4.9
1.1
16
9.2
2.8
13
10
3.4
ND
38
60
28
26
0.2
ND
1
0.8
ND
ND
0.5
0.3
5
ND
DS/Max
15
12
7
ND
34
NR
NR
NR
ND
ND
ND
ND
0.2
ND
1
0.8
ND
ND
0.5
0.2
5
ND
SDS/Ave
ND
ND
ND
ND
34
16
6
0.6
57
0.3
ND
ND
ND
ND
ND
ND
ND
5.4
ND
20
7.4
1.5
8.5
5.1
1.9
ND
35
50
29
16
0.3
ND
2
1
ND
ND
0.7
0.2
9
ND
SDS/Max
41
14
5
ND
60
NR
NR
NR
ND
ND
ND
ND
0.3
ND
2
0.8
ND
ND
0.5
0.1
10
ND
180
-------
Table 15 (continued)
2/26/2001
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1 ,3-Dibromopropanone
1,1,1 -Trichloropropanoned
1,1,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1,1,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrina
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.12
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 5C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC/Sand Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAG Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
ND
0.5
ND
ND
ND
3
0.1
<39
ND
ND
ND
<1
ND
ND
<1
<3
0.2
0.2
ND
ND
ND
DS/Ave
ND
0.2
ND
ND
ND
4
ND
<1h
ND
ND
ND
<1
ND
ND
<3
3
0.2
1
ND
ND
ND
DS/Max
ND
0.2
ND
4
ND
ND
ND
ND
0.2
0.9
ND
SDS/Ave
ND
0.3
ND
ND
ND
8
ND
<1
ND
ND
ND
<1
ND
ND
<1
<3
0.1
0.9
ND
ND
ND
SDS/Max
ND
0.2
ND
6
ND
ND
ND
ND
0.1
1
ND
181
-------
Table 16. DBF results at plant 6 (2/26/01)
2/26/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochlorom ethane
Dibromomethane
Chloroform0
Bromodichloromethane'1
Dibromochloromethane
Bromoform0
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid"
Monobromoacetic acid
Dichloroacetic acid"
Bromochloroacetic acid0
Dibromoacetic acid
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA51
HAA9'
DXAAk
TXAA1
Haloacetonit riles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile'1
Trichloroacetonitriled
Haloacetaldehydes
Dichloroacetaldehyde
Brom ochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
MRL"
|jg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
0.20
0.48
0.51
0.56
0.54
0.06
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.16
0.1
0.1
0.1
Plant 6"
Raw
NDC
ND
ND
ND
0.1
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.1
<0.1
ND
Settled
0.2
0.1
ND
ND
0.3
NRe
NR
NR
ND
ND
ND
ND
ND
ND
10
1.8
ND
ND
ND
ND
ND
10
12
12
ND
ND
ND
0.1
ND
ND
ND
0.3
0.2
0.1
ND
Filter Eff
ND
ND
ND
ND
1
0.8
0.2
ND
2
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
3.2
ND
2.4
ND
ND
ND
16
20
17
2.4
ND
ND
0.2
0.1
ND
ND
0.5
0.3
0.4
ND
Clean/veil Eff
1
2
0.6
ND
4
NR
NR
NR
ND
ND
ND
ND
2.0
1.2
17
4.5
ND
4.7
1.5
ND
ND
25
31
22
6.2
ND
ND
0.5
0.2
ND
ND
1
0.3
0.5
ND
Plant Eff
ND
ND
ND
ND
2
2
0.4
ND
4
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
16
4.3
ND
3.8
1.3
ND
ND
20
25
20
5.1
ND
ND
0.3
0.1
ND
ND
0.8
0.4
0.4
ND
DS/Ave
ND
ND
ND
ND
5
5
1
ND
11
0.4
ND
ND
ND
ND
ND
ND
ND
2.8
1.2
22
7.1
1.0
5.7
2.0
ND
ND
33
42
30
7.7
ND
ND
0.9
0.3
ND
ND
1
0.5
1
ND
DS/Max
1
4
1
ND
6
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.6
0.3
ND
ND
1
0.8
0.5
ND
S DS/Ave
ND
ND
ND
ND
2
3
0.6
ND
6
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
18
4.1
ND
3.1
ND
ND
ND
21
25
22
3.1
ND
ND
0.6
0.2
ND
ND
1
0.5
0.6
ND
SDS/Max
2
3
0.6
ND
6
NR
NR
NR
ND
ND
ND
ND
ND
ND
0.7
0.2
ND
ND
2
0.5
0.6
ND
182
-------
Table 16 (continued)
2/26/2001
Compound
Haloketones
Chloropropanone
1 ,1-Dichloropropanoned
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,3-Dibromopropanone
1 ,1 ,1-Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.5
0.11
0.10
3
3
0.10
0.11
3
3
3
0.12
3
0.12
0.1
3
3
0.12
0.1
1.90
0.16
2
Plant 6"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Settled
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filter Eff
ND
0.6
ND
ND
ND
0.3
ND
<1h
ND
ND
ND
<1
ND
ND
ND
ND
ND
0.1
ND
ND
ND
Clean/veil Eff
ND
1
ND
0.6
ND
ND
ND
ND
ND
0.3
ND
Plant Eff
ND
0.9
ND
ND
ND
0.4
ND
<1
ND
ND
ND
<1
ND
ND
ND
ND
ND
0.1
ND
ND
ND
DS/Ave
ND
2
ND
ND
ND
0.8
0.2
<1
ND
ND
ND
<1
ND
ND
ND
ND
ND
0.4
ND
ND
ND
DS/Max
ND
1
ND
0.3
ND
ND
ND
ND
ND
0.4
ND
S DS/Ave
ND
1
ND
ND
ND
0.4
ND
<1
ND
ND
ND
<1
ND
ND
ND
ND
ND
0.4
ND
ND
ND
SDS/Max
ND
1
ND
0.4
ND
ND
ND
ND
ND
0.5
ND
183
-------
Table 17. Occurrence of other DBFs" at plants 5 and 6
Compound
Halomethanes
Bromodichloromethane0
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Haloacids
Chloroacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Bromodichloroacetic acid
Trichloroacetic acid
3,3-Dichloropropenoic acid
Trichloropropenoic acid
3,4,4-Trichloro-3-butenoic acid
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Tribromoacetonitrile
Haloaldehvdes
Dichloroacetaldehyde
Trichloroacetaldehyde
2-Bromo-2-methylpropanal
*Iodobutanal
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone
1 -Bromo- 1 -chloropropanone
1,1,1 -Trichloropropanone
1 -Bromo- 1 , 1 -dichloropropanone
1,1, 3 ,3 -Tetrachloropropanone
1,1, 1 ,3 -Tetrachloropropanone
1 -Bromo- 1 ,3 ,3 -trichloropropanone
l,l-Dibromo-3,3-dichloropropanone
Pentachloropropanone
Halonitromethanes
Trichloronitromethane
Miscellaneous Halosenated DBFs
Hexachlorocyclopentadiene
Dichloroacetic acid methyl ester
Non-halosenated DBFs
Glyoxal
Methyl glyoxal
Hexanoic acid
Decanoic acid
Hexadecanoic acid
Plant 6 (2/26/01)
C102
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
.
X
X
X
C1O2 + C12/NH2C1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Plant 5 (10/22/01)
03
X
X
X
X
X
X
X
X
X
.
-
X
X
03 + C12
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
X
X
aDBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique
bCompounds listed in italics were confirmed through the analysis of authentic standards;
haloacids and non-halogenated carboxylic acids identified as their methyl esters.
184
-------
Table 18. DBF results at plant 5 (8/13/01)
8/13/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA51
HAA9J
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
MRLJ
ug/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.5
0.1
0.1
Plant 5C
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2°
1°
2°
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.4°
ND
0.1°
ND
GAG Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Plant Eff
ND
ND
ND
ND
9
11
5
0.5
26
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
18
11
4.2
12
7.9
2.6
ND
34
56
33
23
0.2
ND
2
1
0.8
ND
ND
ND
ND
0.8°
ND
11°
ND
DS/Ave
ND
ND
ND
ND
15
15
6
0.6
37
ND
ND
ND
ND
ND
ND
ND
ND
2.5
ND
21
12
4.2
16
8.6
2.8
ND
44
67
37
27
0.2
ND
2
1
0.9
ND
ND
ND
ND
1°
ND
15°
ND
OS/Max
20
17
6
0.7
44
ND
ND
ND
ND
ND
ND
ND
0.2
ND
2
1
0.7
ND
0.8°
ND
18°
ND
SDS/Ave
ND
ND
ND
ND
12
11
5
0.4
28
ND
ND
ND
ND
ND
ND
ND
ND
7.1
1.2
40
14
4.4
18
1.1
2.0
ND
71
88
58
21
0.3
ND
3
1
0.3
ND
4°
2
17°
ND
SDS/Max
25
18
6
0.5
50
ND
ND
ND
ND
ND
ND
ND
0.3
ND
5
0.8
0.2
ND
ND
ND
ND
1°
ND
26°
ND
Quality control problems with haloacetaldehydes
185
-------
Table 18 (continued)
8/13/2001
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanoned
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
ug/L
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.5
0.10
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
2.0
0.5
0.2
0.1
0.25
Plant 5C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7
0.4
ND
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
GAG Inf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
Plant Eff
ND
0.6
ND
ND
5
ND
ND
ND
ND
ND
ND
ND
ND
0.7
0.2
ND
0.4
0.8
0.8
ND
2
0.3
ND
ND
DS/Ave
ND
0.5
ND
ND
5
ND
ND
ND
ND
ND
ND
ND
ND
0.9
0.2
0.1
0.6
1
0.7
ND
1
0.4
ND
ND
DS/Max
ND
0.2
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
0.8
0.2
ND
0.7
ND
NR
SDS/Ave
ND
0.3
ND
ND
6
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
0.6
3
1
ND
ND
SDS/Max
ND
0.2
ND
ND
5
ND
ND
NRe
NR
ND
ND
ND
0.5
0.1
ND
1
ND
0.8
ND
ND
NR
186
-------
Table 19. DBF results at plant 6 (8/13/01)
8/13/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform
Bromodichloromethane'1
Dibromochloromethaned
Bromoform
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acidd
Dichloroacetic acid"
Bromochloroacetic acidd
Dibromoacetic acid
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA51
HAA91
DXAAk
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
MRLa
^g/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.5
0.1
0.1
Plants"
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2°
0.7°
1°
ND
Settled
0.2
0.1
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.8
1.2
ND
ND
ND
ND
ND
5
6
6
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
ND
ND
ND
10
5
0.9
ND
16
0.8
ND
ND
ND
ND
ND
ND
ND
ND
3.7
29
8.2
ND
20
7.5
ND
ND
53
68
37
28
ND
ND
2
0.3
ND
ND
ND
ND
ND
ND
0.8°
3°
ND
Clean/veil
18
8
2
ND
28
0.5
ND
ND
ND
ND
ND
ND
6.3
ND
38
11
1.2
21
7.9
1.5
ND
67
87
50
35
ND
ND
2
0.5
ND
ND
ND
ND
4°
ND
Plant Eff
ND
ND
ND
ND
17
8
1
ND
26
0.9
ND
ND
ND
ND
ND
ND
ND
6.2
ND
40
11
ND
22
8.0
1.2
ND
68
88
51
31
ND
ND
2
0.5
ND
ND
ND
ND
ND
ND
ND
4°
ND
DS/Ave
ND
ND
ND
ND
14
8
2
ND
24
0.5
ND
ND
ND
ND
ND
ND
ND
5.3
3.5
40
12
1.7
19
8.1
1.3
ND
70
91
54
28
ND
ND
2
0.6
0.2
ND
ND
ND
4°
ND
DS/Max
9
8
2
0.1
19
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
0.7
0.2
ND
ND
ND
3°
ND
S DS/Ave
ND
ND
ND
ND
NRe
6
1
ND
NR
0.5
ND
ND
ND
ND
ND
ND
ND
4.5
ND
48
14
1.9
25
10
1.5
ND
79
105
64
37
ND
ND
3
0.4
0.1
ND
6°
2
10°
ND
SDS/Max
18
11
2
0.1
31
ND
ND
ND
ND
ND
ND
ND
ND
ND
3
0.7
0.1
ND
ND
ND
ND
3°
0.6
6°
ND
Quality control problems with haloacetaldehydes
187
-------
Table 19 (continued)
8/13/2001
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1 -Dibromopropanone
1 ,1,1-Trichloropropanone
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 , 1 , 1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
M9/L
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.5
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
2.0
0.5
0.2
0.1
0.25
Plant 6"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3
0.3
ND
ND
Settled
ND
0.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
Filt Eff
ND
1
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
4
0.3
ND
ND
Clean/veil
ND
0.7
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
NR
Plant Eff
ND
0.9
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
0.2
ND
ND
ND
2
0.5
ND
ND
DS/Ave
ND
2
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
1
ND
ND
ND
DS/Max
ND
1
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.3
ND
NR
S DS/Ave
ND
2
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
0.3
0.5
0.5
ND
ND
SDS/Max
ND
2
ND
ND
0.3
ND
ND
NR
NR
ND
ND
ND
0.1
ND
ND
0.9
ND
ND
ND
ND
NR
188
-------
Table 20. Additional target DBF results (ug/L) at plants 5 and 6 (8/13/01)
8/13/2001
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloro ac etaldehy de
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (ng/L as Cl")
Cyano formaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethyglyoxal
trans -2-Hexenal
Plant 5a
Raw
0
0
0
0
0
0
10.5
<0.1
<0.1
<0.1
<0.4
<0.1
OE1
0
0
0
0
0
0
<0.1
<0.1
<0.1
2.4
GACFE
0
0
0
0
0
0
11.5
<0.1
0.1
0.1
0.8
O.I
PE
0.1
2.1
0.8
0
0
0
284
O.I
O.I
0.1
1.8
O.I
DS/ave
0.2
1.8
1.1
0
0
0
257
O.I
0.1
0.1
1.2
O.I
SDS/max
0.3
5.1
1.5
4.4
0
0
327
O.I
0.1
0.1
1.9
O.I
Plant 6
Raw
0
0
0
0
0
0
12.7
O.I
O.I
0.1
O.4
O.I
Settled
0.3
0.5
0
0
0
0
52.9
0.1
0.1
1.6
O.I
FE
0.2
2.5
0.4
2.5
0
0
203
O.I
O.I
0.1
0.5
O.I
PE
0.1
3.5
0.6
4.7
0
5.6
245
O.I
0.1
0.1
1.2
O.I
DS/ave
0.1
2.8
1.0
4.8
0
4.1
238
O.I
0.1
0.1
1.4
O.I
SDS/max
0.1
4.2
1.2
5.5
0
3.9
241
O.I
0.1
0.1
1.6
O.I
aGAC FE = GAC filter effluent
Table 21. Halogenated furanone results (ug/L) at plants 5 and 6 (8/13/01)
8/13/2001
Compound
MX
ZMX
EMX
Mucochloric acid (ring)
Mucochloric acid (open)
Plant 5
GACFE
O.04
O.04
O.04
O.04
O.04
PE
O.04
O.04
O.04
O.04
O.04
DS/ave
O.04
<0.04
O.04
O.04
O.04
Plant 6
Raw
O.04
O.04
O.04
O.04
O.04
Settled
O.04
O.04
O.04
O.04
O.04
FE
O.04
O.04
0.23
O.04
O.04
PE
0.31
O.04
O.04
O.04
O.04
DS/ave
0.30
O.04
0.12
O.04
O.04
189
-------
Table 22. DBF results at plant 5 (10/22/01)
10/22/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acid
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
MRLd
^g/L
0.2
0.2
0.5
0.5
0.5
0.1
0.1
0.1
0.5
0.5
0.52
0.1-0.5q
0.5
1.0
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.9
1.1
0.5
0.1
0.1
Plants"
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
0.4
ND
1
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC Inf
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
0.4
0.6
Plant Eff
ND
ND
ND
ND
10
19
12
2
43
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.5
4.2
2.5
2.7
3.8
2.0
ND
10
20
11
8.5
0.2
ND
1
1
0.9
ND
ND
ND
ND
1
0.5
3
ND
DS/Ave
ND
ND
ND
ND
34
31
19
2
86
<0.5P
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.9
4.9
2.1
6.4
6.2
2.5
ND
14
28
13
15
0.4
ND
4
2
1
ND
ND
ND
ND
2
0.2
8
ND
DS/Max
NRe
NR
20
1
NR
NR
NR
ND
ND
ND
NR
ND
ND
ND
4
2
0.7
ND
2
1
8
ND
S DS/Ave
ND
ND
ND
ND
58
30
14
2
104
ND
ND
ND
ND
ND
ND
ND
ND
4.1
1.2
28
19
5.2
9.4
8.3
3.0
ND
48
78
52
21
0.4
ND
2
2
1
ND
4
ND
13
ND
SDS/Max
60
30
12
2
104
ND
NR
ND
ND
ND
NR
ND
0.5
ND
3
1
0.6
ND
ND
ND
ND
3
ND
22
ND
190
-------
Table 22 (continued)
10/22/2001
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanone
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1-Trichloropropanoned
1,1 ,3-Trichloropropanone
1-Bromo-1 ,1-dichloropropanone
1,1,1-Tribromopropanone
1,1 ,3-Tribromopropanone
1,1 ,3,3-Tetrachloropropanone
1,1 ,1 ,3-Tetrachloropropanone
1,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1-0.3q
0.1-0.7q
2.5
0.10
0.5-2q
0.1
0.1
0.1
0.10
0.1
0.5
0.5-21"
0.5
0.5
0.2
0.5-2q
0.25
Plants"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
GAC Inf
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
0.2
ND
ND
ND
ND
ND
ND
ND
NR
Plant Eff
ND
0.7
ND
ND
4
ND
0.4
ND
ND
ND
0.1
ND
ND
0.3
0.4
0.6
0.3
ND
ND
2
ND
ND
ND
ND
DS/Ave
ND
0.8
ND
ND
5
ND
ND
ND
ND
ND
ND
ND
ND
1
0.5
0.5
2
ND
ND
2
ND
ND
ND
ND
DS/Max
ND
0.7
ND
ND
4
ND
ND
ND
ND
ND
ND
ND
ND
1
0.5
0.4
2
ND
NR
S DS/Ave
ND
0.5
ND
ND
4
ND
ND
ND
ND
ND
ND
ND
0.1
2
0.3
0.2
1
ND
ND
ND
ND
S DS/Max
ND
0.2
ND
ND
3
ND
ND
ND
ND
NR
ND
ND
0.5
2
0.2
0.1
NR
1
1
ND
ND
NR
p<0.5 = Detected by GC/MS below its MRL of 0.5 |jg/L;
quality assurance problem with gas chromatograph method
qHigher MRL for SDS samples
lower MRL for SDS samples
191
-------
Table 23. DBF results at plant 6 (10/22/01)
10/22/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9'
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
MRLa
ug/L
0.2
0.2
0.5
0.5
0.5
0.1
0.1
0.1
0.5
0.5
0.52
0.1-0.5q
0.5
1.0
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.9
1.1
0.5
0.1
0.1
Plant 6"
Raw
NDC
ND
ND
ND
0.5
0.1
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.4
ND
ND
ND
Settled
0.6
0.2
ND
ND
0.8
0.5
NR
ND
ND
ND
NR
ND
ND
ND
2.8
1.3
ND
ND
ND
ND
ND
2.8
4.1
4.1
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
Filt Eff
ND
ND
ND
ND
13
12
4
0.4
29
3
ND
ND
ND
ND
ND
ND
ND
ND
ND
9.7
4.7
1.6
4.6
3.7
2.2
ND
16
27
16
11
ND
ND
1
0.6
0.2
ND
ND
ND
ND
2
0.4
ND
ND
Clean/veil
NRe
NR
6
0.5
NR
2
NR
ND
ND
ND
NR
ND
2.4
ND
13
6.6
2.2
7.4
4.8
2.3
ND
25
39
22
15
ND
ND
2
0.9
0.3
ND
2
0.5
3
ND
Plant Eff
ND
ND
ND
ND
18
21
7
0.5
47
3
<0.5P
ND
ND
ND
ND
ND
ND
2.2
ND
12
6.3
2.0
6.5
4.5
2.1
ND
23
36
20
13
ND
ND
2
1
0.4
ND
ND
ND
ND
2
0.5
2
ND
DS/Ave
ND
ND
ND
ND
24
24
8
0.5
57
4
<0.5
ND
ND
ND
ND
ND
ND
2.6
ND
14
7.2
2.2
6.9
4.5
2.0
ND
26
39
23
13
0.4
ND
3
1
0.4
ND
2
0.7
3
ND
DS/Max
NR
NR
NR
0.5
NR
NR
NR
ND
ND
ND
NR
ND
ND
ND
NR
NR
NR
ND
8
0.8
2
0.9
S DS/Ave
ND
ND
ND
ND
17
19
8
0.6
45
3
<0.5
ND
ND
ND
ND
ND
ND
3.0
ND
23
11
3.1
10
6.2
2.0
ND
39
58
37
18
0.4
ND
3
1
0.4
ND
12
2
6
ND
SDS/Max
22
26
6
0.8
55
2
NR
ND
ND
ND
NR
ND
ND
ND
4
2
0.7
ND
ND
0.5
ND
12
3
6
1
192
-------
Table 23 (continued)
10/22/2001
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Bromonitrom ethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitrom ethane
Dibromochloronitrom ethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
ug/L
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1-0.3q
0.1-0.7q
2.5
0.10
0.5-2q
0.1
0.1
0.1
0.1
0.1
0.5
0.5-21"
0.5
0.5
0.2
0.5-2q
0.25
Plant 6"
Raw
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
ND
Settled
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
Filt Eff
ND
1
ND
ND
2
ND
0.4
ND
ND
ND
0.1
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
Clearwell
ND
0.9
ND
ND
2
ND
0.5
ND
ND
ND
0.2
ND
ND
ND
ND
ND
0.2
ND
NR
Plant Eff
ND
1
ND
ND
2
ND
0.4
ND
ND
ND
0.1
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
DS/Ave
0.1
2
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
0.4
0.6
ND
ND
ND
DS/Max
0.2
2
ND
ND
NR
ND
ND
ND
ND
ND
0.4
ND
ND
ND
ND
ND
0.5
ND
NR
SDS/Ave
ND
2
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
0.6
ND
ND
ND
ND
SDS/Max
ND
NR
0.1
ND
2
ND
ND
ND
ND
NR
0.5
ND
ND
0.3
ND
ND
0.9
0.8
0.5
ND
ND
NR
193
-------
Table 24. DBF results at plant 5 (4/15/02)
4/15/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9J
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
MRL"
^g/L
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.1
0.5
0.5
0.5
0.1
0.5
2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.96
0.5
0.5
0.1
0.1
Plant 5"
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
NR
ND
ND
0.1
ND
GAC Inf
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
NR
0.5
ND
0.3
0.3
Plant Eff
ND
ND
ND
ND
11
14
7
0.9
33
ND
ND
ND
ND
ND
ND
ND
ND
2.2
ND
12
5.3
1.9
6.9
7.3
2.1
ND
23
38
19
16
0.4
ND
NR
1
0.4
ND
ND
ND
ND
2
0.5
6
ND
DS/Ave
ND
ND
ND
ND
26
17
8
0.9
52
ND
ND
ND
ND
ND
ND
ND
ND
3.6
ND
17
6.3
1.9
11
7.7
2.1
ND
34
50
25
21
0.3
ND
1
1
0.4
ND
ND
ND
ND
2
ND
6
ND
DS/Max
NRe
NR
NR
0.7
NR
ND
NR
ND
ND
ND
ND
NR
0.5
ND
NR
0.8
0.4
NR
3
ND
13
ND
SDS/Ave
ND
ND
ND
ND
49
26
7
1
83
ND
ND
ND
ND
ND
ND
ND
ND
6.2
1.1
26
6.4
2.4
9.2
7.1
2.0
ND
45
60
35
18
0.8
ND
5
2
0.6
ND
4
0.7
22
ND
SDS/Max
NR
NR
NR
1
NR
ND
NR
ND
ND
ND
ND
NR
0.6
ND
NR
1
0.6
NR
ND
ND
ND
4
0.6
18
ND
194
-------
Table 24 (continued)
4/15/2002
Compound
Haloketones
Chloropropanone
1 , 1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanoned
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
ug/L
0.1
1.0
0.1
0.5
0.5
0.1
0.3
>5
0.1
0.1
0.1
0.5
0.2
0.1
0.1
0.1
0.1
0.1
0.5
2
0.5
0.5
0.2
0.5
0.25
Plant 5C
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
ND
GAC/Sand
ND
ND
ND
ND
ND
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
GAG Inf
ND
ND
ND
ND
ND
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
Plant Eff
ND
<1S
ND
ND
4
ND
0.4
ND
ND
ND
ND
ND
0.6
ND
0.4
ND
ND
1
ND
ND
ND
0.8
ND
ND
ND
DS/Ave
ND
1
ND
ND
8
ND
0.4
ND
ND
ND
ND
ND
2
ND
0.5
ND
ND
1
ND
ND
ND
0.7
ND
ND
ND
DS/Max
ND
NR
ND
ND
NR
ND
NR
NR
ND
ND
ND
ND
ND
0.7
ND
ND
3
ND
NR
SDS/Ave
ND
ND
ND
ND
13
ND
ND
ND
ND
ND
ND
ND
ND
0.7
0.3
ND
3
0.7
ND
ND
ND
SDS/Max
ND
NR
ND
ND
NR
ND
NR
NR
ND
ND
ND
ND
ND
0.3
ND
ND
3
ND
ND
ND
ND
NR
<1 = Detected by GC/MS below its MRL of 1.0 ug/L;
quality assurance problem with gas chromatograph method
195
-------
Table 25. DBF results at plant 6 (4/15/02)
4/15/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetra chloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5'
HAA9'
DXAAk
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
MRLa
ug/L
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.1
0.5
0.5
0.5
0.1
0.5
2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.96
0.5
0.5
0.1
0.1
Plant 6"
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
Settled
ND
0.4
ND
ND
0.4
ND
NR
ND
ND
ND
ND
NR
ND
ND
5.2
ND
ND
ND
ND
ND
ND
5.2
5.2
5.2
ND
ND
ND
NR
ND
ND
NR
0.5
ND
0.2
ND
Filt Eff
ND
ND
ND
ND
8
6
2
0.4
16
1
<1S
ND
ND
ND
ND
ND
ND
2.3
ND
16
5.0
ND
5.0
3.1
1.2
ND
23
33
21
9.3
ND
ND
0.7
0.4
ND
ND
ND
ND
ND
5
1
2
0.9
Clean/veil
NRe
NR
NR
0.4
NR
NR
NR
ND
ND
ND
ND
NR
2.4
ND
21
5.8
1.2
7.0
4.0
3.2
ND
32
45
28
14
ND
ND
NR
ND
0.2
NR
3
0.6
3
ND
Plant Eff
0.2
ND
ND
ND
13
10
3
0.4
26
1
<1
ND
ND
ND
ND
ND
ND
2.5
ND
22
8.3
1.2
6.7
4.0
3.5
ND
32
48
32
14
0.1
ND
1
0.6
0.1
ND
ND
ND
ND
2
ND
2
ND
DS/Ave
ND
ND
ND
ND
19
10
2
0.2
31
1
<1
ND
ND
ND
ND
ND
ND
2.8
ND
27
5.5
ND
8.6
3.4
2.2
ND
38
50
33
14
0.2
ND
1
0.6
<0.5P
ND
4
ND
4
ND
DS/Max
NR
NR
NR
ND
NR
ND
NR
ND
ND
ND
ND
NR
ND
ND
NR
ND
ND
NR
6
ND
4
ND
S DS/Ave
ND
ND
ND
ND
13
11
3
0.4
27
0.7
<1
ND
ND
ND
ND
ND
ND
3.3
ND
27
6.7
1.6
7.2
4.0
1.1
ND
39
51
35
12
0.2
ND
4
0.9
0.2
ND
5
0.7
4
ND
SDS/Max
18
10
3
0.5
32
0.5
ND
ND
ND
ND
ND
ND
0.2
ND
2
1
0.2
ND
ND
ND
ND
6
0.8
4
ND
196
-------
Table 25 (continued)
4/15/2002
Compound
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
M9/L
0.1
1.0
0.1
0.5
0.5
0.1
0.3
>5
0.1
0.1
0.1
0.5
0.2
0.1
0.1
0.1
0.1
0.1
0.5
2
0.5
0.5
0.2
0.5
0.25
Plant 6"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
ND
Settled
ND
NR
ND
ND
ND
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
Filt Eff
ND
2
ND
ND
2
ND
0.6
ND
ND
ND
ND
ND
0.3
ND
0.1
ND
0.1
0.5
ND
ND
ND
ND
ND
ND
ND
Clean/veil
ND
NR
ND
ND
NR
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
NR
Plant Eff
ND
2
ND
ND
2
ND
<1
ND
ND
ND
ND
ND
0.8
ND
0.1
ND
ND
0.8
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
3
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
1
0.6
ND
ND
ND
DS/Max
ND
NR
ND
ND
NR
ND
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
NR
S DS/Ave
ND
2
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
2
ND
ND
ND
ND
SDS/Max
ND
3
ND
ND
0.9
ND
ND
NR
ND
ND
ND
ND
1
ND
0.1
ND
ND
NR
ND
ND
ND
ND
ND
197
-------
Table 26. Additional target DBF results (ug/L) at plants 5 and 6 (4/15/02)
4/15/2002
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Monochloroacetamide
Monobromoacetamide
2,2-Dichloroacetamide
Dibromoacetamide
Trichloroacetamide
TOX (ng/L as Cl")
TOBr (ng/L as Br")
TOC1 (ng/L as Cl")
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethyglyoxal
trans -2-Hexenal
Plant 5
Raw
0
0
0
0
0
0
0
0
0
0
26.0
5.5
26.9
<0.1
<0.1
<0.1
<0.1
<0.1
OE1
0
0
0
0
0
0
0
0
0
0
0.1
<0.1
<0.1
0.8
0.8
Comb FE
0
0
0
0
0
0
0
0
0
0
54.4
10.1
25.8
<0.1
<0.1
<0.1
<0.1
0.4
PE
0.4
2.0
0.4
0.7
0
0
0
0.5
0
0.3
177
41.5
161
0.1
O.I
O.I
0.4
0.1
DS/max
0.5
2.0
0.4
0.2
0
0
0
0.2
0.1
0.1
259
36.0
194
0.1
O.I
O.I
0.2
0.1
SDS/max
0.6
2.8
0.6
0.4
0
0
0
0.5
0
0
247
51.0
220
O.I
O.I
O.I
0.3
0.1
Plant 6
Raw
0
0
0
0
0
0
0
0
0
0
29.7
11.9
17.3
0.1
O.I
O.I
0.1
0.1
Settled
0.7
1.0
0
0
0
0
0
0
0
0
90.2
33.2
76.3
0.1
O.I
O.I
0.1
0.2
FE
1.6
2.3
0.5
0
0
0
0
0.8
0.1
0.2
154
25.9
152
0.1
O.I
O.I
0.5
0.1
PE
1.4
2.8
0.5
0
0
0.2
0
2.7
0.2
1.1
210
0.1
O.I
O.I
0.1
0.1
DS/max
2.1
4.9
0.4
0
0
0.8
0
7.6
0
2.2
243
19.2
229
0.1
O.I
O.I
0.1
0.1
SDS/max
1.7
3.9
0.7
0
0
0.3
0.1
9.4
0.2
4.1
0.1
0.4
O.I
0.1
0.5
Table 27. Halogenated furanone results (ug/L) at plants 5 and 6 (4/15/02)
4/15/2002
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
Red-MX
EMX
ZMX
Ox-MX
Mucochloric acid (ring)
Mucochloric acid (open)
Plant 5
Comb FE
0.02
0.02
0.02
O.02
O.02
O.02
O.02
O.02
0.02
0.02
0.02
0.02
0.02
PE
0.02
0.02
0.02
0.03
O.02
O.02
O.02
O.02 (0.01)
0.02
0.02
0.02
0.02
0.31
DS/max
0.02 (0.012)
0.02
0.02
O.02
O.02
O.02
O.02
O.02
0.02
0.02
0.02
0.02
0.40
SDS/max
0.02
0.02
0.02
O.02
O.02
O.02
O.02
O.02
0.02
0.02
0.02
0.02
0.02
Plant 6
Raw
0.02
0.02
0.02
O.02
O.02
O.02
O.02
O.02
0.02
0.02
0.02
0.02
0.02
Settled
0.02
0.02
0.02
O.02
O.02
O.02
O.02
0.02
0.02
0.02
0.02
0.02
0.02
FE
0.02
0.04
0.02
0.05
O.02
O.02
0.05
0.04
0.02
0.02
0.02
0.02
0.08
PE
0.02
0.02
0.02
O.02
O.02
O.02
O.02
0.58
0.02
0.23
0.02
0.02
0.08
DS/max
0.02
0.02
0.02
0.11
O.02
O.02
0.09
0.28
0.02
0.02
0.02
0.02
0.11
198
-------
Summary of tables for halogenated or
DBF Analyses (Laboratory)
Halogenated organic DBFs (MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
j;anic and other nonhalogenated organic DBFs
1 1/27/00
Tables 12-
13
Table 14
2/26/01
Tables 15-
16
Table IT
8/13/01
Tables 18-
19
Table 20
Table 21
10/22/01
Tables 22-
23
Table 17b
4/15/02
Tables 24-
25
Table 26
Table 27
Tlant 6
bPlant 5
Halomethanes. For the five sample dates, pre-ozonation/post-chlorination at plant 5
resulted in the formation of 18-43 |ig/L of the four regulated trihalomethanes (THM4) in the
plant effluent samples. Chlorine dioxide/chlorine/chloramine disinfection at plant 6 resulted in
the formation of 4-47 |ig/L of THM4.
Figure 6 shows the effect of bromide on THM speciation in the distribution systems of
both utilities. Because of the lower level of bromide in this source water in February 2001 (0.04-
0.05 mg/L), the major THM species were chloroform and bromodichloromethane, whereas in
November 2000 (bromide = 0.08 mg/L), there was a higher mixture of brominated species
formed.
Figure 6
Effect of Bromide on THM Speciation in Plant 5 Distribution System/
Average Detention Time: 11/27/00 Br" = 0.08 mg/L; 2/26/01 Br" = 0.05 mg/L
Effect of Bromide on THM Formation and Speciation in
Plant 6 Distribution System/Average Detention Time:
11/27/00 Br~ = 0.08 mg/L; 2/26/01 Bf = 0.04 mg/L
Figure 7 shows the impact of pre-ozonation/post-chlorination at plant 5 versus chlorine
dioxide/chlorine/chloramine disinfection at plant 6 on THM formation and speciation for the
August 13, 2001 sampling. On this date, both plant effluents had 26 |ig/L THM4. At plant 6,
the major THM formed was chloroform, whereas at plant 5 the major THM formed was
bromodichloromethane. Although both plants treated water with a similar amount of bromide
(0.05-0.06 mg/L), the amount of TOC at the point of chlorination was lower at plant 5 than at
199
-------
Figure 7
Impact of Ozonation/Chlorination at Plant 5 versus Chlorine
Dioxide/Chlorine/Chloramine Disinfection at Plant 6 on
Trihalomethane Formation and Speciation (August 13, 2001)
Plant 5 SDS/Max
Plant 5 Eff
Plant 6 SDS/Max
Plant 6 Eff
plant 6: 2.3-2.8 mg/L in the plant 5 filter effluent versus 4.5-4.7 mg/L in the plant 6 filter
influent and effluent. At plant 5, the ozonation and biofiltration processes provided additional
TOC reduction. As a result, the bromide-to-TOC ratio was higher at plant 5 than at plant 6.
Other research has shown that a higher bromide-to-TOC ratio can result in a shift in speciation to
the more brominated THMs (Symons et al., 1993). In addition, in some waters, pre-ozonation
has been found to shift the THM formation to more brominated species (Jacanglo et al., 1989)
because ozone converts some of the bromide to hypobromous acid.
Because plant 6 used chloramines in the distribution system, the THMs were found to not
increase significantly in concentration in the SDS testing in August 2001 (Figure 7), where the
SDS/maximum sample was held for seven days. Because plant 5 used free chlorine in the
distribution system, the THMs were found to increase in concentration in the SDS testing in
August 2001 (Figure 7), where the SDS/maximum sample was held for seven days. In this plant
5 SDS sample, the major THM was chloroform rather than bromodichloro-methane. The THM
speciation at plant 5 is consistent with the difference in kinetics of halogenation between
hypobromous acid and chlorine; that is, halogenation by hypobromous acid is quicker (Krasner
et al., 1996). Thus, bromodichloromethane formed quicker than chloroform (plant effluent
sample), whereas more of chloroform formed while the SDS sample was held for seven days.
Figure 8 shows more fully the effect of reaction time on THM formation in the SDS
testing conducted on February 26, 2001. The concentration of chloroform increased over time,
200
-------
Figure 8
Effect of Reaction Time on THM Formation in
Plant 5 SDS Testing (2/26/01): Time 0 = Plant Effluent
-Chloroform -••-•Bromodichloromethane
Dibromochloromethane --x--'Bromoform
140
160
the formation of bromodichloromethane plateaued out during the SDS testing, and the amounts
of the more brominated species were at their maximum values in the plant effluent. Again, this
phenomenon was due to the fact that the kinetics of brominated DBF formation are faster than
the kinetics of chlorinated DBF formation (Krasner et al., 1996).
In addition, low levels of certain iodinated THMs (e.g., dichloroiodomethane) were
detected in selected samples, especially at plant 6 (Figure 9). In October 2001, 3 |ig/L of
dichloroiodomethane was detected in the plant 6 effluent, whereas 0.5 |ig/L was detected in the
plant 5 effluent. Bromochloroiodomethane was also detected in the plant 6 effluent in February
2001 using broadscreen GC/MS techniques (Table 17). Waters that contain bromide may also
contain iodide. Iodide is oxidized to hypoiodous acid in the presence of ozone, chlorine, or
chloramines (Bichsel and von Gunten, 2000). Hypoiodous acid can react with the TOC to form
iodinated THMs. Bichsel and von Gunten (2000) found that ozone could also oxidize iodide to
iodate and, depending on ozonation conditions, form little to no iodinated THMs; whereas
chlorine lead to the formation of iodate and iodinated THMs. Although iodate was not measured
in this study, the use of ozone at plant 5 did result in the formation of less iodinated THMs in the
finished water than at plant 6.
Haloacids. Pre-ozonation/post-chlorination at plant 5 resulted in the formation of 10-34
|ig/L of the five regulated haloacetic acids (HAAS) in the plant effluent samples, whereas
chlorine dioxide/chlorine/chloramine disinfection at plant 6 resulted in the formation of 20-68
201
-------
Figure 9
Seasonal Formation of Dichloroiodomethane at
Plant 6 and Plant 5: Plant Effluent Samples
1.0
D)
13-Aug-01
26-Feb-01
0.0-K
27-Nov-OO
Plant 6
Plant 5
|ig/L of HAAS. In addition, all nine HAAs (HAA9) were measured, which includes all of the
brominated HAA species. The levels of HAA9 in the plant 5 effluent were 20-56 |ig/L, whereas
the levels of HAA9 in the plant 6 effluent were 25-88 |ig/L.
Figure 10 shows the effect of bromide on HAA speciation in SDS testing at plant 5 (a
similar effect was observed at plant 6). Because of the lower level of bromide in this water in
February 2001, the two major HAAs were di- and trichloroacetic acid (DCAA and TCAA),
whereas in November 2000 there was a higher mixture of brominated species formed.
Figure 11 shows the effect of the two disinfection schemes on the seasonal formation of
THMs and HAAs in the plant effluents of plant 5 and plant 6. At plant 5, the sum of the
dihalogenated HAAs (DXAAs) was somewhat higher than the sum of the trihalogenated HAAs
(TXAAs) (Figure 11). This is consistent with the research of Reckhow and Singer (1984), in
which ozonation was found to control the formation of TCAA better than that of DCAA.
At plant 6, in the settled water after chlorine dioxide disinfection, almost all of the HAAs
that were formed were DXAAs; no TXAAs were detected (Figure 12). (In addition, the level of
THMs was almost non-detectable at this sample location.) At this point in the treatment process,
only chlorine dioxide disinfection had been utilized. In other DBF research, chlorine dioxide has
been shown to produce little or no THMs and TXAAs, whereas DXAAs were formed (Zhang et
al., 2000). After the addition of free chlorine at plant 6, the levels of HAAs increased, including
the formation of TXAAs (Figure 12). However, DXAAs still predominated in the plant 6
samples (more so than at plant 5) (Figure 11).
202
-------
Figure 10
Effect of Bromide on HAA Speciation in Plant 5 SDS Testing/
Average Detention Time: 11/27/00 Br" = 0.08 mg/L; 2/26/01 Br" = 0.05 mg/L
25
D)
Figure 11
Seasonal Formation of Trihalomethanes and Haloacetic Acids
at Plant 5 and Plant 6: Plant Effluent Samples
60
13-Aug-01
26-Feb-01
27-Nov-OO
203
-------
Figure 12
Effect of Chlorine Dioxide/Chlorine/Chloramine Disinfection at Plant 6
on HAA Formation and Speciation: 2/26/01
HDXAABTXAA
oc
Qn
"5
3 20
3
X 15
m
n -
CIO2 C
i
r
i
2
r
NH
1
2CI
r
Settled
Filter Eff Clearwell Eff Plant Eff
DS/Ave
SDS/Ave
In the presence of chlorine, HAAs were formed in the plant 5 SDS testing (Figure 13).
The SDS/average samples for plant 5 in November 2000 - August 2001 were held for three days.
The increase in formation of the DXAAs was much higher than for the TXAAs, which may be
due (in part) to the ability of ozone to better destroy TXAA precursors. In the presence of
chloramines, HAA concentrations were typically stable within analytical variability in the plant 6
SDS testing (Figure 13). The SDS/average samples for plant 6 in November 2000 - August 2001
were held for four days.
In addition to the target HAAs, other haloacids were detected in selected samples by the
broadscreen GC/MS methods (Table 17). Plant 6—which had 0.04 mg/L bromide in February
2001—produced two other chlorinated acids (i.e., di- and trichloropropenoic acid). These were
detected following the chlorine dioxide disinfection. A different chlorinated acid was detected at
plant 5 after post-chlorination (3,4,4-trichloro-3-butenoic acid).
UNC detected 3,3-dichloropropenoic acid in finished waters from several samplings
(plant 5 and plant 6, November 2000; plant 6, August 2001; and plant 5, April 2002). Levels
ranged from 0.7 to 4.7 |ig/L in the finished waters, and generally increased in concentration in
the distribution system.
Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be
produced at approximately one-tenth the level of the THMs (Oliver, 1983). This was also
generally observed in the plant 5 and plant 6 samples (Figure 14). Trichloroacetonitrile
(TCAN)—an Information Collection Rule (ICR) DBF—was not detected. Likewise, the
204
-------
Figure 13
Impact of Residual Disinfectant on Formation of Haloacetic Acids in
Simulated Distribution System Samples with Average Detention Time:
Chlorine at Plant 5, Chloramines at Plant 6
20%
Plant 5
TXAAs
Plant 5
DXAAs
27-Nov-OO
26-Feb-01
13-Aug-01
Plant 6
TXAAs
Plant 6
DXAAs
'Negative value = decrease in concentration rather than an increase
Figure 14
Relationship of the Sum of HANs (up to 6 Species) to THM4
at Plant 5 and Plant 6
• Filter Eff • Clear. Eff • Plant Eff • DS/Ave • DS/Max • SDS/Ave • SDS/Max
D)
'
-------
brominated analogues of TCAN were not detected in the plant 5 samples. However, at plant 6,
dibromochloroacetonitrile was detected in an SDS sample in October 2001 and
tribromoacetonitrile was detected in February 2001 by the broadscreen GC/MS methods (Table
17). In addition, sub-|ig/L levels of another target HAN (i.e., chloroacetonitrile) were detected in
selected samples at both utilities.
Haloketones. The level of 1,1,1-trichloropropanone (1,1,1-TCP)—which is a precursor
to chloroform formation—was higher at plant 5 (Figure 15). More of this haloketone (HK)
formed with free chlorine than with chloramines. The level of 1,1-dichloropropanone (1,1-DCP)
was typically higher at plant 6 (Figure 15). The latter compound was often detected in the settled
water after chlorine dioxide disinfection. Thus, at plant 6, chlorine dioxide and chloramines
were found to be better at controlling the formation of 1,1,1-TCP (and THMs and TXAAs) than
the formation of 1,1-DCP (and DXAAs).
Figure 15
Effect of Ozone/Chlorine Disinfection at Plant 5 and
Chlorine Dioxide/Chlorine/Chloramine Disinfection at Plant 6
on the Formation of Haloketones
• Settled • Filter Eff • Clear. Eff • Plant Eff BDS/Ave DOS/Max HSDS/Ave USDs/Max
1,1-DCP 1,1,1-TCP
Plant 6 (11/27/00)
1,1-DCP 1,1,1-TCP
Plant 6 (2/26/01)
1,1-DCP 1,1,1-TCP
Plant 5 (11/27/00)
1,1-DCP 1,1,1-TCP
Plant 5 (2/26/01)
In addition to the formation of low levels of HK compounds from the ICR (i.e., 1,1-DCP
and 1,1,1-TCP), low levels of some of the target HKs were detected in selected samples. In
addition to the target HKs, other HKs were detected in selected samples by the broadscreen
GC/MS methods (Table 17). A number of these HKs were analogous to the di- and
tetrahalogenated target HKs, except that these were mixed bromochloro species.
Haloaldehydes. In addition to the formation of chloral hydrate (trichloroacetaldehyde)—
an ICR DBF—dichloroacetaldehyde was formed. The level of chloral hydrate was higher at
plant 5. More of this DBF formed with free chlorine than with chloramines. On the other hand,
206
-------
dichloroacetaldehyde was often higher in concentration at plant 6. In addition, brominated
analogues of both of these haloacetaldehydes were detected in selected samples.
In addition to the target haloaldehydes, two other haloaldehydes were detected in selected
samples by the broadscreen GC/MS methods (Table 17). Another brominated aldehyde
(2-bromo-2-methylpropanal) and an iodinated aldehyde were detected (tentatively identified as
iodobutanal). This is the first report of an iodoaldehyde as a DBF in drinking water. High
resolution mass spectrometry confirmed the presence of the iodine in the structure of this
molecule, and also its overall empirical formula (C^yOI, molecular weight of 198). At this
point, the identification is tentative, however—it is highly likely that the molecule is an iodo-
aldehyde with four carbons, but the exact isomer assignment cannot be determined by its mass
spectrum. An attempt to obtain synthetic standards of iodobutanal forms is currently underway
in order to obtain a confirmed assignment.
Halonitromethanes. Low levels of chloropicrin (trichloronitromethane) (an ICR DBF)
were detected. Other halonitromethanes (HNMs) were detected in selected samples. The levels
of chloropicrin and the bromine-containing trihalonitromethanes were higher at plant 5
(Figure 16). Other research has shown that pre-ozonation can increase the formation of
chloropicrin upon post-chlorination (Hoigne and Bader, 1988). Similar to the THM speciation in
the plant effluent samples in August 2001 (Figure 7), in terms of the trihalonitromethanes, mixed
bromochloro species predominated at plant 5, whereas the trichloro species was the only
trihalonitromethane detected at plant 6 on that sample date (Figure 16).
Figure 16
Impact of Ozonation/Chlorination at Plant 5 versus
Chlorine Dioxide/Chlorine/Chloramine Disinfection at
Plant 6: Plant Effluents (August 13, 2001)
1.0-r
<
207
-------
The relative speciation of brominated and chlorinated HNMs (for the di- and
trihalogenated species) was compared to the HAAs, THMs, and the dihaloacetonitriles (DHANs)
for the August 2001 data. Each DBF can be abbreviated based on the number of halogens and
the speciation of the halogens as follows: RBryClz, where the number of bromine and chlorine
atoms are y and z, respectively, and R corresponds to the remainder of the DBF molecule (i.e.,
carbon, hydrogen, oxygen, and nitrogen atoms). The concentration of each DBF was
"normalized" by dividing its concentration by the sum of the concentrations of all of the DBFs
for that "subclass" of DBFs (RXy+z) (Figure 17). For example, the concentration of DCAA was
divided by the sum of all the DXAAs.
Figure 17. Plant 5 effluent (August 13, 2001)
Relative Speciation of Brominated and Chlorinated DBFs:
Halonitromethanes (HNMs), Haloacetic Acids (HAAs),
Dihaloacetonitriles (DHANs), Trihalomethanes (THMs)
DHAN/THM
HAA
HNM
For the dihalogenated DBFs (RX2), the dichlorinated species represented 53 to 78 % of
the sum of the dihalogenated DBFs in that class of DBFs. The bromochloro species represented
22 to 33 % of the class sum, and the dibromo species represented 0 to 21 % of the class sum. For
the trihalogenated DBFs (RX3), the trichlorinated, bromodichlorinated, dibromochlorinated, and
tribrominated species represented 20 to 53 %, 35 to 43 %, 12 to 40 %, and 0 to 2 % of the class
sum, respectively. For the TFDVIs, HAAs, DHANs, and HNMs, there was a similar relative
speciation of brominated and chlorinated DBFs for the dihalogenated species and a similar
relative speciation of brominated and chlorinated DBFs for the trihalogenated species.
Halogenatedfuranones. Tables 21 and 27 show the results for halogenated furanones in
the August 2001 and April 2002 samplings for plant 5 and plant 6. Data are included for 3-
chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3-
208
-------
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); the reduced
form of MX (Red-MX); brominated forms of MX and EMX (BMXs and BEMXs); and
mucochloric acid (MCA), which can be found as a closed ring or in an open form. Results are
displayed graphically in Figures 18 and 19.
The combination of ozonation and biofiltration (with GAC filters) removed MX and MX-
analogue precursors in plant 5, whereas chlorine dioxide pretreatment at plant 6 did not. At plant
6, intermediate chlorination and chloramine post-disinfection produced MX and MX-analogues
(Tables 21 and 27). In August 2001, MX was not detected at the plant 6 filter effluent, whereas
it was detected in the plant 6 effluent (310 ng/L) (Figure 18). Alternatively, EMX was detected
at the plant 6 filter effluent (230 ng/L), but it was not detected in the plant effluent. EMX is the
open ring analogue of MX, and these two halogenated furanones are in equilibrium with each
other. It appears as if EMX may have been converted to MX between the plant 6 filter effluent
and the plant effluent.
In the second sampling of plants 5 and 6 (4/15/02) for halogenated furanones, brominated
MX-analogues were also measured, but did not appear, except in low concentrations (up to 50
ng/L) (Figure 19), within plant 6 due to the low concentration of bromide (0.06 mg/L) in the
source water. The reduced form of MX (red-MX) increased in concentration from the filter
effluent (40 ng/L) to the plant effluent (580 ng/L) at plant 6 due to residual chloramines (3.2
mg/L) reaction with TOC (3.88 mg/L). Mucochloric acid (MCA open) was detected in the plant
effluent (310 ng/L) of plant 5 due to the filter effluent chlorine (2.5 mg/L dose) and clearwell
effluent chlorine (1.02 mg/L dose) reacting with the TOC (-3.5 mg/L) of the combined filter
effluent.
Figure 18
Plants 5 and 6 (8/13/01)
I MX • ZMX • EMX DMCA (ring) DMCA (open)
0.45
0.40
ro o
0.15
0.10
0.05
0.00
GACFE
O3+GAC
PE DS/ave
CI2
Plant 5
Raw
Settled
CIO2
PE DS/ave
CI2+NH3
Sampling Point
209
-------
Figure 19
Plants 5 and 6 (4/15/02)
• BMX-1 HBEMX-1
• Red-MX BEMX
1 nn
I .UU
n Qn
.•. n on
0) ^», U.oU
C _J
2 O) n yn
5 -
3 w n Rn
il c u-bu
_ o
^s n ^n
3> re U'5U
ro £ n An
C U.4U
0) 0)
O) O „
O^ n ^n
^ U.OU
75 0
I O n on
n m
Onn
.uu
i 1
Comb FE
O3+GAC
• BMX-2 DBEMX-2 HBMX-3 DBEMX-3 BMX
• ZMX DOx-MX HIVICA (ring) IIMCA (open)
PE
Pla
DS/max
CI2
nt5
S DS/max
Raw
1=1
Settled
CIO2
_| 1_
-ft
FE
CI2+Filter
Plant 6
PE
CI2+
-U-
I I
DS/max
NH3
Sampling Points
210
-------
Volatile Organic Compounds. Methyl ethyl ketone (MEK) was detected in the raw water
of both plants on August 13, 2001 at concentrations of 3-7 |ig/L. The level of MEK decreased
through the treatment plant and in the distribution system. MEK was detected in the raw water
on October 22, 2001 and April 15, 2002 at 0.6-0.7 |ig/L and in other selected samples at similar
concentrations. Methyl tertiary butyl ether (MtBE) was detected in the raw water of both plants
on August 13, 2001 at a concentration of 0.3-0.4 |ig/L. The level of MtBE was unchanged
through the treatment plant. MEK is an industrial solvent and MtBE is a gasoline additive.
Other HalogenatedDBFs. A few additional, miscellaneous halogenated DBFs were also
detected. UNC methods detected dichloroacetamide at 1.5, 5.6, and 2.7 |ig/L in finished water
from plant 6 (11/27/00, 8/13/01, and 4/15/02) (Tables 14, 20, and 26). Dichloroacetamide was
also observed in finished water from plant 5 at 0.5 |ig/L in April 2002 (Table 26). Levels either
increased or remained fairly steady in the distribution system and in SDS testing. Also, four
additional haloamides— monochloroacetamide, monobromoacetamide, dibromoacetamide, and
trichloroacetamide—were found in finished water samples collected in April 2002 from both
plants (Table 26). Bromochloromethylacetate was observed in November 2000 in finished
waters from plant 6(1.1 |ig/L), but was not detected in the distribution system or SDS testing
(Table 14), presumably due to degradation.
Broadscreen GC/MS analyses revealed the presence of hexachlorocyclopentadiene and
dichloroacetic acid methyl ester in finished water collected from plant 6 in February 2001 (Table
17). These compounds were not observed in the corresponding raw, untreated water.
Non-HalogenatedDBFs. A few non-halogenated DBFs were detected in finished waters
from plant 5 and plant 6. Dimethylglyoxal was identified at 2.1 and 1.7 |ig/L in finished waters
from plant 5 and plant 6, respectively (November 2000, Table 14). It was also found in later
samplings from both plants (Tables 20 and 26), and it did not appear to degrade in the
distribution system, Thms^-hexenal was also identified in waters from two samplings (Tables
14 and 26) and appears to be formed both by ozonation and treatment with chlorine dioxide.
However, it does not appear to be stable; levels were diminished at the plant effluent.
Broadscreen GC/MS analysis revealed the presence of glyoxal and methyl glyoxal in
both the ozone effluent and the finished water from plant 5 (Table 17). Also, decanoic acid and
hexadecanoic acid were found in finished waters from plant 6 at levels significantly higher than
in the raw, untreated water (Table 17).
REFERENCES
Aieta, E. M., and J. D. Berg. A review of chlorine dioxide in drinking water treatment. Journal
of the American Water Works Association 78(6):62 (1986).
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
211
-------
Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomethanes during disinfection and
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784
(2000).
Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992).
Delcomyn, C. A., H. S. Weinberg, and P. C. Singer. Measurement of sub-|ig/L levels of bromate
in chlorinated drinking waters. Proceedings of the American Water Works Association Water
Quality Technology Conference, American Water Works Association: Denver, CO, 2000.
Douville, C. J., and G. L. Amy. Influence of natural organic matter on bromate formation during
ozonation of low-bromide drinking waters: a multi-level assessment of bromate. In Natural
Organic Matter and Disinfection By-Products: Characterization and Control in Drinking Water
(S.E. Barrett, S.W. Krasner, & G.L. Amy, eds.), pp. 282-298, American Chemical Society:
Washington, D.C., 2000.
Hoigne, J., and H. Bader. The formation of trichloronitromethane (chloropicrin) and chloroform
in a combined ozonation/chlorination treatment of drinking water. Water Research 22(3):313
(1988).
Krasner, S. W., W. H. Glaze, H. S. Weinberg, P. A. Daniel, and I. N. Najm. Formation and
control of bromate during ozonati on of waters containing bromide. Journal of the American
Water Works Association 85(1):73 (1993).
Krasner, S. W., M. J. Sclimenti, R. Chinn, Z. K. Chowdhury, and D. M. Owen. The impact of
TOC and bromide on chlorination by-product formation. In Disinfection By-Products in Water
Treatment: The Chemistry of Their Formation and Control (R. A. Minear and G.L. Amy, eds.),
pp. 59-90, CRC Press/Lewis Publishers: Boca Raton, FL, 1996.
Kuo, C.-Y., H.-C. Wang, S. W. Krasner, and M. K. Davis. lon-chromatographic determination
of three short-chain carboxylic acids in ozonated drinking water. In Water Disinfection and
Natural Organic Matter: Characterization and Control (R. A. Minear & G.L. Amy, eds.), pp.
350-365, American Chemical Society: Washington, D.C., 1996.
Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors.
Environmental Science & Technology 17(2):80 (1983).
Reckhow, D. A., and P. C. Singer. The removal of organic halide precursors by preozonation
and alum coagulation. Journal of the American Water Works Association 76(4):151 (1984).
Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water
Works Association 85(1):51(1993).
212
-------
van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily
assimilable organic carbon in drinking water. Journal of the American Water Works Association
74(10):540 (1982).
van der Kooij, D., and W. A. M. Hijnen. Substrate utilization by an oxalate consuming Spirillum
species in relation to its growth in ozonated water. Applied Environmental Microbiology 47:551
(1984).
Volk, C. J., and M. W. LeChevallier. Effects of conventional treatment on AOC and BDOC
levels. Journal of the American Water Works Association 94(6): 112 (2002).
Zhang, X., S. Echigo, R. A. Minear, and M. J. Plewa. Characterization and comparison of
disinfection by-products of four maj or disinfectants. In Natural Organic Matter and
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W.
Krasner, and G. L. Amy, eds.), pp. 299-314, American Chemical Society: Washington, D.C.,
2000.
213
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EPA REGION 3: PLANTS 3 AND 4
Plant Operations and Sampling
On November 13, 2000, February 5, 2001, August 1, 2001, October 16, 2001, and
January 28, 2002, plants 3 and 4 (EPA Region 3) were sampled. Plants 3 and 4 operated in
parallel on a common source water (Figures 1-2).
The treatment processes at plant 3 (Figure 3) included flocculation, coagulation,
sedimentation, and filtration. The settled water was first filtered through a multimedia filter and
then through a granular activated carbon (GAC) filter. The raw water was disinfected with free
chlorine. In November 2000, August 2001, and October 2001, ammonia was added to convert
the chlorine to chloramines after a 30-sec or 1-min chlorine contact time, whereas ammonia was
not added until the plant effluent in February 2001. (Information on the disinfection scheme for
January 2002 is not available.) After the GAC and at the plant effluent, additional chlorine was
added. In addition, in August and October 2001, chlorine was applied at the end of the
sedimentation basin.
The treatment processes at plant 4 (Figures 1-2) included flocculation, coagulation,
sedimentation, and filtration. The settled water was filtered through a GAC filter. Chlorine was
applied to the raw and filtered waters and at the plant effluent. Chloramines were not used at
plant 4.
Plant 3 was sampled at the following locations (Figure 3):
(1) raw water
(2) the rapid mix effluent (prior to ammonia addition)
(3) the GAC influent
(4) the GAC effluent
(5) the plant effluent
Plant 4 was sampled at the following locations:
(1) GAC influent
(2) GAC effluent
(3) the plant effluent
In addition, plant effluent samples were collected for both plants, and simulated distribution
system (SDS) testing was conducted for average and maximum detention times for that time of
year (Table 1). Furthermore, the distribution systems for both plants were sampled at two
locations, one representing an average detention time and the other representing a maximum
detention time. (Raw water was not sampled at plant 4, as it is the same as is used at plant 3.)
214
-------
Chlorine & Polymer
Aluminum Sulfate
i
(Aqua Ammonia)
36 * Raw"WatVr"iriV *
3 Stage
Flocculation
Jewel
Sedimentation
Basin
Plant 4 Plant 4 Tank
Distribution Q.75 M.G.
Ammonia (Anhydrous)
Zinc Orthophosphate
,FIUOride_(Hyrdofluosilicic Acid)
CaUStiC Soda (Sodium Hydroxide)
Caustic |
I
•r
\
Wood Tub Filter Bldg.
1
^^^— Chlorine
1
f
Soda >w
(p"°'4) |^«Rum
•
Ch — 7-^
t ^
1
X i '
36" Raw Water Line
Plant 4
Clearwell
2 M.G.
¥
To
Plant 3
Distribution
• Raw Water
— Raw Water with Chemicals Added
• - Settled Water
— Finished Water
Figure 1. Chemical application points at plants 3 and 4.
Rapid Mix
Effluent
3 Stage
Flocculation
Jewel
Sedimentation
Basin
Plant 4 - GAC Influent
(Applied Settled Water)
Plant 4 - Distribution
t(Max & Average)
/\ Plant 4 Tank
i ( ) 0.75 M.G.
Plant 4 \^^y
Effluent ^™-'
Wood Tub Filter Bldg.
K
n—f^._.
I Plant 4 - f I |—
j GAC Effluent T° j
I (Wood Tub Filtered Water) ^^ \
r 1
36" Raw Water Line
Plant 4
Clearwell
2 M.G.
i
i
Plant 3
Effluent
Plant 3
Plant 3
GAC Influent
(Multi-media filtered)
Plant 3
Distribution
(Max & Average)
j GAC Effluent |
I (GAC Pressure Filters) .
* 1 '
Raw Water
— — — — - Raw Water with Chemicals Added
Settled Water
^— • ^— • Finished Water
Figure 2. Sampling points at plants 3 and 4.
215
-------
fi-
River Pump Station
2-Stagc Rapid Mix
Basin
"Raw Water Sample"
"Plant 3 Effluent"
Polymer_
Chlorine .
Basin
(Aqua Ammonia)
'Plant 3 GAC - Influent"
H ^
J
ncculation
(Chlorine) ^
)
(
Multi - Media Filters
Chlorine _
Sodium Hydroxide
Fluoride -
Zinc Orthophosphate
Distribution
Storage
High Service
Pump Station
"Plant 3 GAC - Effluent"
Figure 3. Simplified line diagram of chemical application and sampling points at plant 3.
Table 1. SDS holding times (hr) at plants 3 and 4
Sample
Plant 3 average detention time
Plant 3 maximum detention time
Plant 4 average detention time
Plant 4 maximum detention time
11/13/00
20
28
20
28
2/5/01
18
48
20
30
8/1/01
18
48
8
24
10/16/01
77
140
77
140
1/28/02
NAa
NA
NA
NA
aNA = Not available
On the day of sampling, information was collected on the operations at each plant
(Tables 2-3). In February 2001, several of the plant 4 filters had been removed from service. In
order to maintain filtered water quality on the plant 4 side, plant 3 carbon contactor filtered
(CCF) water was added to the plant 4 suction (clearwell). Thus, 6.0 million gallons per day
(mgd) of plant 3 CCF water was added to the plant 4 side. This resulted in 35 % of the plant 4
water being plant 3 CCF water. This affected the results of the plant 4 distribution-system and
SDS samples. Likewise, in August and October 2001, blending occurred at the entrance to the
plant 4 distribution system, which was a combination of plant 4 and "deep bed GAC" filtered
waters (the plant 4 effluent was a combination of water from the plant 3 clearwell and the plant 4
clearwell).
216
-------
Table 2. Operational information at plant 3
Parameter
Plant flow (mgd)
Coagulant21 dose (mg/L)
GAC filter loading rate (gpm/sq ft)
GAC EBCTb (min)
Chlorine dose at rapid mix (mg/L)
Ammonia dose at rapid mix eff. (mg/L as N)
Chlorine dose at end of sed. basin (mg/L)
Chlorine dose at GAC effluent (mg/L)
Chlorine dose at plant effluent (mg/L)
Ammonia dose at plant effluent (mg/L as N)
11/13/00
8
60
6.14
14.9
o o
J.J
0.55
0
1.2
2.05
0.85
2/5/01
10
39
7.7
11.9
5.7
0
0
1.2
2.5
0.90
8/1/01
9
56
6.91
13.3
6.6
0.9
4.0
1.3
2.03
0.82
10/16/01
9
91
6.91
13.3
6.6
0.9
3.0
1.3
2.8
0.94
1/28/02
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
aAluminum sulfate [A12(SO4)3 14H2O]
bEmpty bed contact time
Table 3. Operational information at plant 4
Parameter
Plant flow (before addition of plant 3 GAC
effluent) (mgd)
Flow of plant 3 GAC effluent added to plant
4 (mgd)
Coagulanta dose (mg/L)
GAC filter loading rate (gpm/sq ft)
GAC EBCT (min)
Chlorine dose at rapid mix (mg/L)
Chlorine dose at entrance of plant 4 (filtered
water) clearwell (mg/L)
Chlorine dose at plant effluent (mg/L)
11/13/00
11.8
0
60
1.3
11.5
4.5
NA
0.6
2/5/01
11
6.0
39
1.2
12.9
5.7
NA
0.4
8/1/01
11
4.2
56
1.13
13.3
7.6
1.35
1.2
10/16/01
9.9
4.9
91
1.01
14.8
6.0
1.21
0.9
1/28/02
NA
NA
NA
NA
NA
NA
NA
NA
aAluminum sulfate
Water Quality
On the day of sampling, information was collected on the water quality at each plant
(Tables 4-5). At plant 3, seasonal control of disinfection by-products (DBFs)—especially
trihalomethanes (THMs)—was being achieved using pre-chloramination. During warmer
months (e.g., August, October, November), ammonia was added to convert the chlorine to
chloramines after a 1-min chlorine contact time, whereas ammonia was not added until the plant
effluent during colder months (e.g., February).
217
-------
Table 4. Water quality information at plant 3
Location
Raw
RMb eff.
GAC inf.
GAC eff.
Plant eff.
DSd/ave.
DS/max
SDS/ave.
SDS/max
pH
11/13/00
7.3
6.1
6.2
6.0
7.4
7.5
7.3
7.4
7.5
2/5/01
6.9
5.9
5.5
5.5
7.2
7.2
7.2
7.2
7.2
8/1/01
7.3
6.3
6.0
6.1
7.4
7.4
7.4
7.4
7.4
10/16/01
7.6
6.0
6.0
5.9
7.4
7.4
7.4
7.4
7.4
1/28/02
NA
NA
NA
NA
NA
NA
NA
NA
NA
Temperature (°C)
11/13/00
13.9
13.9
13.9
13.9
13.9
13.9
13.9
13.9
13.9
2/5/01
7
7
9
8
10
9
9
9
9
8/1/01
25.6
25.6
25.6
24.6
25.6
26.4
26.4
24.5
24.5
10/16/01
18.9
18.9
18.1
18.9
19.6
20.2
20.2
20.2
20.2
1/28/02
NA
NA
NA
NA
NA
NA
NA
NA
NA
Disinfectant Residual3 (mg/L)
11/13/00
—
2.2
0.9
0.1
3.2
2.5
2.0
2.5
2.4
2/5/01
—
3.5
0.5
0
3.5
2.6
2.4
2.3
2.0
8/1/01
—
3.2
1.6
NDC
3.1
2.8
2.4
2.8
2.4
10/16/01
—
3.2
1.6
ND
3.8
2.8
2.4
2.4
2.0
1/28/02
NA
NA
NA
NA
NA
NA
NA
NA
NA
al 1/13/00, 8/1/01, 10/16/01: Chlorine residuals (values shown in italics) at rapid mix effluent; chloramine (or total) residuals at other locations
2/5/01: Chlorine residuals (values shown in italics) at rapid mix effluent, GAC influent and effluent; chloramine residuals at other locations
bRM = Rapid mix
CND = Not detected
DS = Distribution system
Table 5. Water quality information at plant 4
Location
GAC inf.
GAC eff.
Plant eff.
DS/ave.
DS/max
SDS/ave.
SDS/max
PH
11/13/00
6.2
6.2
7.2
7.0
6.8
7.1
7.1
2/5/01
5.5
5.5
6.8
6.5
6.5
6.2
6.2
8/1/01
6.1
6.0
6.9
6.9
6.9
6.9
6.9
10/16/01
6.0
6.0
7.2
7.2
7.0
7.0
7.0
1/28/02
NA
NA
NA
NA
NA
NA
NA
Temperature (°C)
11/13/00
13.9
13.9
13.9
13.9
13.9
13.9
13.9
2/5/01
7
7
8
8
9
9
9
8/1/01
25.6
24.5
24.5
25.2
25.2
24.5
24.5
10/16/01
18.9
18.9
19.6
20.2
20.2
20.2
20.2
1/28/02
NA
NA
NA
NA
NA
NA
NA
Chlorine Residual (mg/L)
11/13/00
2.6
0.6
1.1
1.8
1.2
1.4
1.1
2/5/01
1.4
0.8
1.2
1.0
0.5
0.5
0.5
8/1/01
1.5
0.4
1.2
0.8
0.9
0.8
0.8
10/16/01
0.9
0.4
1.2
1.0
0.8
0.7
0.4
1/28/02
NA
NA
NA
NA
NA
NA
NA
218
-------
Data were also collected for total organic carbon (TOC) and ultraviolet (UV) absorbance
(Table 6). The TOC ranged from 4.3 to 6.4 mg/L, and the UV absorbance from 0.090 to 0.187
cm"1. At plants 3 and 4, coagulation removed 30-59 % of the TOC and GAC filtration removed
another 4-23 %. At plant 3, GAC filtration was used to prevent taste-and-odor problems in the
finished water and for the removal of other micropollutants, but it was not installed for DBF
precursor (TOC) removal. The GAC is only regenerated once every three years at plant 3. At
plants 3 and 4, coagulation, GAC filtration, and chlorination cumulatively reduced the UV
absorbance by 67-84 %.
Table 6. TOC and UV removal at plants 3 and 4
Location
11/13/2000
Raw water
Plant 3 GAC inf.
Plant 3 GAC eff.
Plant 4 GAC inf.
Plant 4 GAC eff.
02/05/2001
Raw water
Plant 3 GAC inf.
Plant 3 GAC eff.
Plant 4 GAC inf.
Plant 4 GAC eff.
08/01/2001
Raw water
Plant 3 GAC inf.
Plant 3 GAC eff.
Plant 4 GAC inf.
Plant 4 GAC eff.
10/16/2001
Raw water
Plant 3 GAC inf.
Plant 3 GAC eff.
Plant 4 GAC inf.
Plant 4 GAC eff.
01/28/2002
Raw water
Plant 3 GAC inf.
Plant 3 GAC eff.
Plant 4 GAC inf.
Plant 4 GAC eff.
TOC
(mg/L)
4.37
2.34
2.2
2.47
2.31
6.44
2.63
2.46
2.70
2.59
6.25
2.63
2.02
3.24
2.69
5.9
2.87
2.37
4.13
3.58
4.27
2.40
2.23
2.85
2.45
uva
(cm'1)
0.091
0.041
0.028
0.027
0.029
0.187
0.038
0.033
0.036
0.033
0.14
0.034
0.023
0.03
0.032
0.113
0.036
0.028
0.047
0.037
0.090
0.030
0.029
0.031
0.029
SUVA"
(L/mg-m)
2.08
1.75
1.27
1.09
1.26
2.90
1.44
1.34
1.33
1.27
2.24
1.29
1.14
0.93
1.19
1.92
1.25
1.18
1.14
1.03
2.11
1.25
1.30
1.09
1.18
Removal/Unit (%)
TOC
—
46%
6.0%
43%
6.5%
—
59%
6.5%
58%
4.1%
—
58%
23%
48%
17%
—
51%
17%
30%
13%
—
44%
7.1%
33%
14%
UV
—
55%
32%
70%
-7.4%
—
80%
13%
81%
8.3%
—
76%
32%
79%
-6.7%
—
68%
22%
58%
21%
—
67%
3.3%
66%
6.5%
Removal/Cumulative (%)
TOC
—
46%
50%
43%
47%
—
59%
62%
58%
60%
—
58%
68%
48%
57%
—
51%
60%
30%
39%
—
44%
48%
33%
43%
UV
—
55%
69%
70%
68%
—
80%
82%
81%
82%
—
76%
84%
79%
77%
—
68%
75%
58%
67%
—
67%
68%
66%
68%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm-1)/DOC (mg/L) or UV (m-1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.091/cm = 0.091/(0.01 m) = 9.1/m, DOC = 4.37 mg/L, SUVA = (9.1 m-1)/(4.37 mg/L) = 2.08 L/mg-m)
219
-------
Table 7 shows other water quality parameters for the raw source water for plants 3 and 4.
Note, that source water received a tremendous amount of rainfall the weekend before the August
2001 sampling, which may have diluted some of these water quality parameters.
Table 7. Miscellaneous water quality parameters in plants 3 and 4 raw water
Date
11/13/2000
02/05/2001
08/01/2001
10/16/2001
01/28/2002
Bromide
(mg/L)
0.058
0.022
0.05
0.2
0.023
Alkalinity
(mg/L)
69
27
49
61
38
Ammonia
(mg/L as N)
0.07
0.1
0.08
0.09
0.12
Bromide was lowest in winter (0.02 mg/L) and highest in summer and fall (0.05-
0.2 mg/L). The source water for plants 3 and 4 is a river, with intakes located 1.5 miles upstream
of the confluence with another river. This area is influenced by the tides and is prone to flow
reversal at the intakes. As much as 70 % of the source water can be contributed from the latter
river, especially during low-flow conditions. Tidal influences were the source of bromide and
should also have been a source of iodide.
The source water was relatively low in alkalinity. The addition of coagulant and chlorine
depressed the pH of this low-alkalinity water to 5.5-6.3. Raw-water ammonia ranged from 0.07
to 0.12 mg/L as N.
DBFs
Tables 8-17 show results for the DBFs that were analyzed at the Metropolitan Water
District of Southern California (MWDSC) for sampling periods 11/13/00, 2/5/01, 8/1/01,
10/16/01, and 1/28/02. Tables 18 (2/5/01), 19 (10/16/01), and 20 (10/16/01) show results for
additional target DBFs that were analyzed at the University of North Carolina (UNC), which
include halofuranones. Table 21 shows results from broadscreen DBF analyses conducted at the
U.S. Environmental Protection Agency (USEPA) for sampling periods 11/13/00, 8/1/01, and
1/28/02.
Summary of tables for halogenated organic and other nonhalogenated organic DBFs
DBF Analyses (Laboratory)
Halogenated organic DBFs (MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
11/13/00
Tables 8-9
Table 21
2/5/01
Tables 10-11
Table 18
8/1/01
Tables 12-13
Table 21
10/16/01
Tables 14-15
Table 19
Table 20
1/28/02
Tables 16-17
Table 21
220
-------
Table 8. DBF results at plant 3 (11/13/00)
11/13/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAA1
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Haloketones
Chloropropanone
1 ,1-Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1 -Tri chloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRLa
M9/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.10
0.10
0.50
0.10
0.59
0.53
0.22
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
Plants"
Raw
NDd
ND
ND
ND
0.7
0.7
0.3
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Rapid Mix
5
4
1
0.7
11
NR9
NR
ND
ND
ND
0.7
ND
ND
0.5
0.2
ND
ND
0.2
0.5
ND
1
0.2
0.2
0.1
GAC Inf
ND
ND
ND
ND
7
9
3
0.8
20
2
NR
ND
ND
ND
ND
0.8
ND
ND
12
7.1
1.2
10
3.3
1.2
ND
24
36
21
15
ND
ND
0.9
0.3
ND
ND
0.3
1
ND
ND
1
0.2
<3'
ND
ND
0.2
ND
GACEff
ND
ND
ND
ND
9
9
2
0.4
20
1
NR
ND
ND
ND
ND
0.3
3.2
ND
ND
ND
ND
ND
ND
ND
ND
3.2
3.2
ND
ND
ND
ND
0.2
ND
ND
ND
ND
0.1
ND
ND
0.3
ND
ND
ND
ND
ND
ND
Plant Eff
ND
ND
ND
ND
12
13
5
0.7
31
2
NR
ND
ND
ND
0.5
0.3
ND
ND
6.7
3.0
1.0
6.0
2.6
1.1
ND
14
20
11
9.7
ND
ND
1
0.9
0.3
ND
ND
0.5
ND
ND
0.9
ND
<3
ND
ND
0.2
ND
SDS/Ave
ND
ND
ND
ND
16
17
7
1
41
2
NR
ND
ND
ND
0.6
0.3
4.2
ND
6.9
3.1
1.0
5.6
2.5
1.0
ND
18
24
11
9.1
ND
ND
2
1
0.2
ND
0.3
0.6
ND
ND
1
0.1
ND
ND
ND
0.1
ND
SDS/Max
20
19
8
1
48
NR
NR
ND
ND
ND
0.9
ND
ND
2
1
0.3
ND
0.3
0.6
ND
1
ND
0.1
ND
DS/Ave
ND
ND
ND
ND
14
15
6
0.8
36
2
NR
ND
ND
ND
0.9
0.3
3.9
ND
6.4
3.0
ND
5.6
2.4
1.1
ND
16
22
9.4
9.1
ND
ND
1
0.8
0.2
ND
0.1
0.3
ND
ND
1
ND
<3
ND
ND
0.1
ND
DS/Max
18
19
7
1
45
NR
NR
ND
ND
ND
0.4
ND
ND
2
1
0.2
ND
0.2
0.5
ND
1
ND
0.1
ND
221
-------
Table 8 (continued)
11/13/2000
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde™
Chloral hydrate6'"1
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
Mg/L
0.16
0.20
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 3b
Raw
0.1
ND
ND
ND
ND
ND
ND
ND
1.0
NR
Rapid Mix
0.8
0.8
0.2
ND
ND
ND
NR
GAC Inf
2
4
0.2
ND
ND
ND
0.1
ND
1.0
NR
GAC Eff
0.2
ND
ND
ND
ND
ND
ND
ND
1.0
NR
Plant Eff
0.8
2
ND
ND
ND
ND
ND
ND
1.1
NR
SDS/Ave
1
4
0.1
ND
ND
ND
ND
ND
1.0
NR
SDS/Max
1
4
0.2
ND
ND
0.1
NR
DS/Ave
0.6
2
ND
ND
ND
ND
ND
ND
1.1
NR
DS/Max
2
4
ND
ND
ND
0.2
NR
MRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
"Plant 3 sampled at (1) raw water, (2) effluent of rapid mix, (3) GAC influent and (4) effluent,
(5) plant effluent, (6) SDS testing of plant effluent held for average detention time and (7) held for maximum detention time,
(8) DS at average detention time and (9) at maximum detention time.
°Plant 4 sampled at (1) GAC influent and (2) effluent, (3) plant effluent,
(4) SDS testing of plant effluent held for average detention time and (5) held for maximum detention time,
(6) DS at average detention time and (7) at maximum detention time.
dND = Not detected at or above MRL
eDBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
fTHM4 = Sum of 4THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
9NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance
hHAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid)
'HAA9 = Sum of 9 haloacetic acids
'DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
kTXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
'<3: Concentration less than MRL of 3 |jg/L
mBromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs
222
-------
Table 9. DBF results at plant 4 (11/13/00)
11/13/2000
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAAj
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloketones
Chloropropanone
1 , 1-Dichloropropanone8
1,3-Dichloropropanone
1 , 1-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
MRLa
Mg/L
0.15
0.20
0.14
0.11
0.10
0.10
0.12
0.10
0.10
0.50
0.10
0.59
0.53
0.22
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
3
0.10
0.10
3
3
3
0.10
0.10
Plant 4C
GAG Inf
ND
ND
ND
ND
30
17
5
1
53
1
NR
ND
ND
ND
0.5
0.3
7.7
1.0
24
7.0
1.0
27
11
1.7
ND
61
81
32
40
ND
ND
5
1
0.1
0.2
0.4
1
ND
ND
5
0.3
<3
ND
ND
0.6
0.3
GAG Eff
ND
ND
ND
ND
33
21
6
1
61
1
NR
ND
ND
0.6
0.3
0.4
12
ND
23
6.4
ND
27
11
1.7
ND
61
81
29
40
ND
ND
5
1
0.1
0.2
0.5
1
ND
ND
5
0.3
<3
ND
ND
0.8
0.2
Plant Eff
ND
ND
ND
ND
43
28
7
1
79
1
NR
ND
ND
ND
2
0.8
6.4
ND
27
8.0
1.0
32
13
2.0
ND
66
89
36
46
0.1
ND
5
1
0.2
0.1
0.3
0.9
ND
ND
5
0.2
<3
ND
ND
0.4
0.1
SDS/Ave
ND
ND
ND
ND
56
33
7
0.9
97
1
NR
ND
ND
ND
2
0.7
11
1.5
30
9.4
1.2
34
14
2.3
ND
78
103
41
50
0.1
ND
5
2
0.2
ND
0.2
0.3
ND
ND
6
0.2
<3
ND
ND
0.4
0.3
SDS/Max
61
37
8
0.9
107
NR
NR
ND
ND
ND
2
0.1
ND
6
2
0.2
ND
0.2
0.3
ND
7
0.2
0.4
0.3
DS/Ave
ND
ND
ND
ND
41
24
6
1
72
1
NR
ND
ND
ND
2
0.7
5.1
ND
22
5.9
ND
24
9.7
1.6
ND
52
69
28
36
ND
ND
5
1
0.1
0.1
0.2
1
ND
ND
5
0.4
<3
ND
ND
0.7
0.2
DS/Max
46
27
7
0.9
81
NR
NR
ND
ND
ND
2
0.1
ND
5
1
0.1
0.1
0.3
0.8
ND
5
0.3
0.4
0.2
223
-------
Table 9 (continued)
11/13/2000
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehydem
Chloral hydrate8 m
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin8
Miscellaneous Corrmounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLa
ug/L
0.16
0.20
0.10
0.10
3
0.10
0.10
1.90
0.16
0.50
Plant 4C
GAC Inf
4
12
0.1
ND
ND
ND
0.2
ND
0.8
NR
GACEff
5
13
0.1
ND
ND
ND
0.2
ND
0.8
NR
Plant Eff
3
14
ND
ND
ND
ND
0.2
ND
0.8
NR
SDS/Ave
2
18
ND
ND
ND
ND
0.2
ND
0.9
NR
SDS/Max
3
22
ND
ND
ND
0.3
NR
DS/Ave
3
15
ND
ND
ND
ND
0.2
ND
0.9
NR
DS/Max
3
15
ND
ND
ND
0.2
NR
224
-------
Table 10. DBF results at plant 3 (2/5/01)
02/05/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodom ethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochlorom ethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAA'
TXAA"
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,3-Dibromopropanone
1 ,1 ,1 -Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
ug/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
0.20
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.5
0.11
0.1
N/A"
N/A
0.10
0.10
N/A
N/A
N/A
0.12
N/A
0.58
Plant 3"
Raw
NDd
ND
ND
ND
0.5
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
NR
ND
ND
NR
NR
NR
ND
NR
ND
Rapid Mix
5.5
1.0
ND
ND
6.5
NR9
NR
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
ND
1.1
ND
1.6
0.3
0.4
ND
GAC Inf
ND
ND
ND
ND
15
3.1
0.4
ND
18
0.29
ND
ND
ND
ND
ND
ND
ND
3.6
ND
25
1.7
ND
28
2.4
ND
ND
57
61
27
30
ND
ND
2.4
0.2
ND
ND
ND
0.9
ND
NR
NR
3.1
0.2
NR
NR
NR
0.7
NR
ND
GAC Eff
ND
ND
ND
ND
21
3.7
0.6
0.1
25
0.27
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.2
ND
ND
15
1.3
ND
ND
19
21
4.2
16
ND
ND
1.6
ND
ND
ND
ND
0.5
ND
NR
NR
2.4
0.2
NR
NR
NR
0.5
NR
ND
Plant Eff
ND
ND
ND
ND
27
5.3
0.8
0.1
33
0.30
ND
ND
ND
ND
ND
ND
ND
2.3
ND
11
1.2
ND
19
1.9
ND
ND
32
35
12
21
ND
ND
2.2
0.2
ND
ND
ND
0.6
ND
NR
NR
2.5
0.2
NR
NR
NR
0.4
NR
ND
DS/Ave
ND
ND
ND
ND
33
5.9
0.8
0.3
40
0.31
ND
ND
ND
ND
ND
ND
ND
2.8
ND
12
1.2
ND
21
1.9
ND
ND
36
39
13
23
ND
ND
2.4
0.2
ND
ND
ND
1.0
ND
NR
NR
2.7
0.2
NR
NR
NR
0.6
NR
ND
DS/Max
37
6.0
0.9
0.3
44
NR
NR
ND
ND
ND
ND
ND
ND
ND
2.4
0.2
ND
ND
ND
1.1
ND
2.6
0.2
0.4
ND
SDS/Ave
ND
ND
ND
ND
33
5.8
0.9
0.3
40
0.26
ND
ND
ND
ND
ND
ND
ND
2.6
ND
11
1.2
ND
19
1.8
ND
ND
33
36
12
21
ND
ND
2.4
0.2
ND
ND
ND
1.1
ND
NR
NR
2.4
ND
NR
NR
NR
0.2
NR
ND
SDS/Max
40
6.4
0.9
0.3
48
NR
NR
ND
ND
ND
ND
ND
ND
ND
2.5
0.3
ND
ND
ND
1.2
ND
2.4
0.2
0.4
ND
225
-------
Table 10 (continued)
02/05/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitrom ethane
Chloropicrin6
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL"
ug/L
0.16
0.1
0.1
0.1
0.1
N/A
N/A
0.12
0.1
1.9
0.16
2
Plant 3"
Raw
ND
ND
ND
ND
ND
NR
NR
ND
ND
ND
0.4
ND
Rapid Mix
0.8
ND
1.0
0.2
ND
ND
0.4
ND
GAC Inf
2
0.1
3.0
0.2
ND
NR
NR
ND
0.8
ND
0.5
ND
GAC Eff
1
0.1
1.8
0.1
ND
NR
NR
ND
0.2
ND
0.5
ND
Plant Eff
1
0.1
2.7
ND
ND
NR
NR
ND
0.3
ND
0.4
ND
DS/Ave
1
0.1
3.8
ND
ND
NR
NR
ND
0.4
ND
0.5
ND
DS/Max
1
0.1
3.6
ND
ND
ND
0.5
ND
SDS/Ave
2
0.1
3.4
ND
ND
NR
NR
ND
0.5
ND
0.4
ND
SDS/Max
2
0.1
3.6
ND
ND
ND
0.6
ND
"N/A = Not applicable
226
-------
Table 11. DBF results at
02/05/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform8
Bromodichloromethane8
Dibromochloromethane8
Bromoform8
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid8
Monobromoacetic acid8
Dichloroacetic acid8
Bromochloroacetic acid8
Dibromoacetic acid8
Trichloroacetic acid8
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAAj
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile8
Bromochloroacetonitrile8
Dibromoacetonitrile8
Trichloroacetonitrile8
Haloketones
Chloropropanone
1,1-Dichloropropanone8
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,3-Dibromopropanone
1,1,1 -Trichloropropanone8
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
plant 4 (2/5/01)
MRL5
Mg/L
0.15
0.20
0.14
0.11
0.1
0.1
0.10
0.12
0.25
0.20
0.60
0.51
0.56
0.54
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.17
0.1
0.5
0.11
0.1
N/A
N/A
0.10
0.10
N/A
N/A
N/A
0.12
N/A
0.58
Plant 4C
GAC Inf
ND
ND
ND
ND
24
3.3
0.5
0.1
28
0.27
ND
ND
ND
ND
ND
ND
ND
5.1
ND
32
1.9
ND
33
3.5
1.0
ND
70
77
34
38
ND
ND
2.6
0.2
ND
0.1
ND
1.0
ND
NR
NR
3.2
0.3
NR
NR
NR
0.5
NR
ND
GACEff
ND
ND
ND
ND
27
3.8
0.5
ND
31
0.25
ND
ND
ND
ND
ND
ND
ND
5.5
ND
31
1.9
ND
35
3.6
1.0
ND
72
78
33
40
ND
ND
2.8
0.2
ND
0.1
ND
1.0
ND
NR
NR
3.3
0.3
NR
NR
NR
0.6
NR
ND
Plant Eff
ND
ND
ND
ND
29
4.3
0.7
0.1
34
0.29
ND
ND
ND
ND
ND
ND
ND
4.7
ND
25
1.7
ND
35
3.3
ND
ND
65
70
27
38
ND
ND
2.7
0.2
ND
0.1
ND
0.9
ND
NR
NR
3.1
0.2
NR
NR
NR
0.6
NR
ND
DS/Ave
ND
ND
ND
ND
33
4.7
0.7
0.1
39
0.28
ND
ND
ND
ND
ND
ND
ND
5.7
ND
25
1.7
ND
35
3.6
ND
ND
66
71
27
39
ND
ND
2.8
0.3
ND
0.1
ND
1.0
ND
NR
NR
3.2
0.3
NR
NR
NR
0.5
NR
ND
DS/Max
33
4.7
0.7
0.3
38
NR
NR
ND
ND
ND
ND
ND
ND
ND
2.8
0.3
ND
0.1
ND
1.0
ND
3.3
0.2
0.5
ND
SDS/Ave
ND
ND
ND
ND
36
5.3
0.8
0.1
42
0.29
ND
ND
ND
ND
ND
ND
ND
6.3
ND
28
1.9
ND
38
4.6
ND
ND
72
79
30
43
ND
ND
3.2
0.3
ND
0.1
ND
1.0
ND
NR
NR
3.7
0.3
NR
NR
NR
0.6
NR
ND
SDS/Max
42
6.1
0.9
ND
49
NR
NR
ND
ND
ND
ND
ND
ND
ND
3.4
0.4
ND
0.1
ND
1.0
ND
4.0
0.2
0.5
ND
227
-------
Table 11 (continued)
02/05/2001
Compound
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLd
ug/L
0.16
0.1
0.1
0.1
0.1
N/A
N/A
0.12
0.1
1.9
0.16
2
Plant 4C
GAG Inf
2
0.1
3.2
ND
ND
NR
NR
ND
0.8
ND
0.5
ND
GAG Eff
3
0.1
3.6
ND
ND
NR
NR
ND
0.8
ND
0.4
ND
Plant Eff
2
0.1
4.5
ND
ND
NR
NR
ND
0.6
ND
0.5
ND
DS/Ave
2
0.1
4.4
ND
ND
NR
NR
ND
0.6
ND
0.5
ND
DS/Max
2
0.1
4.7
ND
ND
ND
0.6
ND
SDS/Ave
2
0.1
6.9
ND
ND
NR
NR
ND
0.7
ND
0.5
ND
SDS/Max
2
0.1
7.5
ND
ND
ND
0.7
ND
228
-------
Table 12. DBF results at
08/01/2001
Compound
Halom ethanes
Chloromethane
Bromomethane
Bromochlorom ethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAA1
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1,1-Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1-Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1 ,1 ,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
plant 3 (8/1/01)
MRLJ
pg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.5
0.52
0.1
0.5
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.1
0.10
0.1
Plant 3"
Raw
NDd
ND
ND
ND
0.2
0.1
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
A/DC
A/DC
ND
Rapid Mix
3
0.9
0.2
ND
4.1
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.6
0.1
ND
ND
ND
0.9
ND
ND
1
ND
ND
ND
ND
NDD
NDD
ND
GAC Inf
0.3
ND
ND
ND
8
4
0.8
ND
13
<0.5°
ND
ND
ND
ND
ND
ND
ND
3.9
1.2
25
6.5
1.1
16
4.6
1.2
ND
47
60
33
22
ND
ND
4
0.8
0.2
ND
ND
ND
ND
0.1
2
ND
ND
2
ND
0.5
ND
ND
NDD
2 pa
0.1
GAC Eff
ND
ND
ND
ND
14
5
0.6
ND
20
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.6
ND
ND
ND
ND
ND
ND
2
2
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
0.1
0.2
ND
ND
0.2
ND
ND
ND
ND
NDD
jpa
0.2
Plant Eff
ND
ND
ND
ND
16
7
2
0.3
25
ND
ND
ND
ND
ND
ND
ND
ND
2.2
ND
6.4
2.7
1.0
2.2
1.5
ND
ND
12
16
10
3.7
ND
ND
0.9
0.7
0.6
ND
ND
ND
ND
0.1
0.4
ND
ND
0.8
ND
0.2
ND
ND
NDD
o.eff
0.3
DS/Ave
ND
ND
ND
ND
19
8
2
0.3
28
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8.7
3.2
1.0
2.3
1.4
ND
ND
12
17
13
3.7
ND
ND
1
0.8
0.7
ND
0.1
1
ND
ND
0.5
ND
ND
ND
ND
NDD
NDD
ND
DS/Max
18
7
2
0.2
27
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
0.8
0.5
ND
0.1
1
ND
ND
0.2
ND
ND
ND
ND
NDD
NDD
ND
SDS/Ave
ND
ND
ND
ND
19
8
2
0.4
29
ND
ND
ND
ND
ND
ND
ND
ND
2.3
ND
7.3
3.1
ND
2.2
1.4
ND
ND
12
16
10
3.6
ND
ND
2
0.9
0.8
ND
0.3
0.8
ND
ND
0.8
ND
ND
ND
ND
NDD
NDD
ND
SDS/Max
NR9
NR
NR
0.5
NR
NR
ND
ND
ND
ND
ND
ND
ND
ND
2
1
0.8
ND
0.3
1
ND
ND
0.4
ND
ND
ND
ND
NDD
NDD
ND
229
-------
Table 12 (continued)
08/01/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
MIL
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
2.0
0.5
0.2
0.1
0.25
Plant 3"
Raw
ND
ND
A/D[
A/DC
ND
ND
ND
ND
ND
ND
ND
ND
28
1
ND
ND
Rapid Mix
0.8
ND
NDO
NDO
ND
ND
ND
ND
ND
ND
NR
GAC Inf
4
2
3pu
1 pu
ND
ND
ND
ND
ND
ND
ND
ND
12
1
ND
ND
GAC Eff
0.9
ND
o.eff
NDO
ND
ND
ND
ND
ND
ND
ND
ND
15
1
ND
ND
Plant Eff
1
ND
9Pn
A/DD
ND
ND
ND
ND
ND
ND
ND
ND
5
1
ND
ND
DS/Ave
3
0.5
2?n
A/DD
ND
ND
ND
ND
ND
5
1
ND
ND
DS/Max
3
ND
2 pa
NDa
ND
ND
ND
ND
ND
ND
NR
SDS/Ave
2
0.4
jpn
NDa
ND
ND
ND
ND
ND
2
0.9
ND
ND
SDS/Max
4
0.5
jpn
NDa
ND
ND
ND
ND
ND
ND
NR
°<0.5: Detected by SPE-GC/MS, but below
pLow spike recoveries for 1,1,1,3- and 1,1,3
MRL for SPE-GC/MS
,3-tetrachloropropanone and for chloral hydrate and tribromoacetaldehyde.
230
-------
Table 13. DBF results at plant 4 (8/1/01)
08/01/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1 -Trichloropropanone6
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
Mg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.11
0.5
0.5
0.52
0.1
0.5
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.10
0.1
0.10
0.1
0.1
0.1
0.29
0.14
0.1
0.10
0.1
Plant 4°
GAG Inf
ND
ND
ND
ND
22
7
1
ND
30
ND
ND
ND
ND
ND
ND
ND
ND
20
ND
56
8.7
ND
68
12
1.9
ND
144
167
65
82
0.3
ND
10
1
0.8
ND
ND
ND
ND
0.1
3
ND
ND
8
ND
0.7
ND
ND
A/DD
2 pa
ND
GACEff
ND
ND
ND
ND
27
9
1
ND
37
ND
ND
ND
ND
ND
ND
ND
ND
16
ND
25
4.5
ND
49
8.7
1.3
ND
90
105
30
59
0.4
ND
10
1
0.3
ND
ND
ND
ND
0.2
2
ND
ND
7
ND
0.7
ND
ND
A/DD
-------
Table 13 (continued)
08/01/2001
Compound
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Comoounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLa
^g/L
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
2.0
0.5
0.2
0.1
0.25
Plant 4°
GAC Inf
8
2
16ff
2?u
ND
ND
ND
ND
ND
ND
ND
ND
24
2
ND
ND
GACEff
4
0.4
gpn
A/DD
ND
ND
ND
ND
ND
ND
ND
ND
23
2
ND
ND
Plant Eff
3
0.4
6PQ
A/DD
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
DS/Ave
3
0.3
4pn
A/DD
ND
ND
ND
ND
ND
0.5
1
ND
ND
DS/Max
3
0.3
4pn
A/DD
ND
ND
ND
ND
ND
ND
NR
S DS/Ave
5
0.3
jpO
A/DD
ND
ND
ND
ND
0.2
0.6
0.9
ND
ND
SDS/Max
5
0.4
1lff
NDD
ND
ND
ND
ND
0.2
ND
ND
ND
ND
NR
DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
pLow spike recoveries for 1,1,1,3- and 1,1,3,3-tetrachloropropanone and for chloral hydrate and tribromoacetaldehyde.
232
-------
Table 14. DBF results at plant 3 (10/16/01)
10/16/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAK
Haloacetonit riles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1-Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1-Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRLJ
Mg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.25
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.2
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.90
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.5
Plant 3"
Raw
NDd
ND
ND
ND
ND
0.2
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Rapid Mix
1
2
0.8
0.2
4
NR9
NR
ND
ND
ND
ND
ND
NR
ND
0.5
0.4
0.5
ND
0.3
0.7
ND
ND
0.6
ND
0.5
ND
ND
0.5
ND
ND
GAC Inf
ND
ND
ND
ND
8
13
7
2
30
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
7.8
3.5
9.8
8.2
3.2
ND
27
47
25
21
0.5
ND
2
2
2
ND
ND
ND
ND
0.5
1
ND
0.4
1
ND
1
ND
ND
2
0.4
ND
GAC Eff
ND
ND
ND
ND
12
14
6
0.8
33
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
0.1
ND
ND
ND
ND
0.4
0.2
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
Plant Eff
ND
ND
ND
ND
18
24
11
2
55
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.6
3.4
2.6
1.2
3.3
2.0
ND
8.4
17
11
6.5
0.3
ND
0.7
1
0.7
ND
ND
ND
ND
0.6
0.4
ND
0.1
0.5
ND
0.4
ND
ND
0.4
ND
ND
DS/Ave
ND
ND
ND
ND
19
26
12
3
60
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.7
3.6
2.6
1.4
3.4
2.1
ND
8.7
18
11
6.9
0.4
ND
0.8
2
0.7
ND
0.5
0.4
ND
ND
0.5
ND
0.2
ND
ND
ND
ND
ND
DS/Max
20
27
14
2
63
NR
NR
ND
ND
ND
ND
ND
NR
ND
0.9
2
0.8
ND
0.6
0.4
ND
0.1
0.5
ND
0.1
ND
ND
ND
ND
ND
S DS/Ave
ND
ND
ND
ND
16
24
10
4
54
0.5
ND
ND
ND
ND
NR
ND
ND
ND
ND
3.4
4.2
3.0
1.4
2.4
1.7
ND
7.8
16
11
5.5
0.4
ND
1
2
1
ND
0.4
0.3
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
S DS/Max
23
36
22
3
84
NR
NR
ND
ND
ND
NR
ND
NR
ND
2
2
1
ND
0.5
0.4
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
233
-------
Table 14 (continued)
10/16/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehyde
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
MIL
0.22
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.5
0.25
Plant 3"
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
1
ND
ND
Rapid Mix
0.9
ND
0.3
ND
0.2
ND
ND
ND
ND
ND
ND
NR
GAC Inf
4
2
4
1
0.3
ND
ND
ND
ND
0.1
0.5
0.6
ND
3
1
ND
ND
GAC Eff
0.2
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
Plant Eff
0.7
ND
0.7
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
ND
1
ND
ND
DS/Ave
1
1
1
0.1
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
DS/Max
1
1
2
ND
0.1
ND
ND
ND
ND
ND
ND
NR
SDS/Ave
1
1
0.7
ND
NR
ND
0.2
ND
ND
ND
ND
0.9
ND
ND
SDS/Max
2
2
1
ND
NR
ND
0.2
ND
ND
0.2
ND
NR
234
-------
Table 15. DBF results at plant 4 (10/16/01)
10/16/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanone6
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
MRL"
Mg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.25
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.2
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.90
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.5
Plant 4°
GAG Inf
ND
ND
ND
ND
26
27
10
1
64
ND
ND
ND
ND
ND
ND
ND
ND
2.5
1.2
23
15
3.3
25
18
5.5
ND
55
94
41
49
0.9
ND
6
2
2
0.1
ND
ND
ND
0.3
2
ND
0.2
3
ND
2
ND
ND
1
0.2
ND
GACEff
ND
ND
ND
ND
30
32
11
1
74
0.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
7.5
1.5
22
15
4.4
ND
38
64
23
41
0.9
0.1
6
2
1
ND
ND
ND
ND
0.3
2
ND
0.1
3
ND
1
ND
ND
0.4
0.3
ND
Plant Eff
ND
ND
ND
ND
34
34
13
2
83
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
17
7.2
2.8
20
12
3.8
ND
40
63
27
36
0.9
0.2
5
2
0.6
0.1
ND
ND
ND
0.4
1
ND
ND
3
ND
0.9
ND
ND
0.3
0.1
ND
DS/Ave
ND
ND
ND
ND
34
36
14
2
86
0.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
17
7.3
2.9
20
12
3.9
ND
40
63
27
36
0.9
0.1
5
2
1
ND
0.4
1
ND
ND
3
ND
1
ND
ND
0.3
0.1
ND
DS/Max
48
45
18
1
112
NR
NR
ND
ND
ND
ND
ND
NR
0.1
7
3
0.9
ND
0.5
0.3
ND
ND
3
ND
0.7
ND
ND
0.2
0.1
ND
SDS/Ave
ND
ND
ND
ND
60
64
32
3
159
1
ND
ND
ND
ND
NR
ND
ND
2.3
1.2
15
12
4.1
17
12
4.3
ND
40
68
31
33
1
ND
8
4
2
ND
0.3
0.3
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
SDS/Max
69
68
37
2
176
NR
NR
ND
ND
ND
NR
ND
NR
ND
7
4
2
ND
0.3
0.6
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
235
-------
Table 15 (continued)
10/16/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLd
ug/L
0.22
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
0.5
0.25
Plant 4C
GAG Inf
5
2
9
0.1
0.4
ND
ND
ND
ND
0.1
ND
ND
ND
3
0.8
ND
ND
GAG Eff
5
2
9
0.1
0.4
ND
ND
ND
ND
0.2
ND
ND
ND
2
1
ND
ND
Plant Eff
3
1
7
ND
0.2
ND
ND
ND
ND
0.2
ND
ND
ND
1
1
ND
ND
DS/Ave
4
1
8
ND
0.2
ND
ND
ND
ND
0.2
2
1
ND
ND
DS/Max
4
2
12
0.1
ND
ND
ND
ND
ND
0.2
ND
NR
SDS/Ave
2
1
15
ND
NR
ND
0.2
ND
ND
ND
2
1
ND
ND
SDS/Max
2
1
8
ND
NR
ND
0.2
ND
ND
0.2
ND
NR
236
-------
Table 16. DBF results at plant 3 (1/28/02)
01/28/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA91
DXAAJ
TXAAK
Haloacetonit riles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1 -Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1-Trichloropropanone6
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRLJ
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.5
0.5
0.5
0.5
0.5
0.1
0.52
1.0
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
1
0.1
0.1
0.5
0.5
0.5
0.95
0.1
0.10
0.1
0.1
0.5
0.1
1.0
0.1
0.1
0.10
0.10
N/A
Plant 3"
Raw
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.11
ND
ND
NR
Rapid Mix
NR9
NR
NR
NR
NR
ND
NR
NR
ND
ND
NR
ND
ND
ND
NR
NR
ND
NR
0.1
0.4
ND
ND
ND
ND
NR
ND
ND
ND
ND
NR
GAC Inf
ND
ND
ND
ND
20
4
2
ND
26
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
19
2.6
ND
20
5.6
2.0
ND
39
49
22
28
ND
ND
3
0.5
ND
ND
ND
ND
ND
0.3
1
ND
ND
2
ND
1
ND
0.20
0.20
ND
NR
GAC Eff
ND
ND
ND
ND
16
6
3
0.6
26
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.3
ND
ND
9.8
2.7
1.2
ND
14
18
4.3
14
ND
ND
1
0.2
ND
ND
ND
ND
ND
0.3
0.7
ND
ND
1
ND
ND
ND
0.10
ND
ND
NR
Plant Eff
ND
ND
ND
ND
200
7
4
0.6
320
ND
ND
ND
ND
ND
ND
ND
ND
2.5
ND
7.8
1.6
ND
13
4.4
1.6
ND
23
31
9.4
19
ND
ND
1
0.3
<0.5°
ND
ND
ND
ND
0.3
0.7
ND
ND
1
ND
ND
ND
ND
ND
ND
NR
DS/Ave
ND
ND
ND
ND
NR
8
5
0.6
NR
ND
ND
ND
ND
ND
ND
ND
ND
2.8
ND
7.6
1.5
ND
12
4.0
1.4
ND
22
29
9.1
17
ND
ND
NR
0.4
<0.5
ND
0.3
0.6
ND
ND
1
ND
<1r
ND
0.10
ND
ND
NR
DS/Max
NR
NR
NR
NR
NR
ND
NR
NR
ND
ND
NR
ND
ND
ND
NR
NR
ND
NR
0.4
0.2
ND
ND
NR
ND
NR
ND
ND
ND
ND
NR
S DS/Ave
ND
ND
ND
ND
NR
10
4
0.7
NR
ND
ND
ND
NR
NR
ND
ND
ND
2.7
ND
9.3
5.2
ND
13
1.5
2.8
ND
25
35
15
17
NR
NR
NR
1
<0.5
ND
NR
1
NR
NR
1
NR
ND
NR
NR
NR
NR
NR
S DS/Max
NR
NR
NR
NR
NR
ND
NR
NR
ND
ND
NR
ND
ND
ND
NR
0.7
0.2
NR
0.3
NR
ND
ND
NR
ND
NR
ND
0.10
0.20
ND
NR
237
-------
Table 16 (continued)
01/28/2002
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate6
Tribromoacetaldehyde
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin6
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 ,1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRL"
MIL
0.98
0.5
0.1
0.1
N/A
0.1
0.10
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
2.5
0.25
Plant 3"
Raw
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
Rapid Mix
0.6
ND
0.2
ND
ND
ND
ND
ND
ND
NR
NR
GAC Inf
3
ND
3
ND
ND
ND
ND
ND
ND
0.5
0.5
ND
ND
ND
0.6
ND
ND
GAC Eff
1
ND
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
Plant Eff
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
0.6
ND
ND
DS/Ave
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
DS/Max
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
NR
SDS/Ave
NR
NR
NR
NR
ND
NR
NR
NR
ND
<0.5
ND
0.7
ND
ND
SDS/Max
3
ND
4
ND
ND
0.2
ND
ND
1
NR
NR
qResults in italics tentative due to problems with quality assurance
r<1: Detected by SPE-GC/MS, but below MRL for SPE-GC/MS
238
-------
Table 17. DBF results at plant 4 (1/28/02)
01/28/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform6
Bromodichloromethane6
Dibromochloromethane6
Bromoform6
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid6
Monobromoacetic acid6
Dichloroacetic acid6
Bromochloroacetic acid6
Dibromoacetic acid6
Trichloroacetic acid6
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA5h
HAA9'
DXAAJ
TXAAK
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile6
Bromochloroacetonitrile6
Dibromoacetonitrile6
Trichloroacetonitrile6
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone6
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1,1,1 -Trichloropropanone6
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.5
0.5
0.5
0.5
0.5
0.1
0.52
1.0
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
1
0.1
0.1
0.5
0.5
0.5
0.95
0.1
0.1
0.1
0.1
0.5
0.1
1.0
0.1
0.1
0.10
0.10
N/A
Plant 4°
GAG Inf
ND
ND
ND
ND
200
9
3
ND
320
ND
ND
ND
ND
ND
ND
ND
ND
2.3
ND
21
3.3
ND
26
6.8
2.8
ND
49
62
24
36
0.3
ND
4
0.8
0.3
ND
ND
ND
ND
0.3
2
ND
ND
4
ND
<1
ND
0.3D
0.1U
ND
NR
GAG Eff
ND
ND
ND
ND
200
6
2
ND
280
ND
ND
ND
ND
ND
ND
ND
ND
2.6
ND
21
3.2
ND
28
6.9
2.5
ND
52
64
24
37
ND
ND
3
0.6
ND
ND
ND
ND
ND
0.4
1
ND
ND
3
ND
<1
ND
0.20
ND
ND
NR
Plant Eff
ND
ND
ND
ND
200
8
3
ND
310
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.0
17
2.6
ND
21
5.8
1.9
ND
39
49
20
29
ND
ND
2
0.6
ND
ND
ND
ND
ND
0.4
0.7
ND
ND
3
ND
<1
ND
ND
ND
ND
NR
DS/Ave
ND
ND
ND
ND
NR
8
2
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
16
2.4
ND
21
5.8
1.8
ND
37
47
18
29
ND
ND
NR
0.8
<0.5
ND
0.4
0.5
ND
ND
3
ND
1
ND
ND
ND
ND
NR
DS/Max
NR
NR
NR
NR
NR
ND
NR
NR
ND
ND
NR
ND
ND
ND
NR
0.2
ND
NR
0.4
0.8
ND
ND
NR
ND
NR
ND
ND
ND
ND
NR
SDS/Ave
ND
ND
ND
ND
NR
11
5
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
2.5
ND
19
3.5
ND
24
5.3
ND
ND
46
54
23
29
0.3
ND
NR
1
0.3
ND
ND
ND
ND
0.4
0.6
ND
ND
3
ND
ND
ND
0.10
ND
ND
NR
SDS/Max
NR
NR
NR
NR
NR
ND
NR
NR
ND
ND
NR
ND
0.3
ND
NR
2
0.4
NR
0.2
0.5
ND
ND
NR
ND
NR
ND
0.10
ND
ND
NR
239
-------
Table 17 (continued)
01/28/2002
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate8
Tribromoacetaldehyde
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin8
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
1 , 1 ,2,2-Tetrabromo-2-chloroethane
Benzyl chloride
MRLd
ug/L
0.98
0.5
0.1
0.1
N/A
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.5
0.5
0.2
2.5
0.25
Plant 4C
GAG Inf
2
ND
9
ND
ND
ND
0.1
ND
ND
0.6
0.6
ND
ND
ND
0.6
ND
ND
GAG Eff
3
ND
5
ND
ND
ND
0.2
ND
ND
0.4
0.6
ND
ND
ND
0.7
ND
ND
Plant Eff
1
ND
2
ND
ND
ND
0.2
ND
ND
ND
0.5
ND
ND
ND
0.6
ND
ND
DS/Ave
1
ND
2
ND
ND
ND
0.2
ND
ND
ND
ND
0.7
ND
ND
DS/Max
1
ND
3
ND
ND
0.2
ND
ND
ND
NR
NR
SDS/Ave
1
ND
10
ND
ND
ND
0.2
ND
ND
0.7
0.7
ND
ND
ND
0.7
ND
ND
SDS/Max
1
ND
17
ND
ND
0.2
ND
ND
1
NR
NR
240
-------
Figure 4
Seasonal Variability in Trihalomethane Formation at Plants 3 and 4
111/13/2000 D 2/5/2001 • 8/1/2001 • 10/16/2001 D1/28/2002
Pre-Chloramination at Plant 3
Plant 3 Effluent
Plant 4 Effluent
Halomethanes. Figure 4 shows the seasonal variability in THM formation at plants 3 and
4. The sum of the four regulated THMs (THM4) ranged from 31 to 83 |ig/L in the plant 4
effluent. The highest formation was in October 2001 when the bromide level was the highest.
Note, during most sampling events, plant 4 effluent represented a blend of plant 4 and plant 3
waters. For example, in August 2001, the plant 4 effluent had 31 jig/L THM4. Based on a plant
4 flow of 11 mgd-with 37 |ig/L THM4 in the GAC effluent-and the addition of 4.2 mgd of
plant 3 GAC effluent-with 20 |ig/L THM4-the theoretical THM4 for the plant 4 effluent was 32
Hg/L. Because the plant 4 distribution system had a free chlorine residual, THM formation
increased to 38-39 |ig/L.
TFDVI4 ranged from 25 to 55 |ig/L in the plant 3 effluent. Pre-chloramination at plant 3
was more effective at minimizing TFDVI formation in November 2000 than in October 2001,
most likely due to the difference in bromide concentrations between these two periods (0.06
versus 0.2 mg/L, respectively). Pre-chloramination was not required in February 2001, as the
water temperature (7-10°C) and bromide (0.02 mg/L) were relatively low during this time period.
Thus, pre-chloramination was used at plant 3 at the times of the year in which TFDVI formation
would be too high with pre-chlorination (e.g., summer and fall).
Figure 5 shows the impact of bromide on TFDVI speciation in plant 3 effluent. In October
2001, when the bromide level was the highest, there was the greatest shift in speciation to
brominated TFDVIs. In February 2001 and January 2002, when the bromide concentration was
the lowest, chloroform was the major THM species formed.
241
-------
In terms of iodinated THMs, dichloroiodomethane was typically detected in some of the
samples each quarter. When detected, the concentration of this iodinated THM ranged from 0.25
to 2 ng/L. In November 2000, bromodiiodomethane and iodoform were also detected in selected
samples. Dichloroiodomethane and/or bromochloroiodomethane were also found using
broadscreen-gas chromatography/mass spectrometry (GC/MS) methods (carried out by the
USEPA) in finished water from plant 3 and plant 4.
Figure 5
Impact of Bromide on Trihalomethane Speciation
in Plant 3 Effluent
Date
01/28/2002
10/16/2001
08/01/2001
02/05/2001
11/13/2000
Bromide
(mg/L)
0.023
0.2
0.05
0.022
0.058
1/28/2002
' 10/16/2001
8/1/2001
2/5/2001
11/13/2000
Haloacids. Figure 6 shows the seasonal variability in haloacetic acid (HAA) occurrence
at plants 3 and 4. The sum of the five regulated HAAs (HAAS) ranged from 39 to 66 |ig/L in the
plant 4 effluent. The sum of all nine species (HAA9) ranged from 49 to 89 |ig/L. The plant 4
effluent typically represented a blend of plant 4 and plant 3 waters. For example, in August
2001, the plant 4 effluent had 61 |ig/L HAAS and 74 |ig/L HAA9. Based on a plant 4 flow of 11
mgd before the addition of 4.2 mgd of plant 3 GAC effluent, the theoretical HAAS and HAA9
for the plant 4 effluent was 65 and 76 |ig/L, respectively. HAAS and HAA9 were 8.4-32 and 17-
35 ng/L, respectively, in the plant 3 effluent. The highest HAA occurrence in the plant 3
effluents was during the winter.
242
-------
100
90
80
70
60
50
40
30
20
10
0
Figure 6
Seasonal Variability in Haloacetic Acid Occurrence at Plants 3 and 4
111/13/2000 D 2/5/2001 • 8/1/2001 1110/16/2001 D1/28/2002
*Pre-Chloramination at Plant 3
o>
Plant 3 Effluent
Plant 4 Effluent
At plant 3, the concentration of HAA9 in the GAC influent was 36-61 |ig/L, whereas the
level in the GAC effluent ranged from not detected (ND) to 21 |ig/L. Figure 7 shows that when
the water temperature was warmer, HAAs were effectively removed, whereas when the water
was colder, the removal of dihalogenated HAAs (DXAAs) was somewhat diminished and the
removal of trihalogenated HAAs (TXAAs) was significantly impacted. GAC can provide a
medium for biological activity, which can result in the control of HAAs. Other research has
demonstrated that HAAs can be removed by GAC filtration, presumably by biodegradation
processes within the filter bed (Singer et al., 1999). In another study, DXAAs were found to be
much better biodegraded than TXAAs in a distribution system with no
disinfectant residual, and the removal effectiveness was significantly impacted by water
temperature (Baribeau et al., 2000).
In contrast, HAAs were typically not removed during GAC filtration at plant 4 (Figure 8),
and when they were the percentage removed was much less than at plant 3. At plant 3, GAC was
used in a post-filtration contactor, whereas at plant 4 GAC was used as a filter media in wood tub
filters. In addition, there was little to no disinfectant residual in the plant 3 GAC effluents,
whereas there was a free chlorine residual in the plant 4 GAC effluents. The operational use of
GAC was different at the two plants.
243
-------
Figure 7
100%
0%
Impact of Temperature on Removal
of Haloacetic Acids on Plant 3 GAC Filter
SDXAA Removal DTXAA Removal • Temperature
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
Figure 8
60%
Impact of Temperature on Removal
of Haloacetic Acids on Plant 4 GAC Filter
• DXAA Removal DTXAA Removal •Temperature
-10%
244
-------
Figure 9 shows how HAAs were reformed during post-GAC chlorination, whereas
THMs—which were not removed during GAC filtration—increased in formation through the
treatment process. The levels of HAAs formed during post-GAC chlorination were less than
what was initially formed by pre-chlor(am)ination. Because the HAAs were effectively removed
by GAC during the warmer months, HAA occurrence in the plant effluent was primarily from
the post-GAC chlorination. Alternatively, during the colder months, HAAs in the plant effluent
were from a combination of HAAs not removed by GAC and that formed during post-GAC
chlorination. Thus, HAA occurrence in the plant effluent was higher in the winter at plant 3.
Figure 9
Formation and Removal of Trihalomethanes
and Haloacetic Acids at Plant 3
I Rapid Mix nGAC Influent BGAC Effluent • Plant Effluent
HAAs not sampled at rapid mix
THM4
DXAA
-02/05/2001
TXAA
THM4
DXAA
-10/16/2001
TXAA
245
-------
Figure 10 shows the impact of bromide on HAA speciation in the plant 3 GAC influent.
In October 2001, when the bromide level was the highest, there was the greatest shift in
speciation to brominated HAAs. In February 2001 and January 2002, when the bromide
concentration was the lowest, dichloro- and trichloroacetic acid were the major HAA species
formed.
Figure 10
Impact of Bromide on Haloacetic Acid Speciation
in Plant 3 GAC Influent
Date
01/28/2002
10/16/2001
08/01/2001
02/05/2001
11/13/2000
Bromide
(mg/L)
0.023
0.2
0.05
0.022
0.058
1/28/2002
10/16/2001
8/1/2001
2/5/2001
11/13/2000
Figure 11 shows the impact of disinfection scenario on HAA speciation in plants 3 and 4
GAC influent samples. At plant 4, pre-chlorination resulted in the formation of more TXAAs
than DXAAs. Likewise, Cowman and Singer (1996) found that the TXAAs were the dominant
HAA species in their study during chlorination. At plant 3, during pre-chloramination, DXAAs
were formed to a higher extent than the TXAAs. Krasner and co-workers (1996) found that
chloramines minimized the formation of THMs and TXAAs better than that of DXAAs.
Likewise, Cowman and Singer (1996) found that DXAAs were the principal HAA species
formed from chloramination.
February 2001 results from IMC also show the presence of another target halo-acid, 3,3-
dichloropropenoic acid, at levels of 1.5 and 0.9 |ig/L, respectively, in finished waters from plant
3 and plant 4 (Table 18). 3,3-Dichloropropenoic acid, as well as trichloropropenoic acid, was
also identified in broadscreen GC/MS analyses carried out by the USEPA.
246
-------
Figure 11
Impact of Disinfection Scenario on HAA Speciation
in Plant 3 and 4 GAC Influent Samples
i Plant 3 DXAAs
] Plant 3 TXAAs - - A- • Plant 4 DXAAs
-Plant4TXAAs
Pre-Chloramination at Plant 3
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be
produced at approximately one-tenth the level of the THMs (on a weight basis) (Krasner et al.,
1989). In the latter study, the 25th and 75th percentile ratios of HANs to THMs were 0.065 and
0.147, respectively. The HAN to THM relationship had originally been established between
dichloroacetonitrile (DCAN) and chloroform (trichloromethane [TCM]) (Oliver, 1983).
Figure 12 shows that DCAN formation in GAC influent samples at plants 3 and 4 was
equal to or higher than one-tenth the level of chloroform. A linear regression of the data, except
for the August 2001 data that were atypical, indicated that DCAN was -17 % of the level of
chloroform. This value was somewhat higher than the 75th percentile ratio observed by Krasner
and colleagues (1989).
In these samples, the pH ranged from 5.5 to 6.2. In other research, THM formation has
been shown to be lower at acidic pH and DCAN formation has been higher at acidic pH, whereas
dichloroacetic acid (DCAA) formation was found to be relatively insensitive to pH (Stevens et
al., 1989). Figure 13 shows the relationship between DCAN and DCAA formation for these
samples. A linear regression of the data, including the August 2001 samples, indicated that
DCAN was -18 % of the level of DCAA. These results suggest that the pH of chlorination
within plants 3 and 4 was, in part, impacting the relative formation of DCAN, chloroform, and
DCAA.
247
-------
Figure 12
Dichloroacetonitrile (DCAN) Formation as a Function of Chloroform
(TCM) Formation in Plants 3 and 4 GAC Influent Samples
12
10 -
6
D)
-------
DCAN was 0.9-4 and 0.1-1.6 |ig/L in the plant 3 GAC influent and effluent, respectively.
Figure 14 shows that the concentration of DCAN was significantly reduced in passing through
the GAC when the water temperature was warm. DCAN was 2.6-10 and 2.8-10 |ig/L in the
plant 4 GAC influent and effluent, respectively. The level of DCAN was generally unchanged in
passing through the plant 4 GAC filters (Figure 14). Likewise, the brominated analogues of
DCAN were reduced in concentration in passing through the plant 3 GAC filter when the water
temperature was warm, whereas the plant 4 GAC filters had no significant impact. Similar to the
HAAs, the plant 3 GAC filter resulted in a significant reduction in the concentration of the
HANs, and the phenomenon was temperature sensitive, whereas the plant 4 GAC filter did not
significantly reduce the concentration of the HANs.
Figure 15 shows the impact of bromide on HAN speciation in plant 3 GAC influent. In
October 2001, when the bromide level was the highest, there was the greatest shift in speciation
to brominated HANs. In February 2001 and January 2002, when the bromide concentration was
the lowest, DCAN was the major HAN species formed.
The plant 4 effluent typically represented a blend of plant 4 and plant 3 waters. For
example, in August 2001, the plant 4 effluent had 6 jig/L DCAN. Based on a plant 4 flow of 11
mgd before the addition of 4.2 mgd of plant 3 GAC effluent, the theoretical DCAN concentration
for the plant 4 effluent was 7 |ig/L.
Finally, sub-|ig/L levels of one of the EPA study HANs (i.e., chloroacetonitrile) were
detected in selected samples. Broadscreen GC/MS analyses also revealed the presence of
tribromoacetonitrile in one sample (finished water from plant 3, November 2000).
Haloketones. Figure 16 shows the impact of bromide on haloketone (HK) speciation in
plants 3 and 4 GAC influent samples. Specifically, the two HK species in the Information
Collection Rule (ICR) (1,1-dichloro- and 1,1,1-trichloropropanone) were evaluated along with
two brominated analogues included in the EPA DBF study (1,1-dibromo- and l-bromo-1,1-
dichloropropanone). In October 2001, when the bromide level was the highest, there was an
increase in the formation of both of these brominated HKs when compared to the August 2001
sampling, which was accompanied by decreases in the concentrations of the corresponding
chlorinated species.
In addition to the formation of selected brominated species, other EPA study HKs (e.g.,
chloro-, 1,1,3-trichloro-, 1,1,3,3-tetrachloro-, and 1,1,1,3-tetrachloropropanone) were detected in
selected samples. Furthermore, pentachloropropanone and hexachloropropanone were detected
at plants 3 and 4 in November 2000, August 2001, and January 2002 by the USEPA using
broadscreen-GC/MS methods.
249
-------
100%
Figure 14
Impact of Temperature on Removal
of Dichloroacetonitrile on GAC Filters
I Plant 3 DCAN Removal DPIant4 DCAN Removal "Temperature
8/1/2001 10/16/2001 1/28/2002
-20%
Figure 15
Impact of Bromide on Haloacetonitrile Speciation
in Plant 3 GAC Influent
4.o-r
Date
01/28/2002
10/16/2001
08/01/2001
02/05/2001
11/13/2000
Bromide
(mg/L)
0.023
0.2
0.05
0.022
0.058
1/28/2002
10/16/2001
8/1/2001
2/5/2001
11/13/2000
xxyvx
250
-------
Figure 16. Impact of bromide on haloketone speciation in plants 3 and 4 GAC influent
samples: bromide = 0.05 and 0.2 mg/L on 8/1/01 and 10/16/01, respectively.
Plant 4, 10/16/01
Plant 4, 8/1/01
Plants, 10/16/01
Plant 3, 8/1/01
Plant 4, 10/16/01
Plant 4, 8/1/01
Plants, 10/16/01
Plants, 8/1/01
Figure 17 shows that the concentrations of 1,1-dichloro- and 1,1,1-trichloropropanone
were significantly reduced in passing through the GAC when the water temperature was warm.
The levels of these two HKs were generally unchanged in passing through the plant 4 GAC
filters (Figure 18). Likewise, many of the EPA DBF study HKs were reduced in concentration in
passing through the plant 3 GAC filter when the water temperature was warm, whereas the plant
4 GAC filters had no significant impact. Similar to the HAAs, the plant 3 GAC filter resulted in
a significant reduction in the concentration of many of the HKs, and the phenomenon was
temperature sensitive, whereas the plant 4 GAC filter did not significantly reduce the
concentration of the HKs.
Figure 19 shows how most HKs that were reduced in concentration in the plant 3 GAC
filter were reformed during post-GAC chlorination, whereas chloropropanone—which was not
removed during GAC filtration—increased somewhat in concentration through the treatment
process. The levels of HKs formed during post-GAC chlorination were less than what was
initially formed by pre-chlor(am)ination.
251
-------
Figure 17
Impact of Temperature on Removal
of Haloketones on Plant 3 GAC Filter
11,1-Dichloropropanone Removal D1,1,1-Trichloropropanone Removal "Temperature
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
Figure 18
Impact of Temperature on Removal
of Haloketones on Plant 4 GAC Filter
11,1-Dichloropropanone Removal D1,1,1-Trichloropropanone Removal •Temperature
50%
-10%
not available
252
-------
Figure 19
Formation and Removal of Haloketones
at Plant 3: 10/16/01
I Rapid Mix HGAC Influent I1GAC Effluent • Plant Effluent
D)
-------
Figure 20
Impact of Bromide on Haloacetaldehyde Speciation
in Plant 3 GAC Influent
111/13/2000 • 2/5/2001 • 8/1/2001 • 10/16/2001 D1/28/2002
Bromochloroacetaldehyde and chloral hydrate co-eluted in 11/13/00 sample
I
Dichloroacetaldehyde Bromochloroacetaldehyde
Chloral hydrate
Tribromoacetaldehyde
Figure 21
Impact of Disinfection Scenario on Haloacetaldehyde Speciation
In Plants 3 and 4 GAC Influent Samples
Plant 3 Dihalogenated Acetaldehydes
•A-- Plant 4 Dihalogenated Acetaldehydes
1 Plant 3 Trihalogenated Acetaldehydes
• Plant 4 Trihalogenated Acetaldehydes
*Pre-Chloramination at Plant 3
romocnloroaceta
and chloral hydrat
co-eluted in 11/13/00 sarri
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
254
-------
Young and colleagues (1995) observed that chloral hydrate production was minimized by
chloramination, whereas the formation of DC AN was similar during chlorination and
chloramination, and where DCAN was produced from the reaction of chloramines with reaction
by-products such as dichloroacetaldehyde. The relative formation of di- and trihalogenated
acetaldehydes with pre-chlorination versus pre-chloramination was similar to that observed for
DXAAs and TXAAs (Figure 11).
Figure 22 shows that the concentrations of dichloroacetaldehyde and chloral hydrate were
significantly reduced in passing through the GAC when the water temperature was warm. The
levels of these two haloacetaldehydes were generally unchanged in passing through the plant 4
GAC filters (Figure 23). Likewise, the brominated haloacetaldehydes were reduced in
concentration in passing through the plant 3 GAC filter when the water temperature was warm,
whereas the plant 4 GAC filters typically had no significant impact. Similar to the HAAs, the
plant 3 GAC filter resulted in a significant reduction in the concentration of the
haloacetaldehydes, and the phenomenon was temperature sensitive, whereas the plant 4 GAC
filter typically did not significantly reduce the concentration of the haloacetaldehydes.
Figure 22
Impact of Temperature on Removal
of Haloacetaldehydes on Plant 3 GAC Filter
• Dichloroacetaldehyde Removal D Chloral Hydrate Removal • Temperature
100%
0%
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
255
-------
Figure 23
Impact of Temperature on Removal
of Haloacetaldehydes on Plant 4 GAC Filter
• Dichloroacetaldehyde Removal D Chloral Hydrate Removal B Temperature
80%
-60%
*Negative value corresponds to sample with more haloacetaldehyde in filter effluent than in filter influent
Figure 24 shows how some of the haloacetaldehydes were reformed during post-GAC
chlorination at plant 3. The levels of haloacetaldehydes formed during post-GAC chlorination
were less than what was initially formed by pre-chlor(am)ination.
Broadscreen analyses carried out at the USEPA also revealed the presence of four
haloaldehydes that were not among the targeted list (Table 21). These are tentatively identified
as 2-bromo-2-methylpropanal, iodobutanal, dichloropropenal, and 4-chloro-2-butenal. The
identification of iodobutanal represents the first time that an iodinated aldehyde has been
identified as a DBF. This compound was not present in the mass spectral library databases, but
high resolution electron ionization (El) mass spectrometry confirmed the empirical formula
assignment of C4H7OI (molecular weight of 198). An exact isomer assignment for this molecule
was not possible from the MS data obtained.
256
-------
Figure 24
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
Formation and Removal of Haloacetaldehydes
at Plant 3: 10/16/01
I Rapid Mix UGAC Influent lOGAC Effluent • Plant Effluent
a
9)
O
0
ro
x
Dichloroacetaldehyde Bromochloroacetaldehyde
Chloral hydrate
Tribromoacetaldehyde
Halonitromethcmes. Sub-|ig/L levels of chloropicrin (trichloronitromethane) were
detected in selected samples. Dichloronitromethane was detected in selected samples in October
2001 and in January 2002. Brominated analogues of chloropicrin were detected in the plant 3
GAC influent in October 2001 when the bromide concentration was the highest (Figure 25).
Because the occurrence of these DBFs were typically at or near their minimum reporting levels
(MRLs), it was not possible to study their fate through the GAC filters on most sample dates.
However, the data from February 2001 (Figure 26) suggest that chloropicrin was removed during
GAC filtration at plant 3, not plant 4, even though the water temperature was relatively cold.
Dichloronitromethane was also detected in finished water in August 2001 using broadscreen
GC/MS techniques.
257
-------
Figure 25
Impact of Bromide on Halonitromethane Speciation in Plant 3 GAC Influent:
Bromide = 0.02 and 0.2 mg/L on 1/28/02 and 10/16/01, Respectively
o
Figure 26
Formation and Removal of Chloropicrin
at Plants 3 and 4: 2/5/01
NS = Not Sampled
Rapid Mix
GAC Influent
GAC Effluent
Plant Effluent
258
-------
Volatile Organic Compounds (VOCs). Carbon tetrachloride, which is a VOC and a
possible DBF, was detected (0.3-0.8 |ig/L) at both plants in November 2000, but was not found
in the raw water (MRL = 0.06 |ig/L). As mentioned in a previous chapter, carbon tetrachloride
has been detected by some utilities in gaseous chlorine cylinders (EE&T, 2000), due to
imperfections in the manufacturing process or improper cleaning procedures.
Methyl tertiary butyl ether (MtBE) was detected in the raw water on all of the sample
dates, with concentrations of 0.4 to 1 ug/L (Figure 27). The level of MtBE was unchanged
through either treatment plant. GAC at plant 3 did not remove MtBE. MtBE is a VOC (e.g., a
gasoline additive), not a DBF, but is of concern due to widespread contamination of source
waters.
Figure 27
Occurrence of Methyl tertiary Butyl Ether (MtBE)
in Raw Water and in Plant 3 and 4 Effluents
! Plant 3 Effluent
]Plant 4 Effluent --A-- Plant Influent
11/13/2000
2/5/2001
8/1/2001
10/16/2001
1/28/2002
Methyl ethyl ketone (MEK) was detected in the raw water on August 1, 2001 at a
concentration of 28 |ig/L (Figure 28). The level of MEK decreased through both treatment
plants. MEK is an industrial solvent. The tremendous amount of rainfall the weekend before the
sampling may have contributed to the presence of this solvent in the raw water (e.g., due to
runoff). MEK was detected in the raw water on October 16, 2001 at 0.6 |ig/L. After pre-
chlor(am)ination, the level of MEK was 3 |ig/L. MEK is also a DBF (an oxidation by-product).
MEK was removed on the plant 3 GAC in October 2001, but only a small percentage of it was
removed on the plant 4 GAC. MEK is a carbonyl, and various carbonyls have been shown to be
biodegradable on biologically active filters (Krasner et al., 1993).
259
-------
Figure 28
Occurrence of Methyl Ethyl Ketone (MEK)
in Raw Water and in Plant 3 and 4 Effluents
I Raw Water HGAC Influent UGAC Effluent • Plant Effluent
Plants: 8/1/01
Plant 4: 8/1/01
Plants: 10/16/01 Plant 4: 10/16/01
HalogenatedFuranones. Table 20 presents data for 3-chloro-4-(dichloromethyl)-5-
hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3-(dichloromethyl)-4-
oxobutenoic acid, otherwise known as EMX; and mucochloric acid (MCA), which can be found
as a closed ring or in an open form. In October 2001, MX was detected at 0.18 ug/L (180 ng/L)
in the finished water of plant 3 (which used chlorine-chloramine disinfection), which was higher
than levels reported in a survey of Australian waters (<90 ng/L) (Simpson and Hayes, 1998).
However, water quality and treatment/disinfection schemes may be different in Australia than in
the United States. In particular, regulatory requirements in Australia are significantly different
than in the United States. Subsequently, MX levels dropped in the distribution system to 0.013
ug/L (13 ng/L). EMX levels were 0.10 ug/L in the finished water, but dropped to 0.03 ug/L in
the distribution system. Mucochloric acid (ring form) was 0.53 ug/L in the GAC influent and
0.05 ug/L in the GAC effluent. Likewise, the open form of mucochloric acid was 0.11 and 0.014
ug/L in the GAC influent and effluent, respectively. Similar to that of many other DBFs in this
study, MCA (ring and open forms) was removed on the biologically-active GAC filters. MCA
(ring form) was partially re-formed at 0.13 ug/L in the finished water, and its concentration
remained steady at 0.12 ug/L in the distribution system. The open form of mucochloric acid was
re-formed in the finished water (0.03 ug/L) and continued to increase in the distribution system
(0.16 ug/L). The concentrations of MCA ring and open forms were qualitative, due to sample
matrix co-elutants on the GC column. Due to the relatively high level of bromide in the source
water (0.2 mg/L), brominated MX analogs (BMXs) would be expected; however, they were not
analyzed for in these samples.
260
-------
Plant 4, which used chlorine disinfection (applied both to the raw and filtered waters),
showed much lower levels of MX (0.015 |ig/L) in the finished water, but higher levels (0.02
|ig/L) in the chlorinated distribution system. Only a small amount of EMX was detected in
finished water from plant 4 (0.011 |ig/L), which decreased to below detection in the distribution
system. Mucochloric acid levels (both ring and open forms) were higher in the finished water
from plant 4 (0.71 and 0.19 |ig/L) than in plant 3 (0.13 and 0.03 |ig/L), which contributed to total
levels of MX analogs being higher in plant 4 (Figure 29). At plant 4, spent GAC filters were not
effective in removing the MX analogues initially formed. This is similar to what was observed
for many other DBFs in this study.
Other HalogenatedDBPs. A few additional halogenated DBFs were also detected. UNC
methods detected dichloroacetamide at 1.2 |ig/L in finished water from plant 3 in February 2001
(Table 18). Dichloroacetamide was also observed in the distribution system (2.1 |ig/L, plant 3)
in October 2001 (Table 19). In addition, broadscreen GC/MS analyses revealed the presence of
trichlorophenol and trichlorobenzene-l,2-diol (Table 21) in plant 3 water pre-treated with
chlorine (January 2002). These halo-phenols were not observed in the corresponding raw,
untreated water, and were not detected in the plant effluent.
Non-HalogenatedDBFs. Targeted non-halogenated DBFs observed included trans-2-
hexenal (plant 4, February 2001) (Table 18) and dimethylglyoxal (plant 4, October 2001) (Table
19). Levels were 0.7 and 1.4 |ig/L, respectively. Several carboxylic acids were also identified
as DBFs using broadscreen GC/MS analysis (Table 21). Many carboxylic acids are also seen in
the raw, untreated water. However, many were also judged to be formed as DBFs, as their levels
increased substantially (2-3X) in the treated waters versus the raw, untreated waters.
261
-------
Table 18. Additional target DBF results (ug/L) at plants 3 and 4 (2/5/01)
2/5/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Dichloroacetamide
TOX (ug/L as CD
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
/raws-2-Hexenal
Plant 3a
C12/NH2C1
Raw
0
0
0
0
0
0
0.6
<0.1
<0.1
<0.1
<0.4
<0.1
FI
0.4
4.7
0.5
0.7
0
0
105.1
<0.1
<0.1
<0.1
<0.4
<0.1
FE
0.3
2.9
0.5
0.5
0
0
47.4
<0.1
<0.1
<0.1
<0.4
<0.1
PE
0.4
4.3
0.7
1.5
0
1.2
87.3
<0.1
<0.1
<0.1
<0.4
<0.1
DS
0.3
3.8
0.3
0.4
0
1.0
88.0
<0.1
<0.1
<0.1
<0.4
<0.1
SDS
0.3
3.7
0.5
1.6
0
1.9
110.1
<0.1
<0.1
<0.1
<0.4
<0.1
Plant 4
C12
FI
1.9
3.9
0.9
1.0
0
0
127.6
<0.1
<0.1
<0.1
<0.4
<0.1
FE
2.2
3.8
0.6
0.6
0
0
31.8
<0.1
<0.1
<0.1
<0.4
<0.1
PE
0.5
3.5
0.8
0.9
0
0.5
188.3
<0.1
<0.1
<0.1
<0.4
0.7
DS
0.5
3.6
0.6
0.9
0
0.4
154.9
<0.1
<0.1
<0.1
<0.4
0.7
SDS
0.4
3.6
0.5
1.2
0
0.6
138.5
<0.1
<0.1
<0.1
<0.4
0.6
treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent
(FE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention
time, and (6) simulated distribution system (SDS) at maximum detection time.
Table 19. Additional target DBF results (ng/L) at plants 3 and 4 (10/16/01)
10/16/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
Dichloroacetamide
TOX (ug/L as Cl")
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
/ra«5-2-Hexenal
Plant 3"
C12/NH2C1
Raw
0
0
0
0
0
0
29.1
<0.1
<0.1
<0.1
<0.4
<0.1
FI
1.2
5.1
3.1
0
0
1.8
216.0
<0.1
<0.1
<0.1
<0.4
<0.1
FE
0
0.5
0
0
0
0.2
82.3
<0.1
<0.1
<0.1
<0.4
<0.1
PE
0
0.5
0
0
0
0
161.0
<0.1
<0.1
<0.1
<0.4
<0.1
DS
0.5
1.2
0.9
0
0
2.1
162.0
<0.1
<0.1
<0.1
<0.4
<0.1
SDS
0.6
1.6
1.5
0
0
4.8
141.0
<0.1
<0.1
<0.1
<0.4
<0.1
Plant 4
C12
FI
1.9
5.4
1.1
0
0
0
291.0
<0.1
<0.1
<0.1
<0.4
<0.1
FE
0.4
4.2
1.5
0
0
0
278.0
<0.1
<0.1
<0.1
<0.4
<0.1
PE
0.4
4.4
1.8
0
0
0
278.0
<0.1
<0.1
<0.1
1.4
<0.1
DS
0.5
4.8
2.0
0
0
0
257.0
<0.1
<0.1
<0.1
1.6
<0.1
SDS
0.6
6.1
2.8
0
0
0
323.0
<0.1
<0.1
<0.1
2.4
<0.1
treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent
(FE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention
time, and (6) simulated distribution system (SDS) at maximum detection time.
262
-------
Table 20. Halogenated furanone results (ug/L) at plants 3 and 4 (10/16/01)
10/16/01
Compound
MX
EMX
Mucochloric acid (ring)
Mucochloric acid (open)
Plant 3a
C12/NH2C1
Raw
<0.02
<0.02
<0.02
<0.02
FI
0.03
<0.02
0.53
0.11
FE
<0.02
0.05
0.05
<0.02
(0.014)
PE
0.18
0.10
0.13
0.03
DS
<0.02
(0.013)
0.03
0.12
0.16
Plant 4
C12
FI
0.05
<0.02
0.86
0.25
FE
<0.02
0.02
1.00
0.13
PE
<0.02
(0.015)
<0.02
(0.011)
0.71
0.19
DS
0.02
<0.02
0.47
0.14
treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent
(FE), (4) finished water at plant effluent (PE), and (5) distribution system (DS) at average
detention time. Value in parenthesis is less than the MRL.
1.20
Figure 29. Halogenated furanones.
Plants 3 and 4 (10/16/01)
I MX • EMX D MCA (ring) • MCA (open)
Sampling Sites
263
-------
Table 21. Occurrence of other DBFs" at plants 3 and 4
Compound
Halomethanes
Bromodichloromethane
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Haloacids
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Trichloroacetic acid
3,3-Dichloropropenoic acid
Trichloropropenoic acid
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Tribromoacetonitrile
Haloaldehvdes
Dichloroacetaldehyde
Trichloroacetaldehyde
2-Bromo-2-methylpropanal
lodobutanaf
Dichloropropenaf
4-Chloro-2-butenal
Haloketones
1 , 1 -Dichloropropanone
1,1,1 -Trichloropropanone
1 -Bromo- 1 , 1 -dichloropropanone
1,1, 3 ,3 -Tetrachloropropanone
Pentachloropropanone
Hexachloropropanone
Halonitromethanes
Dichloronitromethane
Miscellaneous Halosenated DBFs
Trichlorophenol
Trichlorobenzene- 1 ,2-diol
11/13/00
Plant 3
C12/NH2C1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
8/1/01
Plant 3
C12/NH2C1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
Plant 4
C12
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
1/28/02
Plants
Pre- C12
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Plants
C12/NH2C1
X
X
X
X
X
X
X
X
X
X
X
X
X
-
264
-------
Table 21 (continued)
Compound
Non-halosenated DBFs
3-Methylbutanoic acid
Pentanoic acid
Hexanoic acid
Heptanoic acid
Octanoic acid
Nonanoic acid
Decanoic acid
Dodecanoic acid
Tetradecanoic acid
Pentadecanoic acid
Hexadecanoic acid
Octadecanoic acid
Butanedioic acid
Pentanedioic acid
Hexanedioic acid
Octanedioic acid
Decanedioic acid
Undecanedioic acid
11/13/00
Plant 3
C12/NH2C1
-
X
X
X
X
-
-
-
-
-
X
-
-
-
-
-
-
-
8/1/01
Plant 3
C12/NH2C1
-
-
-
-
-
-
-
-
-
-
-
X
-
-
-
-
-
-
Plant 4
C12
X
-
-
-
-
-
-
X
-
-
-
-
-
-
-
-
-
-
1/28/02
Plants
Pre- C12
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Plants
C12/NH2C1
-
-
-
-
X
X
X
X
X
X
X
-
X
X
X
X
X
X
aDBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique.
bCompounds listed in italics were confirmed through the analysis of authentic standards;
haloacids and non-halogenated carboxylic acids identified as their methyl esters.
°Exact isomer not known.
SDS Testing. Because plant 3 used chloramines, most DBFs were found to be relatively
stable in concentration in the distribution system and in SDS testing. Because plant 4 used free
chlorine, THMs and some of the other DBFs were found to increase in concentration in the
distribution system and in SDS testing. Figure 30 shows that there was an increase in THM
formation—especially for the bromochloro species—during the maximum detention time
(140-hr) SDS test of the plant 3 effluent in October 2001 when the bromide level was the
highest. However, the formation of the THMs increased by a much higher amount during SDS
testing of the plant 4 effluent.
Figure 31 shows the formation and stability of the HANs in SDS testing in October 2001.
Although DCAN can undergo base-catalyzed hydrolysis (Stevens et al., 1989), DC AN was
stable (and continued to form) in SDS testing at plants 3 and 4, as the pH was 7.0-7.4. The other
HANs, including chloroacetonitrile (an EPA study DBF), were stable during this SDS testing.
Figure 32 shows the formation and stability of the haloketones in SDS testing in October
2001. Stevens and colleagues (1989) found 1,1,1-trichloropropanone to be more sensitive to pH
than DCAN. In the SDS testing, it did degrade over time. In addition, its brominated analogue
l-bromo-l,l-dichloropropanone, as well as 1,1,3,3-tetrachloropropanone, were detected in the
plant effluent samples but not in the SDS testing. Alternatively, chloropropanone was stable
during this SDS testing.
265
-------
Figure 30
Formation of Trihalomethanes in Simulated Distribution System (SDS)
Testing (10/16/01): Chloramine and Chlorine Residuals in Plants 3 and
4 SDS Tests, Respectively; Average and Maximum Detention Times of
77 and 140 hr, Respectively
IPIantSEff
IPIant4Eff
D Plant 3 SDS/Ave
D Plant 4 SDS/Ave
1 Plant 3 SDS/Max
• Plant4SDS/Max
Chloroform
Bromodichloromethane Dibromochloromethane
Bromoform
Figure 31
Formation and Stability of Haloacetonitriles in SDS Testing (10/16/01)
IPIantSEff
IPIant4Eff
D Plant 3 SDS/Ave
D Plant 4 SDS/Ave
m Plant 3 SDS/Max
D Plant 4 SDS/Max
Chloroacetonitrile
NR = Not reported
Dichloroacetonitrile Bromochloroacetonitrile Dibromoacetonitrile
266
-------
Figure 33 shows the formation and stability of the haloacetaldehydes in SDS testing in
October 2001. Chloral hydrate can also undergo base catalyzed hydrolysis (Stevens et al., 1989).
In the SDS testing of the chlorinated water from plant 4, it initially increased in formation and
then was somewhat degraded at maximum detention time. Many non-THM DBFs are known to
simultaneously form and degrade in a chlorinated distribution system. Alternatively, dichloro-
and bromochloroacetaldehyde were stable during this SDS testing.
Figure 32
Formation and Stability of Haloketones in SDS Testing (10/16/01)
IPIantSEff
IPIant4Eff
• Plant 3 SDS/Ave
D Plant 4 SDS/Ave
• Plants SDS/Max
• Plant 4 SDS/Max
Chloropropanone
1,1-Dichloro-
propanone
1,1,1-Trichloro-
propanone
1-Bromo-1,1-
di chloro-
propanone
1,1,3,3-
Tetrachloro-
propanone
267
-------
Figure 33
16
14
12
10
Formation and Stability of Haloacetaldehydes
in SDS Testing (10/16/01)
I Plant 3 Eff
i Plant 4 Eff
D Plant 3 SDS/Ave
D Plant 4 SDS/Ave
• Plant 3 SDS/Max
D Plant 4 SDS/Max
D)
8 6
ro
.o
I
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate
REFERENCES
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
Baribeau, H., S. W. Krasner, R. Chinn, and P. C. Singer. Impact of biomass on the stability of
haloacetic acids and trihalomethanes in a simulated distribution system. Proceedings of the
American Water Works Association Water Quality Technology Conference, American Water
Works Association: Denver, CO, 2000.
Cowman, G. A., and P. C. Singer. Effect of bromide ion on haloacetic acid speciation resulting
from chlorination and chloramination of aquatic humic substances. Environmental Science &
Technology 30(1): 16 (1996).
Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to
AWWA Research Foundation, Denver, CO, 2000.
268
-------
Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta.
The occurrence of disinfection by-products in US drinking water. Journal of the American
Water Works Association 81(8):41 (1989).
Krasner, S. W., M. J. Sclimenti, and B. M. Coffey. Testing biologically active filters for
removing aldehydes formed during ozonation. Journal of the American Water Works
Association 85(5):62 (1993).
Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E.
Barrett. Effects of water quality parameters on DBF formation during chloramination.
Proceedings of the American Water Works Association Annual Conference, Vol. D, American
Waterworks Association: Denver, CO, 1996.
Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors.
Environmental Science & Technology 17(2):80 (1983).
Simpson, K.L. and K. P. Hayes. Drinking water disinfection by-products: an Australian
perspective. Water Research 32(5): 1522 (1998).
Singer, P. C., H. Arora, E. Dundore, K. Brophy, and H. S. Weinberg. Control of haloacetic acid
concentrations by biofiltration: a case study. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 1999.
Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane
disinfection by-products. Journal of the American Water Works Association 81(8):54 (1989).
Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and
related halogenated disinfection by-products in chlorinated and chloraminated water; application
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical
Society National Meeting, Chicago, IL, American Chemical Society: Washington, D.C., pp.
748-751, 1995.
269
-------
EPA REGIONS 5 AND 7: PLANTS 9 AND 10
Plant Operations and Sampling
The Mississippi River is the source of water for many drinking-water-treatment plants
(WTPs). Plant 10 (in EPA Region 5) treated water from the Mississippi River. In addition, plant
9 (in EPA Region 7) treated water from the Mississippi River; however, the water that was
treated at plant 9 was a combination of water from the Mississippi River and another river that
flowed into the Mississippi. On January 10, 2001, April 9, 2001, August 27 or September 5,
2001, November 26, 2001, and February 25, 2002, plant 10 and plant 9 were sampled.
Plant 10 had two different treatment trains (Figure 1):
• One train consisted of Aldrich purification units. Chlorine, alum, polymer, and powdered
activated carbon (PAC) were added to the raw water. The water underwent flocculation,
sedimentation, and filtration. Chlorine and ammonia were added to the filtered water to form
chloramines in January and April 2001. Alternatively, chlorine and ammonia were both
added to the raw water in November 2001 and February 2002 to form chloramines. During
the September 2001 sampling, plant 10 used chlorine only. Many utilities that use
chloramines switch back to the use of chlorine only once per year to control the growth of
nitrifying bacteria in the distribution system.
Figure 1. Schematic of treatment process at plant 10
C12 (+NH3) + , ,. . . . _.
Alum + Polymer Mississippi River
+ PAC
PAC
C12 (+NH3)
alum
C19 + alum
Aldrich
Purification
Units: Flocculation
+ Sedimentation +
Filtration
NH
Cl, + NH,
Settling
Basins
No. 1 & 2
Clear Well
Settling
Basins
No. 4 & 5
+ NH,
Clear Well
Distribution
270
-------
• The other train at plant 10 consisted of conventional treatment. PAC was applied to the raw
water. Then within this train, there were parallel treatment basins:
• Chlorine and alum were added at mixing tank number 2. Ammonia (to form
chloramines) was added immediately after the mixing tank in January 2001, April 2001,
and February 2002, but not during the September 2001 sampling. The water underwent
sedimentation in basins 1 and 2. Basins 1 and 2 were out of service for repairs in
November 2001.
• (The raw water for basins 4 and 5 was a mixture of water from the two intakes, one for
the Aldrich purification units and the other for the conventional treatment train.)
Chlorine and alum were added at mixing tank number 1. No ammonia was added to this
portion of the conventional train in January, April or September 2001. Alternatively,
chlorine and ammonia were both added at mixing tank number 1 in November 2001 and
February 2002 to form chloramines. Chlorinated (or chloraminated) water underwent
flocculation and sedimentation (in basins number 4 and 5).
• The water from all four settling basins was then filtered through granular activated
carbon (GAC) filters. The GAC was operated for taste-and-odor control and not for the
removal of DBF precursors. Chlorine and ammonia (to form chloramines) was added to
the filtered water in January 2001, April 2001, November 2001, and February 2002, but
not during the September 2001 sampling, when only chlorine was added.
At plant 9 (Figure 2), initially, the water underwent pretreatment with polymer addition.
Then the water was lime softened. The softened water was then chlorinated and treated with
ferric sulfate ^62(804)3] in the conditioning chamber. At the end of the conditioning chamber,
ammonia was added to form chloramines. The water then passed through a series of settling
basins. PAC was added to the effluent of basin #6. The water was then treated with additional
ferric sulfate, polymer, chlorine, and ammonia. Finally, the water underwent filtration.
Plant 10 was sampled at the following locations:
Aldrich Purification Units Train
(1) raw water
(2) the filter effluent (January 2001 only)
(3) the clearwell effluent
Conventional Treatment Train
(4) raw water
(5) the effluent of basins 4 and 5
(6) the effluent of basins 1 and 2 (except for November 2001)
(7) the filter effluent
(8) the clearwell effluent (January 2001 only)
Combined Plant
(9) the finished water
271
-------
__i -
^ )
v_y
Finished Water
Pumping Station
V
Clearwell
'
v
i~_j i~_j ^^
^^^^^^^^^^^^^
Filters
V
'
h
Waste
Vashwater
V
i '
v
i,' V
J
1 m Treatment
Residuals
Secondary Secondary
Sedimentaion Conditioning
Basins (9-7) Basin
r \i r u
PROCESS FLOW DIAGRAM
PLANT 9
Figure 2. Plant 9 water treatment plant
272
-------
In addition, finished water from the point of entry was collected and simulated distribution
system (SDS) testing was conducted for average and maximum detention times for that time of
year (Table 1). In November 2001, a separate SDS sample at maximum detention time was
prepared for the University of North Carolina (UNC), which used water from the clearwell of the
conventional treatment train. Furthermore, the distribution system was sampled at one to two
locations, one representing an average detention time and the other representing a maximum
detention time (January 2001 only).
Plant 9 was sampled at the following locations:
(1) raw water
(2) softened water
(3) water from the primary conditioner
(4) the effluent of basin #6
(5) the filter influent
(6) and the finished water
In addition, finished water was collected and SDS testing was conducted for average and
maximum detention times for that time of year (Table 1). Furthermore, the distribution system
was sampled at two locations, one representing an average detention time and the other
representing a maximum detention time.
Table 1. SDS holding times at Mississi
Sample
Plant 10 average detention time
Plant 10 maximum detention time
Plant 9 average detention time
Plant 9 maximum detention time
ppi River WTPs
1/10/01
4hr
5 days
3 days
6 days
4/9/01
4hr
5 days
3 days
6 days
8/27 or
9/5/01
4hr
5 days
2 days
3 days
11/26/01
4hr
5 days
2 days
4 days
2/25/02
4hr
5 days
2 days
3 days
On the day of sampling, information was collected on the operations at each plant
(Tables 2-3).
Table 2. Operational information at plant 10
Parameter
Aldrich Purification Units Train
Plant flow for this train (mgd)
Chlorine dose at plant influent (mg/L as C12)
Ammonia dose at plant influent (mg/L as NH3-N)
Alum dose at plant influent (mg/L)
Polymer dosage at plant influent (mg/L)
PAC dosage at plant influent (mg/L)
Permanganate dose at plant influent (mg/L)
Chlorine dose at combined filter eff. (mg/L as C12)
NH3 dose at combined filter eff. (mg/L as NH3-N)
Conventional Treatment Train
PAC dosage at intake (mg/L)
Permanganate dose at intake (mg/L)
1/10/01
8
10
0
96
3.7
1
0
2
0.6
1
0
4/9/01
8
17
0
96
3.5
1.8
0
1.6
0.8
1
0
9/5/01
11
16
0
35
2.r
0.5
2.2
3.6
0
0.7
2.0
11/26/01
10
10
2.0
60.4
2.0
1.2
0
0.8
0.8
0
0
2/25/02
8
9.7
1.7
76.6
3.5
3.0
0
0
0
0
1.7
273
-------
Table 2 (continued)
Parameter
Train for Basins 1 and 2
Plant flow for these basins (mgd)
Chlorine dose at mixing tank no. 2 (mg/L as C12)
NH3 dose immediately after mixing tank no. 2
(mg/L as NH3-N)
Alum dose at mixing tank number 2 (mg/L)
Train for Basins 4 and 5
Plant flow for these basins (mgd)
Chlorine dose at mixing tank no. 1 (mg/L as C12)
NH3 dose at mixing tank no. 1 (mg/L as NH3-N)
Alum dose at mixing tank number 1 (mg/L)
Polymer dosage at mixing tank number 1 (mg/L)
Combined Conventional Treatment Train
GAC filter loading rate (gpm/sq ft)
GAC empty bed contact time (min)
Chlorine dose at combined filter eff. (mg/L as C12)
NH3 dose at combined filter eff. (mg/L as NH3-N)
1/10/01
10
6
1
54
22
6
0
54
0
NAb
NA
2
0.6
4/9/01
11
6
1
50
20.6
14
0
50
1.1
2
5.6
3
0.6
9/5/01
11
6.7
0
53.2
25.8
9.1
0
45.6
0
2
5.6
3.6
0
11/26/01
0
—
—
—
27.5
4.9
0.9
55.4
0
2
5.6
3.7
0.7
2/25/02
8
7.5
1.5
51
20.0
5.7
1.2
51
0
2
5.6
1.9
0.5
aAt intake
bNA = Not available
Table 3. Operational information at plant 9
Parameter
Plant flow (mgd)
Polymer dosage at plant influent (mg/L)
Lime dosage in softening basins (mg/L)
Chlorine dose at cond. chamber (mg/L as C12)
Fe2(SO4)3 dose at conditioning chamber (mg/L)
Polymer dosage at conditioning chamber (mg/L)
NH3 dose at end of cond. chamber (mg/L as NH3-N)
PAC dosage at Basin 6 effluent (mg/L)
Fe2(SO4)3 dose at influent to Basin 9 (mg/L)
Polymer dosage at influent to Basin 9 (mg/L)
Chlorine dose at influent to Basin 9 (mg/L as C12)
Ammonia dose at inf. to Basin 9 (mg/L as NH3-N)
Chlorine dose at clearwell effluent (mg/L as C12)
Ammonia dose at clearwell eff. (mg/L as NH3-N)
1/10/01
122
1.0
108
2.52
6.8
0.5
1.44
2.4
8.6
1.0
1.92
1.44
0
0
4/9/01
88-94
3.0
77
2.3
6.8
1.5
1.2
6.0
6.8
0.4
2.9
1.6
0
0
8/27/01
82
2.0
101
2.88
8.6
1.0
1.92
6.0
6.8
0.4
2.4
1.92
0.24
0.12
11/26/01
70
2.0
101
2.16
3.4
1.0
1.68
1.2
3.4
0.4
2.16
1.8
0
0
2/25/02
84
2.5
103
2.0
3.4
1.0
1.6
1.2"
0
0
2.3
1.8
0
0
aPAC dosage at Basin 1 influent
Water Quality
On the day of sampling, information was collected on water quality at each plant
(Tables 4-5). Data were collected for total organic carbon (TOC) and ultraviolet (UV)
absorbance (Tables 6-7). The raw water in January 2001, April 2001, summer (August or
September) 2001, November 2001, and February 2002 at plant 10 was somewhat higher in TOC
than at plant 9 (4.0-5.9 versus 3.4-5.0 mg/L). Nonetheless, both utilities had a moderate loading
of DBF precursors.
274
-------
At plant 10, in the Aldrich purification units in January 2001, April 2001, September
2001, November 2001, and February 2002, 14-32 % of the TOC and 18-47 % of the UV was
removed. At plant 10, in the conventional treatment train in January 2001, April 2001,
September 2001, November 2001, and February 2002, coagulation removed 17-27 % of the TOC
and filtration removed another 2-17 %. The overall TOC removal in the conventional treatment
train was 28-34 %. In addition, the overall UV removal in the conventional treatment train was
41-62%.
At plant 9, in April 2001, August 2001, November 2001, and February 2002, softening
removed 19-28 % of the TOC, whereas in January 2001 no TOC was initially removed during
the softening process. At plant 9, with downstream coagulation and filtration, the overall TOC
removal on these three sample dates was 17-34 %. In addition, the overall UV removal was 11-
45 %.
Tables 8-9 show the values of miscellaneous other water quality parameters in the raw
water at plant 10 and plant 9, respectively. The raw water in January 2001, April 2001, summer
(August or September) 2001, November 2001, and February 2002 at plant 9 was higher in
bromide than at plant 10 (0.06-0.36 versus 0.05-0.08 mg/L). Nonetheless, both utilities had a
moderate loading of inorganic DBF precursors.
275
-------
Table 4. Water quality information at plant 10
Location
pH
1/10/01
4/9/01
9/5/01
11/26/01
2/25/02
Temperature (°C)
1/10/01
4/9/01
9/5/01
11/26/01
2/25/02
Disinfectant Residual3 (mg/L)
1/10/01
4/9/01
9/5/01
11/26/01
2/25/02
Aldrich Purification Units Train
Raw water
Filter eff.
Clearwell
8.01
7.67
7.56
8.32
7.51
7.50
8.21
7.39
7.60
8.5
7.8
7.6
8.67
7.84
7.70
1.5
2.7
—
13.1
14.7
14.9
28.1
29.8
28.4
13.3
14.2
13.5
7.5
8.2
9.5
—
1.3
3.7
—
2.4
4.2
—
2.1
4.0
—
5.4
5.6
—
5.0
4.9
Conventional Treatment Train
Raw water
Basins 4&5
Basins 1&2
Filter eff.
Clearwell
8.03
7.38
7.49
7.37
7.45
8.38
7.36
7.47
7.37
7.54
8.33
7.24
7.22
7.16
7.70
8.5
7.8
NS
7.6
7.5
8.68
7.79
7.80
7.75
7.64
0.7
0.3
0.4
3.5
2.6
13.3
14.0
14.1
14.7
15.0
28.0
29.2
27.4
28.3
28.0
14.7
16.1
NS
13.2
13.1
6.4
5.8
5.6
6.1
7.9
—
1.9
4.7
0.3b
3.2
—
3.3
4.1
0.2b
3.6
...
2.4
0.7
0.4
3.4
—
o o
J.J
NS
0.4
3.8
—
5.3
3.9
1.1
3.6
Combined Plant
Finished
DSVave
DS/max
SDS/ave
SDS/max
SDS/max
for UNC
7.48
7.53
7.47
7.51
7.52
—
7.41
7.48
NSd
7.46
7.39
—
7.68
7.54
NS
7.63
7.56
—
7.5
7.4
NS
7.5
7.5
7.5
7.69
7.38
NS
7.65
7.57
—
3.0
2.4
10.4
2.9
2.5
—
14.4
13.1
NS
14.8
15.3
—
27.5
26.4
NS
27.6
26.4
—
12.3
13.5
NS
12.2
11.8
11.5
6.5
7.4
NS
6.3
5.6
—
3.7
2.4
1.7
3.5
2.9
—
3.7
3.3
NS
3.5
1.8
—
3.5
3.1
NS
2.9
0.3
...
3.4
3.1
NS
3.2
0.9
1.0
3.6
3.0
NS
3.0
2.3
—
aChlorine residuals (values shown in italics) at Basins 4 & 5 effluent in January and April 2001, and all sample locations in September 2001; chloramine
residuals at other locations.
bGAC filters removed chlorine.
°DS = Distribution system
dNS = Not sampled
276
-------
Table 5. Water quality information at plant 9
Location
Raw
Softened
1° cond.
Basin #6
Filter inf.
Finished
DS/ave
DS/max
SDS/ave
SDS/max
pH
1/10/01
8.10
9.97
9.74
9.66
9.21
9.59
9.74
9.48
9.18
9.09
4/9/01
8.00
10.2
9.85
9.68
9.31
9.70
9.35
9.33
9.26
9.26
8/27/01
8.64
9.82
9.66
9.76
9.34
9.23
9.15
9.38
9.19
9.29
11/26/01
8.26
10.1
9.97
9.65
9.39
9.35
9.10
9.20
9.36
9.38
2/25/02
8.24
9.37
9.35
9.32
9.12
9.12
9.23
9.28
8.93
8.9
Temperature (°C)
1/10/01
1.1
1.5
1.4
2.2
2.2
1.4
3.7
4.0
8.9
6.7
4/9/01
14.4
14.4
15.6
15.6
15.6
15.6
18.9
18.9
16.0
16.5
8/27/01
28.3
27.0
26.9
26.1
26.7
27.2
28.0
28.4
24.4
25.0
11/26/01
12.8
13.3
13.3
13.3
14.4
13.3
13.1
13.2
15.6
13.9
2/25/02
8.3
8.6
8.6
9.4
9.8
8.9
9.8
9.8
7.8
7.2
Disinfectant Residual3 (mg/L)
1/10/01
—
—
1.60
1.60
2.50
2.45
2.45
2.40
2.45
2.35
4/9/01
—
—
1.50
1.10
2.25
2.25
2.15
2.15
2.20
2.10
8/27/01
—
—
1.10
0.95
2.25
2.40
2.25
2.10
2.20
2.10
11/26/01
—
—
2.20
1.50
2.65
2.65
2.30
2.20
2.40
2.30
2/25/02
—
—
1.60
1.55
2.60
2.60
2.55
2.40
2.45
2.4
aChlorine residuals (values shown in italics) at primary (1°) conditioner in January, April, and August 2001; chloramine residuals at other locations.
277
-------
Table 6. TOC and UV removal at plant 10
Location
01/10/2001
Aldrich Raw
Aldrich Filter Eff.
Conventional Raw
Basins 4 & 5 Eff.
Basins 1 & 2 Eff.
Combined Filter Eff.c
04/09/2001
Aldrich Raw
Aldrich Clearwell Eff.
Conventional Raw
Basins 4 & 5 Eff.
Basins 1 & 2 Eff.
Combined Filter Eff.
09/05/2001
Aldrich Raw
Aldrich Clearwell Eff.
Conventional Raw
Basins 4 & 5 Eff.
Basins 1 & 2 Eff.
Combined Filter Eff.
11/26/2001
Aldrich Raw
Aldrich Clearwell Eff.
Conventional Raw
Basins 4 & 5 Eff.
Basins 1 &2 Eff.
Combined Filter Eff.
02/25/2002
Aldrich Raw
Aldrich Clearwell Eff.
Conventional Raw
Basins 4 & 5 Eff.
Basins 1 & 2 Eff.
Combined Filter Eff.
TOC
(mg/L)
4.83
3.57
5.11
4.12
4.04
3.42
4.01
2.86
4.22
3.08
3.11
3.03
5.45
4.68
5.87
4.39
4.89
4.22
4.98
3.64
5.04
4.0
NS
3.43
4.52
3.08
4.91
3.67
3.57
3.24
uva
(cm'1)
0.113
0.063
0.127
0.057
0.079
0.053
0.093
0.051
0.103
0.035
0.053
0.039
0.148
0.078
0.152
0.066
0.075
0.067
0.122
0.100
0.127
0.089
NS
0.070
0.099
0.075
0.111
0.083
0.072
0.065
SUVAb
(L/mg-m)
2.34
1.76
2.49
1.38
1.96
1.55
2.32
1.78
2.44
1.14
1.70
1.29
2.72
1.67
2.59
1.50
1.53
1.59
2.45
2.75
2.52
2.23
...
2.04
2.19
2.44
2.26
2.26
2.02
2.01
Removal/Unit (%)
TOC
—
26%
...
19%
21%
17%
—
29%
...
27%
26%
1.6%
—
14%
...
25%
17%
3.9%
...
27%
—
21%
...
14%
...
32%
—
25%
27%
12%
UV
—
44%
...
55%
38%
7.0%
—
45%
...
66%
49%
-11%
—
47%
...
57%
51%
-1.5%
...
18%
—
30%
...
21%
...
24%
—
25%
35%
22%
Removal/Cumulative (%)
TOC
—
26%
...
19%
21%
33%
—
29%
...
27%
26%
28%
—
14%
...
25%
17%
28%
...
27%
—
21%
...
32%
...
32%
—
25%
27%
34%
UV
—
44%
...
55%
38%
58%
—
45%
...
66%
49%
62%
—
47%
...
57%
51%
56%
...
18%
—
30%
...
45%
...
24%
—
25%
35%
41%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (crrT1)/DOC (mg/L) or UV (rrT1)/DOC (mg/L),
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA)
(e.g., UV = 0.113/cm = 0.113/(0.01 m) = 11.3/m, DOC = 4.83 mg/L, SUVA = (11.3 rrT1)/(4.83 mg/L) = 2.34 L/mg-m)
GRemoval/unit compared to basins 4 & 5 effluent
278
-------
Table 7. TOC and UV removal at plant 9
Location
01/10/2001
Raw
Softened Water
Primary Conditioner
Basin #6 Eft.
Filter Inf.
Finished Water
04/09/2001
Raw
Softened Water
Primary Conditioner
Basin #6 Eff.
Filter Inf.
Finished Water
08/27/2001
Raw
Softened Water
Primary Conditioner
Basin #6 Eff.
Filter Inf.
Finished Water
11/26/2001
Raw
Softened Water
Primary Conditioner
Basin #6 Eff.
Filter Inf.
Finished Water
02/25/2002
Raw
Softened Water
Primary Conditioner
Basin #6 Eff.
Filter Inf.
Finished Water
TOC
(mg/L)
3.39
3.51
3.09
3.20
2.85
2.80
4.96
3.58
3.61
4.05
3.51
3.49
4.22
3.40
3.19
2.97
2.79
2.77
3.61
2.69
2.89
2.43
2.29
2.37
3.37
2.67
3.34
2.50
2.55
2.48
uva
(cm'1)
0.063
0.049
0.055
0.056
0.059
0.056
0.137
0.076
0.078
0.089
0.078
0.076
0.093
0.068
0.052
0.058
0.056
0.058
0.082
0.047
0.054
0.050
0.051
0.053
0.074
0.049
0.050
0.051
0.054
0.055
SUVAb
(L/mg-m)
1.86
1.40
1.78
1.75
2.07
2.00
2.76
2.12
2.16
2.20
2.22
2.18
2.20
2.00
1.63
1.95
2.01
2.09
2.27
1.75
1.87
2.06
2.23
2.24
2.20
1.84
1.50
2.04
2.12
2.22
Removal/Unit (%)
TOC
...
-3.5%
12%
-3.6%
11%
1.8%
—
28%
-0.8%
-12%
13%
0.6%
—
19%
6.2%
6.9%
6.1%
0.7%
...
25%
-7.4%
16%
5.8%
-3.5%
—
21%
-25%
25%
-2.0%
2.7%
UV
...
22%
-12%
-1.8%
-5.4%
5.1%
—
45%
-2.6%
-14%
12%
2.6%
—
27%
24%
-12%
3.4%
-3.6%
...
43%
-15%
7%
-2.0%
-3.9%
—
34%
-2.0%
-2.0%
-5.9%
-1.9%
Removal/Cumulative (%)
TOC
—
-3.5%
8.8%
5.6%
16%
17%
—
28%
27%
18%
29%
30%
—
19%
24%
30%
34%
34%
—
25%
20%
33%
37%
34%
—
21%
1%
26%
24%
26%
UV
...
22%
13%
11%
6.3%
11%
—
45%
43%
35%
43%
45%
—
27%
44%
38%
40%
38%
...
43%
34%
39%
38%
35%
—
34%
32%
31%
27%
26%
UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998)
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm-1)/DOC (mg/L) or UV (m"'
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values
(e.g., UV = 0.063/cm = 0.063/(0.01 m) = 6.3/m, DOC = 3.39 mg/L, SUVA = (6.3 m-1)/(3.39
)/DOC (mg/L),
in calculating SUVA)
mg/L) = 1.86 L/mg-m)
On the January 2001, April 2001, September 2001, November 2001, and February 2002
samplings, the raw water at plant 10 contained up to 0.16 mg/L of ammonia (Table 8).
Theoretically, it takes 7.6 mg/L of chlorine to breakpoint chlorinate 1.0 mg/L of ammonia-
nitrogen. The theoretical inorganic chlorine demand (up to 1.2 mg/L) was significantly less than
the initial chlorine dose applied at each of the trains when prechlorination was practiced (6-17
mg/L) (Table 2).
279
-------
Table 8. Miscellaneous water quality parameters in raw water at plant 10
Location
01/10/2001
Aldrich Train Raw
Conventional Train Raw
04/09/2001
Aldrich Train Raw
Conventional Train Raw
09/05/2001
Aldrich Train Raw
Conventional Train Raw
11/26/2001
Aldrich Train Raw
Conventional Train Raw
02/25/2002
Aldrich Train Raw
Conventional Train Raw
Bromide
(mg/L)
0.08
0.07
0.05
0.05
0.07
0.07
0.05
0.05
0.05
0.05
Alkalinity
(mg/L)
199
199
176
173
148
149
189
186
175
188
Ammonia
(mg/L as N)
0.15
0.16
NDb
0.08
0.04
ND
0.05
0.07
0.06
0.14
Chlorine
Demand3 (mg/L)
1.1
1.2
0
0.6
0.3
0
0.4
0.5
0.5
1.1
Chlorine demand from ammonia = 7.6 * ammonia (mg/L as N)
bND = Not detected
Table 9. Miscellaneous water quality parameters in raw water at plant 9
Date
01/10/2001
04/09/2001
08/27/2001
11/26/2001
02/25/2002
Bromide
(mg/L)
0.19
0.06
0.1
0.2
0.36
Alkalinity
(mg/L)
221
99
175
182
171
Ammonia
(mg/L as N)
0.37
0.05
ND
0.07
0.1
Chlorine
Demand3 (mg/L)
2.8
0.4
0
0.5
0.8
Chlorine demand from ammonia = 7.6 * ammonia (mg/L as N)
In January 2001, the raw water at plant 9 contained 0.4 mg/L of ammonia, whereas in
April 2001, August 2001, November 2001, and February 2002 it only had up to 0.1 mg/L of
ammonia (Table 9). The theoretical inorganic chlorine demand in January 2001 (2.8 mg/L) was
somewhat higher than the initial chlorine dose applied at the conditioning chamber (2.5 mg/L)
(Table 3). Alternatively, the theoretical inorganic chlorine demand in February 2002 (0.8 mg/L)
was lower than the initial chlorine dose applied at the conditioning chamber (2.0 mg/L).
280
-------
DBFs
Tables 10 and 11 (1/10/01), Tables 13 and 14 (4/9/01), Tables 16 and 17 (8/27-9/5/01),
Tables 18 and 19 (11/26/01), and Tables 22 and 23 (2/25/02) show results for the halogenated
organic DBFs that were analyzed for at Metropolitan Water District of Southern California
(MWDSC). Table 12 (1/10/01) and Table 20 (11/26/01) show results for additional target DBFs
that were analyzed for at UNC. Table 20 (11/26/01) show results for halogenated furanones that
were analyzed for at UNC. Table 15 (4/9/01 [plant 10], 8/27/01 [plant 9], and 2/25/02 [plant
10]) shows results from broadscreen analyses conducted at the U.S. Environmental Protection
Agency (USEPA).
Summary of Tables for DBFs for Mississippi River WTPs
DBF Analyses (Laboratory)
Halogenated organic DBFs (MWDSC)
Additional target DBFs (UNC)
Halogenated furanones (UNC)
Broadscreen analysis (USEPA)
1/10/01
Tables 10-
11
Table 12
4/9/01
Tables 13-
14
Table 15a
8/27 or
9/5/01
Tables 16-
17
Table 15b
11/26/01
Tables 18-
19
Table 20
Table 21
2/25/02
Tables 22-
23
Table 15a
aPlant 10
bPlant 9
Halomethanes. Chlorine and/or chloramine disinfection at plant 10 in January and April
2001 resulted in the formation of 71-84 and 54 |ig/L of the four regulated tribalomethanes
(THM4) in the Aldrich purification units and in basins 4 and 5, respectively. THM formation
was lower in the effluent of basins 1 and 2 in January (30 |ig/L of chloroform) and April 2001
(31 |ig/L of TFDVI4) because free chlorine was only present in mixing tank number 2 before
ammonia addition (upstream of basins 1 and 2). Chlorine only disinfection in September 2001
resulted in the formation of 144, 144, and 174 |ig/L of TFDVI4 in the Aldrich purification units, in
basins 4 and 5, and in basins 1 and 2, respectively. Another major difference between the three
seasons was temperature: 0.3-3°C in January 2001, 13-15°C in April 2001, and 26-30°C in
September 2001 (Table 4). Thus, TFDVI formation was significantly higher in September 2001
due to the presence of only free chlorine (no chloramines) and the warmer water temperature. In
contrast, the use of chloramines only at plant 10 in November 2001 and February 2002 resulted
in the formation of 12-19 and 8-14 |ig/L of TFDVI4 in the Aldrich purification units and in basins
4 and 5, respectively.
Chlorine/chloramine disinfection at plant 9 in January 2001, April 2001, August 2001,
November 2001, and February 2002 resulted in the formation of 6-8 |ig/L of TFJJVI4. There was
no seasonal variability in the concentration of THM4 at this plant during this time period. The
very low concentration of TFJJVIs at plant 9 suggests that there was minimal free chlorine contact
time prior to ammonia addition.
Although there were large differences in the total amounts of TFJJVIs formed, both WTPs
produced a high percentage of the THMs as chloroform, followed by bromodichloromethane,
when the raw-water bromide was less than or equal to 0.1 mg/L. Figure 3 shows the impact of
281
-------
bromide on THM speciation at plant 9. As the concentration of bromide increased, the formation
of chloroform decreased and the formation of dibromochloromethane increased.
Figure 3. Impact of bromide on THM speciation in finished water at plant 9
0.06
Bromide
(mg/L)
0.36
Dichloroiodomethane was detected at plant 10 in November 2001 and February 2002.
Dichloroiodomethane, bromochloroiodomethane, and chlorodiiodomethane (February only) were
detected at plant 9 in November 2001 and February 2002. Bromide was at its highest in the
influent of plant 9 in the latter two months. In addition, two of the iodinated TFDVIs were
detected by the broadscreen gas chromatography/mass spectrometry (GC/MS) methods at both
WTPs (dichloroiodomethane and bromochloroiodomethane; Table 15).
Dibromomethane, a volatile organic compound (VOC), was detected (0.13 |ig/L)—
slightly above the minimum reporting level (MRL) (0.11 |ig/L)—in a SDS sample of plant 9 in
January 2001. In other research, this dihalogenated methane had been detected in a high-
bromide water that had been disinfected with chloramines (Krasner et al., 1996). In addition,
bromomethane was detected at its MRL (0.2 |ig/L) in a plant 9 distribution system sample in
November 2001.
282
-------
Table 10. DBF results at plant 10 (1/10/01)
01/10/2001
Compound
Haomethanes
Chloromethane
Bromom ethane
Bromochloromethane
Dibromom ethane
Chloroform"
Bromodichloromethane"
Dibromochloromethane"
Bromoform"
THM4r
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Ha oanptin acids
Monochloroacetic acid"
Monobromoacetic acid"
Dichloroacetic acid"
Bromochloroacetic acid"
Dibromoacetic acid"
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA'
TXAA1
Ha nanptnnitrilps
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile"
Bromochloroacetonitrile"
Dibromoacetonitrile"
Trichloroacetonitrile"
Halnkptnnps
Chloropropanone
1 , 1 -Dichloropropanone"
1 ,3-Dichloropropanone
1 , 1-Dibromopropanone
1 , 1 , 1-Trichloropropanoned
1 , 1 ,3-Trichloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1 , 1 , 1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 , 1,3,3-Tetrachloropropanone
1 , 1 ,3,3-Tetrabromopropanone
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitrom ethane
Dibromonitromethane
Chloropicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRLJ
M9/L
0.15
0.20
0.14
0.11
0.1
0.10
0.07
0.6
0.25
0.20
0.6
0.5
0.6
0.14
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
N/A
0.10
0.10
N/A
N/A
N/A
0.10
0.10
0.16
0.10
0.10
0.10
0.10
N/A
0.10
0.10
N/A
0.16
N/A
Aldrich"
Raw
NDC
NU
ND
NU
0.1
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
NR
Filt Eff
60
NR"
NR
ND
NR
NR
NR
ND
ND
ND
ND
10
1.0
29
6.1
1.0
54
11
1.7
ND
95
114
36
67
ND
ND
4
2
0.2
0.5
ND
1
ND
4
0.1
0.6
ND
5
1
4
ND
ND
ND
1
NR
Clean/veil
ND
ND
ND
ND
60
20
4
ND
84
ND
ND
ND
ND
ND
ND
0.3
10
ND
29
6.0
1.0
55
10
1.7
ND
95
113
36
67
ND
1
4
2
0.2
0.6
ND
1
ND
NR
4
0.1
NR
NR
NR
0.3
ND
5
1
5
ND
ND
NR
ND
1
NR
ND
NR
Conventional"
Raw
ND
ND
ND
ND
0.1
0.1
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
NR
ND
ND
NR
NR
NR
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
NR
ND
NR
Basins 4&5
ND
ND
ND
ND
40
12
2
ND
54
ND
ND
ND
ND
ND
ND
ND
8.8
ND
24
4.6
ND
44
9.1
1.4
ND
77
92
29
55
ND
ND
3
1
0.1
ND
ND
0.9
ND
NR
3
0.1
NR
NR
NR
0.4
ND
4
1
3
ND
ND
NR
ND
0.8
NR
ND
NR
Basins 1&2
30
NR
NR
ND
NR
NR
NR
ND
ND
ND
ND
1.3
ND
19
3.7
ND
22
5.3
1.0
ND
42
52
23
28
ND
ND
2
0.5
ND
0.2
ND
1
ND
2
0.1
0.3
ND
2
1
1
ND
ND
ND
0.9
NR
Filt Eff
ND
ND
ND
ND
45
13
2
ND
60
ND
ND
ND
ND
ND
ND
ND
7.8
ND
21
4.4
ND
45
9.2
1.3
ND
74
89
25
56
ND
ND
2
0.5
ND
0.4
ND
0.7
ND
NR
3
0.1
NR
NR
NR
0.2
ND
4
0.9
2
ND
ND
NR
ND
0.8
NR
ND
NR
Clean/veil
ND
ND
ND
ND
40
12
2
ND
54
ND
ND
ND
ND
ND
ND
ND
6.5
ND
23
4.9
ND
40
8.5
1.2
ND
70
84
28
50
ND
ND
2
0.6
ND
0.3
0.2
0.8
ND
NR
3
0.1
NR
NR
NR
0.2
ND
4
1
3
ND
ND
NR
ND
0.8
NR
ND
NR
Combined Plant"
Finished
ND
ND
ND
ND
45
13
2
ND
60
ND
ND
ND
ND
ND
ND
0.07
6.0
ND
24
5.1
ND
43
9.1
1.4
ND
73
89
29
54
ND
ND
2
0.7
0.1
0.4
0.2
0.8
ND
NR
3
0.1
NR
NR
NR
0.2
ND
4
1
3
ND
ND
NR
ND
0.8
NR
ND
NR
DS/Ave
ND
ND
ND
ND
50
15
2
ND
67
ND
ND
ND
ND
ND
ND
0.1
6.9
ND
24
5.1
ND
44
8.8
1.4
ND
75
90
29
54
ND
ND
3
0.9
0.1
0.4
ND
0.9
ND
NR
3
0.2
NR
NR
NR
0.2
ND
4
1
4
ND
ND
NR
ND
0.9
NR
ND
NR
DS/Max
60
NR
NR
ND
NR
NR
NR
ND
ND
ND
ND
ND
ND
3
1
0.1
ND
ND
1
ND
3
0.2
0.3
ND
4
2
4
ND
ND
ND
1
NR
SDS/Ave
ND
ND
ND
ND
45
14
2
ND
61
ND
ND
ND
ND
ND
ND
0.08
7.2
ND
24
4.8
ND
35
8.2
1.0
ND
66
80
29
44
ND
ND
2
0.7
0.1
ND
ND
0.8
ND
NR
3
0.1
NR
NR
NR
0.4
ND
4
1
3
ND
ND
NR
ND
0.8
NR
ND
NR
SDS/Max
60
NR
NR
ND
NR
NR
NR
ND
ND
ND
ND
ND
ND
3
1
0.1
ND
ND
1
ND
3
0.1
0.3
ND
5
2
4
ND
ND
ND
1
NR
283
-------
Table 11. DBF results at Plant 9 (1/10/01)
01/10/2001
Compound
Ha lorn ethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform
Bromodichloromethane0
Dibromochloromethane
Bromoform
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acid
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAAS9
HAA9"
DXAA'
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Trichloroacetonitrile"
Haloketones
Chloropropanone
1,1-Dichloropropanone
1 ,3-Dichloropropanone
1 , 1 -Dibromopropanone
1,1,1-Trichloropropanone
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1 ,1 ,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Dibromonitromethane
Chloropicrin"
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertian/ butyl ether
Benzyl chloride
MRL"
M9/L
0.15
0.20
0.14
0.11
0.1
0.10
0.07
0.6
0.25
0.20
0.6
0.5
0.6
0.14
0.06
2
1
1
1
1
1
1
1
2
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
N/A
0.10
0.10
N/A
N/A
N/A
0.10
0.10
0.16
0.10
0.10
0.10
0.10
N/A
0.10
0.10
N/A
0.16
N/A
Plant 9k
Raw
NDC
ND
ND
ND
ND
0.1
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
NR
NR
NR
0.2
ND
ND
ND
ND
ND
ND
NR
ND
ND
NR
0.3
NR
1uCond
ND
ND
ND
ND
1
0.5
0.2
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.2
1.0
1.0
ND
ND
ND
ND
3.2
4.2
4.2
ND
ND
ND
0.1
ND
ND
0.1
ND
0.3
ND
NR
ND
ND
NR
NR
NR
ND
ND
ND
0.3
0.2
ND
ND
NR
ND
ND
NR
ND
NR
Basin #6
ND
ND
ND
ND
2
0.7
0.3
ND
3
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.5
1.1
1.2
ND
ND
ND
ND
3.7
4.8
4.8
ND
ND
ND
0.1
ND
ND
0.1
ND
0.3
ND
NR
ND
ND
NR
NR
NR
ND
ND
0.5
0.1
0.2
ND
ND
NR
ND
ND
NR
ND
NR
Fill Inf
3
NRe
NR
ND
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.3
0.1
ND
0.1
ND
0.2
ND
ND
ND
ND
ND
0.6
0.1
0.5
ND
ND
ND
ND
NR
Finished
ND
ND
ND
ND
3
2
0.8
0.7
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.1
1.4
1.3
ND
ND
ND
ND
4.4
5.8
5.8
ND
ND
ND
0.3
0.1
ND
ND
ND
0.2
ND
NR
ND
ND
NR
NR
NR
ND
ND
0.6
ND
0.5
ND
ND
NR
ND
ND
NR
ND
NR
DS/Ave
ND
ND
ND
ND
3
2
1
1
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.4
1.6
1.7
ND
ND
ND
ND
5.1
6.7
6.7
ND
ND
ND
0.3
0.2
ND
ND
ND
0.2
ND
NR
ND
ND
NR
NR
NR
ND
ND
0.6
ND
0.5
ND
ND
NR
ND
ND
NR
0.3
NR
DS/Max
3
NR
NR
1
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.1
ND
ND
ND
0.2
ND
ND
ND
ND
ND
0.8
ND
0.3
ND
ND
ND
ND
NR
S DS/Ave
ND
ND
ND
0.13
3
2
1
0.7
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.5
1.5
1.5
ND
ND
ND
ND
5.0
6.5
6.5
ND
ND
ND
0.2
0.1
ND
ND
ND
0.2
ND
NR
ND
ND
NR
NR
NR
ND
ND
0.9
ND
0.2
ND
ND
NR
ND
ND
NR
ND
NR
S DS/Max
3
NR
NR
0.8
NR
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.1
ND
ND
ND
0.2
ND
ND
ND
ND
ND
1
ND
0.1
ND
ND
ND
ND
NR
Plant 9 sampled at (1) raw water, (2) primary conditioner, (3) basin #6 effluent, (4) filter influent,
(5) finished water, distribution system (DS) at (6) average and at (7) maximum detention times,
and SDS testing of finished water at (8) average and at (9) maximum detention times
284
-------
"MRL = Minimum reporting level, which equals method detection limit (MDL)
or lowest calibration standard or concentration of blank
bPlant 10 sampled at train for Aldrich Purification units at (1) raw water, (2) filter influent, and (3) clean/veil effluent;
at conventional treatment train at (4) raw water, (5) basins 4&5 effluent, (6) basins 1&2 effluent, (7) combined filter effluent, and (8) clean/veil effluent;
and for combined treated waters at (9) finished water, distribution system (DS) at (10) average and at (11) maximum detention times,
and SDS testing of finished water at (12) average and at (13) maximum detention times
CND = Not detected at or above MRL
dDBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required)
eNR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance
fTHM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform)
9HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid)
hHAA9 = Sum of 9 haloacetic acids
'DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid)
'TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid)
Table 12. Additional target DBF results (iig/L) at Mississippi River WTPs (1/10/01)
1/10/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
2,2-Dichloroacetamide
TOX (ug/L as CD
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
/raws-2-Hexenal
Plant 9a
Raw
0.0
0.0
0.0
0.0
0.0
0.0
7.4
0.1
O.I
0.1
O.4
0.1
PC
0.0
0.0
0.0
0.0
0.0
0.0
58.7
0.1
O.I
0.1
O.4
0.1
PE
0.0
0.9
0.0
0.0
0.0
0.0
64.4
0.1
O.I
0.1
O.4
0.1
DS
0.0
0.9
0.0
0.0
0.0
0.0
55.7
0.1
O.I
0.1
O.4
0.1
SDS
0.0
0.9
0.0
0.0
0.0
0.0
61.5
0.1
O.I
0.1
O.4
0.1
Plant 10b
Raw
0.0
0.0
0.0
0.0
0.0
0.0
13.7
0.1
O.I
0.1
O.4
0.1
B4&5
0.5
4.6
0.8
0.5
0.0
2.1
222
0.1
O.I
0.1
O.4
0.1
B1&2
0.8
3.9
2.0
0.4
0.0
1.5
252
0.1
O.I
0.1
O.4
0.1
FE
0.8
3.7
0.7
0.6
0.0
1.9
203
0.1
O.I
0.1
O.4
0.1
PE
0.4
3.6
1.3
0.8
0.0
1.7
237
0.1
O.I
0.1
O.4
0.1
"Plant 9 sampled at (1) raw water, (2) primary conditioner (PC), (3) finished water at plant effluent (PE),
(4) distribution system (DS) at average detention time, and (5) SDS at maximum detection time.
bPlant 10 sampled at (1) raw water, (2) effluent of basins 4 and 5 (B4&5), (3) effluent of basins 1 and 2
(B1&2), (4) filter effluent (FE), and (5) PE.
285
-------
Table 13. DBF results at plant 10 (4/9/01)
04/9/2001
Compound
Halomethanes
Chloro methane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform"
Bromodichloromethane"
Dibromochloromethane"
Bromoform"
THM4r
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodo methane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid"
Monobromoacetic acid"
Dichloroacetic acid"
Bromochloroacetic acid"
Dibromoacetic acid"
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA'
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile"
Bromochloroacetonitrile"
Dibromoacetonitrile"
Trichloroacetonitrile"
Haloketones
Chloro pro panone
1 , 1 -Dichloropropanone"
1,3-Dichloropro panone
1 , 1 -Dibromopropanone
1,1,1 -Trichloropropanone"
1 , 1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1,1,3,3-Tetrabromopropanone
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitro methane
Bromochloronitro methane
Dibromonitromethane
Chloropicrin"
Miscellaneous Compounds
Methvl ethvl ketone
Methvl tertiarv butvl ether
Benzyl chloride
MRL"
M9/L
0.5
0.20
0.14
0.11
0.1
0.1
0.1
0.1
0.2
0.20
0.5
0.5
0.5
0.5
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.2
0.1
0.5
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.14
0.1
0.10
0.6
0.22
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
1.9
0.16
NA
Aldrich'
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clean/veil
ND
ND
ND
ND
54
15
2
ND
71
ND
ND
ND
ND
ND
ND
0.12
ND
13
ND
33
5.6
ND
37
13
1.9
ND
83
104
39
52
0.5
ND
8
1
ND
0.4
0.8
1
ND
ND
6
ND
0.6
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.4
ND
ND
2
ND
ND
ND
Conventional'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
ND
ND
ND
ND
40
12
2
ND
54
ND
ND
ND
ND
ND
ND
ND
ND
14
ND
36
6.5
ND
40
15
2.2
ND
90
114
43
57
0.2
ND
7
1
ND
0.2
0.5
0.9
ND
ND
8
ND
0.8
ND
ND
ND
0.1
ND
2
ND
ND
ND
ND
0.4
ND
ND
2
ND
ND
ND
Basins 1&2
22
8
0.8
ND
31
ND
NR
ND
ND
ND
ND
ND
4.0
ND
23
3.7
ND
24
5.1
1.1
ND
51
61
27
30
ND
ND
3
0.5
ND
0.2
ND
1
ND
ND
2
0.3
0.4
ND
0.1
ND
0.1
ND
2
0.4
ND
0.2
ND
0.2
ND
ND
2
NR"
Filt Eff
ND
ND
ND
ND
46
14
2
ND
62
ND
ND
ND
ND
ND
ND
0.11
ND
8.6
ND
21
3.0
ND
35
11
1.6
ND
65
80
24
48
0.2
ND
3
0.5
ND
0.3
0.7
0.6
ND
ND
6
ND
0.5
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
0.3
ND
ND
2
ND
ND
ND
Combined Plant'
Finished
ND
ND
ND
ND
50
10
1
ND
61
ND
ND
ND
ND
ND
ND
0.10
ND
7.5
ND
27
5.3
ND
37
12
1.8
ND
72
91
32
51
0.1
ND
3
0.4
ND
0.2
0.5
0.5
ND
ND
3
ND
0.3
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
DS/Ave
ND
ND
ND
ND
45
14
2
ND
61
ND
ND
ND
ND
ND
ND
0.13
ND
7.5
ND
25
4.8
ND
35
11
1.6
ND
68
85
30
48
0.3
ND
4
0.7
ND
0.3
0.9
1
ND
ND
4
ND
0.4
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.3
ND
ND
2
ND
ND
ND
SDS/Ave
ND
ND
ND
ND
42
13
2
ND
57
ND
ND
ND
ND
ND
ND
0.10
ND
7.8
ND
28
5.0
ND
36
12
1.6
ND
72
90
33
50
0.2
ND
4
0.7
ND
0.3
0.7
1
ND
ND
5
ND
0.4
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.3
ND
ND
2
ND
ND
ND
SDS/Max
54
16
2
ND
72
ND
NR
ND
ND
ND
ND
ND
0.3
ND
4
1
ND
0.1
0.6
2
ND
ND
3
ND
ND
ND
ND
ND
ND
ND
3
0.2
ND
ND
ND
0.1
ND
ND
3
NR
Plant 10 sampled at train for Aldrich Purification units at (1) raw water and (2) clearwell effluent;
at conventional treatment train at (3) raw water, (4) basins 4&5 effluent, (5) basins 1 &2 effluent, and (6) combined filter effluent;
and for combined treated waters at (7) finished water and (8) DS at average detention time,
and SDS testing of finished water at (9) average and at (10) maximum detention times
286
-------
Table 14. DBF results at Plant 9 (4/9/01)
04/9/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethane
Bromoform0
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acidd
Dichloroacetic acid"
Bromochloroacetic acid
Dibromoacetic acidd
Trichloroacetic acid"
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA'
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitriled
Dibromoacetonitrile
Trichloroacetonitrile"
Haloketones
Chloropropanone
1 ,1-Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1-Dibromopropanone
1,1,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1,1,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate0
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin"
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
MRL*
ug/L
0.15
0.20
0.14
0.11
0.1
0.1
0.1
0.1
0.2
0.20
0.5
0.5
0.5
0.5
0.06
0.1
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.2
0.1
0.5
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.14
0.1
0.10
0.6
0.22
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
1.9
0.16
NA
Plant 9R
Raw
ND°
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1uCond
ND
ND
ND
ND
6
1
0.1
ND
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
11
1.4
ND
1.1
ND
ND
ND
12
14
12
1.1
ND
ND
0.4
ND
ND
ND
ND
0.7
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
0.1
ND
ND
0.1
ND
ND
ND
Basin #6
ND
ND
ND
ND
5
1
ND
ND
6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
12
1.3
ND
1.3
ND
ND
ND
13
15
13
1.3
ND
ND
ND
ND
ND
ND
ND
0.3
ND
ND
0.1
ND
ND
ND
ND
0.1
0.1
ND
2
ND
ND
0.1
ND
0.1
ND
ND
ND
ND
ND
ND
Fill Inf
6
2
0.3
ND
8
ND
NRe
ND
ND
ND
ND
ND
ND
ND
0.3
0.1
ND
ND
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.1
ND
ND
0.2
NR
Finished
ND
ND
ND
ND
6
2
0.3
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
15
2.9
ND
2.7
ND
ND
ND
18
21
18
2.7
ND
ND
0.3
0.1
ND
ND
ND
0.4
ND
ND
0.4
0.3
0.1
ND
0.1
ND
0.1
ND
3
0.2
ND
0.4
ND
0.1
ND
ND
0.2
ND
ND
ND
DS/Ave
ND
ND
ND
ND
5
3
0.4
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
2.6
ND
2.1
ND
ND
ND
16
19
17
2.1
ND
ND
0.1
0.1
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.2
ND
ND
0.1
ND
ND
ND
DS/Max
6
3
0.4
ND
9
ND
NR
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.2
ND
ND
0.1
NR
SDS/Ave
ND
ND
ND
ND
7
3
0.3
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
18
2.4
ND
2.3
ND
ND
ND
20
23
20
2.3
ND
ND
0.1
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.2
ND
ND
0.1
ND
ND
ND
SDS/Max
7
2
0.3
ND
9
ND
NR
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
0.2
ND
ND
ND
NR
287
-------
Table 15. Occurrence of other DBFs at Mississippi River WTPs: finished waters at plant
effluents
Compound
Halomethanes
Bromodichloromethane0
Dibromochloromethane
Bromoform
Dichloroiodomethane
Bromochloroiodomethane
Haloacids
Dichloroacetic acid
Bromochloroacetic acid
Dibromoacetic acid
Bromodichloroacetic acid
Trichloroacetic acid
3,4,4-Trichloro-3-butenoic acid
cis-2-Bromo-3-methylbutenedioic acid
Haloacetonitriles
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Dibromochloroacetonitrile
Haloaldehvdes
2-Bromo-2-methylpropanal
Haloketones
1 , 1 -Dichloropropanone
1 -Bromo- 1 -chloropropanone
1,1,1 -Trichloropropanone
1 -Bromo- 1 , 1 -dichloropropanone
1,1, 3-Tribromo-3-chloropropanone
1,1,3, 3-Tetrabromopropanone
Pentachloropropanone
Hexachloropropanone
Halonitromethanes
Dichloronitromethane
Bromochloronitromethane
Bromodichloronitromethane
Halofuranones
Ox-MX
Miscellaneous Halosenated DBFs
1 ,2-Dichloroethylbenzene
Dichlorophenol
Tetrachlorocyclopentadiene
Hexachlorocyclopentadiene
Bromopentachlorocyclopentadiene
Non-halosenated DBFs
Glyoxal
4-Methylpentanoic acid
Dodecanoic acid
Plant 10
4/9/01
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
2/25/02
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
-
Plant 9
8/27/01
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-
X
X
aDBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique.
bCompounds listed in italics were confirmed through the analysis of authentic standards;
haloacids and non-halogenated carboxylic acids identified as their methyl esters.
288
-------
Table 16. DBF results at
09/05/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodome thane
Chlorodiiodome thane
Bromodiiodome thane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acid
Bromochloroacetic acidd
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA'
TXAAJ
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1 -Dibromopropanone
1 ,1 ,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3, 3-Tetra Chloropropanone
1 ,1 ,1 , 3-Tetra Chloropropanone
1 ,1 ,3,3-Tetrabromopropanone
plant 10 (9/5/01)
wfm?
Mg/L
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.1
0
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.91
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
Aldrich'
Raw
ND°
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Clearwell
ND
ND
ND
ND
100
40
4
ND
144
ND
ND
ND
ND
ND
ND
0.3
ND
9.0
1.2
64
9.4
ND
91
19
1.2
3.3
165
198
73
115
1
ND
22
1
0.2
ND
0.5
0.5
ND
ND
7
ND
ND
ND
ND
0.2
0.3
ND
Conventional'
Raw
ND
ND
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
ND
ND
ND
ND
100
40
4
ND
144
ND
ND
ND
ND
ND
ND
ND
ND
5.9
1.1
51
9.0
1.0
90
16
1.9
2.7
149
179
61
111
0.6
ND
21
2
0.4
0.2
0.8
ND
ND
0.7
0.6
ND
ND
9
ND
0.3
ND
ND
0.2
0.3
ND
Basins 1&2
120
50
4
ND
174
ND
ND
ND
ND
ND
ND
ND
6.5
1.2
53
9.0
1.0
85
18
1.1
2.5
147
177
63
107
0.8
ND
23
2
ND
0.2
0.7
1
ND
ND
8
ND
ND
ND
ND
1
0.8
ND
Fill Eff
ND
ND
ND
ND
110
40
4
ND
154
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
13
2.4
ND
73
16
1.1
ND
86
106
15
90
0.6
ND
9
0.6
ND
0.1
ND
ND
ND
0.8
0.9
ND
ND
6
ND
ND
ND
ND
ND
0.5
ND
Combined Plant'
Finished
ND
ND
ND
ND
120
40
4
ND
164
ND
ND
ND
ND
ND
ND
ND
ND
2.4
ND
24
4.4
ND
80
17
1.7
ND
106
130
28
99
0.7
ND
12
1
ND
0.1
ND
ND
ND
0.8
0.8
ND
ND
7
ND
ND
ND
ND
ND
0.4
ND
DS/Ave
ND
ND
ND
ND
150
50
6
ND
206
ND
ND
ND
ND
ND
ND
ND
ND
5.2
1.0
41
6.1
ND
87
18
1.2
2.4
134
162
47
109
0.9
ND
19
2
0.3
ND
1
0.4
ND
ND
7
ND
ND
ND
ND
0.3
0.3
ND
S DS/Ave
ND
ND
ND
ND
120
30
4
0.2
154
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
26
5.4
ND
82
18
1.8
ND
108
133
31
102
1
0.2
16
1
ND
ND
0.7
0.5
ND
ND
7
ND
ND
NRe
ND
0.3
0.4
ND
SDS/Max
270
60
9
0.2
339
ND
ND
ND
ND
ND
ND
ND
0.9
0.3
18
1
0.2
ND
0.8
0.2
ND
ND
0.8
ND
ND
NR
ND
0.1
0.2
ND
289
-------
Table 16 (continued)
09/05/2001
Compound
Haloacetaldehydes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrated
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitro methane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1,1,2,2-Tetrabromo-2-chloroethane
MRLa
ug/L
0.221
0.5
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.505
2.1
0.5
0.2
0.5
0.1
Aldrich'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.6
ND
ND
Clean/veil
4
2
29
ND
ND
0.3
ND
ND
2
ND
1.0
ND
ND
Conventional'
Raw
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.3
ND
ND
Basins 4&5
4
2
22
ND
ND
0.4
ND
ND
1
0.9
ND
ND
0.6
1.0
ND
ND
Basins 1&2
7
2
22
ND
ND
0.2
ND
ND
0.8
NR
ND
Fill Eff
3
0.7
16
ND
ND
ND
ND
ND
0.8
0.5
ND
ND
0.6
1.0
ND
ND
Combined Plant'
Finished
4
ND
16
ND
ND
ND
ND
ND
0.7
0.6
ND
ND
0.6
0.9
ND
ND
DS/Ave
3
ND
26
ND
ND
0.2
ND
ND
1
0.6
0.8
ND
ND
S DS/Ave
4
1
28
ND
ND
0.2
ND
ND
0.7
0.7
1.0
ND
ND
SDS/Max
2
ND
62
ND
ND
0.3
ND
ND
1
NR
ND
290
-------
Table 17. DBF results at plant 9 (8/27/01)
08/27/2001
Compound
Halomethanes
Chlorom ethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform11
Bromodichloromethane'1
Dibromochloromethane
Bromoform'1
THM4*
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodom ethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acid
Monobromoacetic acid0
Dichloroacetic acid"
Bromochloroacetic acid
Dibromoacetic acid"
Trichloroacetic acid
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9"
DXAA1
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitrile
Bromochloroacetonitrile0
Dibromoacetonitrile
Trichloroacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanone0
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1,1,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
VglL
0.2
0.2
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.52
0.1
0.5
0.1
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.91
0.1
0.10
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.10
0.1
Plant 9K
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1uCond
ND
ND
ND
ND
4
2
0.3
ND
6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8.4
1.7
ND
1.3
ND
ND
ND
9.7
11
10
1.3
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
0.7
ND
ND
0.3
ND
ND
ND
ND
ND
ND
ND
Basin #6
ND
ND
ND
ND
4
2
0.5
ND
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
11
1.6
ND
1.1
ND
ND
ND
12
14
13
1.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
Filt Inf
5
2
0.9
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
Finished
ND
ND
ND
ND
4
2
1
ND
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
15
2.9
1.1
1.3
1.0
ND
ND
17
21
19
2.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
DS/Ave
ND
ND
ND
ND
6
3
1
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
18
3.5
1.3
1.6
1.0
ND
ND
21
25
23
2.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS/Max
8
2
0.7
ND
11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SDS/Ave
ND
ND
ND
ND
5
3
1
ND
9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
17
3.7
ND
1.2
ND
ND
ND
18
22
21
1.2
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SDS/Max
5
2
1
ND
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.4
ND
291
-------
Table 17 (continued)
08/27/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate0
Tribromoacetaldehyde
Halonitromethanes
Bromonitrom ethane
Dichloronitromethane
Bromochloronitrom ethane
Dibromonitromethane
Chloropicrin
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous ComDounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRL"
Mg/L
0.221
0.5
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.51
2.1
0.5
0.2
0.5
0.1
Plant 9K
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
ND
ND
TCond
1
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basin #6
1
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
0.6
ND
ND
ND
ND
ND
ND
ND
ND
NRe
ND
Finished
1
ND
0.3
ND
ND
ND
ND
ND
ND
ND
0.6
ND
1
ND
ND
ND
DS/Ave
0.9
ND
0.2
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
DS/Max
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
SDS/Ave
0.2
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
SDS/Max
0.9
0.8
0.6
ND
ND
ND
ND
ND
ND
0.6
ND
ND
NR
ND
292
-------
Table 18. DBF results at
11/26/2001
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodome thane
Chlorodiiodome thane
Bromodiiodome thane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acid
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA'
TXAAJ
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1 -Dibromopropanone
1 ,1 ,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
plant 10 (11/26/01)
wfm?
Mg/L
0.2
0.2
0.5
0.5
0.2
0.1
0.1
0.11
0
0.5
0.5
0.52
0.1
0.5
2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.1
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.10
0.1
0.1
0.1
0.1
0.1
2.5
0.14
0.10
0.10
0.5
Aldrich'
Raw
ND°
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
Clearwell
ND
ND
ND
ND
13
5
0.6
ND
19
1
ND
ND
ND
ND
ND
0.3
ND
ND
1.2
16
2.3
ND
6.5
1.1
ND
ND
24
27
18
7.6
ND
ND
2
ND
ND
ND
ND
1
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
Conventional'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
ND
ND
ND
ND
10
4
0.4
ND
14
1
ND
ND
ND
ND
ND
ND
ND
2.8
ND
14
2.0
ND
5.4
ND
ND
ND
22
24
16
5.4
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
Basins 1&2
NSm
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Fill Eff
ND
ND
ND
ND
12
4
0.4
ND
16
0.9
ND
ND
ND
ND
ND
ND
ND
ND
1.0
6.2
ND
ND
4.4
ND
ND
ND
12
12
6.2
4.4
ND
ND
0.7
ND
ND
ND
ND
ND
ND
ND
0.6
ND
ND
0.8
ND
ND
ND
ND
ND
ND
ND
Combined Plant'
Finished
ND
ND
ND
ND
12
4
0.5
ND
17
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
11
2.4
ND
6.1
1.0
ND
ND
17
21
13
7.1
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
0.8
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
ND
ND
ND
14
5
0.6
ND
20
1
ND
ND
ND
ND
ND
ND
ND
3.5
1.3
13
2.2
ND
6.0
ND
ND
ND
24
26
15
6.0
ND
ND
2
0.3
ND
ND
ND
1
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
S DS/Ave
ND
ND
ND
ND
12
5
0.6
ND
18
1
ND
ND
ND
ND
ND
ND
ND
ND
1.2
11
2.4
ND
6.1
1.0
ND
ND
18
22
13
7.1
ND
ND
1
0.2
ND
ND
ND
0.8
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
SDS/Max
NAn
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
293
-------
Table 18 (continued)
11/26/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRLJ
ug/L
1.1
0.5
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.90
0.5
0.2
0.25
0.5
Aldrich'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
Clearwell
4
0.9
2
ND
ND
ND
ND
ND
0.8
ND
ND
ND
ND
Conventional'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
2
0.6
1
ND
ND
ND
ND
ND
0.4
ND
ND
ND
ND
ND
ND
ND
Basins 1 &2
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Filt Eff
2
ND
1
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
Combined Plant'
Finished
2
0.6
1
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
DS/Ave
3
1
2
ND
ND
0.1
ND
ND
0.7
ND
ND
ND
ND
SDS/Ave
2
1
1
ND
ND
0.1
ND
ND
0.6
ND
ND
ND
ND
SDS/Max
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
mNS = Not sampled
"NA = Not available
294
-------
Table 19. DBF results at plant 9 (11/26/01)
11/26/2001
Compound
Halomethanes
Chlorom ethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform11
Bromodichloromethane'1
Dibromochloromethane
Bromoform'1
THM4*
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodom ethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochlorom ethane
Haloacetic acids
Monochloroacetic acid0
Monobromoacetic acid
Dichloroacetic acid"
Bromochloroacetic acid"
Dibromoacetic acid
Trichloroacetic acid0
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9"
DXAA1
TXAA'
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitrile
Dibromoacetonitrile0
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanone0
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1,1,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
VglL
0.2
0.2
0.5
0.5
0.2
0.1
0.1
0.11
0.5
0.5
0.52
0.1
0.5
2
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.10
0.1
0.14
0.1
0.5
0.5
0.5
0.1
0.10
0.1
0.1
0.1
0.1
0.1
2.5
0.14
0.10
0.10
0.5
Plant 9K
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1uCond
ND
ND
ND
ND
4
2
0.9
ND
7
<0.5°
ND
ND
ND
ND
ND
ND
ND
ND
1.2
5.1
1.8
1.0
ND
ND
ND
ND
7.3
9.1
7.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basin #6
ND
ND
ND
ND
2
2
0.9
0.1
5
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
1.3
5.0
2.2
1.3
ND
ND
ND
ND
7.6
9.8
8.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
2
2
2
0.4
6
NRe
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
Finished
ND
ND
ND
ND
3
3
2
0.4
8
1
ND
ND
ND
ND
ND
ND
ND
ND
1.2
6.2
2.5
2.1
ND
ND
ND
ND
9.5
12
11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
0.2
ND
ND
4
5
4
1
14
2
<0.5
ND
ND
ND
ND
ND
ND
2.4
1.2
7.9
4.2
3.0
ND
ND
ND
ND
15
19
15
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS/Max
6
6
4
1
17
NR
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
SDS/Ave
ND
ND
ND
ND
2
2
2
0.5
7
1
ND
ND
ND
ND
ND
ND
ND
2.9
ND
6.2
3.4
1.9
ND
ND
ND
ND
11
14
12
ND
ND
NA
NA
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
NA
NA
NA
NA
SDS/Max
NA"
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
295
-------
Table 19 (continued)
11/26/2001
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrin
Bromodichloronitrom ethane
Dibromochloronitrom ethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRL"
Mg/L
1.1
0.5
0.1
0.1
0.1
0.1
0.1
0.10
0.1
0.5
0.5
0.90
0.5
0.2
0.25
0.5
Plant 9K
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
1U Cond
1
ND
0.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basin #6
2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
2
ND
0.1
ND
ND
ND
ND
ND
ND
NR
ND
Finished
2
ND
ND
ND
ND
ND
ND
ND
ND
0.7
1
2
ND
ND
ND
ND
DS/Ave
3
ND
0.6
ND
ND
0.2
ND
ND
0.3
0.8
ND
ND
ND
DS/Max
2
ND
0.4
ND
ND
0.1
ND
ND
ND
NR
ND
SDS/Ave
NA
NA
NA
NA
NA
ND
ND
ND
NA
1
ND
ND
ND
SDS/Max
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.7
ND
3
NA
NA
°<0.5 = Less than MRL (0.5 |jg/L)
296
-------
Table 20. Additional target DBF results (iig/L) at Mississippi River WTPs (11/26/01)
11/26/01
Compound
Monochloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
3,3-Dichloropropenoic acid
Bromochloromethylacetate
TOX (ug/L as Cl")
Cyanoformaldehyde
5-Keto-l-hexanal
6-Hydroxy-2-hexanone
Dimethylglyoxal
/raws-2-Hexenal
Soft.
0.0
0.0
0.0
0.0
0.0
2.8
<0.1
<0.1
<0.1
0.3
<0.1
PC
0.4
4.6
0.2
0.0
0.0
82.7
<0.1
<0.1
<0.1
0.3
<0.1
Plant 9C
PE
0.0
5.0
0.2
0.0
0.0
66.4
<0.1
<0.1
<0.1
0.2
<0.1
DS
0.0
0.0
99.2
NA
NA
NA
NA
NA
SDS
0.0
1.1
0.0
0.0
0.0
<0.1
0.1
<0.1
0.4
<0.1
Raw
0.0
0.0
0.0
0.0
0.0
29.5
<0.
<0.
<0.
<0.
<0.
B4&5
0.0
4.6
0.6
0.4
0.0
207
<0.1
0.1
O.I
0.7
O.I
Plant
B1&2
NA
O.I
0.1
O.I
0.1
O.I
10d
FE
0.0
2.5
0.4
0.4
0.0
144
O.I
0.1
O.I
0.1
O.I
PE
0.0
2.3
0.80
0.4
0.0
175
O.I
0.1
O.I
0.3
O.I
SDS
0.0
O.I
0.1
O.I
0.1
O.I
°Plant 9 sampled at softened water rather than at raw water.
dPlant 10 also sampled at SDS at maximum detection time.
Table 21. Halogenated furanone results
at Mississippi River WTPs (11/26/01)
11/26/01
Compound
BMX-1
BEMX-1
BMX-2
BEMX-2
BMX-3
BEMX-3
MX
EMX
ZMX
Ox-MX
Mucochloric acid
(ring)
Mucochloric acid
(open)
Plant 9C
Soft.
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
O.02
(0.01)
O.02
O.02
0.02
(0.01)
PC
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.03
O.02
0.03
0.03
PE
0.02
0.02
0.02
0.02
0.02
0.02
O.02
(0.018)
0.02
0.02
O.02
0.08
0.08
DS
0.02
0.02
0.02
0.02
0.02
0.02
O.02
(0.013)
0.02
O.02
O.02
0.07
0.10
SDS
0.02
0.02
0.02
0.02
0.02
0.02
NA
NA
NA
NA
NA
NA
Plant 10e
Raw
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
O.02
O.02
O.02
0.02
B4&5
0.03
0.02
0.02
0.02
0.02
0.02
0.40
0.02
O.02
O.02
O.02
0.02
FE
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.04
O.02
0.03
0.03
PE
0.02
0.02
0.02
0.02
0.02
0.02
0.06
0.02
O.02
O.02
O.02
0.02
ePlant 10 sampled at (1) raw water, (2) B4&5, (3) FE, and (4) PE.
297
-------
Table 22. DBF results at
02/25/2002
Compound
Halomethanes
Chloromethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroformd
Bromodichloromethaned
Dibromochloromethaned
Bromoformd
THM4f
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodome thane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochloromethane
Haloacetic acids
Monochloroacetic acidd
Monobromoacetic acidd
Dichloroacetic acidd
Bromochloroacetic acid
Dibromoacetic acidd
Trichloroacetic acidd
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA1
TXAAJ
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitriled
Dibromoacetonitriled
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1 ,1 -Dichloropropanoned
1 ,3-Dichloropropanone
1 ,1 -Dibromopropanone
1 ,1 ,1 -Trichloropropanoned
1 ,1 ,3-Trichloropropanone
1-Bromo-1,1-dichloropropanone
1,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
plant 10 (2/25/02)
wfm?
Mg/L
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.2
0.5
0.5
0.5
0.1
0.52
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.2
0.2
1.0
0.1
0.5
0.5
0.955
0.5
1.0
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.10
0.10
0.1
Aldrich'
Raw
ND°
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
Clearwell
ND
ND
ND
ND
8
3
0.5
<0.2P
12
<0.5
ND
ND
ND
ND
ND
ND
ND
2.5
ND
12
2.2
ND
6.2
1.3
3.0
ND
21
27
14
11
ND
ND
0.4
ND
ND
ND
ND
<1q
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
Conventional'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
ND
ND
ND
ND
5
2
0.4
<0.2
8
ND
ND
ND
ND
ND
ND
ND
ND
2.9
ND
13
2.2
ND
6.9
1.4
4.0
ND
23
30
15
12
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
<1
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
Basins 1&2
NRe
NR
NR
ND
NR
NR
ND
NR
ND
ND
ND
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
ND
ND
NR
NR
ND
ND
NR
NR
ND
ND
NR
ND
0.1
ND
ND
ND
ND
ND
Fill Eff
ND
ND
ND
ND
8
3
0.4
<0.2
12
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
2.7
ND
11
2.6
2.9
ND
25
33
17
17
ND
ND
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
Combined Plant'
Finished
ND
ND
ND
ND
10
4
0.6
<0.2
15
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
2.7
ND
11
2.6
2.5
ND
25
33
17
16
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
<1
ND
ND
0.9
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
ND
ND
ND
11
5
0.7
<0.2
17
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
2.7
ND
11
2.5
2.7
ND
25
33
17
16
ND
ND
0.4
ND
ND
ND
ND
<1
ND
ND
1
ND
ND
ND
ND
ND
ND
ND
S DS/Ave
ND
ND
ND
ND
11
5
0.7
<0.2
17
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
12
2.0
ND
6.9
1.4
1.4
ND
19
24
14
9.7
ND
ND
0.4
ND
ND
ND
ND
<1
ND
ND
0.7
ND
<1
ND
ND
ND
ND
ND
SDS/Max
NR
4
0.7
ND
NR
NR
ND
NR
ND
ND
ND
ND
ND
ND
NR
NR
ND
ND
NR
NR
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
298
-------
Table 22 (continued)
02/25/2002
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 ,1 ,2,2-Tetrabromo-2-chloroethane
MRLJ
ug/L
0.98
0.5
0.1
0.1
0.1
0.1
0.10
0.1
0.10
0.25
0.5
0.5
0.5
0.5
0.2
0.5
0.11
Aldrich'
Raw
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
Clearwell
2
0.5
0.8
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
Conventional'
Raw
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Basins 4&5
2
ND
0.7
ND
ND
ND
ND
ND
ND
0.3
0.5
ND
ND
ND
ND
ND
ND
Basins 1&2
3
0.6
2
ND
ND
ND
0.1
ND
ND
ND
NR
ND
Filt Eff
2
ND
0.9
ND
ND
ND
ND
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
Combined Plant'
Finished
2
ND
1
ND
ND
ND
ND
ND
ND
0.6
ND
ND
ND
ND
ND
ND
ND
DS/Ave
2
0.7
1
ND
ND
ND
ND
ND
ND
0.7
ND
0.7
ND
ND
SDS/Ave
4
1
2
<1
ND
ND
ND
ND
ND
0.6
ND
1
ND
ND
SDS/Max
3
0.9
2
ND
ND
ND
0.1
ND
ND
NR
NR
ND
p<0.2 = Less than MRL (0.2 ug/L)
q<1 = Less than MRL (e.g., 1 ug/L)
299
-------
Table 23. DBF results at plant 9 (2/25/02)
02/25/2002
Compound
Halomethanes
Chlorom ethane
Bromomethane
Bromochloromethane
Dibromomethane
Chloroform
Bromodichloromethane'1
Dibromochloromethane
Bromoform'1
THM4*
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Carbon tetrachloride
Tribromochlorom ethane
Haloacetic acids
Monochloroacetic acid0
Monobromoacetic acid
Dichloroacetic acid"
Bromochloroacetic acid"
Dibromoacetic acid
Trichloroacetic acid0
Bromodichloroacetic acid
Dibromochloroacetic acid
Tribromoacetic acid
HAA59
HAA9h
DXAA1
TXAA1
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Dichloroacetonitriled
Bromochloroacetonitrile
Dibromoacetonitrile0
Trichloroacetonitriled
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Tribromoacetonitrile
Haloketones
Chloropropanone
1,1-Dichloropropanoned
1 ,3-Dichloropropanone
1,1-Dibromopropanone
1 ,1 ,1 -Trichloropropanone0
1 ,1 ,3-Trichloropropanone
1 -Bromo-1 ,1 -dichloropropanone
1 ,1 ,1 -Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrachloropropanone
1,1,1 ,3-Tetrachloropropanone
1 ,1 ,3,3-Tetrabromopropanone
MRL"
VglL
0.2
0.2
0.5
0.5
0.2
0.2
0.2
0.2
0.5
0.5
0.5
0.1
0.52
0.5
0.2
0.5
2
1
1
1
1
1
1
1
2
0.1
0.1
0.2
0.2
1.0
0.1
0.5
0.5
0.96
0.5
1.0
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.10
0.10
0.1
Plant 9K
Raw
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1uCond
ND
ND
ND
ND
3
4
2
0.4
9
<0.5°
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
6.2
3.7
3.0
1.1
1.2
ND
ND
10
15
13
2.3
ND
ND
0.4
0.8
<1q
ND
ND
ND
ND
ND
<1
ND
ND
0.5
ND
ND
ND
ND
ND
ND
ND
Basin #6
ND
ND
ND
ND
1
2
1
<0.2P
4
<0.5
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
4.0
2.4
2.2
ND
ND
ND
ND
6.2
8.6
8.6
ND
ND
ND
ND
ND
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
NRe
NR
NR
NR
NR
NR
ND
NR
ND
ND
ND
ND
ND
ND
NR
NR
<1
ND
ND
NR
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
Finished
ND
ND
ND
ND
2
2
2
0.3
6
<0.5
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
4.9
3.0
2.7
ND
ND
ND
ND
7.6
11
11
ND
ND
ND
0.2
0.2
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS/Ave
ND
ND
ND
ND
4
3
1
0.3
8
0.5
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
7.6
2.6
2.2
1.3
ND
ND
ND
11
14
12
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DS/Max
NR
NR
NR
NR
NR
NR
ND
NR
0.6
ND
ND
ND
ND
ND
NR
NR
<1
ND
ND
NR
ND
ND
NR
ND
ND
ND
ND
ND
ND
ND
S DS/Ave
ND
ND
ND
ND
2
3
2
0.4
7
<0.5
<0.5
ND
ND
ND
ND
ND
ND
ND
ND
4.5
3.4
1.8
ND
ND
ND
ND
6.3
10
10
ND
ND
ND
ND
ND
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SDS/Max
1
2
1
0.2
4
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2
0.4
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
300
-------
Table 23 (continued)
02/25/2002
Compound
Haloacetaldehvdes
Dichloroacetaldehyde
Bromochloroacetaldehyde
Chloral hydrate"
Tribromoacetaldehyde
Halonitromethanes
Chloronitrom ethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitrom ethane
Chloropicrind
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Miscellaneous Compounds
Methyl ethyl ketone
Methyl tertiary butyl ether
Benzyl chloride
1 , 1 ,2,2-Tetrabromo-2-chloroethane
MRL"
Mg/L
0.98
0.5
0.1
0.1
0.1
0.1
0.10
0.1
0.10
0.25
0.5
0.5
0.5
0.5
0.2
0.5
0.11
Plant 9K
Raw
ND
ND
0.5
<1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1U Cond
1
ND
0.4
ND
ND
ND
ND
ND
ND
ND
0.6
0.6
ND
ND
ND
ND
ND
Basin #6
2
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Filt Inf
2
ND
0.3
ND
ND
ND
ND
ND
ND
ND
NR
ND
Finished
2
ND
0.1
ND
ND
ND
ND
ND
ND
ND
0.6
0.6
ND
ND
ND
ND
ND
DS/Ave
2
<0.5
0.5
<1
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
DS/Max
2
ND
0.1
ND
ND
ND
ND
ND
ND
ND
NR
ND
SDS/Ave
2
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SDS/Max
3
0.5
0.7
<1
ND
ND
ND
ND
ND
ND
0.9
0.9
ND
ND
ND
301
-------
Haloacids. At plant 10 in January and April 2001, chlorine and/or chloramine
disinfection resulted in the formation of 83-95, 77-90, and 42-51 |ig/L of the five regulated
haloacetic acids (HAAS) in the Aldrich purification units, in basins 4 and 5, and in basins 1 and
2, respectively. As with the THM results, less HAAs were produced in basins 1 and 2 in January
and April 2001 because of the earlier addition of ammonia to form chloramines. Chlorine only
disinfection in September 2001 resulted in the formation of 165, 149, and 147 |ig/L of HAAS in
the Aldrich purification units, in basins 4 and 5, and in basins 1 and 2, respectively. In contrast,
the use of chloramines only at plant 10 in November 2001 and February 2002 resulted in the
formation of 21-24 |ig/L of HAAS in the Aldrich purification units and in basins 4 and 5.
At plant 9 in January 2001, April 2001, August 2001, November 2001, and February
2002, chlorine/chloramine disinfection resulted in the formation of 4-18 |ig/L of HAAS. Higher
formation of HAAs was observed in April and August as compared to in January 2001, with
intermediate HAA formation in November 2001 and February 2002.
In addition, all nine HAAs (HAA9) were measured, which included all of the brominated
HAA species. At plant 10, the level of HAA9 in the Aldrich purification units, in basins 4 and 5,
and in basins 1 and 2, was 104-114, 92-114, and 52-61 |ig/L, respectively, in January and April
2001 and was 177-198 |ig/L in September 2001. In contrast, with chloramines only, HAA9 was
24-30 |ig/L in November 2001 and February 2002 in the Aldrich Purification units and in basins
4 and 5. At plant 10, HAA formation was higher than THM formation. At plant 9, the level of
HAA9 in the finished water was 6-21 |ig/L.
When pre-chlorination was used at plant 10 (January, April, and September 2001),
trihalogenated HAAs (TXAAs) were in higher proportion than the dihalogenated species
(DXAAs) (e.g., Ill versus 61 |ig/L in basins 4&5 in September 2001). In other research,
TXAAs were found to constitute the greatest mole fraction of HAA9 in chlorinated waters at pH
8 (Cowman and Singer, 1996). (The plant 10 waters were chlorinated at pH levels in the range
of 7 to 8.) When pre-chloramination was used at plant 10 (November 2001 and February 2002),
DXAAs were in higher proportion than the TXAAs (e.g., 16 versus 5 |ig/L in basins 4&5 in
November 2001). In other research, chloramines have been shown to produce little or no THMs
and TXAAs, whereas DXAAs formed (Krasner et al., 1996). With either pre-chlorination or pre-
chloramination at plant 10, in each HAA subgroup (monohalogenated HAAs [MXAAs],
DXAAs, TXAAs), the fully chlorinated species (monochloro-, dichloro-, and trichloroacetic
acid) predominated, followed by the bromochloro species (bromochloro- and
bromodichloroacetic acid) (Figure 4).
At plant 9, most of the HAAs that were formed were DXAAs; very low amounts of
TXAAs were detected (Figure 5). In other research, pH (in the range of 5 to 9.4) had no
significant effect on dichloroacetic acid formation, whereas trichloroacetic acid formation was
lower at pH 9.4 than at the lower pH levels (and THM formation was higher with increasing pH)
(Stevens et al., 1989). The THM and HAA (DXAA versus TXAA) data (Figure 5) suggest the
following: (1) minimal free chlorine contact time and the very high pH of chlorination (typically
-10) initially impacted the DBF formation and speciation; and (2) the presence of chloramines in
302
-------
Figure 4. HAA speciation in Basins 4&5 at plant 10 in September 2001
Monochloroacetic acid
oo/
Dibromoacetic acid Monobromoacetic acid
1%
Bromochloroacetic acid
5%
Dichloroacetic acid ^^^^^^^^^^^^^^
2g
-------
Figure 5. Impact of chloramines and pH of chlorination (~10) on THM and
HAA formation and speciation at plant 9: August 27, 2001
Primary
Conditioner
Basin #6
Effluent
Finished
Water SDS/Average
Detn Time
flow in the conventional treatment train was from basins 4&5, the data for the former basins
were used to estimate the combined filter influent concentrations. In the latter month, when the
water temperature was 6°C, the DXAAs and TXAAs were not removed, and the MXAAs were
not detected (ND) in the filter effluent. These results are consistent with other research in which
DXAAs were found to be biodegradable, whereas TXAAs were not, and the phenomenon was
temperature dependent (Baribeau et al., 2000).
304
-------
Figure 6. Seasonal variations in removal of HAAs through GAC filters at plant 10: water
temperature at filters provided by each sample date (ND = not detected in filter effluent)
120%
0%
TXAAs
01/10/2001 (0.3-3.5 C)
04/09/2001 (14-15C)
09/05/2001 (27-29 C)
11/26/2001 (13-16C)
02/25/2002 (6 C)
DXAAs
MXAAs
Figure 7 shows a comparison of DXAA and TXAA speciation at the two Mississippi
River WTPs. The use of either chloramines or disinfection at pH levels of >9 favored DXAA
formation over TXAA formation at plant 9, whereas pre-chlorination at pH 7-8 at plant 10
(January, April, and summer 2001) resulted in somewhat more TXAA formation than DXAA
formation. Alternatively, pre-chloramination at pH 7-8 at plant 10 (November 2001 and
February 2002) resulted in somewhat more DXAA formation than TXAA formation. Also,
GAC filtration (in the conventional treatment trains) at plant 10 was more effective at removing
DXAAs than TXAAs (especially in summer 2001). Thus, the difference in HAA speciation at
these two utilities reflected the different effects of chlorine and chloramines, as well as pH and
GAC filtration, on HAA formation and control.
305
-------
Figure 7. Impact of chloramines and chlorine, pH and GAC filtration
on HAA speciation at plant 9 and plant 10
I
x
Q
Plant 9
Primary P|ant 10
Conditioner Flnlsned
2/25/2002
11/26/2001
Summer 2001
4/9/2001
1/10/2001
Water
Aid rich
Plant 10
Purification Conv- Train
Units Filter
Effluent
In addition to the target HAAs, two other haloacids were detected at plant 10 in April
2001 by the broadscreen GC/MS methods: 3,4,4-trichloro-3-butenoic acid and c/5-2-bromo-3-
methylbutenedioic acid (Table 15). November 2001 results from UNC also show the presence of
another target halo-acid, 3,3-dichloropropenoic acid, at a level of 0.4 jig/L in finished waters
from plant 10 (Table 20).
Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be
produced at approximately one-tenth the level of the THMs (Oliver, 1983). In the plant 10
samples, a comparison was made between the four HANs in the Information Collection Rule
(ICR) (HAN4) (dichloro- [DCAN], bromochloro-, dibromo-, and trichloroacetonitrile [TCAN])
and THM4. The ratio of HAN4 to THM4 (on a weight basis) for the January, April, and
September 2001 samplings was 8, 15, and 16 %, respectively.
A similar relationship was also observed (in part) in the plant 9 samples. Because the
THM concentrations were at low |ig/L levels at plant 9, the ICR HANs were detected at sub-
|ig/L levels. The major HAN formed, DCAN, typically went down in concentration in the plant,
distribution system, and/or SDS samples. DCAN undergoes base-catalyzed hydrolysis (Croue
and Reckhow, 1989), so it is not surprising that it would not be stable at the pH of treatment and
distribution at plant 9 (i.e., pH = 9-10).
306
-------
Similar to the HAAs (Figure 6), seasonal variations in the removal of DC AN through
GAC filters was evaluated (Figure 8). In January 2001 and February 2002, the concentration of
DC AN was 74-80 % of the level in the flow-weighted filter influent. In April and November
2001, when the water temperature was warmer, DC AN was reduced in concentration by 30-47
%. In September 2001, when the water temperature was the warmest, DCAN was reduced in
concentration by 58 %. These results are similar to the seasonal removal of DXAAs (Figure 6).
Figure 8. Seasonal variations in removal of other DBFs through GAC filters at plant 10:
water temperature at filters provided by each sample date (results arranged in order of
decreasing water temperature); N/A = not available
120%
01/10/2001 (0.3-3.5 C)
02/25/2002 (6 C)
11/26/2001 (13-16C)
04/09/2001 (14-15C)
09/05/2001 (27-29 C)
A comparison of HAN formation was made between the primary conditioner at plant 9
(at the beginning of the treatment process, prior to downstream base-catalyzed hydrolysis) and
the effluent of basins 4&5 at plant 10 (before GAC filtration) for January, April, and November
2001 (Figure 9). The ratio of HAN4 and THM4 (on a weight basis) was 6-10 % at plant 9 and 8-
16 % at plant 10. The ratio was somewhat higher at plant 10, probably because of the lower pH
of chlorination, which minimized base-catalyzed hydrolyis of the HANs.
In addition to the ICR HANs, other target HANs (chloro-, bromo-, bromodichloro-, and
dibromochloroacetonitrile) were detected in selected samples at plant 10. (The latter HAN was
detected during the broadscreen GC/MS analyses [Table 15]). None of the other target HANs
were detected at plant 9.
307
-------
Figure 9. Relative formation of HANs to THMs at the Mississippi River WTPs
1/10/2001
Plant 10 Basins 4&5
Plant 9 Primary Conditioner
4/9/2001
Summer 2001
Haloketones. In addition to the formation of low levels of haloketone (HK) compounds
from the ICR (1,1-dichloro- and 1,1,1-trichloropropanone), low levels of some of the target HKs
were detected in some of the samples at plant 9 and plant 10 (Figure 10). At plant 10, the
formation of 1,1,1-trichloropropanone was much higher, especially when pre-chlorination was
utilized (e.g., April 2001). In other research, 1,1,1-trichloropropanone was detected at acidic and
neutral pH levels, but was not detected at a pH of 9.4 (Stevens et al., 1989). Thus, the presence
of chlorine for longer contact times at a lower pH level resulted in more formation of this HK at
plant 10. Alternatively, 1,1-dichloropropanone levels were comparable at both plants in April
2001, suggesting that pH did not impact this HK to the same extent. When pre-chlorination was
used at plant 10, the level of 1,1,1-trichloropropanone was much higher than that of 1,1-
dichloropropanone, whereas when pre-chloramination was used the levels of the two HKs were
similar (Figure 10).
Figure 11 shows the impact of distribution-system disinfectant on the formation and
stability of THMs and HKs at plant 10, comparing the SDS samples set up for a maximum
detention time (five days) to the original finished water. In April 2001, when chloramines were
used, the concentrations of the THMs and many of the HKs were relatively constant. However,
there was a significant increase in the formation of 1,1-dichloropropanone. In other research,
chloramines were found to control the formation of THMs and TXAAs better than they control
the formation of DXAAs (Krasner et al., 1996). Thus, 1,1-dichloropropanone may continue to
form in chloraminated water. In September 2001, when chlorine was used, the concentration of
308
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Figure 10. Haloketone formation in finished waters at plant 9 (4/9/01) and plant 10 (4/9/01
and 11/26/01) (haloketones not detected in finished water at plant 9 on 11/26/01)
Plant 10: 11/26/01
Plant 10: 4/9/01
Plants: 4/9/01
Figure 11. Plant 10 (N/A = not available):
Impact of Distribution-System Disinfectant on the Formation and
Stability of THMs and Haloketones in SDS/Maximum Detention Time
Samples: Chloramines on 4/9/01, Chlorine on 9/5/01
04/09/01
09/05/01
309
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the THMs significantly increased, the concentration of chloropropanone was unchanged, and the
concentrations of some of the other HKs decreased to varying degrees, especially that of 1,1,1-
trichloropropanone (from 7 to 0.8 |ig/L). In other research, 1,1,1-
trichloropropanone was shown to decrease in the presence of chlorine, perhaps as a result of the
direct reaction of chlorine with this HK (Reckhow and Singer, 1985).
In addition to the target HKs, other HKs were detected in selected samples by the
broadscreen GC/MS methods (Table 15). Two of these HKs were analogous to the di- and
tetrahalogenated HKs monitored for by MWDSC, except that these were mixed bromochloro
species. Another two HKs that were detected at these WTPs by the broadscreen GC/MS
methods was pentachloro- (PCP) and hexachloropropanone (HCP). MWDSC had attempted to
include PCP and HCP in its target compound list, but they both degraded immediately and
completely in water under all conditions evaluated (Gonzalez et al., 2000).
Haloaldehydes. In addition to the formation of chloral hydrate (trichloroacetaldehyde)
(an ICRDBP), low levels of the target haloacetaldehydes (e.g., dichloroacetaldehyde) were
detected at plant 10 (Figure 12). In January 2001, April 2001, and February 2002, chloraminated
water was in settling basins 1&2 (with upstream pre-chlorination in mixing tank number 2)
(Figure 1), whereas in September 2001, chlorine only was in settling basins 1&2. The sum of the
concentration of the two dihalogenated acetaldehydes (2.4-3.6 |ig/L) was greater than the sum of
the concentration of the two trihalogenated acetaldehydes (0.2-2 |ig/L) when the water was
chloraminated. When the water was chlorinated, chloral hydrate formation (22 |ig/L) was much
greater than the formation of the sum of the two dihalogenated acetaldehydes (9 |ig/L). In
addition, the warmer water temperature in September 2001 contributed to more haloacetaldehyde
formation overall.
In February 2002, pre-chloramination in basins 4&5 versus chlorine/chloramines in
basins 1&2 resulted in much more control of chloral hydrate (0.7 versus 2 |ig/L) than for
dichloroacetaldehyde (2 versus 3 |ig/L). In other research, chloramines were found to minimize
the formation of chloral hydrate, whereas certain dihalogenated DBFs were formed to greater
extents (Young et al., 1995). Consistent with that research, the formation of dihalogenated
acetaldehydes was favored over trihalogenated species at plant 10 when chloramines were used,
especially with pre-chloramination.
310
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Figure 12. Haloacetaldehyde formation and speciation in Basins 1&2 at plant 10:
chlorine/chloramines in January 2001, April 2001, and February 2002; chlorine only in
September 2001 (Basins 4&5 with pre-chloramination in February 2002 provided for
comparison)
2/25/02: Basins 4&5
2/25/02: Basins 1&2
09/05/2001
04/09/2001
01/10/2001
At plant 9, dichloroacetaldehyde formation was typically greater than that of chloral
hydrate (Figure 13). This was due, in part, because chloral hydrate undergoes base-catalyzed
hydrolysis at high pH (e.g., ~9) (Stevens et al., 1989). With the measurement of dihalogenated
and/or brominated analogues of chloral hydrate, the haloacetaldehydes represented the third
largest class of DBFs formed at plant 9 (on a weight basis).
311
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Figure 13. Seasonal variations in the formation and speciation of the haloacetaldehydes
in the finished water of plant 9
02/25/2002
11/26/2001
08/27/2001
04/09/2001
01/10/2001
Figure 14 shows the relative speciation of the sum of the two measured dihalo-
acetaldehydes (DXAs) to the sum of the four measured species. At plant 9, DXAs represented
55 to 100 % (median = 89 %) of the measured haloacetaldehydes (HAs). At plant 10, the DXAs
represented 64 to 92 % of the haloacetaldehydes in basins 1&2 when chloramines were used and
29 % of this class of DBFs when chlorine only was used. In February 2002, when pre-
chloramination was used in basins 4&5, the DXAs represented 74 % of the haloacetaldehydes
(Figure 12).
As with the other classes of DBFs, the formation of the chlorinated species at plant 10
was highest for each subclass of haloacetaldehyde, and the bromochloro species was next highest
in concentration (Figure 12).
312
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Figure 14. Impact of chloramines and chlorine, and pH on haloacetaldehyde (HA)
speciation (e.g., dihaloacetaldehydes [DXAs]) at the Mississippi River WTPs (NS = not
sampled)
I/)
<
In
3
Q
1/10/2001
4/9/2001
Summer 2001
Plant 9 Finished Water
Plant 10 Basins 1&2
11/26/2001
2/25/2002
Similar to the HAAs (Figure 6) and DC AN (Figure 8), seasonal variations in the removal
of dichloro- and trichloroacetaldehyde [chloral hydrate]) were examined (Figure 8). In January
2001 and February 2002, the concentrations of these two haloacetaldehydes were 84-119 % of
the levels in the flow-weighted filter influents. In April 2001, when the water temperature was
warmer, dichloroacetaldehyde was reduced in concentration by 37 % (data were not available
(N/A) for chloral hydrate). However, in November 2001, when the water temperature was
similar to that in April 2001, there was no reduction in the concentration of the
haloacetaldehydes though the GAC filters. In September 2001, when the water temperature was
the warmest, dichloroacetaldehyde and chloral hydrate were reduced in concentration by 39 and
27 %, respectively. These results are similar, in part, to the relative seasonal removal of DXAAs
and TXAAs (Figure 6) and DC AN (Figure 8).
In addition to the target haloaldehydes, one other haloaldehyde was detected at both
WTPs by the broadscreen GC/MS methods: 2-bromo-2-methylpropanal (Table 15).
Halonitromethanes. Low levels of chloropicrin (trichloronitromethane) (an ICR DBF)
were detected at plant 10. This DBF was only detected in the April and November 2001 samples
at plant 9. Other halonitromethanes (HNMs) were detected in selected samples from both WTPs
313
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Figure 15. Halonitromethane formation at the Mississippi River WTPs in
August/September 2001
Bromopicrin
Dibromochloronitromethane
Bromodichloronitromethane
Chloropicrin
Dibromonitromethane
Bromochloronitromethane
Dichloronitromethane
Bromonitromethane
(e.g., Figure 15). Although there was a large difference in THM and HAA formation between
the two utilities, the difference in HNM formation was not as high.
As with the HAAs, there are nine HAN species and nine NHMs (two monohalogenated
species, three dihalogenated species, and four trihalogenated species). The relative speciation of
brominated and chlorinated HANs and HNMs (for the di- and trihalogenated species) was
compared to the HAAs for the effluent of basins 4&5 from the September 2001 sampling. Each
DBF can be abbreviated based on the number of halogens and the speciation of the halogens as
follows: RBryClz, where the number of bromine and chlorine atoms are y and z, respectively,
and R corresponds to the remainder of the DBF molecule (i.e., carbon, hydrogen, oxygen, and
nitrogen atoms). The concentration of each DBF was "normalized" by dividing its concentration
by the sum of the concentrations of all of the DBFs for that "subclass" of DBFs (RXy+z)
(Figure 16). For example, the concentration of dichloroacetic acid was divided by the sum of all
the DXAAs.
For the dihalogenated DBFs (RX2), the dichlorinated species represented 84 to 100 % of
the sum of the dihalogenated DBFs in each class of DBFs examined. The bromochloro species
represented 0 to 15 % of the class sums, and the dibromo species represented 0 to 2 % of the
class sums. For the HAAs, HANs, and HNMs, there was a similar relative speciation of
brominated and chlorinated DBFs for the dihalogenated subclass. For the trihalogenated DBFs
), the trichlorinated, bromodichlorinated, dibromochlorinated, and tribrominated species
314
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Figure 16. Effluent of Basins 4&5 at plant 10:
Relative Speciation of Chlorinated and Brominated Species:
Haloacetic Acids (HAAs), Haloacetonitriles (HANs),
Halonitromethanes (HNMs): Septembers, 2001
HANs
HNM
HAA
represented 20 to 81 %, 14 to 80 %, 0 to 2 %, and 0 to 2 % of the subclass sums, respectively.
Although not shown in this figure, for THM4, chloroform, bromodichloromethane,
dibromochloromethane, and bromoform represented 69, 28, 3, and 0 % of that class sum,
respectively. The relative speciation of the THMs was in between that of the speciation for the
HAAs and the HNMs. The reason the relative speciation for the trihalogenated HANs may have
been different is probably due to the relative instability of TCAN. In other research, TCAN has
been shown to undergo base-catalyzed hydrolysis in the pH range of 7 to 8, whereas it is stable at
pH 6 (Croue and Reckhow, 1989). The pH of basins 4&5 was 7.2, so it is likely that TCAN
simultaneously formed and degraded in these basins.
For plant 9, the relative speciation of brominated and chlorinated HNMs (for the
trihalogenated species) was compared to the THMs, the dihaloacetonitriles (DHANs), and the
DXAAs for the February 2002 finished water (Figure 17). (TXAAs and dihalogenated HNMs
were not detected in this sample.) For the RX2, the dichlorinated species represented 33 to 46 %
of the sum of the dihalogenated DBFs in that subclass of DBFs (on a weight basis). The
bromochloro species represented 28 to 33 % of the subclass sum, and the dibromo species
represented 25 to 33 % of the subclass sum. For the RX3, the trichlorinated, bromodichlorinated,
dibromochlorinated, and tribrominated species for the HNMs and THMs represented 0 to 32 %,
32 to 50 %, 32 to 50 %, and 0 to 5 % of the class sum, respectively. In February 2002, the raw-
water bromide level was the highest for the plant 9 samples. For the THMs, HAAs, DHANs,
and HNMs, there was a similar relative speciation of brominated and chlorinated DBFs at plant
9, with a shift to more of the brominated species.
315
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Figure 17. Relative speciation of chlorinated and brominated species in finished water
at plant 9 (2/25/02): dihaloacetic acids (DXAAs), dihaloacetonitriles (DHANs),
trihalomethanes (THMs), trihalogenated halonitromethanes (tri-HNMs)
0.50
0.00
RCI2
RBrCI
RBr2
RCI3
RBrCI2
DHAN/THM
DXAA/tri-HNM
RBr2CI
RBr3
Halogenatedfuranones. Table 21 shows the results for halogenated furanones in the
November 2001 sampling for plant 9 and plant 10. Data are included for 3-chloro-4-
(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3-
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found
as a closed ring or in an open form. Results are displayed graphically in Figure 17.
There was an increase in the concentrations of MCA-ring and MCA-open in the presence
of chloramines at plant 9 (11/26/01) (Table 21). Brominated analogues of MX were not detected
at plant 9. Plant 10 showed a significant formation of MX, with a levels of 400 ng/L observed
after treatment with chloramines (in a sample collected from settling basins 4 & 5) (Figure 18).
However, subsequent GAC filtration removed the MX, with no MX measured in the filter
effluent. This is consistent with the removal of other DBFs in this study during the filtration
process, which was probably due to biodegradation and not adsorption. Following the addition
of chloramines after GAC filtration, MX was reformed at a significantly lower level in the plant
effluent (60 ng/L). Two brominated analogues of MX (BMX-1 and BMX-3) were also formed at
316
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Figure 18. Halogenated furanones.
Plants and Plant 10 (11/26/01)
• BMX-1
DMCA (ring)
• BMX-2 • BMX-3
• MCA (open) BBEMX-1
• MX
• BEMX-2
• EMX
DBEMX-3
• ZMX
• Ox-MX
0.50
Sampling Point
plant 10 (30 and 20 ng/L, respectively), but GAC filtration was effective in removing them
completely, and they were not reformed in the plant effluent samples (Table 21). In samples
collected in April 2001 from plant 10, ox-MX was qualitatively identified in the plant effluent
using broadscreen GC/MS analysis (Table 15).
Volatile Organic Compounds (VOCs). Carbon tetrachloride, which is a VOC and a
possible DBF, was detected (0.07-0.3 |ig/L) in several samples at plant 10, but was not found in
the raw water (MRL = 0.06 or 0.2 |ig/L). As mentioned in a previous chapter, carbon
tetrachloride has been detected by some utilities in gaseous chlorine cylinders (EE&T, 2000),
due to imperfections in the manufacturing process or improper cleaning procedures.
Methyl tertiary butyl ether (MtBE) was detected in the raw water of plant 10 on
September 5, 2001 at a concentration of 1.6 |ig/L. The level of MtBE decreased somewhat
through plant 10. MtBE was detected (0.7-1 |ig/L) in the distribution system and in SDS testing
for plant 10 on February 25, 2002, but was not detected (with an MRL of 0.2 |ig/L) in the raw
water. MtBE was detected (0.2-0.3 |ig/L) in the raw water samples for plant 9 in January and
August 2001, but was not detected in the WTP samples (with an MRL of 0.2 |ig/L). MtBE is a
gasoline additive.
Methyl ethyl ketone (MEK) was detected in plant 9 on August 27, 2001 at 0.5-1 |ig/L,
but was not detected at or above the MRL of 0.5 |ig/L in the raw water. MEK was detected (1
|ig/L) in the raw water for plant 9 on November 26, 2001, and was detected in some downstream
samples at 0.8-1 |ig/L. MEK was detected in the plant 10 conventional treatment train at 0.6
317
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Hg/L on September 5, 2001, but was not detected at or above the MRL of 0.5 jig/L in the raw
water. MEK was detected (2 |ig/L) in the raw water for the Aldrich purification units at plant 10
on February 25, 2002, but was not detected in the treated water. MEK is an industrial solvent
and it may also be a DBF. Because the level in the two WTPs in the summer 2001 samples was
barely above the MRL, it can not be determined for sure if its presence was due to low-level raw-
water contamination (as was observed in November 2001 at plant 9 and in February 2002 at
plant 10 ) or if it was produced during the disinfection process.
Other HalogenatedDBFs. A few additional, miscellaneous halogenated DBFs were also
detected. UNC methods detected dichloroacetamide at 1.7 |ig/L in finished water from plant 10
(1/10/01) (Table 12). In addition, broadscreen GC/MS analyses revealed the presence of 1,2-
dichloroethylbenzene, tetrachlorocyclopentadiene, hexachlorocyclopentadiene, and
bromopentachlorocyclopentadiene in finished water collected from plant 10 in April 2001 (Table
15). Dichlorophenol was identifed in finished water from plant 9 (Table 15). These compounds
were not observed in the corresponding raw, untreated water.
Non-HalogenatedDBFs. Very few non-halogenated DBFs were detected in finished
waters from plant 10 or plant 9. Dimethylglyoxal was identified at 0.2 and 0.3 |ig/L in finished
waters from plant 9 and plant 10, respectively, in November 2001 (Table 20). Broadscreen
GC/MS analysis revealed the presence of glyoxal and dodecanoic acid in finished water from
plant 10 (April 2001), and 4-methylpentanoic acid was found in finished waters from plant 9
(August 2001) (Table 15).
REFERENCES
American Public Health Association (APHAj. Standard Methods for the Examination of Water
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment
Federation: Washington, DC (1998).
Baribeau, H., S. W. Krasner, R. Chinn, and P. C. Singer. Impact of biomass on the stability of
haloacetic acids and trihalomethanes in a simulated distribution system. Proceedings of the
American Water Works Association Water Quality Technology Conference, American Water
Works Association: Denver, CO, 2000.
Cowman, G. A., and P. C. Singer. Effect of bromide ion on haloacetic acid speciation resulting
from chlorination and chloramination of aquatic humic substances. Environmental Science &
Technology 30(1): 16 (1996).
Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite.
Environmental Science & Technology 23(11): 1412 (1989).
Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to
AWWA Research Foundation, Denver, CO, 2000.
318
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Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly
identified disinfection by-products in drinking water. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 2000.
Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E.
Barrett. Effects of water quality parameters on DBF formation during chloramination.
Proceedings of the American Water Works Association Annual Conference, Vol. D, American
Waterworks Association: Denver, CO, 1996.
Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors.
Environmental Science & Technology 17(2):80 (1983).
Reckhow, D. A., and P. C. Singer. Mechanisms of organic halide formation during fulvic acid
chlorination and implications with respect to preozonation. In Water Chlorination: Chemistry,
Environmental Impact and Health Effects, Vol. 5 (R.L. Jolley et al., eds.); Lewis Publishers, Inc:
Chelsea, MI, 1985.
Singer, P. C., H. Arora, E. Dundore, K. Brophy, and H. S. Weinberg. Control of haloacetic acid
concentrations by biofiltration: a case study. Proceedings of the American Water Works
Association Water Quality Technology Conference, American Water Works Association:
Denver, CO, 1999.
Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane
disinfection by-products. Journal of the American Water Works Association 81(8):54 (1989).
Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and
related halogenated disinfection by-products in chlorinated and chloraminated water; application
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical
Society (ACS) National Meeting, Chicago, IL, American Chemical Society: Washington, D.C.,
pp. 748-751, 1995.
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CONCLUSIONS
This Nationwide DBF Occurrence Study revealed that many of the high priority
DBFs can occur in finished drinking water at levels similar to those of the commonly
measured DBFs. For example, iodo-THM levels ranged from 0.2 to 15 |ig/L and
brominated nitromethane levels were as high as 3 |ig/L. In addition, MX levels measured
in this study were significantly higher than previously reported. Specifically, MX levels
were often above 100 ng/L, with a maximum concentration of 310 ng/L; brominated
forms of MX (BMX-1 and BEMX-3) reached 170 and 200 ng/L, respectively. These
results suggest that some of the high priority DBFs should be the focus of new health
effects research, particularly for the bromonitromethanes that are being shown to be
significantly more genotoxic in mammalian cells than MX and most currently regulated
DBFs. It has also been hypothesized that the iodinated species may be more carcinogenic
than the brominated species. Given the levels of iodo-THMs that can be formed in
waters high in bromide/iodide, it is recommended that the iodo-THMs also be targeted
for expanded/accelerated health effects studies.
Several haloamides were quantified for the first time in this study and found to be
present at levels similar to other commonly measured DBFs (low |ig/L levels). This is a
new class of DBF that has not been previously measured in treated, potable waters, and
may be important due to the levels found.
With respect to treatment processes, we found that the use of ozone removed MX-
analogue precursors, and that GAC filters removed MX-analogues via adsorption and/or
biodegradation. However, it was also shown that post-chlorination or chloramination
following GAC filtration can contribute to MX-analogue re-formation. Chlorine and
ClO2-chlorine were confirmed as the major producers of MX-analogues, as previously
observed by Kronberg (1999). MX did not form from C1O2 disinfect on per se, rather
C1O2 oxidation did not destroy MX precursors (as ozone, another alternative disinfectant,
does). The high concentrations of MX-analogues (>100 ng/L) observed in these water
treatment plants were greater than that previously reported. Either previous methods for
the detection of MX-analogues (all published concentrations <90 ng/L) may have
systematically underestimated the true concentrations, due to degradation of the MX-
analogues during lengthy sample storage and processing, or higher concentrations were
detected in this study because utilities that treat waters high in TOC and/or bromide were
included.
This study has also revealed that some of our previous understanding of the
formation and control of DBFs with alternative disinfectants was not complete. For
example, it has been assumed from past THM data that alternative disinfectants are a
good means of controlling other potentially hazardous, halogenated DBFs. However, the
results show here that some DBFs—particularly iodo-THMs and dihaloacetaldehydes—
can occur at higher concentrations in treatment plants using alternative disinfectants.
Thus, while alternative disinfectants can control the formation of the four currently
regulated THMs, they do not necessarily control all halogenated DBFs of concern.
Consider that MX was found at its highest level at a treatment plant that disinfected a
320
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high-TOC water with chlorine dioxide, chlorine, and chloramines. Alternatively, at
another plant that treated the same water with ozone, biodegradation (on GAC filter), and
chlorine, halogenated furanone formation was significantly lower. As discussed above,
this probably reflects differences in the ability of C1O2 and ozone—as well as
biodegradation and GAC filtration—to destroy MX precursors, which were probably
quite high in this high-TOC water.
Many new DBFs were identified through the course of this study. In particular,
iodinated acids were identified for the first time, along with a DBF tentatively identified
as iodobutanal. Therefore, iodo-THMs are not the only possible iodinated DBFs that can
form. Several new brominated acids were also identified, with carbon chain lengths of
three and four being common, as well as the presence of diacids and double bonds in
their structures. One of the high priority DBFs that was quantified in this study—3,3-
dichloropropenoic acid—is an example of a chlorinated, three-carbon acid; it was
frequently found in treated waters at levels ranging from 0.4 to 1.5 |ig/L in finished
waters. Therefore, the presence of haloacids other than the regulated, two-carbon
haloacetic acids must be realized.
The stability of DBFs in potable water distribution systems and in simulated
distribution system (SDS) tests varied. In most cases where chloramination was used for
disinfection, the DBFs were relatively stable. However, when free chlorine was used,
THMs and other DBFs, including haloacetic acids, increased in concentration in the
distribution system and in SDS testing. Haloacetonitriles generally were stable (at the
distribution-system pH levels encountered in this study) or increased in concentration in
the distribution system, but many of the haloketones were found to degrade.
Halonitromethanes and dihaloacetaldehydes were also generally found to be stable in
distribution systems. MX analogues were sometimes stable and sometimes degraded
somewhat in the distribution system and during SDS testing. When MX analogues
showed some degradation in the distribution system, they were generally still present at
detectable levels, indicating that they do not completely degrade. Many times, the
brominated analogues of MX (BMXs) were stable in the distribution system.
321
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APPENDIX
-322-
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EXPERIMENTAL METHODS
CHEMICAL STANDARDS (for Methods Developed at MWDSC)
When commercial standards were not available, standards were synthesized for the
project. The initial phase of the project required a survey of chemical companies to obtain as
many of the target compounds as possible. The remaining compounds were then synthesized.
This led to a step-wise approach to incorporating compounds as they became available for
analysis. When synthesized materials were prepared in less than 10-mg allotments, additional
standards were sometimes needed later in the project.
At Metropolitan Water District of Southern California (MWDSC), multiple methods
were used to test for DBFs. It was necessary to make up two independent sets of stock solutions,
in methyl tertiary butyl ether (MtBE) and methanol, depending on the solvent requirements of
each technique. Each "pure" standard from the MtBE set was characterized individually to
determine whether there were any impurities, to note what the impurities were and at what level
(percentage). Many of the discovered impurities were, in fact, other DBFs. When all the
standards were combined into spiking solutions, any additionally added DBFs (impurities) had to
be accounted for through the use of correction factors, either to the final results or to the
standards being used to generate calibration curves. When correction factors were applied,
reported concentrations were more accurate because they reflected the true composition of the
combined set of calibration standards.
Stock Solutions
Several commercially available certified standards and mixes were purchased (Table 1).
These mixes were spiked directly or used to create additional compound class mixtures for
calibration purposes and spikes of unknown samples.
Typically, at the beginning of each quarter, new stock solutions were prepared in MtBE
and methanol. In September 2000, the first set was created that would last through the Fall 2000
quarter's sampling. The next set of stock solutions covered all of the Winter 2001 quarter and
the samples from early Spring 2001. Another set was created in May 2001 and was used through
the end of the year, covering both Summer and Fall 2001 quarter's samplings. The last set of
stock solutions was made in January 2002, and was used with the final phase of sampling in the
Winter 2002 quarter and an early Spring 2002 sampling.
The MtBE-diluted compounds were tested in full-scan mode to verify the electron impact
(El) mass spectrum of the pure compound and also to check for impurities or degradation
products present (Figures 1-7). As part of an on-going check of the standards, the individual
stock solutions would be periodically checked to note any changes in the calculated purity or the
impurities present. Initially, the solutions were checked every 4-6 weeks. Subsequently, after
approximately 3 month's usage, new stock solutions would be created, and the previous set
stored for future reference.
323
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Table 1. Certified commercial standards used at MWDSC
Certified Mixes
Bromochloromethane
Supelco 4-8067
2000 ug/mL in methanol
Carbon Tetrachloride
Supelco 40360-U
5000 uQ/mL in methanol
Chloral Hydrate
Supelco 4-7335-U
1000 nQ/mL in acetonitrile
Dibromomethane
Supelco 4-8339
2000 uQ/mL in methanol
EPA 524.2 Fortification Solution
Supelco 47358-U
2000 uQ/mL in methanol
EPA 551 B Halogenated Volatiles
Supelco 4-8046
2000 jig/mL in acetone
or
HCM-551B (Ultra Scientific)
5000 j^g/mL in methanol
EPA 624 Calibration Mix B
Supelco 46967-U
2000 ^g/mL in methanol
Methyl Tert-Butyl Ether
Supelco 4-8483
2000 ug/mL in methanol
Trihalomethane Calibration Mix
Supelco 4-81 40-U, 2000 ^g/mL in MeOH
or
THM-521 (Ultra Scientific)
5000 ng/mL in methanol
2 -But a none
Supelco 4-8877
2000 yg/mL in MeOH/H2O 90:10
Compound
Bromochloromethane
Carbon tetrachloride
Chloral hydrate
Dibromomethane
4-Bromofluorobenzene
1 ,2-Dichlorobenzene-d4
Fluorobenzene
Bromochloroacetonitrile
Chloropicrin
Dibromoacetonitrile
Dichloroacetonitrile
1,1-Dichloropropanone
Trichloroacetonitrile
1 ,1 ,1 -Trichloropropanone
Bromo methane
Chloroethane
Chloromethane
Trichlorofluoromethane
Vinyl chloride
Methyl terfEbutyl ether
Bromodichloromethane
Bromoform
Chloroform
Dibromochloromethane
Methyl ethyl ketone
Standards Used in Method3
LLE-GC/ECD
X
X
X
X
X
X
X
X
X
X
X
X
P&T-GC/MS
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
SPE-GC/MS
X
X
X
X
X
X
X
X
X
X
X
aLLE-GC/ECD: Liquid/liquid extraction-gas chromatography/electron capture detection
P&T-GC/MS: Purge-and-trap - GC/mass spectrometry
SPE-GC/MS: Solid-phase extraction - GC/MS
324
-------
010302A
100-1
Magnet EI+
TIC
2.78e7
010302B
100-1
o-l
010302C
100-1
Magnet EI+
TIC
5.63e7
Magnet EI+
TIC
6.35e7
010302D
100-1
Magnet EI+
010302E
100-1
Magnet EI+
TIC
5.63e7
010302F
100-1
Magnet EI+
TIM ' TIC
4.72e7
i Time
10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 1. Full-scan total ion chromatograms of iodomethanes from January 2002 stock solution. DBF abbreviations provided
in Table 2.
325
-------
010902C
I %-
Magnet EI+
TIC
3.12e7
010902D
100-1
04=!-H"»
011002A
100-1
Magnet EI+
TIC
1.67e7
04T"
010902G
100-1
Magnet EI+
TIC
2.19e7
(H
010902E
100-]
Magnet EI+
TIC
1.40e7
Magnet EI+
TIC
3.16e7
i Time
7.50
10.00
12.50
15.00
17.50 20.00 22.50 25.00 27.50 30.00 32.50
35.00
37.50
40.00 42.50 45.00 47.50
50.00 52.50 55.00
Figure 2. Full-scan total ion chromatograms for haloacetonitriles from January 2002 stock solution;
a poor result for bromodichloroacetonitrile required the use of the May 2001 stock solution. DBF abbreviations provided in
Table 2.
326
-------
010802A
Magnet EI+
TIC
3.38e7
010802B
100-1
Magnet EI+
TIC
4.35e7
010802C
100-1
Magnet EI+
TIC
4.88e7
010802E
100-1
Magnet EI+
TIC
5.59e7
010802D
100-1
Magnet EI+
TIC
6.17e7
i Time
10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 3. Full-scan total ion chromatograms of chloropropanones from January 2002 stock solution. DBF abbreviations
provided in Table 2.
327
-------
010802G
Magnet EI+
TIC
3.03e7
I %-
o-i
010802F
100n
Magnet EI+
TIC
2.61e7
010802H
100n
Magnet EI+
TIC
3.24e7
010902A
100n
Magnet EI+
TIC
6.91e7
010902B
100n
Magnet EI+
TIC
4.24e7
i Time
10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 4. Full-scan total ion chromatograms of bromopropanones from January 2002 stock solution. DBF abbreviations
provided in Table 2.
328
-------
010702H
100q
-------
010402E
Magnet EI+
TIC
8.09e7
o-1
010402F
100-1
Magnet EI+
TIC
7.11e6
BCA
o-1
010402G
100-1
Magnet EI+
TIC
5.40e7
1 Time
7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 6. Full-scan total ion chromatograms of haloacetaldehydes from January 2002 stock solution; peaks marked with an
"x" are solvent impurities. DBF abbreviations provided in Table 2.
330
-------
010402C
CT
Magnet EI+
TIC
3.23e7
I %-
010402A
100-1
Magnet EI+
TIC
4.32e7
010402B
100-1
BC
Magnet EI+
TIC
8.11e7
0 I
010402D
100-1
Magnet EI+
7.7!e?
i Time
10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 7. Full-scan total ion chromatograms of miscellaneous compounds from January 2002 stock solution. DBF
abbreviations provided in Table 2.
331
-------
Many of the additional peaks present in the pure compounds resulted from the synthesis
procedure, where yields were less than 100 percent. Alternatively, some of the initially pure
compounds may have been unstable and degraded over time, forming degradation products,
some of which were other DBFs. In addition, some "impurities" were attributed to radical
reactions or thermal lability of some compounds in the hot injection port and/or oven of the gas
chromatograph (GC) (see section on GC Conditions below).
To obtain the highest accuracy in quantitation, the compound purities were taken into
account to determine proper concentration values for standards. Thus, a 1.0 mg sample quantity
weighed and diluted to 1.0 mL with solvent produced a 1000 mg/L stock solution. In the case
that the compound was 90 % pure, the effective concentration of the stock solution was 900
mg/L.
Tables 2-4 detail DBF purities presented by chemical class. The identification for the
impurities for the Winter 2002 quarter stock solutions is presented in Table 2. From the
information in Table 2, combined chemical class mixtures were prepared at lower levels, such as
50 mg/L for solid-phase extraction (SPE). These individual master solutions were the spiking
solutions used for standards preparation and also for the spiking of samples. The entire 47-
compound set for SPE method development was achieved by combining six sets of mixtures that
generally contained a particular chemical class. This approach was superior to quantitating
individual compounds for every analysis. In addition, compound classes like the
halonitromethanes, which had a propensity to degrade faster than other compound classes, could
be made up more often as needed. Also, calibration curves could be prepared, which just
included specific chemical classes, when more in-depth probing of sample concentrations was
necessary.
Correction Factors
There are several ways to correct for concentration anomalies with the standards:
(1) Calculate the actual concentration of each standard and apply it to the data analysis software.
(2) Calculate the actual concentration of each standard and generate accurate calibration curves
by hand for each compound of interest. (3) Determine the adjustment necessary to correct a
standard and apply a correction factor to the final results. The first solution is by far the best
because it applies the correction to standards early on in the data analysis process, and all
subsequent samples are referenced against the correct curves. This was eventually applied to
data generated using the Varian Star Workstation software for results of purge-and-trap (P&T)
gas chromatography/mass spectrometry (GC/MS) and SPE-GC/MS. The second solution is
extremely time-consuming because all raw areas need to be transported to an alternative software
package for graphing purposes. This approach is necessary if the analysis software does not
allow customization of individual concentration levels. The third solution is the quickest and
easiest to implement because it looks at the overall adjustment for each of the standards and
corrects the sample values after the fact.
332
-------
Table 2. Making of stock solutions in MtBE for Winter 2002 Quarter
Compound
THM/551BMix
Chloroform (trichloromethane)
Bromodichloro methane
Dibromochloromethane
Bromoform (tribromomethane)
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
Trichloroacetonitrile
1,1-Dichloropropanone
1 ,1 ,1-Trichloropropanone
Chloropicrin (trichloronitromethane)
lodomethane Mix
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform (triiodomethane)
Haloacetonitrile Mix
Chloroacetonitrile
Bromoacetonitrile
Tribromoacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Haloketone Mix
Chloropropanone
1,3-Dichloropropanone
1 , 1 ,3-Trichloropropanone
1,1,3,3-Tetrachloropropanone
1,1, 1 ,3-Tetrachloropropanone
1 -Bromo-1 , 1 -dichloropropanone
1 , 1 -Dibromopropanone
1,1 ,1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
1,1,3,3-Tetrabromopropanone
Halonitromethane Mix
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitro methane
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin (tribromonitromethane)
Haloacetaldehvde Mix + Misc.
Dichloroacetaldehvde
Bromochloroacetaldehvde
Tribromoacetaldehvde
Tribromochloromethane
Carbon tetrachloride
1,1,2,2-Tetrabromo-2-chloroethane
Benzvl chloride
Abbreviation
TCM
BDCM
DBCM
IBM
DCAN
SCAN
DBAN
TCAN
1,1 -DCP
1,1,1-TCP
TCNM
DCIM
BCIM
DBIM
CDIM
BDIM
TIM
CAN
BAN
TBAN
BDCAN
DBCAN
CP
1,3-DCP
1,1,3-TCP
1,1,3,3-TeCP
1,1,1,3-TeCP
1,1,1-BDCP
1,1 -DBP
1,1,1-TBP
1,1,3-TBP
1,1,3,3-TeBP
CNM
BNM
DCNM
BCNM
DBNM
BDCNM
DBCNM
TBNM
DCA
BCA
TBA
TBCM
CT
1,1,2,2-TeB-2-CE
BC
Stock
Date
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
4/6/01
12/27/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/27/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
12/28/01
Weight
mg
6.7
7.1
8.0
5.3
7.1
4.3
2.8
5.3
6.6
2.4
6.8
4.1
6.2
4.2
6.0
6.0
4.5
5.5
6.2
6.6
4.0
4.3
7.3
4.1
5.2
5.9
5.5
6.2
7.4
5.3
1.4
7.5
6.1
4.7
6.0
3.3
Cone.
(mg/L)
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
6700
7100
8000
5300
7100
4300
2800
5300
6600
2400
6800
4100
6200
4200
6000
6000
4500
5500
6200
6600
4000
4300
7300
4100
5200
5900
5500
6200
7400
5300
1400
7500
6100
4700
6000
3300
Checked
Date
1/3/02
1/3/02
1/3/02
1/3/02
1/3/02
1/3/02
1/9/02
1/9/02
1/9/02
1/16/02
1/9/02
1/8/02
1/8/02
1/8/02
1/8/02
1/8/02
1/8/02
1/8/02
1/8/02
1/9/02
1/9/02
1/7/02
1/7/02
1/7/02
1/7/02
1/7/02
1/7/02
1/7/02
1/7/02
1/4/02
1/4/02
1/4/02
1/4/02
1/4/02
1/4/02
1/4/02
Purity
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
93.3%
96.7%
97.2%
86.3%
91.5%
99+%
99+%
99+%
99+%
91 .0%
41.1%
98.1%
99+%
97.7%
94.9%
91 .7%
76.2%
94.1%
98.6%
99.2%
99+%
98.8%
99+%
99+%
89.5%
76.9%
99+%
99+%
99+%
99+%
50.1%
99+%
92.4%
99+%
92.1%
99+%
Adjusted
Cone. (mg/L)
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
6250
6850
7800
4550
6500
4300
2800
5300
6600
2200
2800
4000
6200
4100
5700
5500
3450
5200
6100
6550
4000
4250
7300
4100
4650
4550
5500
6200
7400
5300
700
7500
5650
4700
5550
3300
Impurities
BDIM (2.8%)
TIM (2.2%)
DBIM (4.3%), TIM (4.1%)
CT (4.0%), DCAN (2.5%)
TBAN (36.3%), DBAN (16.7%), TBM (6.0%)
1,1 -DCP (1.9%)
1,1,3,3-TeCP (2. 3%)
1,1,1,3-TeCP (2. 2%)
CT (7.2%)
DCNM (1.2%)
DBCNM (8.1%), DBNM (2.4%)
TBNM (23.1%)
DCA (47.7%)
333
-------
Table 3. Correction factors for Winter 2002 Quarter when all standards were used
Compound
THM/551BMix
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
Dichloroacetonitrile
Bromoch loroaceton itrile
Dibromoacetonitrile
Trich loroaceton itrile
1 , 1 -Dichloropropanone
1,1,1-Trichloropropanone
Chloropicrin
lodomethane Mix
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodo methane
lodoform
Haloacetonitrile Mix
Chloroacetonitrile
Bromoacetonitrile
Tribromoacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Haloketone Mix
Chloropropanone
1,3-Dichloropropanone
1 ,1 ,3-Trichloropropanone
1 .1 ,3.3-Tetrachloropropanone
1 ,1 ,1,3-Tetrachloropropanone
1 -Bromo-1 . 1 -dichloropropanone
1,1-Dibromopropanone
1,1,1 -Tribromopropanone
1 , 1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrabromopropanone
Halonitromethane Mix
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitro methane
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Haloacetaldehvde Mix + Misc.
Dichloroacetaldehvde
Bromoch loroacetaldehvde
Tribromoacetaldehvde
Tribromochloromethane
Carbon tetrachloride
1.1.2.2-TeB-2-CE
Benzvl chloride
Purity
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
93.3%
96.7%
97.2%
86.3%
91 .5%
99+%
99+%
99+%
99+%
91 .0%
41.1%
98.1%
99+%
97.7%
94.9%
91 .7%
76.2%
94.1%
98.6%
99.2%
99+%
98.8%
99+%
99+%
89.5%
76.9%
99+%
99+%
99+%
99+%
50.1%
99+%
92.4%
99+%
92.1%
99+%
Impurities
BDIM (2.8%)
TIM (2.2%)
DBIM (4.3%), TIM (4.1%)
CT (4.0%), DCAN (2.5%)
TBAN (36.3%), DBAN (16.7%), TBM (6.0%)
1,1-DCP(1.9%)
1,1,3,3-TeCP(2.3%)
1.1.1.3-TeCP(2.2%)
CT (7.2%)
DCNM (1 .2%)
DBCNM (8.1%). DBNM (2.4%)
TBNM (23.1%)
DCA (47.7%)
Contributions for a 10 ug/L Standard
1.46 ppbfrom DBCAN
0.27ppbfrom BDCAN
4.06 ppbfrom DBCAN
0.19 ppbfrom CP
0.47 ppbfrom BDIM
0.29 ppbfrom DBIM
0.25 ppbfrom CDIM; 0.45 ppbfrom BDIM
8.83 ppbfrom DBCAN
0.24 ppbfrom 1.1.3-TCP
0.23 ppbfrom 1,1,3,3-TeCP
0.12 ppbfromCNM
0.27 ppbfrom BCNM
0.90 ppbfrom BCNM
3.00 ppbfrom DBNM
9.52 ppbfrom BCA
0.94 ppbfrom 1,1,1-BDCP; 0.44 ppbfrom BDCAN
Corrected
"10 Std"
11.46
10.27
14.06
10.19
10.47
10.29
10.70
18.83
10.24
10.23
10.12
10.27
10.90
13.00
19.52
11.38
Correction
Factor
1.15
1.03
1.41
1.02
1.05
1.03
1.07
1.88
1.02
1.02
1.01
1.03
1.09
1.30
1.95
1.14
334
-------
Adjustments were necessary when all compounds were added together into a single
combined solution (Table 3). The column labeled "Corrected 10 Std" represents the
concentration of the entire mass of material in a standard that was a sum of all the compounds
and impurities. The values for each pure standard were corrected in the process of making
intermediate solutions, such as the 50-mg/L compound class mixture discussed above. For
example, if the stock solution concentration for chlorodiiodomethane (Table 2) was 5300 mg/L
and the compound's purity was 86.3 %, then the actual, rounded concentration of 4550 mg/L was
used to calculate what was required to produce an exact 50 mg/L intermediate standard. Further
dilutions were prepared to produce a "10 ng/L" standard. Because of the added impurities, the
effective concentrations for some compounds were above 10
When a compound had a 91.0 % purity, 1 1.0 |ig/L of that material was required to
achieve a concentration of 10 |ig/L for the analyte of interest (e.g., bromodichloroacetonitrile
[BDCAN]); whereas, when a compound had a 41.1 % purity, 24.3 |ig/L of that material was
required to achieve a concentration of 10 jig/L for the analyte of interest (e.g., dibromo-
chloroacetonitrile [DBCAN]) (Table 3). In terms of the contribution of impurities, for example,
in Winter 2002, 2.5 % of the BDCAN standard was dichloroacetonitrile (DCAN) and 16.7 % of
the DBCAN was dibromoacetonitrile (DBAN) (Table 3). Because 1 1.0 |ig/L of the BDCAN and
24.3 |ig/L of the DBCAN materials were required to prepare 10 |ig/L standards, the contributions
of the impurities were in actuality 2.5 % x 1 1.0 |ig/L = 0.27 |ig/L DCAN and 16.7 % x 24.3
|ig/L = 4.06 |ig/L DBAN. Even though the purity of the standards for DCAN and DBAN were
each 99+ %, the contributions from the impurities in the BDCAN and DBCAN standards,
respectively, resulted in the 10 |ig/L calibration standard having 10 + 0.27 = 10.27 |ig/L DCAN
and 10 + 4.06 = 14.06 |ig/L DBAN. Moreover, in some cases, such as for carbon tetrachloride —
which was obtained as a high-purity standard — it was also found as an impurity in two of the
synthesized standards (BDCAN and 1,1,1-bromodichloropropanone [1,1,1-BDCP]). Thus, the
correction factor for carbon tetrachloride reflected the contributions from the two sources of
impurity (Table 3).
The correction factors were applied to samples to correct values obtained with the
standard calibration curves (Method #3). Alternatively, the factors were applied to the standards
to graph accurate calibration curves, and the sample values were read directly from the chart
(Method #1).
Finally, only those compounds that were measured with an analytical technique were
counted in the correction factor calculations. For example, several DBFs (e.g., DBCAN) were
ultimately dropped from the SPE-GC/MS method due to stability issues with the dechlorination
agent ascorbic acid. Thus, the impurity contributions of DBCAN — tribromoacetonitrile (TBAN)
(36.3 %), DBAN (16.7 %), and bromoform (tribromomethane, TBM) (6.0 %) — were no longer
present in the SPE-GC/MS standards. TBAN was also removed from the SPE method, so its
correction factor did not make any difference. DBAN's and TBM's correction factors of 1.41
and 1.15 were no longer needed with the elimination of DBCAN from the SPE method. Thus,
each of the analytical methods required a modification of Table 3 to reflect the compounds that
were being included in each method's combined standard.
335
-------
GC Conditions
For checking the purity of the standards, the original GC temperature program followed
the U.S. Environmental Protection Agency (USEPA) Method 551.1 procedure (Munch and
Hautman, 1995), using a DB-1 capillary column (J&W Scientific/Agilent, Folsom, CA; 1.0 |j,m
film thickness, 0.25 mm ID x 30 m). Initially, the following program was used: hold at 35°C for
22 min; increase to 145°C at 10°C/min and hold at 145°C for 2 min; increase to 225°C at
20°C/min and hold at 225°C for 15 min. The GC injector temperature was 200°C, and the
detector temperature was 290°C.
An additional temperature ramp to 260°C was eliminated because all of the compounds
eluted during the third step of the temperature program. In addition, an injector temperature of
200°C caused significant degradation of some compounds. The injector temperature was set at
117°C based on an earlier GC method, which prevented the degradation of the thermally labile
compound bromopicrin (Krasner et al., 1991). Furthermore, it was possible that some of the
"impurities" found were actually radical reaction products formed in a hot injection port. Chen
et al. (2002) saw similar behavior to bromopicrin with other trihalocompounds (e.g., the
trihaloacetonitriles and other trihlonitromethanes).
The initial purity checks for the study—September 2000 and January 2001—used an
injector temperature of approximately 115°C, while work continued to refine the GC temperature
conditions. An updated GC program was adopted for the stock solutions starting with the May
2001 set. This new method improved chromatography and helped to eliminate some of the
impurities by further dropping the injection temperature—from 115 to 89°C as well as
lowering the oven temperature at which many of the DBFs eluted. The new temperature
program was as follows: hold at 35°C for 23 min; increase to 139°C at 4°C/min; increase to
301°C at 27°C/min and hold at 301°C for 5 min. The injector temperature was 89°C.
Table 4 summarizes the purity checks performed during the study. For
tribromoacetonitrile, bromodichloroacetonitrile, dbromochloroacetonitrile, and bromopicrin,
there was no significant change in purity with the switch from EPA Method 551.1's GC
temperature program to the updated GC program in May 2001. For other compounds, such as
the iodomethanes, there was a significant change (improvement) in purity with the updated GC
temperature program: up to 25 % for iodoform and 37 % for bromodiiodomethane. Most
compounds improved or stayed the same. Only two compounds appeared to diminish in purity
after the GC temperature program change: 1,1,3-tribromo-propanone (1,1,3-TBP) and
bromochloroacetaldehyde (BCA). Some compounds, such as 1,1,3-TBP, have stability issues, in
general. A fresh standard of 1,1,3-TBP from Helix Biotech provided more pure material to
complete the last set of Winter 2002 quarter stock solutions. BCA was always problematic
because synthesized standards always contained a large contribution from dichloroacetaldehyde
(DCA). The small loss in purity for BCA in May 2001 could have resulted from difficulty in
quantitation of DCA.
336
-------
Table 4. Purity checks of synthesized standards
Compound
Source
Purity
Sep-00
Purity
Jan-01
Puritya
May-01
Status Puritya
Summer-01 Jan-02
lodomethanes
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
lodoform
Agbarb
Agbar
Agbar
Agbar
Agbar
Agbar
Agbar
Agbar
Agbar
Agbar
Mallinckrodt,0 99%
94.7%
75.3%
13.4%
65.0%
Gone
74.4%
New 85.4%
New 89.7%
New 86.5%
New 52.7%
New 56.0%
73.3%
90.2%
96.4%
99+%
68.3%
93.8%
99+%
93.3%
96.7%
97.2%
86.3%
91 .5%
99+%
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
Tribromoacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Aldrich,d 99%
Aldrich. 97%
UNCe
UNC, 93%, <10ma
UNC, 60%, < 10 mg
UNC, <10mg
99+%
99+%
97.2%
92.6%
41 .6%
99+%
99+%
95.2%
92.4%
36.4%
99+%
99+%
99+%
94.8%
42.1%
99+%
99+%
99+%
Running low 91 .0%'
Gone
New 41.1%
Haloketones
ChlorocroDanone
1 ,3-Dichloropropanone
1 .1 .3-TrichlorocroDanone
1 ,1 ,3,3-Tetrachloropropanone
1 ,1 ,1 ,3-Tetrachloropropanone
1 -Bromo-1 .1 -dichlorocroDanone
1,1-Dibromopropanone
1 ,1 ,1-Tribromopropanone
1 ,1 ,3-Tribromopropanone
1 ,1 ,3,3-Tetrabromopropanone
Aldrich. 95%
Aldrich, 95%
Fluka.g85%
UNC
Helix Biotech," 93.5%
UNC
Helix Biotech, 86.0%
UNC. 95%
UNC
Helix Biotech, 92.5%
Can Syn Corp'
Helix Biotech, 97.5%
Can Syn Corp
Helix Biotech, 96.1%
TCI America,' 98%
96.4%
99+%
92.0%
90.4%
Not available
75.0%
36.0%
89.0%
89.0%
99+%
88.9%
98.4%
78.1%
71 .5%
66.3%
63.1%
17.0%
48.4%
84.2%
99.0%
98.0%
99+%
99.6%
99.0%
92.4%
77.6%
38.4%
97.0%
55.8%
99+%
98.1%
99+%
97.7%
Running low
New 96.5% 94.9%
Running low
New 82.7% 91.7%
76.2%
Running low
New 94.0% 94.1%
Running low
New 98.1% 98.6%
Gone
New 97.6% 99.2%
99+%
337
-------
Table 4 (continued)
Compound
Source
Purity
Sep-00
Purity
Jan-01
Puritya
May-01
Status
Summer-01
Puritya
Jan -02
Halonitromethanes
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Bromodichloronitromethane
Dibromochloronitromethane
Bromopicrin
Can Syn Corp
Helix Biotech, 97.2%
Aldrich. 90%
Can Syn Corp
Helix Biotech, 98.6%
Can Syn Corp
Helix Biotech, 87.1%
Maiestic Researchk
Can Syn Corp, < 10 mg
Can Syn Corp, 98.3%
Helix Biotech, 95.8%
Can Syn Corp, < 10 mg
Can Syn Corp, 95.2%
Helix Biotech, 97.1%
Columbia Org Chem Co,' 95%
Not available
99.8%
99+%
Not available
21.3%
55.8%
Not available
97.9%
Not available
98.7%
96.5%
82.8%
77.4%
Not available
Not available
95.9%
99+%
99+%
99+%
97.4%
97.1%
New 99+%
New 99+%
99+%
Gone
New 98.5%
New 99+%
Running low
New 85.3%
New 99+%
New 99+%
98.8%
99+%
99+%
89.5%
76.9%
99+%
99+%
99+%
Haloacetaldehydes
Dichloroacetaldehvde
Bromochloroacetaldehyde
Tribromoacetaldehvde
TCI America, 95%
UNC, < 10 mg
UNC, < 10mq
Aldrich, 97%
99+%
57.2%
99+%
92.2%
52.0%
91 .4%
99+%
45.3%
99+%
Gone
99+%
New 50.1%
99+%
Miscellaneous
Carbon tetrachloride
Tribromochloromethane
1,1,2,2-TeB-2-CE
Benzyl chloride
Sucelco."1 99.97%
UNC, 90%
Helix Biotech, 90.3%
Can Syn Corp
Fluka, 99.5%
99+%
73.4%
Not available
99+%
99+%
76.4%
Not available
99+%
99+%
94.9%
Not available
99+%
Running low
New 84.3%
78.7%
99+%
92.4%
92.1%
99+%
aUpdated GC Program
bAgbar: Aigues of Barcelona (Spain)
°Mallinckrodt (Phillipsburg, N.J.)
dAldrich Chemical Company (St. Louis, Mo.)
eUNC: Synthesized by University of North Carolina at Chapel Hill
'stock solution from May 2001
9Fluka Chemical Co. (St. Louis, Mo.)
hHelix Biotech (New Westminster, B.C., Canada)
'Can Syn: Synthesized by Can Syn Chem Corp (Toronto, Ont., Canada)
'TCI America (Portland, Ore.)
kMajestic Research: Synthesized by George Majetich, University of Georgia (Athens, Ga.)
'Columbia: Synthesized by Columbia Organic Chemical Co., Inc. (Camden, S.C.)
mSupelco (Bellefonte, Pa.)
338
-------
Problematic Compounds
Hexachloropropanone (HCP) andPentachloropropanone (PCP). Hexachloropropanone
(HCP) may undergo a haloform-type reaction in the presence of nucleophiles; consequently, it
can degrade in acetone or methanol. Thus, HCP stock solutions were prepared in MtBE to check
retention times. HCP and pentachloropropanone (PCP), however, degraded immediately by 100
% in water under all conditions. Trihalomethyl-ketones may react with hydroxide ions under
basic conditions, forming a haloform and a carboxylate anion. Thus, HCP should form
trichloroacetic acid (TCAA) and chloroform. This hydrolysis was investigated by spiking
distilled water with 30 (ig/L of HCP. An aliquot of the 30 (ig/L HCP spiked water was acidified,
extracted, and methylated with a solution of sulfuric acid/methanol. GC analysis showed the
presence of 29.6 ng/L of TCAA, which was also confirmed by GC/MS. A liquid/liquid
extraction-GC analysis of another aliquot of the spiked sample showed the presence of 28.6 (ig/L
of chloroform. Thus, the hydrolysis of HCP, forming TCAA and chloroform, was confirmed. A
similar experiment was not performed with PCP-spiked water. However, the expected
degradation by-products for this haloketone are dichloroacetic acid and chloroform.
l,l,2,2-Tetrabromo-2-chloroethane (l,l,2,2-TeB-2CE) and l,l,l,2-Tetrabromo-2-
chloroethane (l,l,l,2-TeB-2CE). These compounds presented great difficulty in terms of
synthesis. A standard of l,l,2,2-TeB-2CE was ultimately available in relatively high purity from
Can Syn Corp., whereas the l,l,l,2-TeB-2-CE was available at 28 % purity from Can Syn Corp.,
and as a small sample from the University of North Carolina (UNC) (Figure 8). The impurities
of the first tetrabromochloroethane (TeBCE) sample (Figure 8a) are tribromodichloroethane
(TBDCE) and pentabromoethane (PBE), based on the elution order of the compounds and also
on the theoretical isotopic patterns for subsequent losses of bromine from each impurity.
A second standard from Can Syn Corp contained both TeBCE isomers together. There is
very little difference between B^CHCB^Cl and BrsCCHBrCl. Both have the same mass, which
leads to similar retention times, and the two peaks co-eluted, even using the updated GC program
(Figure 9b). Furthermore, the mass spectra are nearly the same, with the exception that the
BrsCCHBrCl has a small contribution from CBr3+ (at only about 8 % of the most abundant
peak). Thus, the "3+1" TeBCE (l,l,l,2-tetrabromo-2-chloroethane) cannot be easily
distinguished from the "2+2" TeBCE (l,l,2,2-tetrabromo-2-chloroethane).
A decision was made to test for the l,l,2,2-TeB-2-CE species, in part, because a standard
of sufficient purity was available. In addition, it was not clear if the compound in the original
study in which it was identified was the "3+1" or the "2+2" species. Any TeBCE compounds
that were present would co-elute and be reported as a combined TeBCE result.
339
-------
a)
062901B
100-1
0| i i i i I i i i i I i
072001A
10Ch
Br2CHCBr2Cl Sample
TeBCE
TBDCE
PBE
Magnet EI+
TIC
8.22e7
b)
c)
082101D
10CH
I I I I I I I I I I I I I
UNC Sample
111111111111111111111
Magnet EI+
TIC
3.08e7
28 °/ -
Br3CCHBrCl Sample
n
— ^
Magnet EI+
TIC
7.07e7
30.00
32.00 34.00 36.00 38.00 40.00 42.00 44.00 46.00
48.00 50.00 52.00 54.00
n-Trrp " Time
56.00 58.00 60.00
Figure 8. Total ion chromatograms for TeBCE samples: (a) Original shipment of l,l?2,2-tetrabromo-2-chloroethane; (b) Target
compound l,14?2-tetrabromo-2-chloroethane at reported 28 % purity; (c) UNC sample.
340
-------
a)
062901B
100-,
b)
072001A
100n
0-
082101D
100-,
Br2CHCBr2Cl Sample
Br3CCHBrCl Sample
Magnet EI+
TIC
8.22e7
Magnet EI+
TIC
3.08e7
c)
Magnet EI+
TIC
7.07e7
UNC Sample
i=i^i Time
54.00
53.00
53.10
53.20
53.30
53.40
53.50'=
53.60
53.70
53.80
53.90
Figure 9. Expanded view of TeBCE samples: (a) Original shipment of l,l?2,2-tetrabromo-2-chloroethane; (b) Target compound
l,14?2-Tetrabromo-2-chloroethane at reported 28 % purity;
(c) UNC sample.
341
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REFERENCES
Chen, P. H., S. D. Richardson, S. W. Krasner, G. Majetich, and G. L. Glish. Hydrogen
abstraction and decomposition of bromopicrin and other trihalogenated disinfection byproducts
by GC/MS. Environmental Science & Technology 36(15):3362 (2002).
Krasner, S. W., et al. Analytical Methods for Brominated Disinfection By-Products.
Proceedings of'the 1990 American Water Works Association Water Quality Technology
Conference; American Waterworks Association: Denver, CO, 1991.
Munch, D. J., and D. P. Hautman. Method 551.1. Determination of
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography
with Electron Capture Detection. Methods for the Determination of Organic Compounds in
Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati, OH: U.S. Environmental
Protection Agency, 1995.
342
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SOLID PHASE EXTRACTION-GAS CHROMATOGRAPHY/
MASS SPECTROMETRY METHOD
A solid phase extraction (SPE)-gas chromatography/mass spectrometry (GC/MS) method
was developed for quantifying several of the targeted DBFs for this study (Figure 1). SPE offers
an alternative extraction means to conventional liquid-liquid extraction, and the use of a mass
spectrometric detector provides specificity that is not possible with electron capture detection
(BCD) included in EPA Method 551.1. With the method developed here, concentration of 100
mL of drinking water by SPE provided a sufficient concentration factor to achieve low |ig/L
detection.
EXPERIMENTAL
Instrumentation
A Varian Saturn 2000 ion trap mass spectrometer (Varian Analytical Associates Inc.,
Walnut Creek, CA) equipped with a 3800 GC and a CTC A200s autosampler (CTC Analytics,
Switzerland) was used. Early methods development was performed on a VG TS-250 medium-
resolution mass spectrometer (VG Tritech - now Micromass, Inc., Manchester, England). A
Hewlett-Packard/Agilent Model 5890 GC (Palo Alto, CA) was used for separations and was
partially controlled by an Optic 2 injector (AI Cambridge Ltd., Cambridge, England). Both full-
scan and selected ion monitoring (SIM) analyses were conducted.
Sample Preparation
Varian Bond Elut PPL (Varian Associates, Inc., Harbor City, CA) SPE cartridges were
used for extraction of drinking water. Certified standard mixtures were obtained from Ultra
Scientific (North Kingstown, RI). HCM-551B contains the following compounds at a level of
5000 |ig/mL in acetone: bromochloroacetonitrile, chloropicrin, dibromoacetonitrile,
dichloroacetonitrile, 1,1-dichloropropanone, trichloroacetonitrile, and 1,1,1-trichloropropanone.
THM-521 mix contains chloroform, bromodichloromethane, dibromochloromethane, and
bromoform at a level of 5000 |ig/mL in methanol.
For the DBFs investigated in this study, stock solutions were prepared by accurately
measuring 1.0 mL of methanol (Burdick & Jackson, purge and trap grade, Muskegon, MI) into a
capped 1.4 mL autosampler vial and weighing it. Approximately 2-3 jiL of pure standard were
pulled into a clean syringe and spiked under the solvent after piercing the septum. The
additional weight by difference, between 2-5 mg, was used to calculate an approximate
concentration value. Alternatively, solid compounds were weighed by difference and deposited
directly into an empty autosampler vial before solvent was added. The septum caps were
changed before storage of the samples. Using diluted versions of these stock solutions, the
purity of the stock solutions could be obtained, and adjustments made to the initial calculations
(see separate section on Standards).
SPE was performed using a commercially available 12-port Visiprep vacuum manifold
and 1/8-inch Teflon tubing with weighted stainless steel ends (Supelco Chromatography,
Bellafonte, PA). Samples (100 mL) were placed in clean and dry 125-mL Erlenmeyer flasks that
had been rinsed several times in pure water and baked for 1 hour at 130 °C. The Teflon tubing
was heated for 10 min at 130 °C.
•3 A O
343
-------
Rinse Bond Elut PPL cartridge with
methanol and dichloromethane
V
Water sample, 100 ml_
SPE extraction under vacuum using
transfer line to sample, ~20 mins.
V
Elut resin with 2 ml of 50:50 hexane:dichloromethane
into 3.5 ml clear vial
V
Transfer 0.5 ml to autosampler vial
V
Transfer the final extract to conical
autosampler vial (no headspace)
V
Analysis by
GC/MS
Add 10 u.L of 1-Chlorooctane IS
Figure 1. Summary of the SPE-GC/MS method used for analyzing 35+ DBFs in drinking
water.
344
-------
Six 3-mL SPE cartridges were conditioned by adding two 3 mL aliquots of methanol to
the cartridge and allowing it to drain under vacuum, followed by two 3 mL aliquots of
dichloromethane (Mallinckrodt Baker Inc., Paris, Kentucky). The samples were then attached to
the vacuum manifold using the Teflon tubing and tube adapters. The flow rates were between 2
and 7 mL/minute for all samples for complete passage of the water through the sorbent. The
vacuum lines were closed individually upon completion of the water transfer. To avoid loss of
compounds, the vacuum was not applied to the sorbents any longer than necessary once the
water had eluted.
The Teflon tubing from each sample cartridge was removed and the vial rack inserted
with six 3.5-mL collection vials. Two mL of a 1:1 mixed solvent system of hexane (Aldrich
Chemical Co., THM grade, Milwaukee, WI) and dichloromethane was used as the elution
solvent and placed at the top of the sorbent. (It was not possible to use MtBE as a solvent, due to
the Varian ion trap mass spectrometer being located in a MtBE-free environment in the
laboratory). The individual manifold valves were opened and 10 drops were allowed to pass
through the sorbent material. The six samples were eluted sequentially, 10 drops at a time, until
no solvent was left in the cartridge. To complete the procedure, 0.5 mL of the top portion phase
was transferred to an autosampler vial capped with a Teflon-lined septum. Ten |jL of a 10 mg/L
1-chlorooctane standard (Chem Service, West Chester, PA) was added as the internal standard.
Standards and Check Sample
One advantage of a sector-based mass spectrometer is the dynamic range that can be
achieved. Unlike an ion trap mass spectrometer, ions are separated in space and do not suffer
from so-called "space charge" phenomena. Beginning with the first St. Louis/East St. Louis
sample set (January 2001), a protocol was established that included standards made at the
following levels: 1.0, 2.5, 5.0, 10, 20, 30, 40, 50, 60, 75, and 100 |ig/L in pure water and
adjusted to pH 3.5 (for initial analyses using the TS-250 sector mass spectrometer). These
higher values (up from 40 |ig/L previously) were used to bracket some of the higher THM
concentrations that were seen at some earlier utilities. It was not feasible to spike a mixed set of
DBFs for any given standard because of software processing limitations. Any higher
concentration data points that were skewing the calibration curve or causing undesirable effects
were eliminated. Using this method, very linear curves were produced for most of the 43
compounds analyzed by SPE-GC/MS.
The "check standard" can either be a newly extracted standard or a reinjection of one of
the calibration standards. For the early utilities, the original calibration standards were used as
check standards because it was very important to make sure that the instrument response had not
drifted over the extended runs of the instrument (up to 38 hours). The final check was typically a
50 |ig/L or 40 |ig/L standard that was used to prove the instrument was still responding correctly.
In this way, the check standard was certifying the run, and not necessarily the method.
New calibration standards were required to address the inability to use MtBE as the
primary solvent for the SPE method. Migrating the method to the Varian ion trap mass
spectrometer also set restrictions on the concentration range of standards that could be run on the
instrument to avoid saturation of the trap and potential carryover to subsequent samples. Careful
evaluation of the ion trap's sensitivity at full scan led to the following recommendations for
standard concentrations: 0.25, 0.50, 1.0, 2.5, 5.0, 7.5, 10, 15, 20, 30, and 40 |ig/L. Only the
345
-------
range 0.25 jig/L to 30 jig/L would be used for calibration purposes because of a ten-point limit
with the Star Workstation software. The 40 |ig/L standard would be used for optional processing
should THM concentrations exceed this range. This became an acceptable protocol because all
DBF concentrations typically were below 40 |ig/L, with the exception of chloroform, which was
later dropped from the SPE method due to co-elution with the 1:1 hexane:methylene chloride
solvent system. The final check standard and all sample spikes were at a level of 10 |ig/L.
Gas Chromatography
Prior to June 2001, when the TS-250 sector mass spectrometer was used, the primary
column was a DB-1, 30-m, 0.25-mm ID column with a l-|im film thickness (J & W
Scientific/Agilent, Folsom, CA). The Optic 2, an advanced programmable temperature injector
unit, was used to develop the EPA method in conjunction with the TS-250 mass spectrometer.
The unit comes with its own injector replacement for the Hewlett Packard 5890 GC and controls
the flow of helium carrier gas, the injection temperature, and the split valves. The Optic 2
injector was set at 110 °C and was operated in a splitless mode with a head pressure of 8.0 psi on
the column. Injection volume was 3 jiL. The temperature program followed EPA Method
551.1: 1) Hold at 35 °C for 22 min; 2) increase to 145 °C at 10 °C/min and hold at 145 °C for 2
min; and 3) increase to 225 °C at 20 °C/min and hold at 225 °C for 10 min.
After June 2001, when the Saturn ion trap mass spectrometer was used, the primary
column was a DB-1, 30-m, 0.25-mm ID column with a l-|im film thickness (J & W
Scientific/Agilent, Folsom, CA). The Model 1079 injector was set at 90 °C and was operated in
a splitless mode. Injection volume was 3 jiL. The temperature program was changed to match
the LLE-GC/ECD method being developed: 1) Hold at 35 °C for 23 min; 2) increase to 139 °C
at 4 °C/min; and 3) increase to 301 °C at 27 °C/min and hold at 301 °C for 5 min. This program
will be referred to as the updated GC program.
Mass Spectrometry
Electron ionization (El) spectra show similar fragmentation patterns depending on the
class of compound (Table 1). Using a defined sample list and methodology, software is capable
of integrating individual channels to extract out the peaks of interest. After peak integration, the
resulting areas are used to form calibration curves for each compound, which can then be applied
to unknown samples.
Selected ion monitoring was used to achieve greater sensitivity with the TS-250 mass
spectrometer. Because the DBFs measured are less than a few hundred Daltons in mass and
contain similar functional groups, it was possible to monitor selected ion traces that comprised
common fragment ions for all the compounds. This provided a significant enhancement in
sensitivity for the older TS-250 sector mass spectrometer.
346
-------
Table 1. Fragmentation matrix for DBFs measured using selected ion monitoring. A bold
"X" indicates the quantitation ion; "xc" is the confirmation peak. A strike through the x
indicates a false peak.
C
-------
acid would have to be separated. Separate additions of ascorbic acid and sulfuric acid was also
wise because it would be difficult to know the appropriate dose of acid to achieve the required
pH for water utilities where the buffering capacity of the water was unknown. It was decided
that an acid kit, which would include an eyedropper bottle with dilute sulfuric acid and pH test
strips, would accompany each set of ice chests sent to the utilities, so that the sampler operators
could add the necessary acid in the field. The quenching agent, ascorbic acid, in its granular
form, would be added to each container at the Metropolitan Water District of Southern California
(MWDSC) before shipping. For the 125 mL bottles filled for SPE-GC/MS analysis, two 2 mg
scoops were used to achieve the -4.0 mg and a solution concentration of 31 mg/L.
Each utility was given a detailed set of instructions and told not to rinse out the bottles
(because they contained preservative). Only vials and bottles containing a red cap would require
pH adjustment with acid. This situation worked out well because when unforeseen delays arose
for the utility sampling, the bottles could be kept for several weeks both before the sampling and
after the sampling without compromising the DBF preservation. When samples returned to the
laboratory, their pH was re-checked and adjusted if necessary.
Ice Chest Containers
When each of the ice chests was opened, there was a set of paperwork immediately on
top (sampling instructions, sample collection sheets, and a return Federal Express label). There
was a sheet attached to the inside of each ice chest identifying it as belonging to the MWDSC
and labeling the appropriate utility to which it was sent. Additional information included the
identification of ice chests intended for simulated distribution system (SDS) samples or
assimilable organic carbon (AOC) samples. The large ice chests contained four blue ice packs.
The small ice chests contained one or two ice packs, depending on space. All ice packs were
shielded from the sample bags by Styrofoam, peanut-filled plastic bags. It was important to
isolate the cold packs from the samples to prevent freezing of the water and breakage.
The sulfuric acid solution containers were placed in small white boxes located usually
along with the SDS ice chests. These acid kits included an eyedropping amber bottle, two
additional plastic eyedroppers in case of breakage, and a set of pH test strips.
RESULTS AND DISCUSSION
Detection Limits
TS-250Mass Spectrometer. Because the TS-250 instrument was older and was subject to
drift during the course of a day's analysis, calibration standards were run with each set of
samples to insure the most accurate results. A set of three 10 jig/L standards, comprising 20 of
the DBFs, were extracted using SPE and analyzed the same day on three separate occasions. The
results were interpreted for daily standard deviation and for the overall standard deviation for all
9 samples. The overall standard deviation was multiplied by 2.896 (student t-value for 8 degrees
of freedom at 98% confidence) to get the approximate method detection level (Table 2).
A daily precision of 1.1 |ig/L was observed for samples that underwent off-line SPE.
However, when comparisons were made of data taken over multiple days, this variance increased
to 2.2 |ig/L. Overall detection limits were set at 3 jig/L because of the requirement that
348
-------
standards be run on a daily basis. This limit appeared reasonable because the instrument was
capable of detecting 1 |ig/L levels.
The solid phase extraction technique is probably at its limit for reproducibility (for low
ppb levels). SPE, unlike P&T, is performed manually over the course of several hours. Human
error will play some role in the extraction process, but there is also a significant time segment
where the sample is either exposed to a hood environment or direct vacuum, which can
potentially contribute to the loss of some compounds.
Errors in quantitation of samples can also occur due to the SIM scan speed of the magnet.
For SIM acquisition, the dwell time for each m/z measurement must be sufficiently long to
adequately sample the ion population, but sufficiently short to collect as many samples per
eluting peak as possible. By setting a residence time of 50 msec per m/z measured and allowing
time for the magnet to switch to next mass, there is a necessary scan time of 2.17 seconds/scan.
Often, this amounts to only 5 to 8 samples per chromatographic peak, which can cause errors
because a peak area approximated by only 5 to 8 data points will be inherently less accurate than
one sampled by many more points to give better peak resolution.
Table 2. Detection limit study for selected compounds showing both daily and overall
standard deviations for a typical 10 ug/L standard
Compound
Chloroform
Dichloroacetaldehyde
Chloroacetonitrile
Chloropropanone
Trichloroacetonitrile
Di Chloroacetonitrile
Bromodichloromethane
1 , 1-Di Chloropropanone
Bromoacetonitrile
Chloropicrin
Dibromochloromethane
Bromonitromethane
Bromochloroacetonitrile
1,1,1 -Tri Chloropropanone
1,3-Di Chloropropanone
Bromoform
Dibromoacetonitrile
1 , 1 ,3-Trichloropropanone
Benzyl Chloride
lodoform
RT
(min.)
5.98
6.20
7.46
8.15
8.80
10.17
10.50
12.70
14.50
19.81
20.61
21.00
21.26
26.38
27.14
28.12
28.48
30.75
32.66
37.86
ABC
4/10 4/10 4/10
9.0 9.4 9.7
17.7 15.2 16.2
9.9 12.7 14.7
6.2 7.1 13.3
10.3 10.5 10.7
10.7 11.1 12.1
9.3 9.7 10.4
9.1 9.6 10.1
10.6 12.5 13.9
10.5 10.2 11.1
10.3 10.5 11.4
11.6 12.3 13.7
11.7 11.9 12.8
11.9 12.2 12.9
12.5 13.9 14.4
10.9 11.2 12.4
12.3 12.6 13.3
16.4 14.8 15.4
10.3 10.6 11.6
12.4 12.7 13.3
D E F
4/12 4/12 4/12
5.9 6.2 6.3
13.7 13.0 13.9
11.7 13.7 13.3
12.1 12.8 13.5
5.6 6.1 5.9
8.3 10.0 10.4
5.8 6.9 6.8
9.2 10.3 10.9
11.9 13.8 15.5
4.6 5.7 5.9
5.8 7.4 7.6
8.3 11.9 13.5
7.9 9.8 10.0
9.0 10.4 10.9
11.2 12.0 13.5
6.8 8.7 8.9
7.9 9.5 10.0
11.3 11.6 10.8
6.9 8.1 8.4
7.2 8.2 8.2
G H I
4/18 4/18 4/18
8.6 9.5 10.1
9.6 11.5 11.2
8.4 12.2 12.4
11.6 11.7 13.9
7.7 8.5 8.9
7.5 9.0 10.9
7.8 8.9 10.3
8.0 9.9 11.1
6.5 9.7 11.8
6.9 8.4 9.4
6.5 9.1 10.7
5.9 9.2 10.6
6.4 8.4 9.9
6.3 8.6 10.0
4.8 8.7 9.6
6.4 8.7 10.3
6.4 7.8 9.2
8.3 9.9 9.0
5.9 7.1 7.8
10.2 9.6 9.3
Daily Std. Deviation
4/10
0.4
1.3
2.4
3.9
0.2
0.7
0.6
0.5
1.7
0.5
0.6
1.1
0.6
0.5
1.0
0.8
0.5
0.8
0.7
0.5
4/12
0.2
0.5
1.1
0.7
0.3
1.1
0.6
0.9
1.8
0.7
1.0
2.7
1.2
1.0
1.2
1.2
1.1
0.4
0.8
0.6
4/18
0.8
1.0
2.3
1.3
0.6
1.7
1.3
1.6
2.7
1.3
2.1
2.4
1.8
1.9
2.6
2.0
1.4
0.8
1.0
0.5
AVE
Cone.
8.3
13.6
12.1
11.4
8.2
10.0
8.4
9.8
11.8
8.1
8.8
10.8
9.9
10.2
11.2
9.4
9.9
11.9
8.5
10.1
SD
AVE
1.7
2.6
1,9
2.8
2.0
1.5
1.7
1.0
2.7
2.4
2.0
2.6
2.1
2.1
3.1
2,0
2.4
2.9
1.9
2.2
Averages 1.0 1.0 1.6 2.2
RSD (Estimated
% IMDL, ug/t
20 5
19 7
16 6
25 8
25 6
15 4
20 5
10 3
23 8
29 7
23 6
24 7
21 6
20 6
27 9
21 6
24 7
24 8
22 6
22 6
21.5 6.3
349
-------
Extraction Efficiency
The extraction efficiency of the Bond Elut sorbent was tested at three different standard
concentrations, 10 |ig/L, 25 |ig/L, and 50 |ig/L, to determine whether there were any sample
loading concerns with the sorbent's capacity. Most of the anticipated values for DBFs in
drinking water would be well below 50 |ig/L. Compounds within the same compound family
exhibited similar extraction efficiencies. The important observations were that recoveries were
good (74% average) and higher concentrations of analytes, up to 500 |ig/L, do not saturate the
capacity of the Bond Elut sorbent.
Early Observations
VOC concentrations can become altered if excessive headspace or high temperatures are
present. For analysis, the headspace was minimized by using 100 jiL conical autosampler vials
(that hold -300 jiL when filled to top) for storage, rather than the typical 1.4 mL autosampler
vials. For samples that sit on top of the GC for extended runs, they are exposed to high
temperatures. A Tekmar water bath circulating system was attached to the sample tray to
remove some of the heat load. The water bath's temperature was set to maintain a temperature of
21.0 °C (about room temperature) on the sample tray, which minimized sample
degradation/volatilization for extended runs. Chloroform and bromodichloromethane showed
the most improvement for spike recovery.
The heavier iodo-TFDVIs, haloacetonitriles, and halonitromethanes showed much reduced
recoveries for 10 ppb-spiked samples. This was either an expected limitation for the SPE
procedure, or the lower injection temperature used discriminated against these heavier (higher
boiling point) compounds. Significantly raising the injection temperature, however, would have
caused many more problems with degrading species. It was discovered later that some of these
compounds (bromodichloro-, dibromochloro-, and tribromoacetonitrile, and bromodichloro-,
dibromochloro-, and tribromonitromethane) were not preserved using ascorbic acid.
Several analytes were found to coelute on the GC. Bromochloroacetaldehyde (retention
time of 12.6 min.) co-eluted with trichloroacetaldehyde, which was not present in the method,
but has been seen in many samples and was part of the Information Collection Rule.
Chloropicrin (retention time of 21.8 min.) co-eluted with bromodichloroacetonitrile. An easy
separation was achieved by using different quantitation masses — m/z 117 for chloropicrin and
m/z 108 for bromodichloroacetonitrile. The m/z 117 contribution from
bromodichloroacetonitrile, if present, was negligible and small enough to ignore.
Tribromoacetaldehyde (retention time of 32.8 min.) co-eluted with tribromoacetonitrile.
An alternate quantitation peak, m/z 251, was chosen for tribromoacetaldehyde, at reduced
sensitivity, to effect a clean separation from tribromoacetonitrile and other nearby species.
Bromonitromethane was sandwiched between dibromochloromethane and
bromochloroacetonitrile, which did not allow baseline resolution for that quantitation channel,
m/z 93.
Dibromoiodomethane, 1,3-dibromopropanone, tribromoacetaldehyde, and
tribromoacetonitrile all eluted within 0.1 min of each other. Alternate channels eliminated major
overlaps, but sensitivity was reduced. Chloro-, 1,1-dichloro-, 1,1,1-trichloro-, 1,1-dibromo-, 1-
bromo-l,l-dichloro-, and 1,1,1-tribromopropanone were difficult to quantitate because of
-------
common fragmentation patterns produced. The highest ion abundance came from m/z 43
(COCH3), which showed a low level persistent background throughout the run. Another co-
eluting system — dibromoacetonitrile/bromodichloronitromethane (retention time of 33.9 min.) -
- was eliminated by using different mass channels. Improved chromatography or the use of a
different polarity column could also correct this problem.
Choice of Analytical Columns
CP-1301 Column. The CP-1301 column was installed on the TS-250 mass spectrometer
to evaluate its performance for separating the targeted DBFs. The GC temperature program was
the latest that MWDSC had been using, with the exception that this column could not go beyond
a maximum temperature of 250 °C. This lowered maximum temperature caused a lower overall
sensitivity for late eluting compounds.
Peaks that were not baseline-resolved included dichloronitromethane and
dibromochoromethane, bromoacetonitrile and dichloroiodomethane, and
bromochloronitromethane and bromoform. Another difficult problem was that of co-eluting
species, which for the CP-1301 column included: chloroform + others, carbon tetrachloride +
others, dichloroacetonitrile + bromodichloroacetonitrile, 1,1-dibromopropanone +
bromochloroiodomethane, and dibromoiodomethane + benzyl chloride. Peaks for
dichloroacetaldehyde, bromochloracetaldehyde, trichloroacetaldehyde, tribromonitromethane,
and 1,1,3,3-tetrabromopropanone were not found, or, they were problematic for analysis using
this column/setup. Bromodichloronitromethane and dibromochloronitromethane were not
included in this mixture analyzed. Figure 2 shows the CP-1301 column performance for the
targeted DBFs.
DB-5 Column. A DB-5 column was installed on the TS-250 mass spectrometer and was
used to analyze the same spiking mixture. There were a lot of co-eluting peaks, although it was
clear that trichloroacetaldehyde and bromochloroacetaldehyde were well separated. Another
benefit of this column was that there was better signal-to-noise, compared to the CP-1301
column, particularly at the high end of the chromatogram where degradation of compounds and
column bleed is normally a problem.
Peaks that were not baseline resolved included bromochloronitromethane and 1,1,1-
trichloropropanone; 1,1,3-trichloropropanone and tribromochloromethane; and 1,1,1-
tribromopropanone and bromodiiodomethane. Co-eluting peaks included dichloroacetaldehyde
+ others; chloroacetonitrile + trichloroacetonitrile; bromonitromethane +
bromochloroacetonitrile; dibromoiodomethane + tribromoacetonitrile + benzyl chloride; and
chlorodiiodomethane + 1,1,3,3-tetrachloropropanone.
-------
Magnet EI+
TIC
4.65e7
10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00
Figure 2. CP-1301 column performance using full DBF set. Compounds not detected
include dichloroacetaldehyde, bromochloroacetaldehyde, tribromoacetaldehyde,
tribromonitromethane, and l,l?3,3-tetrabromopropanone. Compound abbreviations are
found in Table 3.
DB-1 Column. As a comparison between the DB-5 column and a DB-1 column, the two
columns are profiled side-by-side in Figure 3, which shows unambiguous peak identities when
converting between the two chromatograms. As a general rule, the DB-1 column was preferred
because, in conjunction with individual mass traces, it allowed for the separation of all the
targeted DBFs, except for the trichloroacetaldehyde-bromochloroacetaldehyde conflict. In
general, DB-1 improvements over DB-5 included: a) separation of chloroacetonitrile and
trichloroacetonitrile, b) separation of bromonitromethane and bromochloroacetonitrile, c)
separation of bromochloronitromethane and 1,1,1-trichloropropanone, d) separation of 1,1,3-
trichloropropanone and tribromochloromethane, e) partial separation of dibromoiodomethane,
tribromoacetonitrile, and benzyl chloride, f) separation of chlorodiiodomethane and 1,1,3,3-
tetrachloropropanone, and g) separation of 1,1,1-tribromopropanone and bromodiiodomethane.
DB-624 Column. The DB-624 column used on the Varian Saturn ion trap mass
spectrometer was very similar in polarity to the CP-1301 column tested. It is the column
currently used by MWDSC for the EPA Method 524.2 purge-and-trap analyses. Many of the
heavier DBFs, such as the halonitromethanes were not well recovered from this column, partially
due to the polarity and lowered maximum temperature. The DB-624 column was replaced with a
DB-1 column to achieve the same performance, as was being done for the LLE-GC-ECD and
SPE-GC/MS (TS-250 mass spectrometer) methods. The replacement option made it necessary
352
-------
PQ
Q
PQ
Q
Figure 3. DB-5 column versus DB-1 column performance using full DBF set.
to re-evaluate purge-and-trap operation with a DB-1 column for a more limited set of
compounds.
Improved Temperature Program
The updated GC temperature program was officially adopted in June 2001 for the SPE-
GC/MS method used on the TS-250 mass spectrometer and all subsequent work on the Saturn
ion trap mass spectrometer. The updated GC temperature program, along with a lower injection
temperature of 90 °C was used for the latest set of stock solutions to get new retention times for
all of the DBFs (Table 3).
In attempting to translate the retention times obtained from the older results to those
found by utilizing the updated GC program, it was noted that simple linear equations can be used
to approximate new retention times. During the first 23 min of the temperature programs, both
results are the same because both hold the GC oven at 35 °C for the isothermal portion of the
programs. The correlation of the retention times after 23 min is not a mirror image because of
the differences in ramp rates between the two temperature programs (see Gas Chromatography
section above). Figure 4 shows the two linear approximations that can be used for estimating the
new GC retention times. The equation y = 0.9972x + 0.0699 for the 0 to 23 minute portion of
the graph is synonymous with y = x, with a very small offset.
-------
Table 3. VG TS-250 mass spectrometer quantitation ions for selected ion monitoring and
elution order before and after update to GC program
Compound
Chloroform
Dichloroacetaldehyde
Chloroacetonitrile
Chloropropanone
Carbon Tetrachloride
Trichloroacetonitrile
Dichloroacetonitrile
Bromodichloromethane
Chloronitromethane
Bromochloroacetaldehyde
1 , 1 -Dichloropropanone
Dichlorordtromethane
Bromoacetonilrile
Chloropicrin
Bromodichloroacetordtrile
Dibromochloromethane
3 romonitromethane
Bromochloroacetonitrile
Dichloroiodome thane
Bromochloronitromethane
1,1, 1-Trichloropropanone
1 , 3 -Dichloropropanone
Bromoform
Dibromoacetonitrile
Bromodichloronitromethane
Dibromochloroacetonitrile
1 , 1 -Dibromopropanone
Bromochloroiodo methane
Dibromonitromethane
1 -Bromo- 1 , 1-dichloropropanone
1 , 1 ,3-Trichloropropanone
Tribromochloromethane
Dibromochloronitrome thane
Dibromoiodomethane
Tribromoacetaldehyde
Tribromoacetonitrile
Benzyl chloride
Chlorodiiodome thane
1,1,3,3-Tetrachloropropanone
1,1,1,3-Tetrachloropropanone
Bromopicrin
Bromodiiodomethane
1,1, 1-Tribromopropanone
1 , 1 ,3-Tribromopropanone
[odoform
1,1,3,3-Tetrabromopropanone
Abbreviation
TCM
DCA
CAN
CP
CT
TCAN
DCAN
BDCM
CNM
BCA
DCP
DCNM
BAN
TCNM
BDCAN
DBCM
BNM
BCAN
DCIM
BCNM
1,1,1-TCP
1,3-DCP
IBM
DBAN
BDCNM
DBCAN
1,1-DBP
BCIM
DBNM
1,1,1-BDCP
1,1,3-TCP
TBCM
DBCNM
DBIM
TEA
TBAN
BC
CDIM
1,1,3,3-TeCP
1,1,1,3-TeCP
TBNM
BDIM
1,1,1-TBP
1,1,3-TBP
TIM
1,1,3,3-TeBP
Quantitation
m/z
83
49
75
43
117
108
74
83
49
49
43
83
119
117
108
127
93
74
83
129
43
77
173
118
163
154
43
127
173
43
77
207
207
173
251
198
91
175
83
77
251
219
43
121
127
120
Confirmation
m/z
49
83
77
49
49
49
49
79
N/A
130
93
N/A
79
49
154
91
79
N/A
127
79
83
49
91
79
49
74
173
175
43
127
83
79
79
127
173
79
N/A
127
N/A
49
91
127
251
93
267
173
TS-250 Retention Time, Minutes
(MtBE, 551.1 GC Program)
6.80
7.04
8.36
9.11
9.38
9.79
11.42
11.69
12.57
14.06
15.01
16.16
21.83
21.90
22.68
23.25
23.29
25.25
26.03
27.08
27.80
28.75
29.05
29.32
29.66
29.80
30.10
30.88
31.22
32.68
32.75
32.82
33.09
33.36
33.46
33.70
35.36
35.94
36.14
37.63
38.31
40.48
TS-250 Retention Time, Minutes
(MtBE, Updated GC Program)
6.92
7.10
8.47
9.12
9.47
9.85
11.38
11.73
12.42
12.57
14.08
14.95
16.10
21.83
21.92
22.73
23.10
23.52
26.67
28.05
30.00
31.38
33.12
33.88
33.87
34.28
34.88
35.18
35.93
37.45
38.25
39.10
40.92
41.17
41.40
41.53
42.22
42.62
43.00
43.53
46.48
47.42
47.90
50.70
51.47
53.75
The interconversion between the two GC programs was helpful for determining where
peaks would appear in a chromatogram, and it could be used to check the location of new peaks
or impurities. The software method used for processing all SIM data was updated on 6/5/01 to
reflect these new retention times, as well as the new correction factors for the latest set of stock
solutions.
-------
55.00
50.00 -
45.00 -
40.00 -
c
.2 35.00 -
£
&• 30.00 -
2
O)
g 25.00 -
Q.
o
•s
•D
20.00 -
15.00 -
10.00
5.00
.A''
5.00 10.00 15.00 20.00 25.00 30.00
EPA Method 551.1 Retention Times (min.)
35.00
40.00
y = 1.9648X -23.13
R2= 0.9988
y = 0.9972X + 0.0699
R2= 0.9998
0 to 24 minutes
25 to 40 minutes
0 to 24 minutes
25 to 40 minutes
Figure 4. Correlation of retention times before and after GC program update.
Problematic Compounds
All subsequent work utilized the DB-1 column for compound separation.
Chloronitromethane was found to co-elute with bromochloroacetaldehyde (and
trichloroacetaldehyde). There was no solution available at this time (Figure 5). It may be
possible to analyze for bromochloroacetaldehyde using only m/z 130 at about 40% of the
sensitivity of the m/z 49 peak. There was not, however, sufficient quantities of
bromochloroacetaldehyde to warrant further methods development on the
bromochloroacetaldehyde and trichloroacetaldehyde co-elution.
Chloropicrin co-eluted with bromodichloroacetonitrile. Selection of different mass
channels can eliminate this conflict (Figure 6). Bromodichloroacetonitrile and
trichloronitromethane can be separated on the DB-5 column. The analysis of
bromodichloroacetonitrile by SPE-GC/MS was later dropped because it required ammonium
chloride for a quenching agent and preservative.
-------
Mass Spectra
CNM
50 ppb Extracted Standard
CNM-BCA
060401H
100-1
1220
SIR of 28 Channels EI+
1295 TIC
/\ 9.21e5
060401H
100-1
SIR of 28 Channels EI+
48.984
1.07e5
BCA
SIR of 28 Channels EI+
129.901
4.17e4
\
12.00 12.20 12.40 12.60 12.80 13.00 13.20 13.40
Figure 5. Chloronitromethane (CNM) co-elutes with bromochloroacetaldehyde (BCA)
(which co-elutes with trichloroacetaldehyde (TCA)). Chloronitromethane is not amenable
to SPE-GC/MS analysis.
Mass Spectra
50 ppb Extracted Standard
TCXM • BDCAN
SIR of 28 Channels EI+
TIC
1.50e7
SIR of 28 Channels EI+
116.907
2.91e6
20.50 21.00 21.50 22.00 22.50 23.00 23.50
Figure 6. Chloropicrin (TCNM) co-elutes with bromodichloroacetonitrile (BDCAN). Both
are amenable to SPE-GC/MS analysis.
356
-------
Mass Spectra
50 ppb Extracted Standard
BDCNM+DBA.N
060401H
100n
051401K1841 (33.852)
100n
SIR of 28 Channels EI+
TIC
3.19e7
^ j
u
34.19
i
U
"TIC"
35.86
I 35.11
fl
i_J
I
SIR of 28 Channels EI+
162.854
7.42e5
051701D 1846(33.880)
100n
SIR of 28 Channels EI+
117.929
1.07e7
32.00 33.00 34.00 35.00 36.00 37.00
Figure 7. Bromodichloronitromethane (BDCNM) co-elutes with dibromoacetonitrile
(DBAN). Both are amenable to SPE-GC/MS analysis.
Bromodichloronitromethane co-eluted with dibromoacetonitrile. Selection of alternate
mass channels eliminates a conflict (Figure 7). However, bromodichloronitromethane was later
dropped from the SPE method because it too required ammonium chloride as a quenching agent
and preservative.
Holding Study
As was stated in the Early Observations section of this chapter, certain heavier
haloacetonitriles and halonitromethanes showed consistently poor quantitation in earlier work on
this project. Before the final year of sampling was to begin, it was necessary to revisit the choice
of ascorbic acid as a general quenching agent and preservative for all DBFs that were being
studied by SPE, LLE, P&T, and SPME methods. Many of these compounds were not available
during the initial methods development period. Thus, an experiment was carried out to evaluate
the stability of DBFs stored with ascorbic acid at a pH of 3.5.
-------
The results were surprising because it was discovered that six compounds were not
amenable to this ascorbic acid/pH 3.5 combination. To summarize the results by DBF class:
THMs-
lodo-THMs -
Haloacetonitriles -
Chloropropanones -
Bromopropanones -
Halonitromethanes
Haloacetaldehydes
Miscellaneous -
No problems through Day 21.
No problems through Day 21.
No problems through Day 21, except bromodichloro-,
dibromochloro-, and tribromoacetonitrile showed no recovery
between Day 0 and Day 3 (Figure 8).
No problems through Day 21. 1,1 -Dichloropropanone was
difficult to quantitate.
No problems through Day 21. 1,1,3-Tribromopropanone had a
slow decay.
No problems through Day 21, except
Bromodichloronitromethane, dibromochloronitromethane, and
tribromonitromethane showed no recovery.
Difficult to quantitate. Tribromoacetaldehyde had fast decay.
Both carbon tetrachloride and benzyl chloride had slow decays.
According to the plots of concentration vs. time (Figure 8), it appeared as if the following
DBFs were highly unstable in the presence of ascorbic acid at pH 3.5: bromodichloro-,
dibromochloro-, and tribromoacetonitrile, and bromodichloro-, dibromochloro-, and
tribromonitromethane. Previous research has shown that trichloroacetonitrile can undergo base-
catalyzed hydrolysis, but it is stable at acidic pH. The brominated versions of some of these
DBFs (i.e., tribromoacetonitrile, bromodichloroacetonitrile, and dibromochloroacetonitrile) may
be even more unstable and may break down in the presence of ascorbic acid. However,
tribromonitromethane was stable at pH 4 in the presence of ammonium chloride, so it was
possible that heavy, brominated DBFs may be stable in the presence of ammonium chloride at
pH3.5.
A new holding study was carried out to evaluate ammonium chloride as a quenching
agent/preservative at pH 3.5. Ascorbic acid at pH 3.5 was tested in parallel on DBFs of interest
(e.g., bromodichloro-, dibromochloro-, and tribromoacetonitrile, and bromodichloro-,
dibromochloro-, and tribromonitromethane). The hypothesis was confirmed, and additional
sample bottles containing ammonium chloride quenching agent/preservative were added for the
LLE-GC-ECD method. These six compounds were dropped from the SPE method because of
the additional work load that would have been involved in sampling and extraction.
358
-------
CAN-WI
CAN-WE
BAN-WI
BAN-WE
DCAN-WI
DCAN-WE
BCAN-WI
BCAN-WE
DBAN-WI
DBAN-WE
TCAN-WI
TCAN-WE
BDCAN-WI
— W— BDCAN-WE
— •— DBCAN-WE
TBAN-WI
TBAN-WE
Day
Figure 8. Ascorbic acid/pH 3.5 holding study results for haloacetonitriles (Weymouth
filtration plant influent and effluent).
Migration to Saturn Ion Trap Mass Spectrometer
The SPE method was implemented on the ion trap mass spectrometer as a backup system
in the event that the TS-250 mass spectrometer would become unusable for the project. If, at the
end of this additional methods development period, the ion trap results were much better, then
the SPE method would be permanently migrated to the Saturn 2000 ion trap mass spectrometer
for all subsequent work. Restrictions to this work included: a) not using MtBE as the extraction
solvent, and b) keeping the instrument as "stock" as possible for easy switch-over to purge-and-
trap operation. Most of the initial testing occurred during late June 2001, when the performance
of the existing DB-624 GC column and alternative solvents were tested. It was found that unless
the original procedure was kept intact, from development with the TS-250 mass spectrometer, it
would be difficult to achieve similar results. From previous work comparing different GC
columns, a switch to the preferred DB-1 column was necessary. Because of the extra efforts
involved in switching columns frequently, it was hoped that the DB-1 column could be used for
both SPE and P&T analysis on the same instrument. Initial work would include optimizing some
instrumental parameters, automating the system, running full calibration curves (0.5 - 30 |ig/L),
and injecting a suite of samples to establish a preliminary MDL. The results of this SPE work on
the ion trap mass spectrometer showed that low-level detection was possible for almost all of the
compounds that were part of the original SPE technique performed on the TS-250 instrument.
-------
Results for chloroform, dichloroacetaldehyde, chloroacetonitrile, and chloropropanone
could not be obtained because they co-eluted with the hexane solvent that was now part of the
solvent extraction system. Of the solvents listed below, w-hexane was a logical choice based on
the boiling point of the solvents. If the solvent is too volatile, the extraction process would
become more difficult because SPE extractions occur under vacuum. Unfortunately, hexane is
very non-polar and does not remove as many DBFs from the Bond Elut sorbent material. A
mixed solvent system of 50:50 hexane/methylene chloride allowed full extraction of the DBFs,
and, at the same time, avoided bringing MtBE and larger amounts of MeCl2 into the VOC room,
where they are routinely determined as part of the VOC method (Table 4).
Solvents* Boiling Point (°C) Comments
Ethyl ether 34.6
Pentane 36.1
Methylene chloride 39.8 VOC compound
Carbon disulfide 46.5
Methyl tert-buty\ ether 55.2 VOC compound
Chloroform 61.2 VOC compound
w-Hexane 69.0
Benzene 80.1 VOC compound
Cyclohexane 80.7
Iso-octane 99.3
Toluene 110 VOC compound
*Recommended for non-polar columns (100% methyl or 5% phenyl, 95% methyl)
Compound Notes
Dichloroacetonitrile had a co-elution problem with an unknown impurity that seemed to
be present in the standards. The co-elution also occurred when MtBE was used as the extraction
solvent on the TS-250 instrument, but there was not sufficient resolution to resolve the co-eluting
peak from dichloroacetonitrile, and the two peaks were integrated together to produce a
systematic error.
Bromonitromethane was a minor problem for quantitation because it eluted between
dibromochloromethane and bromochloroacetonitrile, both of which have small m/z 93
contributions to bromonitromethane's main quantitation mass channel. On the TS-250
instrument, this problem could be solved by manually re-integrating the peaks.
Chloronitromethane and bromochloracetaldehyde were eliminated from the SPE method
because of their co-elution on the DB-1 column with chloral hydrate (TCA) and each other.
360
-------
Table 4. Varian Saturn 2000 performance with 1:1 Hexane/MeCl2 solvent system and
updated GC program. Shaded compounds were later removed from the SPE method.
Compound
Saturn 2000 Retention Time
Using Updated GC Program
Quantitation
mlz
Confirmation
mil
Lowest Standard Estimate
(Ion Trap. DB-1. SpHtless)
1,1,1,3-Tetrachloropropanone showed an unrecoverable co-elution with an impurity late
in the chromatographic run (retention time of 42.1 min.). There was no solution to this problem,
so poor quality assurance (QA) data was obtained for this compound, following migration to this
method.
1,1,3,3-Tetrabromopropanone (retention time of 53.1 min.) exhibited poor quantitation
for standards and was the latest eluting compound of all the DBFs studied. Either 1,1,3,3-
tetrabrompropanone was slowly degrading or quantitation of this compound was made difficult
because of poor signal-to-noise in this section of the chromatographic run, when the GC oven
was doing its final ramp to 301 °C. The baseline rises significantly about 52 min into the run.
Multiple Quantitation Ions
The main obstacle for quantitation of SPE results was low signal-to-noise of the
chromatographic peaks. The electron capture detector is inherently more sensitive for detection
for halogenated compounds (as low as 0.10 ppb). SPE and P&T are comparable for minimum
reporting levels, generally 0.20 to 0.25 ppb. The peaks are often much sharper and more distinct
using P&T because of a lack of solvent and full injection of the sample aliquot.
A new strategy of using multiple quantitation ions for improving SPE sensitivity was
tested. In the past, the SPE method used the most optimum ion channel for high abundance and
361
-------
minimal interference problems from other peaks. In this new strategy, the original quantitation
ion was added to the next-largest ion that was a significant contribution to the El mass spectrum.
This provided up to a two-fold improvement for some compounds. About one-third of the
compounds showed improvement, with a previous reporting level of 1.0 |ig/L now becoming
0.50
MDL and Sample Reporting
All of the remaining 35 compounds gave results comparable to or better than those
obtained in the past using the TS-250 instrument. In several cases, the lowest calibration
standards could be dropped to 0.25 |ig/L. (In previous work, the lowest calibration point was 1
|ig/L, and a reasonable MDL was established at 3 |ig/L).
The ten calibration standards for the Varian ion trap were at concentrations of 0.25, 0.50,
1.0, 2.5, 5.0, 7.5, 10, 15, 20, and 30 |ig/L. After calibration curves had been established, the data
files for 0.25 jig/L - 5.0 jig/L standards were duplicated and processed as if they were actual
samples to check the accuracy and integrity of the calibration curves. Table 5 shows these
results. If the reported values were within 30% of the theoretical values, then the results were
designated in bold type, and the lowest, reliable values to report are shown in a shaded highlight.
As an example, the results for a recent Alameda County Water District sampling on 3/19/02
showed that the values used for SPE results reporting could be set much lower than those
produced from a simple MDL comparison (Table 5). Because this was such an important survey
study, and real world results are often below 5 |ig/L for any given DBF, it was necessary to
extract all available information that we could from this SPE method.
Success with Migration of SPE Technique to Ion Trap
The SPE technique was successfully implemented on the Saturn 2000 ion trap mass
spectrometer. Full-scan mode on the Saturn ion trap provided more mass spectral information
and improved the sensitivity over the TS-250 instrument. The ion trap mass spectrometer
provided full automation and overnight runs, along with more reliable operation. Because both
the SPE and P&T methods used the same instrument for analysis, comparison of results was
much better. Because of these advantages, the Saturn 2000 ion trap mass spectrometer was used
for all subsequent samplings.
Comparison of SPE to P&T and LLE
The pursuit of multiple analytical techniques for the Nationwide DBF Occurrence Study
led to a complementary scheme for data analysis and interpretation — the liquid-liquid extraction
technique would be the primary method used for quantitation, and other techniques such as P&T,
SPE, or SPME could provide true confirmation of a compound's presence. Not all the techniques
could analyze for each compound. Table 6 shows the comparison of results using SPE, P&T,
and LLE techniques. The results were very consistent. Because this is only a comparison of
362
-------
how SPE results compare to the other techniques, many of the compounds that were part of this
study, but were not amenable to SPE, were intentionally left off the table.
Table 5. Minimum reporting levels (MRLs) for Alameda County Water District sampled
on 3/19/02. A concentration in bold represents values that lie within the + 30% range.
Shading represents the lowest reportable level for this study set.
Compound
Haiomethanes
BDCM
DBCM
IBM
TBCM
DCIM
ECIM
DBIM
CDIM
BDIM
TIM
Haloacetonitriles
BAN
DC AN
6CAN
DBAN
TCAN
Haloketones
1,1-DCP
1,3-DCP
1.1-DBP
U.I-TCP
1,1,3-TCP
1,1.1-BDCP
1,1,1-TBP
1.1,3-TBP
1,1,3,3-TeC.p
1,1,1,3-TeCP
1.1,3,2-TeBP
Haioacetaldehyde
TBA
Halonitroinethanes
BNM
DCNM
BCNM
DBNM
TCNM
Misc. Compounds
CT
BC
1.1,2.2-T*BCE
Quantitation
Ions
83+35
127+129
171+173
207*209
83465
127+129
127+173
127+175
219+221
127+267
119+121
74
74+76
1 18+120
100+110
43+63+33
77+78
43+79+173
43+97+125
77+33
43+97+I2S
43+79+251
121+123
83+35
77+79
120+122
172+173
95
83+35
127+129
171+173
117+119
117+119
9 i +1 26
141+299
0.28 UflJL
(0.1 75 - 0-325)
Range
0.229
0.219
0.250
0.253
0401
0.1W
0.50 ugJL
(0.350-0.850)
Range
0701
0.641
0.665
0.476
0.534
0665
OJ81
1.095
0.5S2
0.544
0.537
0.808
0.595
0.678
0.640
0.509
0.552
I.OugtL
(0.700-1 300)
Range
0.835
0.860
0.95}
0.8 18
0.845
0.842
0.714
0.701
1.027
0.539
0.842
0.697
0.79}
1.0«
1.031
1.119
1.083
1.039
0.923
1.035
O.S41
2.6 uglL
(1 .750-3 250)
Range
2.355
2.48»
2.659
2.119
2.417
2J1I>
2.244
2.381
1.990
1.96*
2.450
2.876
2.401
2370
2.341
2.935
2.014
2.334
2.961
2.441
2.949
1.989
1.830
2.543
2.111
2.25«
2.475
1.978
2.138
1.463
6.0 uglL
(3500-6.500)
Range
4.014
3.910
4.221
7445
4.406
4.068
4.424
4.516
5.S99
4.014
0820
3.317
3.S63
3.798
j.708
3.351
4.154
4.229
4.024
3.504
3.953
4.235
J.»48
3.505
6.380
5.092
3.778
4.220
3.999
4.095
6.515
7811
5.821
Minimum Reporting
Level
1 0 ppb
0 25 ppb
1.Q ppb
0.25 ppb
0.25 ppb
0 25 ppb
1.0 ppb
0.50 ppb
2.5 ppb
2.5 ppb
1.0 ppb
2.5 ppb
0 50 ppb
0.50 ppb
0.50 ppb
2 5 ppb
2.5 ppb
1.0 ppb
0.50 ppb
2 5 ppb
1 Oppb
2.5 ppb
5 0 ppb
2 5 ppb
?> 5 pfjb
»>5ppb
2 5 ppb
5 0 ppb
1 0 ppb
5 0 ppb
O.SO ppb
0.50 ppb
1 0 ppb
0.25 ppb
5 0 ppb
MDL Comparison
4 ppb
6 ppb
5 ppb
5 ppb
4 ppb
4 ppb
3 ppb
4 ppb
4 ppb
4 ppb
12 ppb
6 ppb
5 ppb
4 ppb
3 ppb
5 ppb
5 ppb
5 ppb
4 ppb
7 ppb
4 ppb
9 ppb
11 ppb
Sppb
12 ppb
3 ppb
0 ppb
lOppb
10 ppb
8 ppb
7 ppb
4 ppb
4 ppb
4 ppb
Not Available
363
-------
Table 6. Comparison of results for SPE, P&T, and LLE analysis for Alameda County
Water District. Patterned boxes denote that the compound was not reported for that
method.
Alameda If | I i i | \
County | I s | ! | i s ! I i
Water I ^ l£ IE !E i 5 i I i 1 ^ I
District L ll 11 fl ll I L i I- I ?~ ^ I
n., r-,,-,-. i & 2 '& - '£ -- * Q 2? : J &= : c & : .£ *• : O
3/1 &/02 IS £ ?r- il € Q i-- w «? • ij ?•;. • £ t- : O ^"- * W
CONCLUSIONS
There was no one universal method that could be used to analyze all targeted DBFs.
LLE-GC-ECD is the most universal of all the techniques, but it does not provide the definitive
results that a mass spectrometric technique provides. Of the two mass spectrometry techniques
examined (P&T-GC/MS and SPE-GC/MS), P&T-GC/MS excelled at measuring volatiles and
benefited from being a solvent-less technique. SPE, on the other hand, can make use of a variety
of sorbents to target specific families of compounds or to provide general screening results, as
was the case for this study.
The solid phase extraction technique was developed to incorporate as many compounds
as possible. To this end, we achieved our goal. In future work, we hope to improve upon the
technique by taking advantage of many new sorbents that have appeared on the market, which
offer improved extraction efficiencies that should provide lower detection limits. We are also
pursuing an on-line solid phase extraction apparatus that will remove the need for an operator to
extract the cartridges by hand, which should improve reproducibility. A fully automated on-line
SPE system would offer the flexibility to screen many compounds, ranging from volatiles to
semi-volatiles, with full mass spectrometric detection and limited user intervention.
364
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LIQUID-LIQUID EXTRACTION-GAS CHROMATOGRAPHY-
ELECTRON CAPTURE DETECTION METHOD
INTRODUCTION
Different versions of the gas chromatographic (GC) method were used during the course
of this disinfection by-product (DBF) occurrence project since the method was still undergoing
major development during the utility sampling phase. A short description of the final version of
the method will be given, followed by a history highlighting some of the major changes that
occurred during the method development. The method changes improved the scope and quality
of the method over the development period.
METHOD SUMMARY
The basic method used GC with a salted liquid-liquid extraction (LLE) procedure to
quantitate and confirm 47 drinking water DBFs (Figure 1). For this method, two different GC
columns were operated simultaneously (DB-1 and DB-5), which permitted the separation and
quantitation for all of the analytes. The method included two different internal standards used as
reference peaks. Samples were collected in two analytical fractions; however each fraction used
the same sample preparation method. The two analytical fractions were used to accommodate
the use of two different chemical preservatives (ascorbic acid and ammonium chloride). The
method required two separate extractions and two GC injections of each sample to achieve the
quantitation for all 47 DBFs. Sample preparation included collection of a 30 mL volume of
sample, salting with 11 g of sodium sulfate and 1 g of copper sulfate, and extraction with 3 mL
of methyl tertiary-butyl ether (MtBE). A mechanical platform shaker was used for automated
sample extraction. The copper sulfate enhanced analyte recovery and aided in the extract
transfer process. An autosampler injected sample extracts onto a split-splitless GC injection
port, and a two-channel data system simultaneously collected the two chromatograms for each
injection.
365
-------
Add 2 mL MtBE w/internal standard
(1,2-dibromopropane)
Add 1/2 g copper
sulfate
Add 8 g sodium
sulfate
Mechanical Shake for 5 minutes
Let stand for 5 minutes
Transfer ca. 1/2 ml to autosamplervial
Figure 1. Summary of the LLE-GC-ECD method.
Sample Preparation
A 30 mL glass syringe was used to transfer samples into 40 mL glass vials. Daily
procedural calibration standards were prepared with each set of samples using acidified reagent
water. Sample matrix spikes and sample duplicates were prepared with each sample set. The
MtBE extraction solvent contained two different internal standards. Because the MtBE was
prepared with the internal standard, additional steps of adding the internal standard to each
sample extract was eliminated. After 3 mL of MtBE was added, 11 g of dried sodium sulfate and
1 g of copper sulfate were added. The sample was capped and shaken briefly by hand before
placing into a sample holder. After the solvent and salt were added to all of the samples, they
were shaken using a vortex mixer for 11 min. A disposable Pasteur pipette was used to transfer
approximately 2 mL of extract evenly between the two autosampler vials. One vial was stored in
a freezer as a backup extract, and the other vial was was used for analysis.
366
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Gas Chromatography Method
This GC method accomplished the separation and quantitation of 47 drinking water
DBFs. The method involved the simultaneous analysis of one sample injection on two different
analytical columns. The two different columns were attached to one injection port, allowing
each sample to be analyzed by a GC equipped with two electron capture detectors (BCD). The
two channels of data were collected simultaneously and processed sequentially. Unlike previous
GC methods where one column is used as the primary analytical column for quantitation and a
secondary column is used as a confirmation column, this method used both columns as primary
analytical columns, with each column also used for confirmatory analysis. Using two different
analytical columns allowed coeluting peaks to be resolved.
Two sets of samples collected from the each location because two different sample
preservatives were required. Forty-one compounds were preserved and collected using ascorbic
acid (AA). Ammonium chloride (AC) was used to preserve six other compounds (tri-
halonitromethanes) that could not be preserved using ascorbic acid. Both the ammonium
chloride and the ascorbic acid fractions were analyzed using the dual primary column analysis
method. When analyzing the ascorbic acid fraction, one column could separate 25 compounds,
and the other column could separate the other 16 compounds. Some compounds could be
resolved on both columns, while other compounds could be resolved only on one of the columns.
When a compound was separated on both columns, one column was used as the primary
quantitation column, and the other column used for confirmation. Table 1 lists which DBFs
coelute for each column. Ascorbic acid was used as a preservative for all sampling locations.
Later in the study, ammonium chloride was used as a preservative for a smaller subset of those
same sampling locations
When ammonium chloride-preserved samples were analyzed using the dual primary
column analysis, 4 compounds could be resolved on one column, and the other two on the other
column. Both columns were used for confirmation, as described for ascorbic acid-preserved
samples. Ammonium chloride-preserved samples were extracted and analyzed using the same
LLE procedure and GC conditions as for ascorbic acid-preserved samples.
Four separate GC software methods were developed to allow all 47 compounds to be
analyzed. The 47 compounds were analyzed by producing four different chromatograms and
calibrating most of the compounds twice. Data processing was done in pairs for each analytical
fraction to enable cross-checking between columns. This aided in the analyte identification and
detection process.
The primary column "A" was a DB-1 (J & W Scientific/Agilent, Folsom , CA, 30-m,
0.25- mm ID, l-|im film thickness); primary column "B" was a DB-5 (J & W Scientific/Agilent,
Folsom, CA, 30-m, 0.25-mm ID, l-|im film thickness). Both analytical columns were installed
onto a single GC injector (Model 3600, Varian Analytical Instruments, Walnut Creek, CA). The
GC was equipped with two ECDs and an autosampler (Varian Analytical Instruments, Walnut
Creek, CA). The autosampler injected 4.7 jiL of extract onto a Model 1077 split-splitless
injector operated in the splitless mode. The "A" and "B" channel BCD outputs were connected
to a PE Nelson 970 interface (Perkin Elmer Corp., San Jose, CA).
367
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Table 1. Gas chromatographic interferences for disinfection by-product analysis"
1
2
3
4
5
6
7
1
2
3
4
5
6
DB-1 (10 coelutions)
cnm+bca+tca
tcnm+bdcan
1133tecp+13dbp
dban+bdcnm
(ban+i)A
DB-5 (14 coelutions)
can+tcan
Cnm+lldcp
Bnm+bcan
113tcp+tbcm
tba+dbim
bc+tban
1133tecp+cdim
A ban appears to coelute with an interference peak
Shouldered Peaks*
bnm & bean & i
13dcp & i
tbm&i
bcim & lldbp
dbim & i
1 1 Itbp & i
*i=unknown interference
Shouldered Peaks
tea & dean
1 Idbp & dban & bcim
Bdim & i
Compound Abbreviations are Shown in Table 3
The GC operating conditions shown in Table 2 were optimized to enhance sensitivity. A
low injection temperature of 87 °C was used to minimize degradation of thermally labile
compounds. A large injection volume of 4.7 jiL was chosen to increase sensitivity. Column
flow rates and other conditions were adjusted to maximize resolution and detection for each
compound.
368
-------
Table 2. Gas chromatograph operating conditions
GC Temper
Flow rates:
ature Progran
i:
Temperature (°C):
Rate (°C/minute):
Time (minutes):
35
23
Helium carrier gas at 35°C
Head Pressui
-e 14.3
osi
4
139
27
0
301
5
DB-1 Column = 2.3 ml/min
DB-5
Column=_J
Rear Injector Variant model 1077 capillary split/splitless
Split ratio = 12
Injector temperature = 87 °C
Injection mode splitless
Split valve program 0.89 min
(rela\
'=2)
3ml/r
Detector Varian Nickel 63 Electron Capture Detector (BCD)
Two reaular size ECD's (model # 02-001972-00)
Operating Temperature = 297 °C
Make-up gas Nitrogen at 29.3 mL/min
Autozero on
Ranee 10
Vari an model 8200 Autosampler
QthervParan
Injection Volume = 4.7 uL
Solvent plug size= 0. 1 uL
Slow injection rate= 2.3 uL/sec
Upper air eap and lower air eap selected
Viscosity = 4
Resevoir pressure= 27psi
Resevoir solvent= MtBE
leters
Thermal stat
ilize tir
ne=1.07
min
Column standby temperature= 1 1 7 °C
Column A and B installed:
GC= Varian model 3600
lin
A=J&W DB-1. 30 meter. 0.25 mm I.D., 1 micron film thickness
B=J&W DB-5. 30 meter 0.25 mm I.D.. 1 micron film thickness
A central laboratory eas manifold system supplies nitroeen and helium eas
Dual channel data aquisition 1 volt input to model 970 PE Nelson Interface/Buffer
Chromatosraphv Software PE Turbochrome Navieator (ver4.1) 1987-1995
369
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Calibration and Data Processing
Two sets of calibration standards were prepared from five different intermediate stock
solutions (Table 3). The ascorbic acid spiking solutions contained the first 41 compounds (Table 3),
and used 7 different concentration points (over the range of 0.1 - 80 |ig/L) for the calibration curve.
An additional high concentration point was added for THM analyses to enable the concentration
range to extend to 120 |ig/L (ppb). Ammonium chloride spiking solutions contained 6 compounds
(trihalonitromethanes) (Table 3), and used 7 different concentration points (over the range of 0.5 - 20
|ig/L) for the calibration curve. Calibration standards were prepared daily from stock solutions.
Standards and blanks were prepared in pH-adjusted, distilled water (adjusted to 3.5 with concentrated
sulfuric acid). Direct standards (non-extracted standards) were also prepared with each daily batch of
extractions. Individual stock solutions were prepared on an annual basis, intermediate stock
solutions were prepared quarterly, and spiking solutions were prepared bimonthly. All sample
extracts and standard solutions were stored in the freezer at -11 °C.
Method Development Highlights
A short chronology of the major steps in the method development will be discussed. Each
step is included because it has affected the type and quality of the project data. The variations in
methods used over the project period can help to identify differences in the data over the utility
sampling period.
The GC method development started in December 1998 and continued through the end of the
utility sampling phase (April 2002). From February 1999 to August 2000, initial GC-ECD, purge-
and-trap-GC/MS, and solid phase microextraction (SPME)-GC/MS methods were developed. In
October 2000, due to operational problems with the Varian 3500A GC, two other GCs (a Varian
3500B and a Varian 3600) were configured for the dual column-GC-ECD analyses. Between
February and March 2001, adjustments were made to the GC temperature program to achieve better
separations. Higher quality-control spike concentrations of THM standards (50 ppb) were also made
during this time. In March 2001, 9 additional compounds were added to the GC method
(dichloronitromethane, bromochloronitromethane, tribromonitromethane, 1,1-dibromopropanone, 1-
bromo-l,l-dichloropropanone, 1,1,1-tribromopropanone, 1,1,3-tribromopropanone, 1,1,1,3-
tetrachloropropanone, and bromodichloroacetonitrile). Between May and July 2001, the extraction
method was improved to increase the concentration factor and improve analyte recoveries. At this
point, ammonium chloride was also introduced as a second preservation chemical, and the remaining
4 analytes were added to the method (tetrabromochloroethane, dibromochloronitromethane,
bromodichloronitromethane, and chloronitromethane), for a total of 47 analytes. An additional
internal standard (2-bromo-l-chloropropane) was also added to aid in analyte identification.
Table 4 shows the improved recoveries that were accomplished by the adjustments in the
LLE-GC-ECD method. Table 5 shows the method reporting limits (MRLs) for the LLE-GC-ECD
method compared to the SPE-GC/MS and P&T-GC/MS methods. In general the LLE-GC-ECD
method reporting limits were the same or lower than other methods (Table 5).
370
-------
Table 3. Stock standard calibration preparation
btl
A
1
2
3
4
1
2
-•j
J
4
5
6
7
1
B
1
2
3
4
5
6
7
C
1
2
3
4
5
6
D
1
2
3
4
5
6
7
8
9
10
1
1
2
-•j
3
4
5
6
F
1
9
jL
3
4
5
6
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
Compounds
lOOppm THM & mix
chloroform
bromodichloromethane
chlorodibromomethane
bromoforrn
Dichloroacetonitrile
bromochloroacetonitrile
dibromoacetonitrile
tri chl oroacetonitrile
1 , 1 -dichloropropanone
1,1,1 -trichloropropanone
chloropicrin
1 , 1 .2.2-tetrabromo- 1 -chloroethane
lOOppm Halomethane mix
Bromochloroiodomethane
Dichloroiodomethane
Dibromoiodomethane
Chlorodiiodome thane
Bromodiiodomethane
lodoform
Tribromochlorome thane
lOOppm Halo(acetonitrile & me
Bromoacetonitrile
Chloroacetonitrile
Dichloroacetaldehvde
Bromochloroacetaldehyde
Tribromoacetaldehvde
chloral
lOOppm Hatoketone mix
Chloropropanone
1 ,3 -Dichloropropanone
1,1,3 -Trichloropropanone
1 , 1 ,3 ,3 -Tetrachloropropanone
1,1,1.3 -Tetrachl oropropanone
1 -Bromo 1 , 1 dichloropropanone
1 , 1 -Dibromopropanone
1.1,1 -Tribromopropanone
1,1,3 -Tribromopropanone
1 , 1 ,3 ,3 -Tetrabromopropanone
lOOppra Halonitrometfaanes + 1
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Bromochloronitromethane
Dibromonitromethane
Benzyl chloride
30ppm AC Mix
Bromopicrin
Tribromoacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Bromodichloronitromethane
Dibromochloronitromethane
tcm
bdcm
cdbm
tbm
dean
bean
dban
tcan
1,1 -dcp
1,1,1-tcp
tcnm
tebce
bcim
dcim
dbim
cdim
bdim
tim
tbcm
staldehyd
ban
can
dca
bca
tba
tea
CP
1.3 -dcp
1.1. 3 -top
1,1,3,3-tecp
1,1,1,3-tecp
l-bl,ldcp
1,1 -dbp
1,1,1-tbp
1,1,3-tbp
1,1,3,3-tebp
craix
cnm
bnm
dcnm
bcnm
dbnrn
be
tbnm
tban
bdcan
dbcan
bdcnm
dbcnm
Stk
Date
11/28
11/28
9/28
4/6
4/6
4/6
4/6
4/6
4/5
4/6
j) mix
9/28
4/5
4/6
7/17
4/6
9/23
4/10
4/5
4/5
4/6
4/6
4/6
6/29
4/6
6/29
4/6
9/28
4/5
4/5
4/10
4/5
4/5
4/5
4/6
4/6
4/10
4/5
4/5
Stk
PPm
2000
Supelco
4-8140u
MeOH
2000
Supelco
4-8046
acetone
55 Ib
dbp
mix
3700
3400
2100
3500
3900
4800
6900
4200
4400
2000
4600
2400
3200
1000
2100
6500
1900
2000
2200
2700
1800
2600
2200
6400
5300
3100
2900
1950
3600
2300
3300
3700
2400
3500
3800
4400
Chk
Date
6/29
5/16
5/16
5/16
5/17
5/16
5/17
5/16
5/10
5/10
5/14
7/19
5/14
5/14
5/14
5/15
5/15
5/15
5/15
5/15
5/15
5/15
5/15
5/14
5/14
5/14
5/14
5/14
5/14
5/14
5/14
5/10
5/14
5/14
5/14
Puritv
99+
99+
78.7
96.4%
90.2%
99.0%
68.3%
93.8%
99.0%
94.9%
99+%
99+%
99.0%
54.1%
99.0%
99+%
98.0%
99.0%
99.6%
99.0%
92.4%
77.6%
94.0%
97.0%
97.6%
99.0%
99.0%
99.0%
99.0%
97.4%
97.1%
99+%
99.0%
99.0%
94.8%
42.1%
99.0%
99.0%
Adj
cone
2000
ppm
2000
ppm
2912
3300
1900
3500
2650
4500
6900
4000
4400
2000
4600
1298
3200
1000
2050
6500
1900
2400
2050
2100
1700
2500
2150
2000
5300
3100
2900
1900
3500
2300
3300
3700
2300
1500
3800
4400
uL in
ImLACN
50
50
35
32.0
54.0
28.6
38.0
23.0
15.0
26.0
23.0
50.0
24.0
78.0
32.0
100.0
50.0
15.4
54.0
42.0
50.0
50.0
60.0
40.0
48.0
50.0
19.0
34.0
36.0
54.0
30.0
44.0
9.1
8.1
13.1
20.0
8.0
6.9
cone
PPm
100.0
100.0
101.9
105.6
102.6
100.0
100.7
103.5
103.5
104.0
101.2
100.0
110.4
101.3
102.4
100.0
102.5
100.1
102.6
100.8
102.5
105.0
102.0
100.0
103.2
100.0
100.7
105.4
104.4
102.6
105.0
101.2
30.0
30.0
30.1
30.0
30.4
30.4
371
-------
Table 4. Improved extraction method comparison showing increased compound recoveries
A Method
BMethod
% Improved
A Method
B Method
% Improved
A Method
B Method
% Improved
A Method
B Method
tcm
107
74.
45
dcim
257
118
118
JTBA
294
129
128
can
516
272.
90
bcnm
3388
2082
63
than
1653
621
166
cp
137
86.
59
llltcp
2030
632
221
BC
12
6
100
TCAN
2093
1065_
97
13dcp
1159
427
171
_CDIM
101
47
115
DCAN
2022
1171
73
IBM
291
173
68
1133teop
184
73
152
BDCM tea dcnm
1489 ! 2690 418
310J 1674] 176...
380 61 138
dban ! dbcan lldbp
2547 ! 875 ! 3876
1441 ! 249! 2911
77 ! 251 ! 33
mstecp | tbnmi BJDIM
1868 j 2! 265
431 ! 1! 107
333 ! 100 ! 148
BAN
7537
2071.
263
dbnm
2912
1899
53
llltbp
184
71
159
bdcan
4115
1598
158
llldobp
577
169
241
llltbp
1834
1249
47
brim
2502
506
394
11 Step
945
262
261
tini
247
76
225
bean
2793
.52.6.
431
them
102
49
108
1133tebp
96
47
104
dbim
29
14
107
Extract 30 mL sample with 3 mL MtBE + CuSO4+ Na2SO4 - 1 1 min shake
Extract 20 mL sample with 4ml MtBE + Na2SO4 only - 5 min shake
CONCLUSIONS
The GC method produced various levels of data quality, as it was developed throughout
the sampling period. The GC method became more reliable and robust over the development
period. The final method was capable of measuring the 47 DBF analytes in this study.
372
-------
Table 5. Method reporting limit comparison of three analytical methods
No.
A
1
2
3
4
1
2
3
4
5
6
7
1
B
1
2
3
4
5
6
7
C
1
2
3
4
5
6
D
1
2
3
4
5
6
7
8
9
10
E
1
2
3
4
5
6
F
1
2
3
4
5
6
Compounds
IBOppm THM & 551B mix
chloroform
broraodichlorom ethane
chlorodibromom ethane
bromoform
Dichloroacetonitrile
bromochloroacetonitrile
dibromoacetonitrile
trichloroacetonitrile
1,1-dichloropropanone
1,1,1 -trichl oropropan on e
chloropicrin
1 , 1 .2.2-tetrabromo- 1 -chloroethaue
IQOppm Halomethane mix
Bromoc hi oroiodom ethane
Dichloroiodom ethane
Dibromoiodomethane
Chi orodii odorn ethane
Broraodii odom ethane
lodoform
Tribroraochlorom ethane
lOOppm Halo(acetonltrile & acetalds
Bromoacetonitrile
Chloroacetonitrile
Dichloroacetaldehvde
Bromochloroacetaldehyde
Tribromoacetaldehvde
chloral
lOOppm Haloketone mix
Chloropropanoue
1 ,3-Dichloropropanone
1 ,1.3-Trichloropropanone
1 , 1.3.3-Tetrachloropropanone
1,1. 1.3-Tetrachloropropanone
1 -Bromo 1 , 1 dichloropropanone
1 , 1-Dibromopropanone
1,1, 1-Tribromopropanone
1,1,3-Tribromopropanone
1,1,3,3-Tetrabroraopropanone
lOOppm Hatomtromethanes + be mi:
Chloronitroraethane
Bromonitromethane
Dichloronitromethane
Bromoc hloronitrom ethane
Dibromonitrom ethane
Benzyl chloride
SQppm AC Mix
Bromopicrin
Tribromoacetonitrile
Bromodichloroacetonitrile
Dibromochloroacetonitrile
Bromodichloronitromethane
Dibromochloronitrom ethane
symbol
tcm
bdcm
dbcm
tbm
dean
bean
dban
lean
1,1-dcp
1,1,1-tcp
tcnra
tebce
bcim
dcim
dbim
cdim
bdim
tim
tbcm
hyde) mix
ban
can
dca
bca
tba
tea
cp
1,3-dcp
1,1,3-tcp
1,1.3.3-tecp
1.1.1.3-tecp
l-bl,ldcp
1.1-dbp
1,1,1-tbp
1,1,3-tbp
1,1,3,3-tebp
;
cnm
bum
dcnm
bcnm
dbnm
be
tbnm
than
bdcan
dbcan
bdcnm
dbcnm
GC-
mrl
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.5
5.0
0.5
0.5
0.1
0.5
2.0
0.5
0.1
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.1
2.0
0.5
0.5
0.5
0.5
0.5
0.5
;JLE
count
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
SPE
mrl count
0.5 ! 1
0.5 ! 2
2.5 ! 3
5 ! 4
0.5 ! 5
.5 ! 6
0.5 ! 7
1 ! 8
1 ! 9
0.5 i 10
2.5 I 11
1 ! 12
1 ! 13
1 ! 14
2.5 ! 15
5 ! 16
2.5 1 17
0.5 ! 18
5 ! 19
5 ! 20
2.5 I 21
2.5 I 22
5 I 23
5 I 24
1 ! 25
0.5 ! 26
5 ! 27
5 ! 28
5 ! 29
2.5 I 30
0.25 ! 31
2.5 ! 32
0.5 ! 33
0.25 ! 34
W
mrl
0.2
0.2
0.5
0.5
0.2
1.0
0.5
0.5
1.0
0.5
0.5
0.5
0.5
0.5
2.5
0.2
0.5
0.5
0.5
0.5
0.5
feT
count
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
5 T3
373
-------
CLOSED-LOOP STRIPPING ANALYSIS METHOD
Closed-loop stripping analysis (CLSA) has been successfully applied in the past for the
determination of volatile organic compounds (VOCs) of intermediate molecular weight,
including many taste-and-odor species. Typically, the compounds are stripped from 1 L of water
by a recirculating stream of air, and trapped on a carbon filter cartridge. Extraction of the
cartridge to a small, 20 uL volume produces unusually high concentration factors of 50,000:1 -
enough to quantitate low ng/L levels. Although originally scheduled for the U.S. Environmental
Protection Agency (USEPA) disinfection by-product (DBF) study, this technique proved less
than desirable for continued research given the emerging successes of both solid phase extraction
(SPE) and solid phase microextraction (SPME) techniques. It was discontinued during the
Summer of 1999.
EXPERIMENTAL
Instrumentation
The instrument used for this work was a VG TS-250 medium resolution mass
spectrometer (VG Tritech, Manchester, England) equipped with a Digital PDF-11/53 computer
(Digital Equipment Corporation, Maynard, MA). Samples were injected using a CTC A200S
autosampler (Leap Technologies, Chapel Hill, NC). A HP 5890 (Hewlett-Packard, Palo Alto,
CA) gas chromatograph was used for separations and partially controlled by an Optic 2 injector
(AI Cambridge, Cambridge, England).
Chromatography
A DB-1 column was used (30-m, 0.25-mm ID, 1-um film thickness) (J&W
Scientific/Agilent, Folsom, CA). The GC oven temperature program used was based on EPA
Method 551.1 (an initial temperature of 35 °C, which was held for 22 min, followed by an
increase at a rate of 10 °C/min to 145 °C, which was held for 2 min; followed by an increase at a
rate of 20 °C/min to 225 °C, which was held for 15 min).
General Procedure
The procedure for CLSA was taken from Standard Methods for the Examination of
Water and Wastewater (20th ed., 1998). For standards, 900 mL of organic pure water (OPW)
was placed into a 1-L glass stripping bottle. Seventy-two grams of sodium sulfate were added
with rapid mixing until the salt was mostly dissolved. The sample was then spiked with a
cocktail mix, covered, placed into a water bath at room temperature (22 °C), and stripped for 2
hours. The 1.5 mg carbon filter was extracted with dichloromethane, carbon disulfide (CS2), or
methyl tertiary butyl ether (MtBE) and brought to a final volume of 20 uL, if needed. The
infinitesimally small sample was transferred into a special conical-shaped autosampler vial for
storage. After a 2 uL injection to the GC, the remaining extract was covered with a fresh Teflon
cap and stored in the freezer for future reference. A detailed description of the method can be
also found at Krasner et al. (1983).
374
-------
RESULTS AND DISCUSSION
Initial DBF Testing - Extraction Efficiency
Stripping efficiencies can be optimized by adjusting stripping time, temperature, and use
of salt to increase the ionic strength of the water. A preliminary check of DBF compatibility was
done using a mixture of DBFs spiked in organic pure water. The spiking mix (5 uL of the 200
ppm mixture) was added to 900 mL of pure water to give an actual concentration of 1.1 ug/L in
the water. At 100% analyte recovery, this is equivalent to a 50-ppm unextracted standard.
Stripping time was two hours.
Table 1. Extraction efficiency of select DBFs
Compound
chloroacetonitrile
chloropropanone
carbon tetrachloride
bromoacetonitrile
dichloroiodomethane
1 ,3-di chloropropanone
bromochloroiodomethane
1,1,3-trichloropropanone
chlorodiiodomethane
bromodiiodomethane
hexachloropropanone
iodoform
RT (min)
7.3
7.9
8.7
15.2
24.8
27.5
29.6
31.0
33.2
35.7
37.4
38.1
No Salt No Salt
CS2 CS2 DUP
ND ND
ND ND
6% ND
ND ND
14% 15%
ND ND
37% 23%
ND ND
37% 22%
26% 19%
ND ND
8% 6%
72 g Salt 72 g Salt
CS2 CS2 DUP
ND ND
ND ND
ND 9%
ND ND
24% 19%
ND ND
50% 36%
ND ND
49% 40%
60% 40%
ND ND
22% 14%
72 g Salt 72 g Salt
MeCI2 MeCI2 DUP
ND ND
ND ND
3% 15%
ND ND
25% 44%
ND ND
44% 71%
ND ND
57% 76%
47% 61%
ND ND
21% 24%
This preliminary check of the CLSA method pointed out potential problems that would
need to be addressed. First, the results were highly irreproducible for duplicate analyses without
any internal standard. The sample concentrations listed in Table 1 were obtained from raw area
counts of the compound peaks. There can be many variables introduced during the stripping
procedure to cause such a wide variance in results, such as minute air leaks in the stripping
apparatus, differences in the filter flow rates (age of filter, contamination), temperature
differences during stripping, and analyte loss during the final extraction. For some haloketones
and haloacetonitriles (chloropropanone, 1,3-dichloropropanone, 1,1,3-trichloropropanone,
chloroacetonitrile, and bromoacetonitrile), there were no detectable recoveries. For the iodinated
THMs and carbon tetrachloride, results showed that the use of salt improved the stripping
efficiency. Also, dichloromethane was a better solvent compared to carbon disulfide.
375
-------
CHClBrI
10CH
CC14
CHC12I
CHC1I,
CHBrI,
CHI,
10.000
15.000
20.000
25.000
30.000
35.000
40.000
45.000
Figure 1. Two-hour closed-loop stripping analysis of iodinated THMs and carbon
tetrachloride. Elution solvent was dichloromethane.
Figure 1 shows the best case scenario for iodo-THMs and carbon tetrachloride, utilizing
72 grams of sodium sulfate and dichloromethane for extraction. Stripping time was 2 hours.
Traditional DBFs
Initial attempts to apply closed-loop stripping analysis to the new DBFs that are part of
this project failed to yield immediate results for any compounds other than iodinated species and
carbon tetrachloride. The targeted compounds included chloropropanone, 1,3-
dichloropropanone, 1,1,3-trichloropropanone, hexachloropropanone (later found to immediately
hydrolyze in water), bromoacetonitrile, and chloroacetonitrile.
376
-------
DCAN
a)
TCAN
DBAN
1,1,1-TCP
BCAN
U-DCP
b)
-JW
TCAN
DCAN
1,1-DCP
BCAN
AJ
1,1,1-TCP
DBAN
Figure 2. a) Direct injection of 200 ppm of DBF mixture for comparison, b) CLSA extract
of DBF mixture in MtBE.
It was suggested that some of the EPA method 551.1 DBFs should be attempted since
there was some evidence that it should be possible to strip these compounds (Croue and
Reckhow 1989). Therefore, the following standards were obtained and analysed by CLSA:
dichloro-, dibromo-, and trichloroacetonitrile, and 1,1-dichloro-, and 1,1,1-trichloropropanone.
Results from these compounds were more promising. A series of experiments was performed to
evaluate the effect of extraction solvent and stripping time for the compounds. All of the
compounds were spiked both with the DBF mixture and an added 1-chlorooctane internal
standard/surrogate. For consistency and ease of results interpretation, all samples were stripped
on the same apparatus and on the same day. Three solvents were tested, including MtBE,
dichloromethane, and carbon disulfide. A 30-min stripping time was also evaluated as an
alternative to the traditional 1-2 hour time.
The MtBE solvent peak eluted at 4 min and continued until about 5.5 min, with tailing.
Quantitative peaks occurred after 7 min and continued throughout the 50-min run. The
1-chlorooctane internal standard eluted at 34 min and was not shown in Figure 2. All peaks were
identified using their NIST library mass spectra.
Overall, MtBE was best at removing the compounds from the carbon filter, followed by
MeCl2, and then CS2. An additional benefit of using MtBE is that it allows extracts to be run on
a GC equipped with an electron capture detector (ECD), which is not possible for chlorinated
solvents. In addition, it was confirmed that a 1-hour strip was preferred over a 30-min strip time,
377
-------
although there is a point of diminishing returns. Generally, anything over two hours does not
increase analyte recoveries significantly.
The use of higher stripping temperatures improved stripping efficiency. However,
attempts at 40 °C were unsuccessful because of moisture condensation onto the carbon filter.
Despite attempts to heat the entire air system using heater tape to avoid cold spots, the large
volume of humid air moving through the system inevitably spoiled any attempts to produce
successful results. Commercially-designed systems (e.g. Mass Evolution, Inc., Houston, TX)
can use slightly wider glass cartridge holders and heating blocks to allow higher temperature
operation.
CONCLUSIONS
At the start of this work, many of the DBFs that were planned for the Nationwide DBF
Occurrence Study had yet to be received. This work represents only a portion of the compounds
that could have been tested. But, based on these preliminary results, it seems unlikely that CLSA
would have been a good universal screening device for new DBFs (i.e. limited compatibility,
large sampling requirement, poor reproducibility). Table 2 lists the compounds tested and
whether they were amenable to closed-loop stripping analysis.
REFERENCES
Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite.
Environmental Science & Technology 23(11): 1412 (1989).
Krasner, S. W., C. J. Hwang, and M. J. McGuire. Water Science & Technology 15: 127 (1983).
Munch, D. J., and D. P. Hautman. Method 551.1. Determination of
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography
with Electron Capture Detection. Methods for the Determination of Organic Compounds in
Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati, OH: U.S. Environmental
Protection Agency, 1995.
Standard Methods for the Examination of Water and Wastewater, 20th ed.\ American Public
Health Association: Washington, D.C., 1998.
378
-------
Table 2. Summary of compounds tested for closed-loop stripping analysis
Compound
lodomethanes
Dichloroiodomethane
Bromochloriodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
Triiodomethane (iodoform)
Haloacetonitriles
Chloro acetonitrile
Bromo acetonitrile
Dichloro acetonitrile
Bromochloroacetonitrile
Dibromo acetonitrile
Trichloro acetonitrile
Haloketones
Chloropropanone
1 , 1 -Dichloropropanone
1 ,3 -Dichloropropanone
1,1,1 -Trichloropropanone
1 , 1 ,3 -Trichloropropanone
Misc. Compounds
Carbon tetrachloride
CLSA Extraction?
YES
YES
YES
YES
YES
YES
NO
NO
YES
YES
YES
YES
NO
NO
NO
YES
NO
YES
379
-------
PURGE-AND-TRAP GAS CHROMATOGRAPHY/MASS SPECTROMETRY METHOD
The method used for the analysis of volatile organic compounds (VOCs) and volatile and
semi-volatile disinfection by-products was a purge-and-trap (P&T) gas chromatography (GC)/
mass spectrometry (MS) method based on U. S. Environmental Protection Agency (USEPA)
Method 524.2 (Figure 1). The methods development included the addition of several volatile
and semi-volatile DBFs and some changes to the GC conditions (i.e., analytical column and
column temperature program).
EXPERIMENTAL
Instrumentation
The instrument used was a Varian Saturn 2000 mass spectrometer (Varian Analytical
Associates Inc., Walnut Creek, CA) equipped with a 3800 gas chromatograph (GC). A Tekmar
LSC2000 concentrator (Tekmar Co., Cincinnati, OH) and a Varian Archon P&T autosampler
(Varian) were used for automated sampling.
Sample Preparation
Information about the analytical standards used for this P&T method are outlined in
Table 1. Standard mixes were obtained from Ultra Scientific (North Kingstown, RI), which
contained the following compounds at a level of 5000 |ig/mL each in acetone: dichloro-,
bromochloro-, dibromo-, and trichloroacetonitrile, 1,1-dichloro- and 1,1,1-trichloropropanone,
and chloropicrin. The trihalomethane mix (Ultra Scientific) contained chloroform,
bromodichloromethane, dibromochloromethane, and bromoform at a level of 5000 |ig/mL each
in methanol. Each of the VOCs was prepared from separate, individual solutions containing
chloromethane, bromomethane, dibromomethane, bromochloromethane, carbon tetrachloride,
methyl tertiary butyl ether, and methyl ethyl ketone, all of which were obtained from Supelco
(Bellefonte, PA) at either a 2000 or 5000 jig/mL level. An EPA Method 524.2 Fortification
Solution (Supelco) contained the internal standards for this analysis, fluorobenzene (FB), and the
surrogates, 4-bromofluorobenzene (BFB) and !,2-dichlorobenzene-d4(l,2-DCP-d4), at
concentrations of 2000 |ig/mL each in methanol. The other target DBFs were obtained in the
highest purity available from sources listed in Table 1.
Stock Solutions from Neat Compounds
For all of these new, target DBFs that were being investigated in this project, stock
solutions were prepared by either of two different methods. First, those DBFs that were prepared
from pure, neat compound as follows. An accurately measured portion of 1.0 mL of methanol
solvent (Burdick & Jackson, purge and trap grade, Muskegon, MI) was placed into a capped 2.0
mL autosampler vial and weighed. Approximately 2-3 jiL of the neat compound was pulled into
a cleaned syringe and spiked into the solvent after piercing the septum. The additional weight by
difference, between 2-5 mg, was used to calculate the concentration of each compound. The
septum caps were changed before storage. Alternatively, those DBFs that were solid were
prepared by weighing the standard in the autosampler vial and adding solvent.
380
-------
25-mL sample aliquot
V
1-ML
"fortification solution"
Sparge with helium for
11 minutes onto
VOCARB 4000 trap
V
Desorb trap at 240 °C for 4 minutes
V
Transfer to GC injector
V
Analysis by GC/MS
Figure 1. Summary of the Purge and Trap-GC/MS method used for analyzing DBFs in
drinking water.
381
-------
Standard Spiking Solutions
A standard DBF spiking solution was prepared by diluting all of the target compounds to
a final volume of 1 mL of methanol (Burdick & Jackson). Table 2 outlines the concentrations
and volumes of the standard solutions used to prepare the DBF spiking solution. This solution
was used to prepare P&T calibration standards.
Internal Standard and Surrogates
The internal standard and surrogates were prepared as follows. Into a 5-mL volumetric
flask was measured 4.5 mL of methanol. A 62.5 jiL aliquot of the "fortification solution" was
added to the methanol and the volume brought up to 5 mL. This solution was then transferred to
the Archon autosampler standard solution reservoir. The Archon autosampler then adds a 1 |iL
standard addition to the sample water prior to purge-and-trap concentration for a final
concentration of 1 |ig/L.
Calibration Standards and Check Samples
Calibration standards were prepared at the levels of 0.2, 0.5, 1.0, 2.5, 5.0, 10, 20, and 40
|ig/L. An appropriate amount of the DBF spiking solution was added to a 50-mL volumetric
flask containing purified water (Ultra Resi-analyzed, J.T. Baker, Phillipsburg, NJ). This solution
was then transferred to a 40-mL vial containing 2 drops of 1 M H2SO4 to bring the pH down to
3-3.5, then capped with an open-top cap and Teflon-silicon septa. Calibration standards were
prepared every time a set of samples was analyzed, approximately every two weeks.
Check standards were analyzed at the beginning and end of each analytical run. These
check standards were prepared in the same way as calibration standards, but at the 5 or 10 jig/L
level.
382
-------
Table 1. P&T-GC/MS DBF target analyte sources
Compound Class/DBF
Source
Compound Class/DBF
Source
THMMix
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
55IB Mix
Di chl oroacetonitril e
Bromochloroacetonitrile
Dibromoacetonitrile
1,1 -Dichloropropanone
1,1,1 -Trichloropropanone
Chloropicrin
lodomethanes
Dichloroiodomethane
Bromochl oroi odomethane
Dibromoiodomethane
Chl orodii odomethane
Bromodiiodomethane
Haloketones
Chloropropanone
1,3 -Di chl oropropanone
1,1,3 -Trichloropropanone
1,1 -Dibromopropanone
Ultra Scientific3
Ultra Scientific
AGBARb
AGBAR
AGBAR
AGBAR
AGBAR
Aldrichf
Aldrich
Fluka11
UNCC; Helixd
Halonitromethanes
Chloronitromethane
Bromonitromethane
Di chl oronitromethane
Haloacetonitriles
Chloroacetonitrile
Bromoacetonitrile
VOCs
Chloromethane
Bromomethane
Dibromomethane
Bromochl oromethane
Carbon tetrachloride
MTBE
MEK
Miscellaneous
Benzyl chloride
Internal Standard
Fluorobenzene
Surrogates
4-Bromofluorobenzene
,2-Dichlorobenzene-d4
Can Syne; Helix
Aldrich
Can Syn; Helix
Aldrich
Aldrich
Supelcog
Supelco
Supelco
Supelco
Supelco
Supelco
Supelco
Fluka
Supelco
Supelco
Supelco
"Ultra Scientific (North Kingstown, R.I.)
bAGBAR: Aigues of Barcelona (Spain)
°UNC: Synthesized by University of North Carolina at Chapel Hill
dHelix Biotech (New Westminster, B.C., Canada)
eCan Syn: Synthesized by Can Syn Chem Corp. (Toronto, ON, Canada)
fAldrich (St. Louis, Mo.)
8Supelco (Bellefonte, Pa.)
hFluka (St. Louis, Mo.)
TOO
383
-------
Table 2. Standard spiking solution preparation
Compound
THM/551BMix
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
EPA 55 IB Mix
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
1 , 1 -Dichloropropanone
1,1,1 -Trichloropropanone
Chloropicrin
lodomethane Mix
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
Haloacetonitrile Mix
Chloroacetonitrile
Bromoacetonitrile
Haloketone Mix
Chloropropanone
1 ,3 -Dichloropropanone
1,1,3 -Trichloropropanone
1 , 1 -Dibromopropanone
Halonitromethane Mix
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Miscellaneous
Benzyl chloride
Volatiles Mix
Chloromethane
Bromomethane
Dibromomethane
Bromochloromethane
Carbon Tetrachloride
MtBE
MEK
Abbrev.
Name
TCM
BDCM
DBCM
TBM
DCAN
BCAN
DBAN
1,1 -DCP
1,1,1-TCP
TCNM
DCIM
BCIM
DBIM
CDIM
BDIM
CAN
BAN
CP
1,3-DCP
1,1,3-TCP
1,1 -DBF
CNM
BNM
DCNM
BC
CIMe
BrMe
DBM
BCM
CC14
Cone.
(mg/L)
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
3500
5200
3400
4200
4800
3700
5700
2700
4100
3500
3300
2700
5200
5000
3100
2000
2000
2000
2000
5000
2000
2000
Purity
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
93.3%
96.7%
97.2%
86.3%
91.5%
99+%
99+%
98.1%
99+%
97.7%
94.1%
98.8%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
99+%
Adjusted
Cone.
(mg/L)
5000
5000
5000
5000
5000
5000
5000
5000
5000
5000
3250
5050
3300
3600
4400
3700
5700
2650
4100
3400
3100
2650
5200
5000
3100
2000
2000
2000
2000
5000
2000
2000
Actual
Transfer Vol. (uL)
50 mg/L Std
10
10
10
10
10
10
10
10
10
10
17
9.9
15
14
11
13.5
9
19
12
15
16
19
10
10
16
25
25
25
25
10
25
25
Final
Concentration
(50 mg/L Std)
50
50
50
50
50
50
50
50
50
50
55.25
49.995
49.5
50.4
48.4
49.95
51.3
50.35
49.2
51
49.6
50.35
52
50
49.6
50
50
50
50
50
50
50
384
-------
Gas Chromatography
A DB-624 GC column was used (30-m, 0.25-mm ID, 1.4-jim film thickness) (J & W
Scientific/Agilent, Folsom, CA). The 1079 injector was set at 220 °C with a split ratio of 30:1.
The column temperature program used was developed for a wide range of VOCs: an initial oven
temperature of 35 °C, which was held for 4 minutes, followed by an increase at a rate of 4
°C/min to 50 °C, with no time hold, followed by an increase at a rate of 10 °C/min to 175 °C,
which was held for 2 min, then a final increase at a rate of 20 °C/min to 200 °C, which was held
for 1.5 min. The total temperature run time was 25 min. This temperature program was used
until January 2002.
For analyses performed after June 2001, a DB-1 GC column was used (30-m, 0.25-mm
ID, l-|im film thickness) (J & W Scientific/Agilent), and the 1079 injector was set at 220 °C
with a split ratio of 20:1. The same column temperature program that was used with the DB-624
column was used with the DB-1 column. A modified temperature program was used beginning
in January 2002 to match the work that was developed for the LLE-GC/ECD method:
isothermal column temperature at 35 °C held for 23 min, followed by an increase at a rate of 4
°C/min to 139 °C, with no time hold, followed by an increase at a rate of 27.7 °C/min to a final
temperature of 250 °C, which was held for 5 min. Total run time was 58.0 min.
Mass Spectrometry
Electron ionization (El) was used on the Saturn GC/mass spectrometer. Table 3 outlines
the mass spectrometer parameters used for this method.
Purge-and-Trap (P&T) Analysis
The P&T concentration was carried out using the Varian Archon autosampler, which
prepared a 25 mL aliquot of sample for transfer to the Tekmar LSC 2000 concentrator. The 40-
mL sample vials were placed in the Archon autosampler, where a 25-mL aliquot was taken.
Prior to transfer to the LSC 2000, 1 jiL of the "fortification solution" was added. Once the
sample was transferred to the LSC 2000 concentrator, it was sparged for 11 min at room
temperature with helium, at a flow rate of 15 mL/min, onto a VOCARB 4000 trap (Supelco).
The analysis continued with a desorption preheating of the trap to 240 °C and final desorption of
the sample for 4 min. At this point the sample was then "injected" onto the Varian GC attached
to the Saturn mass spectrometer.
Sample Preservation
Samples were collected in nominal 40-mL vials with Teflon-faced silicon septa and
polypropylene open-top screw caps. The sample vials were filled with 1.4 mg of ascorbic acid to
quench any residual oxidant present at the time of sampling. A solution of freshly prepared
sulfuric acid was used to reduce the pH to within the 3-3.5 range to provide stability of the target
analytes and was added prior to capping the sample bottle. This reduction in pH was necessary
in order to eliminate the possibility of base-catalyzed hydrolysis that many of the target analytes
are susceptible to at higher pH. Samples were stored during transit to the laboratory in ice chests
with ice-packs to keep them cold. Upon arrival at the laboratory, the samples were placed in a
10 °C refrigerator for longer-term storage.
385
-------
Table 3. Saturn ion trap mass spectrometer conditions
Segment 1 filament off, no data acquisition
Segment 2 start time
end time
emission current
scan time
low mass
high mass
ionization mode
ion preparation technique
El auto mode:
scan segment 1
scan segment 2
scan segment 3
scan segment 4
maximum ionization time
target TIC
prescan ionization time
background mass
RF dump value
1 AGC - automatic gain control
1.0 min.
50 min.
25|iA
1.00 sec
41 m/z
400 m/z
El AGC 1
none
Mass range
10 to 70
71 to 78
79 to 150
151 to 650
ion. storage
level
35 m/z
35 m/z
35 m/z
3 5 m/z
ion. time
factor
120%
70%
100%
68%
25000 |isec
30000
counts
100 jisec
45 m/z
650 m/z
RESULTS AND DISCUSSION
Detection Limits
Detection limits were determined in two different ways. The first was strictly by
observing the lowest level standard that could be seen and measuring the peak area counts.
Based on a signal-to-noise ratio of 5 or greater, a detection limit was initially used. This
technique resulted in a wide variety of observed levels for each of the target analytes. The
second method used was a statistical evaluation of seven replicates run on two successive days.
This method yielded significantly higher detection limits for the target analytes. The method
detection limit (MDL) was determined for each analyte as follows:
386
-------
MDL = t (S)
t = 2.65 (student t value for 13 degrees of freedom and 99 percent
confidence level)
S = standard deviation of the 14 replicate analyses
These MDLs were used as minimum reporting levels (MRLs), except where the instrumental
detection limit proved to be higher. Often, the MRLs corresponded to the lowest level standard
on the calibration curve. Table 4 shows the DL and MDL for each of the P&T target
compounds. Where NA is reported for a compound, the opportunity to calculate the MDL was
not available, as the compound was added very late in the project for P&T analysis. This table
shows that these compounds are amenable to P&T analysis.
Table 4. Detection limits for purge-and-trap DBF analysis
Compound
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
Dichloroacetonitrile
Bromochloroacetonitrile
Dibromoacetonitrile
1 , 1 -Dichloropropanone
1,1,1 -Trichloropropanone
Chloropicrin
Dichloroiodomethane
Bromochloroiodomethane
Dibromoiodomethane
Chlorodiiodomethane
Bromodiiodomethane
Benzyl chloride
DL
(ng/L)
0.2
0.2
0.2
0.5
0.2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
MDL
(ng/L)
0.684
0.732
0.727
0.716
0.945
NA
NA
0.775
0.755
NA
0.819
0.748
1.28
0.669
0.811
0.624
Compound
Chloromethane
Bromomethane
Dibromomethane
Bromochloromethane
Carbon Tetrachloride
MtBE
Methyl ethyl ketone
Chloropropanone
1 ,3 -Dichloropropanone
1 , 1 ,3 -Trichloropropanone
1 , 1 -Dibromopropanone
Chloronitromethane
Bromonitromethane
Dichloronitromethane
Chloroacetonitrile
Bromoacetonitrile
DL
(ng/L)
0.2
0.2
0.5
0.5
0.2
0.2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.2
2.5
MDL
(ng/L)
0.903
1.02
0.775
0.654
0.906
0.721
0.617
1.19
NA
NA
NA
NA
NA
NA
0.775
1.12
DL = detection limit; MDL = method detection limit
387
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Evaluation of Analytical Columns
A DB-624 column was initially installed on the Saturn GC/MS in the early phase of the
project. This was due to the fact that the instrument was shared with another group analyzing
VOCs for compliance purposes. As the project progressed, it was determined that other
arrangements needed to be made in order to accommodate the addition of analyzing solid phase
extraction (SPE) samples on the same instrument.
The DB-624 column is a medium polarity column and is the column used by the
Metropolitan Water District of Southern California (MWDSC) for EPA Method 524.2 (P&T) for
compliance VOC monitoring. An evaluation of this column compared to the DB-1 was
necessary in order to determine whether it was suitable for the SPE method. It was determined,
and discussed in further detail in the SPE section, that the DB-624 column was unsuitable for the
SPE method.
A total ion chromatogram (TIC) comparison between the DB-624 column and a DB-1
column is shown in Figure 2. Because the DB-1 column showed significantly improved
resolution of the analytes, it was determined that this column would be optimal for P&T
analyses. One of the problems associated with the use of the DB-624 column was the coelution
of some target compounds, such as chloropropanone and bromodichloromethane. This was not a
problem with the DB-1 column.
Other Changes to P&T Method
Other changes to the P&T method included the use of only a selected list of VOCs
combined with the other target DBFs. Initially the P&T method relied on the use of two separate
sets of calibration standards and separate calibration curves. By paring down the VOC list to
only the target VOCs of interest in this study and combining them with the target DBFs had
some major advantages. One advantage was a simpler calibration step in which all of the P&T
method compounds could be analyzed in a single P&T run. This eliminated the need to process
sample data files twice. Also, the elimination of any coelution interferences between those
VOCs that were part of a larger cocktail of analytes and some of the target DBFs. Some of the
target DBFs that exhibited coelution problems were chloropropanone, bromodichloromethane,
1,1,1-trichloropropanone, chlorodiiodomethane, and bromochloroiodomethane. These
compounds were difficult to separate from VOCs that were contained in the original cocktail of
more than 60 VOC compounds. Chloropropanone and bromodichloromethane were resolved
simply by changing to the DB-1 column.
Improved Temperature Program
An updated GC column temperature program was used beginning in January 2002.
Figure 3 shows a TIC for a 10 |ig/L standard analyzed with the updated column temperature
program. This improvement allowed for better separation of the analyte peaks. The temperature
program used was similar to the one used for the LLE and SPE analyses, except that a lower
final temperature of 250 °C was used instead of 301 °C.
388
-------
uu
a
u
o
\ \
MCounts-
'SIT-
o
o
UU
UUu
kCourHs •
3
Q
Figure 2. Comparison TIC between DB-624 and DB-1 columns for purge-and-trap analysis.
A) All target DBFs on DB-1 column; B) VOCs on DB-624 column; C) Target DBFs on DB-624
column.
389
-------
\
a
f*>
Q
\
< o
O Q
Q m
Q.
O
o
CD
Q
O
Q
Jl
D.
O
o_ «2
CD 71 CD
Q o> ft
O
DO
CO
Q
S /
I
10
I
20
!
3O
Figure 3. TIC for a 10 ug/L Purge-and-trap DBP/VOC standard on DB-1 column with extended column temperature
program.
390
-------
Holding Study
Sample stability data was used from previous work done using SPE or LLE
methods, and was not repeated for the P&T analysis. The P&T analysis used the same
sample bottles and preservation scheme as the SPE and LLE methods (ascorbic acid
preserved) samples. To summarize these results by compound family:
VOCs - Stable through Day 21.
THMs - Stable through Day 21.
lodo-THMs - Stable through Day 21.
Haloacetonitriles - Stable through Day 21
Chloropropanones - Stable through Day 21.
Halonitromethanes - Stable through Day 21.
Miscellaneous - Benzyl chloride showed a slow decay.
Samples were generally analyzed within 2-3 days after receipt at MWDSC. This allowed
for time to reanalyze samples if necessary and to allow for the instrument to be used for
the SPE analyses later.
Improvements on the Saturn Ion-trap
One of the improvements made for the analysis of the P&T analytes was the use
of multiple quantitation ions to increase the sensitivity. In previous analyses, a single ion
was used to quantitate analyte peaks. The result of this change was an increase in
selectivity for the target analytes.
CONCLUSIONS
EPA Method 524.2 was used as the basis for these analytes, but it was modified in
such a way that an expanded list of compounds could be analyzed. The only real changes
were the analytical column used and the column temperature program. The P&T
concentrator parameters and the internal standard/surrogates remained the same. This
P&T method was capable of analyzing for 32 DBFs as part of the Nationwide DBF
Occurrence Study. Of those 32 compounds included in this method, 11 were originally
analyzed as VOC compounds. The remaining 21 compounds represent additional
compounds not normally associated with a P&T type of analysis. This P&T method
allowed for confirmation of results obtained from SPE and LLE methods, as well as the
solid phase microextraction method developed later.
391
-------
REFERENCES
Munch, D. J., and D. P. Hautman. Method 551.1. Determination of
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas
Chromatography with Electron Capture Detection. Methods for the Determination of
Organic Compounds in Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati,
OH: U.S. Environmental Protection Agency, 1995.
392
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METHOD FOR HALOGENATED FURANONES (MX-ANALOGUES)
METHOD SUMMARY
For the Nationwide DBF Occurrence Study, a method was developed for the
analysis of the following halogenated furanones: MX, MCA, BMX-1, BMX-2, and their
open forms (see full names in Glossary; structures in Figure 1). This method evolved from
the previous methods of Holmbom et al. (1981), Hemming et al. (1986), and Kronberg et al.
(1988, 1991) which required large volumes of water for concentration onto XAD resins and
lengthy processing times that endanger the stability of the MX-analogues. Because of their
complexity, these methods do not incorporate adequate quality assurance (QA)/quality
control (QC) components to validate their resulting data. In order to accurately assess the
concentrations of MX-analogues in drinking water, a liquid-liquid extraction (LLE)-gas
chromatography (GC)-electron capture detection (BCD) method was developed, which uses
smaller sample volumes and shorter processing times to protect compound stability.
For the new method, the chlorine quenching agent, ammonium sulfate [100 |jL of 40
mg/mL (NFL^SOJ was added to acid-washed amber glass sample bottles (250 mL) fitted
with Teflon-lined screw caps prior to sending the bottles to the water treatment plants for
duplicate sample collection. Field blanks filled with DIW were included. Sample bottles
were returned to UNC in a cooler with ice packs, shipped by overnight delivery.
Immediately upon arrival, or within 5 hours, the samples were removed from the cooler, and
analyzed for MX and MCA after they had reached room temperature (the BMX analysis
was performed one week following receipt of samples). The calibration samples were
prepared on the day of extraction, at 0, 50, and 250 ng/L MX and MCA (or 0, 100, and 500
ng/L BMX-1,2,3) in DIW in 250 mL volumetric flasks. One sample from each plant was
collected in a 1 L amber bottle to allow for a matrix spike sample (250 ng/L MX and MCA
or 500 ng/L BMX-1,2,3).
Prior to extraction, each 250-mL sample was spiked with MBA as a surrogate
standard at 250 ng/L, and acidified to pH 2 with sulfuric acid. Each sample was extracted
twice with 50 mL of MtBE in a 500 mL glass separately funnel. The combined extract was
collected in a 125 mL amber bottle (fitted with a Teflon-lined screw cap) containing two
approximately 8 g of calcium chloride (CaCb), and shaken to remove residual water
dissolved in the MtBE. The extract was transferred (without CaCl2) to a 250 mL round
bottomed flask and reduced to a few mLs by rotary evaporation at 40°C. The reduced
extract was transferred to a 20 mL centrifuge tube, with a few mL rinse of MtBE. This
extract was further reduced to about 500 \\L by nitrogen (N2) gas. To this reduced MtBE
extract was added 2 mL of 14% BF3/MeOH, and the tube was sealed with a Teflon-lined
screw cap. The solution was mixed and heated at 70°C for 4 hours in an oven. After
returning to room temperature, the derivatization agent and pH were neutralized by adding 4
mL of 10% NaHCO3, with mixing.
•3 r\o
393
-------
Cl
MX
Cl
Cl
Cl
HO
MCA (mucochloric acid)
Cl
Cl
Cl
H O
open form MCA
Cl
Cl
O
OH
H Cl
EMX
Cl
O
OH
OH Cl
ox-EMX
Br
Figure 1. Structures of halogenated furanones (MX-analogues).
394
-------
The MXR-analogues were back-extracted twice into 1 mL hexane. The combined 2
mL hexane extract was collected in a 10 mL centrifuge tube and reduced to <250 |jL by N2
gas. The internal standard hexachlorobenzene (HCB) was added (5 |jL of 500 ng/mL
HCB/hexane) to the hexane extract, which was brought to a final volume of 250 |jL. The
final hexane extract was transferred to an amber crimp-topped vial with a 300 |jL glass
insert for GC-ECD analysis. The MX and MCA samples were separated by gas
chromatography on a HP-5MS column (30-m x 0.25 mm ID x 0.25 |j,m film thickness) at a
temperature program of 105°C for 1 min, 2.5°C/min to 140°C, and 20°C/min to 280°C, with
an injection temperature of 200°C and a detector temperature of 300°C. The BMX samples
were separated by gas chromatography on a Phenomenex ZB5 column (60-m x 0.25 mm ID
x 0.25 |j,m film thickness) at a temperature program of 100°C for 1 min, 20°C/min to 150°C,
PC/min to 185°C, and 20°C/min to 280°C, with an injection temperature of 160°C and a
detector temperature of 300°C. Calibration curves for each component were constructed
using analyte area relative to the internal standard (HCB). Calculated concentrations of
analytes were corrected by percent recovery in the matrix spike sample. Relative areas of
the analytes to the surrogate standard (MBA) were not reliable for duplicate calibration
samples.
Because method development continued during the first year of plant surveys, no
halogenated furanone data is presented during the first two seasons. The plant data and
discussion is included among the results for each utility elsewhere in this report. The
minimum reportable limit for MX-analogues was 40 ng/L. Non-zero concentrations below
40 ng/L are given in parentheses, to indicate relative values extrapolated from the
calibration curves.
INTRODUCTION
The detection of the disinfection by-product (DBF) 3-chloro-4-(dichloromethyl)-5-
hydroxy-2(5H)-furanone (MX) in chlorinated drinking water in Finland in the early 1980's
caused great concern in the scientific and public health communities because MX was found
to account for 20-60% of the mutagenicity in chlorinated drinking water. Later research
showed that MX was also carcinogenic to rats (at a dose of 400 |j,g MX per kg body mass
per day) (Komulainen et al., 1997). Other compounds similar to MX (referred to as MX-
analogues), including ZMX, EMX, red-MX, ox-MX, mucochloric acid (MCA), and
brominated forms of MX--BMX-1, BMX-2, BMX-3 (Figure 1) have also been identified in
drinking water.
Following the initial identification of MX in Finland (Kronberg and Vartiainen,
1988), MX and MX-analogues were also detected in drinking waters from the United States,
the United Kingdom, Australia, Canada, Spain, China and Japan, in levels ranging from 0.1
to 90 ng/L (Andrews et al., 1990; Horth, 1990; Huixian et al., 1995; Meier et al., 1987;
Simpson and Hayes, 1993; Simpson and Hayes, 1998; Smeds et al., 1995; Suzuki and
Nakanishi, 1990; Wright et al., 2002). MX has been detected primarily in waters treated
with chlorine, less so with the use of chlorine dioxide or chloramines, and very minimally in
ozonated waters with post-chlorination (Holmbom and Kronberg, 1988).
395
-------
The structural components responsible for the mutagenicity of MX are the
and Cl substituents in a cis arrangement on a carbon-carbon double bond (Figure 1). The
mutagenity of these substituents is enhanced by incorporation into the 5-hydroxy-2(5H)-
furanone ring system or an open structure that can readily transform to this ring system
under the conditions of mutagenic testing (Ishiguro et al., 1987). Therefore, when
comparing the relative mutagenicities of the MX-analogues (Figure 1), EMX, ox-EMX and
MCA are less mutagenic than the other MX-analogues. The mutagenicity of halogenated
furanones is also enhanced by the presence of the C-5 hydroxyl group (Kronberg and
Franzen, 1993), making red-MX less mutagenic than MX (LaLonde et al., 1991). Bromine
substitution with chlorine substituents can increase the toxicity of the compound, as found
for THMs and the BMX-analogues (Bull, 1993; Ramos et al., 2000). The bromine
substituents originate from natural bromide ions found in many coastal ground and surface
waters.
While mutagenicity in Salmonella cannot be used to determine carcinogenicity in
humans, MX is still considered a potential human carcinogen. Because MX and other
analogues are highly mutagenic and there is very little occurrence data for them (particularly
for the brominated-MX analogues), they received a high priority for inclusion in this
Nationwide DBF Occurrence Study
ANALYTICAL METHOD DEVELOPMENT
Previous Methods
Method development for the detection of MX in drinking water began in the 1980's,
at first catalyzed by Holmbom's identification of MX in kraft chlorination effluent
(Holmbom et al., 1981). Soon after, Hemming et al. (1986) and Kronberg et al. (1988)
detected MX in chlorinated drinking waters. The methods of Hemming et al. (1986) and
Kronberg et al. (1988) became the key methods that were used to detect MX thereafter.
The stability of MX is very sensitive to the pH of an aqueous solution. The ring
form is predominant at low pH, but as the pH rises, the ring opens to ZMX, which
tautomerizes to EMX, and at higher pH levels (above pH 8), degrades to smaller products
(Kronberg and Christman, 1989, Figure 2). Hemming et al. (1986) and Kronberg et al.
(1988) adjusted the pH to stabilize the ring form. The extraction method consisted of
acidification of a large volume sample (10 L), concentration on a mixture of XAD resins,
elution with ethyl acetate, and solvent reduction to dryness by rotary evaporation and
nitrogen gas. Methylation of the hydroxyl group on the MX ring structure was achieved by
heating with sulfuric acid in methanol (Figure 3).
396
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Cl HO
Degradation
pH>8
Figure 2. MX degrades as pH increases.
HO
Cl
MX
MXR
Cl HO
Cl OCH3
Figure 3. Methylation of MX-analogues with sulfuric acid in methanol.
397
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Methylation converts the alcohol group on the MX ring to a methyl ether group, but
the carboxylic acid groups of the open forms of MX (ZMX and EMX) are changed to esters,
and the aldehyde groups to dimethyl acetal groups (Figure 3). Thus, to simplify naming the
methylation products, they are all referred to as "esters," i.e. MX becomes MXR. The
esterified MX (MXR) was recovered by neutralization with sodium bicarbonate aqueous
solution, and back-extraction into hexane. The reduced hexane extract (100 |j,L) was
analyzed by capillary gas chromatographic (GC) separation and high resolution mass
spectrometric detection (HRMS), with a detection limit of 2 ng/L MX. In some cases,
researchers used high performance liquid chromatography (HPLC) prior to methylation to
remove natural organic carbon contaminants (Kronberg et al., 1985a; Meier et al., 1987).
The HPLC separation involved first concentrating XAD extracts of drinking water to
dryness by rotary evaporation, followed by soxhlet extraction with diethyl ether (Et2O),
extraction with 2% sodium bicarbonate to remove strong acids, acidification of the aqueous
phase to pH 2 with HC1, re-extraction with EtaO, transfer to 30% methanol/water, separation
into 2 mL fractions by a CIS semi-prep column using a 30-100% methanol/water gradient,
followed by a 100% hold for 10 min, methylation of the weak acid fractions, and detection
of MXR-analogues by GC/MS (Meier et al., 1987). Other researchers applied a silica
column clean-up step to the final hexane extract (Suzuki and Nakanishi, 1995), or multiple
reaction monitoring during mass spectrometric detection (Simpson and Hayes, 1993) to
isolate the MX-analogues from interfering co-contaminants such as natural organic matter
(NOM).
Identification of MX-analogues. The structure of MX was first determined by
HRMS, UV and IR spectroscopy (Holmbom et al., 1981). Padmapriya et al. (1985) reported
the IR, UV, and *H NMR spectra for MX and MXR, and the 13C NMR spectrum for MX.
No identification spectra have been previously published for ZMX. Kronberg et al. (1988)
identified EMX by its *H NMR and mass spectra, and EMXR by its mass spectrum.
Kronberg et al. (1991) identified ox-EMX, ox-EMXR, ox-MXR and red-MX by their mass
spectra. LaLonde et al. (1990) identified red-MX by its IR, *H NMR, and 13C NMR spectra,
and MCA by its *H NMR spectrum. Nawrocki et al. (2000) identified MCR by its mass
spectrum. Lloveras et al. (2000) identified BMX-1, BMX-2, and BMX-3 by their *H NMR,
13C NMR and mass spectra. Peters (1991) identified BMXR-1, BMXR-2, and BMXR-3 by
their mass spectra.
Derivatization Efficiency. Kronberg et al. (1988) achieve derivatization of MX by
addition of 2% sulfuric acid in methanol (H2SO4/MeOH, Figure 3), heated at 70°C for 1
hour. While the efficiency of this reaction has not been reported for the derivatization of
MX, some researchers have compared the use of ^SO/t/MeOH to other derivatization
agents. Diazomethane (CH2N2) does not successfully methylate MX and its analogues
(Kronberg et al., 1991). Although H2SO4/MeOH can adequately methylate MX, it cannot
methylate the diacidic MX-analogues (ox-MX and ox-EMX). A 14% boron trifluoride
methanol complex (BF3/MeOH) solution, heated at 70°C for 12 hours, was successfully
applied to ox-MX and ox-EMX (Kanniganti et al., 1992). Meier et al. (1987) claimed that
the derivatization yield of EMX is related to the derivatization time (using Amberlite IR 120
sulfonated polystyrene cation exchange resin in methanol, in a sealed tube, at 70°C for 16-
18 hours). Huixian et al. (1995) compared the MXR yield from derivatization with
398
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saturated BF3/MeOH to the method with 2% H2SO4/MeOH, and found that saturated
BF3/MeOH was the more efficient derivatization agent regardless of reaction time (1-8
hours at 95°C in water bath). Overall, BFs/MeOH has shown to be the best derivatization
agent, with reaction time significantly affecting the product yield.
Extraction Efficiency. Holmbom et al. (1984) evaluated a number of organic
solvents and solid phases to extract MX from aqueous solutions; mutagenicity was
measured as an indicator of MX recovery. Ethyl acetate (EtAc) completely extracted the
mutagenicity (70-90%), while dichloromethane (50-70%) and pentane (<10%) recovered
less of the mutagenicity. Rotary evaporation of EtAc extracts did not degrade the
mutagenicity (even after 10 min at 40°C and 1.5 kPa). Adsorption of MX onto XAD-4 resin
recovered similar amounts of mutagenicity as EtAc. Although MX can ionize in aqueous
solution, anion-exchange solid phase materials are not appropriate for isolating MX from
chlorinated aqueous samples. MX behaved as a neutral compound when applied to the
anion exchange DEAE-Sepharose column due to the MX ring structure.
Acidification prior to resin adsorption (XAD-2/8 resin adsorption/acetone elution)
was essential for adequate recovery of MX in the protonated form (Figure 2) from spiked
water samples and to maintain the stability of MX at low pH (Meier et al., 1987). MX was
measured in terms of mutagenicity assays. XAD-2/8 recovery of mutagenicity from
acidified (pH 2), chlorinated MX-spiked drinking water samples was only 55% effective.
Subsequent extraction and FtPLC isolation recovered only 18% of the remaining MX,
resulting in an overall 10% MX recovery through XAD-2/8 adsorption, EtaO extraction,
HPLC separation, and derivatization procedures. These percent recoveries were not taken
into account when reporting MX concentrations, and no apparent method calibration
solutions were analyzed to monitor recoveries at different MX concentrations. MX
concentrations were determined relative to a derivatized MX standard by high resolution
GC/MS analysis. Recoveries of MX from water samples buffered at higher pH levels (pH
8) were 0-1%; the high pH favors MX in the ionized form and does not promote extraction
from aqueous solution. Poor extraction recovery of MX from drinking water onto XAD
resins was also attributed to complexation with chlorinated humic materials. When
evaluated separately, the methyl-methacrylate polymer XAD-8 recovered more MX than the
styrene-divinyl benzene copolymer XAD-2 (92 vs. 22 % MX recovery) from a fortified
deionized water sample (20 L, 50 ng/L MX) at pH 2; MX recovery was measured by
mutagenicity (Schenck et al., 1990). MX recovery was also significantly enhanced by
reducing XAD-8 adsorption time; a total sample collection time of 25 hours recovered 92 %
MX, whereas 56 hours recovered only 38 % MX (see stability section).
The octanol-water partition coefficient, Kow, is indicative of how much of an analyte
is likely to partition out of water into a highly polar organic solvent. MX is fairly
hydrophilic with a Kow of 11.9 (mg/L octanol / mg/L water) at pH 2 (Holmbom et al., 1984).
The Kow value should be lower in neutral pH surface and drinking waters, and therefore MX
is less susceptible to bioaccumulation in these waters. The Kow of MX open (ZMX or
EMX) in the neutral acid form was computed to be 1.16, using CLOGP, ver3.5 (Biobyte
Inc., Pomona, CA) (DeMarini et al., 2000). The variability of these Kow values is likely due
to the difference between the ring and open forms of MX, and the pH considered.
399
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Kronberg et al. (1991) used mucobromic acid (MBA, Figure 4) as an internal
standard to assess recovery of MX-analogues through the derivatization process, by spiking
MBA into the EtAc extract prior to derivatization (derivatization standard). However, MBA
was determined to be an inappropriate surrogate standard (by spiking MBA into the original
water sample prior to acidification and XAD adsorption) for the XAD/HPLC MX method
(Simpson and Hayes, 1993), because MBA is more susceptible than MX to intermolecular
hydrogen bonding with natural organics. The levels of MX recorded were corrected for
recovery losses, based on separate MX method recovery experiments (average 10%
recovery, consistent with Meier et al. 1987). Higher levels of total organic carbon (TOC) in
drinking water have been associated with lower recovery of MX (Meier et al. 1987). The
high Kow (11.9 mg/mg) for MX, may indicate the likelihood that MX would strongly
associate with NOM as a highly polar solvent, and not be easily extracted by XAD. The
major loss of MX was seen in the HPLC fractionation steps (average 60% recovery in this
step, Simpson and Hayes, 1993), but these steps are only necessary in high TOC waters.
Multiple reaction monitoring (MRM) by mass spectrometry was investigated as an
alternative method to HPLC for removal background natural organic interferences, and it
showed some promise (Simpson and Hayes, 1993). MRM eliminates interference from co-
extracting compounds by monitoring compound-specific metastable transitions between
selected parent and daughter ions of the target analyte.
Br Br Br
HCT ^0 H O
MBA ring MBA open
Figure 4. Mucobromic acid (MBA) isomers.
Stability of MX-Analogues. MX hydrolysis, isomerization, and decomposition
processes in aqueous solution are strongly dependent on pH (Holmbom et al., 1989). MX is
stable at pH 2 but starts to degrade at pH 4 and above. Beyond pH 6.5, the water solubility
of MX increases rapidly, due to ring opening and dissociation (tautomerization), as
determined by extraction of aqueous MX solutions with ethyl acetate at different pH values
(Holmbom et al., 1984). The degradation of MX at pH 5-7 correlates with the formation of
EMX (Simpson and Hayes, 1993). However, EMX also degrades over time at neutral or
alkaline pH (Holmbom and Kronberg, 1988). When acidified to pH 2, EMX completely
converts to MX. The BMX-analogues also show tautomerization, degrading over time (48
hours) from the ring forms to the open forms and finally to degradation products, as
measured in a pH 7.4 phosphate-buffered aqueous solution by HPLC/UV (Ramos et al.,
2000), similar to MX in Figure 2.
400
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Meier et al. (1987) measured the mutagenic activity of MX spiked distilled water
samples at 4°C. It was constant at pH 2, 4, and 8 over 14 days, but declined to 30% at pH 6
after 14 days. At 23°C, the order of stability was pH 2 > pH 4 > pH 8 > pH 6, where pH 2
was constant. The loss of activity in pH 4-8 followed first-order decay kinetics. ZMX
occurred in MX solutions buffered at pH 6, but less at pH 8 (stored for 7 days at 23°C). The
pKa value of MX was determined to be 5.3 by NMR spectroscopy (Streicher, 1987).
However, the pKa of MX open (ZMX or EMX) was computed to be 1.85, using the SPARC
method (DeMarini et al., 2000). The variability of these two pKa values is likely due to the
difference between the ring and open forms of MX.
Meier et al (1987) determined the half-lives of MX in distilled water at 23°C to be
12.9 days at pH 4, 4.6 days at pH 8, and 2.3 days at pH 6, by measuring loss in
mutagenicity. When MX was spiked into tap water samples buffered at pH 6 and 8, stored
at 23°C, the same losses in mutagenicity were seen as those in distilled water. This work
was confirmed by measuring MX concentration at pH 2-9 in MX spiked Milli-Q water by
HPLC/UV analysis (Simpson and Hayes, 1993). Simpson and Hayes (1993) recovered 95%
of the original MX in pH 2 Milli-Q water stored at 20°C after 14 days. At the same
temperature, the half-life of MX at pH 8(11.3 days) was much longer than that for pH 6
(5.4 days). However, at 23 °C, the half-life of MX at pH 8 was 4.6 days. This agrees with
rates of hydrolysis at pH 7.0 measured by Croue and Reckhow (1989) at 20°C, k = 0.9±0.5 x
10'6 s'1 (-0.07 days'1) and tm~ 8.9 days.
MX has been shown to degrade in the presence of increasing concentrations of
chlorine (10-100 mg/L C12), buffered at pH 8 (Schenck et al., 1990; Simpson and Hayes,
1993). The second order rate constant for MX degradation by chlorine was estimated to be
32.3 L mol"1 min"1, based on the reaction rate over the first 10 min and initial concentrations
of 20 mg/L MX and 40-120 mg/L C12 (Schenck et al., 1990). MX degradation was also
observed at lower residual chlorine concentrations (0.5-3 mg/L Cb) that might be practical
levels found in drinking water treatment plant effluents. Chlorine and MX reacted at about
a 5:1 molar ratio, and the reaction was complete within 1 day (Schenck et al., 1990). MX
can be converted to EMX, ox-MX and ox-EMX in the presence of chlorine (Simpson and
Hayes, 1993). However, in the presence of chloramine (10-100 mg/L NH^Cl), MX converts
to only EMX, due to the fact that chloramine is not as strong of an oxidizing agent as
chlorine. EMX, ox-MX and ox-EMX were qualitatively identified as disinfection by-
products, but their levels were not quantified in these studies.
Due to the MX degradation by chlorine, some researchers tried to quench the
residual chlorine prior to MX analysis. Simpson and Hayes (1993) identified Z-ascorbic
acid (Figure 5, note similar furanone structure to MX) as the best quenching agent for MX,
because nucleophiles in other quenching agents (e.g., sodium thiosulfate or sodium sulfite)
destroy MX by removing chlorine atoms (Croue and Reckhow, 1989). The rates of
decomposition of MX significantly increase in the presence of sulfite (100 (jM) at 20°C, k =
22±3 x 10"6 s"1 and ti/2~ 8.7 hours (Croue and Reckhow, 1989). Suzuki and Nakanishi
(1990) suggest that quenching residual chlorine is unnecessary; after acidification, their
samples were purged with nitrogen gas and the residual chlorine was reduced to 0.2 mg/L;
401
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no difference in MX concentration was observed between purged and non-purged samples.
However, considering the MX degradation by chlorine observed by Schenck et al. (1990),
quenching of residual chlorine is necessary for a 0.3 mg/L chlorine residual and above.
HO OH
OH
Figure 5. Structure of ascorbic acid (Vitamin C).
Summary of Current Methods for Analysis of MX-Analogues in Drinking Water
MX, ZMX, EMX, and MCA. The method of Kronberg et al. (1991) for extraction of
MX, ZMX, EMX, and MCA from aqueous solutions involves first acidifying the solution to
pH 2, passing the solution through a mixture of XAD-4 and XAD-8 resins (1:1), and eluting
the adsorbed compounds with ethyl acetate (EtAc). However, liquid-liquid extraction has
met with some success. By extracting 250 mL of a solution with successive 40, 20, and 20
mL volumes of diethyl ether, 77% of MX was recovered (Kanniganti et al., 1992). MBA
was added to the EtAc extract as the derivatization standard. The EtAc extract was blown
down to dryness, derivatized with 250 |iL of 2% H2SO4/MeOH at 70°C for 1 hour,
neutralized with 2% NaHCOs/deionized water (DIW), and extracted twice with 250 jiL of
hexane. The hexane extract was then concentrated down to 100 jiL and decafluorobiphenyl
was added as an internal standard. The extract was analyzed by gas chromatography on a
DB-1 column (30m), with a temperature program of 110°C for 3 min, 6°C/min to 165°C, and
the resolved compounds detected by HRMS, single ion monitoring mode (Kronberg et al.,
1991). The extract can also be separated on a DB-5 column (30-m x 0.25 mm ID x 0.25 |j,m
film thickness), using the temperature program 50°C for 1 min, 2.5°C/min to 150°C, 5°C/min
to 300°C (Kanniganti et al., 1992).
red-MX. The method of Kronberg et al. (1991) for extraction of red-MX from
aqueous solutions involves first acidifying the solution to pH 2, passing the solution through
a mixture of XAD-4 and XAD-8 resins (1:1), and eluting the adsorbed compounds with
ethyl acetate. Since the EtAc extract did not require derivatization, 2,3-dibromo-2(5H)-
furanone (red-MBA) was added as an internal standard, and the extract was reduced to 100
jiL with nitrogen gas. The EtAc extract was separated by gas chromatography on a DB-1
column (30 m), with a temperature program of 110°C for 3 min, 6°C/min to 165°C. Red-
MX is detected by HRMS based on retention time and most abundant ions: m/z 165 and 167
for (M-C1)+, 171 and 173 for (M-CHO)+.
ox-MX and ox-EMX. The method of Kronberg et al. (1991) for extraction of ox-
MX and ox-EMX from aqueous solution involves first acidifying the solution to pH 2,
passing the solution through a mixture of XAD-4 and XAD-8 resins (1:1), and eluting the
402
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adsorbed compounds with ethyl acetate. MBA was added to the EtAc extract as the
derivatization standard. The EtAc extract was blown down to dryness, derivatized with 250
|iL of 12% BF3/MeOH at 100°C for 12 hours, neutralized with 2% NaHCO3/DIW, and
extracted twice with 250 jiL of hexane. The hexane extract was then concentrated down to
100 jiL and decafluorobiphenyl added as an internal standard. The extract was analyzed by
gas chromatography on a DB-5 column (60 m), with a temperature program of 160°C for 3
min, 6°C/min to 190°C. Ox-EMX elutes immediately prior to ox-MX using GC/MS
(HP5890 GC/VG 70-250 SEQ mass spectrometer, resolving power 1000). The LLE method
using diethyl ether has also been applied successfully to these compounds (Kanniganti et al.,
1992).
BMX-Analogues. The method for analysis of BMX-1, BMX-2, and BMX-3 is very
similar to that of MX (Suzuki and Nakanishi, 1995). The BMX-analogues were measured
in Japanese drinking waters by acidifying 10 L samples to pH 2, passing them through 50
mL XAD-8 resins, eluting with 150 mL EtAc, and concentrating down to 5 mL by rotary
evaporation at 40°C. Three mL of this extract was spiked with 100 ng MBA as the
derivatization standard, and evaporated to dryness with nitrogen (N2) gas. The residue was
methylated with 250 |iL of 2% H2SO4/MeOH for 1 hour at 70°C, neutralized by 500 |iL of
2% NaHCOs/DIW, and extracted twice with 500 |jL hexane. The hexane extract was then
passed through a 500 mg Sep-Pak silica column, eluted with 1 mL hexane and 5 mL ethyl
acetate:hexane (1:7), and only the last 4 mL fraction was collected and concentrated to 100
|jL with N2. Separation was achieved using a 30-m x 0.25 mm ID DB-5MS GC column,
injection temperature 160°C, temperature program 50°C for 2 min, 50-120°C at 40°C/min,
120°C for 2 min, 120-135°C at 2°C/min, 135-180°C at 6°C/min, 180°C for 5 min. The
components were detected by HRMS using a VG Autospec-Ultima mass spectrometer.
Spike recoveries ranged from 71 to 122%.
The BMX compounds are susceptible to thermal degradation in the injection port of
a GC. An injection temperature of 160°C produced a larger BMX-3 signal (HRMS) than
200°C, in a calibration range of 0-1000 pg/|J,L. Calibration solutions were made from
standards of the esterified BMX compounds. Detection limits were also dependent on
compound stability in the GC injection port. The detection limit for MX was 0.1 ng/L,
whereas BMX-3 was 0.5 ng/L, using a 60,000:1 concentration factor. BMX-1 and BMX-2
showed intermediate thermal degradation (and intermediate detection limits) to MX and
BMX-3.
Opportunities for Improvement of Existing Methods. A unified method needs to be
developed for the analysis of all MX-analogues in drinking water in a single extract, which
accounts for sample preservation and recovery of MX-analogues through each processing
step. Routine analysis by GC-ECD instead of high resolution GC/MS would make the
method more amenable for environmental and water treatment laboratories in the United
States. Evaluation of quenching agents for residual chlorine and biocides to prevent
microbial regrowth would improve sample preservation and prevent degradation of MX-
analogues. Evaluating percent recoveries from each processing step based on detection of
individual halogenated furanones, rather than by mutagenicity, would also prove more
403
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valuable in the development of an analytical method for the detection of MX-analogues in
drinking water.
New Method Development
Identification and Quantification of Standards. Development of a method for the
analysis of MX-analogues (Figure 1) in drinking water began by first identifying and
quantifying the compounds in synthesized and commercially available standards. The only
commercially available MX-analogues were MX, mucochloric acid (MCA), and
mucobromic acid (MBA, surrogate standard), from Sigma-Aldrich (St. Louis, MO). The
other components were provided in small mg quantities from the labs of individual
researchers. Leif Kronberg (Abo Akademi, Finland) synthesized EMX (75% purity) and
ox-EMX (Kronberg et al., 1991). Ramiah Sangaiah (UNC) synthesized MX, red-MX, and
ox-MX (Kronberg et al., 1991; Padmapriya et al., 1985). Angel Messeguer (CSIC, Spain)
synthesized BMX-1, BMX-2, and BMX-3 (Lloveras et al., 2000). Starting with MX
(Sigma-Aldrich), the identities and purities of the compounds were confirmed by 1H and 13C
nuclear magnetic resonance, electron ionization and chemical ionization mass spectrometry.
Qualitative and Quantitative NMR. Milligram quantities of MX-analogues (Figure
1 + MBA) were dissolved in deuterated methanol (Aldrich, 99.8 atom %D), and transferred
to 5 mm NMR tubes to a height of 60 mm (~1 mL). All spectra were obtained on an Inova
500 MHz NMR instrument. 1,4-Dioxane (Aldrich, 99.8%) was chosen as the internal
standard due to its volatility, and ease of removal from the MX analogues after NMR
analysis. 1,4-Dioxane interferes with only one chemical shift in MXR. Carbon- 13 NMR
spectra were obtained for four MX analogues in decoupling mode.
Purity Assay Calculations. Thirty |iL of 1,4-Dioxane (density: 1.0337 g/mL) was
spiked into 1 mL of deuterated methanol, for a concentration of 30.1 mg/mL in the primary
stock solution. Five |iL of the primary stock solution was spiked into each NMR sample,
which is equivalent to 150.5 jig 1,4-dioxane per sample. The quantitative ^NMR
spectrum of BMX-3 revealed a dioxane peak at 5 3.65 ppm with a peak area equivalent to 8
H's. The peak area of dioxane was then set to 8.00, so that all other areas would be
calculated relative to dioxane. The Ring H of BMX-3 at 5 6.35 ppm is equivalent to 1 H
with a peak area of 7.03. The weight of BMX-3 in the NMR tube was calculated by
Equation 1.
Wunk = Wstd x -^- x ^2*. x AisL (Equation 1, Willard et al., 1988) where
Nunk Mstd Astd
A = peak area
N = number of protons
M = molecular weight
W = weight present.
For BMX-3,
8H350.79gtool
WBMXJ = 150ii x. mgBMX-3
olVLA-j rc?iTT oo i i / 1 r> ^
1H 88.11g/mol 8
404
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The solution in the NMR tube was then transferred to a tared 4 mL amber vial and
dried under gentle flow of nitrogen gas. When the deuterated methanol evaporated to
dryness, the vial was placed in a vacuum manifold to ensure removal of the solvent. The
vial was then weighed on a microscale and the weight of the NMR sample by difference was
5.5 mg. Therefore, BMX-3 is 76% pure as measured by proton NMR. The remaining NMR
samples were assessed for purity in the same manner (Table 1). The ox-MX and red-MX
standards were prepared without addition of the internal standard dioxane. However, they
could still be quantified relative to residual MX remaining in the standard from the synthesis
reaction. Ox-MX was found to be 17% pure relative to MX, and red-MX was 88% pure
relative to MX, by *H NMR.
Table 1. Purity of Standards by Quantitative *H NMR
Compound
MX (Sigma)
MX ester
BMX-1
BMX-2
BMX-3
MCA
MBA
Ox-MX
Red-MX
Calculated Weight
(mg)
3.46
1.58
0.76
1.06
4.21
4.98
6.65
Original Weight
(mg)
5.2
2.64
4.0
4.0
5.5
6.0
10.4
Percent Purity
66%
60%
19%
27%
76%
83%
63%
17%
88%
The brominated MX-analogues (BMX-1, BMX-2, BMX-3) were synthesized
overseas and arrived as one neat 10 mg mixture of BMX-1 and BMX-2, as well as one neat
5 mg BMX-3. Therefore, BMX-1 and BMX-2 had to be separated by high performance
liquid chromatographic (HPLC) fractionation (Lloveras et al., 2000). The 10-mg mixture of
BMX-1 and BMX-2 was dissolved in 1.5 mL of deuterated methanol (CD3OD) and the *H
NMR spectrum was obtained by an Inova 500 MHz instrument. The NMR sample was
transferred from the NMR tube to a 4 mL amber vial with two successive washes with
regular methanol (Burdick & Jackson THM-free methanol). The methanol was evaporated
under gentle flow of nitrogen gas. The residue was then diluted to 100 |jL and transferred to
an HPLC vial with a 350 |jL insert. Twenty-five (jL aliquots of the BMX mixture were
injected onto the Waters HPLC system. The course of the separation was monitored at
?i=254 on a photodiode-array detector, using 25:75 acetonitrile (ACN): 0.05 M buffer
HCOOHiEtsN pH 3.2 as the eluent system, at a flow rate of 2.5 mL/min (Beckman
Ultrasphere ODS 5 |j,m x 10 mm x 25 cm). The compounds eluted in the order of, first, an
unknown, second, BMX-1, and third, BMX-2. The latter two peak eluates were collected
with an automated fraction collector.
Each 35-mL fraction was separately extracted in a 125 mL separately funnel with
two 50 mL aliquots of Ethyl Acetate (Mallinckrodt AR). The aqueous layer was removed
405
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(and stored in the refrigerator in case re-extraction was needed). The organic layer was
extracted with 40 mL of brine (DIW saturated with NaCl, Mallinckrodt AR), and the
aqueous layer was removed and disposed. The organic layer was dried over a funnel filled
with a glass wool plug and ample sodium sulfate (Na2SO4, EM Science, Granular), and
collected in a round bottom flask. The -100 mL organic layer was dried down to 1 mL with
a rotary evaporator. The remaining 1 mL was loaded onto a preparatory thin-layer-
chromatography (TLC) silica plate with a Pasteur pipette and developed for 1 hour with a
mobile phase of 1:1 ethyl acetate and hexane (Mallinckrodt AR) in a glass development
chamber. BMX-1 gave an RF value of 0.51, and the RF of BMX-2 was 0.24.
406
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Compound Identification Confirmation by Direct Probe Mass Spectrometry. The
electron ionization mass spectra of MX and red-MX were acquired and confirmed by
literature spectra (Kronberg et al., 1991; LaLonde et al., 1990; Padmapriya et al., 1985).
The mass spectrum of ox-MX was not previously published, so it is included below (Figure
6). It was found to contain significant contamination from MX (Figure 6, Table 2).
File
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_1.5E6
L1.4E6
il.3E6
il.2E6
L1.2E6
L1.1E6
il.OE6
L9.5E5
.8.7E5
L8.0E5
i7.3E5
L6.6E5
L5.8E5
L5.1E5
U.4E5
L3.6E5
L2.9E5
_2.2E5
L1.5E5
O.OEO
m/z
Figure 6. Background-subtracted direct insertion probe El mass spectrum of
synthesized ox-MX (1.81 mg/niL, molecular ion = 232,17% pure by proton NMR).
Table 2. Ox-MX fragmentation
m/z
187
133
107
73
Fragment ion
(M-CO2H)+
MX contaminant
C3HC12+
C3H2C1+
407
-------
Derivatization of MX-Analogues for GC-ECD and GC/MS Detection. Gas
chromatography with electron capture (GC-ECD) and mass spectrometric (GC/MS)
detection were chosen as the ideal separation and detection methods for the analysis of MX-
analogues because these types of instrumentation are widely used by environmental and
water utility laboratories across the United States. However, the majority of the MX-
analogues contain one or more hydroxyl groups that can react with unprotected silanol
groups on the solid phases of gas chromatographic open tubular columns. Therefore, a
methylating agent was chosen to protect the hydroxyl groups of the MX-analogues and
allow separation of the MX-analogues on a GC column. The boron-trifluoride methanol
complex (BF3/MeOH, Sigma) was chosen in order to effectively methylate all of the MX-
analogues; this is the only methylating agent suitable for ox-MX (Kronberg et al., 1991).
The limiting concentration of BFs/MeOH was unclear from previous work
(Kanniganti et al., 1992), and was evaluated by adding increasing volumes of 14%
BF3/MeOH to a 1 mL solution of MX in methanol (25 |ig/L MX/MeOH) (THM-free
methanol, Burdick & Jackson). By varying the amount of BF3/MeOH added, the
concentration changed from 7% BFs/MeOH with a 1 mL addition, to 9% with 2 mL, and
10.5% with 3 mL. Each mixture was sealed with a Teflon-lined, open-top screw cap and
heated in a heating block at 70°C (just above the boiling point of methanol, 67°C, to
encourage reflux) for 16 hours (Ball, 1998, personal communication). To halt the
derivatization reaction after 16 hours, a saturated solution of sodium bicarbonate in
deionized water (10% NaHCOs) was added until the pH approached neutral (pH 7). The
methylated MX in the neutral solution was then back-extracted with 1 mL of hexane (Ultra-
Resi grade 95%, J.T. Baker). The neutral pH of the aqueous fraction ensured that any
underivatized MX would remain ionized and dissolved in water, and would not be extracted
by hexane. The saturated salt solution (10% NaHCOs), used to neutralize the BFs/MeOH,
has been shown to improve extraction recovery of the esters into hexane (Metcalfe et al.,
1966).
When analyzed by GC-ECD on a DB-1701 (30-m x 0.25 mm ID x 0.25 |im film
thickness) fused-silica column, the 9% BF3/MeOH solution gave the largest area response
for MXR. Thereafter, a volume ratio of 2:1 BF3/MeOH to MX/MeOH was utilized for the
derivatization step. The final hexane extract was separated on a DB-1701 column with a
temperature program of 50°C for 1 min, and 2.5°C/min to 250°C, revealing a retention time
of 46.7 min for MXR.
Additional MX-analogues were derivatized with BFs/MeOH, as outlined above, and
analyzed by gas chromatography-ion trap mass spectrometry using both electron ionization
(El) (example in Figure 7, Table 3, ox-MXR) and chemical ionization (CI) modes. The total
ion chromatogram and mass spectra obtained for the esterified mucochloric acid revealed
two products, MCR ring form and MCR open form (the methylated 2,3-dichloro-4-
oxobutenedioic acid) (Kanniganti et al., 1992; Nawrocki et al., 2000). The two peaks eluted
at 12.2 and 20.5 min, on the DB-5 column, with a temperature program of 60°C for 1 min,
2.5°C/min to 250°C, and 250°C for 5 min; injection temperature of 150°C.
408
-------
100%-
75%-
50%-
25%-
0%
Sped
BP 230 (14267 = 100%)
5
9
I!
7
3
10049905. ms
I < i .In
109
I,,, i
26.430 min. Scan: 2643 Chan: 1 Ion: 2204 us RIC: 187037 BC
137 159 1
, , il Ml, In. , i lull, in
230
197
5
—
—
-_
-_
i,, ,. 2V-.
100
1!JO
200 250
m/z
Figure 7. Background-subtracted El mass spectrum for methylated ox-MX (molecular
ion = 260, Rt=26.43 min); agrees with mass spectrum of methylated ox-MX found by
Kronberg et al. (1991).
Table 3. Ox-MXR fragmentation
m/z
229
228
225
201
197
109
107
79
Fragment ion
(M-OCH3)+
(M-CH3OH)+
(M-C1)+
(M-CO2CH3)+
(M-C1-C2H4)+
C2H203C1+
C3HC12+
CO2C1+
The esterified mucobromic acid also contained two peaks (MBR ring and MBR open
forms) (Backlund et al., 1988; Kronberg et al., 1988; Nawrocki et al., 2000), eluting at 19.17
and 25.73 min. This was also the case for the esterified brominated MX-analogues (BMXR-
1 at 25.98 min, BEMXR-1 at 30.70 min, BMXR-2 at 30.14 min, BEMXR-2 at 34.45 min,
BMXR-3 at 34.26 min, BEMXR-3 at 37.59 min). The BMX compounds synthesized by
Angel Messenguer were not pure. Each one contained three components: an unknown
peak, the ring form (BMXR) and the open form (BEMXR). Identities of these esters were
confirmed by spectra in the Ph.D. thesis of Peters (1991).
By GC/MS peak area, red-MX was 66% pure relative to MXR, eluting at 19.08 min,
and ox-MXR was 28% pure relative to MXR (Figure 8, Table 4), eluting at 26.43 min. The
detector response for red-MX following derivatization was considerably lower due to losses
during back-extraction into hexane. Red-MX does not require methylation because it lacks
409
-------
the hydroxyl group present on the MX ring. The identity of ox-MXR was confirmed by
GC/MS (Kanniganti et al., 1992; Kronberg et al., 1991). The mass spectrum of ox-EMXR
could not be obtained due to the small amount of available material and detection limit
constraints on the Saturn II mass spectrometer. The percent purities of the MXR-analogues
are given in Table 5, based on GC/MS peak area.
In order to isolate and quantify EMX, the method required further manipulation.
MX was shown previously to isomerize to EMX above pH 4 (Holmbom et al., 1984).
Therefore, a pH 6 phosphate-buffered aqueous solution containing MX was monitored over
time for production of EMX. Aliquots (1 mL) of this solution were taken at time increments
from 10 min to 24 hours, and extracted with methyl tertiary-butyl ether (MtBE, OmniSolv
grade, EM Science, 1 mL). These MtBE extracts were derivatized with BF3/MeOH, and
extracted with hexane, as outlined above. The hexane extracts were analyzed by GC-ECD
and GC/Ion Trap MS on a DB-5 (30-m x 0.25 mm ID x 0.25 urn film thickness, J&W
Scientific/Agilent, Folsom, CA) column using a temperature program of 60°C for 1 min,
2.5°C/min to 150°C, and held at 150°C, to encompass the eluting compounds' retention
times. Each of the hexane extracts contained three distinct peaks: MXR at 22.85 min,
ZMXR at 28.17 min, and EMXR at 29.34 min, as identified by GC/MS (Kronberg et al.,
1988). The ratio of MXR to ZMXR to EMXR was 34:15:1, and did not change over the
time tested (10 min to 24 hours), as measured by GC-ECD. Therefore, the MX-^EMX
reaction was not observed at pH 6, unless, of course, the reaction completes in less than 10
min. In subsequent investigations, quantification of EMX was determined against a 2%
presence in the MX standard (Table 5). Similarly, quantification of ZMX was determined
against a 31% presence in the MX standard.
Derivatization Reaction Time
The optimum derivatization time for MX in the 1-8 hour range was 4 hours with a
65% yield. Aliquots (1 mL) of MX solution (10 |j,g/mL MX/MeOH) were derivatized with
2 mL of 14%BF3/MeOH at 70°C for 1, 2, 3, 4, 5, 6, 7, and 8 hours. These results enabled
the derivatization time of MX to be reduced from 16 to 4 hours. Then the derivatization
time was evaluated for a mixture of other MX-analogues, for 1-8 hours (Onstad and
Weinberg, 2001). The mixture contained 250 ng of each MX-analogue dissolved in
methanol. Most of the compounds (MX, MCA, MBA, BMX-1, BMX-2, and BMX-3)
approached a threshold derivatization efficiency after 3 hours (see Figure 9), with the
exception of ox-MX, which will not completely derivatize even after 19 hours. Previous
researchers used a derivatization time of 10-16 hours at 70-100°C in combination with a
boron trifluoride methanol complex (Ball, 1998, personal communication; Kanniganti et al.,
1992; Kronberg et al., 1991). A derivatization time of 4 hours was chosen for the
compounds overall.
410
-------
Chromatogram Plot
File: e:\10049905.ms
Sample: 1.81 MG OX-MX
Scan Range: 1 -4200 Time Range: 0.01 -42.00 min.
Sample Notes: 1.81 MG OX-MX
O perato r: G O
Date: 10/4/1999 4:30 PM
R 1C all 1 0049905.r
ox-M X este
Z M X ester
EM X ester
Figure 8. Total ion chromatogram for methylated ox-MX (1.81 mg/mL), with the MX,
ZMX and EMX esters in the mixture.
Table 4. Percent Purity of ox-MXR standard
Compound
MXR
Ox-MXR
ZMXR
EMXR
% TIC
52%
32%
14%
2%
% Area
58%
28%
12%
2%
411
-------
Table 5. Purity of Ester Standards by GC/Ion Trap MS
Compound
MXR
Ox-MXR
Red-MX
BMXR-1
BMXR-2
BMXR-3
MCR
MBR
Percent purity with respect to components (by area)
67% MXR, 3 1% ZMXR, 2% EMXR
28% MXR, 58% ox-MXR, 12% ZMXR,
2% EMXR
66% red-MX, 29% MXR, 8% ZMXR
31% UNK BMX-1, 9% BMXR-1 A, 35%
61% UNK BMX-2, 23% BMXR-2, 16%
41% UNK BMX-3, 41% BMXR-3, 18%
BMXR-1B, 25% BEMXR-1
BEMXR-2
BEMXR-3
18% MCR ring, 82% MCR open
27% MBR ring, 73% MBR open
rng
MCR open
ZMXR
EMXR
MBR ring
MBR open
ox-MXR
246
Derivatization Time (hours)
8
Figure 9. Derivatization of MX-analogues with boron trifluoride/methanol.
412
-------
Back-Extraction of the MXR-analogues into Hexane
The final step in the analysis was evaluated to determine the recovery of the
esterified forms of the MX-analogues during back-extraction from bicarbonate solution to
hexane (Onstad and Weinberg, 2001). Synthesized MXR-analogues were dissolved in
methanol and spiked into an aqueous sodium bicarbonate solution. Results were attainable
for only four of the MX-analogues (Table 6) (red-MX was not extractable by hexane). The
equation used to calculate the partition coefficients (Kd) for MXR-analogues between
sodium bicarbonate solution and hexane follows (Equation 2):
(Eqn.2)
where Kd = partition coefficient at equilibrium
Cs = concentration of MXR-analogue in hexane (ng/mL)
Ca = concentration of MXR-analogue in sodium bicarbonate solution (ng/mL)
MXR and MCR open exhibited the best recoveries by hexane extraction, although
only 60% on average (E in Equation 3 and Table 6). Hexane only recovered 7% of the
original ox-MXR. Red-MX, when included in this mixture, cannot be recovered at all by
hexane. Therefore, other extraction processes are being investigated for red-MX that do not
require derivatization prior to GC-ECD analysis. One possibility could be to analyze the
MtBE extract directly by GC-ECD, after addition of the internal standard (Kronberg et al.,
1991). The fraction of the MXR-analogue extracted (E) was calculated using the following
equation:
where E = the fraction of MXR-analogue extracted
Vs = volume of hexane (mL)
Va = volume of sodium bicarbonate solution (mL)
The "n for 75%" indicates the number of extractions (n) needed to recover 75% of
each MXR-analogue. This value is calculated using the following equation (Equation 4),
setting E equal to 0.75:
„=
log \
where V = Vs/Va
(Eqn.4)
By adding another hexane extraction and combining the two hexane extracts, MXR
and MCR open can be more efficiently recovered from the bicarbonate solution. Two
hexane extractions are consistent with previous methods for the esterified MX-analogues
(Hemming et al., 1986; Kronberg et al., 1991). Recovery of the brominated MXR-
analogues is still under investigation.
413
-------
Table 6. Partitioning of MXR-analogues into Hexane
Compounds
Kd
E (Recovery)
n for 75%
MXR
4.75
54%
1.77
MCR
open
8.58
68%
1.21
ox-MXR
0.29
7%
19.95
red-MX
0.00
0%
NA
NA: not applicable
Instrument Detection Limits and Gas Chromatographic Separation
A mixture of esterified MX-analogues was separated on a DB-5 column (60-m, 0.25
mm ID, 0.25 jim film thickness) (Figure 10) with a mild temperature gradient (2.5°C/min)
from 105 to 195°C, followed by a high temperature gradient (20°C/min) up to 250°C
(Onstad et al., 2000). A shorter column length (30 m) of the same phase did not allow
separation between red-MX and the open form of mucochloric acid ester (MCR open).
Coelution was observed between MX and an unknown component in the standard of BMX-
2 (BMX-2 UNK). However, this coelution does not preclude detection of MX, because MX
can be quantified by the ZMX peak (#14, Table 7), although, with greater variability. Two
peaks are present for BMX-1 ring, which could be due to the presence of diastereomers, as
the ion trap mass spectra appear identical, and the chromatographic retention times are
close. Twelve components in the gas chromatogram are listed in Table 7, in addition to red-
MX, the three BMX unknowns and the internal and surrogate standards. Use of an HP 6890
GC fitted with a micro electron capture detector (ji-ECD) enabled instrument detection
limits of 1 pg/|iL for MXR, MCR, ox-MXR, and red-MX; 16 pg/|iL for BMXR-1 and
BMXR-3; and 25 pg/|iL for BMXR-2, in the final hexane extract.
ECD1 A, (E:\GRETCHEN\GO081100\040F4001.D)
240-
ts
10
15
20
25
30
35 min
Figure 10. GC-ECD chromatogram of 7 MX-analogues and isomers at 20 pg/uL.
414
-------
Table 7. Peak identification in GC-ECD trace
Elution
Order
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Retention Time
10.022
11.597
17.372
17.758
18.159
18.543
21.143
21.143
24.122
24.423
25.087
25.158
25.399
25.998
27.016
29.428
29.719
33.391
33.461
36.641
Compound
3-Bromochlorobenzene (internal standard, IS)
Mucochloric ester (ring) (MCR ring)
unknown component of BMX-1 standard (BMX-1
UNK)
Mucochloric ester (open) (MCR open)
Red-MX
Mucobromic ester (ring) (surrogate standard, MBR
ring)
unknown component of BMX-2 standard (BMX-2
UNK)
MX ester (ring) (MXR)
Ox-MX ester (ox-MXR)
Mucobromic ester (open) (surrogate standard, MBR
open)
unknown component of BMX-3 standard (BMX-3
UNK)
BMX-1 ester (ring) (BMXR-1A)
BMX-1 ester (ring) (BMXR-1B)
ZMX ester (ZMXR), an open form of MXR
EMX ester (EMXR), an open form of MXR
BMX-2 ester (ring) (BMXR-2)
BMX-1 ester (open) (BEMXR-1)
BMX-2 ester (open) (BEMXR-2)
BMX-3 ester (ring) (BMXR-3)
BMX-3 ester (open) (BEMXR-3)
MX recoveries by other organic solvents, ethyl acetate (EtAc, EM Science,
OmniSolv grade) and hexane (Burdick & Jackson, for THM analysis), were compared to
MtBE using the 10:2 aqueous solution (100 ng/mL MX/DIW) to organic solvent extraction
ratio, and a single extraction. Ethyl acetate (94% recovery) recovered similar amounts of
MX as MtBE (83%), while hexane (7%) was relatively unsuccessful at recovering MX from
the aqueous solution. The high recoveries of MX (83% MX with MtBE vs. 58% in previous
experiment) can be explained by the doubling of the derivatization solvent ratio to LLE
extraction solvent (2 mL of 14%BF3/MeOH to 500 |jL of LLE solvent). Thereafter, the
LLE extraction solvent was reduced to 500 |jL with nitrogen (TS^) gas prior to addition of the
derivatization agent. MtBE was chosen as the better extracting solvent over EtAc, because
MtBE can be obtained from manufacturers at a higher level of purity; the GC-ECD trace of
EtAc contained several contaminant peaks in the vicinity of the MXR elution time.
Liquid-liquid extraction was applied to other MX-analogues, and MtBE was
evaluated for recovery of MCA, red-MX, MBA, MX and ox-MX from an aqueous solution
(1 ng/mL each in DIW), using the 20:4 extraction ratio, and triplicate extractions. MtBE
recovers 40-90% of the MX-analogues (Table 8). This translates to a detection limit of 4-9
415
-------
pg/|iL on column, or 200-450 ng/L in a 20 mL drinking water sample. Red-MX and ox-
MX apparently were not recoverable with LLE. ZMX and EMX did not give reproducible
area counts for quantitation. Although the LLE recoveries were good for MCR, MBR and
MXR, there still existed the need for recovery of the other MX-analogues and
preconcentration to achieve lower ng/L levels in drinking water.
Table 8. Percent recoveries of MX-analogues at 1 ng/mL by LLE
Compounds
MCR ring
MCR open
red-MX
MBR ring
MXR
ox-MXR
MBR open
Percent
Recoveries
40%
57%
1%
93%
81%
0%
87%
The MtBE extraction efficiency of MX-analogues from water was next evaluated by
comparing recoveries after the addition of salt (granular sodium sulfate, EMScience) or acid
[sulfuric acid (Aldrich) to pH 2] (Onstad and Weinberg, 2001). Each extraction was of a
20-mL deionized water sample spiked to 5 |ig/L with the MX-analogues. Two standard
mixes were evaluated separately, to prevent co-elution on the gas chromatogram, the first
one containing MX, ox-MX, and BMX-3, and the second one containing MCA, BMX-1,
and BMX-2. Percent recoveries were calculated relative to the GC responses of derivatized
standard mixes (Table 9). The MX-analogues were recovered poorly in the control (28 +
25%), with only three compounds yielding higher that 50% (MXR, ZMXR, and BEMXR-
1). The salting-out approach did not improve extraction efficiency relative to the control
(16 + 17%). Acidification to pH 2 improved the MtBE extraction efficiency of both the
open and ring forms of the MX-analogues (74 + 10%).
Table 9. Extraction Efficiencies of MX-analogues
Compound
MCR ring
MCR open
MXR
ox-MXR
ZMXR
EMXR
BEMXR-1
BEMXR-2
BEMXR-3
average
std dev
Control
16%
11%
61%
0%
55%
12%
41%
53%
0%
28%
25%
Salt
0%
3%
39%
13%
40%
14%
31%
0%
0%
16%
17%
Acid
82%
66%
89%
64%
73%
61%
73%
75%
87%
74%
10%
416
-------
Solid Phase Extraction
Solid phase extraction (SPE) was evaluated as a viable method of preconcentration
and an alternative method of extraction to LLE. The octadecyl silane phase (CIS, J.T.
Baker) was compared to LLE for recovery of MX from a 10-mL aqueous solution (100
ng/mL MX/DIW). The aqueous sample was passed through the SPE column at a rate of < 5
mL/min, and the solid phase was dried using a vacuum. When eluted with 1 mL of
methanol, the CIS column recovered only 25% of MX in aqueous solution.
Using the method development guidelines of Thurman and Mills (1998), different
solid phases and elution solvents were first compared for the recovery of a mixture of MX-
analogues made in the elution solvent, and then solid phase recoveries of a mixture of MX-
analogues spiked into deionized water and tap water were determined. Two different solid
phases, CIS (3 mL, 500 mg) and polyamide (DPA-6S, Supelco, 6 mL, 500 mg) were each
washed with MX-analogue solutions (40 ng/mL chlorinated MX-analogues) made
separately in methanol (Mallinckrodt AR Anhydrous), MtBE, and 14% BF3/MeOH (Table
10), to determine whether there would be irreversible retention of the target analytes on the
solid phase if these were the eluting solvents used in the SPE process. The BFs/MeOH
esterifying reagent dissolved the polyamide (DPA-6S) phase, and created large air pockets,
therefore preventing further investigation of this combination. The BMX compounds were
not included in this preliminary study. The percent recovery results follow.
Table 10. Percent recovery of MX-analogues from Cis and DPA-6S
Compounds:
CIS
spk/MtBE
CIS
spk/MeOH
CIS
spk/BF3/MeOH
DPA-6S
spk/MtBE
DPA-6S
spk/MeOH
MCR
ring
29%
108%
60%
1%
0%
MCR
open
49%
59%
53%
2%
0%
red-
MX
0%
0%
0%
0%
0%
MBR
ring
3%
102%
63%
1%
0%
MXR
38%
122%
65%
0%
8%
ox-
MXR
2%
70%
0%
0%
6%
MBR
open
51%
56%
29%
0%
0%
ZMXR
62%
78%
48%
0%
0%
EMXR
62%
148%
70%
0%
0%
Methanol was chosen to be the best solvent for partitioning of the MX-analogues off
of the CIS solid phase extraction columns (average 83% recovery). BFs/MeOH was the
second best solvent for CIS SPE (average 42% recovery), without heating, during
derivatization. MtBE gave similar recoveries when applied to CIS SPE (average 36 %
recovery). The MX-analogues preferentially partitioned onto the DPA-6S SPE columns
using methanol or MtBE (average 0% recovery). The spiked BFs/MeOH degraded the
DPA-6S phase on contact; this is due to the derivatization reaction which releases
417
-------
hydrofluoric and boric acids. All calculated average percent recoveries were weighted down
by zero recovery of red-MX in all cases. For compounds containing open and ring forms
(MXR, MBR, MCR), the open forms were retained by the solid phase much more than the
ring forms (-100% recovery ofringvs. -60% open on the CIS spk/MeOH ). This was also
evident for ox-MXR. The CIS reverse phase proved to be the most effective phase for
recovery of the MX-analogues (80-100% recovery of select MX-analogues).
Solutions of MX-analogues in deionized water (100 mL volumes at 1 |ig/L MX-
analogues/DIW) were then evaluated for recovery by CIS solid phase, with less favorable
results. Table 11 highlights the recoveries of MX-analogues under neutral (no alteration,
NA) and low pH (acidified to pH 2, AD) conditions, as well as percent breakthrough of
columns in tandem (breakthrough from top column was detected in bottom column).
Recovery of the MX-analogue standard solution (MeOH Mtx) from CIS solid phase was
reevaluated, this time including the BMX compounds. In this case the average percent
recovery of the MeOH Mtx was 50-60%, much lower than the above 80-100%. Solid phase
extraction was very poor with respect to the BMX compounds, both in the NA and AD
solutions. Acidification helped to increase the recovery of the MX-analogues. However,
the pH decrease also caused the ring forms of the MX-analogues to predominate.
Table 11. Recovery of the MX-analogues from spiked DIW by SPE
Sample label:
Compounds
MCR ring
MCR open
red-MX
MBR ring
MXR +
UNK BMX-2
ox-MXR
MBR open
BMXR-1A
BMXR-1B
ZMXR
EMXR
BMXR-2
BEMXR-1
BEMX-2
BMX-3
BEMX-3
Mtx-NA
top
ND
ND
ND
ND
7%
ND
ND
ND
ND
ND
ND
>100%
ND
ND
ND
ND
Mtx-NA
bottom
ND
ND
ND
ND
ND
ND
6%
>100%
ND
ND
ND
83%
ND
ND
ND
ND
Mtx-AD
Top
28%
ND
ND
41%
54%
26%
ND
ND
>100%
ND
16%
>100%
ND
6%
ND
ND
Mtx-AD
bottom
22%
ND
ND
39%
29%
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
MeOH
Mtx
64%
53%
ND
64%
52%
46%
62%
>100%
>100%
54%
40%
>100%
57%
65%
ND
42%
ND: not detected (below 5% recovery), NA: not acidified, AD: acidified to pH 2
418
-------
A number of other solid phases (3 mL, 500 mg) were then compared to CIS for
effective recovery of MX (Table 12). An aqueous solution (260 ng/L MX and 100 ng/L
MBA in DIW) was prepared and passed through Cyclohexyl (J.T. Baker), Cyano (J.T.
Baker), C8 (Phenomenex Strata), C18E (Phenomenex Strata), and CIS (J.T. Baker) in 250
mL quantities, and results were compared to blanks, both in duplicate. Each column was
eluted twice with 500-jiL aliquots of methanol. The methanol eluents were derivatized,
neutralized, and hexane-extracted before analysis by GC-ECD. None of the solid phases
recovered greater amounts of MX than CIS had previously recovered (25%) from spiked
DIW. For this reason, SPE was not considered as a practical alternative preconcentration
method to LLE for the MX-analogues.
Table 12. Comparison of SPE phases for MX recovery from DIW
Solid Phase
Cyclohexyl
Cyano
C8
C18E
CIS
MX
Recovery
16%
0%
9%
15%
6%
Method Calibration Curves
The liquid-liquid extraction method was applied to acidified (pH 2), 100 mL samples
that were spiked with all of the MX-analogues, except ox-EMX (Figure 1) (Onstad and
Weinberg, 2001). The chlorinated tap water samples were quenched of residual chlorine
with ammonium sulfate (Mallinckrodt) prior to extraction. The combined 50 mL MtBE
extracts (2 x 25 mL MtBE) were reduced to 500 jiL with nitrogen gas (UHP, 99.999%).
After derivatization of the MtBE extract and neutralization, the final hexane extract (1 mL)
recovered only -60% of the MXR-analogues, considering the results of the partition
experiments above. Linearity was observed for MX and MX-analogues in deionized and
chlorinated tap waters only at ng/L levels. Example calibration curves are shown in Figures
11 and 12 (MX) and Figures 13 and 14 (MCA). Recoveries of MX and MCA were greatly
reduced in the chlorinated tap water samples (Figures 11 and 12), when the detector
response was expressed as the ratio of MX or MCA areas to the internal standard (HCB).
However, the recoveries were more similar when the detector response was expressed as the
ratio of MX or MCA areas to the surrogate standard (MBA) area (Figures 13 and 14).
Reliable data is obtainable down to 50 ng/L MCA and 75 ng/L MX by liquid-liquid
extraction (100:1 concentration factor) when 100 mL is used as the sample volume.
419
-------
*MXRDIW «MXRTap
50
100 150 200
Concentration (ng/L)
250
300
Figure 11. MX Calibration Curve, using area relative to internal standard.
*MCRDIW »MCRTap
0 50 100 150 200
Concentration (ng/L)
250
300
Figure 12. MCA Calibration Curve, using area relative to internal standard.
420
-------
*MXRDIW «MXRTap
V)
"
0.2
0.1
o
y = 0.0007x
R2 = 0.9419
0 50 100 150 200
Concentration (ng/L)
250 300
Figure 13. Calibration curve for MX, using area relative to surrogate standard.
*MCRDIW aMCRTap
0 50 100 150 200
Concentration (ng/L)
250 300
Figure 14. Calibration curve for MCA, using area relative to surrogate standard.
421
-------
Stability in Aqueous Solutions
In order to stabilize the levels of MX in samples upon collection, they must be
quenched of residual chlorine to prevent further production or degradation of MX by
chlorine, treated with a biocide to prevent microbial degradation of MX, acidified to pH 2 in
order to prevent conversion of MX to open forms (ZMX and EMX) and degradation at high
pH, and stored at low temperatures (less than or equal to 4°C) to prevent thermal
degradation of MX.
Holding temperature of samples was evaluated by storing an aqueous solution (100
ng/mL MX/DIW) at room temperature (25°C) and in a refrigerator (4°C). The samples
were extracted after 24 and 48 hours, using LLE at a 10:2 extraction ratio with MtBE. MX
was more stable at the lower temperature; at 4°C, 63% MX was recovered, while at 25°C,
only 40% MX was recovered. MX recoveries for the two storage temperatures did not
change between 24 and 48 hours.
The stability of MX and MCA in tap water samples was then monitored over 14
days to determine the appropriate holding time for samples (Onstad et al., 2000). Previous
attempts to determine holding time utilized the biocide sodium azide (NaNs) in combination
with a variety of chlorine quenching agents (ammonium sulfate, Z-ascorbic acid, sodium
sulfite, and sodium bisulfate). However, the MX-analogues could not be recovered by
extraction, due to the reaction of sodium azide with the furanone rings in MX-analogues
(Beccalli et al., 2000). Therefore, the biocide was removed from the procedure. In this
case, a 10 L sample of chlorinated tap water was spiked with MX and MCA to a
concentration of 500 ng/L. The water was transferred to 250 mL bottles and quenched of
residual chlorine with aqueous ammonium sulfate solution (100 \\L of 40 mg/mL
(NH4)2SO4) or a combination of ammonium sulfate and sulfuric acid.
The samples were stored at 4°C and extracted in duplicate on days 0, 1,2, 4, 7, and
14. Prior to extraction, each 250-mL sample was spiked with the surrogate standard (MBA)
to a concentration of 500 ng/L. The samples containing only ammonium sulfate as the
quenching agent needed to be acidified prior to extraction (to pH 3), while the other samples
were already acidic (also pH 3). Method calibration samples at concentrations of 0 and 500
ng/L for MX-analogues in deionized water were extracted each day of the study, in order to
calculate concentrations of the MX-analogues in the tap water samples. The MtBE extracts
were reduced from 100 mL to 500 \\L with rotoevaporation and nitrogen gas. After
derivatization of the MtBE extract and neutralization, the final combined 2 mL hexane
extract (2x1 mL hexane) was reduced to 250 \\L with nitrogen gas and then spiked with an
internal standard, hexachlorobenzene (HCB). This process created a concentration factor of
1000.
The first-order plots show that the combination of ammonium sulfate and acid for
quenching stabilized the MX in the tap water samples only slightly longer than ammonium
sulfate alone (Figures 15 and 16). The first-order degradation rate constants are very
similar, as well (k~0.077 days"1, ti/2=9.0 days). This agrees with rates of hydrolysis at pH
7.0 measured by Croue and Reckhow (1989) at 20°C, k = 0.9±0.5 x 10"6 s"1 ( -0.07 days"1 )
422
-------
and ti/2 ~ 8.9 days. The MCA components coeluted with components in the tap water
samples and their stability could not be evaluated in this study. The immediate degradation
of MX in tap water samples calls for rapid sample extraction and processing upon receipt of
samples.
600
-- 500
"01
S 400
c
| 300
i
g 200
c
O 100
= 341.02e-°0763x
R2 = 0.4616
6 8 10 12 14
Days
Figure 15. Degradation of MX in chlorinated tap water quenched with ammonium
sulfate.
600
--;. 500
"3)
£ 400
c
300
200
o
0 100
y = 444.52e
R2 = 0.557
-0.0767X
8
Days
10
12
14
16
Figure 16. Degradation of MX in chlorinated tap water quenched with ammonium
sulfate and preserved with sulfuric acid.
Final Method for Occurrence Study Drinking Water Samples.
The final optimized method developed for the MX analogues is shown in the first
part of this chapter (Method Summary).
423
-------
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428
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CARBONYL, HALOACID, HALOACETATE, AND HALO ACE T AMIDE METHODS
Methods for carbonyl, haloacetate, and haloacetamide target DBFs were developed at the
University of North Carolina (UNC). A listing of these DBFs is presented in Table 1. For many
of the targeted species, no chemical standards were commercially available. Therefore, synthesis
was required for many. Proton nuclear magnetic resonance spectroscopy (NMR) and gas
chromatography (GC) with ion trap mass spectrometry (MS) detection were used to confirm the
identity and establish purities for these synthesized standards. The standards were stored at
-15°C and periodically reassessed for purity. Extraction methods developed included liquid-
liquid extraction (LLE) and solid phase extraction (SPE), which were used in combination with
different derivatization techniques (e.g., methylation or pentafluorobenzylhydroxylamine
[PFBHA] derivatization) and GC with electron capture detection (ECD) or mass spectrometry
(MS) (Table 1). Liquid chromatography (LC) with electrospray ionization (ESI)-MS was also
investigated for two of the target DBFs, but quantitative methods at the low |J,g/L detection limits
were effected through the use of gas chromatography. The stability of these DBFs in water was
also investigated
Table 1. Target carbonyl, haloacid, haloacetate, and haloamide compounds1
Compound
3,3-dichloropropenoic acid
Dimethylglyoxal (2,3-
butanedione)
Chloroacetaldehyde
Bromochloroacetaldehyde
Dichloroacetaldehyde
Bromochloromethyl acetate
2-Chloroacetamide
2,2-Dichloroacetamide
2-Bromoacetamide
2,2-Dibromoacetamide
2,2,2-Trichloroacetamide
Trans-2-hexenal
5-Keto-l-hexanal
Cyanoformaldehyde-oxime
6-Hydroxy-2-hexanone
Abbreviation
DCPA
23BD
CA
BCA
DCA
BCMA
TH
5KH
CNF
6HH
Source of
Standard
Synthesized at
UNC
Aldrich
ChemService
and Aldrich
CanSyn
TCI America
Supelco
Aldrich
Aldrich
Aldrich
Sigma-Aldrich
Aldrich
Acros
Majestic
Research
Can Syn
Majestic
Research
Purity
>95%by
NMR
97%
50%
solution in
water
35%
>95%by
GC/EI-MS
>99.99%
98%
98%
98%
98%
99%
99%
-20%
51%
>95%
Analytical Method
LLE - diazomethane
PFBHA-LLE
PFBHA-LLE
LLE, PFBHA-LLE
LLE, PFBHA-LLE
LLE
LLE
LLE
LLE
LLE
LLE
PFBHA-LLE, SPE-ESI
PFBHA-LLE, SPE-ESI
LLE
PFBHA-LLE, SPE-ESI
Abbreviations: Can Syn: Synthesized by Can Syn Chem Corp (Toronto, ON, Canada); TCI
America (Portland, Ore.); Aldrich Chemical Co. (St. Louis, Mo.); Acros Organics (Pittsburgh,
PA); Majestic Research: Synthesized by Majestic Research (Athens, GA).
429
-------
SAMPLE COLLECTION
Amber glass bottles (20 mL for carbonyl, haloacetate, and haloacetamide samples; 250
mL for haloacid samples) containing a quenching agent and labeled according to sample site and
location, quenching agent added, and date were sent in coolers to each drinking water utility for
sampling. Samples were collected headspace-free in these vials by staff at the water utilities.
Travel blanks were prepared in the same manner, but were pre-filled with deionized water and
capped with no headspace. All bottles for the same sample location and site were individually
wrapped in bubble wrap and packaged together and labeled with the sample site and location.
Bubble-wrapped bottles were then packed into a padded cooler along with a check-list of bottles
sent and ice packs. Once samples were collected at the utility, they were shipped back to UNC
overnight.
CARBONYL METHOD
Figure 1 provides of summary of the procedure used to quantify the carbonyl DBFs in
drinking water samples. Methods published by Yu et al. (1995) and the U.S. EPA (Method 556)
served as the basis for the method used here.
Concentrations of stock solutions prepared are summarized in Table 2. Dilutions were
made using methanol (Dilution I and II) or deionized water (DIW) (Dilution III). Solutions of
the surrogate standard, 4-fluorobenzaldehyde, were made up in methanol, and solutions of the
internal standard (IS), 1,2-dibromopropane, were made up in hexane. Dilution III solutions
could be used for 2-3 days. PFBHA solutions were prepared fresh for each
derivatization/extraction. Stock solutions of all compounds, internal standard and surrogate
standard and their dilutions were stored at 4°C when not in use. Calibration curves were created
using different concentration ranges (in the low |j,g/L range) for each DBF (Table 3).
430
-------
Water sample
20ml
Derivatization
Water bath
2 h, 35°C
< i
< i
< i
< i
< i
.-i
Add 20 |j,L Surrogate standard
(4-fluorobenzaldehyde, 20 mg/L)
Add 200 mg potassium hydrogen
phthalate
Add 1 ml Derivatization agent
(PFBHA, 15mg/ml_)
Add 4 drops of H2SO4 cone.
Add 4 ml hexane + IS
(1,2-Dibromopropane, 100|j,g/L)
Mix for 1 min
Transfer hexane layer to another
vial containing 3 ml 0.2 N H2SO4
Mix for 1 min
Transfer ca. 1 ml to autosampler vial
Figure 1. Summary of procedure used to quantify carbonyl DBFs in water.
431
-------
Table 2. Carbonyl Stock Solutions and Dilutions
Compound
Chloroacetaldehyde
Bromochloroacetaldehyde
f
Dichloroacetaldehyde
Dichloroacetaldehyde
rribromoacetaldehyde
7>a«5-2-hexenal
6-Hydroxy-2-hexanone
5-Keto-l-hexanal
2,3-Butandione
Cyanoformaldehyde-oxime
4-Fluorobenzaldehyde
(Surrogate Standard)
1 ,2-Dibromopropane
(Internal Standard)
Dilution I a
Cone.
(g/LMeOH)
12.035
0.242
0.345
2.156
26.825
8.3
3.204
1.106
10.111
0.956
235.44
939.85
Dilution II a
Cone
(mg/LMeOH)
120.35
9.68
13.80
86.24
10.73
9.96
51.26
11.06
10.11
9.56
23.544
9.3985
Dilution III
Cone
(jUg/LH20)
1203.50
96.80
138.00
862.40
107.30
99.60
512.60
110.60
101.11
95.6
Solutions of the internal standard were made in hexane
Ta
bit 3. Coi
CA
1.204
2.407
6.018
12.035
24.070
icentrati
BCA
0.097
0.194
0.484
0.968
1.936
ons used f<
DCA
1.000
2.001
5.002
10.004
20.008
)r calibrj
TEA
0.107
0.215
0.537
1.073
2.146
ition curve
TH
0.100
0.199
0.498
0.996
1.992
s (solution
23BD
0.101
0.202
0.506
1.011
2.022
s in deion
5KH
0.111
0.221
0.553
1.106
2.212
ized water
6HH
0.513
1.025
2.563
5.126
10.252
)
CNF
2.88
5.8
14.4
28.8
57.6
Derivatization and Extraction
Briefly, the pentafluorobenzylhydroxylamine (PFBHA) derivatization procedure was
carried out as follows. Twenty mL of each drinking water sample was measured and placed into
a 40-mL vial (2 vials per sample). Four 20-mL vials of one sample were also collected from
each treatment plant to determine recoveries. Twenty mL of each calibration standard was also
measured and placed into 40-mL vials (2 vials per sample). Twenty |jL of the surrogate solution
(23.5 mg/L of 4-fluorobenzaldehyde) was then spiked into each calibration and aqueous sample,
and approximately 200 mg of potassium hydrogen phthalate was added to samples for pH
adjustment. One mL of freshly prepared PFBHA (15 mg/mL in deionized water) was then added
to each sample, and samples were placed in a water bath at 35°C for 2 hours. After cooling to
room temperature, 4 drops of concentrated sulfuric acid (approximately 0.05 mL) was added to
prevent the extraction of the unreacted PFBHA reagent, and 4 mL of the internal standard
solution (9.4 mg/L in hexane) was added and mixed for 1 min using a vortex mixer. The
aqueous and hexane layers were allowed to separate, and the hexane layer was transferred to a
separate 20-mL vial that contained 3 mL of 0.2 N sulfuric acid, and was mixed for 1 min using a
432
-------
vortex mixer. Finally, a disposable pipet was used to draw off the hexane layer into a labeled
1.8-mL autosampler vial. Prior to analysis by GC-ECD, samples were stored in the freezer
covered with aluminum foil.
GC-ECD Analysis
GC analyses were carried out on a Baity GC-3 gas chromatograph. Injections of 1 |j,L of
each extract were introduced via a splitless injector onto a DB-1 column (30-m, 0.25 mm ID,
0.25 |j,m film thickness; J&W Scientific/Agilent, Folsom, CA). The GC temperature program
consisted of an initial temperature of 50°C, which was held for 1 min, followed by an increase at
a rate of 4°C /min to 250°C, followed by an increase at a rate of 3°C /min to 280°C, which was
held for 3 min. The injector and the detector were controlled at 150 and 280°C, respectively.
Prior to analyzing the real drinking water extracts, the internal standard solution (in hexane) and
the pure hexane used to prepare this solution were analyzed as blanks.
Results
The retention times obtained for the carbonyl standards are shown in Table 4. Two
isomers were formed for the PFBHA derivatives—syn and anti. When these isomers separated
by GC, both retention times are given below. Figure 2 shows a representative GC
chromatogram, which was used for one of the calibration points. Practical quantitation limits
obtained using this method are listed in Table 5, along with typical coefficient of variations for
triplicate analyses.
Table 4. Retention times for PFBHA-derivatized DBFs
Compound
Chloroacetaldehyde
Dichloroacetaldehyde
Bromochloroacetaldehyde
Cyanoformaldehyde
Trans-2-hexanal
6-Hydroxy-2-hexanone
5-Keto- 1 -hexanal
2,3-Butanedione
4-Fluorobenzaldehyde (Surrogate)
1,2-Dibromopropane (IS)
Abbrev.
CA
DCA
BCA
CFA
TH
6HH
5KH
23BD
4FBA
12DBP
Retention tii
DB-1
30.39
32.37
32.64
35.14
35.50
28.23
28.35
37.26
37.46
39.47
39.90
39.14
39.65
31.57
41.38
41.69
13.44
ne (min)
HP-5MS
18.54
20.55
20.84
23.70
17.37
25.74
27.77
28.10
39.34
29.91
30.09
4.14
433
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count
S480
220
§80
§60
§40
0
12DBP
13.
mir
44
2
-e-
3
-e-
4
-9-
4FBA
41.38
mi
Figure 2. GC-ECD chromatogram showing the different carbonyl-PFBHA derivatives, along with the internal standard (1,2-
dibromopropane [2DBP]) and surrogate standard (4-fluorobenzaldehyde [4FBA]). Abbreviations given in Table 1.
434
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Table 5. Practical quantitation limits (PQLs) for carbonyl DBFs
Compound
Chloroacetaldehyde
Di chl oroacetal dehy de
Bromochloroacetaldehyde
Cyanoformaldehyde
Trans-2-hexanal
6-Hydroxy-2-hexanone
5-Keto-l-hexanal
2,3-Butanedione
PQL (ng/L)
0.2
0.4
0.3
3.0
0.3
0.3
0.8
0.3
Stability of DBFs
In order to determine an appropriate sample handling procedure, a variety of quenching
agents were assessed over a 7-day holding time. Although sodium sulfite appeared to maintain
levels of carbonyl DBFs over the 14-day period, it was not chosen as the quenching agent
because it is capable of participating in side reactions with other precursors to generate the DBFs
studied here. Therefore, for the sake of consistency with other methods used for this study,
ammonium sulfate, which also adequately preserved the DBFs over the 14-day period, was
selected as the quenching agent for these compounds.
Compound Notes
Haloacetaldehydes. PFBHA derivatization in water generated a consistent 85%
conversion of chloro- and diChloroacetaldehyde to the corresponding oximes in a variety of
matrices. For the measurement of bromochloroacetaldehyde, di Chloroacetaldehyde was found to
be a major contaminant in the synthesized product; therefore, the product generated by PFBHA
derivatization contained a mixture of 35% bromochloroacetaldehyde and 38%
di Chloroacetaldehyde. These "standards" were used to quantify the conversion of the aldehyde
to the oxime during in situ derivatizations in water. Derivatizations showed a consistent 75%
conversion. The sum of the syn and anti isomers used for quantitation of
bromochloroacetaldehyde in water.
Cyanoformaldehyde. While the PFBHA oxime standard of this species was synthesized
and successfully characterized, many attempts at the synthesis of the target aldehyde were
unsuccessful. Consequently, only semi-quantitative analysis of this compound could be made.
Trans-2-hexenal. Both syn and anti oxime isomers were formed by PFBHA
derivatization, and the sum of these peaks was used to quantify ^ram--2-hexenal in water.
6-Hydroxy-2-hexanone. Both syn and anti oxime isomers were formed by PFBHA
derivatization, and the sum of these peaks was used to quantify trans-2-hexena\ in water.
5-Keto-l-hexanal. Both syn and anti oxime isomers were formed by PFBHA
derivatization, and the sum of these peaks was used to quantify trans-2-hexena\ in water.
435
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2,3-Butanedione (dimethyl glyoxal). Matrix effects suppressed the ability of the diketone
to form a di-derivatized oxime. However, quantitation was possible by calibrating using both the
mono- and di-oximes and summing their concentration for the overall concentration of 2,3-
butanedione in the original water sample.
3,3-DICHLOROPROPENOIC ACID METHOD
Liquid-liquid extraction (LLE) and diazomethane derivatization were used with GC-ECD
detection to quantify 3,3-dichloropropenoic acid (DCPA) in drinking water samples (a modified
EPA Method 552 approach). A practical quantitation limit (PQL) of 0.3 (ig/L was obtained.
Extraction and Derivatization
Samples were equilibrated to room temperature; two duplicate 20-mL samples were used
to analyze for DCPA. Calibration standards were prepared in deionized water at concentrations
of 1.9, 4.75, 9.5, 19, and 47.5 |J,g/L. Twenty mL of each of the two duplicate samples was
measured into 40-mL vials, and 50 |jL of the surrogate solution (2,3-dibromopropanoic acid, 20
mg/mL) was added to each sample. Concentrated sulfuric acid (1.5 mL) was then added, vials
were cooled to room temperature, and 4 mL of the internal standard (100 |J,g/L in MtBE) was
added to each sample. Approximately 6 g of sodium sulfate was added to each vial and was
mixed by vortex for at least 1 min. The upper ether layer was then transferred to a 2-mL
volumetric flask, magnesium sulfate was added, and flasks were cooled in the refrigerator for 10
min.
Cold diazomethane solution (225 |jL, previously prepared according to a slight
modification of the method of Glastrup (1998)), was added to each flask and returned to the
refrigerator for 30 min. Following this period, flasks were gently removed from the refrigerator
and allowed to come to room temperature for 15 min. The presence of a yellow color should
remain (indicating the presence of an excess of diazomethane reagent). A small scoop of silicic
acid was then added to each sample to quench the excess diazomethane, and 10-15 min was
allowed for the solid to settle. The upper ether layer was ten transferred to labeled autosampler
vials for GC-ECD analysis. If samples could not be analyzed immediately, autosampler vials
containing extracts were stored in the freezer.
GC-ECD Analysis
GC analyses were carried out on a Hewlett-Packard Model 6890 gas chromatograph
(Hewlett-Packard/Agilent, Folsom, CA). Injections of 1 |jL of each extract were introduced via
a splitless injector onto a HP5-MS column (30-m, 0.25 mm ID, 0.25 |j,m film thickness; J&W
Scientific/Agilent, Folsom, CA). The GC temperature program consisted of an initial
temperature of 37°C, which was held for 1 min, followed by an increase at a rate of 5°C /min to
280°C, which was held for 30 min. The injector and the detector were controlled at 180 and
297°C, respectively. Prior to analyzing the real drinking water extracts, the internal standard
solution (1,2-dibromopropane, 200 mg/L in MtBE) and the pure MtBE used to prepare this
436
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solution were analyzed as blanks, surrogate standards were analyzed for retention time checks,
calibration curve samples were analyzed in duplicate, and the internal standard was analyzed
once more. Following the analysis of samples (in order of increasing concentration), the internal
standard was analyzed again.
Stability
3,3-Dichloropropenoic acid showed good stability in water. Degradation was not
detected when ammonium sulfate was used to quench residual chlorine, nor when the aqueous
sample was stored for up to 14 days at 14°C.
HALO ACETATE METHOD
Bromochloromethylacetate was the only haloacetate DBF targeted in this study. A pure
standard was obtained from Supelco and checked for purity using NMR and GC/MS. A liquid-
liquid extraction (LLE)-GC-ECD method similar to that of EPA Method 552.2 was used for
quantifying bromochloromethylacetate in water, except that hexane was used in place of MtBE
as the extraction solvent. LLE with hexane was found to provide a more consistent and higher
recovery (92%) than MtBE (75%). No sample pretreatment or derivatization was necessary for
this compound. The practical quantitation limit (PQL) for this compound with a 1:5
concentration factor was determined to be 0.3
Extraction
Samples were equilibrated to room temperature; two duplicate 20-mL samples were used
to analyze for bromochloromethylacetate in water. Calibration standards were prepared in
deionized water at concentrations of 0.3, 1.0, 5.0, 10.0, and 25.0 [ig/L generating a calibration
curve with a median regression coefficient (r2) of 0.998. Twenty mL of each of the two
duplicate samples was measured into 40-mL vials, 4 mL of the extracting solvent (hexane) and
100 |j,g/L internal standard (1,2-dibromopropane) dispensed, and approximately 6 g of sodium
sulfate added to each vial, which was then capped and mixed by vortex for at least 1 min. The
upper organic layer was then transferred to a 1-mL autosampler vial for analysis by GC-ECD.
Spike recoveries were assessed on the plant effluent or average distribution system samples
through the addition of 5 [ig/L of standard. Typical spike recoveries in these samples fell in the
range 80-110% for all samples analyzed in this project. For a single set of triplicate, spiked
samples, the coefficient of variation was in the range of 6-10%. All plant samples were collected
in vials containing ammonium sulfate to quench residual chlorine. During method development
it was observed that the presence of a chloramine or chlorine dioxide residual had no effect on
the levels of bromochloromethylacetate spiked into plant waters, provided the samples were
stored within 24 hours of collection at 4°C and subsequently analyzed within 14 days. Chlorine-
quenched samples (with ammonium sulfate) could be held under similar conditions without
compromising sample integrity.
437
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Analysis
The GC-ECD conditions were as follows: a 30-m DB-5 column (J&W Scientific/Agilent,
Folsom, CA) with dimensions 0.25 mm ID. and 0.25|j,m film thickness) was operated under the
following oven temperature program: initial temperature of 50 °C held for 1 min, followed by a
temperature gradient of 4°C/min to 250°C, which was held for 3 min. The injector was operated
in the splitless mode at a temperature of 180°C, while the jjECD was held at a temperature of
300°C. The retention time of the target compound under these conditions (and carrier gas flow-
rate of 1 mL/min) was 6.1 min and was well resolved from other co-extracted neutral DBFs, such
as trihalomethanes.
HALOACETAMIDE METHODS
The haloacetamides included in this study are listed in Table 6. Several approaches were
attempted for these compounds including silylation, a novel liquid chromatography (LC)/MS
method, a method involving the conversion of haloacetamides to their corresponding haloacetic
acids by acid-catalyzed hydrolysis, and a direct liquid-liquid extraction-GC-ECD method. The
silylation method, as described in a paper by Le Lacheur et al. (1993) resulted in a practical
quantitation limit of 10 |ig/L. The novel LC/MS method in conjunction with solid-phase
extraction also showed relatively high detection limits (>20 |ig/L). The hydrolysis approach
appeared to be the most promising method when initially tested on standards in deionized water,
but when tested using real drinking water samples containing natural organic matter, it resulted
in the formation of additional halogenated by-products. Finally, a direct LLE with gas
chromatography (GC)-electron capture detection (ECD) proved to be the best method to use for
quantifying the haloacetamide DBFs for this Nationwide Occurrence Study.
Table 6. Listing of haloacetamides included in this study
Compound
Tri chl oroacetami de
Dibromoacetamide
Di chl oroacetami de
Monobromoacetamide
Monochl oroacetami de
Supplier & cat. #
Aldrich
SALOR(Aldrich)
Aldrich
Aldrich
Aldrich
Final cone, of
stock solution
(S/L)
0.98
1.08
1.01
1.02
0.98
Retention Time
By GC-ECD
25.821
27.226
21.799
22.84
17.55
Silylation Method
This method was initially tested using one of the halacetamides—dichloroacetamide.
Three dichloroacetamide/MtBE solutions were used: 108, 54 and 1.08 mg/L. One mL of each
solution was treated with 100 (iL of N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide
(MTBSTFA) and sonicated at 60°C for 1 hour. The solution was then cooled to room
438
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temperature and stored at -20°C until analyzed by GC-ECD using a DB-5 column (J&W
Scientific/ Agilent, Folsom, CA). The reaction is shown below.
MtBE, 60°C, 1 hour
C12-CH-CO-NH2 + CF3-CO-N(CH3)-Si(CH3)2-C(CH3)2-CH3
(mol. wt. = 127) MTBSTFA
Cl2CH-CO-N(CH3)-Si(CH3)2-C(CH3)2-CH3
product, mol. wt. = 241
Silyl derivatives were made at four different concentrations of dichloroacetamide in
MtBE for use as standards. In a typical experiment, a known amount of dichloroacetamide in 2
mL MtBE was measured into a 4-mL vial. Then, 100 jiL of the silylating agent MTBSTFA was
injected and the vial kept at 45°C for 2 hours. After cooling, the sample was analyzed by GC-
ECD and GC/MS using a 30-m, 0.25 mm, 0.25 |im DB-5 column (J&W Scientific/Agilent,
Folsom, CA). The operating conditions were as follows: carrier gas flow rate was 1.2 mL/min,
initial oven temperature 50°C for 1 min then 4°C/min to 250°C; with ECD, the splitless mode
injector temperature was 180°C and detector temperature was 300°C; with ion trap MS, initial
injector temperature was 50°C for 1 min then rapid increase to 250°C. The trap manifold was set
at 180°C and transfer line at 280°C. Emission current was 10 (jA, mass scan range was from 50-
650 Da, and electron multiplier voltage was 1500 V.
The silyl-dichloroacetamide derivative eluted at approximately 15.5 min by GC/MS.
Figures 3 shows the electron ionizaton (El) mass spectrum for the silyl-dichoroacetamide
derivative.
j,yy
80-
60-
40-
20-
0-
/
H
71
57
Ei
I till
J i.l ,11
H
11
J.l ,. 1
X
114
15
114
US
i LiLijUniilki .J t i. . N.I
j i i i i i i r t i t
100 150
i
170
•1 -1'1- '
(M-tBu)+
i .' 111 sm
i,, , Li . 1, . i. . . .1
200 250 '*
Figure 3. El mass spectrum of silyl-dichloroacetamide.
439
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Recovery of Dichloroacetamide from Deionized Water. Six concentrations of
dichloroacetamide in deionized warer were used. Ten mL of each solution was saturated with
sodium sulfate in a 40-mL vial. Five mL of MtBE containing 100pg/|iL dibromopropane
(internal standard) was added and shaken well to extract the dichloroacetamide. The ether layer
was transferred to another vial and dried over anhydrous magnesium sulfate thoroughly before
silylation. MTBSTFA (lOOjiL) was injected into each of the vials and kept at 50°C for 1 hour.
The solution was then cooled to room temperature and transferred to a GC vial for analysis. The
recoveries compared to the standards were very low (4-20%) and suggested that, at least without
additional preconcentration, the application of this method for the analysis of dichloroacetamide
in water would be limited to a practical quantitation limit of 10|ig/L.
Because the recoveries were poor with this method, direct determination of
dichloroacetamide from water by solid phase extraction was also attempted, but was not
successful.
Acid-Catalyzed Hydrolysis Method
Another method investigated was the acid-catalyzed hydrolysis method. This method
involves the acid-catalyzed hydrolysis of the haloacetamide to the corresponding haloacetic acid,
as shown below for dichloroacetamide:
CHC12CONH2 + H2O -> CHC12COOH + NH3
The accepted method (EPA Method 552) for haloacetic acids could then be applied before and
after hydrolysis to determine the amount of this compound accounted for by the haloacetamide.
For the analysis of the haloacetic acids (EPA Method 552), an aqueous sample was
treated with concentrated sulfuric acid, saturated with salt, extracted with MtBE and methylated
with diazomethane and determined as its ester. Assuming that the low molecular weight amide
may undergo acid-catalyzed hydrolysis readily with concentrated sulfuric acid and the heat
generated during the addition, this assumption was tested by making fairly concentrated
solutions of dichloroacetamide in deionized water and subjecting to the procedure for the
analysis of dichloroacetic acid. This procedure produced a recovery of 38 % for
dichloroacetamide.
In order to optimize the method, experiments were carried out to determine the effect of
different acid concentrations on the degree of dichloroacetamide hydrolysis. The following
scenarios were investigated on a 20 mL aqueous sample for a 2 hour reaction: at ambient
temperature (23°C), no acid was compared to the addition of 4 mL sulfuric acid; at a water bath
temperature of 80°C, no acid was compared to 4 and 6 mL of sulfuric acid. A 200 |j,g/L solution
of dichloroacetamide was used, and if the conversion were 100 %, 201.5 ng/L of dichloracetic
acid would be generated. Results shown in Table 7 reveal an optimum conversion with the
addition of 4 mL sulfuric acid at 80°C.
440
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Using the 80°C - 4 mL acid scenario, tests were then made to determine whether the
reaction time could be reduced without significantly impacting recovery. The results are shown
in Table 8.
Table 7. Impact of different reaction conditions on the hydrolysis of dichloroacetamide to
dichloroacetic acid (DCAA)
Sample
Ambient no acid
Ambient - 4 mL acid
80°C - no acid
80°C - 4 mL acid
80°C - 6 mL acid
DCAA measured (ng/L)
23.31
151.2
115.3
195.7
146.0
% Conversion
11.57
75.04
57.22
97.12
72.46
Table 8. Impact of different reaction times on the hydrolysis of dichloroacetamide to
dichloroacetic acid (DCAA) using 4 mL acid at 80°C
Reaction time (hours)
0
0.5
1
2
O
4
DCAA measured (ng/L)
55.4
175.9
183.4
184.4
179.4
177.5
% Conversion
27.49
87.30
91.02
91.51
89.03
88.09
It was apparent that a 1 hour reaction would suffice. Using this optimized set of reaction
conditions, dichloroacetamide solutions in a concentration range from 0 to 200 |j,g/L were taken
through the hydrolysis process and the resultant equivalent amount of DCAA calculated. A plot
of these values shown in Figure 4 indicates an average 82% conversion using a linear regression.
200
DCAA vs Dichloroacetamide
concentrations
50 100 150 200
Dichloroacetamide (ug/L) put into sample
Figure 4. Formation of DCAA from dichloroacetamide over a wide concentration range.
441
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LLE-GC-ECD Method
A final method, involving a simple liquid-liquid extraction (LLE) and GC-ECD analysis
proved to be the best method to use for this study. A 100 mL aliquot of 200 [ig/L
dichloroacetamide in deionized water was prepared by diluting 1 mL of 20 mg/L
dichloroacetamide in MtBE to a final volume of 100 mL with deionized water. Four 20 mL
aliquots were measured into clean 20 mL vials with Teflon-lined screw caps. Four mL of MtBE
and the internal standard (100 ng/L of 2,3 dibromopropane in MtBE) were added to two of the
aliquots, while 4 mL of ethyl acetate (EtAC) was added to the two remaining aliquots. Each vial
was vortexed for 1 min and the solvent layer allowed to separate for five min. The extracts were
compared to a standard of dichloracetamide at the 100% recovery level of 1 mg/L. A 1-mL
sample of the organic layer was then analyzed by GC-ECD under the following conditions:
GC Column: 30-m, 0.25 mm ID, 0.25 [im film thickness HP5-MS (Hewlett-Packard/Agilent,
Folsom, CA); oven temperature program - initial temperature: 37°C, held for 1 min; 5°C/min
increase to 280°C. The injector and detector temperatures were 180 and 300°C, respectively,
and the injector was operated in the splitless mode. The recoveries of each sample are shown in
Table 9.
Table 9. Recovery of dichloroacetamide by liquid-liquid extraction from deionized water
Sample
1
2
3
4
Extraction
solvent
MtBE
MtBE
EtAC
EtAC
Retention
time (min)
10.521
10.521
10.550
10.552
Peak area
7737.71
7509.28
19798
19163.5
Expected
peak area
33255
33255
33255
33255
Recovery (%)
23.27
22.58
59.53
57.63
Based on the percent recoveries, ethyl acetate appeared to be a better solvent for extracting
dichloroacetamide from water. This approach was then expanded for the other haloacetamides
listed in Table 6. The statistical evaluation of this method is presented in Table 10. The linear
calibration range extended from 1 to 50 ng/L, and water samples were spiked at 5
Table 10. Statistical evaluation of LLE method for haloacetamides in water
Compound
Tri chl oroacetami de
Dibromoacetamide
Di chl oroacetami de
Monobromoacetamide
Monochl oroacetami de
PQL
(Hg/L)
0.1
0.1
0.1
0.1
0.1
Average % CV at 1 (ig/L
8.4
6.5
5.4
10.3
11.3
Average Spike
Recovery (%)
95
90
104
88
78
442
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REFERENCES
Methods for the Determination of Organic Compounds in Drinking Water, Supplement 7;
Environmental Monitoring Systems Laboratory, Office of Research and Development, U.S.
EPA: Cincinnati, OH, July 1990; EPA/600/4-90020.
Le Lacheur, R. M., L. B. Sonnenberg, P. C. Singer, R. F. Christman, and M. J. Charles.
Identification of carbonyl compounds in environmental samples. Environmental Science &
Technology 27'(13):27'45 (1993).
Yu, J., H. E. Jeffries, R. M. Le Lacheur. Identifying airborne carbonyl compounds in isoprene
atmospheric photooxidation products by their PFBHA oximes using gas chromatography/ion trap
mass spectrometry. Environmental Science & Technology 29(8): 1923 (1995).
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BROADSCREEN GAS CHROMATOGRAPHY/MASS SPECTROMETRY
(GC/MS) METHODS
Sample Concentration
All water samples (39 L) were concentrated by adsorption on resins (Amberlite
XAD, Supelco). Details about the preparation and cleaning of these resins can be found
elsewhere (Richardson et al., 1994). Water samples were acidified to pH 2 by the
addition of hydrochloric acid prior to passage through the columns containing a
combination of resins (XAD-8 over XAD-2). A maximum ratio of 770:1 (v/v) of water
to resin was used to maximize the adsorption of organic compounds and to minimize
breakthrough. The columns were eluted with ethyl acetate, and residual water was
removed from the ethyl acetate eluents by using separately funnels to drain off the water
layers, followed by the addition of sodium sulfate. Samples were further concentrated by
rotary evaporation (to approximately 5 mL), followed by evaporation with a gentle
stream of nitrogen (to a final volume of 1 mL).
Raw, untreated water was collected at each sampling to enable the distinction of
chemicals that were formed as disinfection by-products (DBFs) in the treatment process
from chemical pollutants that were already present in the raw water. In addition to the
raw water controls, four blanks were also analyzed: (1) ethyl acetate passed through the
XAD resins and concentrated in the same manner as the treated samples; (b) deionized,
distilled water passed through the XAD resins and concentrated; (c) deionized, distilled
water treated with chlorine and concentrated; and (d) deionized, distilled water treated
with chloramine and concentrated. The latter two blanks were done to determine whether
there were any artifacts due to reaction of secondary disinfectants with the ethyl acetate
or with resin impurities. As compared to the raw water samples and the treated samples,
these blanks contained relatively few compounds.
Derivatizations
Methylation derivatizations with boron trifluoride in methanol were used to aid in
identifying carboxylic acids (Kanniganti et al., 1992), and
pentafluorobenzylhydroxylamine (PFBHA) derivatizations were used to identify polar
aldehydes and ketones (Sclimenti et al., 1990).
GC/MS Analysis
High-resolution GC/electron ionization (EI)-MS and GC/chemical ionization
(CI)-MS analyses were performed on a hybrid high-resolution mass spectrometer (VG
70-SEQ, Micromass, Inc.) equipped with a GC (Model 5890A, Hewlett-Packard-
Agilent). The high-resolution mass spectrometer was operated at an accelerating voltage
of 8 kV. Low-resolution analyses were carried out at 1000 resolution and high-resolution
analyses at 10,000 resolution. Positive CI experiments were accomplished by using
methane gas. Injections of 1-2 jiL of the extract were introduced via a split/splitless
444
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injector onto a GC column (DB-5, 30-m x 0.25-mm ID, 0.25-|im film thickness, J&W
Scientific-Agilent). The GC temperature program consisted of an initial temperature of
35°C, which was held for 4 min, followed by an increase at a rate of 9°C/min to 285°C,
which was held for 30 min. Transfer lines were held at 280°C, and the injection port was
controlled at 250°C. Duplicate analyses were also carried out with the GC injection port
held at 140°C to enable the analysis of trihalonitromethanes (THNMs). In previous work,
THNMs were found to decompose at temperatures higher than 170°C (Chen et al., 2002).
Chemical Standards
The following chemicals were prepared synthetically and provided by Can Syn
Chem. Corp. (Toronto, ON, Canada): dichloroiodomethane, bromochloroiodomethane,
iododibromomethane, diiodochloromethane, diiodobromomethane, 2,2-
dibromopropanoic acid, 3,3-dibromopropenoic acid, cis-2,3-dibromopropenoic acid,
tribromopropenoic acid, 2-bromobutanoic acid, cis-2-bromo-3-methylbutenedioic acid,
trans-2,3-dibromobutenedioic acid, bromonitromethane, dichloronitromethane,
bromochloronitromethane, bromodichloronitromethane, 1,1-dibromopropanone, 1,1,1-
tribromopropanone, 1,1 -dibromo-3,3 -dichloropropanone, 1,3 -dibromo-1,3-
dichloropropanone, and l,l,3-tribromo-3-chloropropanone. 1,1,3,3-
Tetrabromopropanone and dibromonitromethane were prepared synthetically and
provided by Majestic Research (Athens, GA). These chemicals were used to confirm
tentative identifications made by mass spectrometry. All other chemicals used for
broadscreen analyses were purchased at the highest level of purity from Aldrich, Chem
Service, and TCI America.
Identification of DBFs
For qualitative identification work, the criteria used for listing an identified
compound as a DBF was its presence in the treated-water samples in quantities at least 2-
3 times greater than in the untreated, raw water (as judged by comparing GC peak areas).
It was important to distinguish a compound as a DBF, even if small amounts of the
compound were present in the raw water, because many compounds that are common
pollutants (or natural contaminants in water) have also been proven to be DBFs.
GC/MS chromatograms were carefully analyzed for the presence of chemicals
that were produced in the treated samples. Each mass spectrum was carefully
background-subtracted to remove closely eluting or co-eluting peaks, after which the
NIST, Wiley, and Athens-EPA mass spectral library databases were searched for a match
of the unknown's mass spectrum. Several common DBFs, such as haloacetic acid methyl
esters, could be quickly identified through a library database match using the large NIST
(>100,000 spectra) and Wiley databases (>200,000 spectra). In addition, the user library
database created at the USEPA laboratory in Athens, GA (>200 spectra, mostly DBFs)
also enabled a rapid identification of many less common DBFs, such as 1,1,3,3,-
tetrabromopropanone and bromochloroiodomethane. Even with a definitive library
match, however, these identifications are listed as tentative until a match of the
unknown's GC retention time could be made with an authentic chemical standard. Only
445
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when both the mass spectrum and the retention time matched were the DBFs listed as
'confirmed'.
Despite the large size of the library databases and the user library that had been
created at the USEPA-Athens, there were many new DBFs identified in this study that
required significant interpretation to enable their identification. This process involved an
initial study and interpretation of the low resolution GC mass spectrum. Ion fragments
and losses from the molecular ion were studied to postulate a tentative structure. The
presence or absence of the molecular ion was determined, and CI-MS was used when the
molecular ion was not present or to confirm a molecular ion that was present. Next, high
resolution EI-MS analyses were made, which allowed the mass-to-charge (m/z) ratio of
an ion to be determined to 3 decimal places. For example, by low resolution mass
spectrometry, a molecular ion can only be assigned a nominal mass (e.g., m/z 200). With
high resolution mass spectrometry, this ion can be measured with greater accuracy (e.g.,
m/z 200.012). With this exact mass, generally a single empirical formula (number of
carbons, hydrogens, oxygens, nitrogens, etc.) can be assigned to the ion. High resolution
EI-MS was used not only for the molecular ions, but also for the fragment ions, which
generally reduced the number of possible empirical assignments from 6-8 to one.
Once the empirical formulas were known, functional groups could be postulated
and overall structures assigned. All possible isomers were considered when making these
tentative assignments. When it was not possible to choose a particular isomer as the
correct assignment for the unknown DBF, an attempt was made to purchase or obtain a
synthetically produced, authentic chemical standards of all the possible isomers so that a
definitive match could be made (of both mass spectra and retention time). When the
identification of a compound was confirmed through the analysis of an authentic
chemical standard, it was denoted in italics in this report. All other DBF identifications
should be considered tentative.
REFERENCES
Chen, P. H., S. D. Richardson, S. W. Krasner, G. Majetich, and G. Glish. Hydrogen
Abstraction and Decomposition of Bromopicrin and Other Trihalogenated Disinfection
Byproducts by GC/MS. Environmental Science & Technology 36:3362 (2002).
Kanniganti, R., J. D. Johnson, L. M. Ball, and M. J. Charles. Identification of
Compounds in Mutagenic Extracts of Aqueous Monochloraminated Fulvic Acid.
Environmental Science & Technology 26(10): 1998 (1992).
Richardson, S. D., A. D. Thruston, Jr., T. W. Collette, T. V. Sullins, K. S. Patterson, B.
W. Lykins, Jr., G. Majetich, and Y. Zhang. Multispectral Identification of Chlorine
Dioxide Disinfection Byproducts in Drinking Water. Environmental Science &
Technology 28(4):592 (1994).
446
-------
Sclimenti, M. J., S. W. Krasner, W. H. Glaze, and H. S. Weinberg. Proceedings of the
American Water Works Association Water Quality Technology Conference; American
Waterworks Association: Denver, CO, 1990.
447
-------
Mass Spectra of Newly Identified DBFs
lodoacetic acid methyl ester
100n
73
34
50,, 52
J 65
61 68
141
108
127
128 140
82 89 93
142
201
- m/z
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
lodobromoacetic acid methyl ester
3441 4451
78
105
8491
,,106
,114
122
210221
278,280
i m/z
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
lodobromopropenoic acid methyl ester (1st isomer)
10Ch
7882
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
nd
lodobromopropenoic acid methyl ester (2n isomer)
121
'.
38
"l
8
4
5
5 51
,,,
3
55
C
S64
75
71
37
I
III
8691 97
84
0
^J-^
89
95
1
30
„
117
110
104
12
127
\
8 149
129
138
147
141 |
1
152
57
164
1
II, I
181
^Q
n
i ,
29
261
'^ 259,
194 207
0
,292
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
rrfz
448
-------
2-Iodo-3-methylbutenedioic acid dimethyl ester
p 31
43
39
38
1
III
5°
44 53
i
66
^
,3 8
1
f
9
8
9£
11
101
111
107
127
126
3
115
1
8
\
159
1
139
128
« 158
155^
,144
I I
187
186
167173 ^
. , , i.
1
3^
III
188!
ff,
38 2
2
» 224,
252
S
253
/ 284
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
m/z
2,2-Dibromopropanoic acid methyl ester
165
43
3941
C
4552
6
5
55
a
60 7~
/ 70,7175
^8793
107
105
5 ^
108 137^,139
[ 135
,109 \
140
/ 158J60
, IU/
1
185
\
x68 184
( ^172 \
37
189
/
190
/ 2ia 215 217 244245,243
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 243 250
nVz
Dibromochloropropanoic acid methyl ester
149
45
55- 7
46
/
,
31 74
5
32 8
91
7
108
97102
112119
1'
-4^ ^-
5 12E
,,,,!,
135
1
to
144
164
150 197,199
/ I on-i 247
157 168 177,1791qn 2/01 245, -249 278 280
I l | f 19° / 217-219 221 /4D> f ("^
-L ,!,,,,,, i -r- , I :\\:\ , ,
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
m/z
3,3-Dibromopropenoic acid methyl ester
213
383941 5253 "gogo ?
Al/ N /!,A ,,73,,,
10
g^1 g.,94103
4,106
211
\
185
t137 149 1^163r165 1831 rW 1^201
215
244
216 242 246
/ 226,223233 | , /247^
40 53 60 70 80 90 100 110 123 130 143 150 160 170 183 193 2D3 210 220 233 243 253
449
-------
c/5-2,3-Dibromopropenoic acid methyl ester
163
53
383941 52
,,\l/ ^
59
54
rf
/T^Y
104/106
,8392 94103
I nil I
107 ,,, 1
/ 119J?013V
B/I35 1^ 158^160
213
211
185 \
183
\
^ 182
(.. \,
187
188 210
/ 196201 \
215 244
/ 242
\
216
, / 229
246
247
(.
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250
nVz
Tribromopropenoic acid methyl ester
40 60
243
394
4 5
5
2
In.
a
60 7981 93°^
241
\
13U33 I
05
706 117,119
(.... .i.C. ....
184
182
147>1f 162 172 1
U it i
186
2°\ \ 213,215
245
2f
261
h 1
291^293
289
33,265 N
295 322324
f7 320
326
,1-327
100 120 140 160 180 200 220 240 260 280 300 320 340
m/z
2-Bromobutanoic acid methyl ester
3"
38
, , ., I I
a
42
5
55
[| 45^50 53
57
9
101
69
60 68
I i i I , , , \ i i i , N , 1 , , , , i 1 i
5100
121
102 107 19n
/ //109 12°^
123
124 133 137 1,
/ \135/,139 1
1
S
52
4-
154
155 167 180
/ 165> \182,183
40 50 60 70
93 100 110 120 130 140 150 160 170 180
nVz
^ra«5-4-Bromo-2-butenoic acid methyl ester
40
75
117
/ 81 85 / 91 \ 97 101 105 111 \ / 126 133,134 / \149 178/
63 70
90 103 110 120 130 140 153 163 170 180
rrfz
450
-------
c/5-4-Bromo-2-butenoic acid methyl ester
100n
53
54
-*
52
81
147
94
149
98101
111
119
140
1I8180
rrVz
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
2,3-Dibromo-2-butenoic acid methyl ester
1;
6
/ 44 50/
9
7\75 8185 94 102 !-°5 117,118
1
1
137
151
3^ ,152 169™,
179
227
258
225
\
199
181 197,
,,201
205 213 224
...I il i.^l i
229
256
^
,,, 236 255
? V r-24,1, \,
260
[27>
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270
Bromodichlorobutenoic acid methyl ester
4
34
V'O6
7
7
81
9
4-
O
88
9
9
91
ll
596
/ 105,107
I i [T
124
7
126
( T 152 /56 167 173,175 199,201 215^217^219
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250
Bromochloro-4-oxopentanoic acid methyl ester
10Ch
55 (fit 7 I 79
7" I vc.81 BQ?1
127 131
40 50 60 70
100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250
451
-------
Dibromo-4-oxopentanoic acid methyl ester
( 01)
10Ch
43
137,139
,107 in ^ f 143149 1511^ 175/177
,I, ,1,1 ii,l i , iTiii, i,, ,i ili 11, ill, i ,i I ili hl i,UI
201 \213 227.229 244246 257^259,265 286J88,290
, rrfz
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
Bromoheptanoic acid methyl ester
41
39
38
5
44
53
45
50
82
68 1
67
59
63 6
\
5
81
\
75
79
83
112
84 96 11°
/ 91
86
97
7 1
1°Tl
39
1
119
5
T 129 W/
191
50
154 161 1^16^173182^,184
,193
222,2
207 1
24
,,225
40 50
70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
m/z
nd
Bromochloroheptanoic acid methyl ester (2n isomer)
8992
6
37,3847f ^S
5
68 77 84
,,l N,2°,,,,,i
c
f
B 107
1C
]
8
,110 1
114
22 1
149
\
31 139142
lill I
169
152
(l 165
171 1
177
227
225
31
182 1
\
«199 223
Yr203 }
229 jgg
^ ^ ,260
40 50 60 70
100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280
Dibromoheptanoic acid methyl ester
39
3^ 5153
1 44 >ij
6
6Q
3
1
8
78 86
tJrf99 T1
1:
21
5
,12
6 1
t1
15
3
156
157
1
161.162
184
73
I
185
/
X86 19^199 221^223 229 269^273 300302,304
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
m/z
452
-------
Bromochlorononanoic acid methyl ester
100n
°/148 157 161 174
/!,,,, ^Siii i L ,i,,\,ilihi mi I,,,/ \,
2042
7,179
180
/ 19V193
35
,207
208 236,238
( ^211 221^223 [,,239^244,
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 232 240 250
^ra«5-2,3-Dibromobutenedioic acid dimethyl ester
5
37
0 7
57 64 73
I
6 a
85
e
1:
103 117
J/104 129
y\\ no ^
51
135 145
iM44^,,
K
180
1?1 II 1?6
59
22
1f ™X^
27
269
1 ^1
r
233^241^243 251
1
273
/ 302
3HXir4
40 60
100 120 140 160 180 200 220 240 260 280 300
453
-------
lodobutanal
100n
198
69
56
45
5052
63
67
127
77
97
82
98 1
/ 105 111
128
169
199
- rrfz
40 50 60 70
90 100 110 120 130 140 150 160 170 180 190 200 210
Dichloropropenal
124
51 53 56
36384p4244 4y 49 55 x 59 62 gg 65 67 f 71 73 75 ^ 7P 81 83 87,
130
- m/z
35 40 45 50 55
70 75 80
90 95 100 105 110 115 120 125 130 135 140
4-Chloro-2-butenal
39
37 3
8
4
4
0
1
4
42 444? 47
, i ,\ i
9
515355576^163^67,6
1C
7
9
70 73
5
77 78 83 QR 90 95 rv-97
i / 81 | °b 87 89/^91 \»/ 100102
4
106
107l09/5l11 115 118
35 40 45 50 55 60 65 70 75
85 90 95 100 105 110 115
rrfz
l-Bromo-l,3,3-trichloropropanone
129
45 ,
42 \
8
5
R7
55
0
83
73 76
69
/
82
,Hl
II
85
88
S
95
hi
6
1
101 108
III I ll.i
1
127
S\ -j
120,
.H Till
23
157
155
131 ^
/
133
/ ,137149152
159
1^160,165 176 I80 195^9\205^^207 238^240,242
40 50
70
90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250
rrfz
454
-------
Ion Trap Mass Spectra (El) of Halogenated Furanone Standards
Red-
MX[3-Chloro-4-(dichloromethyl)-2(5H)-furanone]
100%:
75%-
50%-
25%-
117
107
73
61
83
165
145
135
202
186
220
246-
mlz
vix
100°/
-------
EMX ester [Methyl (2£)-2,4,4-trichloro-3-(dimethoxymethyl)-2-butenoate]
100V
75%-
50%-
25%-
217
5
9
75
I
107
123
!
U
III
I
1
37 151
I Mil ll I I I ll II
169
I
1£
,i ill
205
57
I ll ,,,
ilili
24
_i
5 :
-
j
-
nl 2T5 :
ox-N
100%-
75%-
50%-
25%-
no/
U /
-------
Mucochloric acid (open) [Methyl (2£)-2,3-dichloro-4,4-dimethoxy-2-butenoate]
75%-
193
75
59
169
87
103
119
133
157
147
181
213 229
mil
Mucobromic acid (ring) [3,4-dibromo-5-methoxy-2(5//)-furanone]
75%-
50%-
25%-
149
131
53
„„ 81 104
6,9 I I 93 II 119
163
193
241
212 227
255 272
287
50 ioV is'o
2^0
m/z
Mudobromic acid (open) [(2£)-2,3-dibromo-l,l,4-trimethoxy-2-butene]
75%-
50%-
25%-
75
157
286
237
53
'50
99
259
111
206
223
317
ioV
2^0
3oV
m/z
457
-------
JD1V1.
100%-
75%-
50%-
25%-
0%
S.-1
53
esiei ^it
73
,| J
>OI
iiei f\
in i. ,
; i
10
t-L
7
1 '
I, I I
UI
7
Oil
I
lO^CIlK
135
ii
jie
165 ;
152
i
-
-
—
181 T 217 244 -
„, 181 ,,, L , l,lh 230 ,. ,277
BM:
100%-
75%-
50%-
25%-
0%
C-l
53
lit
150
200 250
m/z
ester (isomer B) [4-[bromo(chloro)methyl]-3-chloro-5-methoxy-2(5//)-furanone]
73
135
107
117
1 h ,1, ,1
lil
i
1 1
1
I i
7
J
16f
i
-
-
_:
194 245 :
181 i 215
277
BEIs
100%-
75%-
50%-
lit
IX- 1 ester [Methyl
75
(2E)-4-bromo-2
150
200 250
m/z
,4-dichloro-3-(dimethoxymethyl)-2-butenoate]
—
-
210 :
-
! 175 291 :
25%-
0%
59
ml
1 03
141
160
193 :
INI I
-
241 ;
il 227 H 263 i ~~-
50
100
150
200 250 300
m/z
458
-------
BMX-2 ester [3-chloro-4-(dibromomethyl)-5-methoxy-2(5//)-furanone]
75%-
25%-
211
73
53
133
101 117
153
241 260 291
50
25V
mil
BEMX-2 ester [Methyl (2£)-4,4-dibromo-2-chloro-3-(dimethoxymethyl)-2-butenoate]
75%-
25%-
75
175
160
117
131 147
205
335
256
229
287
309
367
50
'ado'
35V
mil
BM1
75%-
50%-
25%-
C-3 ester [3-bromo-4-(dibromomethyl)-5-methoxy-2(5//)-furanone]
255
119
53
81
67
225
177
147
197
285
305
335
50 1()o IS'O 2^0 2^0 3^0 3^0 ',
mil
459
-------
BEMX-3 ester [Methyl (2£)-2,4,4-tribromo-3-(dimethoxymethyl)-2-butenoate]
75%-
50%-
25%-
75
53
251
221
97
117
147 171
204
378
300
331
271
351
2^0
mil
460
------- |