Occurrence Assessment for Disinfectants and
Disinfection By-Products (Phase 6a)
in Public Drinking Water
Prepared for
U.S. Environmental Protection Agency
: 401 M Street, S.W.
Washington, DC 20460
EPA Contract 68-CO-0069
Work Assignment No. 1-10
Mr. Brian Rourke Mr. Stig Regli
Project Officer Technical Project Monitor
Prepared by:
Wade Miller Associates, Inc.
1911 N. Ft. Myer Drive
Arlington, VA 22209
August 3,1992
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Final 8/3192
Table of Contents
Page
1. Introduction ................................................ 1-1
2. Summary of Occurrence ........................................ 2-1
3. Disinfectants ................................................ 3-1
3.1 Chlorine, Hypochlorite Ion, and Hypochlorous Acid ............... 3-1
3.2 Chloramine ............................................ 3-3
3.3 Chlorine Dioxide, Chlorate, and Chlorite ....................... 3-5
4. Disinfection By-Products ....................................... 4-1
4.1 Bromate .............................................. 4-1
4.2 Chloral Hydrate ........................................ 4-2
4.3 Dichloroacetic Acid ...................................... 4-3
4.4 Trichloroacetic Acid ..................................... 4-4
4.5 Chloroform ............................................ 4-5
4.6 Bromodichloromethane .................................. 4-10
4.7 Dibromochloromethane .................................. 4-15
4.8 Bromoform ........................................... 4-19
5. References
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Final 813192
Occurrence Assessment for Disinfectants
and Disinfection By-Products (Phase 6a)
in Public Drinking Water
1. Introduction
The EPA Office of Ground Water and Drinking Water (OGWDW) is currently developing
national primary drinking water regulations for disinfectant and disinfection by-product
contaminants. Thirteen contaminants are being considered to be regulated under Phase 6. These
contaminants, referred to as Phase 6a, are the subject of this report.
Occurrence assessments support several aspects of the drinking water reguLatory
development process. Information on the distribution of contaminant occurrence levels in public
water supplies of various source and size characteristics assists OGWDW in estimating the
number of systems and the size of the affected populations currently experiencing contaminant
levels exceeding the Maximum Contaminant Level (MCL) alternatives under consideration. This
information is critical for conducting the cost impact analyses of the regulatory alternatives. The
information on contaminant occurrence levels also supports the identification of the Best
Available Technology (BAT) necessary for setting the MCL and for granting variances. In
addition, the occurrence estimates are used to develop exposure assessments and, subsequently,
the contribution of drinking water, relative to other sources of exposure, to total intake. This
information is important for setting the Maximum Contaminant Level Goal (MCLG) for a
contaminant. The exposure information also is used to estimate the “baseline” health impact
assessment of current levels and for evaluation of the health benefits of the regulatory
alternatives.
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Final 813/92
2. Summary of Data Sources
Exhibit 2.1 summarizes the occurrence data for the disinfectants and disinfection
by-products in the current regulatory effort. Following is a description of the major surveys and
studies including information relevant to the occurrence data.
National Organics Reconnaissance Survey
The USEPA conducted the National Organic Reconnaissance Survey (NORS) in early
1975 in order to examine the occurrence of organic chemicals in drinking waters. The NORS
primary objective was to characterize the extent and presence of chloroform,
bromodichloromethane, dibromochioromethane, and bromoform. Secondary objectives of the
study included the determination of the effects of raw water source and treatment practices on
the formation of these compounds. Eighty water supplies, representing a wide variety of raw
water sources and treatment technologies, were chosen for the study. The water supplies were
geographically distributed so as to obtain national occurrence information. Of the 80 water
supplies, 16 had ground water sources and 64 had surface water sources. A reducing agent was
not added at the time of sample collection; thus, the THM concentrations represent maximum
values due to the consumption of the residual chlorine. -
National Organics Monitoring Survey
The National Organics Monitoring Survey (NOMS) was conducted by the EPA from
March 1976 to January 1977 to identify sources and frequency of occurrence of organics and
inorganics in drinking water supplies. In addition, the survey was intended to provide a data base
in support of establishing maximum contaminant levels (MCL) for the contaminants in the
nation’s drinking water supplies. NOMS was conducted in three phases: Phase I - March to
April 1976; Phase II - May to July 1976; and Phase III - November 1976 to January 1977. In
NOMS, finished water from 113 public water supplies were sampled. Of the 113 supplies, 18
had ground water sources, 91 had surface water sources, and four had mixed ground water and
surface water sources. Finished water from the treatment plants were sampled for chloroform,
bronioform, bromodichioromethane, and dibromochioromethane.
Rural Water Survey
The Rural Water Survey (RWS) was conducted by the EPA between 1977 and 1980 to
evaluate the status of drinking water in rural America as required by Section 3 of the Safe
Drinking Water Act. More than 2,000 households served by 648 public water supplies (494
ground water, 154 surface water) were surveyed. Of the 2655 samples obtained, 800 were
analyzed for purgeable halocarbons, including the four trihalomethanes. It should be noted that
some samples were analyzed up to 27 months after collection. Also, a reducing agent was not
added at the time of sample collection; thus, the THM concentrations represent maximum values
due to the consumption of the residual chlorine.
2-1
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Final 8/3192
Community Water Supply Survey
The Community Water Supply Survey (CWSS) was conducted in 1978 by the EPA to
determine the occurrence of organic and inorganic compounds in public water supplies. Drinking
water samples were provided by 452 systems, including 388 utilities serving populations less than
10,000. The survey included analyses for chloroform, bromoform, bromodichioromethane, and
dibromochioromethane. Finished water samples and distribution system samples were averaged
for each system due to inconsistencies in reporting. It should be noted that the samples were one
to two years old prior to analysis for the THMs. Also, a reducing agent was not added at the
time of sample collection; thus, the THM concentrations represent maximum values due to the
consumption of the residual chlorine.
Ground Water Supply Survey
The Ground Water Supply Survey (GWSS) was conducted from December 1980 to
December 1981 by the EPA to develop data on the occurrence of volatile organic chemicals
(VOC) in ground water supplies. Out of a total of 945 ground water systems, 466 systems were
chosen at random, while the remaining 479 systems were chosen on the basis of location near
industrial, commercial, and waste disposal activities. 618 systems served populations < 10,000
people. The samples were collected at or near the entrance to the distribution system. Analyses
for chloroform, bromodichioromethane, dibromochioromethane, and bromoform were performed
on samples that were dechlorinated at the time of collection. It is likely that many of the small
systems were not disinfecting with chlorine when this survey was conducted.
AWWARF National Trihalomethanes Survey
In 1987 the American Water Works Association Research Foundation (AWWARF)
partially funded a grant awarded to the Metropolitan Water District of Southern California
(MWD) to perform a national survey of THMs. The survey was conducted to determine the
extent and costs of compliance with the ThM maximum contaminant level (MCL).
Questionnaires were completed by 910 utilities, each serving more than 10,000 customers.
Participants provided quarterly total THM concentrations (mean, maximum, and minimum) from
1984 through 1986. Data on each utility’s source of water, chemicals used, populations served,
etc. were obtained. Information on any treatment modifications that were made to achieve
compliance, along with the costs and any water quality problems associated with the changes,
was collected from each utility (Meadow, 1987 and McGuire and Meadow, 1988).
EPA/AMWA/CDHS Study
In 1987, EPA funded a cooperative agreement with the Association of Metropolitan Water
Agencies (AMWA) to study the formation and control of disinfection by-products (DBPs) in
drinking water systems. Utilities using a variety of source water qualities, water treatment
processes, and disinfection schemes were included in the study. Twenty-five utilities nationwide
participated in the study performed by the Metropolitan Water District of Southern California
(MWD) and James M. Montgomery Consulting Engineers, Inc. The California Department of
2-2
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Final 8/3192
Health Services (CDHS) also contracted with MWD to include 10 California utilities in the
baseline phase of the study. Samples of plant influent and clearwell effluent were collected from
each utility on a quarterly basis for 1 year. The effluent samples were analyzed for chlorine
residuals, surrogate parameters, and several chlorination DBPs including THMs, CH, DCAA, and
TCAA. All samples were collected with the appropriate dechiorinating agents. During the
second phase of the project, treatment modification studies were conducted at six utilities in order
to identify, in a preliminary manner, the impact of treatment processes on DBP formation
(Krasner et al., 1989; USEPA and AMWA, 1989).
Water industry Data Base
The Water Industry Data Base (WIDB) was initiated through a joint effort by the
American Water Works Association (AWWA) and the American Water Works Research
Foundation (AWWARF). The purpose of this data base is to support the regulatory and
legislative efforts of AWWA, assist AWWA in focusing research activities, and support
educational endeavors of AWWA and interested parties. The study, conducted between 1989 and
1990, surveyed approximately 600 drinking water systems serving over 50,000 people in the
United States. The response rate was better than 80 percent, resulting in information from
approximately 500 systems in the data base. The survey covered a wide spectrum of information,
including utility characteristics and finances, surface and ground water treatments, water quality
monitoring, and water distribution characteristics. Data on the free chlorine residuals used by
the utilities was also obtained.
AWWA t991 Disinfection Survey
The American Water Works (AWWA) 1991 Disinfection Survey was conducted by the
Disinfection Committee of AWWA’s Water Quality Division. This survey is a follow-up survey
to the 1978 Disinfection Survey. The purpose of this survey was to document current water
industry practices regarding disinfection and water quality control. A total of 283 utilities
participated in this study, responding to questions involving disinfection and quality control,
including: control methodology, chlorine demand, filtration, chlorine dose, contact times, and
total trihalomethane levels. In the 1991 Disinfection Survey, information was provided
concerning free chlorine residual in drinking water and the number of utilities using chlorine,
chloramines, and chlorine dioxide were estimated.
EPA Disinfection By-Product Field Studies
The Technical Support Division (TSD) of the Office of Ground Water and Drinking Water
has conducted several Disinfection By-Product Field Studies. A study of chlorination by-products
was performed from October 1987 to March 1989. Samples of source water, plant effluent, and
water from a far point in the distribution system were collected from 21 community water
supplies (CWS). All the systems used free chlorine at some point in the treatment process and
19 used free chlorine as the residual disinfectant. Some of the utilities used preoxidants (5
ozone; 2 chlorine dioxide) in addition to chlorine. Sixteen systems were treating surface water,
14 served populations <10,000. Concentrations of several DBPs were examined including the
2-3
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Final 8/3/92
four THMs, chioral hydrate (C I- !), dichloroacetic acid (DCAA), and trichioroacetic acid (TCAA).
Residual chlorine measurements were also obtained. The samples were collected with
dechlorination agents, except at the first 3 utilities where the samples were analyzed within 24
hours of sample collection.
A second study from August 1989 to November 1989 was designed to examine the use
of total organic halide (TOX) as a surrogate for chlorination DBPs. Utilities were selected to
obtain samples containing median total THM concentrations in the range of 50-100 ugfL. All
utilities used free chlorine at some point in the treatment process .and the majority used free
chlorine as the residual disinfectant. Thirty of the 31 CWS treated surface water or a
combination of surface and groundwater. Two systems serving populations <10,000 were
sampled. Samples of plant effluent and water from one point in the distribution system were
analyzed for DBPs, chlorine residuals, and surrogate parameters. All samples were collected with
the appropriate dechiorinating agents.
Samples of untreated source water and treatment plant effluent were collected from 20
sites in August and September of 1991, in order to study the occurrence of chlorate. The
samples were also analyzed for chlorite and bromate, and in a few cases, the organic DBPs. Four
CWS used chlorine dioxide in the treatment process; 14 sites used hypochiorite solutions for
chlorination; the remaining 2 CWS used gaseous chlorine. Two systems served populations
<10,000.
As part of an ongoing effort, samples of source water and plant effluent are collected at
utilities participating in EPA’s Comprehensive Performance Evaluation (CPE) Program. The
systems all use chlorine and treat surface water. Nine of the 11 systems sampled between March
1991 and February 1992 served populations <10,000. The samples are analyzed for both organic
and inorganic DBPs, surrogate parameters, and chlorine residuals. All samples are
dechlorinated/preserved.
EPA’s Unregulated Contaminant Database
Currently, the Technical Support Division of the Office of Ground Water and Drinking
Water maintains a database of unregulated contaminants in public drinking water supplies. As
of December 1991, nineteen states had reported data on the individual THMs. The data are a
compilation of studies with multiple analytical methods and detection limits resulting in over
14,000 samples.
2-4
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ExhibIt 2.1: Dlsinfectants and Disinfection By-Products Drinking Water Summary Table
Final 8/319.2
Page 2-5
Survey
(Year)’
1..o tIon
Sample Information
(No. of Samples)
Con ntration (paJL)
Range Mean Median Other
Chlorine
NORS (1975)
Symons Ct aL, 1975
80 Cities Nationwide
Finished Water at
Treatment Plant
0-2.8 mgIL
0.6 mgfL 9
TSD, 1992
(1987-1991)
Disinfection By-Products
Field Studies
Finished Water:
At the Plant (71)
Distrib. System (45)
0.1-5.0 mgfL
0.0-3.2 mgfL
1.7 mgfL
0.7 mg/I..
1.4 mg/L
03 mg/L
AWWARF (1987)
McGuire & Meadow, 1988
Finished Water From:
Lakes
Flowing Streams
Groundwaters
Mixed-supplies
2.2 mg/L’
23 mg/L’
1.2 mgfL’
1.0 mgfL 5
EPA/AM WA/CDHS
(1988-1989)
Krasner et aL, 1989
35 Water Utilities
Nationwide
Samples from Qearwell
Effluent, 4 Quarters (17)
03-5.2 mg/I..
1.5 mgfL
1.0 mg/L
WIDB (1989-1990)
228 SW Plants
215 GW Plants
Residual ailorinc Provided
to the Average Customer
0-3.5 mgJL
0-5 mg/L
0.937 mglL
0.872 mg/L
0.80 mg/L
0.325 mg/L
AWWA Disinfection
Survey (1991)
283 Utilities
in the U.S.
Finished Water Entering
Distribution System
0.07-5.0 mg/I..
1.10 mgfL
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Disinfectants and Disinfection By-Products Drinking Water Summary Table (continued) Final 8/3/92
Page 2-6
Survey
(Year)
Location
Sample Information
(No. of Samples)
Concentration (FlaiL)
Range Mean Median Other
Chlorine Dioxide, Chlorate, and Chlorite
AWWARF (1987)
McGuire & Meadow, 1988
Finished Water From:
Lakes
Flowing Streams
1.0 mg/L
0.6 mgfL’
TSD, 1992
(1987-1991)
Disinfection By-Products
Field Studies
Plants Using 002:
Chlorite at the Plant (4)
Chlorate at the Plant (4)
Plants Not Using 002:
Chlorate at the Plant (30)
Chlorate, Dist. Syst. (4)
15-740
21-330
<10-660
<10-47
240
200
87
18
110
220
16
13
Positive Detects.
100%
100%
60%
75%
Chloramine
AWWARF (1987)
McOuire & Meadow, 1988
Finished Water From:
Lakes
Flowing Streams
Typical dosages:
1.5 mg/L
2.7 mgfL
EPA/AMWA/CDHS
(1988-1989)
Krasncr et al, 1989
3
ater Ut itics
ationwide
Samples from 0e dll
Effluent, 4 Quarters (13)
0.9-5.5
2.3
1.8
TSD, 1992
(1987.1991)
Disinfection By .Products
Field Studies
At the Plant (11)
Distribution System (8)
1.2-3.6
0.1-3.3
2.1
1.4
1.5
1.1
Bromate
-
McGuire et al., 1990
MWD Pilot Plant Studies
Ozonation:
Hydrogen Peroxide/Ozone:
Max. 60
Max.90
TSD, 1992
(1987-1991)
Disinfection By-Products
Field Studies
Finished Water, Plants Not
Using Ozone (33)
DL 5
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Dishifectants and Disinfection By-Products Drinking Water Summary Table (continued) Fina&813/92
Page 2.7
Survey
(Year)
location
Sample Information
(No. of Samples)
Concenfr tlon (#aWL)
Range Mean Median Other
Chloroform
NORS (1975)
Symons ci al., 1975
80 Cities Nationwide
Finished Water at
Treatment Plants
Max. 311
23
NOMS (1976-1977)
Bull and Kopflcr, 1990
113 Community Water
Supplies
Finished Water at
Treatment Plants 4
Max. 540
22 .54.52
Pos. Detections:
92% - 100% ’
CWSS (1978)
Brass ci aL, 1981
450 Watc Supply Systems
Finished Water (1,100):
Surface Water
Ground Water
60
<0.5
Pos. Detections:
97%’
34%’
RWS (1978.1980)
Brass, 1981
>600 Rural Systems
(>2,000 Households)
Drinking Water from:
Surface Water
Ground Water
84’
8.9’
57
<0.5
Pos. Detections:
82%’
17%’
GWSS (1980.198 1)
Westrick et al. 1983
945 OW Systems:
(466 Random)
(479 Nonrandom)
Serving >10,000 (307)
Serving <10,000 (618)
Max. 300
Max. 430
0.5
0
90th percentile:
17
7.8
TSD, 1991
(1984-1991)
Unregulated Contam.
Database - Treatment
FacilitIes from 19 States
Sampled at the Plant
(5,806)
17
5
TSD, 1992
(1987-1991)
Disinfection By-Products
Field Studics
Finished Water:
At the Plant (73)
Distribution System (56)
<0.2-240
<0.2-340
36
57
28
42
Positive Detects:
96
98
EPA/AMWA/CDHS
(1988-1989)
Krasner ci aL, 1989
35 Water Utilities
Nationwide
Samples from aeaiwdu
Effluent for 4 Quarters
Max. 130
9.6-156
14
75% of Data was
Below 33
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Disinfectants and Disinfection By-Products Drlnldng Water Summary Table (continued) Final 8/3/92
Page 2-8
Survey
(Year)
L4 U
Sample information
(No. of Samples)
Concentration (paJL)
nge Mean Median Other
Bromodlchlor.methane
NORS (1975)
Symons Ct aL, 1975
80 Cities Nationwide
Finished Water at
Treatment Plants
Max. 116
8
Pos. Detections:
98%’
NOMS (1976-1977)
Bull and Kopfler, 1990
113 Community Water
Supplies
Finished Water at
Treatment Plants’
Max. 183
5.9-14’
Pos.Detections:
90% ’
CWSS (1978)
Brass et al, 1981
450 Systems
Finished Water (1,100):
Surface Water
Ground Water
12’
5.8’
6.8
<0.5
Pos. Detections:
94%’
33%’
RWS (1978.1980)
Brass, 1981
>600 Rural Systems
(>2,000 households)
Drinking Water from:
Surface Water
Ground Water
17’
7.7’
11
<0.5
Pos. Detections:
76%’
13%’
GWSS (1980-1981)
Westrick et al. 1983
945 GW Systems:
(466 Random)
(479 Nonrandom)
Serving >10,000 (327)
Serving <10,000 (618)
Max. 110
Max. 79
0.4
0
percentile
9.2
6.1
TSD, 1991
(1984-1991)
Unregulated Contam.
Database - Treatment
Facilities from 19 States
Finished Water at
Treatment Plants (4,439)
5.6
3
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studies
Finished Water
At the Plant (73)
Distribution System (56)
<0.2-90
<0.2-100
13
17
11
15
Positive Detects:
96%
98%
EPA/AMWA/CDHS
(1988-1989)
Krasner Ct al., 1989
35 Water Utilities
Nationwide
Samples from Qearwdll
Effluent for 4 Quarters
Max.
4.1-1O
6.6
75% of Data was
Below 14 ug/L
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Disinfectants and Disinfection By-Products Drinking Water Summary Table (continued) Final 8/3192
Page 2-9
Survey
(Year)
Location
Sample Infonnatlon
(No. of Samples)
Concentration ( iaJL)
nge Mean Median Other
Dibromochioromethane
NORS (1975)
Symons et al., 1975
80 Cities Nationwide
Finished Water at
Treatment Plants
Max. 100
2
Pos. Detections:
90%’
NOMS (1976-1977)
Bull and Kopfler, 1990
113 Community Water
Supply Systems
Finished Water at
Treatment Plants’
Max. 280
ND-3
Pos. Detections:
78%’
CWSS (1978)
Brass et al., 1981
450 Systems
Finished Water (1,100):
Surface Water
Ground Water
5.0 ’
6.6’
1.5
<0.5
Pos. Detections:
67% ’
34%3
RWS (1978-1980)
Brass, 1981
>600 Rural Systems
(>2,000 households)
Drinking Water from:
Surface Water
Ground Water
8.5’
9.9’
0.8
<0.5
Positive Detections:
56%’
13%’
GWSS (1980-1981)
Westrick et al. 1983
945 OW Systems:
(466 Random)
(479 Noarandom)
Serving >10,000 (327)
Serving <10,000 (618)
Max. 59
Max. 63
0.7
0
90th Percentile:
9.2
5.6
1 D, 1991
(1984-1991)
Unregulated Contam.
Database - Treatment
Facilities from 19 States
Sampled at the Plant
(4,439)
3.0
1.7
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studies
Finished Water:
At the Plant (73)
In Dist. System (56)
<0.2-41
<0.2-41
4.9
6.6
2.0
3.4
Positive Detects:
92%
93%
EPA/AMWA DHS
(1988-1989)
Krasner et al., 1989
35 Water Utilities
Nationwide
Samples from Clearwdll
Effluent for 4 Quartets
Max. 63
3.6
2.6 4.56
75% of Data was
Below 9.1 Ig/ T I• •
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Disinfectants and Disinfection By-Products Drinking Water Summary Table (continued) FInal 8/3/92
Page 2-10
Survey
(Year)
Location
Sample Iniormatlon
(No. of Samples)
Concentration (pg L)
Range Mean Median Other
Bromoforin
NORS (1975)
Symons et aL, 1975
80 Cities Nationwide
Finished Water at
Treatment Plants
<0.5-92
<0.5
DL 03
NOMS (1976-1977)
Bull and Kopflcr, 1990
113 Community Water
Supply Systems
Finished Water at
Treatment Plants’
<0.3-280
ND-0.3
DL 0.3
CWSS (1978)
Brass et al., 1981
450 Systems
Finished Water (1,100)
from: Surface Water
Ground Water
2.1’
11’
<1.0
<0.5
Pos. Detections:
13%’
26%’
RWS (1978-1980)
Brass, 1981
>600 Rural Systems
(>2,000 Households)
Drinking Water from:
Surface Water
Ground Water
8.7’
12’
<0.5
<03
Pos. Detections:
18% ’
12%’
GWSS (1980-1981)
Westrick et ii. 1983
945 OW Systems:
(4 Random)
(479 Nonrandom)
Serving >10000 (327)
Serving <10,000 (618)
Max. 68
Max. 110
0
0
90th Percentile:
8.3
4.1
ISD, 1991
(1984-1991)
Unregulated Contam.
Database - Treatment
Facilities from 19 States
Sampled at the Plants
(1,40
2.5
1
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studies
Finished Water
At the Plant (73)
In Dint. System (56)
<0.2-6.7
<0.2-10
0.7
1.0
<0.2
<0.2
Positive Detects:
45%
48%
EPA/AMWA/CDHS
(1988-1989)
Krasner et al, 1989
35 Water Utilities
Nationwide
Samples from acarweu
Effluent for 4 Quarters
Max. fl
0.33-O.8V
037
75% of Data was
Below 2.8
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Disintectants and Disinfection By-Products Drinking Water Summary Table (continued) Final 8/3/92
Page 2.11
Survey
(Year)
Location
-
Sample Informat ion
(No. of Samples)
Con ntration (paJL)
i ange Mean Median Other
Chioral hydrate
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studies
Finished Water:
At the Plant (67)
Dist. System (53)
<0.2-25
<0.2-30
5.0
7.8
2.5
4.4
Positive Detects:
90%
91%
EPA/AM WA/CDHS
(1988-1989)
Krasner et al., 1989
35 Water Utilities
Nationwide
Samples from Clearwdil
Effluent for 4 Quarters
‘ .
1.7-3.0’
2.1
75% of Data was
Below 4.1
Dichioroacetic Add
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studics
Finished Water:
At the Plant (72)
In the Dist. System (56)
<0.4-61
<0.4-75
18
21
16
17
Positive Detects:
93%
96%
EPA/AM WA/CDHS
(1988-1989)
Krasner et aL, 1989
35 Water Utilities
Nationwide
Samples from Clearwell
Effluent for 4 Quarters
<0.6-46
5.0-7.3’
6.4
75% of Data was
Below 12
DL = 0.6
Trichioroacetic Add
TSD, 1992
(1987-1989)
Disinfection By-Products
Field Studies
Finished Water:
At the Plant (72)
Dist. System (56)
<0.4-54
<0.4-77
13
15
11
15
Positive Detects:
90%
91%
EPA/AM WA/CDIIS
(19881989)
Krasncr et ., 1989
Water Utilities
Nationwide
Samples from Clearwell
Effluent for 4 Quarters
4.0-5.8 ’
75% of Data was
Below 15.3
DL = 0.6
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Disinfectants and Dtstnfectlon By-Products Drinking Water Summary Table (continued) Final 8/3/92
Page 2-12
Survey
(Year)
Location
Sample Information
(No. of Samples)
Concmifratlori (1g!L)
ge Mean Median Other
Total Trlhalomethane.
AWWARF (1987)
McGuire & Meadow, 1988
727 Cities Nationwide
that serve >10,000 people
(Quarterly mean of
finished water)
677 Cities Nationwide
that serve <10,000 people
10,00025,000
Rivers
Lakes
Ground
Purchased
Mixed
25,000-50,000
Rivers
Lakes
Ground
Purchased
Mixed
>50,000
Rivers
Lakes
Ground
Purchased
Mixed
Overall
Finished Water (2,594)
ND-360
ND-313
64
21
61
37
56
59
20
44
42
49
44
22
49
47
42
36
-
39
18
90th Percentile:
95
NORS (1
Symons ci al. , 1975
80 Cities Nationwide
Finished Water at
Treatment Plant
ND-482
68
41
90th Percentile:
120
NOMS (1976-1977)
McGuire & Meadow, 1988
105 Community Water
Supplies
Finished Water at
Treatment Plant’
“
90th Percentile:
160
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Disinfectants and Disinfection By-Products Drinking Water Summary Table (continued)
Final 8/3/92
Page 2-13
Survey
(Year)
location
Sample Information
(No. of Samples)
Coneentratlon (pg/L)
Range Mean Median Other
Total Haloacetlcadda
TSD, 1992
(1987-1989)
Disinfection By-Products
Field studies
Finished Water:
At the Plant (73)
Dist. System (56)
I I I
<1-86 28
<1-136 38 I I
Dates indicate period of sample collection
2 Median concentrations of the three phases
‘ Of systems sampled
Sampled over 3 Phases
‘ Mean of the Positives
6 Range of medians for individual quarters
‘ Dctcction limit was 0.02 ,igi in the first quarter and 0.1 ugJL , thereafter
Typical dosage used by treatment plants
Approximate value
° Includes DBAA, DCAA, MBAA, MCAA, and TCAA
Abbreviations:
AMWA
AWWA
AWWARF
CDHS
CWSS
DL
OWSS
JMM
MWD
ND
NOMS
NORS
RWS
TSD
WIDB
Association of Metropolitan Water Agencies
American Water Works Association
American Water Works Association Research Foundation
California Department of Health Services
Community Water Supply Survey
Detection limit
Oround Water Supply Survey
James M. Montgomery Engineers, Inc.
Metropolitan Water District of California
Not detected
National Organics Monitoring Survey
National Organics Reconnaissance Survey
Rural Water Survey
Technical Services Division
Water Industry Data Base
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FinoJ 8/3/92
3. Disinfectants
3.1 Chlorine, Hypochionte Ion, and Hypochiorous Acid
Chlorine hydrolyses in water to form hypochiorite and hypochiorous acid. Chlorine and
hypochiorites are used to disinfect drinking water, sewage and wastewater, and swimming pools.
They have also been used for general sanitation and control of bacterial odors in the food
industry. In addition, chlorine is used to manufacture chlorinated lime (a fabric bleach),
detinning and dezincing iron, production of synthetic rubber and plastics, and as a reagent in
synthetic chemistry. Although chlorine is a highly reactive species, its fate and transport in the
environment and distribution in natural waters is not well delineated. Much of the available
information comes from the addition and oxidation reactions with inorganic and organic
compounds known to occur in aqueous solutions. Factors such as reactant concentrations, pH,
temperature, salinity, and sunlight influence these reactions (Stevens and Symons, 1977; Merck
Index, 1989; Johnson and Jensen, 1986; White, 1986).
In the disinfection treatment of drinking water, chlorine is added to water as chlorine gas
(Cl 2 ) or as calcium or sodium hypochiorite. In water, the chlorine gas hydrolyzes to
hypochiorous acid and hypochiorite ion and is measured as free chlorine residual. Maintenance
of a free chlorine residual throughout the distribution system is important as an indicator for
external contamination indicated by an absence of a residual and for continual bacteria kill.
Currently, maximum chlorine dosage is limited by taste and odor constraints and, indirectly, by
regulations on total trihalomethanes (TTHM). Additionally, the implementation of the surface
water treatment rule (SWTR) will increase the number of systems using chlorination and the
degree of chlorine dosage due to contact time requirements.
The Water Industry Data Base (WIDB) contains results from a survey of approximately
600 drinking water systems serving over 50,000 people in the United States, conducted between
1989 and 1990. Based on data from the Water Industry Data Base (WIDB), it has been estimated
that approximately 51% of surface and 77% of ground water systems, serving more than 10,000
people, currently use chlorine for disinfection in the United States. For those serving 25 to
10,000 people, 100% of the systems using surface water and 50% of the community systems
using ground water use chlorine. Fifteen percent of the noncommunity systems using ground
water use chlorine. It is estimated that the population exposed to chlorine from the use of
chlorination alone it community drinking water is 70.3 million from surface water plants and 36
million from ground water plants serving more than 10,000 people, and 17.4 million and 16.1
million from surface and ground water plants serving between 25 and 10,000 people (WIDB,
1990).
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Final 8/3/92
Drinking Water
National Studies
The EPA’s 1975 National Organic Reconnaissance Survey (NORS), sampled drinking
water of 80 U.s. water supplies. Of these 80 supplies, 16 had ground water sources and 64 had
surface water sources. Based on the survey’s results, chlorine residual reportedly ranged from
0-2.8 mg/i., with an approximate median concentration of 0.6 ing/L (Symons Ct aL., 1975).
In 1987, the American Water Works Association Research Foundation (AWWARF)
sponsored a national survey of trihalomethanes (THMs) conducted by the Metropolitan Water
District of Southern California. As part of this survey, alternate treatment technologies were
investigated which would achieve lower THM levels. Based on survey results, typical chlorine
dosage used in drinking water was found to be 2.2 mg/I., 2.3 mg/L, 1.2 mgfL, and 1.0 mg(L for
systems using lakes, flowing streams, groundwaters, and mixed-supplies as their raw water
sources. Overall, doses ranged from 0.1->20 mg/L (McGuire and Meadow, 1988).
The EPA’s Technical Support Division (TSD) has compiled a database of its disinfection
by-products field studies. The studies included a chlorination by-products survey, conducted
from October 1987 to March 1989. In this survey, free chlorine was sampled in finished water
at the treatment plant and in the distribution system. Out of 71 finished water samples,
concentrations ranged from 0.1 to 5.0 mg/L, with a mean of 1.7 mg/L and a median of 1.4 ug/L.
In the distribution system, concentrations from 45 samples ranged from 0-3.2 mg/L, with a mean
and median of 0.7 mgfL and 0.5 mg/L, respectively (TSD, 1992).
Based on WIDB data from 228 surface water plants and 215 ground-water plants, chlorine
residual in drinking water to the average customer was determined. From surface water plants,
chlorine residual ranged from 0 to 3.5 mgfL, with a mean of 0.94 mg/L and a median of 0.80
mg/L. For ground water plants, values ranged from 0 to 5 mg/L with a mean of 0.88 mg/L and
a median of 0.33 mg/L (WIDB, 1990).
Five national surveys reported residual levels for chlorine in U.S. drinking water. The
American Water Works Association’s (AWWA) 1991 Disinfection survey collected data from
a total of 283 utilities. Each facility was asked to respond to questions involving disinfection and
quality control. Based on the survey results, mean free chlorine residuals in drinking water
entering distribution systems were found to range from 0.07 to 5.00 mgfL, with a median of 1.10
mg/L (AWWA, 1991).
Re ionalfLocal Studies
In 1988, four surface water treatment plants participated in full plant studies of various
disinfection schemes. During the employment of chlorine disinfeciion, the average free chlorine
residual for each of three plants was 0.63 mg/L, 0.8 mg/L, and 0.30 mg/L. For the two plants
which used a combination of chlorine and ozone, the average residuals were determined to be
0.52 mgJL and 0.2 mg/L (Jacangelo et al., 1989).
3-2
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Final 8/3/92
In a survey of Kansas ground water supplies in 1986, finished water samples from 31
public supplies were analyzed for free chlorine. Concentrations ranged from 0.2-4.0 mg(L, with
a mean of 1.6 mgfL and a median of 1.3 mgfL from 50 samples (Miller et al., 1990).
In a 1983 survey of 12 full-scale treatment plants from six states, finished water from one
of the plants reportedly had a chlorine residual value of 1.8 mg/L at the entry point to the
distribution system. Two finished water samples from the plant’s distribution system contained
values of 1.3 mg/L and 0.2 mg/L (Singer and Chang, 1989).
Uden and Miller (1983) reported residual chlorine levels in drinking of Amherst,
Massachusetts. Two sets of tap water samples were collected from each of Amherst’s two
treatment plants, with the first set of samples analyzed immediately following collection and the
second set allowed to sit for 24 hours to mimic distribution levels. The first set of samples from
each plant had a level 3 mgfL. After 24 hours, however, residual chlorine was detected in
samples from only one of the plants. The lack of residual was attributed to the natural high
organic content of source waters.
Several studies conducted in 1978 and 1979 analyzed drinking water for chlorine residual.
In New York State, 5 samples from distribution systems of three treatment plants had values
ranging from <0.1-1.2 mgfL, with a median of 0.4 mgfL. The mean of the positives was 0.5
mgfL (Schreiber, 1981). Thirteen surface water plants from nine of the larger cities in North
Carolina had an average residual of 1.5 mg/L in their finished water (Singer et al., 1981). At the
University of Iowa water treatment plant, a residual concentration of 1.5-2.5 mgfL was reported
(Schnoor et al., 1979).
Drinking water from 19 chlorinated surface water supplies in Massachusetts were sampled
for free chlorine residual in a 1976 survey conducted by the state of Massachusetts Department
of the Environment. Finished water samples collected at the plant had a free residual of 0.3-4.0
mg/L, with a mean of 1.3 mg/L. In the distribution system, the free residual chlorine ranged
from 0-2.0 mg/I.. and the mean was 0.2 mg/L (Moore et al., 1981)
Non-Drinking Water
No information was found describing the occurrence of chlorine in ambient water.
3.2 Chloramine
• Chioramine is used as a chemical intermediate in the manufacture of hydrazine and as a
disinfectant. In the disinfection of drinking water, it is used to control taste and odor problems,
limit the formation of chlorinated disinfection byproducts, and maintain a residual in the
distribution system for controlling biofilm growth. At typical pHs of most drinking waters the
predominant chloramine specie is monochioramine. In the environment, monochloramine is
persistent. with first-order decay constants of 0.03 to 0.075 hr 1 in laboratory experiments and
0.28 to 0.31 hr 1 in outdoor chlorinated effluents. In receiving waters, monochloramine is
3-3
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Final 8/3/92
expected to decompose more rapidly, probably through the formation of NHBrC1 and
decomposition of the dihalamine. The half-life of monochioramine in water varies with pH and
salinity. At pH 7 and 25°C, the half-life of monochloramine is 6 hr at 5 parts per thousand (ppt)
salinity and 0.75 hr at 35 ppt salinity; at pH 8.5 and 25°C, the half-life is 188 hr at 5 ppt salinity
and 25 hr at 35 ppt salinity. Monochioramine is expected to decompose in wastewater discharges
to receiving waters via chlorine transfer to organic nitrogen-containing compounds (Johnson and
Jensen, 1986; Jolley and Carpenter, 1982; Norman et al., 1980).
Chioramine occurs in drinking water both as a by-product and intentionally for
disinfection. Chioramine is formed as a by-product of chlorination when source waters contain
ammonia. It is also used as a primary or secondary disinfectant, usually with chioramine being
generated on site by the addition of ammonia to water following treatment by chlorination. The
use of chioratnines has been shown to reduce the formation of certain by-products, notably
trihalomethanes, relative to chlorination alone. Chlorination by-product formation can be
minimized when the ammonia is added prior to or in combination with chlorine by reducing the
chlorine residual of the water being treated. In some plants, however, ammonia may be added
some time after the addition of chlorine, allowing the chlorine residual to react with precursor
chemicals (Bull and Kopfler, 1990; USEPA, 1980b; Cooper et al., 1985):
Based on the Water Industry Data Base (WIDB) data, it has been estimated that 29% of
comm unity surface water systems and 11% of community ground water systems, serving greater
than 10,000 people, use chioramines for disinfection in the United States. There are only a few
community systems serving less than 10,000 people that are expected to use chioramine. It is
estimated that from systems serving greater than 10,000 people, 56.5 million people served by
surface and 7.8 million people served by ground water systems are exposed to chloramines from
disinfection (WIDB, 1990).
Drinking Water
National Studies
In 1987, the American Water Works Association Research Foundation (AWWARF)
sponsored a national survey of trihalomethanes (THMs) conducted by the Metropolitan Water
District of Southern California. As part of this survey, alternate treatment technologies were
investigated which would achieve lower THM levels. Based on survey results, typical chioramine
concentrations used in drinking water were found to be 1.5 mg/L for systems using lakes and 2.7
mg /I.. for systems using flowing streams as their raw water sources (McGuire and Meadow,
1988).
Regional/Local Studies
The Metropolitan Water District of California changed its primary disinfectant to
chloramines in 1984 to ensure compliance with trihalomethane regulations. Its treatment plants
are operated at a chlorine to ammonia-nitrogen ratio of 3:1. The total ammonia-nitrogen dose
3-4
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Final 8/3/92
was 0.5 mg/I. and the chlorine dose was adjusted to result in a total chioramine residual,
primarily monochioramine, of 1.5 mgfL (Krasner et al., 1989a).
Non-Drinking Water
No information was found concerning chioramine occurrence in ambient water. Because
chloramine is found in drinking water due to its uses as a disinfectant and a by-product of
disinfection, it is not expected to be found in significant quantities in raw water sources.
3.3 Chlorine Dioxide, Chlorate, and Chlorite
Chlorine dioxide is used in a variety of industrial applications due to its strong oxidizing
characteristics. In the treatment of drinking water, chlorine dioxide is used as a primary and
secondary disinfectant. As a bleaching agent, it is used to bleach paper.pulp, flour, cellulose, fats
and oils, leather, textiles, and beeswax. In addition, it is used in cleaning and detanning leather,
manufacturing chlorite salts, as an oxidizing agent, bacterIcide, and an antiseptic. Chlorine
dioxide is a strong oxidizer that does not react with organics in the water, as does chlorine, to
produce by-products such as the trihalomethanes. It is fairly unstable and rapidly dissociates into
chlorite and chlorate in water. This dissociation is also reversible with chlorite converting back
to chlorine dioxide. Chlorite ion is the primary product of chlorine dioxide reduction. Formation
of chlorate occurs at lower levels than chlorite, depending on pH and sunlight (Merck Index,
1989).
Chlorite, as the sodium salt, is used in the on-site production of chlorine dioxide and as
a bleaching agent by itself, for paper-pulp, textiles, and straw. Chlorite is also used to
manufacture waxes, shellacs, and varnishes. Chlorate, as the sodium salt, was once used as a
defoliant, to tan leather, and to manufacture dyes, matches, and explosives.
Chlorine dioxide is used by water treatment plants as a disinfectant and in combination
with chlorine to combat taste, odor, and color problems in drinking water. Chlorine dioxide used
to treat water is most commonly generated from the reaction of chlorite and chlorine. Chlorite
and chlorate occurrence in drinking water result from the dissociation of chlorine dioxide in water
(Anderson et aL, 1982; White, 1986).
Based on the information derived from the AWWA Water Industry Data Base (WIDB),
it has been estimated that approximately 10% of surface water plants and 1% of ground water
plants, serving more than 10,000 people, currently use chlorine dioxide for disinfection in the
United States. It is assumed that none of the plants serving fewer than 10,000 people use
chlorine dioxide. It is estimated that from these plants serving greater than 10,000 people, 12.4
million people served by surface and 0.2 million people served by ground water plants are
exposed to chlorine dioxide from disinfection (WIDB, 1990).
3 -5
-------
Final 8/3/92
Drinking Water
National Studies
The EPA’s Technical Support Division (TSD) has compiled a database of its disinfection
by-products field studies. The studies included an occurrence of chlorite and chlorate in drinking
water from a survey conducted from August 1991 to September 1991. In plants using chlorine
dioxide, chlorite concentrations in four finished water samples ranged from 15 to 740 ug/L, with
a mean of 240 ug/L and a median of 110 ugfL. Chlorate concentrations, in four finished water
samples from plants using chlorine dioxide, ranged from 21 to 330 ugfL, with a mean and
median of 200 ugfL and 220 pgfL, respectively. For plants not using chlorine dioxide, chlorate
was measured in 30 finished water samples and 4 distribution samples. Concentrations ranged
from <10-660 1 ugfI.. in finished water samples and the mean and median were 87 pgfL and 16
ug/L, respectively. Distribution samples were found to have a mean concentration of 18 sg/L,
a median of 13 pg/L, and a range of <10-47 ugfL (TSD, 1992).
In 1987, the American Water Works Association Research Foundation (AWWARF)
sponsored a national survey of trihalomethanes (THMs) conducted by the Metropolitan Water
District of Southern California. As part of this survey, alternate treatment technologies were
investigated which would achieve lower THM levels. Based on survey results, typical chlorine
dioxide dosage used in drinking water were found to be 0.6 mg/L for systems using lakes and
1.0 mg/L for systems using flowing streams as their raw water sources (McGuire and Meadow,
1988).
Regional/Local Studies
Limited information was available concerning chlorine dioxide, chlorate, and chlorite
occurrence in drinking water. However, Bull and Kopfler (1990) cited results from three
different studies which reported information concerning the occurrence of the three chemicals in
drinking water. The first of these was a pilot plant study by Lykins and Griese (1986 in Bull and
Kopfler, 1990) in which Ohio River water was dosed with 1.6 mg/L of chlorine dioxide.
Resulting chlorite and chlorate concentrations were 0.3-0.5 mgfL and 1.5-2.0 mg/L, respectively.
Masschelein (1989 in Bull and Kopfler, 1990) reported that 40-60% of chlorine dioxide used in
water disinfection is converted to chlorite in finished water. Depending on the conditions of
disinfection, this percentage ranged from 50-100%. Gordon et al. (1990 in Bull and Kopfler,
1990) found from their own literature review that the chlorite yield was 70% of the chlorine
dioxide dosage used. In addition, they suggested that doses of 4-6 mg/L of chlorine dioxide may
be necessary for disinfection. Based on this information, Bull and Kopfler (1990) estimated that
chlorite concentrations in finished drinking water may be as low as 0.1 mgIL and as high as 2-3
mgfL, with concentrations as high as 10 mgfL in plants where the conditions are poorly
controlled.
Miltner (1977 in Stevens, 1982) reported results from a study designed to determine the
relative proportions of chlorite and chlorate formed from disinfection with chlorine dioxide. A
chlorine dioxide nose of 1.5 mg/L was applied to Ohio River water that was treated at a pilot
3-6
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Final 8/3/92
plant. Results indicated that of the original chlorine dioxide added, approximately 50% was
converted to chlorite (0.7 mgfL), 25% to chlorate (0.4 mgfL), and 25% to chloride (0.3 mgIL).
Non-Drinking Water
No information was found concerning the occurrence of chlorine dioxide, chlorate, and
chlorite in drinking water.
3-7
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Final 813192
4. Disinfection By-Products
4.1 Bromate
Bromate, in its salt form, is a white crystal that is highly soluble in water. In the form
of sodium bromate, it can be used with sodium bromide to extract gold from gold ores. Bromate
is also use to clean boilers and in the oxidation of sulfur and vat dyes. In the food industries,
bromate is used as a maturing agent in malted beverages, as a dough conditioner, and in
confectionery products (Merck Index, 1989).
Bromate (Br0 3 ) occurs in public water systems that treat raw water containing bromide
and other organobromine compounds with ozone. Bromide and organobromine compounds occur
in raw waters from both natural and anthropogenic sources. Bromide can be oxidized to bromate
or hypobromous acid; however, in the presence of excess ozone bromate is the principal product.
In laboratory studies, the rate and extent of bromate formation depends on the ozone
concentration used in disinfection, pH, and contact time. Bromate also may be produced during
chlorination reactions; however, under conditions normally found in drinking water, bromate
formation is expected to be limited (Glaze, 1988; Singer, 1988; Cooper, et al., 1985).
Drinking Water
National Studies
The EPA’s Technical Support Division (TSD) has compiled a database of its disinfection
by-products field studies. The studies included an occurrence of bromate in drinking water from
a survey conducted from August to September 1991. The study analyzed four drinking water
samples from plants not using ozone; however, bromate concentrations were not found above the
detection limit of 10 ug/L (TSD, 1992).
Re ionaIfLocal Studies
In an American Water Works Association (AWWA) study of the effect of coagulation and
ozonation on the formation of disinfection by-products, bromate levels were measured in 18 raw
and 6 coagulated-settLed waters. Overall, bromate levels increased with increased ozone residual.
Bromate formation did not start until the organic demand of the water was exhausted and an
ozone residual was present (AWWA, 1992).
With initial bromide concentrations of <0.2 mgfL, bromate formation was less than 15
ugfL. In general, for an ozone residual 1 mg/L and a bromide concentration <1.13 mgfL, the
bromate level was lower than 40 ug/L. Appreciable levels of brc mate, however, formed water
in water with low bromide waters and low ozone residual. In waters with high bromide Levels,
levels of 5-30 ugfL were formed with an ozone residual less than 0.05 mgfL. Also, bromate
levels were substantially lower for ozonated waters with a pH less than 7.0 (AWWA, 1992).
4-1
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Find 813192
Non-Drinking Water
No information was found concerning the occurrence of bromate in natural waters.
Because bromate occurs in drinking water as a by-product of disinfection, it is not expected to
be found in significant quantities in raw water sources.
4.2 Chloral Hydrate
Chioral hydrate (Cl-fl, also known as trichioroacetaldehyde monohydrate, is used as a
hypnotic or sedative drug in humans and is also used in the manufacture of DDT. CR has been
found to occur as a disinfection by-product in public water systems that chlorinate water
containing humic and fulvic acids. Ozonation prior to chlorination has been found to increase
the levels of Cl-I compared to chlorine disinfection alone. Also, preozonatión followed by
chioramines produces levels of Cl-I below that of chlorine disinfection (Jacangelo et al., 1989;
Merck Index, 1989).
Drinking Water
National Studies
Two studies describe the occurrence of CH in the nation’s drinking water. Case studies
of 35 water utilities nationwide, of which 10 were located in California, sampled for CR in the
clearwell effluent. Samples were taken for four quarters (spring, summer, and fall in 1988 and
winter in 1989). The median for all four quarters was 2.1 pg(L, with the medians of the
individual quarters ranging from 1.7 to 3.0 ug/L. The maximum value found was 22 ugfL For
all four quarters, 75% of the CR levels were below 4.1 pgfL. The detection limits for the survey
were 0.02 pg/L in the first quarter and 0.1 ug/L thereafter (Krasner et at., 1989b; USEPA and
AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey,
conducted from October 1987 to March 1989. In this survey, U-I was sampled in finished water
at the treatment plant and in the distribution system. Out of 67 finished water samples taken at
the plant, concentrations ranged from <0.2-25 ug/L, with a mean of 5.0 ug/L and a median of
2.5 pg/I.. In 53 distribution system samples, concentrations ranged from <0.2-30 pgfL, with a
mean and median of 7.8 jtg/L and 44 pgfL, respectively (TSD, 1992).
Regional/Local Studies
No local or regional studies were found which document the occurrence of CR in drinking
water.
4-2
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Final 8/3/92
Non-Drinking Water
No information was found concerning CH occurrence in ambient water. Because CH is
found in drinking water as a by-product of disinfection, it is not expected to be found in
significant quantities in raw water sources.
4.3 Dichloroacetic acid
Dichloroacetic acid (DCAA) occurs in drinking water as a by-product of disinfection. In
industry, it is used as a chemical intermediate and in the manufacture of pharmaceuticals and has
been used as an agricultural fungicide, and a topical astringent. Its medical uses include
experimental treatment of diabetes and hypercholesterolemia and is being investigated for
possible uses as a hypoglycemic, hypolactemic, and hypolipidemic agent (Merck Index, 1989).
DCAA has been found to occur as a disinfection by-product in public water systems that
chlorinate water containing humic and fulvic acids. Similar to other chlorination by-products
(such as the Trihalomethanes), DCAA levels can be reduced, though not eliminated, when
chioramines are used to disinfect. The reduction is less, however, when chioramination involves
a pre-chiorination step where a free chlorine residual is maintained through a portion of the water
treatment process prior to the addition of ammonia.
Drinking Water
National Studies
Case studies of 35 water utilities nationwide, of which 10 were located in California,
sampled for DCAA in the clearwell effluent. Samples were taken for four quarters (spring,
summer, and fall in 1988 and winter in 1989). The median for all four quarters was 6.4 ug/L,
with the medians of the individual quarters ranging from 5.0-7.3 ug/L. The maximum value
found was 46 1 ug/L. For all four quarters, 75% of the data was below 12 sg/L The detection
limit for the survey was 0.6 1 ug/L (Krasner et al., 1989b; USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey,
conducted from October 1987 to March 1989. In this survey, DCAA was sampled in finished
water at the treatment plant and in the distribution system. For surface water systems, the mean
concentration in finished water for systems serving above and below 10,000 people was 20.7
ug/L and 21.8 ug/L, with the 90th percentile of 33.4 ug/L and 50.0 ug/L for 42 samples and 20
samples, respectively. In the distribution system, the mean was 22.1 ugfL and 27.7 sg/L for
plants serving above and below 10,000, with the 90th percentile concentration of 48.0 pgIL and
41.0 ug/L for 39 samples and 11 samples, respectively. The ground water systems serving less
than 10,000 had a mean DCAA concentration in finished water samples and distribution system
samples, respectively, of 2.7 g/L and 1.9 pg/L for 7 observations and 5 observations, with the
90th percentile of 12.5 ug/L and 4.7 ug/L. For systems serving greater than 10,000, DCAA was
4-3
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FinaL 8/3/92
not detected in single samples taken at the plant and from the distribution system based on a
detection limit of 0.4 ugfL (TSD, 1992).
Re2ionallLocal Studies
Uden and Miller (1983) analyzed drinking water from two Massachusetts treatment plants.
DCAA concentrations were at 63.1 ,ug/L and 123 ug/L immediately after disinfection and 79.5
4 ugIL and 133 ug/L after standing for 24 hours, respectively. Singer and Chang (1989) reported
that the mean for DCAA in the distribution systems for six utilities was 47 1 ug/L, with a range
of 8-79 1 ug/L.
Fair et al. (1988) analyzed drinking water from three community water supplies for
chlorination by-products. DCAA concentrations reported for each of the plants ranged from 5.9-
32 ug/L in finished water at the plants and from 8.9-58 ug/L in the distribution systems.
Non-Drinking Water
No information was found concerning the occurrence of DCAA in natural waters.
Because DCAA occurs in drinking water as a by-product of disinfection, it is not expected to be
found in significant quantities in raw water sources.
4.4 Trichloroacetic acid
Trichioroacetic acid (TCAA), a major by-product of chlorinated drinking water, is used
as a pre-emergence herbicide and a reagent for synthetic medicinal products. In the laboratory
it has been used to precipitate proteins. It is also used in the medical field as a peeling agent for
damaged skin, cervical dysplasia, and removal of tatoos (Pringle et al., 1975; Merck Index,
1990).
TCAA occurs in public water systems that chlorinate water containing humic and fulvic
acids. Similar to other chlorination by-products (such as the THMs), TCAA levels can be
reduced, though not eliminated, when chloramines are used to disinfect. The reduction is less,
however, when chioramination involves a pre-chiorination step where a free chlorine residual is
maintained through a portion of the water treatment process prior to the addition of ammonia.
In addition, it has been shown that the formation of TCAA is reduced substantially at high pH
levels (i.e., around pH 9) (Stevens et al., 1989).
Drinking Water
National Studies
Case studies of 35 water utilities nationwide, f which 10 were located in California,
sampled for TCAA in the clearwell effluent. Samples were taken for four quarters (spring,
summer, and fall in 1988 and winter in 1989). The median for all four quarters was 5.5 gJL,
4-4
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Final 8/3/92
with the medians of the individual quarters ranging from 4.0-5.8 ug/L. For all four quarters, 75%
of the data was below 15.3 ugfL. The detection limit for the survey was 0.6 ugfL (Krasner et
al., 1989b; USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey
conducted from October 1987 to March 1989. In this survey, TCAA was sampled for in finished
water at the treatment plant and in the distribution system. For surface water systems, the mean
concentration in finished water for systems serving above and below 10,000 people was 14.4
ugfL and 14.8 g/L, with the 90th percentile of 28.7 ug/L and 30.4 pg/L for 42 samples and 20
samples, respectively. In the distribution system, the mean was 17.0 4 ug/L and 16.6 pgfL for
plants serving above and below 10,000, with the 90th percentile concentration of 30.6 ugfL and
28.9 u2JL for 39 samples and 11 samples, respectively. The ground water systems serving less
than 10,000 had a mean TCA. concentration in finished water samples and distribution system
samples, respectively, of 1.9 pg/L and 1.1 ug/L for 7 observations and 5 observations, with the
90th percentile of 10.7 1 ugIL and 4.2 ug/L. For systems serving greater than 10,000, TCAA was
not detected in single samples taken at the plant and from the distribution system based on a
detection limit of 0.4 ug/L (TSD, 1992).
Re ionalfLocal Studies
Uden and Miller (1983) analyzed drinking water from two Massachusetts treatment plants.
TCAA concentrations were reportedly at 33.6 and 161 ug/L immediately after disinfection and
72.8 and 160 gtL after standing for 24 hours, respectively. Singer and Chang (1989) reported
that the mean for TCA.A in the distribution systems for six utilities was 49 4 uglL, with values
ranging from 15-103 ugfL.
Fair et al. (1988) analyzed drinking water from three community water supplies for
chlorination by-products. TCAA concentrations reported for each of the plants ranged from <0.1-
54 tg/L in finished water at the plants and from <0.1-77 ug/L in the distribution systems.
Non.Drinldng Water
No information was found concerning the occurrence of TCAA in natural waters.
Because TCAA occurs in drinking water as a by-product of disinfection, it is not expected to be
found in significant quantities in raw water sources.
4.5 Chloroform
Chloroform, also known as trichioromethane, is a nonflammable, colorless liquid with a
sweet odor. It appears to be a natural product of the environment as it is found in some plants.
In industry, chloroform is used as a solvent, chemical intermediate, extractant, and dry cleaning
agent. It is used primarily in the manufacture of fluorocarbon-22 (chiorodifluoromethane) which
is used for refrigerants and fluoropolymer synthesis. Previous applications included uses as an
4-5
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Final 8f3192
anesthetic, in medicinal preparations, and an ingredient of grain fumigants. chloroform releases
to the environment are primarily due to volatilization from industrial uses, however, releases to
water occur from the chlorination of water and sewage and contamination of industrial effluents.
Due to its poor soil adsorptivity, chloroform may also leach into groundwater from spills and
other releases on land. Based on its high vapor pressure (246 mm Hg at 25 C) and moderate
water solubility (8000 mg/I.. at 20 C), chloroform releases to water and land will be lost mainly
by evaporation. Modeling studies indicate the volatilization half-life of chloroform in a lake,
pond, and river would be 9-10 days, 40 hours, and 36 hours, respectively. Chloroform adsorbs
poorly to sediments and can be biodegraded in water and soil (Howard, 1990).
Chloroform, the most prevalent trihalomethane in thinking water, occurs in public water
systems from the chlorination of drinking water and from the contamination of source water from
industrial uses. Chloroform is a by-product of the chlorination of naturally occurring organic
matter in raw water. Several water quality factors affect the formation of chloroform including
Total Organic Carbon (TOC), pH, and temperature. Surface water systems have higher
frequencies of occurrence and higher concentrations of chloroform than ground water systems
because humic and fulvic material are found primarily in surface water sources. Since residual
chlorine levels are maintained in water distribution systems for disinfection purposes, the
formation of chloroform continues throughout the distribution system (Stevens and Symons, 1977;
USEPA, 1980b).
Different treatment practices affect the formation of chloroform. The levels of chloroform
can be reduced, though not eliminated, when chloramines are used to disinfect. The reduction
is less, however, when ch loramination involves a pre-chlorination step where a free chlorine
residual is maintained through a portion of the water treatment process prior to the addition of
ammonia. Preozonation followed by chloramines substantially reduces the formation of
chloroform. Also, the use of chlorine dioxide is expected to produce lower levels of chloroform
than chlorine (USEPA, 1980b).
According to the EPA ’s Toxic Release Inventory, the total release of chloroform to
environmental media, due to manufacturing in 1988, was 26,604,039 lbs. A total of 1,094,441
lbs. was released to surface waters of 0.43% of the total release (USEPA, 1990).
Drinking Water
National Studies
Eight surveys were found which describe the national occurrence of chloroform in
drinking water. In 1975, the National Organics Reconnaissance Survey (NORS), conducted by
the EPA, collected drinking water samples from 80 cities nationwide. The survey sampled for
several organics including trihalomethanes at the water treatment facilities. Eighty percent of the
systems had surface water sources and the remaining 20% had ground water sources. The
median concentration for chloroform was 23 pg/L and the maximum level found was 311 pg/L.
NORS was performed prior to the Total Trihalomethane regulation; therefore. these results may
be higher than current levels (Symons et al.. 1975).
4-6
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Final 8/3/92
The National Organics Monitoring Survey (NOMS) was conducted by the EPA from
March 1976 to January 1977. In NOMS, 113 community water supplies were sampled at the
treatment plants during three phases. Surface water was the major source for 92 of the systems
and ground water was the major source for the remaining 21 systems. Two analytical methods
were employed that measured the chloroform concentrations at the time of sampling and
measured the maximum chloroform concentrations due to the reaction of all the chlorine residual.
Chloroform was detected, over the three phases, in 92% to 100% of the systems sampled. The
median concentrations of the three phases ranged from 22-54.5 ugfL. The maximum value found
was 540 ugfL NOMS was conducted before the enactment of the Total Trihalomethane
regulation; therefore, these results may be higher than current levels (Bull and Kopfler, 1990).
The Community Water Supply Survey (CWSS) was conducted by the EPA in 1978. The
survey examined over 1,100 samples representing over 450 water supply systems. The samples
were taken at the treatment plants and in the distribution systems. In the CWSS, 97% of the
surface water supplies and 34% of the ground water supplies were positive for chloroform. For
surface water supplies the mean of the positives and the overall median were 90 ug/L and 60
ugfL, respectively. The mean of the positives, for ground water supplies, was 8.9 ugfL and the
overall median was below the minimum reporting limit of 0.5 ugfL (Brass et aL., 1981).
The Rural Water Survey (RWS) was conducted between 1978 and 1980, by the EPA, to
evaluate the status of drinking water in rural America. Samples from over 2,000 households,
representing more than 600 rural water supply systems, were examined. In the RWS, 82% of
the surface water supplies and 17% of the ground water supplies were positive for chloroform.
For the surface water supplies the mean of the positives and the overall median concentrations
were 84 jig/L and 57 pg/L, respectively. For the ground water supplies the mean of the positives
was 8.9 ugfL and the overall median was below the minimum reporting limit of 0.5 1 ugfL (Brass,
1981).
The Ground Water Supply Survey (GWSS) was conducted from December 1980 to
December 1981, by the EPA, to develop data on the occurrence of volatile organic chemicals in
ground water supplies. Out of a total of 945 ground water systems, 466 systems were chosen
at random, while the remaining 479 systems were chosen on the basis of location near industrial,
commercial, and waste disposal activities. Samples were collected at or near the entry to the
distribution system. For chloroform, the median of the positives for the randomly chosen systems
serving above and below 10,000 people were 1.4 ugfL and 1.6 ug/L with the occurrence rate of
37.1% and 57%, respectively. The nor-randomly chosen systems had a median of the positives
of 1.9 ugfL and an occurrence rate of 53.2%. The maximum values for systems, random and
non-random, serving above and below 10,000 were 300 ug/L and 430 ug/L, respectively. The
90th percentile for chloroform in systems serving less than 10,000 people was 7.8 ug/L and in
systems serving greater than 10,000 it was 17 1 ug/L (Westrick et al., 1983).
The Technical Support Division (TSD) of the Office of Ground Water and Drinking Water
(OGWDW) maintains an unregulated contaminant database. For chloroform, the database
contains 5,806 samples taken at the treatment facilities from nineteen states between 1984 and
4-7
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Final 8/3/92
1991. The mean and median concentrations were determined to be 17 ug/L and 5 pg/L,
respectively (TSD, 1991).
Case studies of 35 water utilities nationwide, of which 10 were located in California,
sampled for chloroform in the clearwell effluent. Samples were taken for four quarters (spring,
summer, and fall in 1988 and winter in 1989). The median for all four quarters was 14 pgfL with
the medians of the individual quarters ranging from 9.6-15 ug/L The maximum value found was
130 ug/L. For all four quarters, 75% of the data was below 33 ug/L (Krasner et al., 1989b;
USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey,
conducted from October 1987 to March 1989. In this survey, chloroform was sampled for in
finished water at the treatment plant and in the distribution system. For surface- water systems,
the mean concentration in finished water for systems serving above and below 10,000 people was
38.9 ,.ig/L and 42.8 ug/L, with the 90th percentile of 74.4 g/L and 63.5 ugIL for 42 samples and
20 samples, respectively. In the distribution system, the mean was 58.7 1 ugfL and 77.2 ugfL for
plants serving above and below 10,000, with the 90th percentile concentration of 141.0 ug/L and
110.0 ug/L for 39 samples and 11 samples, respectively. The ground water systems serving less
than 10,000 had a mean chloroform concentration in finished water samples and distribution
system samples, respectively, of 2.8 ug/L and 3.6 ugfL for 7 observations and 5 observations,
with the 90th percentile of 10.3 ug/L and 9.4 ugfL For a single sample from ground water
systems serving greater than 10,000, the concentration at the plant and in the distribution system,
respectively, was 0.6 ug/L and 0.8 ugfL (TSD, 1992).
Regional/Local Studies
Fair et aL (1988) analyzed drinking water from three community water supplies for
chlorination by-products. chloroform concentrations reported for each of the plants ranged from
11-100 sgfL in finished water at the plants and from 21-160 ug/L in the distribution systems.
The EPA’s five-year Total Exposure Assessment Methodology (TEAM) study measured
the personal exposures of urban populations to a number of organic chemicals in air and drinking
water in several U.S. cities. As part of the study, running tap water samples, collected from
residences of nearly 850 study participants during the morning and the evening, were analyzed
for chloroform content. Exhibit 4.1 shows chloroform concentrations found in drinking water
from the five cities surveyed.
4-8
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Final 8/3/92
Exhibit 4.1 Chloroform in Tap Water from the EPA TEAM study (ugIL)
Location
Date Sampled
Sample
Size
Mean
Median
Maximum
E lizabethfBayonne,
New Jersey
Fall 1981
Summer 1982
Winter 1983
355
157
49
70
61
17
170
130
33
Los Angeles, CA
Winter 1984
Summer 1984
117
52
14
29
14
33
AntiochlPittsburgh,
California
Spring 1984
71
42
49
Devils Lake,
North Dakota
Fall 1982
24
0.46
1.4
Greensboro,
North Carolina
Fall 1982
24
43
91
Sources: Hartwell. et al. 1987
Wallace et aL, 1988
Wallace et aL, 1987
lJden and Miller (1983) sampled drinking water from two treatment plants in Amherst,
Massachusetts. Two sets of tap water samples were collected at each plant, with the first set of
samples analyzed immediately following collection and the second set allowed to sit for 24 hours
to mimic distribution levels. Chloroform concentrations were reportedly at 39.6 ugfL and 87.4
pgfL immediately after disinfection and 139 ug/L and 190 ug/L after standing for 24 hours,
respectively.
Howard (1990) in his literature review reported results from several additional surveys.
In a Federal survey of finished water supplies, chloroform was found to occur in 70.3% of
ground water supplies (Dyksen and Hess, 1982 in Howard, 1990). Coleman et al. (1976 in
Howard, 1990) reported that a survey of drinking water of five-cities found concentrations
ranging from 1-301 ugfL Drinking water from nine U.S. cities contained chloroform in 88.9%
of the samples, with concentrations ranging from not detected to 57 ug/L and a mean of the
positives of 10.4 ugIL (Heikes and Hopper, 1986 in Howard, 1990). Furlong and Ditri (1986 in
Howard, 1990) reported that a survey of chlorinated drinking water from 40 plants in Michigan
had a detection rate of 80%, with a range of not detected to 201.4 g/L. The mean of the
positives was 33.4 pgfL and the median was 16.7 ug/L.
Non-Drinking Water
The National Screening Program for Organics in Drinking Water (NSP), sponsored by the
EPA, was conducted from June 1977 to March 1981. The survey sampled 169 systems
4-9
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Final 813192
nationwide. Raw water samples were collected at the treatment facilities. In surface water
supplies, the mean and median chloroform concentration for 67 positives were 2.2 ug/L and 0.2
ug/L, respectively, with a maximum concentration of 75 sgIL. In ground water supplies, three
positive detections had a mean concentration of 0.2 ug/L, while supplies using a mixture of
surface and ground water had a mean of 0.3 ugfL for 8 positive detections (Boland, 1981).
The EPA’s 1975 National Organic Reconnaissance Survey (NORS), sampled raw water
sources of 80 U.S. water supplies. Of these 80 supplies, 16 had ground water sources and 64
had surface water sources. Based on the survey’s results, chloroform was detected in raw water
samples from 23 systems with the mean of the positives found to be 0.4 sgfL. Overall,
concentrations ranged from not detected to 1 ug/L, with the detection limit varying from 0.1-0.2
1 ug/L (Symons et aL, 1975).
Three additional surveys were found which analyzed groundwater for chloroform content.
The largest of these surveys collected samples from 1174 community wells and 617 private wells
throughout the state of Wisconsin. As of June 1984, chloroform was detected in 1.1% of the
community wells and 0.32% of the private wells (Krill and Sonzogni, 1986 in Howard, 1990).
The Arizona Department of Environmental Quality conducted a random of survey of Arizona
community water supply wells as part of an effort to determine the baseline water quality of its
groundwater supplies. A total of 40 wells from 3S systems, serving 1,000 or more people, were
sampled from July to September 1986, with 16 of, the wells .resampled in January 011987.
Chloroform concentrations were measured at a maximum concentration of 3.3 ug/L (Ellingson
and Redding, 1988). In a survey of groundwaters in New Jersey, conducted from 1977 to 1979,
chloroform concentrations ranged from 67-490 ugIL (Burmaster, 1982 in Howard, 1990)
Several studies were found which analyzed surface waters for chloroform content. Bellar
et at. (1974 in Wei et a!., 1985) reported that chloroform is present in lakes and streams in
concentrations ranging from 0.1-0.9 ug/L. The Ohio River Valley Water Sanitation Commission
(1982 in Howard, 1990) collected samples from 11 stations along the Ohio River Basin from
1980 to 1981. Chloroform was detected in 72% of the samples analyzed. with 832 samples
containing concentrations between 1-10 ug/L and 27 samples containing concentrations greater
than 10 ugIL. Ewing et a!. (1977 in Howard, 1990) reported that chloroform concentrations
ranged from 1-120 ugIL in samples collected from 204 sites located on 14 heavily industrialized
river basins in the United States, with an occurrence rate of 79%. A survey of 30 sites on the
Delaware River and its tributaries found chloroform concentrations above I ug/L in 93% of its
samples (DeWalle and Chian, 1978 in Howard, 1990). The Ohio River Valley Water Sanitation
Commission (1980 in Howard, 1990) found chloroform in 72% of 232 Ohio River samples. with
concentrations ranging from 0.1-22 ug/L.
4.6 Bromodichloromethane
Bromodichioromethane (BDCM) is a nonflammable, colorless liquid. In nature, it is
biosynthesized by a variety of marine algae where it is released to seawater and eventually to the
atmosphere. Commercial uses of BDCM are limited to its uses as a chemical intermediate for
4-10
-------
Firwi 8/3/92
organic synthesis and as a laboratory reagent. Due to its limited commercial uses, release of
BDCM from its commercial production and uses is not considered significant. Releases to the
environment from anthropogenic sources is predominantly the result of its formation during the
chlorination of drinking, waste, and cooling waters. BDCM has a relatively high vapor pressure
(50 mm Hg at 20°C) and a moderate solubility (4,700 mg/L at 22°C). Volatilization is the
principal mechanism for removal of BDCM from rivers and streams, with a half-life ranging from
33 minutes to 12 days. BDCM is considered to be moderately to highly mobile in soil and
therefore may leach into groundwaters. Results from laboratory screening tests indicate that
biodegradation may be a significant removal process where volatilization is not possible. BDCM
is not expected to adsorb significantly to soil and sediments (Koc of 53-251) (Howard, 1990).
BDCM occurs in public water systems that chlorinate water containing humic and fulvic
acids and bromine that can enter source waters through natural and anthropogenic means.
Several water quality factors affect the formation of BDCM including Total Organic Carbon
(TOC), pH, and temperature. Surface water systems have higher frequencies of occurrence and
higher concentrations of BDCM than ground water systems because organic material is found
primarily in surface water sources. Since chlorine is used as a residual in water distribution
systems for disinfection purposes, the formation of BDCM continues throughout the distribution
system (Stevens and Symons, 1977; Cooper et al., 1985; USEPA, 198Gb).
Different treatment practices affect the formation of BDCM. The levels of BDCM can
be reduced, though not eliminated, when chioramines are used to disinfect. The reduction is less,
however, when chioramination involves a pre-chiorination step where a free chlorine residual is
maintained through a portion of the water treatment process prior to the addition of ammonia.
Preozonation followed by chioramination substantially reduces the formation of BDCM, but
ozonation prior to chlorination may increase the formation of BDCM. Also, the use of chlorine
dioxide is expected to produce lower levels of BDCM than chlorine (Cooper et al. 1985; USEPA,
198Gb).
Drinking Water
National Studies
Eight national studies surveyed United States drinking water for BDCM. In 1975, the
National Or anics Reconnaissance Survey (NORS), conducted by the EPA, collected drinking
water samples from 80 cities nationwide. The survey sampled for several organics including
trihalomethanes at the water treatment facilities. BDCM was found in 98% of the systems
sampled. The median concentration for BDCM was 8 ug/L. The maximum level found was 116
4 ugfL. NORS was performed prior to the Total Trihalomethane regulation; therefore, these results
may be higher than current levels (Symons et al., 1975).
The National Organics Monitoring Survey (NOMS) was conducted by the EPA from
March 1976 to January 1977. In NOMS. 113 community water supplies were sampled during
three phases. Surface water was the major source for 92 of the systems and ground water was
the major source for the remaining 21 systems. Two analytical methods were employed that
4-11
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Final 8/3/92
measured the BDCM concentrations at the time of sampling and measured the maximum BDCM
concentrations due to the reaction of all the chlorine residual. BDCM was detected, over the
three phases, in over 90% of the systems sampled. The median concentrations of the three
phases ranged from 5.9-14 ug/L. The maximum value found was 183 ugh.. (Bull and Kopfler,
1990).
The Community Water Supply Survey (CWSS) was conducted by the EPA in 1978. The
survey examined over 1,100 samples representing over 450 water supply systems. The samples
were taken at the treatment plants and in the distribution systems. In the CWSS, 94% of the
surface water supplies and 33% of the ground water supplies were positive for BDCM. For
surface water supplies the mean of the positives and the overall median were 12 ug/L and 6.8
1 uglL, respectively. The mean of the positives, for ground water supplies, was 5.8 ug/L and the
overall median was below the minimum reporting limit of 0.5 ugfL (Brass et a!., 1981).
The Rural Water Survey (RWS) was conducted between 1978 and 1980, by the EPA, to
evaluate the status of drinking water in rural America. Samples from over 2,000 households,
representing more than 600 rural water supply systems, were examined. In the RWS, 76% of
the surface water supplies and 13% of the ground water supplies were positive for BDCM. For
the surface water supplies the mean of the positives and the overall median concentrations were
17 4 ug/L and 11 4 ug/L, respectively. For the ground water supplies the mean of the positives was
7.7 uglL and the overall median was below the minimum reporting limit of 0.5 ugfL (Brass,
1981).
The Ground Water Supply Survey (GWSS) was conducted from December 1980 to
December 1981, by the EPA, to develop data on the occurrence of volatile organic chemicals in
ground water supplies. Out of a total of 945 ground water systems, 466 systems were chosen
at random, while the remaining 479 systems were chosen on the basis of location near industrial,
commercial, and waste disposal activities. Samples were collected at or near the entry to the
distribution system. For BDCM, the median of the positives for the randomly chosen systems
serving above and below 10,000 people were 1.4 ug/L and 1.6 ugfL, with the occurrence rates
of 35.7% and 54.3%, respectively. The non-randomly chosen systems had a median of the
positives of 2.1 ug/L and an occurrence rate of 50.9%. The maximum values for systems,
random and non-random, serving above and below 10,000 were 110 ug(L and 79 ,ug/L,
respectively. The 90th percentile for BDCM in systems serving less than 10,000 people was 6.1
ug/L and in systems serving greater than 10,000 it was 9.2 ug/L (Westrick et al., 1983).
The Technical Support Division (TSD) of the Office of Ground Water and Drinking
Water (OGWDW) maintains an unregulated contaminant database. For BDCM, the database
contains 4,439 samples taken at the treatment facilities from nineteen states between 1984 and
1991. The mean and median concentrations were determined to be 5.6 pgfL and 3 glL,
respectively (TSD, 1991). -
Case studies of 35 water utilities nationwide, of which 10 were located in California,
sampled for BDCM in the clearwell effluent. Samples were taken for four quarters (spring,
summer, and fall in 1988 and winter in 1989). The median for all four quarters was 6.6 ug/L,
4-12
-------
Find 8/3/92
with the medians of the individual quarters ranging from 4.1-10 ug/L The maximum value
found was 82 ugfL. For all four quarters, 75% of the data was below 14 4 ug/L (Krasner et al.,
1989b; USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey,
conducted from October 1987 to March 1989. In this survey, BDCM was sampled for in finished
water at the treatment plant and in the distribution system. For surface water systems, the mean
concentration in finished water for systems serving above and below 10,000 people was 12.7
1 ug/L and 17.0 4 ugfL, with the 90th percentile of 25.0 ug/L and 29.5 ugfL for 42 samples and 20
samples, respectively. In the distribution system, the mean was 17.4 ig(L and 24.8 ug/L for
plants serving above and below 10,000, with the 90th percentile concentration of 35.3 ugfL and
51.0 ug/L for 39 samples and 11 samples, respectively. The ground water systems serving less
than 10,000 had a mean BDCM concentration in finished water samples and distribution system
samples, respectively, of 1.1 4 ug/L and 2.2 ug/L for 7 observations and 5 observations, with the
90th percentile of 2.6 ug/L and 5.4 ug/L. For a single sample from ground water systems serving
greater than 10,000, the concentration at the plant and in the distribution system, respectively,
was 0.2 ug/L and 0.4 ugfL (I’SD, 1992).
Re ionalfLocal Studies
Fair et al. (1988) analyzed drinking water from three community water supplies for
chlorination by-products. BDCM concentrations reported for each of the plants ranged from 7.5-
30 ug/L in finished water and from 9.9-36 ugIL in the distribution systems.
The EPA’s five-year Total Exposure Assessment Methodology (FEAM) study measured
the personal exposures of urban populations to a number of organic chemicals in air and drinking
water in several U.S. cities. As part of the study, running tap water samples were collected from
residences of nearly 850 study participants during the morning and the evening and analyzed for
BDCM content. Exhibit 4.2 shows BDCM concentrations found in drinking water from the five
cities surveyed.
Furlong and Ditri (1986 in Howard, 1990) detected BDCM in drinking water of 35 of 40
Michigan water treatment plants at a median concentration of 2.7 ugfL.
4-13
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Final 8/3/92
Exhibit 4.2 BDCM in Tap Water from the EPA TEAM study (pg/L)
Location
Date Sampled
Sample
Size
Mean
Median
Maximum
Elizabeth/Bayonne,
New Jersey
Fall 1981
Summer 1982
Winter 1983
355
157
49
14
14
5.4
23
54
16
Los Angeles, CA
Winter 1984
Summer 1984
117
52
11
20
12
24
AntiochfPittsburg,
California
Spring 1984
71
21
17
Devils Lake,
North Dakota
FaIl 1982
24
0.21
1.0
Greensboro,
North Carolina
FaLl 1982
24
7.1
11
Sources: Hartwell, et aL, 1987
Wallace et al., 1988
Wallace ci a!., 1987
Non-Drinking Water
The National Screening Program for Organics in Drinking Water (NSP), sponsored by the
EPA, was conducted from June 1977 to March 1981. The survey sampled 169 systems
nationwide. Raw water samples were collected at the treatment facilities. In surface water
supplies, the mean and median BDCM concentration for 23 positives were 2.8 ug/L and 0.4 pgfL,
respectively, with a maximum concentration of 37 ug/L. In one ground water supply sample
BDCM was found at 0.1 ,ug(L, while one sample from a supply using a mixture of surface and
ground water contained a level of 0.5 pg/L (Boland, 1981).
Two additional surveys were found which analyzed groundwater for BDCM. The Arizona
Department of Environmental Quality conducted a random survey of Arizona community water
supply wells as part of an effort to determine the baseline water quality of its groundwater
supplies. A total of 40 wells from 38 systems, serving 1,000 or more people, were sampled from
July to September 1986, with 16 of the wells resampled in January 1987. BDCM concentrations
were measured at a maximum concentration of 0.8 ugIL (Euingson and Redding, 1988). Fusillo
et al. (1985 in Howard, 1990) analyzed 315 wells in the Potomac-Raritan-Magothy aquifer,
adjacent to the Delaware River, for organic chemicals. BDCM was one of 27 organic chemicals
identified.
4-14
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Final 8/3/92
Several studies wçre found which analyzed surface waters for BDCM. The Ohio River
Valley Water Sanitation Commission (1982 in Howard, 1990) collected samples from 11 stations
along the Ohio River Basin from 1980 to 1981. BDCM was detected in 20.9% of the 4,972
samples analyzed, with most concentrations between 0.1-1.0ug/L. Ewing et al. (1977 in Howard,
1990) reported that surface water from 204 sites located on 14 heavily industrialized river basins
in the United States was analyzed for BDCM. BDCM was detected at 24 sites, with levels
between 1-12 ugfL. In 1981, BDCM was found at levels ranging from trace-0.025 ug(L and not
detected-0.02 ug/L at 16 stations on the Niagara River and 95 stations on Lake Ontario,
respectively (Kaiser et al., 1983 in Howard, 1990).
4.7 Dibromochloromethane
Dibromochioromethane (DBCM) is a nonflammable, colorless liquid. In nature, it is
biosynthesized by a variety of marine algae where it is released to seawater and eventually to the
atmosphere. Commercial uses of DBCM are limited to its uses as a chemical intermediate for
organic synthesis and as a laboratory reagent. Due to its limited commercial uses, release of
DBCM from its commercial production and uses is not considered significant. Releases to the
environment from anthmpogenic sources is predominantly the result of its formation during the
chlorination of drinking, waste, and cooling waters. DBCM has a relatively high vapor pressure
(76 mm Hg at 20 °C) and a moderate solubility (4,400 mgfL at 22°C). Volatilization is the
principal mechanism for removal of DBCM from rivers and streams, with a half-life ranging from
43 minutes to 16.6 days. DBCM is considered to be moderately to highly mobile in soil and
therefore may leach into groundwaters. Results from laboratory screening tests indicate that
biodegradation may be a significant removal process where volatilization is not possible. DBCM
is not expected to adsorb significantly to soil and sediments (Koc of 95-468) (Howard, 1990).
DBCM occurs in public water systems that chlorinate water containing humic and fulvic
acids and bromine that can enter source waters through natural and anthropogenic means.
Several water quality factors affect the formation of DBCM including Total Organic Carbon
(TOC), pH, and temperature. Surface water systems have higher frequencies of occurrence and
higher concentrations of DBCM than ground water systems because humic and fulvic material
are found primarily in surface water sources. Since chlorine is used as a residual in water
distribution systems for disinfection purposes, the formation of DBCM continues throughout the
distribution systems (Stevens and Symons, 1977; USEPA, 1980b; Cooper et a!., 1985).
Different treatment practices affect the formation of DBCM in drinking water. The levels
of DBCM can be reduced, though not eliminated, when chioramines are used to disinfect. The
reduction is less, however, when chioramination involves a pre-chiorination step where a free
chlorine residual is maintained through a portion of the water treatment process prior to the
addition of ammonia. Preozonation followed by chloramination substantially reduces the
formation of DBCM, but ozonation prior to chlorination may increase the formation of DBCM.
Also, the use of chlorine dioxide is expected to produce lower levels of DBCM than chlorine
(USEPA, 1980b; Cooper et al., 1985).
4-15
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Final 8/3/92
Drinking Water
National Studies
Eight national studies surveyed United States drinking water for DBCM. In 1975, the
National Organics Reconnaissance Survey (NORS), conducted by the EPA, collected drinking
water samples from 80 cities nationwide. The survey sampled for several organics including
trihalomethanes at the treatment facilities. DBCM was found in 90% of the systems sampled.
The median concentration for DBCM was 2 ug/L. The maximum level found was 100 1 ugfL.
NORS was performed prior to the Total Trihalomethane regulation; therefore, these results may
be higher than current levels (Symons et al., 1975).
The National Organics Monitoring Survey (NOMS) was conducted by the EPA from
March 1976 to January 1977. In NOMS, 113 community water supplies were sampled during
three phases. Surface water was the major source for 92 of the systems and ground water was
the major source for the remaining 21 systems. Two analytical methods were employed that
measured the DBCM concentrations at the time of sampling and measured the maximum DBCM
concentrations due to the reaction of all the chlorine residual. DBCM was detected, over the
three phases, in 73% of the systems sampled. The median concentrations of the three phases
ranged from under the detection limit to 3 ug/L. The maximum value found was 280 ug/L (Bull
and Kopfler, 1990).
The Community Water Supply Survey (CWSS) was conducted by the EPA in 1978. The
survey examined over 1,100 samples representing over 450 water supply systems. The samples
were taken at the treatment plants and in the distribution systems. In the CWSS, 67% of the
surface water supplies and 34% of the ground water supplies were positive for DBCM. For
surface water supplies the mean of the positives and the overall median were 5.0 1 ugIL and 1.5
ug(L, respectively. The mean of the positives, for ground water supplies, was 6.6 4 ugfL and the
overall median was below the minimum reporting limit of 0.5 pg/L (Brass et al, 1981).
The Rural Water Survey (RWS) was conducted between 1978 and 1980, by the EPA, to
evaluate the status of drinking water in rural America. Samples from over 2,000 households,
representing more than 600 rural water supply systems, were examined. In the RWS, 56% of
the surface water supplies and 13% of the ground water supplies were positive for DBCM. For
the surface water supplies, the mean of the positives and the overall median concentrations were
8.5 ug/L and 0.8 ug/L, respectively. For the ground water supplies, the mean of the positives was
9.9 pgfL and the overall median was below the minimum reporting limit of 0.5 ugfL (Brass,
1981).
The Ground Water Supply Survey (GWSS) was conducted from December 1980 to
December 1981, by the EPA, to develop data on the occurrence of volatile organic chemicals in
ground water supplies. Out of a total of 945 ground water systems, 466 systems were chosen
at random, while the remaining 479 systems were chosen on the basis of location near industrial,
commercial, and waste disposal activities. Samples were collected at or near the entry to the
distribution system. For DBCM, the median of the positives for the randomly chosen systems
4-16
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Final 8/3/92
serving above and below 10,000 people were 2.1 ugfL and 2.9 1 ug/L with the occurrence rates of
31.1% and S 1.6%, respectively. The non-randomly chosen systems had a median of the positives
of 3.9 pgfL and an occurrence rate of 46.3%. The maximum values for systems, random and
non-random, serving above and below 10,000 were 59 ugfL and 63 ugfL, respectively. The 90th
percentile for DBCM in systems serving less than 10,000 people was 5.6 ug(L and in systems
serving greater than 10,000 it was 9.2 4 ugfL (Westrick et al., 1983).
The Technical Support Division (TSD) of the Office of Ground Water and Drinking Water
(OGWDW) maintains an unregulated contaminant database. For DBCM, the database contains
4,439 samples taken at the treatment facilities from nineteen states between 1984 and 1991. The
mean and median concentrations were determined to be 3.0 ug/L and 1.7 ugfL, respectively
(TSD, 1991).
Case studies of 35 water utilities nationwide, of which 10 were located in California,
sampled for DBCM in the clearwell effluent. Samples were taken for four quarters (spring,
summer, fall in 1988 and winter in 1989). The median for all four quarters was 3.6 ugIL with
the medians of the individual quarters ranging from 2.6 to 4.5 ugfL. The maximum value found
was 63 ug(L. For all four quarters, 75% of the data was below 9.1 ug(L (Krasner et aL, 1989b;
USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey
conducted from October 1987 to March 1989. In this survey, DBCM was sampled for in finished
water at the treatment plant and n the distribution system. For surface water systems, the mean
concentration in finished water for systems serving above and below 10,000 people was 4.7 ugfL
and 6.9 1 ug(L, with the 90th percentile of 13.8 pgfL and 24.2 1 ugIL for 42 samples and 20 samples,
respectively. In the distribution system, the mean was 6.3 pgfL and 10.4 4 ugfL for plants erving
above and below 10,000, with the 90th percentile concentration of 17.3 ugfL and 35.0 ug/L for
39 samples and 11 samples, respectively. The ground water systems serving less than 10,000 had
a mean DBCM concentration in finished water samples and distribution system samples,
respectively, of 0.6 ugfL and 1.8 ug/L for 7 observations and 5 observations, with the 90th
percentile of 1.0 ugfL and 3.6 ug(L. For systems serving greater than 10,000, DBCM was not
detected in single samples taken at the plant and from the distribution system based on a
detection limit of 0.2 gfL (TSD, 1992).
RegionalfLocal Studies
Fair et al. (1988) analyzed drinking water from three community water supplies for
chlorination by-products. DBCM concentrations reported for each of the plants ranged from
<0.5-19 ugfL in finished water at the plant and from <0.5 23 ug(L in the distribution systems.
The EPA’s five-year Total Exposure Assessment Methodology (TEAM) study measured
the personal exposures of urban populations to a number of organic chemicals in air and drinking
water in several .U.S. cities. As part of the study, running tap water samples were collected from
residences of nearly 850 study participants during the morning and the evening and analyzed for
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Final 8/3/92
DBCM content. Exhibit 4.3 shows DBCM concentrations found in drinking water from the five
cities surveyed.
Exhibit 4.3 DBCM in Tap Water from the EPA TEAM study ( g/L)
Location
Date Sampled
Sample
Size
Mean
Median
Maximum
Elizabeth/Bayonne,
New Jersey
Fall 1981
Summer 1982
Winter 1983
355
157
49
2.4
2.1
1.4
8.4
7.2
3
Los Angeles, CA
Winter 1984
Summer 1984
117
52
9.4
28
11
32
AntiochfPittsburg,
California
Spring 1984
71
8
6.4
Devils Lake,
North Dakota
Fall 1982
24
0.09
0.45
Greensboro,
North Carolina
FaIl 1982
24
1.2
1.9
Sources: Hartwell, ci aL, 1987
Wallace et al., 1988
Wallace et aL, 1987
Furlong and Ditri (1986 in Howard, 1990) detected DBCM in drinking water of 30 of 40
Michigan water treatment plants at a median concentration of 2.2 pg(L.
Non-Drinking Water
Two surveys were found which analyzed groundwater for DBCM. The Arizona
Department of Environmental Quality conducted a random survey of Arizona community water
supply wells as part of an effort to determine the baseline water quality of its groundwater
supplies. A total of 40 wells from 38 systems, serving 1,000 or more people, were sampled from
July to September 1986, with 16 of the wells resampled in January of 1987. DBCM
concentrations were measured at a maximum concentration of 1.9 ug/L (Ellingson and Redding,
1988). Fusillo et al. (1985 in Howard, 1990) analyzed 315 wells in the Potomac-Raritan-
Magothy aquifer, adjacent to the Delaware River, for organic chemicals. DBCM was one of 27
organic chemicals identified.
Several studies were found which analyzed surface waters for DBCM. The Ohio River
Valley Water Sanitation Commission (1982 in Howard, 1990) collected samples from .11 Stations
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Final 8/3/92
along the Ohio River Basin from 1980 to 1981. DBCM was detected in 9.8% of the 4,972
samples analyzed, with most concentrations found between 0.1-1.0 ugfL. In 1981, DBCM was
found at levels ranging from trace-0.015 ug/L and not detected-0.63 4 ug/L at 16 stations on the
Niagara River and 95 stations on Lake Ontario, respectively (Kaiser et al., 1983 in Howard,
1990).
4.8 Bromoform
Bromoform or tribromomethane is a nonflammable, colorless, heavy liquid with a sweet
chloroform like odor. The compound is reasonably stable toward chemical reactions under most
environmental conditions. Bromoform is used as a chemical intermediate in organic synthesis;
a solvent for waxes, greases, and soil; and an ingredient in fire-resistant chemicals. As a
pharmaceutical, it is used as a sedative and antitussive and as a heavy-dense liquid, it is used as
a gauge-fluid and in solid separations. Due to its relatively high vapor pressure (5.6 mm Hg at
25 °C) and its moderate solubility in water (3.2 gmIL at 30 °C), bromoform is expected to be lost
from rivers and streams primarily through volatilization. In a model river 1 m deep, flowing at
1 rn/sec. and with a wind velocity of 3 mlsec, the volatilization half-life was calculated to be 6.7
hours. Hydrolysis is not an important fate process for bromoform based on a hydrolysis rate of
3.2 x 1011 sec-i (25°C and pH 7) which corresponds to a half-life of 686 years. Its Koc values
of 282 and 100 indicate that bromoform should not sorb significantly onto sediments and soils.
It is expected to be highly mobile in soil: therefore, leaching to groundwater may occur.
Laboratory screening tests suggests biodegradation of bromoform in water may be a significant
removal process (USEPA, 1989).
Bromoform occurs in public water supplies that chlorinate .drinking water containing
humic and fulvic acids and bromine that can enter source waters through natural and
anthropogenic means. Bromide enters source water from its presence in geological formations
and from saltwater intrusion. In addition, bromide enters the environment from the agricultural
use of methyl bromide and the presence of ethylene dibromide in leaded gasoline. Several water
quality factors affect the formation of bromoform including Total Organic Carbon (TOC), pH,
and temperature. Surface water systems are expected to have higher frequencies of occurrence
and higher concentrations of trihalomethanes than ground water systems due to the presence of
organic material; however, the levels of bromoform in ground water supplies are found to be the
same or higher than the levels in surface water supplies due to the higher occurrence of bromide
in ground water sources. Since chlorine is used as a residual in water distribution systems for
disinfection purposes, the formation of bromoform continues throughout the distribution systems
(Stevens and Symons, 1977; Cooper et al., 1985).
Different treatment practices affect the formation of bromoform. The levels of bromoform
can be reduced, though not eliminated, when chloramines are used to disinfect. The reduction
is less, however, when chloramination involves a pre-chlorination step where a free chlorine
residual is maintained through a portion of the water treatment process prior to the addition of
ammonia. Preozonation followed by chioramines substantially reduces the formation of
bromoform, but ozonation prior to chlorinanon may increase the formation of bromoform. Also.
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Final 8/3/92
the use of chlorine dioxide is expected to produce lower levels of bromoform than chlorine
(Cooper et al., 1985).
According to the EPA’s Toxic Release Inventory, the total release of bromoform to
environmental media, due to manufacturing in 1988, was 8,600 lbs through surface water
discharges alone (IJSEPA, 1990).
Drinking Water
National Studies
Bromoform occurrence in United States drinking water was described in eight surveys.
In 1975, the National Organics Reconnaissance Survey (NORS), conducted by the EPA, collected
drinking water samples from 80 cities nationwide. The survey sampled for several organics
including trihalomethanes at the water treatment facilities. The median concentration for
bromoform was below the detection limit of approximately 5 ug/L. The maximum level found
was 92 ugfL. NORS was performed prior to the Total Trihalomethane regulation; therefore, these
results may be higher than current levels (Symons et al., 1975).
The National Organics Monitoring Survey (NOMS) was conducted by the EPA from
March 1976 to January 1977. In NOMS, 113 community water supplies were sampled during
three phases. Surface water was the major source for 92 of the systems and ground water was
the major source for the remaining 21 systems. Two analytical methods were employed that
measured the bromoforrn concentrations at the time of sampling and measured the maximum
bromoform concentrations due to the reaction of all the chlorine residual. The median
concentrations of the three phases all ranged below the detection limit of 0.3 pgIL. The
maximum value found was 280 ug/L. NOMS was conducted before the enactment of the Total
Trihalomethane regulation; therefore, these results may be higher than current levels (Bull and
Kopfler, 1990).
The Community Water Supply Survey (CWSS) was conducted by the EPA in 1978. The
survey examined over 1,100 samples representing over 450 water supply systems. The samples
were taken at the treatment plants and in the distribution systems. In the CWSS, 13% of the
surface water supplies and 26% of the ground water supplies were positive for bromoform. For
surface water supplies the mean of the positives and the overall median were 2.1 ug/L and <1.0
ug./L, respectively. The mean of the positives, for ground water supplies, was 11 4 ugfL and the
overall median was below the minimum reporting limit of 0.5 ug/L (Brass et al., 1981).
The Rural Water Survey (RWS) was conducted between 1978 and 1980, by the EPA. to
evaluate the status of drinking water in rural America. Samples from over 2,000 households.
representing more than 600 rural water supply systems, were examined. In the RWS, 18% of
the surface water supplies and 12% of the ground water supplies were positive for bromoform.
For the surface water supplies the mean of the positives and the overall median concentrations
were 8.7 g/L and <0.5 4 ug/L, respectively. For the ground water supplies the mean of the
4-20
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Final 8/3/92
positives was 12 WL and the overall median was below the minimum reporting limit of 0.5 ugfL
(Brass, 1981).
The Ground Water Supply Survey (GWSS) was conducted from December 1980 ‘to
December 1981, by the EPA, to develop data on the occurrence of volatile organic chemicals in
ground water supplies. Out of a total of 945 ground water systems, 466 systems were chosen
at random, while the remaining 479 systems were chosen on the basis of location near industrial,
commercial, and waste disposal activities. Samples were collected at or near the entry to the
distribution system. For bromoform, the median of the positives for the randomly chosen
systems serving above and below 10,000 people were 2.4 gfL and 3.8 4 ug/L with the occurrence
rates of 15.7% and 30.6%, respectively. The non-randomly chosen systems had a median of the
positives of 4.2 ug/L and an occurrence rate of 30.9%. The maximum values for systems,
random and non-random, serving above and below 10,000 were 68 pg/L and 110 ug/L,
respectively. The 90th percentile for DBCM in systems serving less than 10,000 people was 4.1
pg/L and in systems serving greater than 10,000 it was 8.3 4 ug/L (Westrick et aL, 1983).
The Technical Support Division (TSD) of the Office of Ground Water and Drinking Water
(OGWDW) maintains an unregulated contaminant database. For bromoform, the database
contains 1,409 samples from nineteen states at the treatment facilities between 1984 and 1991.
The mean and median concentrations were determined to be 2.5 1 ug’L and 1 ug/L, respectively
(TSD, 1991).
Case studies of 35 water utilities nationwide, of which 10 were located in California.
sampled for brornoform in the clearwell effluent. Samples were taken for four quarters (spring,
summer, and fall in 1988 and winter in 1989). The median for all four quarters was 0.57 ug/L,
with the medians of the individual quarters ranging from 0.33-0.88 1 ug/L. The maximum value
found was 72 pg/L. For all four quarters, 75% of the data was below 2.8 ugfL (Krasner et al.,
1989b; USEPA and AMWA, 1989).
The EPA’s Technical Support Division (TSD) has compiled a database on data from its
disinfection by-products field studies. The studies included a chlorination by-products survey,
conducted from October 1987 to March 1989. In this survey, bromoform was sampled for in
finished water at the treatment plant and in the distribution system. For surface water systems,
the mean concentration in finished water for systems serving above and below 10,000 people was
0.7 ug/L and 0.9 4 ug/L, ith the 90th percentile of 1.5 g/L and 4.9 ugfL for 42 samples and 20
samples, respectively. In the distribution system, the mean was 0.8 pg/L and 1.4 ugfL for plants
serving above and below 10,000, with the 90th percentile concentration of 3.1 ugfL and 5.1 ug/L
for 39 samples and 11 samples, respectively. The ground water systems serving less than 10,000
had a mean bromoform concentration in finished water samples and distribution system samples.
respectively, of 0.6 g/L and 2.3 g/L for 7 observations and 5 observations, with the 90th
percentile of 2.6 ug/L and 10.0 ug/L. For systems serving greater than 10,000, bromoform was
not detected in single samples taken at the plant and from the distribution system based on a
detection limit of 0.2 ug/L (TSD. 1992).
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Fliwi 8/3/92
Regional/Local Studies
The EPA’s five-year Total Exposure Assessment Methodology (TEAM) study measured
the personal exposures of urban populations to a number of organic chemicals in air and drinking
water in several U.S. cities. As part of the study, drinking water samples from the homes of 188
individuals chosen from Los Angeles and the Antioch/Pittsburg, California areas were sampled
for bromoform in 1984. Running tap water samples were collected in the homes of each
individual in the morning and the evening of the study day. In Los Angeles, 117 residences were
sampled in the winter. Bromoform was found at a mean level of 0.08 1 ug/L and a median of 0.54
gfL. In the summer, the mean and median for samples from 52 residences was 8 ug/L and 3.0
ug/L. In Antioch, samples were collected from 71 residences, with a mean of 0.8 1 ug(L and a
median of 0.58 ug/L (Hartwell, et al., 1987 and Wallace Ct al., 1988).
The EPA’s Region V Organics survey sampled finished water from 83 sites. Bromoform
was found at a median concentration of 1 1 ug/L and a maximum level of 7 1 ug/L. A total of 14%
of the locations sampled contained detectable levels of bromoform (USEPA, 1980a in USEPA,
1989). Furlong and Ditri (1986 in USEPA, 1989) reported that a survey of 40 plants in Michigan
had a median bromoform concentration of 0.1 6 ug/L, with a 7.5% detection rate. Kelley (1985
in USEPA, 1989) sampled 18 drinking water plants in Iowa. Bromoform was detected in 50%
of the samples with a range of 1.0-10 4 ug/L. Fair et al (1988) analyzed drinking water from three
community water supplies for chlorination by-products. Bromoform concentrations reported for
each of the plants ranged from <0.5-2.5 4 ugIL in finished water at the plants and from <0.5.3.1
ug/L in the distribution systems.
Non-Drinking Water
The EPA’s 1975 National Organic Reconnaissance Survey (NORS), sampled raw water
sources of 80 U.S. water supplies. Of these 80 supplies, 16 had ground water sources and 64
had surface water sources. Based on the survey’s results, bromoform was detected in raw water
samples from 2 systems at concentrations of 0.2 and 0.3 ug/L. The detection limit varied from
0.1-0.4 pg/L (Symons et al., 1975).
Three additional surveys were found which analyzed groundwater for bromoform. The
largest of these surveys collected groundwater samples from sites New Jersey from 1977 to 1979.
Out of 1,072 samples tested, 22% were positive for bromoform (Page, 1981 in USEPA, 1989).
Concentrations ranged from the minimum reportable concentration of 0.1-34.7 ug/L (Burmaster,
1982 in USEPA, 1989). The Arizona Department of Environmental Quality conducted a random
survey of Arizona community water supply wells as part of an effort to determine the baseline
water quality of its groundwater supplies. A total of 40 wells from 38 systems, serving 1,000
or more people, were sampled from July to September 1986, with 16 of the wells resampled in
January 1987. Bromoform concentrations were measured at a maximum concentration of 5.4
ug/L (Ellingson and Redding, 1988). Rao et al. (1985 in USEPA, 1989) reported that bromoform
was detected in groundwater from Delaware at a concentration of 20 ug/L.
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Final 813/92
A total of six studies were found which analyzed only surface waters for bromoform. In
a survey of surface waters located near industrial sites, a total of 204 water samples were
analyzed. Bromoform was detected in 3% of the samples (Helz, 1980 in USEPA, 1989). In a
survey of surface waters in New Jersey, 604 samples were collected from 1977 to 1979.
Bromoform was detected at 32.6% of the sites sampled, with a maximum reported concentration
of 3.7 ugfL (Page, 1981 in USEPA, 1989). Veenstra and Schnoor (1980 in USEPA, 1989)
reported that bromoform levels in the Iowa River from October 1977 through October 1978
ranged from <0.5-6 ugfL, with an average concentration of 1.7 ug/L. The detection limit was
0.5 ug/L. In 1981, 17 stations along the lower Niagara River detected bromoform in 35.3% of
water samples analyzed, with levels ranging from trace-6 ng/L (Kaiser et al., 1983 in USEPA,
1989). Bromoform was detected in 12.2% of water sampled from Lake Ontario in 1981.
Concentrations ranged from trace-0.007 ug/L (Kaiser et aL., 1983 in USEPA, 1989). DeWalle
and Chian (1978 in USEPA, 1989) found bromoform in 7% of 30 water samples collected from
the Delaware river basin in February, 1976.
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Final 8/3/92
5. References
Anderson, A.C.; Reimers, R.S.; DeKernion, P. “A Brief Review of the Current Status of
Alternatives to Chlorine Disinfection of Water”; A.JPH; Vol. 72; November, 1982; pp.
1290- 1293.
AWWA; American Water Works Association Disinfection Survey, 1991. Database.
AWWA “Final Report: Effect of Coagulation and Ozonation on the Formation of Disinfection
By-Products”; Prepaied by James M. Montgomery, Inc., Prepared for American Water
Works Association - Water Industry Technical Action Panel, January, 1992; PP. 5-3 to
5-4.
Bellar, T.A.; Litchenburg,. J.J.; Kroner, R.C. “The Occurrence of Organohalide in Finished
Drinking Water,” J. Amer. Water Work Assoc., Vol. 66, 1974, p. 703. Cited in Wel et
al. 1985.
Boland, P.A. “National Screening Program for Organics in Drinking Water Part II: Data”; SRI
International. Prepared for U.S. Environmental Protection Agency under Contract No. 68-
01-4666; March, 1981.
Brass, H.J, “Rural Water Surveys Organics Data”; Drinking Water Quality Assessment Branch,
Technical Support Division, Office of Drinking Water, U.S. Environmental Protection
Agency. Memo to Hugh Hanson, Science and Technology Branch, CSD, ODW, U.S.
Environmental Protection Agency
Brass, H.J.; Weisner, M.J.; Kingsley, B.A. “Community Water Supply Survey: Sampling and
Analysis for Purgeable Organics and Total Organic Carbon (Draft)”; American Water
Works Assoc. Annual Meeting, Water Quality Division; June 9, 1981.
Bull, R.J.; Kopfler, F.C. “Health Effects of Disinfectants and Disinfection By-Products”;
Prepared for: AWWA Research Foundation, August, 1990.
Burmaster, D.E. “The New Pollution-Groundwater Contamination,” Environ.; Vol. 24; 1982; vip.
6-13, 33-6. Cited in USEPA, 1989 and Howard, 1990.
Coleman, W.E. et al. “Analysis and Identification of Organic Substances in Water”; L. Keith Ed.,
Ann Arbor Michigan; Ann Arbor Press; 1976; pp. 305-27. Cited in Howard, 1990.
Cooper, W.J.; Zika, R.G.; Steinhauer, M.S. “Bromide-Oxidant Interactions and THM Formation:
A Literature Review”; Journal AWWA; April, 1985; pp. 116-121.
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Final 813192
DeWalle, F.B.; Chian, S.K. “Presence of Trace Organics in the Delaware River and Their
Discharge by Municipal and Industrial Sources,” Proc. md. Waste Conf., Vol. 32, 1978,
pp. 903-919. Cited in USEPA, 1989 and Howard, 1990.
Dyksen, i.E.; Hess, A.F.; I. Amer. Water Works Assoc.; 1982; pp. 392-403. Cited in Howard,
1990.
Ellingson, S.B.; Redding, M.B. “Random Survey of VOC’s, Pesticides and Inorganics in
Arizona’s Drinking Water Wells”; Arizona Department of Environmental Quality,
Phoenix, Arizona. In: Proceedings of the FOCUS Conference on Southwestern Ground
Water Issues, National Water Well Association; 1988; pp. 223-247.
Ewing, RB. et a!. “Monitoring to Detect Previously Unrecognized Pollutants in Surface Waters,”
EPA-560/6-77-015, 1977. Cited in Howard, 1990.
Fair, P.S.; Barth, R.C.; Flesch, J.J.; Brass, H.J. “Measurement of Disinfection By-Products in
Chlorinated Drinking Water,” Proc. - Water Qual. Technol. Conf., Vol. 15, 1988, pp, 339-
53.
Furlong, E.A.N.; Ditri, F.M. “Trihalornethane Levels in Chlorinated Michigan Drinking Water,”
EcoL Model, Vol. 32, 1986, pp. 215-225. Cited in USEPA, 1989 and Howard, 1990.
Fusillo, T.V. et al.; Groundwater, Vol. 23, 1985; pp. 354-60. Cited in Howard, 1990.
Glaze, W.H. “Summary of Workshop on Ozonation By-Products” from UCLA School of Public
Health’s Workshop on Ozonation By-Products; January 13-15, 1988; Los Angeles,
California; March 18, 1988.
Gordon, 0.; Slootmaekers, B.; Tachiyashiki, S.; Wood, D.W. “Minimizing Chlorite Ion and
Chlorate Ion in Water Treated With Chlorine Dioxide,” Jour. Am. Water Works Assoc.,
Vol. 82, 1990, pp. 160-165. Cited in Bull and Kopfler, 1990.
Hartwell, T.D.; Pellizzari, E.D.; Perritt, R.L.; Whitmore, R.W.; Zelon, H.S.; Sheldon, L.S.;
Sparacino, C.M.; Wallace, L. “Results from the Total Exposure Assessment Methodology
(TEAM) Study in Selected Communities in Northern and Southern California,” Atmos.
Environ., 1987, Vol. 21, No. 9, pp. 1995-2004.
Heikes, D.L.; Hopper, M.L.; J. Assoc. Off Anal. Chem.; Vol. 69; 1986; pp. 990-8. Cited in
Howard, 1990.
Helz, G.R. “Anthropogenic Cl and C2 Halocarbons: Potential Application as Coastal Water-
Mass Tracers”; En: Hydrocarbon Halo. Hydrocarbon Aquaac Environ., B.K. Afghan and
D. Mackey, ED., Plenum Press, NY; pp. 435-444. Cited in USEPA, 1989.
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Howard, P.H. “Handbook of Environmental Fate and Exposure Data for Organic Chemicals”;
Lewis Publishers, Chelsea, Ml; Vol. 2; 1990; PP. 40-47.
Jacangelo, J.G.; Patania, N.L; Reagan, K.M.; Aieta, E.M.; Krasner, S.W.; McGuire, M.J.
“Ozonation: Assessing Its Role in the Formation and Control of Disinfection By-
Products”; Journal AW’WA; August, 1989; pp. 74-84.
Johnson, J.D.; Jensen, J.N. “THM and TOX Formation: Routes, Rates, and Precursors”; Journal
AWWA; April, 1986; pp. 156-162.
Jolley, R.L.; Carpenter, J.H. “A Review of the Chemistry and Environmental Fate of Reactive
Oxidant Species in Chlorinated Water,” In: Water Chlorination, Vol. 4, 1982; pp. 3-47.
Kaiser, K.L.E.; Comba, M.E.; Huneault, H. “Volatile Halocarbon Contaminants in the Niagara
River and in Lake Ontario,” J. Great Lakes Res., Vol. 9, 1983, pp. 212.213. Cited in
USEPA, 1989 and Howard, 1990.
Kelley, R.D. “Synthetic Organic Compounds Sampling Survey of Public Water Supplies,” NTIS
PB85-214427, 1985, p. 1-32. Cited in USEPA, 1989.
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