PRELIMINARY ASSESSMENT OF
SUSPECTED CARCINOGENS IN
DRINKING WATER
(Appendices j
INTERIM REPORT TO CONGRESS
\
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
JUNE 1975
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SUSPECTED CARCINOGENS IN DRINKING WATER
(Appendices)
Interim Report to Congress
Environmental Protection Agency
Washington, D. C.
June 1975
ivhi3.,;,:£;;7AL PROTECTION
W. L 08817
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TABLE OF CONTENTS
I. Inventory of Organics Presently Identified in
Drinking Uater 1
II. National Organics Reconnaissance Survey 12
III. Organic Chemicals Found in Industrial Effluents 101
IV. Monitoring for Radiation in Drinking Water 123
V. Analysis of Inorganic Chemicals in Water
Samples 129
VI. Preliminary Results of Pilot Plants to Remove
Water Contaminants 147
VII. Health Effects Caused by Exposure to Drinking Water
Contaminants . . 199
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APPENDIX I
INVENTORY OF ORGANICS PRESENTLY IDENTIFIED IN DRINKING WATER
Prepared By
Judith L. Mullaney
Robert G. Tardiff
Water Supply Research Laboratory
National Environmental Research Center
Office of Research and Development
Cincinnati, Ohio
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INVENTORY OF ORGANICS PRESENTLY IDENTIFIED IN DRINKING WATER
The following list of 187 compounds was compiled from an exhaustive
search of the chemical literature and from EPA reports generated from
the Agency's analytical activities. These compounds were identified from
only a handful of public water supplies and do not constitute a defin-
itive list of all compounds in all supplies. Because of the restrictive
nature of the analytic systems employed to generate these identities, the
list also is not inclusive of all compounds present in the water samples
analyzed. These identifications represent the result of single or dupli-
cate "grab" samples and, consequently, cannot be used to conclude contin-
uous occurrence. Likewise, fluctuations in concentrations with time
cannot be determined unequivocally from these same samples.
The terminology used in the list is not uniform because caution was
taken to use the terminology employed by the investigator, regardless
of the nomenclature system. For compounds identified by Water Supply
Research Laboratory analysts, the chemical abstract names were assigned
and used on the list.
The concentrations listed are to be considered minimum ranges. The
values represent those reported by the analysts; however, in most cases,
the values reflect concentrations in the extracted samples with extra-
polation to the volume of water employed for the extraction. Since, for
most quantification, the recovery data were not generated for the various
extraction steps, the values must be considered minimum concentrations
in the tap water samples analyzed.
This list of organics identified from potable water is being contin-
uously updated, and information concerning the chemical properties and
toxicity of these agents is being assembled and evaluated. Appendix VII(a)
provides additional information about these compounds.
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REFERENCES
1. Industrial Pollution of the Lower Mississippi River in Louisiana.
U. S. Environmental Protection Agency, Region VI, Dallas, Texas.
Surveillance and Analysis Division, April 1972.
2. Progress Report: Identification of Hazardous Materials, Lower
Mississippi River Basin. U. S. Department of Interior, Federal
Water Quality Administration, Lower Mississippi River Basin Field
Station, October 1970.
3. Burnham, A. K., Calder, G. V., Fritz, J. S., Junk, 6. A., Svec, H. J.
and Vick, R. Trace organics in water: their isolation and identifi-
cation. Journal American Water Works Assn. 65(11): 722-25, 1973.
Iowa State University, Ames, Iowa.
4. Deinzer, Max. Informal memorandum - Recovery from Merrimac River,
Lawrence, Massachusetts. WSRL, NERC-Cinti., Dec. 1972.
5. Burnham, A. K., Calder, G. V., Fritz, J. S., Junk, G. A., Svec, H. J.
and Willis, R. Identification and estimation of neutral organic
contaminants in potable water. Anal. Chem. 44(1) :139-41. 1972
6. Kleopfer, Robert D. and Fairless, Billy J. Characterization of or-
ganic components in municipal water supply. Environ^Sci. and Tech.
£:1036, Nov. 1972.
7. Friloux, James (Acting Chief). Petrochemical wastes as a water
pollution problem in the Lower Mississippi River. Lower Mississippi
Basin Office, Water Quality Office, EPA, Baton Rouge, Louisiana,
Oct. 1971. (Submitted to Senate Subcommittee on air and water
pollution, New Orleans, Louisiana - April 5, 1971.)
8. Tardiff, Robert G. and Deinzer, M. Toxicity of organic compounds in
drinking water. Proceedings of 15th Water Quality Conference,
Feb. 7-8, 1973, University of Illinois, pp.23-27.
9. Finger, James H. Chemical Services Branch, Region IV, EPA, Surveil-
lance and Analysis Division, March 16, 1973. Correspondence to
W. Bowman Crum, Jr. of Water Pollution Control Division, South
Carolina Pollution Control Authority, Columbia, S. Carolina 29211.
10. Finger, James H. Chemical Services Branch, Region IV, EPA Surveil-
lance and Analyses Division, March 16, 1973. Correspondence (to)
Thos. C. Kurimcak, S. Carolina State Board of Health, Columbia,
S. Carolina.
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11. Buhler, Donald R., Rasmusson, M. E. and Nakahue, H. S. Occurence
of hexachlorophene and pentachlorophenol in sewage and water.
Envir. Sci. and Tech. 7(10):929-34, Oct. 1973.
12. Miller, S. S. (Mg. Ed.). Are you drinking biorefractories, too?
Env. Sci and Tech. 7:14, 1973
13. Kleopfer, Robert D., Kansas (Region VII). Correspondence (to)
Dr. L. E. Harris, NERC-Cincinnati, Sept. 19, 1973. EPA-Mass Spec-
trometer Users' Group Newsletter #5, Sept. 1973.
14. Deinzer, M., Melton, R., Mitchell, D., Kopfler, F. and Coleman, E.
Trace organic contaminants in drinking water; their concentration
by reverse osmosis. Presented to Division of Environmental Chem-
istry, A. C. S., Los Angeles, Calif., March 1974.
15. Schafer, M. L., Peeler, J. T., Gardner, W. S., Campbell, J. E.
Pesticides in drinking water: water from the Mississippi and
Missouri Rivers. Env. Sci. Tech. 3(12):1261, 1969.
16. West, I. Pesticides as contaminants. Arch. Environ. Health 9:626,
1964.
17. Weibel, S. R., Weidner, R. B., Cohen,, J. M. and Christiansen, A. G.
Pesticides and other contaminants in rainfall and runoff. JAWWA
58(8):1075, 1966.
18. Young, Clarence L. California Department of Health. Memo March 22,
1974 (to) Henry Ongerth and Dr. Alice Ottoboni. Cellon treated
wood - pentachlorophenol - reservoir covers.
19. Alford, Ann L. Environmental Applications of Advanced Instrumental
Analysis: Assistance Project, FY-72. (EPA 660/2-73-013) NERC,
Corvallis, Oregon. Washington, D. C., G. P. 0., 1973.
20. Melton, R. (Task 05) Application of mass spectrometry and NMR
spectroscopy to identification of organics in drinking water. NERC-
Cincinnati Quarterly Report for April-June 1974.
21. Kleopfer, Robert D. Kansas (Region VII). Correspondence (to)
Dr. W. L. Budde, NERC-Cinti. (Halogenated methanes.) February 12,
1974.
22. Bellar, T. A., Lichtenberg, J. J., and Kroner, R. C. The occurrence
of organohalides in finished drinking waters. MDQRL, NERC-Cincinnati,
JAWWA 66:739, 1974.
10
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23. Scheiman, M. A., Saunders, R. A., and Saalfeld, F. E. Organic
contaminants in the District of Columbia water supply. Chemistry
Division, Naval Research Laboratory, Washington, D. C., 1974.
(Submitted to J. of Biomedical Mass Spectrometry.)
24. New Orleans Area Water Supply Study. (Draft Analytical Report)
Lower Mississippi River Facility, Slide!!, Louisiana, November 1974.
25. Garrison, Arthur W. Technical Assistance Summary: Analysis of
New Orleans Drinking Water. EPA Region VI, Task TA 75-03, November
1974.
26. Saunders, R. A., Blackly, C. H., Kovacina, T. A., Lamontagne, R. A.,
Swinnerton, J. W., Saalfeld, F. E. Identification of volatile
organic contaminants in Washington, D. C. municipal water. Naval
Research Laboratory, Washington, D. C. 20375.
27. Dowty, Betty; Carlisle, Douglas; and Laseter, John L. Halogenated
hydrocarbons in New Orleans water and blood plasma. Science 187
(4171):75-77, Jan. 10, 1975.
28. Melton, R. G. Task 006. Chemical characterization of organics
in tap water and tap water concentrates. WSRL, NERC-Cincinnati
Quarterly Report, October-November 1974.
29. Lee, Ramon G. EPA Region III. Correspondence to R. W. Ludlow, Jr.,
Department Health and Mental Hygiene, Baltimore, Md. about low
levels of organic compounds analyzed in Annapolis water supply.
Jan. 21, 1975.
30. Melton, R. G. and Coleman, Emile. Internal (EPA) memo to Earl
McFarren. GC-MS analysis of White House water. (D. C. Water Supply.)
Feb. 4, 1975.
31. Snyder, Daniel J., III. EPA Regional Administrator Water Supply
Analysis. Press Release delivered at Allegheny Board of Health,
January 30, 1975.
32. Thomas, R. F. Identification of organophosphorus compound in
water. Environmental Protection Agency, Mass Spectrometer Users'
Group Newsletter #14, February 1975, Cincinnati, Ohio 45268.
33. Dressman, R. C. and McFarren, E. F. Detection and measurement of
bis(2-chloro-)ethers and dieldrin by gas chromatography. Presented
at the 2nd Annual Water Quality Technology Conference of the
American Water Works Association, Dallas, December 1-4, 1974.
34. Nordel!, E. Water Treatment for Industrial and Other Uses. New
York, Reinhold Publishing Corp., 1961.
11
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APPENDIX II
NATIONAL ORGANICS RECONNAISSANCE SURVEY
Prepared by
James M. Symons
Water Supply Research Laboratory
National Environmental Research Center
Office of Research and Development
Cincinnati, Ohio
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APPENDIX II
NATIONAL ORGANICS RECONNAISSANCE SURVEY
Table of Contents
Page
A. Objectives 18
B. Selection of Cities 18
C. Procedure 18
1. Engineering Evaluation of Treatment Facilities 18
2. Sampling 20
a. Selected Organic Compounds 20
1) Trihalomethanes, Carbon Tetrachloride,
1,2-Dichloroethane 20
2) Polychlorinated biphenyls, Haloethers and
Organophosphate pesticides 21
3) Vinyl chloride 21
b. General Organic Parameters 21
1) Non-volatile Total Organic Carbon, Ultra-
violet Absorption, Fluorescence 21
c. Comprehensive Organics Analyses 22
1) Organics Purged from Sample 22
2) Organics Extracted from Sample with
Solvent 22
3) Organics Adsorbed on Activated Carbon
from Sample 22
13
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Page
d. Constituents in Drinking Water Regulations 24
1) Inorganics 24
2) Organics - Carbon Adsorbables (CCE-m) 24
3) Pesticides (chlorinated hydrocarbons)
and Herbicides 24
3. Analytic Methods 25
a. Selected Organic Compounds 25
1) Chloroform, Bromodichloromethane, Dibromo-
chloromethane, Bromoform, Carbon Tetra-
chloride, 1,2-Dichloroethane 25
2) Polychlorinated biphenyls 29
3) Bis-(2-chloroethyl) ether, Bis-(2-chloro-
isopropyl) ether 29
4) Vinyl chloride 29
5) Organophosphate Pesticides 30
b. General Organic Parameters 30
1) Non-volatile Total Organic Carbon 30
2) Ultraviolet Absorption 30
3) Fluorescence 30
c. Comprehensive Organic Analyses 30
1) Organics Purged from Sample 31
2) Organics Extracted from Sample with
Solvent 36
3) Organics Adsorbed on Activated Carbon from
Sample 38
d. Constituents in Drinking Water Regulations 40
1) Inorganics 40
2) Organics - Carbon Adsorbable (CCE-m) 40
14
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Page
3} Pesticides (chlorinated hydrocarbons),
2,4-D and Si 1 vex 40
4. Quality Control 42
D. Results 42
1. Source and Treatment Information 44
2. Data from 80 Location Survey 44
a. Raw Water Data 44
b. Finished Water Data 46
1) Organics 46
2) Inorganics 46
3. Confirmation Samples 46
a. Quantitative 46
b. Qualitative 69
4. Comprehensive 5-Location Study 69
a. Groundwater, Miami, Florida 69
1) Selected Compound Analysis 69
2) Organics Purged from Sample 70
3) Organics Extracted from Sample with
Solvent 70
4) Organics Adsorbed from Sample by
Activated Carbon 70
b. Uncontaminated Upland Water, Seattle, Washington- • 73
1) Selected Compound Analysis 73
2) Organics Purged from Sample 73
3) Organics Extracted from Sample with Solvent- • 73
4) Organics Adsorbed from Sample by Activated
Carbon 74
15
-------
c, Raw Water Contaminated by Agricultural Runoff,
Ottumwa, Iowa 74
1) Selected Compound Analysis 74
2) Organics Purged from Sample 75
3) Organics Extracted from Sample with Solvent . . 75
4) Organics Adsorbed from Sample by Activated
Carbon 76
d. Raw Water Contaminated by Municipal Discharges,
Philadelphia, Pennsylvania 76
1) Selected Compound Analysis 76
2) Organics Purged from Sample 78
3) Organics Extracted from Sample by Solvent ... 78
4) Organics Adsorbed from Sample on Activated
Carbon 78
e. Raw Water Contaminated with Industrial Discharges,
Cincinnati, Ohio 79
1) Selected Compound Analysis 79
2) Organics Purged from Sample 79
3) Organics Extracted from Sample by Solvent ... 79
4) Organics Adsorbed from the Sample on Activated
Carbon 79
E. Discussion , 82
1. Are Trihalomethanes Formed by Chlorination and, If So, How
Widespread Is Their Occurrence? 92
a. Trihalomethanes 82
b. 1,2-Dichloroethane and Carbon Tetrachloride .... 82
c. Non-Volatile Total Organic Carbon 82
16
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2. Influence of Source Type and Treatment Practice on
Trihalomethane Formation 84
a. Source Influence 86
b. Treatment Influence 87
1) Chlorination Practice 37
2) Filtration Practice 88
3) Use of Activated Carbon 88
A. Powder 88
B. Granular 88
c. Section Summary 91
3. Alternate Indicators of Organic Contaminant Levels ... 92
4. Organics Found in the 5-Location Study 94
5. Significance of Findings 94
F. Acknowledgements 98
G. References 99
17
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NATIONAL ORGANICS RECONNAISSANCE SURVEY
A. OBJECTIVES
The National Organics Reconnaissance Survey has three major objec-
tives. One, is to determine the extent of the presence of the four
trihalomethanes, chloroform, bromodichloromethane, dibromochloromethane,
and bromoform in finished water, and to determine whether or not these
compounds are created by chlorination. A second objective is to deter-
mine what effect raw water source, and other water treatment practices
have on the formation of these compounds, if they are formed by chlorina-
tion. The third objective is to characterize, as completely as possible
using existing analytic technology, the organic content of finished
drinking water produced from raw water sources representing the major
categories in use in the United States today.
B. SELECTION OF CITIES
For the study of the formation of chlorination by-products, 80 water
supplies were chosen to participate in the NORS in consultation with
State water supply officials. These 80 supplies were geographically dis-
tributed, some being in each of the U.S. EPA's 10 Regions. The supplies
were chosen to represent as wide a variety of raw water sources and
treatment techniques as possible. Table 1 lists the names of the 80
supplies chosen.
Ten of the 80 cities below were chosen as sites for a more compre-
hensive survey of the organic content of the finished water. These
locations were chosen to represent five major categories of raw water
sources. These were: 1) ground water; 2) uncontaminated upland water;
3) raw water contaminated with agricultural runoff; 4) raw water contami-
nated with municipal waste; and 5) raw water sources contaminated with
industrial discharges. Table 2 lists these ten cities by category.
C. PROCEDURE
1. Engineering Evaluation of Treatment Facilities
At each of the 80 sites chosen for study, engineers from the U.S.
EPA Regional Office visited the water treatment plant and evaluated the
facilities. They collected basic information on the raw water source
and treatment facilities, which are enclosed in this report. In addition
to this information these engineers also determined the dosage of various
water treatment chemicals used and their points of application.
18
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TABLE 1
1. Lawrence, Massachusetts 41.
2. Waterbury, Connecticut 42.
3. Boston, Massachusetts (MDC) 43.
4. Newport, Rhode Island 44.
5. New York, New York
6. San Juan, Puerto Rico 45.
7. Passaic Valley Water 46.
Commission, New Jersey 47.
8. Tom's River, New Jersey 48.
9. Buffalo, New York 49.
10. Rhinebeck, New York 50.
11. Philadelphia, Pennsylvania 51.
12. Wilmington Suburban, 52.
Delaware 53.
13. Newark, Delaware (Artesian 54.
Water Co.) 55.
14. Washington, District of 56.
Columbia 57.
15. Baltimore, Maryland 58.
16. South Pittsburgh, 59.
Pennsylvania 60.
17. Strasburg, Pennsylvania 61.
18. Fairfax County Water 62.
Authority, Virginia 63.
19. Hopewell, Virginia 64.
20. Huntington, West Virginia 65.
21. Wheeling, West Virginia 66.
22. Miami, Florida 67.
23. Jacksonville, Florida 68.
24. Atlanta, Georgia 69.
25. Owensboro, Kentucky 70.
26. Greenville, Mississippi
27. Chattanooga, Tennessee 71.
.(Tennessee American Water
Company) 72.
28. Memphis, Tennessee 73.
29. Nashville, Tennessee
30. Charleston, South Carolina 74.
31. Cincinnati, Ohio
32. Chicago, Illinois 75.
33. Clinton, Illinois 76.
34. Indianapolis, Indiana 77.
35. Whiting, Indiana 78.
36. Detroit, Michigan 79.
37. Mt. Clemens, Michigan 80.
38. St. Paul, Minnesota
39. Cleveland, Ohio
40. Columbus, Ohio
Dayton, Ohio
Indiana Hill, Ohio
Piqua, Ohio
Youngstown (Mahoning Valley
San. Dist.)
Milwaukee, Wisconsin
Oshkosh, Wisconsin
Terrebonne Parish, Louisiana
Camden, Arkansas
Logansport, Louisiana
Albuquerque, New Mexico
Oklahoma City, Oklahoma
Brownsville, Texas
Dallas, Texas
San Antonio, Texas
Ottumwa, Iowa
Clarinda, Iowa
Davenport, Iowa
Topeka, Kansas
Cape Girardeau, Missouri
Kansas City, Missouri
St. Louis County, Missouri
Lincoln, Nebraska
Grand Forks, North Dakota
Denver, Colorado
Pueblo, Colorado
Huron, South Dakota
Salt Lake City, Utah
Phoenix, Arizona
Tucson, Arizona
California Water Project at
Coalinga, California
Contra Costa County Water
District, California
Dos Palos, California
Los Angeles, California
(Owens Aqueduct)
San Diego, California (Colorado
River Aqueduct)
San Francisco, California
Seattle, Washington
Douglas, Alaska
Idaho Falls, Idaho
Corvallis, Oregon
Illwaco, Washington
19
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TABLE 2
Ground Water
1) Miami, Florida
2) Tucson, Arizona
Uncontaminated Upland Water
1) Seattle, Washington
2) New York, New York
Contamination by Agricultural Runoff
1) Ottumwa, Iowa
2) Grand Forks, North Dakota
Contamination by Municipal Waste
1) Philadelphia, Pennsylvania
2) Terrebonne Parish, Louisiana
Contamination by Industrial Discharges
1) Cincinnati, Ohio
2) Lawrence, Massachusetts
1 = First Series, sampled in early 1975.
2 = Second Series, to be sampled in the future.
2. Sampling
a. Selected Organic Compounds
1) Trihalomethanes, Carbon Tetrachloride, 1,2-Dichloroethane
Because the six compounds chosen for study were known to be volatile,
a sampling procedure was chosen that would provide for minimum loss of
the six compounds from the water to the atmosphere while the sample was
in shipment or awaiting analysis by the technique of volatile organic
analysis (VOA) (see Section C(3)(2)(l) for analytic technique).
The containers chosen were glass 50-ml "Hypo-Vials"* sealed with
Teflon faced "Tuf-Bond" discs, both available from Pierce Chemical Co.,
*Mention of commercial products does not constitute endorsement by U.S.
20
-------
Rockford, 111. Prior to use, the glass vials were capped with aluminum
foil and muffled at 400°C for at least one hour to destroy or remove any
organic matter interfering with analysis. The bottles were packed,
aluminum foil still in place, along with sufficient discs and aluminum
seals (to secure the discs in place), labels and re-usable ice packs in an
insulated container, and shipped to the appropriate regional office for
sampling. Sufficient materials were provided for taking three raw- and
three finished-water samples.
In the field the vials were filled bubble-free, to overflowing so
that a convex meniscus formed at the top. The excess water was displaced
as the disc was carefully placed, teflon side down, on the opening of the
vial. The aluminum seal was then placed over the disc and the neck of
the vial and crimped into place. A sample taken and sealed in this man-
ner was completely headspace-free at the time of sampling. Usually a
small bubble would form during shipping and storage, however.
The samples were labeled appropriately, repacked with the frozen ice
packs in the original insulated container and returned via air mail to
the Water Supply Research Laboratory in Cincinnati. After receipt at the
laboratory, the samples were refrigerated until analyzed. Samples were
collected from the 80 locations during the period late January to end of
March 1975.
2) Polychlorinated biphenyls, Haloethers, Organophosphate
Pesticides
Samples were collected in glass gallon jugs that had been detergent
washed, tap water rinsed and muffled at 400°C for 15 minutes in an ultra
high temperature oven. Caps were teflon lined. Samples were received
over a period of one month, late January to late February 1975 from the
First Series of the comprehensive analyses locations (Table 2) and were
refrigerated until all could be extracted at the same time.
3) Vinyl chloride
Samples for vinyl chloride in raw and finished water were collected
using the same procedure described in Section C(2)(a)(l) during the period
from the end of January through the end, of February 1975 from the First
Series of the comprehensive analysis locations (Table 2).
b. General Organic Parameters
1) Non-volatile Total Organic Carbon, Ultraviolet Absorption,
Fluorescence
One of the sealed bottles of both raw and finished water described in
in Section C(2)(a)(l), collected from all 80 locations, was used as the
sample for these three parameters.
21
-------
c. Comprehensive Organic Analyses
1) Organics Purged from Sample
All samples were collected from a potable water tap in one predeter-
mined water plant of each study city (First Series - Table 2). With the
exception of Ottumwa, Iowa, the samples for comprehensive volatile organ-
ics analyses were taken from the same tap as the samples for other organic
analyses in the NORS. Samples were collected between the last of January
through the last of February 1975. Prior to sampling, the tap water was
allowed to run at a maximum discharge rate for 15 minutes. During sam- -
pi ing, the discharge rate was adjusted to avoid agitation of the sample.
All samples were collected in glass serum bottles previously muffled at
55C°C for 4 hours, were capped with teflon lined discs, and were sealed
with aluminum caps, as described in Section C(2)(a)(l). The vials con-
taining samples collected for comprehensive volatile organic analyses
were filled completely so that no air would be present; whereas, those
for head gas analyses were filled to within 1/4 inch of the disc to allow
the escape of volatiles into the head space. Samples were stored and
shipped at 4°C and were analyzed 24 to 168 hours after collection.
2) Organics Extracted from Sample with Solvent
Samples were collected in glass gallon jugs that had been detergent
washed, tap water rinsed and%muffled at 400°C for 15 minutes in an ultra
high temperature oven. Caps were teflon lined. Samples were received
over a period of one month, late January to late February 1975 from the
First Series of the comprehensive analyses locations (Table 2) and were
refrigerated until all could be extracted at the same time.
3) Organics Adsorbed on Activated Carbon from Sample
A low flow CAM sampling train was used in the First Series of the
comprehensive analyses locations (Table 2). Each unit consisted of two
3" diameter pyrex glass columns packed with Filtrasorb 300 granular acti-
vated carbon, a teflon-stainless rotameter for flow rate control, and a
volume measuring device to count the liters that passed through the
carbon columns (see Figure 1). The end plates, fittings and valves were
stainless steel. The gaskets and tubing that contacted the water sampled
were teflon or stainless steel. Prior to use in the field the pyrex
glass columns were detergent washed, then muffled in an oven at 400°C for
15 minutes to render them organic free. The units were then placed into
operation by connecting them to a finished water tap at the site sampled
and flushing the fines from the activated carbon columns with twenty
liters of finished water.
The units were then operated, with continuous flow, 24 hours a day
for seven days at a rate of approximately 600 ml/min. The time of sam-
pling and flow rate were selected to result in the passage of at least
6000 liters of finished water through the two columns. Because of
22
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k
LEGEND:
1. TEFLON TUBING
2. STAINLESS STEEL AND TEFLON ROTAMETER
3. STAINLESS STEEL TUBING
4. STAINLESS STEEL VALVE
5. TEFLON GASKETS, STAINLESS STEEL SCREENS AND END PLATES
6. 18" LONG x 3" DIAMETER PYREX COLUMN PACKED WITH
FILTRASORB 300 ACTIVATED CARBON
7. VOLUME MEASUREMENT CONTROL
8. COUNTER
1 5 *
3
6
•
3
4 1 *
5 I I
5
6
\
+
FIGURE 1. CARBON ADSORPTION MONITORING UNIT
23
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difficulties with this procedure the 5 locations were sampled in early
April 1975, rather than in February, when the other samples were taken.
d. Constituents in Drinking Water Regulations
1) Inorganics
Four one-quart plastic cubitainers of water were collected at the
same place, and at approximately the same time, so as to represent essen-
tially one sample. Each was identified by writing the same serial number
on the container. To assist the analyst, each container was also identi-
fied by writing on the outside the preservative added, i.e., no preserva-
tive, HNO-j, HgCl2 or NaOH. The amount of preservative added to each
quart cubitainer and tne analyses carried out on each of the particularly
preserved samples is as follows:
1. Trace metals - 1-1/2 ml of concentrated nitric acid.
2. Nitrates, and methylene blue active substances - 1 ml
of a 20,000 mg/1 solution of mercury (2.21 g HgCl2 per
100 ml).
3. Cyanide - 1-1/2 ml of 2 N sodium hydroxide.
4. Turbidity, color, pH, chloride, sulfate, fluoride,
specific conductance, and total dissolved solids -
no preservative added.
These samples were collected from all 80 locations from the last
week in January through March 1975.
2) Organics - Carbon Adsorbable (CCE-m)
The sampler and sampling techniques described in Reference 1 were
used to collect samples for carbon-chloroform extract (CCE-m). These
samples were collected at the First Series of locations listed in Table 2
from the last week in January through the last week in February 1975.
3) Pesticides (chlorinated hydrocarbons) and Herbicides
These analyses were performed on the sample referred to in Section
C(2)(a)(2).
24
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3. Analytic Methods
a. Selected Organic Compounds
1) Chloroform*, Bromodichloroniethane*, Dibromochloromethane*,
Bromofonn*, Carbon Tetrachloride**, 1,2-Dichlorpethane***
Part I, Routine Analysis. The sample concentration procedure chosen
for the initial step of identification and measurement of the six volatile
halogenated organics was essentially that of Bellar and Lichtenberg.2 In
this procedure, the sample is purged with an inert gas that is passed, in
series, through an adsorbant material that traps and concentrates the
organic materials of interest. The organics are then desorbed from the
trapping material by heating under a gas flow and transferred thusly to
the first few millimeters of a cold gas chromatography (GC) column.
Separation (chromatography) is then carried out with temperature
programming.
During this survey, only single column GC was routinely performed,
mostly because of the shortness of time for completion of the NORS. A
high level of confidence that proper identifications were made was at-
tained by use of the Hall Electrolytic Conductivity Detector operated in
the specific halogen mode. Further assurance of proper identifications
was given by supplementary analysis of 9 each, raw- and finished-duplicate
water pairs (from selected locations) on a second column using a micro-
coulometric detector operated in the oxidative halogen mode. Finally,
the qualitative results of analysis of 15 of the finished water samples
were confirmed by GC/MS analysis (see Part II of this Section).
Apparatus. The glass purging device and stainless steel traps used
in the analyses were fabricated exactly according to Bellar and
Lichtenberg.2 The adsorbant material used in the trap was Tenax-GC,
60/80 mesh (Applied Science, State College, Pa., or Alltech Associates,
Arlington Heights, 111.)
The chromatograph used for analysis was a Varian Model 2100 with one
inlet modified to the general configuration of Bellar and Lichtenberg's
desorber Number 1. The column used for separation of the six compounds
was 12 ft x 2 mm I.D. glass, packed with Tenax GC, 60/80 mesh. The
column effluent was connected via a stainless steel transfer line to a
Tracer Model 310 Hall Electrolytic Conductivity Detector (Tracer, Inc.,
Austin, Texas) for detection and measurement of the compounds. This
detector was chosen as the most suitable for the immediate needs of the
survey.^
*Selected as possible chlorination by-products.
**Selected because of known effect on health.
***Selected because presence in previously sampled finished waters.
25
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]teac[errts_. Blank water and water used for dilution of standards
was prepared by purging distilled water with helium until no interfering
peaks could be detected by use of the complete analytical procedure.
Stock standards were prepared with dilutions of 95% ethanol of the
test compounds. The appropriate final aqueous dilution was made by 1-10
pg/1 injection of an appropriate stock standard directly through the
valve on the 5-ml sampling syringe (see description below) into a blank
water contained therein.
Procedure. The sealed water sample as received from the field, was
heated to 255C in a water bath. Just prior to the actual analysis, the
entire disc-seal combination cap was removed with a "Dekapitator" (Pierce
Chemical Co.). Duplicate aliquots from the sample were each taken as
follows: A glass 5-ml Luer-Lok syringe (plunger removed) was fitted at
the tip with a closed Luer-Lok one-way brass stopcock. The water sample
was poured into the back of the barrel of the syringe until the barrel
was completely full. The plunger was then quickly inserted into the
barrel in such a way as to eliminate air bubbles. The valve was opened
momentarily. The plunger was depressed to the 5 ml mark to expel excess
sample, whereupon the valve was again closed. Only one of these aliquots
was routinely analyzed; the duplicate was simply stored in this configura-
tion until the success of the first analysis was assured.
The syringe assembly containing the aliquot to be analyzed was con-
nected to the Luer-Lok needle that was inserted into the sample inlet of
the purging device (the needle was never withdrawn from the septum). At
the time of analysis the valve was opened and the sample was expelled from
the syringe by depressing the plunger. After this, the valve was closed
until purging was complete. After purging, the water (to be discarded)
was removed by reversing the above procedure.
The technique of purging the sample and desorption of the trap con-
tents onto the GC, column were carried out exactly as described by Bellar
and Lichtenberg. Purging was for 11 minutes with a helium gas flow of
20 ml per minute. Desorption was for three minutes at 180°C with a flow
of helium through the trap onto the GC column of 20 ml per minute (this
was in addition to the carrier gas flow). At this time, the GC column
was at room temperature.
Separation of the compounds was accomplished by first quickly heating
the column to 95°C, following with a 15-minute hold, then programming at
2°C per minute to a final temperature of 180°C with a helium carrier flow
of 20 ml per minute. Conditions for operation of the detector were those
recommended by the manufacturer for optimum performance in the halogen
mode.
Compounds were identifided according to retention time (measured
from beginning of the hold at 95°C) and quantified by comparison of peak
heights relative to standards prepared at similar concentration.
26
-------
Retention data and the range of minimum quantifiable concentrations
(MQC) encountered for the six compounds during the survey are summarized
in Table 3.
TABLE 3
CHROMATOGRAPHIC RETENTION AND SENSITIVITY DATA
Typical
Minimum Quantifiable
Concentration (MQC)**, yg/1
Compound Retention Time (min.)
CHC13
(CH2C1)2
CC14
CHBrCl2
CHBr2Cl
CHBr.
20.3
25.8
27.7*
31.8
41.2
49.7
range obs. during survey
0.1
0.2
1.0
0.2
0.4
1.0
- 0.2
- 0.4
- 2.0
- 0.8
- 2.0
- 4.0
Retention times given were typical. They varied slightly with aging
of the columns and significantly with installation of a replacement column.
MQC was not constant throughout the study because of various changes in
normal operating parameters. No attempt was made to standardize the
MQC; operational parameters were simply adjusted to the optimum for any
given day.
Part II. Confirmation Analysis. As noted above, to add confidence
to the routine analysis for the six chosen volatile halogen containing
organics, replicate samples from selected locations were subjected to
reanalysis for quantitation on a second GC-Detector system and for quali-
tative analysis with a GC/MS system. Table 4 shows the sampling locations
of these confirmation samples.
Quantitative Analysis
The quantitative analysis was similar to Reference 2. The following
details describe the specific procedure.
analysis.
Storage. All samples were stored at 4°C until just prior to
*Broad peak not completely resolved from (CH2C1)2.
**2% scale deflection.
27
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Quantitative Conffrmation
1. Waterbury, Connecticut
7. Passaic Valley Water
Commission, New Jersey
16. South Pittsburgh,
Pennsylvania
30. Charleston, South Carolina
51. Oklahoma City, Oklahoma
60. Kansas City, Missouri
65. Pueblo, Colorado
71. Contra Costa County Water
District, California
79. Corvallis, Oregon
TABLE 4
Qualitative Confirmation
11. Philadelphia, Pennsylvania
21. Wheeling, West Virginia
22. Miami, Florida
30. Charleston, South Carolina
31. Cincinnati, Ohio
41. Dayton, Ohio
51. Oklahoma City, Oklahoma
55. Ottumwa, Iowa
58. Topeka, Kansas
60. Kansas City, Missouri
66. Huron, South Dakota
71. Contra Costa County Water
District, California
72. Dos Palos, California
76. Seattle, Washington
79. Corvallis, Oregon
Extraction. Five ml of each sample was purged for 11 minutes
with nitrogen flowing at 20 ml/min. The purging device was maintained
at 19°C. The sample was introduced into the purging device at 4°C.
Therefore, as the sample was purged it warmed up to 19°C at an unknown
rate.
Concentration. The sample was concentrated using a trap packed
with 18 cm of Davison silica gel, grade 15, 35-60 mesh. Desorption took
place for 4.0 minutes at 200°C.
28
-------
Analytic Procedure. An Infotronics Model 2400 gas
chromatograph equipped with a Dohrman microcoulometric detector (halide
specific mode, oxidative) was used to perform the analyses.
A stainless steel column packed with Porasil-C coated with Carbowax-
400, 100/120 mesh, 6' long, 0.1 inch I.D. was used to perform the separa-
tions. Nitrogen flowing at 50 ml/minute was employed as the carrier gas.
The column was programmed over the following conditions: 1) Desorb into
column for four minutes at <30°C; 2) heat column to 50°C and hold one
minute; and 3} program column to 175°C at 8°/minute.
Using the above mentioned conditions the limit of detection for the
materials of interest were: chloroform, 0.05 yg/1; bromodichloromethane,
0.1 yg/1; dibromochloromethane, 0.1 yg/1; bromoform, ^5 yg/1; 1,2-
dichloroethane, 0.1 yg/1; and carbon tetrachloride, 0.05 yg/1. Methylene
chloride was routinely detected; the limit of detection was 0.05 yg/1.
Other unknown organohalides were detected; unfortunately their concentra-
tions were below the limit of detection for GC/MS identification. By
calculating relative retention times it was found that the same unknown
organohalides were present in many of the water supplies tested.
Qualitative Analysis - GC/MS
A Van'an aerograph 1400 gas chromatograph with a Finnigan 1015C
quadrupole mass spectrometer controlled by a Systems Industries 150 data
acquisition system was used to perform the analyses. A glass column
packed with Porasil-C coated with Carbowax-400, 100/120 mesh, 6' long x
2 mm I.D. was used to perform the separations. Helium at 30 ml/min was
used as the carrier gas. The column was programmed under the following
conditions: 1) Desorb into the column for 4 minutes at <30°C; 2) hold
at <30°C for one minute; 3) heat column to 100°C and hold for three
minutes; and 4) program to 200°C at 8°/min.
Mass range scan
Integration time
Samples/AMU
Total Run
20-350
12
1
30 minutes
2) Polychlorinated biphenyls
See reference 4. Arochlors 1221, 1232, 1242, 1248, 1245, 1260 and
1016 were sought.
3) Bis(2-ch1oroethy1) ether and Bis-(2-chloroisopropy1) ether
See reference 5.
4) Vinyl chloride
Vinyl chloride was analyzed using a modified version of Bellar's
and Lichtenberg's procedure.° Samples were collected in and purged from
29
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70 ml septum sealed vials. This technique was employed to gain greater
sensitivity from purging a larger sample and to eliminate losses to the
headspace in the sample container. A microcoulometric detection system
was employed. A chromasorb 101 column was operated isothermally at 100°C.
5) Organophosphate Pesticides
See reference 7. Phosdrin, Thimet, Diazinon, Disulfoton, Dimethoate,
Ronnel, Merphos, Malathion, Methyl Parathion, Parathion, DEF, Ethion,
Trithion, EPN and Guthion were sought.
b. General Organic Parameters
c
1) Non-volatile Total Organic Carbon
Non-volatile total organic carbon (NVTOC) is determined on an instru-
ment made by Phase Separations Ltd., United Kingdom. Samples are acidi-
fied with nitric acid, purged with nitrogen gas for about 10 minutes to
remove carbon dioxide, then pumped into the instrument at a constant rate
of 0.6 ml/minute for about 10 minutes. After water and ammonia are re-
moved the non-volatile organic carbon is thermally oxidized to carbon
dioxide (002) at 920°C with copper oxide as a catalyst, then reduced to
methane (CH4J at 450°C with nickel in a hydrogen atmosphere. The methane
is analyzed with a flame ionization detector.
2) U1traviolet Absorption
See reference 8.
3) Fluorescence
The Rapid Fluorometric Method (RFM) as described by Sylvia^ and a
fluorescence emission scan was performed. In this latter determination,
the excitation and emission slit widths are 12 nm and 16 nm, respectively.
The aqueous sample is excited at 310 nm and the fluorescence emission
recorded between 370 nm and 580 nm.
c. Comprehensive Organic Analyses
In an attempt to determine as broad a range of organic compounds as
possible in the samples collected from the First Series of the Comprehen-
sive Locations (Table II), three different techniques of concentrating
the organics were used. Because in all three cases the separation tech-
niques involved the use of gas chromatography, only those organics in the
water that can be volatilized and passed through the gas chromatograph were
determined. This means that an undefined number of organic compounds that
were originally in the sample, but non-volatile under the temperature of
gas chromatographic conditions, were not determined. Techniques such as
high pressure liquid chromatography and others would be needed to be
applied to determine organic compounds with these properties.
30
-------
Although three different concentrating techniques were used, they
were not mutually exclusive. This means that certain organic compounds
originally in the water would be determined by all three techniques. In
general, however, one new technique^ was designed to determine the lower
boiling point (more volatile) organic compounds, that were not too solu-
ble in water, while the other two techniques were used to determine or-
ganic compounds with higher boiling points. The concentration technique
used to determine the lower boiling point organics begins by purging
these organics from the liquid sample using helium. The higher boiling
point organics were determined, in general, by liquid-liquid extraction
with ethyl ether, and by adsorption onto granular activated carbon fol-
lowed by desorption with chloroform. Details of all three procedures
are contained in the three sub-sections that follow.
1) Organics Purged from Sample
Types of volatile organic analyses. Analysis for volatile organics
is accomplished by the comparative analysis of three types of samples.
These three types include: (a) head gas analysis in which some of the
volatiles are allowed to escape into the head space above the water
sample, and the gas is removed from the serum bottle and injected directly
into a gas chromatography/mass spectrometry (GC/MS) system; (b) direct
aqueous injection in which a small aliquot of the water sample is injected
directly into a GC/MS system; and (c) active stripping of the organics in
which a carrier gas removes the organics from the sample. The compounds
then are adsorbed on a porous polymer medium, subsequently desorbed,
separated by chromatographic techniques and analyzed with appropriate
detectors. Although the method appears to emphasize the more volatile
compounds, the ability to identify all "volatile" compounds is not within
the scope of the method. Volatility is a chemical characteristic of a
relative nature. The compounds amenable to the technique described below
are those whose volatility is quite high, whose water solubility is quite
low, and whose selective adsorptivity to the trapping medium is relatively
high. Consequently, some volatile compounds may not be recovered by this
technique.
Apparatus
Purging Apparatus. The method of Bellar and Lichtenberg6 was
applied to the purging of volatile organics from tap water samples. Two
modifications were made to the original 5-ml purging device: a scale-up
to 140 ml and to 500 ml. The 5-ml instrument was used for quantisation
with the gas chromatograph and flame ionization detector. The 140-ml
device was employed for quantitative assessment using the gas chromato-
graph with the mass spectrometer as detector in order to increase the
sensitivity of detection. The 500-ml device was utilized for qualitative
analysis only. Samples analyzed in the 500-ml instrument were dechlori-
nated prior to analysis. The actual design of the modified purgers is
presented below.
31
-------
140-ml Burger. This device was built by the Paxton IJoods
Glass Shop, Cincinnati, Ohio. The main difference between this device
and that described by Bellar and Lichtenberg° is the capacity -- the
original capacity was 5 ml; whereas, the modified version has a capacity
of 140 ml.
The device has the appearance of a 140-ml gas washing bottle with:
1. A 29/42 ground-glass joint on the top.
2. A 20-mm medium fritted filter disc on the end of the gas tube
to disperse the helium gas, an additional 5-mm (I.D.) sample port on the
top of the male 29/42 joint.
3. A 6-mm (O.D.) by 9-mm (high) silicone rubber cylindrical in-
jection septum fitted inside the injection port.
4. A 10-gauge and 762-mm long stainless steel hypodermic needle
to penetrate the cylindrical rubber septum.
5. A stainless steel stopcock with male-female Luer-Lock fittings
on the 10-gauge needle.
6. A water jacket surrounding the sample container for temperature
control.
7. A 1/4-inch (O.D.) glass tubing on helium inlet and outlet
ports.
8. A foam trap on the helium outlet trap.
The overall height of the device is approximately 27 cm.
500-ml Purger. The responsibility for the design and con-
struction of this device is the same as for the 140-ml device. The 500-
ml device is virtually identical to the 140-ml device, except for the
higher sample capacity of 500 ml. In addition, the overall height of
this device is approximately 44 cm. Specific modification includes a
3-mm (I.D.) by 6-mm (O.D.) by 42.5-cm (long) teflon tubing that was
attached to the 10-gauge needle tip to prevent splashing during sample
introduction.
Trapping Apparatus. The compounds stripped from the water were
adsorbed onto a porous polymer, Tenax GC of 60/80 mesh. The size of
the adsorbing column was adjusted to complement the size of the 500-ml
stripping device. The trap for the 5-ml and 140-ml device is described
by Bellar and Lichtenberg6, and modifications of the trap for the 500-ml
purger are as follows:
32
-------
1. The stem is fabricated of 1/4-inch stainless steel tubing.
2. The length of the stem from 1/4-inch female swagelock fitting
of the body assembly to the stem tip (trap inlet) is approximately 29 mm.
3. The stem assembly is made from Swagelock part number B-QC6-S-400
and body assembly from Swagelock part number B-QC4-B-400.
Desorption Apparatus. Desorption of organics from the three
traps was accomplished by heat and the passage of helium gas as described
by Bellar and Lichtenberg.5 Three desorption units were utilized to
accommodate the three trapping devices. The desorption unit used for
quantitation with the flame ionization detector and the unit with the
5-ml trap are identical, respectively, to "desorber 1" and "desorber 2"
described by Bellar and Lichtenberg.° The third desorption unit was
employed with the 500-ml trap. This unit is composed of Swagelock part
B-QC6-B-600 and has a total length of 26 cm.
Mass Spectrometry. When the mass spectrometer was employed as a
detector, the following chromatographic conditions were established.
The chromatographic instrument, the Finnigan 9000, was equipped with one
of three columns: (a) ten-foot column packed with Chromosorb 101, (b) ten-
foot column packed with Tenax GC, and (c) five-foot column packed with
Chromosorb 101. All adsorbants were of 60/80 mesh.
Mass spectra were obtained on a Finnigan 1015D quadrupole instrument
operating in the electron impact mode, and data were acquired and ana-
lyzed with the Systems Industries 150 computer system. Using graphic
software, data (i.e., reconstructed gas chromatograms and mass spectra)
were outputted on Tektronix 4010 crt data terminal. Operating parameters
for the mass spectrometer and the data acquisition system are described
below:
Mass Spectrometer. The mass spectrometer was operated in
the following mode:
1. ionization potential = 70 eV
2. emission current = 500 ya
3. ion energy = 4 V
4. repeller potential = 6 V
5. lens potential = 100 V
6. analyzer temperature = 70 degrees C
7. continuous dynode electron multiplier detector = 2.0 KV
33
-------
8. analyzer pressure = 5 x TO"6 Torr
9. output preamplifier = 10-7 amperes/V
10. mass range = 10 to 250 amu
11. daily calibrations according to manufacturer's specifications
Gas Chromatography. Hith the flame ionization detector, a
Perkin-Elmer model 900 was utilized. Samples were analyzed on two
different columns: (a) a six-foot column packed with Chromosorb 101
and (b) a six-foot column packed with Tenax GC. The former allows
separation of compounds that elute early; whereas, the latter favors
shorter retention of the compounds along with improved peak symmetry
for later eluting compounds. Standards of chloroform, bromodichloro-
methane, dibromochloromethane, and of compounds identified from the mass
spectrometric analyses and capable of yielding uncontaminated peaks with
the flame ionization detector were analyzed daily.
Data Acquisition System
Data acquisition parameters were varied only as to the type of sample
analyzed, and not from study city to study city. Four sets of data
acquisition parameters were used: (a) one for qualitative head gas analy-
ses and direct aqueous injection samples, (b) a second for head gas analy-
ses of vinyl chloride, (c) a third for the 500-ml purged sample, and
(d) another for all quantitative 140-ml purged samples.
1. For head gas analyses and direct aqueous injections:
a. software program = IFSS
b. mass range = 26-27, 29-31, 41-64, 72-78, 82-102,
112-133, 146-150 and 239 amu
c. maximum repeat count = 4
d. integration time = 17 msec
e. repeat count before checking lower threshold = 4
f. lower threshold = 4
g. upper threshold = 1
2. For head gas analyses of vinyl chloride:
a. software program = IFSS
b. mass range = 27, 61-64, 83, 85 amu
34
-------
c. maximum repeat count = 8
d. integration time = 68 msec
e. repeat count before checking lower threshold = 8
f. lower threshold = 4
g. upper threshold = 1
3. For the 500-ml purged samples:
a. software program = IFSS
b. mass range = 14-16, 19-27, 29-31, 33-240 amu
c. maximum repeat count = 4
d. integration time = 3 msec
e. repeat count before checking lower threshold = 4
f. lower threshold = 4
g. upper threshold = 4
4. For quantisation using 140-ml purged samples:
a. software program = IFSS
b. mass range = 26-27, 29-31, 41-102, 112-133, 146-150,
166-177, 239 amu
c. maximum repeat count = 4
d. integration time = 4 msec
e. repeat count before checking lower threshold = 4
f. lower threshold = 4
g. upper threshold = 1
Reagents. Water low in organic carbon was prepared by purging
Hi Hi pore Super Q pre-di stilled water with helium at a rate of 60 ml per
minute for 38 hours at 95 degrees C. (Organic-free water was impossible
to obtain.) This water was used for blanks and for the preparation of
standards. Potassium ferrocyanide was used to eliminate chlorine and
chloramines in 500-ml samples to be purged at 95 degrees C.
35
-------
Procedure
Purging. Blanks, 140-ml samples, and 500-ml samples were trans-
ferred in the following manner:
a. inversion of serum bottle,
b. penetration of the septum with a 10-gauge hypodermic
needle connected to the introduction port of the
appropriate purging device,
c. penetration of the same septum with a second hypo-
dermic needle (20-gauge and 6 inches in length)
connected to a helium supply,
d. application of gas (helium at a flow rate of 20 ml/min)
pressure to force the sample out of the bottle.
Organic standards used in the 5-ml and 140-ml purging devices were
prepared by a procedure previously described.6
Additional information about the procedures for purging, adsorption,
desorption and chromatographic and spectral analyses will be presented
in the December 1975 report.
2) Organics Extracted from Sample with Solvent
After measuring the pH of the gallon sample, three liters were trans-
ferred to a six-liter separatory funnel. Fifty mi 11 filters of ethyl ether
were added, and the mixture was shaken for one minute. The sample was
then extracted three times with 75 ml portions of methylene chloride,
and the extracts were combined in a 300-ml erlenmeyer flask. The pur-
pose of the ethyl ether is to improve the extraction efficiency of the
more polar compounds like phenols and acids.
The combined extract was poured through two inches of anhydrous
sodium sulfate in a 19-mm I.D. glass column. As an added precaution,
the anhydrous sodium sulfate was prerinsed with 100-ml methylene chloride
to remove any impurities. The dried extract was collected in a 500-ml
Kuderna-Danish (K-D) flask fitted with a 10-ml ampule graduated in 0.1
ml increments.
After the combined extract had filtered through the sodium sulfate,
the sodium sulfate was rinsed with 50 ml of acetone. This was done for
two reasons: to rinse any residual sample components from the sodium
sulfate, and to introduce a nonchlorinated solvent into the sample for
GC/MS injection.
The pH of the water layer was then adjusted to 2.0 using concentrated
HC1 and the above steps repeated. In the first step, it was not necessary
to add the ethyl ether a second time.
36
-------
When the second extraction was completed, the pH of the water layer
was adjusted to 12.0 using a saturated MaOH solution. Again, the extrac-
tion and drying steps were repeated, ignoring the addition of ethyl ether.
The three sample extracts were now contained in three K-U flasks: the -
neutral compounds extracted from a solution of approximately pH 7, the
acid compounds extracted from a solution of pH 2, and the basic compounds
extracted from a solution of pH 12. The reagent blank was in a separate
K-D flask.
A Snyder column was fitted to each K-D flask, and the extracts were
concentrated on a steam bath to approximately 5 ml. After concentration,
the methylene chloride (BP = 39.8°C) was completely removed and the sample
was contained in acetone (BP = 56.1°C). The acetone was used because one
or two microliters of methylene chloride will cause an excessive increase
in the pressure in the mass spectrometer and automatically shut down the
system, whereas up to 8 microliters of acetone will not cause this un-
desirable situation. The extracts were further concentrated in the ampule
to 100 yl in a warm water bath under stream of clean, dry nitrogen with
repeated rinsing of the inside of the ampule. Five micro!iter injections
were made into the GC/MS.
The GC column used in this study is 6 ft by 2 mm I.D., packed with
Supelcoport (80/100 mesh) coated with 1.5% OV-17 and 1.95% QF-1. The
initial column temperature was 60°C, which was held for 1.5 minutes, then
the temperature was programmed at 8° per minute to a final temperature of
220°C which was held for 15 minutes. The total run time was approximately
35 minutes.
The sample run was set up as follows:
System 150 is on select mode: Cont
Calibrate?: No
Title: Enter appropriate title
Calibration file name: Cal
File name: Enter appropriate file name
Mass range: 33-450
Integration time: 8
Samples/AMU: 1
Threshold:
RT GC Atten: 7
Fast scan opt?:
37
-------
MS range setting?: H
Max run time: 35
Delay between scans (sec)?:
3) Organics Adsorbed on Activated Carbon from Sample
CAM Carbon Proce ss1ng. On removal from the sampling sites, the CAM
carbon cylinders were drained of excess water, sealed and shipped by com-
mercial air carrier to the processing laboratory. The columns were stored
at 4°C until carbon processing could be initiated.
Columns were opened in a special activated carbon handling room de-
signed to minimize the potential for contamination. The activated carbon
was transferred to Pyrex glass dishes and dried at 35-38°C for 48 hours
under a gentle flow of clean air in a mechanical convection oven. The
oven air inlet was equipped with an activated carbon filter to prevent
atmospheric contamination.
The dried activated carbon was transferred to 220-ml Soxhlet extrac-
tors and extracted for 48 hours with chloroform. The chloroform extracts
were filtered through solvent-extracted glass fiber filters to remove
activated carbon fines and then vacuum concentrated at temperatures not
exceeding 27°C in rotary evaporators to final volumes of 30-60 ml. The
concentrated extracts were transferred quantitatively to 10-ml ampules,
several ampules being required to accommodate each extract. The ampules
were purged with dry, clean nitrogen and sealed while the contents were
held at -50°C in a cold bath. The filled ampules were maintained under
refrigeration (4°C) until shipment to the analytical laboratory by air
mail.
Gas Chromatography - Mass Spectrometry. Gas chromatography was per-
formed using a Varian 1400GC with a flame ionization detector. Carbon
chloroform extracts (CCE's) were received in sealed glass ampules from
the R. S. Kerr Environmental Research Laboratory. After each CCE volume
was measured it was concentrated in a Kuderna-Danish apparatus to about
8 ml. Concentration to a final volume of 6 ml was achieved by blowing a
gentle stream of nitrogen over the surface of the extract at room tempera-
ture. Since 6,000 liters of water were passed through each filter, the
organics in each 6-ml extract are 1 million times more concentrated
than in the original water sample. However, the percent adsorption on
carbon, percent desorption into the solvent, and percent loss on concen-
tration of the solvent are unknown and vary with each individual compound.
Therefore, the quantitation of each compound is only approximate and the
quantity of each chemical reported can be considered as its minimum
concentration.
Concentrated extracts were analyzed with a computerized combined
gas chromatograph-mass spectrometer (GC-MS) system. A Finnigan 1015
38
-------
quadrupole mass spectrometer was operated in the electron impact mode
and data was acquired using a System Industries 150 computer interface.
A Varian 1400 gas chromatograph was interfaced directly to the mass
spectrometer with a 9-inch stainless steel capillary tube. The gas
chromatograph contained a 30-meter by 0.4-mm I.D. glass capillary column
(No. 646) coated with Supelco SP-2100 at the Southeast Environmental
Research Laboratory.
Optimized gas chromatographic conditions included multiple tempera-
ture and carrier gas (helium) flow programming. Injection of 0.4 yl of
each sample was made with the GC oven door open, the column at room
temperature (about 30°C), and the MS pressure at 1.5 x 10~5 torr. The
GC oven door was closed 5 minutes after injection and the temperature
slowly increased to about 50° over the next 6 minutes. At 11 minutes
after injection the oven temperature controller was set at 60°. Two
minutes later temperature programming at 2°/min was started. Twenty-
three minutes after injection (80°C) the temperature program rate was
increased to 6°/min and carrier gas flow was increased to produce a
MS pressure of 2.8 x 10-5 torr (previously determined to correspond to
a helium flow of 2 cc/min at room temperature). Thirty-three minutes
after injection (140°C) the temperature program rate was increased to
10°/min. The final temperature of 250°C was maintained for 20 minutes.
Computer-controlled collection of mass spectral data was begun im-
mediately after sample injection. To prevent filament damage as solvent
entered the MS, the ionization current was shut off 2.5 minutes after
injection and turned on again 3.5 minutes after injection. Electron
energy was maintained at 70 eV and filament current at 400 ya. A mass
spectrum from m/e 41 to 350 was acquired approximately every 2.5 seconds
by the PDP-8/e computer.
At the end of data acquisition a computer-reconstructed gas chromato-
gram was plotted. Sample spectra were then chosen and plotted after
appropriate background spectra were subtracted. Spectral matching was
performed using the EPA computerized Mass Spectral Search System at
the National Institutes of Health in Washington, D.C. Tentative identi-
fications of compounds were based on these spectral matches and on inter-
pretation of the mass spectra.
To confirm these identifications, mass spectra and gas chromatographic
retention times of mixtures of standards (when available) were compared
with those of sample components. The retention times of these components
were calculated relative to camphor because it was present in the CCE
blank and therefore in all samples. Camphor also served as the internal
standard used for all the standard mixtures.
Concentrations were calculated with a computer program that compared
the total ion current (TIC) summation of sample component mass spectra
with the TIC summation of a known amount of that compound in the standard
solution. When a standard was not available, a standard compound of
39
-------
similar molecular structure was used to estimate the quantity of the
tentatively-identified sample component.
Processing Blanks. The foregoing discussion of preparation and
analytical methods has been concerned with the processing of actual
samples. However, to assure that components identified were actually
derived from the original samples and were not artifacts, contaminants,
or inherent components deriving from the sampling method itself, the
sampling media, commercial solvents, or the sample preparations, it
was necessary to process blank samples taken through all stages of the
operations in parallel with the actual samples, including washing the
sampling activated carbon with activated carbon treated water to remove
any water soluble materials.
As a consequence of this processing of blanks through the analytical
stage, no components could be accepted as deriving from the finished
water samples unless these components were not present at a significant
level in the blanks relative to the samples.
d. Constituents in Drinking Water Regulations
1) Inorganics
Analytical methods to determine compliance with the requirements of
the regulations shall be those specified in the current (13th) Edition
of Standard Methods for the Examination of Water and Wastewater (SMEWW),
published by the American Public Health Association,10 and/or Methods for
Chemical Analysis of Water and Wastewater (MCAWW), U.S. Environmental
Protection Agency,-1974,11 except for the following which are either not
in the current editions, or are undergoing extensive revision.
Arsenic and Selenium. The atomic absorption spectrophotometer
method is preferable to the wet chemical procedures in the present edi-
tion of SMEWW as these will conserve time and effort in analysis and
produce improved sensitivity, see reference 12. This procedure will
also appear in the 14th Edition of SMEWW and the 1974 Edition of MCAWW.
Cyanide. See reference 13.
Mercury. See reference 14. This procedure will appear in the 14th
Edition of SMEWW and is the same as that appearing in MCAWW.H
2) Organics - Carbon Adsorbable (CCE-m)
See reference 1.
3) Pesticides (chlorinated hydrocarbons), 2,4-D and Silvex
See references 15 and 16. Table 5 lists all the chlorinated hydro-
carbons sought.
40
-------
TABLE 5
Organochlorine Pesticides
a BHC
PCNB
Lindane
Dichloran
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan
p,p' DDE
Dieldrin
Captan
Endrin
DDT
p,p' ODD
Mi rex
Methoxychlor
Tech. Chlordane
Toxaphene
41
-------
4. Quality Control
Accuracy
To test the accuracy of the method as used by Water Supply Research
Laboratory during the survey, a pair of "unknown" standard mixtures was
prepared by another EPA laboratory in the following manner:
Two different stock solutions each containing all of the compounds
of interest were prepared by injecting a known volume of each material
into a volumetric flask containing 90 ml of methyl alcohol. After all of
the compounds were injected into the flask the mixture was diluted to
volume (100.0 ml) and mixed by inverting. Two hundred microliters of
the stock solution was then dosed into 1.0 liter of super-Q water and
mixed by inverting two times. One-half of the dosed water was then trans-
ferred into a 500 ml separatory funnel. Several 60-ml vials were then
filled with the mixture and promptly sealed with Teflon septums. The
samples were stored at 4°C until delivery to Water Supply Research
Laboratory. The blank (Sample D-4) contained only super-Q water. The
calculated concentrations of the dosed mixtures, D-2 and D-3, are listed
with the analytical results in Table 6.
Analysis by the respective laboratories was exactly as described in
the Section C(3)(a)(l), for the determination of the six halogenated
organic compounds: chloroform, bromodichloromethane, dibromochloro-
methane, bromoform, carbon tetrachloride, and 1,2-dichloromethane.
Precision
To test variability of results during a typical day of analysis,
two series of 5 replicate samples were prepared as ten discrete samples
in the same manner as standards were prepared throughout the survey.
One series was at low concentrations and the other at high concentrations.
All of the samples were analyzed exactly as described in Section C
(3)(a)(l) for the determination of the six halogenated organic compounds,
chloroform, bromodichloromethane, dibromochloromethane, bromoform, carbon
tetrachloride, 1,2-dichloroethane. Spiked concentrations and relative
standard deviations (o/XAV) are listed in Table 7.
D. RESULTS
At this time (April 1975), all of the results of the National Organ-
ics Reconnaissance Survey are not complete. Work is continuing on several
facets of the Survey. For this interim report, all of the results avail-
able at the present time will be presented, summarized, and discussed.
The December 1975 report will contain all of the data.
42
-------
CQ
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o
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S- -I- OJ
CO -o E
CU
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1
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s_
O O)
i— C
CM o x:
r— Q CU
o
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i-
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'o.
E
fO
«d- CM
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^" ^ CO CM
CO 0
• *
CO CO CO CT>
CM CM CM r—
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cr> en o co
CO CO «3~ CM
^«
IT) •
&
o> cy* co
r- 0
• •
o cr> o in
^— 1 —
IO UD
• •
•* co LO cr>
t^ vo 10 LO
OJ X) JD CU
3 IT3 03 JD jQ 3
c — 1 1 (O (O r —
fO _J —1 ro
E E
Ol -r- T- «+- M- O»
rs s- s- c c 3
S- Q_ D_ O O i-
^3. CJ C_5 H-^
>~' fO J3 "
CvJ CM CM CM CM CO
1 1 1 1 1 1
t~^l t~*l f~°* (~*l f~} f~*l
CO •*
r— CM
*± CO
CM CO
CM CM
un vo
to in
vo vo
--> -~.
rt3 n3 o <~>
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-------
TABLE 7
SPIKED CONCENTRATIONS AND RELATIVE STANDARD DEVIATIONS
Compound Cone, (yg/1) Rel. o(%) Cone, (yg/1) Rel. o
Chloroform
1 ,2-Dichloroethane
Carbon Tetrachloride
Bromodichloromethane
Dibromochloromethane
Bromoform
2.
1.
2.
2.
2.
4.
6
5
14
5
10
20
18
*
*
20
30
30
7
*
*
7
13
12
*Not determined at high concentrations.
1. Source and Treatment Information
At the time of the preparation of this report, engineering data were
available on the water supplies of 59 locations. Table 8 shows the per-
centages of these 59 locations that used the different categories of
sources studied in this investigation. Table 8 also shows the treatment
practices of these 59 locations. When all the data are in, a study popu-
lation from 25-30 million is expected.
Because a major objective of this study was to determine the effect
of disinfection practices on the formation of the 4 trihalomethanes,
Table 9 shows the distribution of the prechlorination dosages used at
the 42 locations where prechlorination was practiced. In 82% of these
locations the prechlorination dose was between 1 and 6 mg/1. Table 10
shows the distribution of the concentration of chlorine residual, both
free and combined. In general, rather low residuals were present in
the finished waters.studied, and at 20% of the locations there was less
than 0.4 mg/1 of either free or combined residual.
2. 80 Location Study
a. Raw Water Data
The data summarized in Table 11 shows that the six selected compounds
measured in the raw water at the 80 locations were mostly absent or
present in very low concentrations. One location was receiving water
prechlorinated by others and this water did contain some chloroform,
bromodichloromethane and dibromochloromethane. Non-volatile total organic
carbon determinations were made on each sample but were not reported as
they were considered unreliable because of the presence of suspended
solids in the samples. This was also true of the ultraviolet absorp-
tion and fluorescence data.
44
-------
TABLE 8
SUMMARY OF ENGINEERING DATA
(All Percentages are of 59 Locations)
Source
Ground 24%
Lake or Reservoir 37%
River 39%
Mi xed 0%
Treatment
Prechlorination 71%
Filtration 73%
Polyelectrolyte 20%
Powdered Activated Carbon 22%
Granular Activated Carbon 9%
Softening
Precipitative 17%
Zeolite 3%
Taste and Odor Control
Practiced 37%
Note: One location was pre-ozonated and another used ozonation as the only
treatment.
45
-------
TABLE 9
PRECHLORINATION DOSAGES
(All Percentages of 42 Locations)
0-1 mg/1 10%
1-2 mg/1 29%
2-3 mg/1 8%
3-4 mg/1 17%
4-5 mg/1 14%
5-6 mg/1 14%
6-7 mg/1 2%
7-8 mg/1 0%
8-9 mg/1 2%
>10 mg/1 2%
Unknown 2%
b. Finished Hater Data
1) Organics
Table 12 summarizes all.of the data on finished water quality from
the 80 locations. The ultraviolet absorption and fluorescence data were
not presented at this time as their significance, if any, are not currently
known. The range of each measurement is noted at the end of the Table.
To show the central tendency of the data, Table 13 presents the
frequency distribution of the concentrations of six selected organic
compounds measured in all 80 locations as well as the concentration of
finished water non-volatile total organic carbon. Each of these seven
parameters is not evenly distributed over the range but is biased
toward the low concentration end of the range. Therefore, high concen-
trations of these parameters were a somewhat unusual occurrence in this
study.
2) Inorganics
Table 14 contains the concentrations of the inorganic substances in
the Interim Primary Drinking Water Regulations. Very few locations ex-
ceeded the limits.
3. Confirmation Samples
a. Quantitative
The data presented in Tables 15a and 15b show good quantitative con-
firmation of the routine analysis of the six selected compounds in the
46
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TABLE 10
CHLORINE RESIDUAL
(All Percentages of 56 Locations)
Combined Residual - mg/1
0-0.4 63%
0.4-0.8 20%
0.8-1.2 4%
1.2-1.6 2%
1.6-2.0 5%
2.0-2.4 2%
2.4-2.8 4%
Free Residual - mg/1
0-0.4 43%
0.4-0.8 20%
0.8-1.2 5%
1.2-1.6 17%
1.6-2.0 4%
2.0-2.4 7%
2.4-2.8 4%
Free and Combined Residual
Each 0-0.4 mg/1 20%
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TABLE 11 (Cont'd.)
SUMMARY OF RAW WATER ANALYSIS
Nothing found
Chloroform
Bromodichloromethane
Di bromochloromethane
Bromoform
1,2-Dichloroethane
Carbon Tetrachloride
Number of Locations
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Range vyg/l
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TABLE 13
FREQUENCY DISTRIBUTION OF TRIHALOMETHANES
FINISHED WATER
Brornodichloro-
Chloroform methane
Dibromo-
chloromethane
Bromoform
HI <
10 _
Concentration % in Upper % in Upper
Range, yig/1 Range Cone. Range Cone.
in
Upper
in
01 <
10 _
Upper
Range Conc. Range Cone.
NF
0-1
1.1-5
6-10
11-15
16-20
21-25
26-30
31-40
41-50
51-75
76-100
101-150
151-200
201-250
251-300
301-350
0
11
8
8
3
7
5
5
8
10
7
7
2
0
0
2
.3
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.8
.8
.5
.0
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.8
.0
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.5
.5
.5
0
11.3
20.1
28.9
37.7
45.2
50.2
55.2
64.0
74.0
81.5
89.0
97.5
97.5
97.5
100.0
2.5
13.8
13.8
32.5
11.3
. 3.8
1.2
5.0
6.3
1.2
1.2
1.2
2.
16.
30.
62.
73.
82.
83.
88.
95.
96.
97.
93.
5
3
1
6
9
7
9
9
2
4
6
8
11.3
20.0
43.7
5.0
7.5
6.4
1.2
0
2.5
.1.2
0
1.2
11
31
75
80
87
93
95
95
97
98
98
100
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.1
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.6
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68.8
20.0
6.3
2.5
1.2
0
0
0
0
0
0
1.2
68.8
88.8
95.1
97.6
98.8
98.8
98.3
98.8
98.8
98.8
98.8
100.0
NF = None found.
57
-------
TABLE 13 (Cont'd.)
FREQUENCY DISTRIBUTION OF 1,2-DICHLOROETHANE AND CARBON TETRACHLORIDE
FINISHED WATER
1,2-Dichloroethane Carbon Tetrachloride
Concentration % of % _ Concentration % of % <
yg/1 Total Concentration ug/1 Total Concentration
NF
<0.2
0.2
<0.3
0.3
<0.4
0.4
2
6
67.5
12.4
1.3
1.3
1.3
11.2
2.4
1.3
1.3
67.5
79.9
81.2
82.5
83.8
95.0
£7.4
98.7
100.0
NF 87.5 87.5
<2 7.5 95.0
2 2.5 97.5
3 2.5 100.0
NF = None found.
58
-------
TABLE 13 (Cont'd.)
FREQUENCY DISTRIBUTION OF NON-VOLATILE TOTAL ORGANIC CARBON
FINISHED WATER
Concentration
Range % in Upper
mg/1
<0.05
0.05-0.5
0.6-1.0
1.1-1.5
1.6-2.0
2.1-2.5
2.6-3.0
3.1-3.5
3.6-4.0
4.1-4.5
4.6-5.0
5.1-5.5
5.6-6.0
6.1-6.5
6.6-7.0
7.1-9.0
9.1-11.0
11. 1-13.0
Range
4.9
6.2
12.3
13.6
21.0
8.6
12.3
7.4
2.5
6.2
0
2.5
0
0
1.3
0
0
1.2
Concentration
4.9
11.1
23.4
37.0
58.0
66.6
78.9
86.3
88.8
95.0
95.0
97.5
97.5
97.5
98.8
93.8
98.8
100.0
59
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raw and finished waters in the 80 locations. Because of the increased
sensitivity of the method described in Section C(3)(a)(l), Part II,
analysis by that technique often produced a low measurable concentration
where the routine method did not find the compound. This is not an in-
consistency. The differences between the concentrations of the routine'
and confirmation analyses in a few cases is not considered to be
significant.
b. Qualitative
The data in Table 15 shows that the compounds quantified by the
routine analysis were the correct compounds. In no case did the routine
analysis ever quantify a given compound and have a negative confirma-
tion by gas chromatography-mass spectrometry (GC/MS). In few cases,
because one of the GC/MS methods used a larger sample for purging, this
technique would detect the presence of a compound when none was found
by the routine procedure. This is not an inconsistency, and as noted
above, the reverse did not occur.
4. Comprehensive 5-Location Organic Study
Three types of samples were collected from each of the First Series
(Table 2) of locations for a comprehensive organic analysis. Work is
still continuing on all of these 15 samples, therefore the results pre-
sented in the following tables must be considered preliminary. The com-
plete analysis of these samples will be presented in the December report.
a. Groundwater, Miami, Florida
The Carbon-Chloroform Extract (CCE-m) concentration was 0.9 mg/1.
1) Selected Compound Analysis
TABLE 16
Organochlorine Pesticides 2 ng/1 Dieldrin
Organophosphate Pesticides None Found
Polychlorinated Biphenyls None Found
Herbicides None Found
Haloethers None Found
Vinyl chloride - Raw 1.2 yg/1
- Finished 5.6 ug/1*
Sample collected 1/20/75.
*This value includes a trace amount of cyanogen chloride. The reason it
is higher than the raw value is not known at this time.
69
-------
2) Organics Purged from Grab Sample
See Table 17, next page.
3) Organics Extracted from Sample with Solvent
Compounds Detected*
Bromoform
Hexachloroethane
Di-n_ - octyl adipate
Nicotine
TABLE 18
Approximate Concentration,** yg/1
0.2
0.07
20.0
3.3
Sample collected 1/20/75
*List incomplete as samples are still being analyzed.
**Concentrations are probably accurate to within a factor of ten; with
di-n-octyl adipate and nicotine, authentic samples were available and
the concentrations of these are probably accurate to within ±50%.
4) Organics Adsorbed from Sample on Activated Carbon
See Table 19. All of these data were somewhat surprising initially,
as ground water has traditionally been thought of as low in contaminants.
These results may not apply to all ground waters, however, but may only
be representative of areas with relatively high ground water tables and
relatively shallow wells.
70
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TABLE 17
Results reflect a single grab sample taken on January 20, 1975
in Miami, Florida
Compounds Found**
1. acetaldehyde
2. acetone
3. acetylenebromide
4. acetylenechloride
5. acetylenedichloride
*6. benzene
7. bromoform
8. bromomethane
9. carbon disulfide
10. carbon tetrachloride
' *11. chlorobenzene
12. chloroethane
13. chloroform
H. chloromethane
15. cyanogen chloride
16. dibromochloromethane
17. m-dichlorobenzene
18. o-dichlorobenzene
*19. p-dichlorobenzene
20. dichlorobromomethane
21. 1,1 dichloroethane
22. 1,2 dichloroethane
*23. 1,1 dichloroethylene
(vinylidene chloride)
*24. cis-1,2 dichloroethylene
*25. trans 1,2 dichloroethylene
26. dichloromethane
27. methanol
28. 3-methyl butanal
29. 2-methyl butyl nitrile
30. 2-methyl propanal
31. 2-methyl propyl nitrile
*32. toluene
33. 1,1,2 trichloroethane
*34. trichloroethylene
*35. vinyl chloride
*Selected for future quantification.
**List incomplete as analysis is continuing. Any ambiguities in
nomenclature will be corrected in the December 1975 report by using
the systematic name as well as the common name.
71
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TABLE 19
ORGANICS ADSORBED ON ACTIVATED CARBON
FROM MIAMI, FLORIDA SAMPLE
Approximate Concentration
Compounds Found in yg/liter
*1. bromodichloromethane 4.5
*2. bromoform 1.5
*3. camphor 0.5
*4. chlorobenzene 1
*5. chlorodibromomethane 15
*6. p-chlorotoluene 1.5
7. cymeme isomer 0.1
*8. 2,6-di-t-butyl-p-benzoquinone 0.1
*9. di-n-butyl phthalate 5
*10. m-dichlorobenzene 0.5
*11. p-dichlorobenzene 0.5
*12. o-dichlorobenzene 1
*13. diethyl phthalate 1
*14. di-(2-ethylhexyl) phthalate 30
15. di-n-propyl phthalate 0.5
*16. hexachloroethane 0.5
*17. n-propylbenzene 0.05
18. n-propylcyclohexanone 0.2
*19. tetrachloroethylene 0.1
20. 1,1,3,3-tetrachloro-2-propanone 0.2
21. tetramethylbenzene isomer 0.2
*22. tri-n-butyl phosphate 0.5
Confirmed by comparison of MS and RRT with standard.
72
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b. Uncontann'nated Upland Water, Seattle, Washington
The carbon chloroform extract (CCE-m) of this water was 0.1 mg/1.
1) Selected Compound Analysis
TABLE 20
Organochlorine Pesticides 1 ng/1 Dieldrin
Organophosphate Pesticides None Found
Polychlorinated Biphenyls None Found
Herbicides None Found
Haloethers None Found
Vinyl Chloride - Raw None Found
- Finished None Found
Sample collected 1/27/75
2) Organics Purged from Grab Sample
TABLE 21
RESULTS REFLECT A SINGLE GRAB SAMPLE
TAKEN ON JANUARY 27, 1975, IN SEATTLE, WASHINGTON
Compounds Found*
1. acetaldehyde
2. acetone
3. 2-butanone
4. chloroform
5. dibromochloromethane
6. dichlorobromomethane
7. dichloromethane
8. ethanol
9. methanol
10. methyl acetate
11. methyl ether
12. methyl formate
13. 2-methyl propanal
*List incomplete as analysis is continuing. Any ambiguities
in nomenclature will be corrected in the December 1975 report
by using the systematic name as well as the common name.
3) Organics Extracted from Sample by Solvent
None found (sample collected 1/27/75).
73
-------
4) Organics Adsorbed from Sample on Activated Carbon
TABLE 22
ORGANICS ABSORBED ON ACTIVATED CARBON
FROM SEATTLE, WASHINGTON SAMPLE
Compounds Found
*2.
*3.
*4.
*5.
*6.
*7.
8.
9.
acetaldehyde
acetone
bromodi chloromethane
camphor
chloral (trichloroacetaldehyde)
di-n-butyl phthalate
diethyl phthalate
p-ethyltoluene
B-santalene
Approximate Concen-
tration in yg/1 liter
0.1
1
0.1
0.5
3.5
0.01
0.01
0.05
0.01
*Confirmed by comparison of MS and RRT with standard.
c. Raw Water Contaminated by Agricultural Runoff, Ottumwa, Iowa
The carbon-chloroform extract (CCE-m) concentration of this water
was 0,7 mg/1.
1) Selected Compound Analysis
TABLE 23
Organochlorine Pesticides
Organophosphate Pesticides
Polychlorinated Biphenyls
Herbicides
Haloethers
Vinyl Chloride - Raw
- Finished
2ng/l Dieldrin
None Found
None Found
None Found
None Found
None Found
None Found
Sample collected 2/25/75.
74
-------
2) Qrganics Purged From Grab Sample
TABLE 24
Results reflect a single grab sample
taken on February 2, 1975 in Ottumwa, Iowa
Compounds Found**
1. acetaldehyde 10. dichlorobromomethane
2. acetone 11. dichloromethane
*3. benzene 12. dimethyl disulfide
4. 2-butanone 13. ethanol
5. carbon tetrachloride 14. 3 methyl butanal
6. chloroform 15. 3-methyl-2-butanone
7. chloromethane 16. 2-methyl propanal
8. cyanogenchloride *17. toluene
9. dibromochloromethane 18. 1,1,1 trichloroethane
*19. trichloroethylene
*Selected for future quantification.
**List incomplete as analysis is continuing. Any ambiguities in
nomenclature will be corrected in the December 1975 report by using
the systematic name as well as the common name.
3) Qrganics Extracted from Sample with Solvent
TABLE 25
Comp o u n d s F o u n d * * Approximate Concentration, pcj/1*
Benzoic Acid 15
Phenylacetic Acid 4
Sample collected 2/17/75.
*List incomplete as analysis is continuing.
**Concentrations are probably accurate to within a factor of ten;
with benzoic acid authentic samples were available and the con-
centrations of this are probably accurate to with 150%.
75
-------
4) Organics Adsorbed from Sample on Activated Carbon
TABLE 26
Compounds Found
*1. atrazine
*2. camphor
*3. chloropicrin (trichloronitromethane)
*4. cyclohexanone
*5. di-n-butyl phthalate
6. 3-methyl-3-pentanal
7. n-pentanal
*8. 2-pentanone
*9. a-terpeneol
10. tetramethyltetrahydrofuran
Approximate Concentration
_ in yg/liter _
0.1
0.1
0.1
1
0.5
0.1
0.5
0.5
*Confirmed by comparison of MS and RRT with standard.
d. Raw Water Contaminated by Municipal Dishcarges, Philadelphia,
Pennsylvania
The carbon chloroform extract (CCE-m) concentration of this water
was 0.4 mg/1.
1) Selected Compound Analysis
TABLE 27
Organochlorine Pesticides
Organophosphate Pesticides
Polychlorinated Biphenyls
Herbicides
Haloethers
Resample 3/31/75
Vinyl Chloride - Raw
- Finished
None Found
None Found
None Found
None Found
0.4 yg/1 Bis-2
(chloroethyl)ether*
0.5 yg/1 Bis-2
(chloroethyl)ether
None Found
0.27 yg/1**
Sample collected 2/3/75
'''Confirmed qualitatively by mass spectrometer.
**This value represents a combination of vinyl chloride and cyanogen
chloride. Mass spectrometer analysis indicates a greater amount of cyano-
gen chloride than vinyl chloride. The reason the finished water value is
higher than the raw water value is not known at this time.
76
-------
Table 28
Results reflect a single grab sample taken on February 3,
1975, in Philadelphia, Pennsylvania.
Compounds Found**
1. acetaldehyde
2. acetone
3. acetylenechloride
4. acetylene dichloride
*5. benzene
6. bromoform
7. 2-butanone
8. carbon tetrachloride
*9. chlorobenzene
10. chloroethane
11. chloroform
12. chloromethane
13. cyanogenchloride
14. dibromochloromethane
15. m-dichlorobenzene
16. o-dichlorobenzene
*17. p-dichlorobenzene
18. dichlorobromomethane
19. 1,2 dichloroethane
20. 1,1 dichloroethylene
*21. cis,l, 2 dichloroethylene
22. dichloromethane
23. dimethoxymethane
24. ethanol
25. ethyl ether
26. methanol
27. 3-methyl butanal
28. 2-methyl butyl nitrile
29. methyl ether
30. 2-methyl propanal
31. 2-methyl propyl nitrile
32. nitromethane
*33. tetrachloroethylene
*34. toluene
*35. trichloroethylene
*36. vinyl chloride
*Selected for future quantification
**List incomplete as analysis is continuing. Any ambiguities in
nomenclature will be corrected in the December 1975 report by
using the systematic name as well as the common name.
77
-------
2) Organics Purged from Grab Sample
See Table 28 on next page.
3) Organics Extracted from Sample by Solvent
TABLE 29
Compound Found* Approximate Concentration,** ug/1
1,2-Bis(2-chloroethoxy)ethane 0.03
Sample collected 2/3/75
*List incomplete as analysis is continuing.
**Concentration is probably accurate to within a factor of ten.
•
4) Organics Adsorbed from Sample on Activated Carbon
TABLE 30
Compounds Found Approximate Concentration in yg/1
*1. acetaldehyde 0.1
*2. acetophenone 1
*3. bromodichloromethane 1
4. t-butyltoluene 0.01
*5. chloral (trichloroacetaldehyde) 5
*6. chlorodibromomethane 0.5
*7. di-n-butyl phthalate 0.05
*8. diethyl phthalate 0.01
*9. di-(2-ethylhexyl) phthalate . 0.5
10. 1,1,3,3-tetrachloro-2-propanone 1
*Confirmed by comparison of MS and RRT with standard.
78
-------
e. Raw Water Contaminated with Industrial Discharges, Cincinnati>
Ohio
The carbon chloroform extract (CCE-m) concentration of this water
was 0.7 mg/1.
1) Selected Compound Analysis
TABLE 31
Organochlorine Pesticides 1 ng/1 Dieldrin
Organophosphate Pesticides None Found
Polychlorinated Biphenyls None Found
Herbicides None Found
Haloethers None Found
Vinyl Chloride - Raw None Found
- Finished None Found
Sample collected 2/11/75.
2) Orgam'cs Purged from Grab Sample
See Table 32 on next page.
3) Orgam'cs Extracted from Sample by Solvent
TABLE 33
Compounds Found** Approximate Concentrations,* in yg/1
Dibromochloromethane 0.05
Isophorone 0.02
Trimethyl isocyanurate 0.02
Sample collected 2/11/75.
Concentrations are probably accurate to within a factor of ten.
**List incomplete as analysis is continuing.
4) Orgam'cs Adsorbed from the Sample on Activated Carbon
See Table 34.
79
-------
Table 32
* Results reflect a single grab sample taken on February 11,
1975, in Cincinnati, Ohio.
Compounds Found**
1. acetaldehyde
2. acetone
3. acetylenechloride
4. acetylene dichloride
*5. benzene
6. bromoform
7. 2-butanone
8. carbon disulfide
9. carbon tetrachloride
*10. chlorobenzene
11. chloroethane
12. chloroform
13. chloromethane
14. cyanogenchloride
15. dibromochloromethane
16. m-dichlorobenzene
17. o-dichlorobenzene
*18. p-dichlorobenzene
19. dichlorobromomethane
20. 1,2 dichloroethane
21. 1,1 dichloroethylene
*22. cis, 1,2 dichloroethylene
23. dichloromethane ~
24. ethanol
25. ethyl ether
26. methanol
27. 3-methyl butanal
28. 2-methyl butyl nitrile
29. methyl ether
30. 2-methyl propanal
31. 2-methyl propyl nitrile
32. nitromethane
***33. nitrotrichloromethane
(chloropicrin)
*34. tetrachloroethylene
*35. toluene
*36. trichloroethylene
*Selected for future quantification.
**List incomplete as analysis is continuing. Any ambiguities in
nomenclature will be corrected in the December 1975 report by
using the systematic name as well as the common name.
***Alternate for future quantification.
80
-------
TABLE 34
ORGANICS ADSORBED ON ACTIVATED CARBON
FROM CINCINNATI, OHIO SAMPLE
Approximate Concentration
Compounds Found In yg/1iter
*1. bromodichloromethane 1
*2. camphor 0.1
*3. chloral (trichloroacetaldehyde) 2
*4. chlorodibromomethane 0.5
*5. diethyl malonate 0.01
*6. diethyl phthalate 0.1
*7. lindane (Y BHC) 0.01
*8. n-propylbenzene 0.01
*9. tetrachloroethylene 0.1
10. 1,1,3,3-tetrachloro-2-propanone 0.5
*11. tri-n-butyl phosphate 0.05
*12. 1,3,5-triinethyl-2,4,6-trioxo-
hexa-hydrotriazine 0.5
*Confirned by comparison of MS and RRT with standard.
81
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E. DISCUSSION
1. AreTrihalomethanes Formed by Chlorination and If So, How Widespread
is Their Occurrence?
a. Trihalomethanes
The first objective of the national Organics Reconnaissance Survey
was to determine the extent of chlorination by-products in finished
drinking water as reported by Rookl? and Bellar, Lichtenberg and KronerJS
To meet this objective, raw and finished water from 80 locations, repre-
senting a wide variety of raw water sources and water treatment practices,
were sampled for the four trihalomethanes — chloroform, bromodichloro-
methane, dibromochloromethane, and bromoform.
In general, these four compounds were absent from the raw waters
tested or were present in concentrations of less than 1 yg/1. Therefore,
the presence of any of these four compounds in the finished water was
concluded to be caused by chlorination practices.
None of the systems investigated did not disinfect, but one system
practiced ozonation as the only treatment the water received. All of the
finished waters tested contained some chloroform although the system de-
scribed above only contained 0.1 Mg/1. Although a number of finished
waters did not contain bromodichloromethane, dibromochloromethane and
bromoform, the presence of these compounds were concluded to be wide-
spread throughout the finished waters of the nation.
Although the range of concentrations found for each of the four tri-
halomethanes was wide for the type of systems surveyed, the concentrations
of each of the compounds was not evenly distributed throughout the range
but were grouped toward the lower end of the range. Note: Many ground
water supplies in the United States do not chlorinate and therefore would
not contain any trihalomethane, but none of these supplies were included
in the Survey. Based on Figure 2, the theoretical finished water with
the median concentration (one-half of the data above and below) of each
compound, would contain about 21 yg/1 of chlorofrom, 6 yg/1 of bromodi-
chloromethane, 1.2 ug/1 of dibromochloromethane, and bromoform below the
detection limit of the analytic method used. Therefore, although the
presence of these compounds was widespread, in many'of the finished waters
tested in this survey their concentrations were fairly low.
Although most of the finished waters had concentrations of the four
trihalomethanes declining in the same order as those in the theoretical
"median" water described above, this was not true in all cases. The
reasons for concentrations of the heavier compounds being greater than
the lighter ones in some finished water are not known. Rook'7 has postu-
lated that if bromide was present in a water, the chlorine will oxidize
the bromide to bromine and the heavier bromo-compounds would be formed.
Whether this phenomenon occurred in some of the finished waters surveyed
is not known.
82
-------
300
100
50
en
a.
O
5
cc
UJ
u
o
o
UJ
UJ
1
<
X
E
10
1.0
0.5
-o
0.1
2 5 10 20 30 40 50 60 70 80 90 95 98 99
PERCENT EQUAL TO OR LESS THAN GIVEN CONCENTRATION
FIGURE 2. FREQUENCY DISTRIBUTION OF TRIHALOMETHANE DATA
83
-------
1 ! ,Z -Dichl^roethane and Carbon Tetrachlon'de
^ri "lysis was also made of all samples for 1 ,2-Dichloroethane and
i,di'i.'-;ii tetrachloride because they had been found in other drinking waters
previously and had potential health significance. In this Survey, these
two compounds were mostly absent from finished water. In about one-third
ot (.he cases where these compounds were present in the finished water,
they v.vjre also present in the raw water, indicating they were environ-
mental contaminants and were not created during water treatment. The
cause for the appearance of these compounds in the finished water when
they were absent from the raw water is not known at this time.
c Non-Volatile Total Organic Carbon
Iii addition to studying the six specific compounds discussed above,
an attempt was made to investigate the general organic level in finished
drinking waters by measuring the non-volatile total organic carbon
(NVTOC) concentration in all 80 locations. The range of these data was
from less than 0.05 mg/1 to 12.2 mg/1 , but again, the data were grouped
toward the lower end of the range, see Figure 3. The median NVTOC con-
centration (one-half of the data above and below) was 1.5 mg/1.
.,££ £f Source Type and Treatment Practice on Trihalomethane
Fprnjajtum
I'he second objective of ' the Survey was to determine, if possible,
the influence of type of source and treatment practiced on the formation
of chlori nation by-products. An initial examination of the data indi-
cated that the dominant factor influencing the creation of chlorination
by products was the general organic level of the water, provided suffi-
cient chlorine was added to satisfy the chlorine demand.
To test this hypothesis, the total trihalomethane concentration was
Mi si calculated for each finished water. This was done by dividing each
of the four concentrations by the appropriate molecular weight and adding
the quotients together. This yielded a total trihalomethane (TTHM) con-
centration in (jMoles/liter.* These data were then plotted against the
NVTOC concentration of the finished water. The TTHM data was divided
ii'to m'TOC cells in ascending order, each cell having a range of 0.5 mg/1
NVTOC, The average TTHM concentration was then calculated for each cell
arui plotted against the appropriate NVTOC concentration. This analysis
is: appropriate based on the assumption that each cell is sufficiently
large and heterogeneous with respect to the other variables that their
•influence is damped out by the averaging process.
During this analysis, the raw water NVTOC concentration was consid-
er* ed to be a better measure of the level of precursor available to react
1 viM/1 TTHM = 119 ug/1 chloroform if only chloroform was present.
84
-------
I I
.
en
ta
Z
o
5.0
Z
tu
U
O
O
i
cc
<
U
o
a
DC
o
2.0
1.0
P
in
0.5
o
I
O 0.3
O
0.2
i i i i i I i i i i i
5 10 20 30 40 50 60 70 80 90 95
% EQUAL TO OR LESS THAN GIVEN CONCENTRATION
98 99
FIGURE 3. FREQUENCY DISTRIBUTION OF NON-VOLATILE TOTAL ORGANIC CARBON DATA
85
-------
with the chlorine than the finished water NVTOC, particularly in situa-
tions where pre-chlorination is practiced, but the raw water NVTOC data
contained a negative error because of the inconplete combustion of sus-
pended material in the analytic procedure and could not be used. Analy-
sis of the data showed, however, that finished water NVTOC could be used
as an indicator of precursor level because raw- and finished-NVTOC con-
centrations are proportional to one another.*
The good correlation in Figure 4 shows that because most finished
waters contain a residual, meaning an excess of one of the reactants is
present, the concentration of the product (TTHM) is related to the con-
centration of the other reactants (unknown precursors) and further that
the NVTOC concentration is a reasonable indication of their concentrations.
All of the data were then divided into four NVTOC concentration cells,
0-1 mg/1, 1-2 mg/1, 2-3 mg/1, and greater than 3 mg/1 to eliminate the
influence of that variable and then sorted so that like source types and
treatment practices were in the same cells.
a. Source Influence
In the NVTOC 0-1 mg/1 cell, ground water sources had lower average
TTHM concentrations than surface waters. Considering all NVTOC cells
not much difference existed between the various types of surface water.
TABLE 30
SOURCE INFLUENCE
NVTOC Range
0-1 mg/1 1-2 mg/1
Avg. Avg.
TTHM TTHM
Cone. Cone.
n uM/1 n yM/1
2-3 mg/1
Avg.
TTHM
Cone.
n y M/l n
>3 mg/1
Avg.
TTHM
Cone.
uM/1
All Locations 18
Ground Water 9
River Water 7
Lake and Reservoir
Water 2
0.15 20 0.35
0.07 1 -0.32
0.25 10 0,47
0.21
0.21
10 0.56 10 1.07
1 0.11 2 1.65
5 0.60 2 0.98
4 0.61 6 0.90
*Based on these data, coagulation and filtration removed about 30% of the
raw NVTOC on the average, but this percentage is probably low.
86
-------
b. Trea tment In f1uence
1) Chiorination Practice
TABLE 31
CHLORINATION PRACTICE INFLUENCE
NVTOC Range
All Locations
Prechl ori nation
No Prechl ori nation
n
18
10
8
0-1 mg/1
Avg.
TTHM
Cone.
yM/1
0.15
0.23
0.05
n
20
17
3
1-2 mg/1
Avg.
TTHM
Cone.
yM/1
0.35
0.36
0.28
n
10
8
2
2-3 mg/1
Avg.
TTHM
Cone.
yM/1
0.56
0.58
0.48
>3 mg/1
Avg.
TTHM
n
10
7
3
Cone.
yM/1
1.07
1.33
0.45
Little or no Free
Residual 8 0.10 5 0.15 5 0.40 5 0.71
Little or No
Combined Residual 7 0.21 11 0.34 3 0.70 3 1.68
>0.4 mg/1 Free
Residual
In all NVTOC cell locations where prechlorination was practiced
higher average TTHM concentrations resulted than where no preclorination
was practiced. An attempt was made to relate prechlorine dose to average
TTHM production, but the number of locations in each cell was too small
to produce meaningful data. The trend of average TTHM production was
generally higher as prechlorine dose increased, but the data were quite
variable. The data on chlorine residual indicated that finished waters
that did not contain much free chlorine residual had lower TTHM concen-
trations than systems that had higher free chlorine residuals. The two
locations using ozone had very low concentrations of TTHM. In Whiting,
Indiana pre-ozonation is used following pre-chlorination. Whether or not
the reduction in TTHM concentration following ozonation is caused by
simple stripping or reaction of the ozone with the trihalomethanes is not
known at this time. In the other installation, Strasburg, Pennsylvania,
not only was ozonation the only treatment, but also the NVTOC concentra-
tion was only 0.05 mg/1. Both of these factors may have contributed to
the low TTHM concentration.
87
-------
2) Filtration Practice
All of the locations that practice filtration were sorted into NVTOC
concentration cells and then re-sorted based on the use of polyelectrolyte
either as a coagulant or filter-aid. Surface water was the raw water
source for 90% of these plants, so that variable is essentially removed.
This was to determine whether or not polyelectrolyte could aid as a pre-
cursor for TTHM formation. In the study group, the polyelectrolyte dose
varied from 0.02 mg/1 to 3.94 mg/1 (1.27 mg/1 in the raw water, plus
2.67 mg/1 on the filters) on the days of sampling. At two locations the
dose was unknown. Table 32 shows that the use of polyelectrolyte does
not enhance TTHM formation.
TABLE 32
INFLUENCE OF FILTRATION PRACTICE
NVTOC Range
0-1 mg/1
Avg.
TTHM
Cone.
n pM/1 n
1-2 mg/1
Avg.
TTHM
Cone.
uM/1 n
2-3 mg/1
Avg.
TTHM
Cone.
pM/1 n
>3 mg/1
Avg.
TTHM
Cone.
uM/1
All 18 0.1.5
All Filter Plants 10 0.23
With Polyelectro-
lytes 4. 0.26
Without Poly-
electrolytes 6 0.21
20 0.35 10 0.56 10 1.07
13 0.38 7 0.61 10 1.07
0.42
14 0.37
0.81
1.28
0.53 8 1.01
3) Use of Activated Carbon
A. Powdered
Of the treatment plants using powdered activated carbon the dosage
varied from 0.6 mg/1 to 6.5 mg/1. All of these plants were surface
water plants. Table 33 shows that, in NVTOC concentration cells where
sufficient numbers exist for comparison purposes, locations where powdered
activated carbon was used had average TTHM concentrations similar to
those locations without powdered activated carbon. Either powdered
activated carbon cannot remove trihalomethane precursors or the dosages
used were insufficient to accomplish this.
88
-------
TABLE 33 ,
INFLUENCE OF POWDERED ACTIVATED CARBON
0-1 mg/1
Avq.
TTHM
Cone.
NVTOC Range
All
All Filter Plants
n
18
10
yM/1
0
0
.15
.23
n
20
18
1-2 rig/1
Avg.
TTHM
Cone.
jyM
0.
0.
I/I
35
38
n
10
7
2-3 mg/1 ;
Avg.
TTHM
Cone.
v
0
0
M/l
.56
.61
n
10
10
Avq .
rniM
Cone
j.il-1/ 1
1.07
! 07
With Powdered
Activated Carbon 2 0.31 5 0.42 5 0.58
Without Powdered
Activated Carbon 7 0.20 11 0.35 5 0.58
B. Granular
Only six water treatment plants used granular activated carbon as
a combination filtration/adsorption media, and this number is too small
to make an analysis as above. All treat surface water, pre-chlorineto,
and all but one had >0.4 mg/1 free residual in the finished water, "o
some of the variables noted above were eliminated. Because all of the
locations originally sampled were using granular activated carbon that
had been in place for at least several months, the activated carbon w-r;
exhausted for NVTOC removal. This is shown in Table 34; the averane
NVTOC removal at these locations was not much higher than equal to nr
greater than 30 percent NVTOC removal previously reported for all
coagulation-filtration plants. Therefore the TTHM concentration in these
finished waters being higher than the TTHM concentration in the theoreti
cal "median" finished water for the entire survey in 5 out of 6 loC'tfrioris
is not surprising. This is also true when the data are examined on -i
"TTHM production per unit of NVTOC" basis.
Shortly after the Survey samples were taken at one of these locations
the granular activated carbon was removed and replaced with virgin lignite
base material. This location was resampled in an effort to evaluate the
performance of fresh granular activated carbon. The data in fable 34
show a marked improvement in all three of the parameters listed indi
eating the effectiveness of fresh granular activated carbon for1 treatment,
Another attempt was made to evaluate the performance of granular
activated carbon for treating a variety of waters by monitoring th*3
activated carbon (CAM) units installed in the five locations where thp
samples of organics that could be adsorbed on activated carbon frou
89
-------
Table 34
SUMMARY OF GRANULAR ACTIVATED CARBON PLANTS
Location
20
37
1
47
43
57
Avg.
Theo.
Median
Water*
Fresh
Gran.
Act.
Carbon
Finished
Water
NVTOC
Cone.
mg/1
1.0
1.4
1.6
3.2
4.2
4.4
1.5
1.4
% Removal
of NVTOC
>55
>30
>56
>41
>30
>32
>41
«•
>79
TTHM
Concentration
yM/1
0.31
0.41
0.82
1.36
1.19
0.79
0.22
0.08
TTHM/
Fin. NVTOC
pM/mg
0.31
0.10
0.51
0.43
0.28
0.18
0.30
0.15
0.06
*See Figures 2 and 3 for median concentration.
90
-------
finished waters were being collected. The samplers were 3-foot columns
of coal-based granular activated carbon operated downflow at an approach
velocity of 3.2 gallons per minute/square foot, and finished water was
passed through them for seven days. The empty bed contact time was about
7 minutes. Table 35 shows that fresh granular activated carbon produced
low NVTOC concentrations at first in all locations except Miami where
the load was so heavy that a longer contact time would be needed to
produce a lower NVTOC concentration.
c. Section Summary
To test the hypothesis that the use of surface water as a source,
pre-chlorination, and the presence of greater than 0.4 mg/1 free chlorine
residual enhances the formation of trihalomethanes, the data were sorted
on that basis. Out of the entire survey 28 locations met these three
criteria.
TABLE 35
PERFORMANCE OF FRESH COAL-BASED GRANULAR ACTIVATED CARBON SAMPLERS
TREATING FINISHED WATER
Location
Day
Seattle, 0
Washington 7
Ottumwa, 0
Iowa 7
Philadelphia, 0
Pennsylvania 7
Cincinnati, 0
Ohio 7
NVTOC Concentration - mg/1
Influent to Effluent from NVTOC
Sampler Sampler Removed
Miami ,
Florida
0
7
8.1
7.1
1.3
3.5
84%
51%
1.9
0.8
3.6
3.4
2.0
1.9
1.2
1.6
1.9*
0.05
1.6*
0.9
0.3
0.5
0.1
0.1
0%*
94%
56%*
73%
85%
74%
la
94%
*Data Suspect.
Of these, 10 finished waters had an NVTOC concentration less than
the Survey median concentration of 1.5 mg/1, the remainder being equal to
91
-------
or greater than the median. Of those with a' finished water NVTOC concen-
tration below the median concentration, 80% had a TTHM concentration
above the median TTHM concentration. While of those with a finished
water NVTOC concentration equal to or greater than the median concentra-
tion, only 11% had TTHM concentrations below the median TTHM concentration.
While this indicates the general validity of the proposed hypothesis,
a rigorous multiple regression analysis of the data would be helpful.
This analysis will be included in the December 1975 report.
3. Alternate Indicators of Organic Contaminant Levels
Because various organic contaminants vary in toxicity, specific
organic compounds should be monitored in finished waters. This is the
recommended procedure for monitoring organochlorine pesticides, for
example. Except for a few specific examples, this approach is beyond
the capabilities of most water utilities and to some degree even is beyond
the capabilities of researchers, given the current state of organic analy-
sis. Al1 specific organic compounds present in water cannot now be
identified and quantified.
In the absence of measuring for specific organic compounds, the
next best alternative is to measure some organic parameter that includes
a large number of organic compounds and assume that the level of this
parameter is proportional to,the level of toxicity of the water. On
this basis carbon chloroform extract (CCE-m) was included in the Interim
Primary Drinking Water Regulation.
In the National Organics Reconnaissance Survey non-volatile total
organic carbon was the parameter chosen to represent the concentration
of organics in the water. Figure 4 shows NVTOC to be generally propor-
tional to trihalomethane formation, so a measure such as this is probably
useful, but little else is known about NVTOC.
In an effort to find an easier analytic procedure for monitoring
the organic level in water, three other measurements were made on each
raw and finished water in addition to NVTOC concentration. These were
ultraviolet absorption (UV), emission fluorescence scan (EmFC), and the
Rapid Fluorometric Method (RFM). An attempt was made to correlate these
parameters, even though different organics absorb ultraviolet to dif-
fering degrees and some different organics fluoresce to differing degrees.
Therefore, although the a priori judgment was that those three parameters
might not correlate with NVTOC concentrations because they would be
heavily influenced by the types of organics present in the water, the
hypothesis that different waters would be sufficiently similar to make
these procedures useful was tested.
Just as particulates in some raw waters interfered with the NVTOC
measurement, the resultant turbidity interfered with the UV, EmFS, and
RFM measurements. Plots of NVTOC concentration versus each parameter
92
-------
0.9
0.8
0.7
0.6
1 °-5
CD
<
CC
UI
> 0.4
0.3
0.2
0.1
0(5)
(NO.) = NUMBER OF LOCATIONS
IN NVTOC CELL
NOTE:
1 ^MOLE/LITER TTHM =
119 MG/L CHLOROFORM
IF IT WAS ALL CHLOROFORM
FIGURE 4. CORRELATION OF TOTAL TRIHALOMETHANE
CONCENTRATION WITH NON-VOLATILE TOTAL ORGANIC CARBON
I
2 34
FINISHED WATER NVTOC - mg/l
93
-------
for finished water, Figures 5, 6, and 7 show a wide scatter of data. On
Figure 5 a band 1 mg/1 of NVTOC wide includes 39 data points, while
only excluding 28 data points, up to an NVTOC concentration of 3.5 mg/1,
but the overall correlation is not very good. The two fluorescence tech-
niques correlated well with each other but not with NVTOC concentration.
4. Organics Found in the 5-Location Study
Because the qualitative results are incomplete and the quantitative
results are absent, these data cannot be discussed, except to note that
thus far the upland water and the water contaminated by agricultural
runoff have had the fewest organics identified from them.
5. Significance of Findings
Most water treatment plants are not designed to remove soluble organic
compounds from raw water, and disinfection creates some compounds that
were not originally present in the raw water. Therefore, the finding
that all finished waters in the Survey contained one type of organic
compound or another should not be surprising. The presence of an organic
compound in a finished water is not significant, however, unless its con-
centration is such that it poses a health hazard. The data contained in
Appendix II, therefore, must be combined with that in Appendix VII,
"Health Effects Caused by Exposure to Drinking Water Contaminants" before
any significance can be attached to the data contained herein. If a
health hazard is found to exist with any contaminant, then the treatment
information contained in Appendix VI must be applied.
94
-------
.18
.16
.14
I
O .12
1
en
oo
I- .10
3 .08
OC
ui
s
.04
••
•
_ •
• w •
.02 h * • * FIGURE 5 CORRELATION BETWEEN
• * ULTRA-VIOLET ABSORBANCE AND
» • 2 • NON-VOLATILE TOTAL ORGANIC
0 CARBON IN FINISHED WATER
> |_ 1 , . .
234
FINISHED WATER NVTOC, mg/l
95
-------
21
19
17
15
z
Q
O
X
LU
s
D
u.
13
11
FIGURE 6 CORRELATION OF
RAPID FLUORMETRIC METHOD
AND NON-VOLATILE TOTAL
ORGANIC CARBON IN
FINISHED WATER
1
1
I
234
FINISHED WATER NVTOC, mg/l
96
-------
1900
1700
1500
1300
3
o 1100
ui
UJ
oc
O
u 900
O
ui
700
500
300
FIGURE 7
CORRELATION OF EMISSION
FLUORESCENCE SCAN AND NON-VOLATILE
TOTAL CARBON IN FINISHED WATER
100
I
234
FINISHED WATER NVTOC, mg/l
97
-------
F. ACKNOWLEDGMENTS
The following organizational units of EPA contributed to the timely
conduct of the National Organics Reconnaissance Survey and to the prepara-
tion of this report.
Water Supply Research Laboratory, ORD
Methods Development and Quality Assurance
Laboratory, ORD
Southeast Environmental Research Laboratory, ORD
R. S. Kerr Environmental Research Laboratory, ORD
Office of Environmental Sciences, ORD
Office of Monitoring Systems, ORD
National Field Investigations Center - Cincinnati,
OE
Water Supply Division, OWHM
Regional Water Supply Representatives
The EPA personnel whose cooperation and dedication in accomplishing
the many activities that resulted in this report are to be commended
for their outstanding performance within the difficult constraints
involved.
Special commendation is due Mrs. Maura M. Lilly who typed the entire
first draft of this appendix in three working days.
98
-------
G. REFERENCES
1. Buelow, R. W., J. K. Carswell and J. M. Symons, "An Improved Method
for Determining Organics by Activated Carbon Adsorption and Solvent
Extraction (Parts I and II)," Journal American Water Works Associa-
tion, 65_, 57-72, 195-199 (Jan.-March 1973).
2. Bellar, T. A. and J. J. Lichtenberg, "The Determination of Volatile
Organic Compounds at the yg/1 Level in Water by Gas Chromatography,"
USEPA Report, NERC, Cincinnati, EPA-670/4-74-009, Nov. 1974.
3. Stevens, A. A. and J. M. Symons, "Analytical Considerations for
Halogenated Organic Removal Studies," USEPA Water Supply Research
Laboratory, NERC-Cincinnati, Dec. 1974, Prepublication copy.
4. "Method for Polychlorinated Biphenyls in Industrial Effluents,"
National Pollution Discharge Elimination System, Appendix A,
Methods Development and Quality Assurance Research Laboratory,
Cincinnati, Ohio, November 28, 1973.
5. Dressman, R. C. and E. F. McF.arren, "Detection and Measurement of
Bis-(2-chloro) Ethers and Dieldrin by Gas Chromatography," Second
Annual Water Quality Conference of American Water Works Association,
Dallas, Texas, December 2-4, 1974.
6. Bellar, T. A. and J. J. Lichtenberg, "Determining Volatile Organics
at the ug/1 Level in Water by Gas Chromatography," JAWWA. 66,
739-744 (December 1974).
7. "Method for Organophosphorous Pesticides in Industrial Effluents,"
National Pollution Discharge Elimination System, Appendix A,
Methods Development and Quality Assurance Research Laboratory,
Cincinnati, Ohio, November 28, 1973.
8. Dobbs, R. A., R. H. Wise and R. B. Dean, "The Use of Ultraviolet
Absorbance for Monitoring the Total Organic Carbon Content of Water
and Wastewater," Water Research. £, 1173-80 (1972).
9. Sylvia, A., "Detection and Measurement of Microorganics in Drinking
Water," Jour. New Eng. Water Works Assn.. 87_, No. 2 (June 1973).
10. Standard Methods for the Examination of Water and Wastewater,
13th Edition, American Public Health Association, New York,
New York.
11. "Methods for Chemical Analysis of Water and Wastewater," U. S.
Environmental Protection Agency, 1974.
12. Caldwell, J. S., R. J. Lishka, and E. F. McFarren, "Evaluation of
Low-Cost Arsenic and Selenium Determination at Microgram-per-Liter
Levels," JAWWA, 63_, 731 (1973).
99
-------
13. "Cyanide in Water and Wastewater, Industrial Method," No. 119-71W,
April 1972, Technicon Instrument Corp., Tarrytown, New York.
14. Kopp, J. F., M. C. Longbottom, and L. B. Lobring, "Cold Vapor Method
for Determining Mercury," JAWWA. 64, 20 (1972).
15. Organochlorine Pesticides in Water, 1974 Annual Book of ASTM
Standards, American Society for Testing Materials.
16. Georlitz, D. T., and W. L. Lower, Determination of Phenoxy Acid
Herbicides in Water by Electron Capture and Micro Coulometric Gas
Chromatography. Geological Survey Water Supply Paper 1817C, U. S.
Government Printing Office.
17. Rook, J. J., "Formation of Haloforms During Chlorination of Natural
Waters," Water Treatment and Examination. 2_3, Part 2, 234-243 (1974),
18. Bellar, T. A., J. J. Lichtenberg, and R. C. Kroner, "The Occurrence
of Organohalides in Chlorinated Drinking Water," JAWWA, 66_, 703-706,
(December 1974).
100
-------
APPENDIX III
ORGANIC CHEMICALS FOUND IN INDUSTRIAL EFFLUENTS
Southeast Environmental Research Laboratory
Athens, Georgia
and
Office of Research and Development
Environmental Protection Agency
Washington, D.C.
-------
ORGANIC CHEMICALS IN INDUSTRIAL EFFLUENTS
The compositions of industrial effluents are being systematically
studied at the Southeast Environmental Research Laboratory. In
addition, short-term studies for special purposes have been conducted
at the request of Regional and other offices. Table 1 is a composite
list of substances and their sources as of mid-1973. Compounds in
textile mill effluents identified since 1973 are listed in Table 2.
In general the lists of compounds already found in drinking water
appear to have more in common with the lists of compounds occurring in
industrial wastes than the list of compounds occurring in domestic
sewage. Of those substances identified as suspect carcinogens, two,
chloroform and bis (2-chloroethyl) ether appear in industrial wastes
and have not been shown to occur in domestic sewage. It should be
mentioned, however, that there is the possibility that these compounds
are formed during the chlorination of drinking water.
With the presently available information, it would appear that the
organic substances occurring in drinking water are for the large part
of industrial origin. Where special studies have been undertaken to
identify specific compounds causing problems, such as taste and odor,
in water supplies, the results have led to the conclusion that the
causative agents were of industrial origin. It should be kept in mind,
however, that the analyses of drinking water, municipal wastewaters and
industrial effluents is continuing and the final results may present a
somewhat different picture.
102
-------
Table 1
ORGANIC CHEMICALS FOUND IN INDUSTRIAL WASTES
Compound
Sample source
6,8,11,13-Abietatetraen-18-
oic acid
13-Abieten-18-oic acid
Abietic acid
Acenaphthalene
Acenaphthene
Acetophenone
Acetosyringone
Acetovanillone
Paper mill's raw waste and trickling
filter effluent
Paper mill's raw waste and trickling
filter effluent
Paper mill's raw waste and lagoon
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Wood preserving plant's lagoon
effluent
Wood preserving plant's settling
pond
Pesticide plant's raw effluent
Chlorinated paraffin plant's
lagoon
Petrochemical plant's five-day
lagoon effluent
Gulf coast paper mill's settling
pond
Gulf coast paper mill's settling
pond
Paper mill's raw waste and lagoon
103
-------
Table 1 (Continued)
2-Acetylthiophene
Acrylonitrile
Adipic acid
Adiponitrile
Aldrin
m-Anethole
o-Anethole
p-Anethole
Anthraquinone
Anteisomargaric acid
Anteisopentadecanoic acid
Arachidic acid
Arachidonic acid
Behenic acid
Benzaldehyde
Benzyl alcohol
2-Benzothiazole
Paper mill's raw waste
Acrylic fiber plant's settling pond
Nylon plant's raw waste
Nylon plant's raw waste
Pesticide plant's raw effluent
Paper mill's raw waste
Paper mill's raw waste
Paper mill's raw waste
Wood preserving plant's settling
pond
Paper mill's raw waste and five-day
lagoon
Paper mill's five-day lagoon
Paper mill's raw waste
Paper mill's five-day lagoon
Paper mill's raw effluent and five-
day lagoon
Paper mill's raw waste
Petrochemical plant's five-day
lagoon effluent
Latex accelerators and thickeners
plant's holding pond
Synthetic rubber plant's aerated
lagoon
104
-------
Table 1 (Continued)
Biphenyl
Borneol
1-Butanol
2-Butoxyethanol
n-Butylisothiocyanate
Camphor
Caproic acid
Carbazole
Chlordane
Chlordene
o-Chlorobenzoic acid
bis-(2-Chloroethoxy) methane
bis-2-Chloroethyl ether
bis-2-Chloroisopropyl ether
trans-Communic acid
River below textile finishing plant
Paper mill's raw waste and trickling
filter effluent
Petrochemical (alcohols) plant's
raw effluent
Petrochemical plant's five-day
lagoon effluent
Latex accelerators and thickeners
plant's holding pond
Paper mill's raw waste and trickling
filter effluent
Gulf coast paper mill's settling
pond
Nylon plant's raw waste
Wood preserving plant's settling
pond
Pesticide plant's raw effluent
Pesticide plant's raw waste
Chlorinated paraffin plant's lagoon
Synthetic rubber plant's treated
waste
Synthetic rubber plant's treated
waste
Glycol plant's thickening and
sedimentation pond
Paper mill's raw waste and trickling
filter effluent
105
-------
Table 1 (Continued)
o-Cresol
o-Cresol
m-Cresol
p-Cresol
Cumene (isopropylbenzene)
Cyclohexanol
1,5-Cyclooctadiene
p-Cymene
Decane
1-Decanol
Dehydroabietic acid
Diacetone alcohol
Wood preserving plant's settling
pond
Petrorefinery's eight-hour lagoon
effluent
Wood preserving plant's settling
pond
Paper mill's raw waste and lagoon
Petrochemical plant's five-day
lagoon effluent
Nylon plant's raw waste
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste and trickling
filter effluent
Pesticide plant's raw waste
Polyolefin plant's lagoon
Petrochemical (alcohols) plant's
raw effluent
Wood preserving plant's settling
pond
Paper mill's raw waste and trick-
ling filter effluent
Gulf coast paper mill's settling
pond
Tall oil refinery's settling pond
Petrochemical plant's five-day
lagoon effluent
106
-------
Table 1 (Continued)
4,4'-Diamino-dicyclohexyl
methane
Dibenzofuran
2,3-Dibromo-l-propanol
Dibromopropene isomer
Dibutyl amine
Dieldrin
N,N-Di ethylformami de
Diethyl phthalate
3,4-Dihydroxyacetophenone
(pungenin)
3,5-Dimethoxy-4-hydroxy-
acetophenone
2,4-Dimethyldiphenylsulfone
Nylon and polyester plant's
effluent after neutralization
and sedimentation
Wood preserving plant's settling
pond
Wood preserving plant's lagoon
effluent
Nylon plant's settling pond
Acrylic fibers plant's settling
pond
Acrylic fibers plant's settling
pond
Latex accelerators and thickeners
plant's raw effluent
Anaerobic lagoon of yarn finishing
mill
Pesticide plant's raw effluent
Latex accelerators and thickeners
plant's raw effluent
Synthetic rubber plant's settling
pond
Paper mill's trickling filter
effluent
Paper mill's raw effluent and
five-day lagoon
Nylon plant's settling pond
Acrylic fibers plant's settling
pond
107
-------
Table 1 (Continued)
Dimethyl furan isomer
2,6-Dimethyl naphthalene
Dimethyl naphthalene isomer
Dimethyl phthalate
Dimethyl pyridine isomer
Dimethyl quincline isomers
Dimethyl sulfone
Dimethyl sulfoxide
10,12-Dimethyl tridecanoic
acid
4,6-Dinitro-o-cresol
(2-methyl-4,6-dinitro-phenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
3,4-Dinitrotoluene
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Pesticide plant's raw effluent
Plastic (PVA) plant's settling
pond
Synthetic rubber plant's settling
pond
Wood preserving plant's settling
pond
Wood preserving plant's settling
pond
Paper mill's raw waste and trickling
filter effluent
Paper mill's raw waste and trickling
filter effluent
Paper mill's five-day lagoon
Specialty chemical plant's
effluent
Explosives (DNT) plant's raw waste
and settling pond effluent
Explosives (DNT) plant's raw waste
and settling pond effluent
TNT plant's raw effluent
Explosives (DNT) plant's raw waste
and settling pond effluent
108
-------
Table 1 (Continued)
Diphenylene sulfide
Diphenyl ether
3,3-Dlphenylpropanol
2,6-Di-t-butyl-p-benzo-quinone
p-Dithiane
Dodecane
Eicosane (C20)
Endrin
Ethyl carbamate
2-Ethyl-l-hexanol
Ethylidenecyclopentane
Wood preserving plant's settling
pond
Pesticide plant's raw effluent
Petrochemical plant's five-day
lagoon effluent
Surface drainage from closed waste
treatment system of particle
board plant
Synthetic rubber plant's treated
waste
Petrorefinery's lagoon effluent
after activated sludge treatment
Petrorefinery's eight-hour
lagoon effluent
Paper mill's raw effluent
Petrorefinery's lagoon effluent
after activated sludge treatment
Pesticide plant's raw effluent
Paper mill's trickling filter and
aerated lagoon
Gulf coast paper mill's settling
pond
Laboratory sewage
Plastic (PVA) plant's settling pond
River below textile finishing plant
Paper mill's raw waste
109
-------
Table 1 (Continued)
Ethyl isothiocyanate
Ethyl naphthalene isomer
ii
m-Ethyl phenol
Ethyl phenylacetate
o-Ethyl toluene
Eugenol
Fenchyl alcohol
Fenchone
Fluoranthene
Fluorene
2-Formylthiophene
Furfural
Guaiacol
Latex accelerators & thickeners
plant's raw effluent
Petrochemical plant's five-day
lagoon effluent
Pesticide plant's raw effluent
Paper mill's raw waste and lagoon
Resin plant's lime treated holding
pond effluent
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste and lagoon
Paper mill's raw waste and trick-
ling filter effluent
Paper mill's raw waste and trick-
ling filter effluent
Wood preserving plant's settling
pond
Wood preserving plant's settling
pond
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste
Paper mill's raw waste
Synthetic rubber plant's settling
pond
Gulf coast paper mill's settling
pond
110
-------
Table 1 (Continued)
Guaiacol
Heneicosane (C2l)
Heptachlor
Heptachloronorbornene
isomers
Heptadecane
Hexachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloronorbornadi ene
i somers
Hexadecane
Paper mill's raw waste and trick-
ling filter effluent
Petrorefinery's lagoon effluent
after activated sludge treat-
ment
Pesticide plant's raw waste
Pesticide plant's raw effluent
Nylon plant's settling pond
Petrorefinery's eight-hour lagoon
effluent
Petrorefinery's lagoon effluent
after activated sludge treatment
Pesticide plant's raw waste
Chlorinated solvents plant's raw
effluent
Pesticide plant's raw effluent
Pesticide plant's raw waste
Pesticide plant's raw effluent
Nylon plant's settling pond
Petrorefinery's eight-hour
lagoon effluent
Petrorefinery's lagoon effluent
after activated sludge treatment
Paper mill's raw waste
111
-------
Table 1 (Continued)
Hexadecane
Hexadieneal
1-Hexanol
Homovanillic acid
p-Hydroxyacetophenone
p-Hydroxybenzaldehyde
o-Hydroxybenzoic acid
Hydroxybiphenyl isomer
4-Hydroxy-3 methoxypropio-
phenone
p-Hydroxythiophenol
Indan
Indene
Isodrin
Isoeugenol
Isopalmitic acid
Isopentyl alcohol
Isooctyl phthalate
Isopimaric acid
Petrochemical plant's five-day
lagoon effluent
Pesticide plant's raw effluent
Petrochemical (alcohols) plant's
raw effluent
Paper mill's raw waste and five-day
lagoon
Paper mill's raw waste and lagoon
Paper mill's raw waste and lagoon
Paper mill's raw waste
Pesticide plant's raw effluent
Paper mill's raw effluent
Paper mill's raw waste
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Pesticide plant's raw effluent
Paper mill's raw waste and lagoon
Paper mill's five-day lagoon
Laboratory sewage
Nylon plant's raw waste
Paper mill's raw waste and trickling
filter effluent
112
-------
Table 1 (Continued)
Jasmone
Lignoceric acid
Limonene
Linoleic acid
Mandelic acid
Margaric acid
2-Mercaptobenzothiazol e
ii
alpha-Methyl benzyl alcohol
Methyl biphenyl isomer
Methyl 3,4-Dimethoxybenzyl
ether
2-Methyl-4-ethyl dioxolane
Methyl ethyl naphthalene
i somer
1-Methyl indene
3-Methyl indene
1-Methyl naphthalene
Pesticide plant's raw effluent
Paper mill's raw waste
Paper mill's raw waste and trick-
ling filter effluent
Paper mill's raw waste and lagoon
Paper mill's raw waste
Paper mill's raw waste
Synthetic rubber plant's aerated
lagoon
Paper mill's raw waste and lagoon
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste
Fiberglass plant's effluent
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
River below textile finishing
plant
113
-------
Table 1 (Continued)
1-Methyl naphthalene
2-Methyl naphthalene
Methyl naphthalene isomer
Methyl naphthalene isomers
13-Methyl pentadecanoic acid
Methyl phenanthrene
Methyl quincline isomers
o-Methylstyrene
beta-Methylstyrene
Methyl trisulfide
Myristic acid
Naphthalene
Petrorefinery's eight-hour
lagoon effluent
Petrochemical plant's five-day
^ lagoon effluent
Synthetic rubber plant's settling
pond
Petrorefinery's eight-hour lagoon
effluent
Petrochemical plant's five-day
lagoon effluent
Wood preserving plant's lagoon
'effluent
Pesticide plant's raw effluent
Paper mill's five-day lagoon
Wood preserving plant's lagoon
effluent
Wood preserving plant's settling
pond
Petrochemical plant's five-day
effluent
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste
Paper mill's raw waste
Nylon plant's settling pond
Surface drainage from closed treat-
ment of system of particle
board plant
114
-------
Table 1 (Continued)
Naphthalene
ii
2-Naphthoic acid
Neoabietic acid
Nitrobenzene
2-Nitro-p-cresol
o-Nitrophenol
o-Nitrotoluene
m-Nitrotoluene
p-Nitrotoluene
it
Nonachlor
Nonadecane
Nonylphenol
Petrochemical plant's five-day
lagoon effluent
Pesticide plant's raw waste
Wood preserving plant's settling
pond
Paper mill's raw waste
Chemical company's lagoon after
steam stripping
Chemical company's lagoon after
steam stripping
Chemical company's lagoon after
steam stripping
Paper mill's five-day lagoon
TNT plant's raw effluent
DNT plant's raw effluent
DNT plant's raw effluent
Chemical company's lagoon after
steam stripping
DNT plant's raw effluent
Pesticide plant's raw effluent
Petrorefinery's lagoon effluent
after activated sludge treatment
Petrorefinery's eight-hour lagoon
effluent
Anaerobic lagoon of yarn finishing
mill
115
-------
Table 1 (Continued)
Nonylphenol
Norcamphor
beta-Ocimene
1-Octanol
Octachlorocyclopentene
Octadecane
Oleic acid
Octylphenol
Palmitic acid
Palmitoleic acid
Pentachlorocyclopentadiene
isomers
Pentachloronorbornadiene
isomer
River below textile finishing
plant
Paper mill's raw waste
Paper mill's raw waste
Petrochemical (alcohols) plant's
raw effluent
Pesticide plant's raw effluent
Petrorefinery's eight-hour lagoon
effluent
Nylon plant's settling pond
Tall oil refinery's settling pond
Paper mill's raw waste and trickling
filter effluent
River below textile finishing plant
Textile chemical plant's raw
effluent
Tall oil refinery's settling pond
Paper mill's raw waste and trickling
filter effluent
Gulf coast paper mill's settling
pond
Paper mill's five-day lagoon
Pesticide plant's raw effluent
Pesticide plant's raw effluent
116
-------
Table 1 (Continued)
Pentachloronorbornene isomer
Pentachloronorbornadiene
epoxide isomer
Pentachlorophenol
Pentadecane
Pentadecanoic acid
Phenanthrene
Phenol
Pesticide plant's raw effluent
Pesticide plant's raw waste
Pesticide plant's raw waste
Latex accelerators and thickeners
plant's holding pond
Wood preserving plant's raw
effluent
Resin plant's lime treated
holding pond efiluent
Synthetic rubber plant's aerated
lagoon
Wood preserving plant's lagoon
effluent
Petrorefinery's eight-hour
lagoon effluent
Petrorefinery's lagoon effluent
after activated sludge treatment
Paper mill's raw waste
Petrochemical plant's five-day
.lagoon effluent
Paper mill's lagoon
Wood preserving plant's lagoon
effluent
Wood preserving plant's settling
pond
Laboratory sewage
117"
-------
Table 1 (Continued)
Phenol
Phenyl ether
o-Phenylphenol
Pimaric acid
beta-Pinene
Pinene isomer
Polychlorinated biphenyls
(Arochlor 1254)
2-Propionylthiophene
4-n-Propylphenol
Pyrene
Quinoline
Sandaracopimeric acid
Petrorefinery's eight-hour lagoon
effluent
Wood preserving plant's settling
pond
Petrochemical plant's five-day
lagoon effluent
Paper mill's raw waste
Nylon plant's settling pond
River below textile finishing plant
Paper mill's raw waste and trick-
ling filter effluent
Gulf coast paper mill's settling
pond
Paper mill's raw waste
Gulf coast paper mill's settling
pond
Nylon plant's raw waste
Paper mill's raw waste
Paper mill's raw waste and lagoon
Wood preserving plant's settling
pond
Wood preserving plant's settling
pond
Paper mill's raw waste and lagoon
118
-------
Table 1 (Continued)
Stearic acid
Styrene
Syringaldehyde
H
Terpinene-4-ol
alpha-Terpineol
Terpineol isomer
Terpinolene
1,1,2,2-Tetrachloroethane
Tetrachlorophenol isomer
Tetradecane
Textile chemical plant's raw
effluent
Gulf coast paper mill's settling
pond
Petrochemical plant's five-day
lagoon effluent
Synthetic rubber plant's settling
pond
Gulf coast paper mill's settling
pond
Paper mill's lagoon
Paper mill's raw waste
Nylon plant's settling pond
Paper mill's raw waste and trick-
ling filter effluent
Petrochemical plant's five-day
lagoon effluent
Gulf coast paper mill's settling
pond
Paper mill's raw waste
Chlorinated solvents plant's
raw effluent
Wood preserving plant's raw
effluent
Petrorefinery's lagoon effluent
after activated sludge treat-
ment
Petrorefinery's eight-hour lagoon
effluent
119
-------
Table 1 (Continued)
Tetramethylbenzene isomer
2,2'-Thiodiethanol
(Thiodiglycol)
Toluic acid
Trichlorobenzene isomer
Tri chlorocyclopentene
i somers
1,1,2-Trichloroethane
Trichloroguaiacol
n-Tridecane
Triethyl urea
3,4,5-Trimethoxyaceto-
phenone
2,4,6-Trimethylpyridine
2,4,6-Trinitrotoluene
n-Undecane
Pesticide plant's raw waste
Synthetic rubber plant's treated
waste
Chlorinated paraffin plant's
lagoon
River below textile finishing
plant
Textile chemical plant's raw
effluent
Pesticide plant's raw effluent
Chlorinated solvents plant's raw
effluent
Paper mill's raw waste
Petrorefinery's eight-hour
lagoon effluent
Petrorefinery's lagoon effluent
after activated sludge treat-
ment
Paper mill's raw waste
Latex accelerators & thickeners
plant's raw effluent
Paper mill's raw waste and trick-
ling filter effluent
Wood preserving plant's settling
pond
TNT plant's raw effluent
Paper mill's raw waste
120
-------
Table 1 (Continued)
n-Undecane
Valeric acid
Vanillin
Veratraldehyde
o-Xylene
m-Xylene
p-Xylene
2,5-Xylenol
3,4-Xylenol
3,5-Xylenol
Petrorefinery's eight-hour
lagoon effluent
Polyolefin plant's lagoon
Petrorefinery's lagoon effluent
after activated sludge treat-
ment
Nylon plant's raw waste
Paper mill's raw waste and trick-
ling filter effluent
Gulf coast paper mill's settling
pond
Paper mill's raw waste & lagoon
Syntehtic resin plant's settling
pond
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Petrochemical plant's five-day
lagoon effluent
Wood preserving plant's settling
pond
Wood preserving plant's settling
pond
Wood preserving plant's settling
pond
121
-------
Table 2
ORGANIC COMPOUNDS IN TEXTILE EFFLUENTS
Compound
1,2,4-trichlorobenzene
benzole acid (methyl ester)
p-nonylphenol
p-tert -butylphenol
di-n-butyl phthalate
methyl isobutyl ketone
acetophenone
chlorobenzene
p-dichlorobenzene
toluene
ethyl benzene
naphthalene
1-methyl naphtha!ene
dodecane
2-methylpyrrolidone
1,3,5-trimethylbenzene
cymene
tridecane
tetradecane
chloroform
tetrachloroethy1ene
styrene
o-phenylphenol
biphenyl
diphenyl oxide
ethylene dichloride
benzophenone
n-butanol
122
-------
APPENDIX IV
MONITORING FOR RADIATION IN DRINKING WATER
Office of Radiation Programs
Environmental Protection Agency
Washington, D.C.
-------
MONITORING FOR RADIATION IN DRINKING WATER
This appendix focuses on the Environmental Radiation Ambient
Monitoring System. Radium-226 and methods of removing it from water
supplies are the subject of section C(4) of Appendix VI.
The Environmental Radiation Ambient Monitoring System (ERAMS),
which began in July 1973, was developed from previously operating
radiation monitoring netv/orks to form a single monitoring system more
responsive to current and projected sources of environmental radiation.
The ERAMS Drinking Water Component is an expansion of the previous
Tritium Surveillance System which was operated by the Office of
Radiation Programs from 1970 through June 1973. The Drinking Water Com-
ponent consists of 77 quarterly drinking water samples taken from
major population centers and selected nuclear facility environs. Tri-
tium is analyzed on a quarterly basis with grab samples. Tritium, a
long-lived (half-life of 12.3 years) isotope of hydrogen (hydrogen-3),
is produced in nuclear power production and nuclear weapons testing,
and naturally by cosmic radiation. Because it is chemically similar to
hydrogen, tritium readily enters the body as water and is incorporated
into living tissue.
Table 1 presents the tritium concentrations in drinking water at
the Drinking Water Component stations for 1974. The average tritium
concentration was 0.3 nCi/liter. The radiation dose to individuals may
be calculated from the formula:
H (mrem/year) = 0.1C (nCi/liter)
where H is the dose equivalent rate and C represents the tritium con-
centration in body water in nCi/liter (nCi = 10~9 curie). Assuming
that the concentration of tritium in all water taken into the body is
equal to that found in the drinking water, and that the specific
activity of tritium in the body is essentially the same as that in the
drinking water, then the radiation dose to individuals may be estimated.
The highest individual concentration of tritium observed in drinking
water was 6.8 nCi/liter during 1974. This corresponds to a dose of 0.7
mrem/year (0.007 rem/year). The average tritium concentration during
1974 was 0.3 mrem/year. The calculated health effects to the U. S.
population may be estimated by using a risk factor of 7 x 10~4 health
effects per person-rein. Therefore, the calculated number of potential
health effects in the U. S. population would be 4.5 based upon a
constant intake at the average concentration.
124
-------
Table 1
ERAMS Drinking Water Component, 1974
Tritium concentration9 (nCi/liter +
Ala:
Alaska:
Ark:
Calif:
C. Z:
Colo:
Conn:
Del:
D. C:
Fla:
Ga:
Hawaii :
Idaho:
1 nc a 1" "i nn
Dothan
Montgomery
Muscle Shoals —
Anchorage
Fairbanks
Little Rock
Berkeley
Los Angeles
Ancon
Denvei
Platteville
Hartford
Wilmington
Washington
Miami
Tampa
Baxley
Savannah
Honolulu
Boise
Jan-Mar
0
0
0
NS
.5
0
.2
0
.5
.5
.9
0
.3
0
0
0
NS
3.1 + 0.3
0
.3
April -June
0
.2
.3
0
.5
0
.2
0
0
.5
1.0
0
0
.2
0
0
0
6.8 + 0.3
0
0
July-Sept
0
0
.3
.5
.5
0
.2
0
0
.4
.9
.2
.3
0
0
0
NS
3.0
0
NS
2a)b
Oct-Dec
0
0
.2
.4
.3
0
0
0
0
.6
.6
.2
.3
0
0
0
0
2.9
0
.2
125
-------
Table 1 (Continued)
Tritium concentration3 (nCi/liter + 2a)b
Idaho:
111:
Iowa:
Kans:
La:
Maine:
Md:
Mass:
Mich:
Minn:
Miss:
Mo:
Mont:
Nebr:
Nev:
N. H:
N. J:
1 nratinn
Jan-Mar
Idaho Falls .3
Chicago 1.0
Morris 0
Cedar Rapids--- NS
Topeka 0
New Orleans .2
Augusta .2
Baltimore 0
Conowingo 0
Lawrence 0
Rowe .3
Detroit ,-- .4
Grand Rapids — .3
Minneapolis .4
Red Wing 0
Jackson 0
Jefferson City- 0
Helena .3
Lincoln .2
Las Vegas .8
Concord 0
Trenton 0
April-June July-Sept
.3 .6
.6 0
0 0
NS .3
0 .3
0 .3
0 0
NS .3
0 .3
.2 .2
0 NS
.4 .4
0 .3
.3 .5
0 0
0 0
.4 0
.5 .4
.2 .2
.7 .6
.2 .2
NS .2
Oct-Dec
.3
.2
0
.5
0
.3
.2
.5
.3
0
.4
.2
.2
.5
0
.2
0
.4
0
.7
.3
0
126
-------
Table 1 (Continued)
Tritium concentration3 (nCi/liter _+ 2o)b
Location —
Jan-Mar April-June July-Sept Oct-Dec
N. J: Waretown - 0 NS 0 0
N. Mex: Santa Fe .5 NS .5 0
N. Y: Albany - 0 .3 0 .3
Buffalo .3 .2 .2 .5
New York .3 NS .30
Syracuse .6 .6 .5 .7
N. C: Charlotte 0 .7 .3 .2
Wilmington 0-0 .2 .2
N. Dak: Bismarck .5 .5 .7 .4
Ohio: Cincinnati 0 .3 .2 . .2
East Liverpool- .4 .3 .4 .3
Painesville 0 .3 .3 .5
Toledo-— NS NS NS NS
Okla: Oklahoma City— 0 0 .20
Oreg: Portland 0 0 0 .3
Pa: Columbia 0 0 .2 .7
Harrisburg 0 .2 .3 .3
Pittsburg .4 .2 .3 .3
P.R: San Juan 0 000
R.I.: Providence .2 0 0 0
S.C.: Anderson .3 .2 .3 .4
Columbia 0 0 .4 .3
127
-------
Table 1 (Continued)
Tritium concentration9 (nCi/liter +_ 20)b
Location
Jan-Mar April-June July-Sept Oct-Dec
S. C.: Hartsville 0 000
Seneca .2 .4 .3 .3
Tenn: Chattanooga .5 .6 .4 0
Knoxville .4 .400
Tex: Austin 0 000
Va: Doswell 0 0 0 .2
Lynchburg - 0 .2 .2 .2
Norfolk - .2 0 0 .2
Wash: Richland - NS .5 .4 .5
Seattle - .2 0 0 .4
Wise: Genoa 0 0 NS 0
Madison — 0 000
Average 0.2 0.3 0.3 0.2
aThe minimum detection limit for all samples was 0.20 nCi/liter. All
values equal to or less than 0.20 nCi/liter before rounding have been
reported as zero.
bThe 2a error for all samples is 0.20 nCi/liter unless otherwise noted.
NS, no sample.
128
-------
APPENDIX V
ANALYSIS OF INORGANIC CHEMICALS IN WATER SUPPLIES
Water Supply Research Laboratory
National Environmental Research Center
Office of Research and Development
Cincinnati, Ohio
-------
APPENDIX V
ANALYSIS OF INORGANIC CHEMICALS IN WATER SUPPLIES
Table of Contents
Page
A. Interstate Carrier Water Supplies 131
B. Community Water Supply Survey 131
C. Special Studies 131
D. National Organic Reconnaissance Survey Sampling. . . . 132
E. Asbestos Studies 135
130
-------
ANALYSIS OF INORGANIC CHEMICALS IN WATER SUPPLIES
A. INTERSTATE CARRIER WATER SUPPLIES
For many years the federal government has exercised a regulatory
function over the water supplies that provide the water to the watering
points of carriers in interstate commerce. If water is loaded aboard a
train, ship, plane, or bus, the regulation of the actual watering point
is conducted by the Food and Drug Administration, but the regulation of
the water systems that supply the water is done by the Environmental
Protection Agency.
For these interstate carrier supplies, the state agency controlling
community water supplies makes an annual report on the quality of each
supply. Besides the summary on the numerous bacteriological samples,
data are provided from the most recent chemical analyses on the consti-
tuents limited by the Drinking Water Standards. At about three-year
intervals, a joint survey is made by the state agency and the EPA Re-
gional Office of each of these 700 or so supplies. At the time of the
joint survey, a water sample is collected and sent to the Water Supply
Research Laboratory in Cincinnati for analyses of the chemicals limited
by the standards.
Tabulation of these data is made periodically, the latest being
Chemical Analyses of Interstate Carrier Water Supply Systems, October
1973.4 Table II is the summary from this report.
B_. COMMUNITY WATER SUPPLY SURVEY
Water samples are collected at the water plant for chemical analy-
ses in the interstate state carrier surveillance and by most state agen-
cies. Evidence has been developed that for some constituents the water
quality is degraded in distribution. This has been recognized for bac-
teriological sampling but the effect of the distribution system and
household plumbing was not determined by the chemical sampling. The
first comprehensive set of data on water quality at the consumer's tap
was reported in 1970J A comparison of the results of this study with
the 1962 Drinking Water Standards and the American Water Works Associa-
tion's water quality goals are shown in Table I.
C. SPECIAL STUDIES
EPA has conducted some studies in water systems where the water is
particularly corrosive to the distribution system and plumbing. Results
of two of these studies have been reported^ and indicate that a signif-
icant number of homes have lead concentrations exceeding the limits.
This is most noticeable in the first water drawn in the morning. Human
body burden studies are being conducted to see if these high morning
concentrations may lead to a health effect. Table III presents some of
the water data.
131
-------
A cooperative study now underway will obtain data on the inorganic
chemical content of drinking water at a representative set of homes in
the U. S. Water samples are being collected at the homes of persons
included in the current series of the National Health Examination Survey.
Because of the interest of the National Heart and Lung Institute and
EPA in the suggested association of heart disease mortality and soft
drinking water, this detailed analysis of drinking water quality and
health examination results is underway. The study is designed for
health effects research but it will also provide data on water quality
for the chemicals limited by the drinking water standards as well as
86 additional chemicals for which we have little information on occur-
rence in drinking water.
D. NATIONAL ORGANICS RECONNAISSANCE SURVEY SAMPLING
To round out the analyses of NORS and to possibly provide some in-
sight to causes for the developing of the chlorine reaction products,
samples were analyzed for the inorganic chemicals proposed to be limited
by the new drinking water standards. The results of these analyses are
tabulated in Appendix II. Analyses have been completed in all but three
of the water systems included in NORS. The results were as expected
from previous surveys but because samples were collected at the water
plant or well head the pickup of metals in distribution would not be
noted. Three supplies exceeded the flouride limits which is comparable
with the results of the Community Water Supply StudyJ
The three samples exceeding the fluoride limit were collected from
water supplies adding fluoride in an attempt to provide an optimum con-
centration. A larger study of 286 water systems in Wisconsin that fluo-
ridated was conducted in 1968-1970.3 The findings from this study
showed that only 40% of the systems that consistently fluoridated pro-
duced a water with a fluoride concentration within the range specified
in the drinking water standards. These data show that additional sur-
veillance and operator training in methods of good fluoridation practice
may be necessary on a national scale.
The one sample exceeding the lead limit was collected from the
Huntington, West Virginia, water supply. In any large set of water
samples at least one percent exceeds the lead limit which reflects the
use of lead pipe and solder for copper pipes. Lead would be of concern
if it were consistently over the limit at a sampling point.
Two supplies exceeded the new mercury limit, the Artesian Water
Company of New Castle County, Delaware, and the Tennessee American
Water Company of Chattanooga. Mercury was detected at the Chattanooga
Supply in 1970 .also but at half the concentration found in this survey.
The Artesian Water Company uses wells and lower mercury concentrations
were found in the past.
132
-------
Tab-le I
Community Water Supply Study
2595 DISTRIBUTION SAMPLES
FROM 969 PUBLIC WATER
SUPPLY SYSTEMS
Recommended Standards
A. B. S.
Arsenic
Boron
Chloride
Color
Copper
CCE*
Cyanide
Fluoride
Iron
Manganese
Nitrates
Ra-226
Sr-90
Su-lfate
Dissolved
Solids
Turbidity
Zi nc
CAE*
Limit
mg/1
.05
.01
1.0
250.0
15. un
1.0
.2
.01
Varies
0.3
0.05
45.0
3 pCi/1
10 pCi/1
250.0
500.0
1-5. un
5.0
—
Maximum
Concentration
.41
.10
3.28
1950.0
49.0
8.35
.56
.008
4.40
26.0
1.32
127.0
135.9
2.0
770.0
2760.0
53.0
13.0
.81
Percent
Exceeding
0.0
.4
.8
1.2
.7
1.6
1.2
0.0
4.6
8.6
8.2
2.1
.6
0.0
1.8
8.5
2.4
.3
—
Mandatory Standards
Arsenic
Barium*
Boron
Cadmium
Chromium
Col i forms
Cyanide
Fluoride
Gross Beta
Lead
Selenium
Silver
.05
1.0
5.0
.01
.05
1/100 ml.
0.2
Varies
1000 pCi/1
.05
.01
.05
.10
1.55
3.28
.011
.08
TNTC
.008
4.40
154.0
.64
.07
.026
.2
.1
0.0
.2
.2
8.8
0.0
2.1
0.0
1.4
.4
0.0
AWWA
Goal
mg/1
.20
PHS
PHS
—
3.un
.2
.04
PHS
PHS
.05
.01
KHS
PHS
PHS
—
200.0
0.1
1.0
.10
AWWA
PHS
PHS
PHS
PHS
PHS
0.0
PHS
PHS
100 pCi/1
PHS
PHS
PHS
Goals
Percent
Exceedinc
.2
.4
.8
—
9.9
15.5
25.5
0.0
4.6
44.5
31.0
2.1
.6
0.0
—
48.7
90.6
4.4
26.6
Goals
.2
.1
0.0
.2
.2
11.7
0.0
2.1
<.l
1.4
.4
0.0
*These constituents were evaluated only on selected samples.
remainder were assumed not to exceed the limits or goals.
The
133
-------
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134
-------
TABLE III
Percent of Homes with a Sample
Exceeding the DNS
Boston Seattle
Cd 0 7%
Cr 0
Cu 19% 24%
Fe 9% 76%
Pb 65% 24%
Mn - 5%
Zn -0 10%
E. ASBESTOS STUDIES
Because of the potential health effect of asbestos fibers in drink-
ing water, the U. S. Environmental Protection Agency has conducted and
is currently conducting several studies in an attempt to determine how
widespread the problem of asbestos contamination is. This section sum-
marizes the work of EPA's Office of Research and Development and its
early findings relative to this issue.
1. Duluth Study
The possibility of asbestos contamination of drinking water at
Duluth was discussed by Mrs. Arlene Lehto of Duluth at an International
Joint Commission hearing held in Duluth in December 1972. After this,
in March 1973 the U. S. EPA National Water Quality Laboratory in Duluth
began monitoring the Duluth water supply for amphibole mass by x-ray
diffraction. The presence of amphibole fibers was indicated by electron
micrographs. This analytical work is continuing. One report was pub-
lished by Cook et al.5 They indicated that the total content of amphi-
bole minerals in the Duluth water supply averaged 0.19 mg/1 from March
1973 to January 1974.
In June 1973 the U. S. EPA announced that the drinking water of
Duluth and North Shore Lake Superior Communities contained asbestiform
fibers.
135
-------
An extensive sampling program was undertaken by Region V in the
summer of 1973 in order to learn about the extent of the asbestos con-
tamination problem in Western Lake Superior. Fairless reported on the
results of this study.6 Fairless indicated that in Western Lake Superior,
particulate matter from the Silver Bay area was carried by lake currents"
to the Duluth area and then along the southern shore of the lake (north-
ern Wisconsin and Michigan). The trend for results of both amphibole
mass and asbestiform fiber analysis is that the values are lightest at
Beaver Bay, Minnesota, decreasing from there to Duluth, and then to
Ashland, Wisconsin and Marquette, Michigan.
In 1974 a pilot plant was operated at Duluth's Lakewood Pumping
Station for fiber removal research. From May through September Lake
Superior water that was pumped into the distribution system at Duluth
was analyzed for amphibole mass and asbestiform fibers. Analytical
data are shown in Figures 1 and 2. Because of the state of the art in
EM analysis for asbestiform fibers in water, a laboratory can be expect-
ed to be internally consistent on fiber count from sample to sample,
but comparison of results between laboratories is usually not possible.
Because no standard method yet exists, some laboratories may count con-
sistently higher than others or vice versa.
Pilot plant results for raw water at the Lakewood Intake (Duluth's
drinking water) showed amphibole and chrysotile fiber counts typically
in the range of 0.5 x 106 f/1 to 2 x 106 f/1, with some samples either
higher or lower than that range.
The results of EPA work on waters of western Lake Superior have
established firmly the existence of asbestiform fibers. Studies of
ways to reduce the fiber content of drinking water are described else-
where in this report, Appendix VI.
2. Asbestos-Cement Pipe Studies
a. Field Studies
In an effort to study the effect of waters of various corrosive-
ness on asbestos-cement pipe several systems utilizing A/C pipe were
selected for study. In each case, samples were taken of the source and
at two places in the distribution system. These will be followed up by
analyzing samples from the same locations every month for at least nine
months, so as to cover any seasonal variations. Initially three sites
were selected. When these are completed or as time permits, others of
high pH and hardness will also be selected for study.
b. Controlled Pipe-Loop Study
The objective of this study is to determine the influence of
water velocity, aggressiveness of water and elapsed time on the erosion
136
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138
-------
of asbestos fibers from asbestos-cement pipe. The influence of tapping
the pipe wall will also be studied.
To conduct this study, a "pipe-loop" was constructed of 100 ft of
4-inch and 6-inch diameter asbestos cement pipe. Water is pumped through
both pipes at approximately 150 gpm, producing a velocity of 3.8 ft/sec
in the 4-inch pipe and 1.7 ft/sec in the 6-inch pipe. As the water en-
tered the pipe test section, it is filtered through a 1 ym pore diameter
filter. The pH and hardness of the water are adjusted and maintained at
any desired level. Water circulates continuously through the pipe loop.
Each day the water passes through an equivalent of 62 miles of 4-inch
pipe and 28 miles of 6-inch pipe.
Once each week water is diverted from the exit end of each pipe
specimen and 300-500 liters passes through a 0.45 ym pore flillipore
filter. Just prior to sampling, water entering the pipe loop is divert-
ed through large 0.45 ym pore Mi Hi pore filters to assure that during
sampling the water entering the pipe loop is nearly particle-free.
Therefore any fibers appearing at the exit end resulted from the test
length of pipe. After sampling, the Millipore filters are subjected to
EM analysis using the technique cited in Reference 7.
The present plan is to study nine combinations of hardness and pH
ranging from a low hardness, low pH water (hardness - 20 mg/1 as CaC03,
pH = 5.5) to a high hardness, high pH water (hardness - 400 mg/1 as
CaCOs, pH = 9.5). Both the hardness and the pH will be varied between
the extreme limits in three steps.
The current test involves the use of the low hardness, low pH water.
This test has been under way for about two months. Figure 3 shows the
results to date. Because of the large volume of water passed through
the sampling filters, the test is much more sensitive than the routine
analysis for asbestos fibers. This is why such low fiber count can be
reported with some degree of reliability.
3. Finished Wate_r_a_t Various Locations in U. S.
In the process of attempting to develop a procedure for the routine
analysis of asbestos in water the Water Supply Research Laboratory
routinely selected some Interstate Carrier (mostly) Water samples
(finished water) received in our laboratory for chemical analysis. The
developed procedure has now, or soon will be, published in the Proceed-
ings of the Water Quality Technology Conference, AWWA?.
139
-------
The water supplies analysed and the results obtained were as
follows:
City Fibers/1 x Ip6
Duluth, Minnesota 1.1 to 4.8 A
BDL to 0.4 C
Abilene, Texas BDL
Cincinnati, Ohio NSS
Cheyenne, Wyoming NSS
Columbia, South Carolina 0.13 C
Cairo, Illinois NSS
Anchorage, Alaska 0.07 A
Jackson, Mississippi
(2 grids) 0.25 to 0.7 C
Ashland, Kentucky BDL
Pittsburgh, California NSS
N. Troy, Vermont (2 grids) 0.98 to 2.2 C
Enosburg, Vermont 0.-Q5 r
Brattleboro, Vermont 0.11 C
Eden, Vermont (Spring) 0.08 C
St. Louis, Missouri NSS
Seattle, Washington 1.812 A
(Tolt Pipe Line) 2.464 C
Seattle, Washington BDL
(Cedar River System) NSS C
Elizabeth, New Jersey BDL
Amarillo, Texas 0.09 A
Boulder, Colorado BDL
140
-------
City Fibers/1 x 106
Glens Falls, New York BDL
Jonesboro, Arkansas NSS
New Haven, Connecticut NSS
Clarksville, Tennessee 0.09 C
Jersey City, New Jersey 0.16 C
Erie, Pennsylvania 0.07 C
Newport, R. I. (2 grids) 0.04 to 1.0 C
Little Rock, Arkansas 0.27 C
Charlottesville, Virginia NSS
Skidaway Island, Ga.
(2 grids) 1.74 to 2.03 C
Jericho - Underbill,
Vermont NSS
-Crystal Springs, Vermont NSS
Niagara Falls, New York NSS
Rochester, New York BDL
Buffalo, New York 0.13 C
San Francisco, California 1.54 C
Nashville, Tennessee (2 grids) 0.43 to 0.80 C
South Pittsburgh, Pa. 0.21 C
Independence, Missouri (2 grids) 0.36 to 0.58 C
Montgomery, Ala. (2 grids) BDL to 0.12 C
Ft. Lauderdale, Florida NSS
Indianapolis, Indiana 0.18 C
Kansas City, Missouri 0.07 C
141
-------
City Fibers/1 x 1Q6
Springfield, Missouri 0.30 C
Melbourne, Florida NSS
Tulsa, Oklahoma BDL
Wilmington. Delaware 0.29 C
Bethlehem, Pa NSS
Fairbanks, Alaska BDL
Elmira, New York NSS
Muskogee, Oklahoma BDL
Richmond, Harrington, Vt. NSS
Quarry Hill, Vermont NSS
Tuscaloosa, Alabama 0.45 C
Birmingham, Alabama BDL
Topeka, Kansas NSS
Greenville, S. Carolina NSS
Yuma, Arizona 0.12 C
Dayton, Ohio NSS
Washington, D. C. NSS
Sacramento, California NSS
Miami, Florida BDL
San Juan, Puerto Rico NSS
Chattanooga, Tennessee 0.13 C
BDL - Below detection limit
NSS - Not statistically significant (less than 5 fibers in
20 fields)
A - amphibole
C - chrysotile
142
-------
NET CHRYSOTILE FIBERS
OUTLET MINUS INLET
-B 4-INCH ASBESTOS CEMENT PIPE
-A 6-INCH ASBESTOS CEMENT PIPE
10,000
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(-1.000 CONTAMINATION SUSPECTED)
I | I
0
10
15
20
25
30
FIGURE 3. CUMULATIVE VOLUME OF WATER THROUGH SYSTEM - GALLONS x 106
143
-------
As can be noted, of 63 supplies analyzed, only nine supplies (14%)
had counts over 0.5 x 10^ fibers per liter and of these, only five (8%)
were over 1.0 by 10^, namely, Duluth, Minn.; North Troy, Vermont; Seattle
(Tolt) Washington, Skidaway Isl, Ga., and San Francisco, California.
Eleven (18%) had fiber counts below the detection limits of the method.
144
-------
ACKNOWLEDGEMENTS
The first four sections of Appendix V were written by Gunter Craun and
Leland McCabe.
The fifth section on asbestos was prepared by E. McFarren, R. Lishka,
J. Millette, G. Logsdon, R. Buelow, J. Agee, J. Symons, P. Cook, G. Glass,
B. Fairless.
-------
REFERENCES
1. McCabe, L. J., Symons, J. M., Lee, R. D., and Robeck, G. G. Survey
of Community Water Supply Systems, Journal Am. Water Works Assoc.
Vol 62(11), 670-687, November 1970.
2. Craun, G. F., and McCabe, L. J., "Overview of Problems Associated
with Inorganic Contaminants in Drinking Water." Proceedings
National Symposium on the State of America's Drinking Water, Chapel
Hill, North Carolina (In Press).
3. Hertsch, F. F. and Maddox, F. D., Fluoridation Practice in Wisconsin,
Journal Am. Water Works Assoc., Vol 63, 778-782, 1971.
4. USEPA Report, Chemical Analysis of Interstate Carrier Water Supply
Systems, October 1973.
5. Cook, Philip M., Glass, G. E., and Tucker, J. H., "Asbestiform Am-
phibole Minerals: Detection and Measurement of High Concentrations
in Municipal Water Supplies," Science, 185, 853-855 (September 6,
1974).
6. Fairless, B., "Asbestos Fiber Concentrations in the Drinking Water
of Communities Using the "Western Arm of Lake Superior as a Potable
Water Source," U. S. Environmental Protection Agency, Region V,
Surveillance and Analysis Laboratory, Chicago, Illinois, 17 pp.
Mimeo
7. McFarren, E. F., Millette, J. R. and Lishka, R. J., "Asbestos Anal-
ysis by Electron Microscope," In Proceedings AWWA Water Quality
Conference, Dallas, Texas, December 1974 (In Press)
146
-------
APPENDIX VI
PRELIMINARY RESULTS OF PILOT PLANTS TO REMOVE WATER CONTAMINANTS
Prepared by
0. Thomas Love, Jr.
J. Keith Carswell
Alan A. Stevens
Thomas J. Sorg
Gary S. Logsdon
Compiled By
James M. Symons
Water Supply Research Laboratory
National Environmental Research Center
Office of Research and Development
Cincinnati, Ohio
-------
APPENDIX VI
PRELIMINARY RESULTS OF PILOT PLANTS TO REMOVE WATER CONTAMINANTS
Table of Contents
Page
A. Introduction 151
B. Treatment for the Removal of Organic Contaminants .... 151
1. Specific Organic Compounds 151
a. Literature Reports 151
b. Naphthalene 151
c. Bis-(2-chloroethyl) ether and Bis-(2-chlorois-
opropyl) ether 152
d. Chloroform, Bromodichloromethane, Dibromo-
chloromethane, and Bromoform 152
e. 1,2-Dichloroethane and Carbon Tetrachloride • • 152
f. Trihalomethane Precursors 152
1) Description of Pilot Plant 152
2) Chiorination Experiments 155
3) Ozonation Experiments 155
4) Controlled Bench-scale Experiments • • • • '58
2. General Organics , 160
a. Pilot Plant 160
b. Column Studies 160
1) Upflow-Counter-current 160
2) Upflow-cocurrent 163
3. Future Plans 163
a. Pilot Plant Studies 163
b. Controlled Storage Studies 166
c. Column Studies 166
4. Acknowledgments 166
5. References 166
148
-------
Page
C. Treatment for the Removal of Trace Metal Contaminants . . 167
1. Introduction , 167
2. Research Program 167
a. Jar Tests 167
1) Procedure 167
2) Analytic Methods 168
b. Pilot Plant 168
1) Description and Operation 168
2) Analytic Methods 171
3. Results 171
a. Jar Tests s- 171
1) Previous work 171
2) Barium . 171
b. Pilot Plant Studies 172
1) Mercury 172
2) Cadmium 173
3) Arsenic 173
4) Selenium 174
c. Summary of results 174
4. Radium-226 177
a. Introduction 177
b. Results 177
c. Discussion 177
d. Future Plant 178
5. Acknowledgments 178
6. References 179
D. Treatment for the Removal of Asbestiform Fibers 179
1. Introduction 179
2. Scope of Study . . . " 180
149
-------
Page
3. Experimental Methods and Equipment 180
a. Equipment 180
b. Analytical Methods 181
4. Results 182
a. Raw Water Quality 182
b. Asbestiform Fiber Removal by Filtration 183
5. Discussion 186
a. Asbestiform Fiber Removal 186
b. Efforts to Develop Rapid Detection Methods • • • 195
6. Future Research 195
7. Conclusions 196
8. Acknowledgments 197
9. References 197
150
-------
PRELIMINARY RESULTS OF PILOT PLANTS TO REMOVE WATER CONTAMINANTS
A. INTRODUCTION
This report will summarize the in-house and out-of-house research
conducted by the Standards Attainment Branch of the Water Supply
Research Laboratory and their predecessors concerning the treatment
technology required for the removal of specific contaminants present in
raw water. Because many of these projects are on-going, future plans
will also be included. The report will be divided into three general
contaminant areas -- organics, inorganics, and asbestos fibers.
B. TREATMENT FOR THE REMOVAL OF ORGANIC CONTAMINANTS
1. Specific Organic Compounds
a. Literature Reports
In 1965, Robeck, Dostal, Cohen and Kreissl demonstrated that
coal-base granular activated carbon (GAC) partially exhausted for
carbon-chloroform extract (CCE-hf) removal, could reduce the concentra-
tion of dieldrin, lindane, 2,4,5-T, DDT, and parathion dosed into river
water. In the same year Dostal, Pierson, Hager, and Robeck2 showed
that seven compounds, listed below, present in the Kanawha River water
after aeration could be reduced to below detectable concentrations by
fresh (2-day old) GAC. These compounds were bis-2(2-chloroethyl)
ether, 2-ethylhexanol, bis-(2-chloroisopropyl) ether, a-methylbenzyl
alcohol, acetophenone, isophorone and tetralin.
Forty days later, however, all of these compounds with the excep-
tion of acetophenone, had broken through the GAC beds to a depth equal
to an actual contact time of 3.8 minutes. Providing an additional 1.8
minutes of actual contact time did remove these seven compounds at
this time, although another organic, ethyl benzene, was penetrating the
GAC to a depth equal to 7.5 minutes of actual contact time — almost
twice that provided in conventionally operated GAC beds.
b. Naphthalene
About 7 months ago, a coal-base GAC column 28 in. deep was
constructed, and Cincinnati tap water spiked with approximately 30 yg/1
of naphthalene passed down through it at a rate of 2 gpm/ft2. After
7 months of operation, the NVTOC front has penetrated to the extent that
the 50% removal point is approximately 20 in. down the column, whereas
the 50% removal point for naphthalene is only approximately 2 in. down
the column. This test is continuing.
151
-------
c. Bis-(2-ch1oroethy1) ether and Bis-(2-chloroisopropyl;
ether
In recent studies, the effluent from a mini-sampler operating
on Evansville, Indiana, finished water was analyzed and fresh coal-base
GAC was shown to remove all detectable bis-(2-chloroethyl) ether and
bis-(2-chloroisopropyl) ether. No information is available on how long
GAC would continue to remove this material, however.
d. Chloroform. Bromodichloromethane, Dibromochloromethane
and Bromoform
To investigate the ability of GAC to remove chloroform and the
other three trihalomethanes two 28-in. deep glass columns were con-
structed. One contains a coal-base GAC and the other a lignite-base
GAC. The columns were arranged such that Cincinnati tap water flowed
down through the columns at a rate of about 2 gpm/sq. ft. Figure 1
shows that after 4 weeks of operation the ability of the coal-based GAC
to remove chloroform was seriously restricted. The trend of the data
from the lignite-base GAC would indicate that its ability to remove
chloroform was somewhat greater than the coal-base material.
Figure 2 shows a similar result for bromodichloromethane. The
dibromochloromethane concentration applied to these two columns varied
between none found and 4 yg/1. None has yet appeared in the effluent
from either column. N_o bromoform was found in the applied water during
this study. These two columns were started at different times, however,
and therefore received different general organic loads. Whether or not
this influenced the trihalomethane removal patterns is not known at this
time.
e. 1,2-Dichloroethane and Carbon Tetrachloride
No 1,2-Dichloroethane was found in the Cincinnati tap water
during the study. Carbon tetrachloride appeared occasionally at concen-
trations from <0.2 to 5.6 yg/1 in the water applied to the two GAC col-
umns, but none ever appeared in the effluent from either column.
f. Trihalomethane Precursors
1) Description of Pilot Plant
A pilot water treatment plant was constructed of stain-
less steel, Teflon and glass in order to minimize contamination from
structure materials during experimentation on the formation and removal
of trihalomethanes. The pilot plant uses untreated Ohio River water as
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a source, made available through the assistance and cooperation of the
Cincinnati Water Works. Following conventional pretreatment with alum
(without predisinfection), the settled water flow has been divided
between: 1) a dual media (sand/coal) filter (A), 2) a coal-base gran-
ular activated carbon filter (B), and 3) a dual-media filter followed
by a coal-base granular activated carbon filter (CD). The filtered
water is then either ozonated, or chlorinated, or both. Flow, headless,
turbidity, temperature and pH are monitored daily. Figure 3 is a sche-
matic diagram of the pilot plant. Samples for trihalomethane and non-
volatile total organic carbon analysis are collected with zero head-
space in muffled, glass vials. -
2) Chlorination Experiments
The pilot plant has been running continuously and the
first experiments have focused on eliminating the haliform reaction
through removal of the precursors with GAC. Using chlorine dosages of
2-3 mg/1 and contact times of 30 minutes and 4 days, studies have shown
that after 3 to 4 weeks of operation, sufficient materials are being
passed through the GAC beds to produce measurable amounts of chloro-
form (See Table 1). This experiment is continuing.
3) Ozonation Experiments
The purpose of this portion of the organics research
project is to determine whether post-ozonation can be used to oxidize
trihalomethane precursors to compounds that will not react during post-
chlorination. A small (1.5 in diameter) glass contact chamber is used
to provide about 5 minutes of contact time between the pilot plant
filter effluents and an ozone-oxygen gas mixture. Filter A, B or CD
effluents are applied to the top of the contactor, while the ozone-
oxygen output from a pilot-plant scale ozone generator is applied at
the bottom. Both the gas flowrate and the ozone concentration can be
varied. Batches of ozonated effluent are collected for reaction with
various chlorine concentrations.
Initially, disinfection-level (0.5-0.7 mg Oyi H20 ozone
doses, followed by rather high (8 mg C12/1 1^0) post chlonnation doses
were applied to the filter effluents. When very low (<1 yg/1) chloro-
form concentrations were produced after a one-half hour chlorine contact
period, it was decided to dose and store (at 25°C) effluent samples
for a longer time period to follow trihalomethane development. Also,
chlorinated effluent samples (without ozonation) would be stored as a
control to better show any changes produced by the ozone.
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The results of this first storage study show that a dis-
infection-level ozone dose had no apparent effect on the trihalomethane
concentrations produced in Filter B and CD effluents after 6 days of
storage. In Filter A effluent, ozonation appeared to cause an increase
in chloroform concentration and a decrease in bromodichloromethane con-
centration. See Table 2. This latter situation will receive further
study. Other future studies will investigate the effect of higher
ozone doses and/or longer ozone contact periods.
4) Controlled Bench-Scale Experiments
In an effort to understand the mechanism of trihalo-
methane formation and the factors that influence it, experiments are
being conducted under controlled conditions in sealed containers
changing one variable at a time. At the start of the experiment several
containers are prepared in replicate. Periodically over a 7-day period
a container is opened and the trihalomethanes measured. Thus the in-
fluence of the variable under study on the rate and extent of trihalo-
methane formation can be determined.
One bench-scale study investigated the formation of tri-
halomethanes during chlorination of raw and different types of treated
water from the Ohio River. This study was conducted in sealed con-
tainers at constant pH and 25° Celcius. Some preliminary observations
were:
1. When adequate chlorine is added to satisfy chlorine demand
for the duration of the experiment, chlorination of raw water yields
approximately seven times as much chloroform as does chlorination of
the effluent of the dual-media pilot plant filter (A) and approximately
80 times as much as does chlorination of the effluent of the fresh GAC
filter (B) (207yg/l, 32 yg/1, and 2.7 yg/1, respectively, in 7+ days).
The reason the chloroform production is so low in filter effluent
compared to the raw water is not known at this time, but in future
studies settled water will be included in the series to determine at
what step in treatment the precursors are removed.
2. Of the trihalomethanes under study, chloroform is formed in
the highest concentration with bromodichloromethane and dibromochloro-
methane following in approximate rations of 100:15:1.
3. With the waters tested, those with a higher chlorine demand
gave a greater trihalomethane concentration upon chlorination, but
trihalomethane formation accounted for only about 3% of the chlorine
consumed. Therefore other chlorination by-products are being formed,
both organic and inorganic.
158
-------
Sample
TABLE 2
SUMMARY OF OZONATION EXPERIMENT
Bromo- Dibromo-
Chlorine dichloro- chloro-
Contact Time Chloroform methane methane Bromoform
A + C12
A + C12
A + 03 + C12
A + 03 + C12
B + C12
B + C12
B + 03 + C12
B + 03 + C12
CD + C12
CD + C12
CD + 03 + C12
CD + 03 + C12
1/2 hour
6 days
1/2 hour
6 days
1/2 hour
6 days
1/2 hour
6 days
1/2 hour
6 days
1/2 hour
6 days
4
6
NF
15
0.3
2
NF
3
0.2
2
0.2
2
NF
14
NF
8
NF
3
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3
NF
3
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4
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4
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2
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NF
NF
NF
NF
NF
NF
NF
NF
NF
NF
NF
NF = None Found
All Trihalomethane Concentrations in yg/1
159
-------
4. In all waters tested, trihalomethane production continued as
long as a measurable chlorine residual was present, but at a decreasing
rate. The initial rate of chloroform formation in the raw river water
was about 10 yg/l/hr for the first six hours. The rate of formation
was very low, however, for GAC effluent throughout the 7+ days.
2. General Organics
The monitoring of specific organics may be beyond the capability
of most water utilities for some time to come. Therefore, treatment for
the removal of specific organics may be accomplished by providing treat-
ment that will produce a water with a very low concentration of a gen-
eral organic parameter such as non-volatile total organic carbon,
although monitoring for specific organics is the only method of assuring
their removal.
a. Pilot Plant
In addition to the study of the elimination of trihalomethane
precursors, NVTOC concentrations are being measured at various stages
of the pilot plant in an attempt to determine under what conditions
very low NVTOC concentration water can be produced for extended periods
of time.
Figure 4 shows the average relative concentrations of non-
volatile total organic carbon at various stages of treatment for the
first three weeks of operation and operational weeks three to six.
Figure 5 compares the percent removal of NVTOC by coal-base GAC, both
with and without prefiltration of the influent water. The presence of
carryover floe in the influent to filter B is not interfering with NVTOC
removal.
b. Column Studies
1) Upf1ow-counter-current
The objective of this study is to determine if low con-
centrations of NVTOC can be continuously maintained in the effluent of
a GAC filter by periodic removal of a portion of the exhausted GAC,
replacing it with fresh GAC. A small (1.5 in diameter) glass column
has been placed in operation. Cincinnati tap water (approximately 80
ml/min) is applied to the bottom of the column, flows upward tK-ough
the GAC bed, and overflows from the top of the column to a voTjme
measuring device. When the effluent NVTOC limit is exceeded one-half
of the GAC bed is removed (as a slurry) from the bottom of t le column.
and an equal quantity of fresh GAC is added at the top.
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For the initial test series, an 8-inch bed of GAC was
chosen. Preliminary observations, after 20 days of operation, include:
1. The effluent NVTOC limit can be maintained for only 2-3 days
before GAC removal and addition is necessary.
2. Exhaustion of the GAC bed appears to occur much more rapidly
than in similar downflow beds, indicating possible wall effects and/or
flow channelization within the column.
This study will continue, with future efforts directed toward
deeper GAC beds and/or larger diameter columns. Thus far a 16-inch
deep bed is performing more reliably.
2) Upflow - Co-current
In an attempt to compare the performance of various types of
GAC, six 3-inch diameter, 18-inch long columns were filled with six
different types of GAC produced by three different manufacturers. Cin-
cinnati tap water was continuously passed upflow through each column at
a rate of about 3 gpm/sq ft for 32 weeks. The influent and effluent
concentrations of NVTOC and'carbon-chloroform extract (CCE-m) were moni-
tored weekly during this time. Data from each column were averaged for
several four-week intervals and plotted in Figures 6 and 7. All of the
data fell within the envelopes shown, indicating that the type of GAC
had little influence on performance. These data also show that the life
of the GAC in these columns was fairly short for the removal of these
two parameters. References 3 and 4 contain additional information on the
performance of activated carbon.
3. Future Plans
a. Pilot Plant Studies
Current chlorination and ozonation studies will continue to
determine how the aging of the GAC columns will alter the trihalomethane
formation patterns. When these experiments are completed they will be
repeated using lignite-base GAC in the columns. Possible future studies
will cover the influence of powdered activated carbon, pre-disinfection
with chlorine or ozone, addition of chlorine just prior to filtration,
and the use of chlorine dioxide. Also studies on removal of raw water
contaminants will be conducted.
163
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165
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b. Controlled Storage Studies
Possible future controlled storage studies will include
experiments on chlorination of specific trihalomethane precursors and
the influence of temperature and form and concentration of chlorine
residual on the formation of trihalomethane. Also other chlorination
by-products will be studied to follow-up on the finding that nitrome-
thane becomes chloropicrin and m-xylene becomes chlorxylene upon chlor-
ination.
c. Column Studies
Work will continue studying the ability of columns of GAC
operated upflow, downflow, co-, and counter-current to effectively
remove organics as measured by general organic parameters.
Because the column test described in the Naphthalene Section
B(l)(b) was so successful, it will be repeated using other compounds.
Possible candidates are: benzene, bis-(2-chlorethyl) ether, carbon
tetrachloride, phthalic anhydride, beta-chloroethylmethyl ether, octa-
decane, DDT, dieldrin and aldrin.
5. References
1. Robeck, G.G., Dostal, K.A., Cohen, 0. and Kreissl, J.F.,
"Effectiveness of Water Treatment Processes in Pesticide
Removal," Journal American Water Works Association, 57,
2, 181-199 (February 1965).
2. Dostal, K.A., Pierson, R.C., Hager, D.G. and Robeck, G.G.,
"Carbon Bed Design Criteria Study at Nitor, West Virginia,"
JAWWA, 5_7, 5, 663-674 (May 1965).
3. Activated Carbon in Water Treatment, University of
Reading Conference, April 3-5, 1973. The Water Research
Association, Medmenham, Marlow, Buckinghamshire, SL7,
2HD, United Kingdom.
4. Love, O.T., Jr., Carswell, J.K., Stevens, A.A., and
Symons, J.M., "Evaluation of Activated Carbon as a
Drinking Water Treatment Unit Process," Water Supply
Research Laboratory, United States Environmental Pro-
tection Agency, Cincinnati, Ohio, March 1975, 17 pp
Mimeo.
166
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C. TREATMENT FOR THE REMOVAL OF TRACE METAL CONTAMINANTS
1. Introduction
The Federal Proposed Interim Drinking Water Regulations (IDWR)
established limits for a number of substances in water including
various trace metals. For many years, these limits were rarely exceeded
and, therefore, knowledge on treatment methods to remove these contami-
nants from water was of only minor concern. In recent years, however,
the awareness of trace metal contamination has increased for various
reasons, including improved analytical procedures and more frequent
and comprehensive surveillance activities. As a result, this awareness
has stimulated the interest and concern for information and knowledge
on the removal of trace metals from water by conventional treatment
methods.
In anticipation and response to the need for this information, the
Water Supply Research Laboratory, U. S. Environmental Protection Agency
developed a research program on the removal of trace inorganic substan-
ces in water by conventional treatment processes. The trace metals in
the IDWR that have been, or are presently being studied are mercury,
barium, arsenic, selenium, cadmium and radium*. Chromium and lead will
be studied in the near future.
2. Research Program
The WSRL research program consists of two phases: (1) experiments
in the laboratory using jar test apparatus and (2) pilot plant tests
using a 2 gpm water treatment pilot plant.
a. Jar Tests
1) Procedure
The laboratory jar test methods have been described in
detail by Logsdon and Symons^. The waters used in the jar test work were
raw Ohio River water; raw well water from Glendale, Ohio; Cincinnati
tap water; and a Midwestern groundwater containing barium. Except for
the barium-laden water, the test waters were dosed with the contaminant
to be studied, given 2 minutes of rapid mix after addition of the treat-
ment chemical and 20 minutes of slow mix for the coagulation test, or
they were given 3 minutes of rapid mix and 30 minutes of slow mix for
softening. One hour of settling was used for all tests. Analyses were
made for pH, turbidity, alkalinity, and in some cases, hardness, as well
as for contaminant concentration.
*Note: The radium research will be treated separately.
167
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2) Analytic Methods
Two methods were used for metal analyses. An atomic
absorption spectrophotometer was used for analysis of non-radioactive
contaminants in portions of the mercury, barium, and arsenic work, and
occasionally in the selenium experiments. These methods have been
described by Kopp et al.3, McFarren4, and Caldwell, et al.5 In some
experiments, radiotracers were used with stable carriers. Radioactivity
was measured using a shielded Nal (TI) crystal and single-channel
analyzer. When radiotracers were used, the initial contaminant concen-
tration was determined by adding the radioisotope, plus a known volume
of stock carrier solution, to the water being treated and calculating the
initial metal concentration. The removal percentage was taken as equal
to the percentage of reduction of radioactivity.
b. Pilot Plant
1) Description and Operation
The WSRL pilot plant is capable of treating in parallel
two 2 gpm flows of water. The plant has been designed to operate in a
number of different configurations, but has been run primarily in a con-
ventional manner for the metal removal studies with rapid mixing, floc-
culation, sedimentation, and rapid granular filtration.
The test waters used so far, Cincinnati tap water and
raw well water fronr Glendale, Ohio, were stored in a 7500-gallon stain-
less steel tank. This water was pumped to a constant-head tank that
had an overflow line back to the storage tank. Water to be treated was
pumped at 2.1 gpm through two rapid mix tanks having a theoretical
detention time of about 2 minutes each. In the first mixing tank, the
contaminants and, if required, soda ash for pH control, were added. The
coagulant, Ferrifloc, alum, or lime for softening experiments, was intro-
duced into the second mixing tank.
After the rapid mix, the water was flocculated for one
hour in a mechanically mixed flocculation basin, and then settled for
about 6.5 hours (theoretical detention times). Except for excess lime
softening experiments, the settled water was then filtered through either
one or two parallel filter columns (4 1/4-inch diameter) at a rate of
4 gpm/sq ft. The filters were: (1) a dual-media filter containing 20
inches of No. 1 1/4 Anthrafilt over 12 in. of 0.4mm effective size
Muscatine sand and (2) a granular activated carbon filter containing
30 inches of lignite-base, 0.8-0.9 mm effective size, granular activated
carbon. When excess lime softening tests were run, the settled water
was recarbonated to pH about 9.6 and settled (6.5 hours theoretical
detention time) in a second sedimentation basin before being filtered.
Figures 1 and 2 are schematic diagrams of the pilot plant.
168
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Initially, the plant ran continuously for 40 hours
(^ 5000 gallons treated water), but later the time was lengthened to
about 100 hours (^ 12,000 gallons treated water). Grab samples of raw,
settled, and filtered water were obtained periodically in 1-liter cubi-
tainers and preserved with 1.5 ml of concentrated nitric acid prior to
analysis.
2) Analytic Methods
Mercury analysis was done by the flameless atomic absorp-
tion method.^ Arsenic and cadmium analysis was done on a Perkin Elmer
Model 403 Atomic Absorption Spectrophotometer equipped with a graphite
furnace and a Perkin Elmer Model HGA-2000 controller. Selenium analysis
was done using the method of Caldwell et al.^
3. Results
a. Jar Tests
1) Previous Work
Jar test studies have been completed on mercury, barium,
arsenic, selenium and cadmium. Pilot plant tests, on the other hand,
have been only partially completed for mercury, arsenic, selenium, and
cadmium. Because the results of most of the jar test experiments have
been presented in detail by Logsdon and Symons2>6 an(j by Logsdon, Sorg
and Symons', they will not be repeated.
2) Barium
The jar test work on barium removal has been completed,
but the pilot plant studies have not begun. The laboratory experiments
used a midwestern ground water containing 7 to 8 mg/1 of barium. Coagu-
lation with aluminum sulfate and ferric sulfate was expected to remove
barium effectively because the producton of rather insoluble barium
sulfate was anticipated. However, the anticipated results were not
achieved; removals did not exceed 30 percent with either type of coagu-
lant. A possible explanation for the poor removal was supersaturation
of barium sulfate. A series of two-stage coagulation experiments were
carried out using 100 mg/1 of coagulant initially and a 20 mg/1 dose
for the second stage. These studies produced higher barium removals,
giving support to the suggestion that barium sulfate was supersatu-
rated after the first stage of coagulation. Unfortunately, such treat-
ment would not be very practical because of the higher cost required of
two-stage treatment.
171
-------
Barium removal by lime softening was also studied. In
the pH range of 10-11, barium removals exceeded 90 percent; the maximum
removal was near 98 percent. Data from a full-scale ion-exchange soft-
ening plant also showed a 98 percent barium reduction when the initial
barium content was about 11 mg/1.
Finally, laboratory tests showed that 400 mg/1Her of
ActiveX resin could remove about 80 percent of the barium, but that
powdered activated carbon was not effective for barium removal.
b. Pilot Plant Studies
The test waters used in the pilot plant studies to date were
Cincinnati tap water and well water from Glendale, Ohio. The treatment
methods used were alum coagulation, Ferrifloc coagulation, and lime
softening.
1) Mercury
Two types of mercury were selected for study: mercuric
chloride (inorganic form) and methyl mercury chloride (organic form).
Pilot plant test results on inorganics using spiked Cincinnati tap water
generally agreed with the jar test data. For raw water concentrations
of 4.0-7.5 yg/1, removals for settled water ranged from 24 to 70 percent
and for filtered water (dual-media) 47 to 80 percent when the water was
coagulated with 15-72 mg/1 of Ferrifloc. When alum (22 to 62 mg/1) was
used as a coagulant, removals were less than 10 percent for both settled
and filtered water...
Organic mercury removal by activated carbon in combina-
tion with Ferrifloc was studied using Cincinnati tap water spiked with
3.7 to 5.6 yg/1 of mercury. The treatment consisted of adding 4.5 to
5.6 mg/1 of powdered carbon in the first rapid mix tank and 28-35 mg/1
of Ferrifloc in the second rapid mix tank. The mercury removal results
ranged from 5 to 32 percent for settled water; 8 to 38 percent for dual
media filtered water and; 98 to 100 percent for granular activated
carbon filtered water.
Lime softening pilot plant tests using raw well water
have been only partially completed. Preliminary test data, however,
have shown removals for both types of mercury to be significantly higher
than those achieved in the jar test experiments. Inorganic mercury
removals were 10-40 percent higher than in the jar tests with the
settled water, ranging from 45 to 63 percent and filtered water (dual
media) from 69 to 90 percent. When organic mercury was studied, early
test results indicated that some mercury was being removed, as compared
to no removal in the jar tests. Additional lime softening work will be
carried out to determine the reason for the differences.
172
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2) Cadmium
Pilot plant studies have been completed on cadmium using
Cincinnati tap water and the raw well water. In all cases, the results
were in agreement with the jar test data.
The tests showed that cadmium removal was pH dependent
for both alum and Ferrifloc coagulation using Cincinnati tap water
spiked with 0.028 - 0.032 mg/1 of cadmium. For example, when Ferrifloc
was used as the coagulant, removals for the settled water was 20-26 per-
cent at pH 6.8 and 70-80 percent at pH 8.3. Removals for dual media
filtration was about 5-10 percent higher than the settled water.
Lime softening at pH 9.5 and 11.3 was also studied. Cad-
mium removals at both pH values were over 95 percent for the settled
water, dual media filtered water, and granular carbon filtered water.
An eight-week series of direct filtration tests were
also carried out using two granular ac-tivated carbon filters and Cin-
cinnati tap water spiked with 0.028-0.032 mg/1 of cadmium.
Each test run lasted about 100 hours and the filters
were not backwashed between runs. Cadmium removals ranged from 7 to 30
percent for the filter containing 30 inches of Filtrasorb 100 and 17 to
54 percent for the filter containing 30 inches of exhausted Filtrasorb
200.
3) Arsenic
Two forms of arsenic have been studied, Arsenic III
(arsenite) and Arsenic V (arsenate). Because As(III) would probably
be found in ground water, the behavior of As(III) was studied using
only the raw well water. Pilot plant tests on As(V) however, were
carried out using both Cincinnati tap water and the raw well water.
In all cases, the arsenic concentration was near 0.40 mg/1 and results
compared very closely with the jar test data.
Arsenic III removal by lime softening was investigated
at pH 9.5 and 11.3. At pH 9.5, removal for the settled water was 10
percent and for the filtered water 24 percent (GAC) and 26 percent
(dual-media). When the water was softened to 11.3, settled water
removal was 63 percent and filtered water removal 72 percent for both
filters. Although pilot plant tests have not been run to confirm it,
laboratory jar tests showed that when As(III) is oxidized to As(V)
using chlorine, As(III) behaves like As(V). Because higher removals
were obtained on As(V) under all treatment processes studied, arsenite
should, therefore, be oxidized to arsenate before removal is attempted.
173
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Removal of As(V) was studied in the pilot plant using
alum, Ferrifloc and lime. Arsenic removals using Cincinnati tap water
and Ferrifloc were excellent; settled water removals were 91-94 percent
and filtered water (dual media) removals were greater than 98 percent.
When alum was used as the coagulant, removals were somewhat less;
settled water removals ranged from 75 to 86 percent and filtered water
(dual media) removals ranged from 85 to 96 percent.
Softening tests on the raw well water were also investi-
gated at pH 9.5 and 11.3. At pH 9.5, the test data showed an As(V)
removal of 49 percent for the settled water and 53 percent for the
filtered waters. At pH 11.3, As(V) removals were above 98 percent for
both settled and filtered waters.
4) Selenium
The behavior of two forms of selenium has been studied,
selenium IV (selenite) and selenium VI (selenate). Although the jar
test studies have been completed, only limited pilot plant work has been
carried out. Because selenite has been identified as a problem in some
ground waters, SE(IV) was investigated primarily with raw well water.
Removals of 0.1 mg/1 of SE(IV) by lime softening in the laboratory did
not exceed 40 to 50 percent and generally were lower. Coagulation
studies with alum and Ferrifloc were also undertaken with well water
and a surface water. The results of these laboratory experiments found
that Ferrifloc produced higher removals than alum and that removals
for both coagulants decreases as the pH increases from 6 to 8. Re-
movals ranged from about 80 to 20 percent with Ferrifloc and were 10
percent or less with alum when 25 mg/1 of coagulant was used.
The removal of selenate (VI) was uniformly poor for all
jar test and pilot plant studies. Selenate removal by coagulation with
iron or alum (up to 100 mg/1 of coagulant), by softening from pH 9 to
10.8 or by treatment with up to 100 mg/1 of powdered activated carbon
was less than 10 percent for initial selenium concentrations of 0.1
mg/1. Although conventional treatment experiments were unsuccessful in
removing selenate, a short reverse osmosis test showed that this techni-
que could remove it and merits further investigations. During a two-
hour reverse osmosis test run on Cincinnati tap water spiked with 0.1
mg/1 of selenium VI, over 97 percent of the selenium was removed by
the R.O. unit operating at 1.5 liters/minute.
a. Summary of Results
Table I summarizes all of the jar test and pilot plant data
collected thus far. These studies are continuing.
174
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TABLE I
SUMMARY OF RESULTS OF TREATMENT PROCESSES TO REMOVE TRACE
METALS FROM DRINKING WATER
Trace
Metal
Coagulation
Ferric
Alum Sulfate
Softening Absorption
Lime Excess lime Activated
pH 9.5-10 pH 10.6-11 Carbon
Mercury (0)*
CH3HgCl Poor**
Mercury (I),
HgCl2 Poor
Barium
Poor
Jar Test Data
Poor Poor
Fair Fair
Poor Good
Selenium(I) Poor
Se+4 pH<7
Selenium(I)
Se+6 Poor
Arsenic(I),
As+3 Poor
Arsenic(I), Good tot
As+5 very good
pH<8
Cadmium(I) Poor to
Fair
Mercury (0)
CHgHgCl
Poor
Goodt
Good to
very goodt
Goodt
Good
Poor
Fair to
good
pH<7
Poor
Zeolite field data - very goodt
Poor Fair Poor
Poor
Poor
Poor
Fair to
goodt
Good tot
very good
pH<8
Good tot
very good
pH>7.5
Poor
Good
Very
goodt
Goodt
Very
goodt
Very
goodt
Poor
Poor
-
Pilot Plant Data
175
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Table 1 (continued)
Coagulation
Softening Absorption
Trace
Metal
Mercury(I)
HgCl2
Barium
Selenium(I)
Selenium(I),
Arsenic(I),
As+3
Arsenic(I),
As+5
Cadmium(I)
Alum
Poor
-
-
_
-
Good tot
very good
Poor to
fair
Ferric
Sulfate
Fair
-
-
Poor
-
Veryt
good
Good
pH 8.4
Lime
pH 9.5-10
-
-
Poor to
Fair
_
Poor
Fair
Very goodt
Excess lime Activated
pH 10.6-11 Carbon
Good
_
_
_ -
Good
Very Goodt Poor to Fair
Very goodt
* - (0) = Organic; (I) = Inorganic
** - Key - Poor=0-30% removal; Fair=30-60% removal; Good=60-90% removal;
Very good = above 90% removal.
t - Best treatment techniques.
- Not yet tested.
176
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4. Radium-226
a. Introduction
Radium-226 is found in some waters of the USA in excess of the
1962 Public Health Service Drinking Water Standards limit of 3 pCi/1.
If the new Federal Drinking Water Regulations set an even lower limit
for Ra-226, additional water sources would need treatment to meet the
standard.
Radium-226 is usually found in groundwaters, because it is a
geochemical contaminant. It is associated with certain aquifers such as
St. Peter sandstone in the upper Mississippi Valley and Cheyenne sand-
stone in Colorado and New Mexico^. Radium-226 may be found in surface
waters contaminated by radium-bearing springs. Other sources of con-
tamination are leachates from tailings of uranium milling plants^ and
from the phosphate rock mining and milling industry in Florida.
Because Ra-226 more frequently is found in ground waters,
treatment processes used for ground water are of interest. Some basic
information on removal of radium was contained in Straub's report.^
b. Results
A recent study of water treatment plants in Iowa has shown
results similar to those reported by Straub." The Radiochemistry and
Nuclear Engineering Facility (R&NEF), a part of the EPA's Office of
Radiation Programs has contracts with the states of Iowa and Illinois
for studying radium removal by water plants. The following results
have been obtained in the Iowa study to date and are presented in
Table II.
c. Discussion
On the basis of Iowa data, Ra-226 removals of about 75%
could be anticipated for lime softening. If greater removal is needed,
ion exchange or reverse osmosis treatment would be necessary. In
either case, the practice of blending raw and treated water to obtain a
less corrosive water and save capital costs by reducing plant size
could result in a plant effluent having an excessive concentration of
Ra-226. In such a case, corrosion control would have to be accomplished
by methods other than raw water blending, and softening 100% of plant
flow would increase costs at existing softening plants that now bypass
some raw water.
177
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RADIUM REMOVAL BY WATER TREATMENT PROCESSES
Radium pCi/1 %
Treatment Technique raw finished reduction
Greensand for iron removal 6.9 6.7 7%
Iron removal - aeration
and pressure filtration 16 12 25%
Lime-soda softening 6.1 0.9 85%
9.3 2.3 75%
Iron removal followed 49 1.9 96%
by ion exchange 5.7 0.3 95%
softening 6.7 0.2 97%
12 0.5 96%
Reverse osmosis 14 0.6 96%
d. Future Plans
Radium removal 'research contracts are continuing under the
management of R&NEF with water supply engineering input from WSRL. In
addition, WSRL has under consideration a grant application for develop-
ment of detailed construction and operating cost data and estimates
for water treatment plants built and operated primarily for radium
removal.
5. Acknowledgments
The following personnel contributed to this report.
Water Supply Research Laboratory Radiochemistry and Nuclear
Engineering Facility, NERC-
Maura M. Lilly Cincinnati
Thomas J. Sorg William Brinck
Kenneth L. Kropp
Richard Engelmann Iowa Department of Environmental
Bradford L. Smith Quality
Jeffrey Klieve R j Schlickelman
Raymond J. Lishka
James S. Caldwell
Gary S. Logsdon
178
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6. References
1. Interim Primary Drinking Water Standards, Federal
Register, Volume 40, No. 51, Part II, p. 11190-11198,
March 14, 1975.
2. Logsdon, G.S. and J. M. Symons, Journal American Water
Works Association, 6j5, 554 (1973"]^
3. Kopp, J.F., M. C. Longbottom and L. B. Lobring. JAWWA,
61, 20 (1972).
4. McFarren, E. F., JAWWA, 64, 28 (1972).
5. Caldwell, J.S., R.J. Lishka and E. F. McFarren, JAWWA,
65, 731 (1973).
6. Logsdon, G.S. and J.M. Symons, Removal of Trace Inorganics
by Drinking Water Treatment Unit Processes. Water-!973.
American Institute of Chemical Engineers Symposium Series,
™, 136 367-377, (1974).
7. Logsdon, G.S., T.J. Sorg, and J.M. Symons, Removal of
Heavy Metals by Conventional Treatment, Proceedings 16th
Water Quality Conference - Trace Metals in Water Supplies:
Occurrence, Significance and Control, University of
Illinois Bulletin, 71_, 108, 111-133 (April 29, 1974).
8. Straub, C.P., Radium-226 and Water Supplies: Cost-
Benefit-Risk Appraisal, Unpublished Report, 1973.
9. Tsivoglou, E.C. and O'Connell, R.L., Waste Guide for the
Uranium Milling Industry, DHEW, USPHS, DWSPC, RATSEC,
Technical Report, W62-12.
D. TREATMENT FOR REMOVAL OF ASBESTIFORM FIBERS
1. Introduction
The presence of asbestiform fibers in the drinking water of communi-
ties using western Lake Superior as a water source was made known in the
summer of 1973. In the fall and early winter of that year an interagency
agreement for studies of the problem was formulated and signed by the
U. S. Environmental Protection Agency and the U. S. Army Corps of
Engineers. Under this agreement EPA funded the pilot plant research on
179
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asbestiform fiber removal while the Corps of Engineers funded a study
of alternative water sources and sites for construction of a filtration
plant or plants for the Duluth-Cloquet-Superior area.* The Corps also
managed the contract for the entire study, while EPA provided technical
assistance on the filtration. The contractor was Black and Veatch, of
Kansas City.
The pilot plant research was conducted at the Lakewood Pumping
Station in Duluth, with the assistance of the Department of Water and
Gas of the City of Duluth. Pilot plant operations were conducted in the
period from April through September 1974. In this time a total of 227
granular media and 228 diatomaceous earth (DE) filter runs were conduc-
ted.
2, Scope of Study
There were two principal objectives in the research. First, the
pilot plants were to be operated _in such a way that data needed for
engineering design and cost estimates could be obtained. The results
and conclusions related to design and cost factors are being presented
by Robinson et a!.' A paper on DE filtration optimization is being
presented by Baumann.2 The second objective of the study was to obtain
information on the removal of asbestiform fibers. That information is
presented in this paper.
In order to learn how to reduce the asbestiform fiber count by
filtration, a number of variables were studied. Those common to both
granular and DE filtration were filtration rate, seasonal conditions,
and raw v/ater turbidity. Other important variables in the granular
filtration study were filtration with and without sedimentation, dual
media vs. mixed (tri) media, doses and combinations of inorganic salts
and organic polymers, .single-stage vs. multi-stage flash mixing, and
flash mix chambers vs. in-line mixers. Variables important in the DE
study were one-step vs. two-step precoating, vacuum vs. pressure filtra-
tion, DE conditioning with alum or polymers, and body feed doses.
3. Experimental Methods and Equipment
a. Equipment
The apparatus used in the research has been described in the
*buluth-Superior Urban Study, Interim Report on Water Supply for the
Duluth-Superior-Cloquet Area, A Joint Study by the U. S. Army Corps of
Engineers, St. Paul District, and the U. S. Environmental Protection
Agency (March, 1975).
180
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EPA report on the project. Two types of filters, granular media and
DE, were used. All units were situated in Lakewood Pump Station. Raw-
water for all units was drawn from the wet well at the pump station.
Total water flow through individual filter systems generally ranged
from 10 to 20 gpm.
Two granular filters were employed. Both units were Water
Boy package plants with 4.0 square feet of filter surface. Equipment
variations with these units included use of dual media, mixed media, no
settling, tube settlers, single-stage rapid mix and two-stage rapid
mix with propeller mixers, two-stage and three-stage rapid mix with in-
line mixers, alum or ferric chloride as the primary coagulant, anionic,
cationic, and non-ionic polymers, and filtration rates from 2 to 7
gpm/sf.
Two kinds of DE filter systems were employed. Pressure fil-
tration was carried out with an Erdlator filter. In this unit water
was not coagulated and settled, contrary to U. S. Army practice, but
the clear Lake Superior water merely passed through the pretreatment
portions of the Erdlator on its way to the pressure filter. The Erdla-
tor had two pressure vessels, each containing six cylindrical septa.
Total filter surface area for one pressure vessel was 10.0 square feet.
After the filter septum was precoated, body feed could be added dry or
in slurry form.
The gravity, or vacuum DE filter unit consisted of an open
rectangular tank with flat septa. The driving force for filtration was
the difference between atmospheric pressure and the pressure at the
pump intake on the effluent side of the filter. Filter surface was also
10.0 square feet on this unit. Body feed could be added dry or in
slurry form.
Both kinds of DE filters were operated in various ways in
order to evaluate conditioning of DE with alum, cationic polymer and
anionic polymer. On some runs a cationic polymer was added to the raw
water. Single-step vs. two-step precoat was studied. Conditioned
DE was used in precoat situations as well as for body feed. Various
grades of DE, from fine to coarse, were evaluated.
b. Analytical Methods.
Most of the analytical procedures were done in accordance with
Standard Methods^. In addition to laboratory turbidity measurements on
grab samples, continuous flow turbidity data were obtained with both
90° scatter and 15° forward scatter instruments. Grab samples were
obtained for the analyses, including asbestos. Since there is no
181
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standard method for asbestiform fibers in water, analytical methods were
different for each laboratory used. Three analytical laboratories were
involved in this study.
The National Water Quality Laboratory of EPA in Duluth ana-
lyzed raw and filtered samples for suspended solids and amphibole mass.
The x-ray diffraction technique for amphibole mass has been published by
Cook. Although this method measured only amphibole mass irrespective
of shape (by definition fibers have a length:width ratio of 3:1 or
greater), and did not measure chrysotile, the availability of amphibole
mass data within a few days of sample collection made this method a
valuable tool.
Transmission electron microscope analysis of water samples
was done at the Ontario Research Foundation (ORF) and at the University
of Minnesota at Duluth (UMD). The ORF analytical method has been pub-
.lished6. ORF obtained size information on each fiber (length and width)
and confirmed that all fibers were amphibole or chrysotile by electron
diffraction. Electron diffraction was used to identify a portion, but
not all, of the fibers counted by UMD.7
4. Results
The results of all pilot plant filter runs and analyses are
presented in the EPA filtration report and appendices. The data pre-
sented in this paper relate principally to the problems of asbestiform
fiber removal by filtration. Relevant raw water data are also presented
in order to place the filtration results in proper perspective.
a. Raw Water Quality
Water quality parameters of greatest interest in this study
were turbidity, asbestiform fiber count, and amphibole mass. Other
data on pH, alkalinity, hardness, temperature, and suspended solids can
be found in the EPA report.
Most turbidity measurements were made with a Hach 2100A labora-
tory turbidimeter. When a comparison was made between a Monitek in-line
turbidimeter and the Hach 2100A, it was found that although the numeri-
cal readings differed for the two instruments (15° forward scatter vs.
90° scatter), the trends of turbidity variation were quite similar. Both
instruments showed rising or declining turbidities at the same time.
These data were presented in the EPA report.
Turbidity of the raw water at Lakewood changed very little
during most of the five months of pilot plant operation. Except for a
period extending from 2300 hours on June 6 to 0700 hours on June 15,
182
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1974, and other briefer periods, the turbidity of the raw water from the
Lakewood Intake ranged from 0.35 toa 1.0 TU. During the period begin-
ning on June 6, the raw water turbidity ranged from 1.6 to 6.3 TU and
averaged 2.7 TU. Other periods of raw water turbidity in excess of 1.0
TU were relatively short, ranging from a period of 2 hours to one of 29
hours, with the raw water turbidity seldom exceeding 1.5 TU during these
periods.
The turbidity of the raw water transported from the Cloquet
Pipeline Intake was not as low as that from the Lakewood Intake, but it
also varied only over a slight range. The turbidity of the Cloquet raw
water tested was never below 2.0 TU nor above 4.0 TU.
Asbestiform fiber count and amphibole mass concentrations
showed much greater variation than raw water turbidity. Fiber counts
and amphibole mass concentrations are plotted vs. time in Figures 1 and
2 to show the time variation of these parameters.
It should be mentioned that there were no violent storms
during the pilot plant operation, and in the fall and winter of 1974,
amphibole mass concentrations exceeding 1.0 mg/1 were measured during a
storm. The pilot plant was shut down two or three months before the
worst water conditions (high turbidity.and fiber count) occurred because
funds for conducting the study were limited.
During the May-September period of operation, amphibole and
chrysotile fiber counts were frequently in the 0.5 to 1.5 x 10^ f/1
range, and amphibole mass often ranged between 0.05 and 0.2 mg/1. There
were extremes both above and below these values.
b. Asbestiform Fiber Removal by Filtration
It is apparent from the portions of this paper that deal with
the scope of the study and the equipment used that there were numerous
variations in experimental conditions. In order to simplify data
analysis, amphibole mass and asbestiform fiber removal results are pre-
sented for treatment categories that specify such variables as: filter
media, filtration rate, use of sedimentation, inorganic coagulant and
polymer, and type of rapid mixing for granular filtration; and number
of layers of precoat, precoat conditioning, body feed conditioning, and
polymer feed to raw water for DE filtration. Tables 1, 2 and 3 show
summarized results for dual media, mixed media, and diatomite filtra-
tion.
The treatment data are given in terms of the number of filter-
ed samples submitted for analysis and the number of samples with a
183
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185
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result equal to or less than 0.04 x 106 fibers/liter (f/1) (fiber data
from ORF), or equal to or less than 0.005 mg/1 in the case of amphibole
mass data. The amphibole mass detection limit varied according to the
volume of the water sample filtered for analysis. Waters which had a
greater tendency to clog membrane filters had higher- detection limits.
If the detection limit was above 0.005 mg/1, it became impossible to say
whether the amphibole mass in a treated water exceeded 0.005 mg/1.
Samples clouded in this uncertainty were not tabulated in the results
presented herein. For example, in Table 1, treatment category filtra-
tion without sedimentation, alum and nonionic polymer, ^4 gpm/sf, ten
samples are listed as having been analyzed for asbestiform fibers,
while only five are listed as having been analyzed for amphibole mass.
The other five amphibole mass samples had a detection limit that
exceeded 0.005 mg/1.
Tables 1, 2 and 3 show that the more successful variations of
filtration, whether dual media, mixed media, or diatomite, produced
effluents having amphibole mass concentrations and amphibole fiber
counts near the detection limits of the analytical methods employed.
Chrysotile fiber count in filtered water generally exceeded 0.04 x 10°
f/1 for dual media filtration tests and for DE filtration tests not
employing polymer conditioning. Mixed media filter runs employing alurn
and nonionic polymer or alum, anionic polymer and another polymer, and
diatomite runs employing A-23 conditioning of DE or Catfloc B condi-
tioning of raw water did have some runs with effluent chrysotile counts
£0.04 x 106.
5. Discussion
a. Asbestiform Fiber Removal
The initial objective of the filtration research at Lakewood
Pumping Station was the removal of amphibole asbestiform fibers and
turbidity-causing suspended matter. According to the pilot plant
research contract, the principal criterion for successful treatment will
be the economical attainment of virtually complete removal of asbestos-
like fibers as defined by optical and electron microscope analysis using
the best current state of the art. A secondary criterion shall be the
production of water having a turbidity of not more than one turbidity
unit.8 The fibers referred to in the contract were expected to be prin-
cipally amphibole.
In conversations between the WSRL and EPA Region V (Chicago)9,
which was then heavily involved with contracts for analysis of asbesti-
form fiber content of water samples, the Ontario Research Foundation was
determined to be one of the laboratories that could satisfactorily
186
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191
-------
analyze water samples for asbestiform fibers. Thus, ORF became a sub-
contractor for the filtration research conducted by Black and Veatch.
One factor which must be considered when interpreting EM fiber
analysis data is the meaning of the detection limit. When ORF found
zero fibers in ten fields, the reported result was below detectable
limits (BDL), not zero. Depending on the circumstances of the individual
analysis, such as sample volume initially filtered, ORF reported a number
of BDL limits from 0.02 x 106 f/1 to 0.07 x 106 f/1. Most of the time
the detection limit was reported as 0.02 x 10° f/1 although early in the
work 0.04 x 10^ f/1 was frequently reported.
McFarren^0 uses an intermediate category, not statistically
significant (NSS) between BDL and reportable fiber counts. The NSS
finding is applied to observation of less than 5 fibers in 20 fields.
This would correspond to about two fibers in 10 fields for ORF. The
rationale for use of NSS is that fiber counts become less reliable as
fewer fibers are found. The standard deviation varies as l//n , where n
is the number of fibers found Jl Thus the standard deviation is 10%
when 100 fibers are found, and 100% when 1 fiber is found.
For the EM work done by ORF on this project, the finding of
two fibers in 10 fields usually represented 0.04 x 10° f/1. Since the
goal of the research was the "virtually complete removal," 0.04 x 106
f/1 and lower were considered not statistically significant, and the
research goal was considered to have been attained when filtered water
fiber counts were 0.04 x 10^ f/1 or lower.
It is apparent from the data in Tables 1-3 that amphibole
asbestiform fibers could be readily removed by filtration. Additional
evidence to confirm the efficacy of filtration is found in the amphibole
mass data. Many of the filter runs that were sampled contained 0.005
mg/1 or less in the filter effluent. Based on the amphibole mass con-
centration in the raw water, this represented amphibole mass reductions
of ten-fold to forty-fold or more.
Some of the variables considered in the research are to be
found in Tables 1-3. Table 1 contains fiber removal data for dual media
granular filters only. There is nothing in Table 1 that indicates that
sedimentation before filtration was beneficial for amphibole or chryso-
tile fiber removal. For the treatment of clear Lake Superior water,
direct filtration performed as well as filtration with sedimentation.
Ferric chloride appears to be effective for fiber removal,
but alum and nonionic polymer were used in most tests because that was
the combination of treatment chemicals that gave the desired combination
192
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of very low effluent turbidity and longer filter runs. This is explained
in more detail by Robinson et al.
Research results for mixed media filtration are summarized in
Table 2. A comparison of Tables 1 and 2 shows that mixed media filtra-
tion after two-stage flash mix was more effective for chrysotile removal
than dual media filtration after one-stage flash mix, when alum and a
nonionic polymer were used. With the one-stage flash mix arrangement,
polymer was added at the flocculation chamber. Since two variables were
changed at once, it is difficult, if not impossible, to decide which
affected fiber removal more.
Another variable studied in the mixed media system was three-
stage rapid mix. The purpose of the triple mix was to add and mix
sequentially three conditioning chemicals, anionic polymer, alum, and
cationic or nonionic polymer, with the objective of establishing, at
different times in the treatment process, environments in which positive,
and then negative, surface charges predominated. Unfortunately, two
chemicals were added to a common barrel (mixing chamber) in the propel!or
type flash mixed system, so valid data were obtained only for in-line
mixers. The results of three-stage rapid mixing are encouraging for
both amphibole and chrysotile removal.
Diatomite filtration for asbestiform fiber removal may appear
to be less successful than granular filtration, but this is not the case.
More operational variations were tried with diatomite, and some were
not successful. Some successful techniques were found, however, and
these are found in Table 3.
Effective filtration techniques for removal of amphibole mass
and fibers were the following:
a. alum conditioning of both precoat and body feed;
b. precoat conditioning with anionic polymer and body
feed conditioning with alum;
c. conditioning of the raw water with Catfloc B and in
some cases, alum conditioning of the precoat also.
Diatomite filtration techniques most effective for removal of
both chrysotile and amphibole involved the following:
d. conditioning of precoat with anionic polymer and
conditioning of body feed with alum;
e. conditioning of raw water with Catfloc B.
193
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The treatment scheme in case d involved both negative (anionic
polymer) and positive (alum coated DE) charges. A system in which
Catfloc B was added to raw water before filtration through unconditioned
DE would also involve both positive (Catfloc B) and negative charge
systems, since diatomite ordinarily has a negative surface charge.^
However, plain diatomite probably would not be as electronegative as
diatomite coated with an anionic polymer.
Experiments with anionic polymers were conducted because of a
fundamental difference in chrysotile and amphibole. Parks^2 summarized
the work of numerous investigators in an article on the isoelectric
point or zero point of charge of complex oxide minerals in water. The
zero point of charge, or pH at which there is no net charge on the par-
ticle, is in the pH 10-11 range for chrysotile, but it is pH 5 for
cummingtonite (an amphibole). In the 7-8 pH range used in filtration
tests at Duluth, chrysotile would have a positive surface charge while
cummingtonite, like clays and most bacteria, would be negative. It
follows that in order to overcome the surface charges of both amphibole
and chrysotile, it would be necessary to use treatment chemicals carry-
ing positive and negative surface charges, respectively. The treat-
ment chemicals should be introducted to the water separately so that
the coagulation is not confined to reaction between only the treatment
chemicals.
It would be logical to ask why amphibole and chrysotile fibers
do not coagulate themselves since they are of opposite surface charge.
A probable answer is that there are so few present, even when the con-
centration is 1()6 f/1. For example, if a liter of water contained 105
chrysotile fibers with 0.04 ym diameter and 1 ym length, the total vol-
ume of fibers would be ^10~9 1 or 0.001 microliter. Also, 1Q6 amphibole
with 0.2 urn diameter and 1 ym length would occupy a volume of 3 x 10"°
1 or 0.03 microliters.
The addition of polymers to raw water in this work should have
resulted in molecular concentrations on the order of 10'^ to 10'"
molecules per liter, depending upon the dose and molecular weight of
the polymer, and assuming that every polymer molecule was a separate
entity (the same assumption made for asbestiform fibers).
It is obvious that polymer molecules very greatly outnumber
(by a factor of 10& to 10^) asbestos particles, so the chances for a
polymer-fiber collision would be much better than for a fiber-fiber
collision. Thus polymer conditioning is needed for fiber removal, and
since surface charges differ with type, different polymers are needed
to remove amphibole and chrysotile.
194
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One other factor that may be related to fiber removal or,
conversely, to the ability of fibers to pass through filters, is fiber
size. For all filters, the typical size of chrysotile fibers in the
effluent was smaller than the typical size in the raw water. This size
relationship was also true for amphiboles in DE filtrate. Because only
25 amphibole fibers were observed and sized for granular media tests,
this small sample was more subject to distortion by a typical fibers
and was not very suitable for a chi-square analysis. The factor of
particle size is probably less important than surface charge, since
particles in the water, both before and after filtration are in the size
range (M ym) suggested by Yao'^ to have minimum removal efficiency by
granular filtration.
Filtration results can be summarized briefly. The methods
found more effective than others for removal of both amphibole and
chrysotile were mixed media filtration employing alum and an anionic
polymer and two-stage flash mixing; and pressure diatomite filtration
employing Catfloc B added to the raw water and no conditioning of the
DE. Methods showing potential for further research are three-stage
flash mixing with sequential addition of anionic polymer, alum, and
cationic or nonionic polymer, followed by flocculation and filtration;
and pressure DE filtration with anionic polymer conditioning of the
precoat and alum conditioning of the body feed.
b. Efforts to Develop Rapid Detection Methods
A limited effort to learn about rapid detection of asbestiform
fibers was made in this research, but the principal objective was to
learn about fiber removal by filtration. Other efforts to develop a
rapid fiber detection method are underway, sponsored by EPA and other
Federal agencies. One method being investigated involves placing a
water sample in a laser light beam measuring scattered light from inci-
dent angles of about 10° to 135°, and relating variations of light
intensity and incidence angle to the types of particles present in
water. One of the goals of these efforts is to provide a technique
that is practical for monitoring both amphibole and chrysotile asbesti-
form fibers in water at filtration plants. Such a technique should be
rapid enough to permit a plant operator to make meaningful changes in
the treatment process in order to hold fiber content of the filtered
water to a minimum. Until a more rapid method is available, water
filtration plants on Lake Superior should use the x-ray diffraction
method, along with occasional EM analyses.
6. Future Research
Information developed in this pilot plant research permits a number
of questions to be formulated for future study. Among the ideas that
195
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could be investigated are the following:
a. Ways to improve chrysotile removal by anionic polymer
conditioning of DE or by the use of three-stage mixing and combination
of three conditioning chemicals in granular filtration.
b. Effect of high algal counts on filter performance.
c. Fiber removal during times of highest amphibole mass
and fiber count.
d. Verification of POPO optimization of diatomite filtration,
e. Additional filtration experiments at 5 to 6 gpm/ft with
yrcuiular filters.
f. Effect of mixing intensity on filtration, and a compari-
son of back-mixing vs. in-line mixing.
g. Further laboratory development, followed by pilot plant
tests, of an operator's method for monitoring the presence of asbesti-
form fibers in water.
A number of the suggestions for future work represent an extension
of past work into promising study areas. Additional research is needed
to increase the knowledge of the water treatment profession on the
topic of asbestiform fiber removal by filtration.
7. Conclusion's
a. No discernible tie was evident between the Duluth raw
water turbidities and the asbestiform fiber levels.
b. At finished water turbidities of less than 0.1 TU, the
amphibole fiber count and mass determinations were usually below the
detection limits of the analytical method used.
c. A general association was indicated between the NWQL
amphibole mass concentration and the ORF amphibole fiber counts in the
Duluth raw water.
d. No relationship was observed between the counts of the
amphibole and the chrysotile fibers in the Duluth raw water.
e. Based on achieving BDL or near it, 32 of 34 MM-2
(granular) runs and 21 of 23 MM-1 runs were successful for amphibole
196
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removal. Only 8 of 34 MM-2 runs and 2 of 23 MM-1 runs were successful
for chrysotile removal. Alum and nonionic polymer worked best in granu-
lar filters,
f. Amphibole fiber removal accomplished by the tri-media
filter exceeded that accomplished by the dual media filters and the DE
filters.
g. For the pressure DE tests, 19 of 27 were successful for
amphibole removal, but only 4 of 27 were successful for chrysotile
removal. Vacuum DE filtration (BIF) was not found suitable for treat-
ing the raw water being tested.
h. A medium grade precoat and a fine grade body feed were
most effective in turbidity and asbestiform fiber removal by DE
filtration.
i. For the Duluth raw water, two treatment conditions, alum
coated or plain precoat, with a cationic polymer introduced to the raw
water, and an anionic polymer added to the precoat and alum coated
body feed were most effective in turbidity and asbestiform fiber re-
moval filtration.
8. Acknowledgments
The following EPA personnel contributed to this report:
E. McFarren
R. Lishka
J. Millette
G. Logsdon
J. Symons
M. Lilly
M. Lubratovich
P. Cook
G. Glass
B. Fairless
9. References
1. Robinson, J.H., et a!., Direct Filtration of Lake Superior
Water for Asbestiform Solids Removal. Presented at Annual
Conference, American Water Works Association, Minneapolis,
Minnesota (1975).
197
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2. Baumann, E.R., Diatomite Filter for Asbestiform Fiber Removal
from Water. Presented at Annual Conference, American Water
Works Association, Minneapolis, Minnesota (1975).
3. Direct Filtration of Lake Superior Water for Asbestiform
Fiber Removal. By Black and Veatch, Consulting Engineers, U.S.
Environmental Protection Agency, National Environmental
Research Center - Cincinnati, Water Supply Research Laboratory
(April 1975). Summary Report #EPA 670/2-75-050a and six
appendices #EPA 670/2-75-050b to EPA 670/2-75-050g.
4. Standard Methods for the Examination of Water and Wastewater.
APHA, AWWA, WPCF, New York (13th Edition 19TTJ:
5. Cook, Philip M., Semi-quantitative Determination of Asbestiform
Amphibole Mineral Concentrations in Western Lake Superior
Water Samples. Proc. 23rd Annual Conference on Applications
of x-ray Analysis, Denver, Colorado (1974).
6. Chatfield, E.J. and Pullen, H., Measuring Asbestos in the
Environment. Canadian Research and Development, 7:6:23
(Nov.-Dec. 19741".
7. Carter, Robert E., Private Communication to Mr. 0. J. Schmidt.
8. Contract No. DACW 37-74-C-0079, Department of the Army,
St. Paul District, Corps of Engineers (February 1974).
9. Fair!ess, William. Memorandum from U. S. EPA Region V to
Water Supply Research Laboratory.
10. McFarren, Earl F., et al., Asbestos Analysis by Electron
Microscope. Presented at Second Annual Water Quality Technol-
ogy Conference, AWWA, Dallas, Texas (1974).
11.. Chatfield, E.J., Private communication to,Mr. 0. J. Schmidt.
12. Parks, George A., Aqueous Surface Chemistry of Oxides and
Complex Oxide Minerals. Symposium on Equilibrium Concepts
in Natural Water Systems, Proc. 151st Meeting Am. Chem. Soc.
Pittsburgh, Pa. (1966). published as Equilibrium Concepts
in Natural Water System, W. Stumm, ed., (1967), p. 121.
13. Yao, K., et al., Water and Waste Water Filtration: Concepts
and Applications. Environmental Science and Technology, 5:11:1105
(November 1971).
198
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APPENDIX VII
HEALTH EFFECTS CAUSED BY EXPOSURE TO DRINKING WATER CONTAMINANTS
Organics Section Prepared by
Robert 6. Tardiff
Inorganics Section Prepared by
Gunther Craun
Lei and McCabe
Water Supply Research Laboratory
National Environmental Research Center
Office of Research and Development
Cincinnati, Ohio
-------
HEALTH EFFECTS CAUSED BY EXPOSURE TO DRINKING WATER CONTAMINANTS
The following sections on the toxicity of organics and inorganics
found in drinking water reflect the views of the respective authors of
those sections and not necessarily the views of the Environmental
Protection Agency. These reports provide necessary preliminary informa-
tion with which to assess the health effects of these contaminants and
will be carefully reviewed along with other investigations, such as that
of the Science Advisory Board, in future discussions.
A. TOXICITY OF ORGANICS PRESENT IN DRINKING WATER
1. Introduction
Over the years, the occurrence of organic materials in all tap
water has been acknowledged almost universally. Until relatively
recently, data describing such occurrence has been almost exclusively
the result of gross measurements such as carbon-chloroform-extracts and
non-volatile-total organic-carbon. The advent and application of more
sophisticated analytical tools, such as the mass spectrometer, has led
to the conclusive identification of some of the organic components of
drinking water. Appendix I ,is the most recent compilation of compounds
that have been found in various potable supplies. Recent estimates by
the Water Supply Research Laboratory of E.P.A. indicate that of all the
compounds present the identified compounds may account for no more than
10 percent by weight.
The compounds in Appendix I are not all unique to drinking water.
Concurrent exposure by various segments of the U.S. population exists
via some foods, ambient air, occupational environment, and/or household
products (e.g., over-the-counter medications, cleaning solutions, and
cosmetics). For some compounds, particularly some of those suspected of
being by-products of chlorination of tap water (e.g., dibromochloro-
methane and brotnodichloromethane), man's exposure is restricted solely
to potable water and to foods processed with that water.
Many factors enter into the hazard/safety evaluation of organics in
drinking water. Among them is determination of the toxicity of the
materials to which man is exposed. Toxicity data include a broad range
of biological parameters, a few of which are listed below:
1. the amount of material required for the production of acute
illness arid mortality;
2. the ways in which a compound is handled metabolically by the
body;
200
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3. the types of diseases and specific organs affected from repeated
exposures for a part or all of the lifespan;
4. the reversability or irreversability of the lesions;
5. the particular groups of the populations that might be at
greater risk to intoxication; and
6. the factors, both endogenous and exogenous, that alter the
toxicity of foreign compounds and/or compromise the organism's
ability to respond to insults from foreign compounds.
The central objective from the investigations of such questions is
the identification of what will occur in man through the utilization of
predictive experimental animal models. Well designed and closely con-
trolled experimentation can yield information valuable in protecting man
against exposure to hazardous doses of a chemical or mixture of compounds,
Epidemiologic surveillance can monitor body burdens and health status as
a function of exposure levels and durations of exposure to insure against
the possibility of incorrect extrapolations and to guard against the un-
expected sensitivity in population subsets.
2. Acute Toxicity
Data on acute doses required for intoxication serve, first, as a
yardstick against which to compare one compound with another and, second,
as a starting point in the design of repeated exposure and metabolism
studies. The comparative evaluations of acute toxicity have been forma-
lized into a rating system (1) which is described in Table 1.
The compounds listed in Appendix I underwent a literature search to
find data on acute toxicity and to categorize the relative toxicities
according to the rating system of Gleason et_. a_l_. (1). Table 2 displays
the results of this evaluation. Most of the compounds for which data
are available are in the categories "moderate" and "very" toxic. For
30 percent of all the compounds, no acute toxicity data were available
from which to assign a rating.
While individual compounds are usually rated for their acute toxic
potential, mixtures of these agents can be similarly classified. Tardiff
and Deinzer (2) reported that extracts of organir.s from drinking water
were tested in mice and found to have LDso values that classified the
mixtures as "very" toxic. The mixtures represented approximately 30 per-
cent of the organics originally present in the tap water samples used.
It should be remembered that acute toxicity measurements for these
contaminants are based upon doses that are far greater than those en-
countered from drinking water. Acute toxicity does not necessarily bear-
any relationship to chronic toxicity which is more relevant to low-lpvfl
201
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TABLE 1
CLASSIFICATION SYSTEM FOR ACUTE TOXICITY OF CHEMICALS (1)
Toxicity Rating Probable Lethal Dose for Man
or Class or LD5Q for Experimental Animals
6 - Super Toxic less than 5 mg/kg
5 - Extremely Toxic 5 to 50 mg/kg
4 - Very Toxic 50 to 500 mg/kg
3 - Moderately Toxic 500 to 5000 mg/kg
2 - Slightly Toxic 5 to 15 gm/kg
1 - Practically Non-toxic greater than 15 gm/kg
TABLE 2
ACUTE TOXICITY RATINGS OF COMPOUNDS IDENTIFIED IN DRINKING WATER
Toxicity Rating Number of Compounds
6 - Super Toxic 1
5 - Extremely Toxic 7
4 - Very Toxic , 47
3 - Moderately Toxic 62
2 - Slightly Toxic 11
1 - Practically Non-toxic 3
Unknown ". 56
202
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human exposure to organic chemicals in drinking water. The following
section discusses chronic toxicity.
3. Chronic Toxicity/Carcinogenicity
Exposure to repeated small quantities of environmental chemicals
suggests a greater possibility of chronic, rather than acute, intoxica-
tion. One of the more serious irreversible expressions of chronic
toxicity is carcinogenesis. Because of the nature of the disease,
chemically-induced carcinogenesis is considered one of the more dread
toxic properties. However, an entire spectrum of chronic—but non-
neoplastic--diseases can be equally serious personal and societal trage-
dies. Attention must be focused on all forms of chronic illness whose
etiology is environmental agents.
The determination that a compound at ambient concentrations is or
is not a tumorgenic risk to man is a relatively difficult task as ac-
knowledged by scientists of the National Cancer Institute. The observa-
tion of a neoplastic response in an experimental species from exposure
to a chemical invokes many questions. Perhaps one of the most significant
questions concerns whether the animal model in which the carcinogenic
expression was observed is predictive of the same response in man. Thus,
of itself, a chemical may be a carcinogen in an experimental species
(e.g., the mouse); however, the same chemical may not necessarily be a
carcinogenic hazard to man. It must be emphasized that such a model can
be validated by specific and definitive studies, but that such studies
may not have been performed at the time the neoplastic response is dis-
covered.
In an effort to take into account all factors that enter into the
evaluation of a compound's carcinogenic property, operational definitions
were generated by the Water Supply Research Laboratory of E.P.A. with
assistance from the National Cancer Institute. Those definitions are
listed in Table 3. The definitions reflect the necessity to make reli-
able and accurate judgments about the agents. Thus, relatively few
compounds meet the criteria for "positive" carcinogen as exemplified by
the brevity of the list of occupational carcinogens (OSHA list of 14
compounds). However, many more compounds are classified as "suspect"
carcinogens because of the lack of sufficient and appropriate informa-
tion from which to definitely predict or acknowledge the hazard to man.
(Acknowledgment of the effect via human data is never a goal with respect
to cancer but may be a reality because of accidents or misjudgments.)
Preceding considerations were related only to qualitative aspects
of carcinogenesis: Is a compound a carcinogen or not? Is it a carcin-
ogenic hazard to man or not? Such a consideration excludes the concept of
potency;-namely, how potent is one compound vs. another in the induction
of tumors. Stated differently, potency involves how much of a compound
and how long an exposure are required to develop tumors in a defined
population. For some time, oncologists have spoken of "strong" and
203
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TABLE 3
CLASSIFICATION SYSTEM AND CRITERIA FOR THE
DEFINITION OF CARCINOGENIC PROPERTIES OF CHEMICALS*
Class#1 - Positive or Recognized Carcinogen
Criteria: a. On an acceptable list of human carcinogens (e.g., the
OSHA list)
b. Strong experimental evidence - many species and
strains, etc.
c. Strong evidence or strong suspicion as to cause and
effect in man
Class #2 - Suspect. Possible or Potential Carcinogen
Criteria: a. Structure similar to proven carcinogen
b. Positive response in one species
c. Mutagencity data
d. No epidemiologic evidence
e. Either not tested or tests inadequate
Class $3 - Unknown Carcinogenic Potential
Criteria: a. Tests limited in time
b. Tests limited in dose schedule
c. Insufficient number of animals
d. Route of administration not relevant
e. Improper species and/or strain used
f. Dose schedule not relevant: strong overlay of toxicity
g. Role of contaminants
h. Not tested & no structure-activity suspicion
Class #4 - Negative or Non-carcinogenic
Criteria: a. Repeated tests in many species and strains
b. Adequate protocols
c. Confirmed in several laboratories
d. Established non-carcinogenic in the absence of
contaminants
e. Strong epidemiologic evidence that it is non-carcinogenic
in man
* System developed in collaboration with the National Cancer Institute.
204
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"weak" carcinogens implying a difference in dose to obtain the same
effects (e.g., 50 percent tumor formation). If, for example, a compound
at environmental levels requires 100 years of exposure to induce tumor
formation in man, this compound may be regarded as a relatively small •
cancer hazard to society as compared to one which requires only a decade
to obtain a similar response.' Although the regulatory agencies will
wish to exercise control over all carcinogenic substances within their
respective jurisdictions, consideration of potency may assist in estab-
lishing priorities for control measures and for allocation of resources.
/
The recognition of the tumor-inductive property of chemicals led*,to
a cursory examination of biological literature to determine the evideace
both positive and negative, for carcinogenic responses induced by the
chemicals identified in tap water (Appendix I). The results of this
evaluation are listed in Table 4. The "positive" or known carcinogens
are aldrin, benzene, benzopyrene, carbon tetrachloride, DDT, 2,4-dichlor-
ophenol, dieldrin, and 2,4-dimethyl phenol.
The "negative" or non-carcinogens are acetic acid, acetone, barbital,
benzoic acid, ethanol, and methanol. Of the 187 compounds, there was no
data and insufficient structure-activity information to make a judgment
of 137 chemicals (i.e., over 70 percent of those found to have been
present in tap water and to which some humans were exposed). It must be
concluded that although more information must be obtained on "suspect"
carcinogens, a great deal more experimental evidence must be learned
about the chronic toxicity of a substantial number of compounds. Con-
tinued search for additional chronic toxicity data may yield additional
pertinent information on these compounds.
A few studies (3-5) have been reported in which organic mixtures
extracted from drinking water were administered repeatedly to determine
carcinogenic potential. The results indicated that, in mice, carbon
extracts elicited neoplastic responses when injected but not when in-
gested (3,4). In another investigation (5), injections of carbon extract
of organics from drinking water failed to induce tumor formation.
TABLE 4
CARCINOGENICITY CLASSIFICATION OF COMPOUNDS
IDENTIFIED IN DRINKING WATER
Class Number of Compounds
1 - Positive 8
2 - Suspect 35
3 - Unknown . 138
4 - Negative 6
205 -
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4. Ongoing Research
The Water Supply Research Laboratory of E.P.A. is actively engaged
in investigating the toxicity of organics in drinking water for the
purpose of identifying hazards and risks to man's health via this mode
of exposure and of determining, if no hazard exists, the magnitude of "
the margin of safety from environmental exposures.
Toxicologic experimentation on the organics in drinking water is
guided by Principles for Evaluating Chemicals in the Environment (6).
A two-pronged approach is being used to investigate the organics in
tap water. The first studies the biological effects of individual com-
pounds. The second is aimed at the elucidation of the toxic properties
of mixtures of organics which are present in tap water.
Several classes of compounds identified in potable water are under
active investigation with regard to their toxicity in experimental ani-
mals. These classes include the chlorinated ethers, the chlorinated and
brominated benzenes, and the halogenated methanes. Investigations are
designed (1) to determine the most significant animal model through
studies of comparative metabolism and (2) to uncover pathologic changes
resulting from varying levels of repeatedly administered compounds in
appropriate experimental species.
The chloro-ethers of immediate interest are bis(2-chloroethyl)
ether and bis(2-chloroisopropyl) ether. The metabolism of these agents
is being studied in several species including sub-human primates in
order to determine the species that most closely resembles man in its
metabolism so that additional toxicity studies may be performed in a
species that is more predictive of man's response. Base-line data are
being obtained on the effects from single and relatively short-term
repeated exposures in one classical model. A specialized model is being
utilized to determine possible carcinogenic potential. Investigations
have been designed to establish any mutagenic activity that might be of
concern to man. Because very little is known of the toxicity of these
compounds (although they are chemically related to a potent toxicant and
carcinogen), a broad scope of experimentation is required on these com-
pounds.
Halogen-substituted benzenes demonstrate a relatively long biologi-
cal half-life that suggests accumulation in the body with repeated expo-
sures with consequent chronic toxicity. Because of evidence suggesting
the acute alteration of zenobiotic metabolism, these compounds are being
studied to determine their potential interaction with other foreign com-
pounds to alter toxicity (e.g., synergistic responses). The entire
homologous series of chlorine- e.nd bromine-substituted benzenes are
under investigation.
206
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Halogenated methanes (dibromochloromethane and bromodichloromethane)
are possible chlorination by-products for which there is presently no
toxicity information. A broad spectrum of experimentation is planned
including comparative metabolism and comparative toxicity with special
emphasis on chronic toxicoses.
The investigation of the toxicity of mixtures of organics from tap
water is described schematically in Figure 1. Extracts or concentrates
of organics from municipal water supplies can be screened with biological
systems to determine what types of toxicity problems to investigate
further and to establish which water supplies may have the greater poten-
tial for adverse health effects.
Presently extracts are being obtained from five U.S. cities that
represent the major types of water sources for drinking water. These
extracts will be subjected to the four screening systems identified in
Figure 1. The LDso is utilized as a reference for comparison with the
toxicity of known compounds and with the toxicity of other concentrates.
The in vitro systems are used predominantly to predict possible mutagenic
and carcinogenic expressions in vivo. The teratology assay is performed
in whole animals and indicates the ability to induce birth deformities.
Positive responses in any of the screening assays initiate an
attempt to isolate the effects in subfractions of the extracts. By iso-
lating a few fractions with biological activity, it is then more feasible
to identify the constituents within the active fractions rather than in
the entire concentrate.
Chemical identification of components requires a reconfirmation of
the pure agent in the positive screens. Subsequent to reconfirmation,
the active compounds are subjected to more definitive investigations for
ultimate evaluation of impact on man.
Throughout these investigations, substantial efforts are expended
in coordination and collaboration with scientists and administrators of
other federal agencies such as the National Cancer Institute, the Food
and Drug Administration, and the National Institute of Environmental
Health Sciences. Through such interactions, governmental resources are
maximally utilized for the benefit of the citizens.
5. References
(1) Gleason, Marion N., Gosselin, Robert E., Hodge, Harold C.,
and Smith, Roger P. Clin i cal Toxicology of Commercia1
Produc t s: Acute P o i s o n in g. 3d ed. BaVtimore, Williams and
Wilkins, Co., 1969.
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(2) Tardiff, Robert G. and Deinzer, M. "Toxicity of organic
compounds in drinking water." In: Proceedings of 15th Water
Quality Conference, Feb. 7-8, 1973, University of Illinois,
pp. 23-37.
(3) Hueper, W. C. and Payne, W. W. "Carcinogenic effects of raw
and finished water'supplies." Amer. J. Clin. Path. 39(5):475-8^
May 1963.
(4) Hueper, W. C. and Ruchoft, C. C. "Carcinogenic studies on
adsorbates of industrially polluted raw and finished water
supplies." Arch. Ind. Hyg. Occup. Med. 9:488-95, 1954.
(5) Dunham, Lucia J., O'Gara, Roger W., and Taylor, Floyd B.
"Studies on pollutants from processed water: collection from
three stations and biologic testing for toxicity and carcino-
genesis." Amer. J. Public Health 57(12):2178-85. December 1967.
(6) Principles for Evaluating Chemicals in the Environment.
Washington, D.C., National Academy of Sciences, 1975.
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B. TOXICITY OF INORGANIC CHEMICALS PRESENT IN DRINKING WATER
1. Introduction
Because of health effects concerns the concentration of several
inorganic chemicals are limited in drinking water. Limits for arsenic,
barium, cadmium, chromium, cyanide, fluoride, lead, mercury, nitrate,
selenium, and silver have been proposed and published in the Federal
Register (1) under provisions of P.L. 93-523: Safe Drinking Water Act.
In the 27-year period 1946-1973, there were 405 waterborne disease
outbreaks but only 10 of these outbreaks were related to inorganic chem-
ical poisonings. Deaths were more likely to be associated with these
chemical-caused outbreaks; seven deaths occurred as well as 210 cases of
illness (2). Cancer has not been attributed to have been caused by con-
tamination of drinking water with inorganic chemicals in this country.
None of the inorganic chemicals have been limited in drinking water
because the chemical was considered to be a carcinogen but for several
of the chemicals (arsenic, cadmium, chromium, nitrate, and selenium)
consideration was given to data concerning carcinogenic effects. Beryl-
lium and nickel are not limited in drinking water but are two additional
metals that should be considered for carcinogenic effects.
2. Arsenic
In certain parts of the world the high levels of arsenic found in
drinking water have been associated with a high rate of arsenicism and
skin cancer in the population (3). Tseng et. a!. (12) reported a geo-
graphical correlation in Taiwan between levels of arsenic exposure in
well water and the frequencies of skin cancer, hyperpigmentation, Kera-
tosis, and a peripheral vascular disorder (Blackfoot disease). A dose-
response relationship was seen between the occurrence of skin lesions,
including cancer, and the arsenic content of the water. No excessive
occurrence of other cancers has been reported in areas where the water
contains arsenic. The available studies consistently point to a causal
relationship between skin cancer and heavy exposure to inorganic arsenic
in drugs, in drinking water with a high arsenic content, or in the occu-
pational environment.
Adequate oral studies on arsenic trioxide in the mouse and on lead
arsenate, calcium arsenate, sodium arsenate, arsenic trioxide and sodium
arsenite in the rat gave negative results.
It should be noted that OSHA has formally proposed a new limit for
inorganic arsenic of 4 yg/m3; the previous limit suggested by NIOSH was
50 yg/m^ (5). The 4 yg/m^ limit represents an-arsenic intake of 40 pg
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per work week. Extrapolating to water exposure the 40 yg/week of arsenic
would represent a 4 yg/liter intake for water. Applying a safety factor
of 100, the comparable drinking water standard would be 0.04 yg/1.
Arsenic has usually been considered a geochemical contaminant and
high concentrations have been noted in ground water in selected areas of
the southwest and northwest of the country. Water supplies exceeding
the limit of 0.05 nig per liter are located in California, Oregon, and
Nevada. Arsenic was related to five, or half of the inorganic chemical-
caused water poisonings in the past 27 years, and the reasons for these
poisonings are most varied. One outbreak of ten cases and three deaths
resulted when an arsenical weed killer was dumped into a well in West
Virginia. These are the only murders that have been noted in the review
of waterborne outbreaks. Two outbreaks concerned the back-siphonage of
arsenic compounds into water supplies, and there were five cases of ill-
ness and four deaths resulting. Recently, a well was drilled at a new
factory site in Minnesota and people working there became ill (10).
Arsenic was detected in their blood and investigation revealed arsenic
in the well water of 11.8 - 21 mg/liter. The site had been used to mix
grasshopper bait many years before and it is likely that some unused
pesticide had been buried where the well was drilled. Two girls in a
Nevada family became ill and, after some difficulty of diagnosis, it was
determined that they had arsenic poisoning. The well at the family ranch
varied between 0.5 - 2.75 mg/liter of arsenic from natural causes.
Health effects research planned for arsenic includes a study of body
burden in areas where arsenic is high in drinking water. The mutageni-
city of arsenic will be determined by use of cultured mammalian cells.
3. Beryllium
Bone and lung cancers have been produced experimentally in animals
and 20 malignant tumors have been recorded among the 735 cases of beryl-
lium disease; however, the available evidence was not considered suffi-
cient to positively incriminate beryllium as a carcinogen in humans (6).
Beryllium is classified as an experimental carcinogen by the American
Conference of Government Industrial Hygienists (7). They define an ex-
perimental carcinogen as industrial substances found to be capable of
inducing tumors under experimental conditions in animals and have estab-
lished a TLV of 0.002 mg/m3 of air.
Beryllium will be tested for mutagenicity in a cultured mammalian
cell test system.
4. Cadmium
Several studies suggest that occupational exposure to cadmium oxide
may increase the risk of prostate cancer in man but the size of the
groups studied was considered small (3). It was recently reported that
there was an increased risk of death due to malignant neoplasms in a
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study of 283 cadmium smelter workers (5). No data are available to
suggest that non-occupational exposure to cadmium constitutes a carcino-
genic hazard. Studies of rats and mice showed that a level of 5 mg/1
cadmium acetate given in drinking water until death did not significantly
increase the incidence of tumors (3). The estimated intake of cadmium
from drinking water is 3 yg per day (1).
Health effects research currently being conducted and planned is in
regard to the possible role of cadmium in hypertension and cardiovascular
disease. The mutagenicity of cadmium will be tested in a cultured mam-
malian cell test system. The relative bioavailability of cadmium in
water as opposed to cadmium in foodstuffs is also being determined.
5. Chromi urn
There is an excessive risk of lung cancer among workers in the
chromate-producing industry (3,4). It is likely that exposure to one or
more chromium compounds is responsible, but the identity of this or these
is not known. There is no evidence that non-occupational exposure to
chromium constitutes a cancer hazard. The NAS reports that no^ harmful
effects on the health of man are known to have resulted from the presence
of chromium in public drinking water at current concentrations (4).
Studies of rats and mice shewed that a level of 5 mg/1 chromic acetate
given in drinking water until death did not significantly increase the
incidence of tumors at various sites as compared with controls (3). The
estimated intake of chromium from drinking water is 5 yg per day (1).
No health effects research is planned other than testing the muta-
genicity of chromium in a cultured mammalian cell test system.
6. Nickel
There has been an excessive risk of cancers of the nasal sinus and
lung among nickel refinery workers and it is probable that nickel in some
form is carcinogenic (3,4). There is no evidence to suggest that non-
occupational exposure to nickel constitutes a cancer hazard (3). The
estimated intake of nickel from drinking water is 10 vg per day (1).
It is planned to produce a criteria document recommending a drinking
water standard for nickel. The mutagenicity of nickel will be determined
by use of a cultured mammalian cell test,system.
7. Nitrate
Nitrate concentrations in drinking water have been limited because
of the possibility of developing methemoglobinemia in infants who were
fed water high in nitrate. A few community water systems exceed the
nitrate limit but in many rural areas the farm wells have a very high
concentration of nitrate. It has been hypothesized that in high concen-
trations the nitrogen might combine with amines in contaminated water or
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in the gastrointestinal tract to form nitrosamines, a recognized carcino-
gen. The development of nitrosamines has been demonstrated experimental1>
using much higher concentrations of nitrates or nitrites than are known
to occur in water. It has been pointed out that a few counties of Texas
that had nitrate-in-ground-water problems had higher cancer rates but a
suitable data base for an epidemiological study was not available.
The production of nitrosamines in cured meat is being researched by
other agencies. The concentrations of nitrate and nitrite are greater
when these chemicals are used as a preservative of food than drinking
water concentrations.
8. Selenium
In 1962 the drinking water limit was lowered to 0.01 mg per liter
primarily out of concern for possible carcinogenic properties of the
element. Since that time evidence has been developed indicating that
selenium could both cause and prevent cancer. Several animal studies
showed that tumors were developed from exposure to selenium. In the
North Central and Rocky Mountain Regions of the country there are areas
that are geochemically rich in selenium. Forage crops and plants in
these areas often contain more than 100 parts per million of selenium.
Cows, sheep, and horses in these areas may die from consuming enough
selenium in forages to develop selenium toxicity. Research has shown
that grain from selenium-rich areas had a higher selenium content and
when used as poultry feed, it promoted the growth of chickens and tur-
keys. It was proposed that selenium be used as an additive to animal
feed.
The Commissioner of the Food and Drug Administration reviewed the
carcinogenic problem of selenium last year (11). Me concluded that
selenium could be safely used as an additive to swine, turkey, and
chicken feed because of its nutritive value and lack of health hazard
when used at prescribed concentrations. The inadequacy of the toxi-
cological studies that produced tumors was reviewed.
Research is being conducted on the comparative availability of
selenium from food and water so that a drinking water limit can be estab-
lished with consideration given to intake from food. A study is planned
to determine the human body burden in areas where selenium is high in
drinking water. Mutagenic screening tests will also be conducted.
9. Consequences
Apparently, the inhalation exposure to fumes or dust in the indus-
trial setting produces a very different biological effect that the in-
gestion exposure from food and water. An increased risk of developing
cancer is not expected from consuming water contaminated with beryllium,
cadmium, chromium, or nickel. There are other health effects that re-
quire limiting the concentration of these elements in drinking water.
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Arsenic has been demonstrated to be a carcinogen in Drinking water
but may not present as serious a problem as indicated from industrial
inhalation exposure. Epidemiological research should be conducted to
see if a lower drinking water limit is necessary.
More information is needed on the formation of nitrosamines and
on-going research should provide this. Selenium apparently does not
present a cancer problem.
10. References
(1) Train, R. E. Primary Drinking Water, Proposed Interim
Standards.
(2) McCabe, L. J. Problem of Trace Metals in Water Supplies - An
Overview. Proceedings 16th Water Quality Conference,
University of Illinois (1974).
(3) IARC Monographs on the Evaluation of Carcinogenic Risk of
Chemicals to Man, Some Inorgan ic and OrganometaHic Compounds,
Volume 2, International Agency for Research on Cancer, Lyon
(1973).
(4) National Academy of Sciences, Medical and Biologic. Effects of
Environmental Pollutants, ChromTuTTTl^B^ro^309"-022l7^Tn974;
Nickel (TSBN 0-309-02314-9) 1975.
(5) Toxic Materials News, Vol. 2(7), p. 53 (1975).
(6) Preliminary Air Pollution Survey of Beryllium and its Compounds,
USDHEW, Raleigh, North Carolina ("1969).
(7) ACGIH, P.O. Box 1937, Cincinnati, Ohio.
(8) McCabe, L. J. e_t. a\_. , "Survey of Community Water Supply
Systems." JAWWA, 62(11), 670 (1970).
(9) Kopp, J. F., and Kroner, R. C., Trace Metals in Waters of the
U.S., Cincinnati, Ohio.
(10) Feinglass, E. J. Arsenic Intoxication from Well Water in the
United States. New England J. Med. 2887~828(1973JTFederal
Register 40(5"!) 11990-11998 (March 14, 1975).
(11) Schmidt, A. M. Selenium in Animal Feed, Federal Register 39(5)
1355-1358 (January 8, 197TT
(12) Tseng, W. P., Chu, H. M., How, S. W., Forg, J. M., Lin, C. S.,
and Yels. Prevalence of Skin Cancer in an Endemic Area of
Chronic Arsenicism in Taiwan, J. Nat. Cancer Inst. 40, 454-463 (1968)
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A US GOVERNMENT PRINTING OFFICE-1975— 210-810/13
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