600883010
&EPA
United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory May 1983
Cincinnati OH 45268
Research and Development
Treatment of Volatile
Organic Compounds in
Drinking Water
-7.
<»***»"**"
Vtny\ chloride
Oo
7-Av
7'3-r>.
Or°ethane
f4-Dich»orobenzene
(AC-V
-------
-------
EPA-600/8-83-019
May 1983
TREATMENT OF VOLATILE ORGANIC COMPOUNDS IN DRINKING WATER
by
0. Thomas Love, Jr
Richard J. Miltner
Richard G. Eilers
Carol A. Fronk-Leist
Drinking Water Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This paper has been reviewed in accordance with the U.S. Environmental
Protection Agency's peer and administrative review policies and approved for
publication. Mention of trade names or commercial products does not consti-
tute endorsement or recommendation for use.
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FOREWORD
The U.S. Environmental Protection Agency was created because of
increasing public and government concern about the dangers of pollution to
the health and welfare of the American people. Noxious air, foul water, and
spoiled land are tragic testimonies to the deterioration of our natural
environment. The complexity of that environment and the interplay of its
components require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem
solution; it involves defining the problem, measuring its impact, and
searching for solutions. The Municipal Environmental Research Laboratory
develops new and improved technology and systems to prevent, treat, and
manage wastewater and solid and hazardous waste pollutant discharges from
municipal and community sources, to preserve and treat public drinking water
supplies, and to minimize the adverse economic, social, health, and
aesthetic effects of pollution. This publication is one of the products of
that research and provides a most vital communications link between the
researcher and the user community.
Volatile organic compounds are increasingly being detected in drinking
water sources, and particularly in ground waters once thought to be pris-
tine. These compounds are not disinfection by-products, but pollutants
entering our ground water aquifers through improper chemical storage/
handling, or wastewater disposal activities. This report describes some of
those contaminants and examines the results of water treatment research to
minimize their concentrations at the consumer's tap.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
iii
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ABSTRACT
Volatile chlorinated and non-chlorinated compounds occur in both
untreated and treated drinking water. Because volatilization is restricted,
ground waters rather than surface waters are more likely to have high con-
centrations of these compounds. This document reviews properties, occur-
rence, and experiences, particularly laboratory and pilot scale, with the
control of the following compounds:
tri- and tetrachloroethylene; cis- and trans-l,2-dichloroethylene;
1,1-dichloroethylene; vinyl and methylene chloride; 1,1,1-tri-
chloroethane; 1,2-dichloroethane; carbon tetrachloride; benzene;
chlorobenzene; 1,2-, 1,3-, and 1,4-dichlorobenzene; and 1,2,4-
trichlorobenzene
Conventional water treatment will not generally reduce the concentra-
tions of these compounds, but they can be reduced by aeration, adsorption on
granular activated carbon or synthetic resins, or combinations of these
processes. Boiling can also be effective for home treatment of these con-
taminants.
IV
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CONTENTS
Foreword iii
Abstract iv
Figures yi
Tables ix
Acknowledgements x
1. Introduction 1
2. Occurrence 2
3. Individual Compound Descriptions and Treatment Experiences . . 5
Trichloroethylene 9
Tetrachloroethylene 17
Cis-l,2-dichloroethylene 23
Trans-1,2-dichloroethylene 29
1,1-Dichloroethylene 31
Vinyl chloride l 35
1,1,1-Trichloroethane 37
1,2-Dichloroethane 45
Carbon tetrachloride 47
Methylene chloride 53
Benzene 55
Chlorobenzene 57
1,2-Dichlorobenzene 59
1,3-Dichlorobenzene 61
1,4-Dichlorobenzene 63
1,2,4-Trichlorobenzene 65
4. Discussion of Treatment Alternatives 67
5. Estimated Treatment Costs 81
6. Summary 97
References 99
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FIGURES
Number Page
1. Simplified manufacturing scheme for industrial solvents 4
2. Isotherms for trichloroethylene adsorption on activated carbon. . . 12
3. Removal of trichloroethylene by adsorption on granular
activated carbon and polymeric resin 14
4. Isotherms for tetrachloroethylene adsorption on activated carbon. . 20
5. Illustration of USEPA-DWRD pilot scale treatment used at
contaminated well site in New Jersey 21
6. Isotherms for cis-1,2-dichloroethylene adsorption on activated
carbon 24
7. Removal of cis-1,2-dichloroethylene by adsorption on granular
activated carbon and polymeric resin 25
8. Isotherm for trans-1,2-dichloroethylene adsorption on activated
carbon 30
9. Isotherm for 1,1-dichloroethylene adsorption on activated carbon. . 32
10. Removal of 1,1-dichloroethylene on granular activated carbon or
polymeric resin 33
11. Isotherms for 1,1,1-trichloroethane adsorption on activated carbon 39
12. Removal of 1,1,1-trichloroethane on granular activated carbon or
polymeric resin 41
13. Isotherms for 1,2-dichloroethane adsorption on activated carbon . . 46
14. Carbon tetrachloride in raw and treated water at Cincinnati, Ohio 48
15. Isotherms for carbon tetrachloride adsorption on activated
carbon 50
16. Desorption of carbon tetrachloride from granular activated
carbon and polymeric resin 51
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FIGURES (cont'd)
Number Page
17. Isotherms for methylene chloride adsorption on activated carbon. . 54
18. Isotherms for benzene adsorption on activated carbon 56
19. Isotherm for chlorobenzene adsorption on activated carbon. .... 58
20. Isotherms for dichlorobenzene adsorption on activated carbon ... 60
21. Isotherm for 1,2,4-trichlorobenzene adsorption on activated
carbon 66
22. Comparison of Henry's Law Constants for selected organics 69
23. Comparison of actual and theoretical removal of trichloroethylene
and tetrachloroethylene from drinking water by aeration 70
24. Comparison of actual and theoretical removal of 1,1,1-trichloro-
ethane, carbon tetrachloride, and 1,2-dichloroethane from
drinking water by aeration 71
25. Comparison of actual and theoretical removal of cis- and trans-
1,2-dichloroethylene, methylene chloride, and 1,1-dichloro-
ethylene from drinking water by aeration 72
26. Comparison of actual and theoretical removal of benzene, chloro-
benzene, 1,2-, 1,3-, and 1,4-dichlorobenzene, and 1,2,4-tri-
chlorobenzene from drinking water by aeration 73
27. Comparison of isotherm adsorption capacities on activated carbon . 75
28. Removal of volatile organic compounds by aeration and adsorption
on granular activated carbon (pilot scale study) 77
29. Estimated activated carbon usage to achieve target effluent
qualities 84
30. Water treatment system configuration for economic analysis of
volatile organic contaminant removal 86
31. Cost of trichloroethylene removal (90-99%) (October 1980 dollars,
influent concentration of 1-1000 yg/L, design flow of 0.5 mgd) . 87
32. Cost of tetrachloroethylene removal (90-99%) (October 1980
dollars, influent concentration of 1-1000 yg/L, design flow
of 0.5 mgd) 88
vii
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FIGURES (cont'd)
Number Page
33. Cost of 1,1,1-trichloroethane removal (90-99%) (October 1980
dollars, influent concentration of 1-1000 yg/L, design flow
of 0.5 mgd) 89
34. Cost of carbon tetrachloride removal (90-99%) (October 1980
dollars, influent concentration of 1-1000 yg/L> design flow
of 0.5 mgd) 90
35. Cost of cis-l,2-dichloroethylene removal (90-99%) (October 1980
dollars, influent concentration of 1-1000 yg/L, design flow
of 0.5 mgd) 91
36. Cost of 1,2-dichloroethane removal (90-99%) (October 1980.
dollars, influent concentration of 1-1000 yg/L, design flow
of 0.5 mgd) 92
37. Cost of trichloroethylene removal (October 1980 dollars,
effluent concentrations of 0.1-100 yg/L, design flow of 0.5
mgd, operating at 60% capacity) 93
38. Cost of trichloroethylene removal (90-99%) (October 1980
dollars, influent concentration of 1-1000 yg/L, operating
flow is 50% of design flow) 94
vi i i
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TABLES
Number Page
1. Comparative Data for Selected Volatile Organic Compounds 6
2. Removal of Trichloroethylene from Drinking Water by Diffused-
Air Aeration 10
3. Removal of Trichloroethylene from Drinking Water by Boiling. ... 16
4. Removal of Tetrachloroethylene from Drinking Water by
Diffused-Air Aeration 19
5. Removal of Tetrachloroethylene from Drinking Water by Adsorption . 21
6. Removal of Tetrachloroethylene from Water by Boiling 22
7. Removal of Cis-l,2-Dichloroethylene by Adsorption 27
8. Removal of Cis-l,2-Dich1oroethylene from Water by Boiling 28
9. Removal of 1,1,1-Trichloroethane from Drinking Water Using a
Pilot Scale Forced Draft Packed Tower 38
10. Removal of 1,1,1-Trichloroethane From Drinking Water by Boiling. . 43
11. Removal of Carbon Tetrachloride from Drinking Water by Boiling . . 52
12. Effects of Aeration on a Solvent-Contaminated Ground Water .... 68
13. Adsorption of Volatile Organic Compounds by Granular Activated
Carbon, Summary 76
14. Adsorption of Trichloroethylene and Related Solvents by
Ambersorb ®XE-340, Summary 78
15. Removal of Volatile Organic Compounds from Drinking Water
by Boiling, Summary 79
16. Estimated Air to Water Ratios Necessary to Achieve Desired
Treatment, Summary 82
17. Estimated Carbon Usage Necessary to Achieve Desired
Treatment, Summary 83
IX
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ACKNOWLEDGEMENTS
Major contributors to this report are: K. L. Kropp, 8. L. Smith, R.
S. Canter, C. H. Nyberg, J. F. Morton, P. G. Pierson, M. M. Lilly, G. L.
Contner, and Walter C. Elbert.
The cooperation and assistance provided by water utility and regulatory
personnel in the states of Connecticut, New Hampshire, Rhode Island, New
Jersey, and Pennsylvania is greatly appreciated.
Special recognition is expressed to Mr. Charles D. Larson, USEPA Region
I, Boston, and Mr. Melvin Haupman, USEPA Region II, New York, for their help
in conducting field studies.
The efforts of Dr. James M. Symons, Mr. Alan A. Stevens, Mr. Gordon G.
Robeck, Mr. Walter A. Feige, Dr. Robert M. Clark, Mr. James Westrick, Mr.
Thomas Thornton, Dr. Jessica Barren, and Ms. Jane Horine for providing valu-
able editorial and technical comments are acknowledged.
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SECTION 1
INTRODUCTION
Sixteen synthetic organic compounds—trichloroethylene, tetrachloro-
ethylene, cis- and trans-l,2-dichloroethylene, 1,1-dichloroethylene, vinyl
chloride, 1,1,1-trichloroethane, 1,2-dichloroethane, carbon tetrachloride,
methylene chloride, benzene, chlorobenzene, 1,2-, 1,3-, and 1,4-dichloro-
benzene, and l,2,4-trichlorobenzene--are undergoing review for possible
inclusion in the National Revised Primary Drinking Water Regulations (1).*
This report relates some occurrence experiences, describes the general
properties of these organic compounds, and summarizes some of the available
treatment data. Most of this treatment information was obtained through
laboratory and pilot scale studies in which aeration and adsorption were
selected as treatment options. Cost estimates for these treatment processes
were made by combining theory with the available empirical data.
This report is intended to be used as a "working document" whereby up-
dated information, particularly from full scale treatment installations, can
be inserted in the appropriate category where, presently (1982), data may be
sparse or absent.
*Parenthetical numbers in the text are literature citations. See Refer-
ences.
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SECTION 2
OCCURRENCE
Volatile organic chemicals are introduced into drinking water by
different means. Carbon tetrachloride, for example, is a known contaminant
of chlorine produced by the graphite-anode process (2), and disinfection
with chlorine produced by this process can be a significant source of carbon
tetrachloride in treated drinking water (3). Similarly, other products used
in the production and distribution of water are sometimes sources of contam-
inants. Tetrachloroethylene is leached from polyvinyl-toluene-lined
asbestos cement pipe (4), trichloroethylene is present in certain joint
compounds used in reservoir liners and covers*, and vinyl chloride has been
found as a residual monomer in polyvinyl chloride pipe manufactured before
1977 (5).
Discovering sources of contamination is sometimes complicated by
analytical error. In one documented instance, trichloroethylene was thought
to have been produced by chlorine used for disinfection, but improved
quality control in the laboratory led to the discovery that the material
thought to be trichloroethylene was actually a trihalomethane (6).
Because these compounds are volatile, they are seldom detected in con-
centrations greater than a few micrograms per liter (ng/L) in surface water
sources. There is, however, one exception. Surface water vulnerable to
wastewater discharges may contain elevated concentrations of organic
solvents during periods of ice cover, when volatilization of these solvents
is restricted. Seeger's group (7) sampled Ohio River water at Cincinnati
during the winter of 1977, when there were almost 800 miles of upstream ice
cover, and found atypically high concentrations of compounds such as carbon
tetrachloride and tetrachloroethylene.
High concentrations of volatile compounds occur most frequently in
ground water. Several possible sources for these contaminants have been
suggested (8). Included are industrial discharges (either through spreading
on the land or improper disposal at dumps), landfill leachates, septic tank
degreasers and similar products from individual households, sewer leaks,
accidental spills, water from cleaning and rinsing of tanks and machinery,
leaking storage tanks, and treated wastes reintroduced into aquifers as
ground water recharge. Solvents can enter an aquifer and be transported
great distances because they have little affinity for soils (9-11). Recent
*Private communication, Albert E. Sylvia, Commonwealth of Massachusetts,
Lawrence Experiment Station, Lawrence, MA (1980).
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sampling (12 through 15, among others) has revealed solvent-contaminated
ground waters in several states. The number of water utilities affected is
likely to increase when other states examine the organic quality of their
ground water.
Contaminated ground water usually contains two or more predominant
organic compounds and several identifiable ones of lesser concentration.
One reason for this might be related to solvent purity. In the manufactur-
ing of these solvents, the end product depends on the temperature, degree of
acidification, and chlorination, so a commercial grade solvent might have
varying amounts of several related compounds (Figure 1). Another reason for
the presence of a variety of solvents in one location might be biological
degradation of a parent compound in the ground (16).
Frequently, within a well field, one well may be uncontaminated, yet a
nearby well may contain as high as 2 milligrams per liter (mg/L) of tri-
chloroethylene and several hundred micrograms per liter (vg/L) of tetra-
chloroethylene and 1,1,1-trichloroethane. However, another well within the
same area, but perhaps drawing from a different aquifer may contain a
preponderance of 1,1,1-trichloroethane and cis-l,2-dichloroethylene, and
have only minimally detectable quantities of trichloroethylene. Finally,
the concentrations of contaminants in a well can be variable. For example,
at a project in Connecticut (described in detail later in the text),
1,1,1-trichloroethane concentrations ranged from 12 to 214 yg/L over the
year-long study. Although contamination from improper pump lubricants or
from well drilling aids is not likely to be major, the potential should be
recognized.
Sometimes the source of contamination is not obvious. Crane and
Freeman (18), for example, reported trichloroethylene and tetrachloro-
ethylene as two of several solvents detected in the effluent from the
anion-cation exchange resin used in their laboratory. The source of this
contamination was traced to the distribution plant where the resin was sent
for regeneration. The ground water used in the regeneration process was
contaminated with organic solvents, which then contaminated the resin.
Once an aquifer is contaminated, the water purveyor or other user might
either seek an alternative source or provide treatment to reduce contaminant
concentrations. Section 3, following, is a compilation of contaminant prop-
erties and treatment data, where such data are available.
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CH2 =CH2
Ethylene
C\,—I
FeCU
CH2CICH2CI
1,2-Dichloroethane
(ethylene dichloride)
CHCI = CCI2
Trichloroethylene
(TCE)
Heat
HCI-
FeCI3-
CH2 = CHCI
Vinyl chloride
Excess CI2
+ heat
CCI2 = CCI2
Tetrachloroethylene
(perchloroethlene)
r
CH3CHCI2
1,1-Dichloroethane
Cl,
CH2CICHCI2
1,1,2-Trichloroethane
CI2
CH3CCI3
1,1,1 -Trichloroethane
(methyl chloroform)
NaOH or lime
CCI4
Carbon tetrachloride
Heat -
CH4
Methane
1
CH2CI2
Methylene chloride
Heat +
catalyst
CH2 = CCI2
1,1 -Dichloroethylene
(vinylidene chloride)
Cl,
CHCI = CHCI
1,2-Dichloroethylene
Figure 1. Simplified Manufacturing Scheme for Industrial Solvents (17)
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SECTION 3
INDIVIDUAL COMPOUND DESCRIPTIONS AND TREATMENT EXPERIENCES
The properties of the sixteen organic chemicals most commonly detected
in ground water (1) are summarized in Table 1. Each compound is then
discussed separately in an identical format that includes a molecular struc-
ture drawing of the compound, other names for the compound, some of its
principal uses, and finally, the available treatment information. The term
"conventional treatment" includes the processes of chemical coagulation,
flocculation, sedimentation, precipitative softening, filtration, and dis-
infection with chlorine.
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TABLE 1. COMPARATIVE DATA FOR SELECTED VOLATILE ORGANIC COMPOUNDS
Molecular weight,
g/mole
Density, g/ml
Boiling point, °c
atmospheric
azeotropic
(w/H20)
1.46
1.62
1.22
62
0.92
86.7 i21
73.2(19) 88.5(20)
60
NR
S°'"bimy-"9/L J5SI&, »»'-'«.
Vapor pressure,
™n Hg (21,22)
Henry's Law Constant
cone, fairj^
cone, (water)
xlO~3 atm-m3
74
18.6
206
48
NR
6300(22)
271
32
NR
40(22)
495
-14
NR
TTITPtrl
133
1.34
74.1
65(19)
i- 1,2-df^-
99
1.24
83.5
71.6(19
,20)
60(21,22) 4400(21) 8700(21,22)
2660
100
82
°-48,(21) 1.1(21)
0-49(22) 1.2(22)
11.7
28.7
7.8(21,22) 50(22)
301(21)
5.;
Threshold odor
concentration, pg/L
Parachor (27)
Molar refraction
(27)
150
?.'2(22)1} 0.05(21,22)
500(25,26) 300(25)
6400(24)
4.92
1.10
2000(25,26)
Calculated from solubility and vapor pressure.
NR - Not re
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TABLE 1. (Cont'd.)
Chloromethanes Benzene
Parameter
Molecular weight,
g/mole
Density, g/mL
Boiling point, °C
atmospheric
azeotropic
(w/H20)
Solubility, mg/L
Vapor pressure,
mm Hg (21, 22)
Henry's Law Constant
cone, (air)
cone, (water)
xlO3 atm-m3
mole (23)
Threshold odor
concentration, yg/L
Parachor (27)
Molar refraction
(27)
carbon
tetrachloride
154
1.59
76.7
66.8(19)
800(21-23)
91.3(22)
1.2(21,22)
30.2
(30)
220.0
26.30
methyl ene
chloride
85 78
1.33 0.89
40 80
38.4(19) 69.4(19)
19,400(22) 1780(29)
438(22) 95(29)
0.10(22) 0.22(21
0.12(21)
3.19 5.55
NR 31,300(25)
146.6 207.1
16.56 26.2
mono-
113
1.11
132
90.2(28)
448(21)
15(21)
) 0.19(21)
3.93
NR
244.1
31.2
1,2-di-
147
1.31
180
NR
100(21)
1.0(21)
0.08(21)
1.94
NR
280.5
36.1
Chlorobenzenes
1,3-di-
147
1.29
173
NR
123(21)
2.0(21)
0.13(21)
1.94
NR
280.5
36.1
1,4-di-
147
1.25
147
NR
79(21)
1.0(21)
0.10(21)
1.94
NR
280.5
36.1
1,2,4-tri-
182
1.45
219
NR
30(21)
0.29(23)
0.06*
1.42
NR
317.2
40.9
. . — _ _ . • — — — — —
Calculated from solubility and vapor pressure.
tTest inconclusive. Two of seven panel members reported detection at a
NR - Not reported.
concentration of 400 yg/L.
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TRICHLOROETHYLENE* Cl Cl
Structure
Cl
Other Names (31-33)
TCE; 1,1,2-trichloroethylene; 1,2,2-trichloroethylene; trichloroethene;
acetylene trichloride; ethinyl trichloride; ethylene trichloride; Triclene;
Trie! ene; Trilene; Trichloran; Trichloren; Algylen; Trimar; Triline; Tri ;
Trethylene; Westrosol ; Chlorilen; Gemalgene; Germalgene; Benzinol; 1,1-
dichloro-2-chloroethylene; Blacsolv; Blancosolv; Cecolene; 1-chloro- 2,2-
dichloroethylene; Chlorylen; Circosolv; Crawhaspol ; Dow-tri; Dukeron;
Fleck-flip; Flock-flip; Lanadin; Lethurin; Nalco 4546; Nialk; Perm-a-clor;
Petzinol; Philex; Triad; Trial; Trisol; Anamenth; Chlorylen; Densinfluat;
Fluate; Narcogen; Narkosoid; Threthylen; Threthylene; Tri Ten
Tri chl oroethyl ene is commercially produced by chlorinating ethylene
(CHz = CH2) or acetylene (CH = CH) . Its use is declining because of strin-
gent regulations; however, it has been a common ingredient in many household
products (spot removers, rug cleaners, air fresheners), dry cleaning agents,
industrial metal cleaners and polishers, refrigerants, and even anesthetics
(17, 29, 34). Its ubiquitous use is perhaps why trichl oroethyl ene is the
organic contaminant most frequently encountered in ground water.
Conventional Treatment
Two studies were found in the literature in which trichloroethylene was
identified and measured before and after conventional water treatment. In
both studies, the trichloroethylene concentration in the source was lower
than 1 yg/L, but no significant removals were observed through the treatment
plant (7, 35).
Aeration
Pilot scale laboratory and field aeration studies were conducted using
a 4-cm (1.5-in) diameter glass column, approximately 1.2 m (4 ft) long, with
a fritted glass diffuser in the bottom. Water was introduced at the top of
the column to give a counter-current flow. In the laboratory, trichloro-
ethylene was added to Cincinnati, Ohio, tap water to give concentrations of
approximately 100 to 1000 yg/L. The water was aerated at varying tempera-
tures. Trichloroethylene was stripped from the water at an efficiency of
from 70 to 92 percent using an air-to-water ratio (volume-to-volume) of 4:1,
and a contact time of 10 minutes (Table 2). An identical aerator consist-
ently removed over 80 percent of the trichloroethylene from a contaminated
*See Table 1, page 6, for properties.
9
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TABLE 2. REMOVAL OF TRICHLOROETHYLENE FROM DRINKING WATER BY DIFFUSED-AIR AERATION
Location Average
Average effluent concentration, yg/L Remarks
of influent
study concentration, pg/L 1:1
"Spiked"
Cincinnati, Ohio
tap water
1064
397
241
110
73
796
223
136
40
22
Air-to-water
2:1 3:1 4:1
614
273
110
28
14
508
102
61
18
8
319
82
53
9
6
ratios
8:1 16:1
53
22 <1
8 2
3 <1
1 <1
20:1
4-cm (1.5-in) diam.
<1 counter-current flow
3 glass column with acti-
<1 vated carbon filtered
<1 air; 10 min. contact
time. Water temperature
6-16°C. Depth = 0.8m.
Contaminated well
New Jersey
in
Contaminated well
on Long Island (36)
112
64
5:1
72a
Air-to-water ratios
10:1 15:1
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well in New Jersey with a mean influent concentration of 3.3
Nebolsine Kohlman Ruggiero Engineers (NKRF.) (36) also evaluated
diffused-air aeration on a pilot scale at a well site on Long Island, New
York (see Table 2). They used a rectangular aeration tank [6.6m x 1.2m x
0.6m deep (16 ft3)] having four diffusers and a 27-cm (10.5-in) diameter
Plexiglas column having a single diffuser and observed TCE removal effi-
ciency. Retention times ranged from 5 to 20 minutes and air-to-water ratios
from 5:1 to 20:1. The highest removal efficiency was 73 percent. In a
follow-up study (37) that employed a 76-cm (30-in) diameter column, 3m (10
ft) in length and with five diffusers, the efficiency of removal ranged from
69 percent to 90 percent, with air-to-water ratios from 5:1 to 30:1. The
trichloroethylene concentration in the unaerated water ranged from 132 to
313 ug/L.
Joyce (38) reported concentrations of trichloroethylene ranging from
4.5 to 22 ug/L at Smyrna, Delaware, after water containing 20 to 70 ug/L
trichloroethylene was passed through an induced-draft, redwood slat aerator.
Also, the advanced waste treatment research conducted in southern California
at Water Factory 21, although not focused directly on drinking water, showed
that trichloroethylene concentrations of approximately 1 to 2 vg/L were
removed with 98 percent effectiveness. This was accomplished through an
ammonia-stripping tower with an air-to-water ratio of approximately 3000 to
1 (when the fan was operating). Similar removal efficiencies for volatile
organic chemicals were observed on wastewater passed through a polyeth-
ylene-packed decarbonator operating with an air-to-water ratio of about 22
to 1 (24,39).
Adsorption
Dobbs and Cohen (40) developed an adsorption isotherm for trichloro-
ethylene in distilled water by using pulverized Filtrasorb® 300* activated
carbon. The Drinking Water Research Division, USEPA, followed the same
procedure but used both Filtrasorb® 300 and Witcarb 950t pulverized carbons.
These data are illustrated in Figure 2 as Freundlich isotherms. With a
trichloroethylene concentration of 100 yg/L, the capacity predicted from
these isotherms ranges from 7 to 10 mg trichloroethylene per gram of acti-
vated carbon (mg/g). Other than isotherm data, little information has been
reported on the effects of powdered activated carbon for removing high
concentrations of this contaminant. Singley's group (41) observed a 50
percent reduction in trichloroethylene concentrations (from 1.5 to 0.7
ug/L) at the Sunny Isles Water Treatment Plant, North Miami Beach, Florida.
The reduction was accomplished with a powdered activated carbon dosage of 7
mg/L.
A great deal more adsorption data have been developed for granular
adsorbents. In the summer and fall of 1977, the Drinking Water Research
Division installed pilot scale adsorption columns of 4 cm (1.5 in) diameter
*Calgon Corporation, Pittsburgh, PA.
tWitco, Inc., New York, N.Y.
11
-------
100
Freundlich
Parameters
EQUILIBRIUM CONCENTRATION,
mg/L
- •• —
„„„,„„
12
-------
and 80 cm (31 in) media depth near contaminated wells at water utilities in
Connecticut and New Hampshire. At the Connecticut installation, an indus-
trial waste lagoon was thought to have contaminated the well field. The
affected waterworks had just completed two years of pumping the contaminated
well to waste, yet volatile organics were still present. At both locations,
granular activated carbon (Filtrasorb® 400) and a synthetic resin, (Amber-
sorb® XE-340*, were exposed to the contaminated water.
In the New Hampshire study, trichloroethylene was the predominant
contaminant, and concentrations ranged from 120 to 276 yg/L. Unfortunately,
after 18 weeks, the test column became clogged with what appeared to be
precipitated iron. When cleaning was attempted, the contaminant wavefront
was- disrupted; the study was ended after 23 weeks (Figure 3). In the
Connecticut study, trichloroethylene was one of the lesser contaminants, and
its concentrations ranged from less than 1 yg/L to 10 yg/L. The test
columns were sampled weekly for one year, were then allowed to run continu-
ously for one year, and were finally resampled. While trichloroethylene was
removed to below detection (0.1 yg/L) for the first year, the granular acti-
vated carbon was exhausted after two years. This means the adsorption
capacity was between 61,570 and 123,340 bed volumes, or 0.7 to 1.4 mg/g.
The resin, however, was still removing trichloroethylene to "below detec-
tion" at the time (Figure 3).
In laboratory studies with trichloroethylene concentrations at the 2
mg/L level, Neely and Isacoff (42) reported the equilibrium capacity on
XE-340 was 84 mg/g (25,200 m3/m3). A pilot scale field study on Long Island
(37) further evaluated the XE-340 resin. In this project, 10-cm (4-in)
diameter columns with different depths of resin (to vary contact times) were
examined. Trichloroethylene capacity to breakthrought on the XE-340 resin
was approximately 12 mg/g (29,500 m3/m3). The influent trichloroethylene
concentrations ranged from 132 to 313 yg/L, and the resin depths varied from
0.3 to 1.2 m, giving contact times of 2 to 8 minutes.
In Montgomery County, Pennsylvania, some homes with private wells
contaminated with trichloroethylene have used Culligan adsorption units.
These home treatment devices contain approximately 40 kg (87 Ibs) of granu-
lar activated carbon and reportedly maintain effluent trichloroethylene
concentrations below 5 yg/L for several months (43). Information on the
effectiveness of other home treatment units to remove trichloroethylene,
particularly the small, low flow cartridges containing only a few grams of
activated carbon, is not yet available.
Boiling
Boiling is sometimes suggested as a means of ridding drinking water of
*Rohm and Haas Co., Philadelphia, PA.
tUnless otherwise indicated, breakthrough is the length of service when at
least 0.1 ug/L of the contaminant is consistently detected in the effluent
from the adsorbent. Length of service is expressed in both time and bed
volumes (m3 water/m3 adsorbent).
13
-------
LU
Columns
cleaned
F-400
(activated carbon)
D
New Hampshire groundwater
EBCT = 9 min.
NF »••
0 2 4 6 8 10 12 14 16 18 20 22 24
2,240 6,720 11,200 15,680 20,160 24,640
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
12
10
Connecticut groundwater
EBCT = 8.5 min.
I I I I
I T
r
Columns sampled
after two years
04 8 12 16 20 24 28 32 36 40 44 48 104
4,740 14,230 23,720 33,210 47,000 52,180 123,340
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
Figure 3. Removal of Trichloroethylene by Adsorption on Granular Activated
Carbon and Polymeric Resin.
14
-------
volatile organics. Table 3 shows the results from four studies conducted by
the USEPA in which 12 water samples were boiled for varying times. Because
boiling is not a standardized procedure, conditions are likely to vary
between households. Lataille (44) for example, noted the importance of
water depth to boiling efficiency. She found trichloroethylene was more
efficiently removed by boiling from a vessel containing 2 to 5 cm (1 to 2
in) of water than from one having greater water depths (Table 3).
15
-------
TABLE 3. REMOVAL OF TRICHLOROETHYLENE FROM DRINKING WATER BY BOILING
Time of boiling,
minutes
0
(before heating)
1
2
3
5
A
142
25
17
12
5
Trichloroethylene concentration, ug/L
B C D
1262
237
186
136
65
137
45
44
35
23
1107
589
389
261
118
176
28
20
20
11
1830 730 1460 2920 2000
279
no
57
20 12 17 194 6*, 29f, 500J
A - Spiked tap water from Cincinnati, Ohio
B - Spiked distilled water
C - Contaminated well water from Pennsylvania
D - Spiked tap water from Lexington, Massachusetts
* Water depth = 2 cm (1 in)
f Water depth = 5 cm (2 in)
$ Water depth = 11 cm (5 in)
Studies A-C by Drinking Water Research Division, USEPA, Cincinnati, Ohio.
Water depth approximately 10 cm (4 in).
Study D by USEPA Region I, Surveillance and Analysis Laboratory, Lexington,
Massachusetts (44).
Note: Blank spaces indicate no tests conducted.
16
-------
TETRACHLOROETHYLENE* Cl,
Structure
Cl'
Other Names (31-33)
PCE; perchloroethylene; 1,1,2,2-tetrachloroethylene; tetrachloroethene;
Ankilostin; carbon bichloride; carbon dichloride; Didakene; ENT-1860;
ethylene tetrachloride; NC1-C04580; Nema; Perawin; Perc; Perclene; PerSec;
Tetrales; Tetracap; Tetropil; Antisal; Fedan-Un; Tetlen; Tetraguer;
Tetraleno
Tetrachloroethylene is commercially produced by chlorinating acetylene
(CH = CH) or 1,2-dichloroethane (CH2C1CH2C1), also known as ethylene
dichloride. This solvent is widely used in dry cleaning, textile dyeing,
metal degreasing, and in the synthesis of fluorocarbons (17, 34). Tetra-
chloroethylene has been used to apply polyvinyl-toluene liners to asbestos-
cement pipe. This solvent leaches into finished drinking water from newly
laid pipe, as well as from pipe that has been installed for several years
(4). Tetrachloroethylene concentrations from this source range from a few
micrograms per liter to several milligrams per liter, the higher concentra-
tions coming from dead-ends, where water flow is not continuous. Specifi-
cations placed on new pipe can alleviate this source of contamination, but
treatment for existing polyvinyl-toluene lined pipe in the ground is a
problem that needs attention.
Conventional Treatment
Although tetrachloroethylene is mainly a groundwater contaminant, it
has been found in low, measurable concentrations in some surface waters. In
one instance, tetrachloroethylene was monitored before and after coagula-
tion, sedimentation, and filtration, and these processes, it was shown, were
ineffective for lowering its concentration (7).
Oxidation
Oxidation by ozone has been suggested, and, though Glaze (45) has shown
that ozonation can reduce tetrachloroethylene concentrations, optimum condi-
tions and subsequent by-products are unknown. Hoigne and Baden (46)
achieved a 40 percent reduction in tetrachloroethylene concentration
(initial concentration 500 yg/L) in lake water with an ozone dose of 3.3
mg/L.
*See Table 1, page 6, for properties.
17
-------
Aeration
Diffused-air aeration is effective for stripping tetrachloroethylene
from water. Laboratory studies have found that 30 to 60 percent of tetra-
chloroethylene can be removed at an air-to-water ratio of 1:1. Laboratory
and pilot scale field studies have shown at least 95 percent removal of
tetrachloroethylene at higher air-to-water ratios (Table 4). McCarty's
group (24) reported 94 percent removal of tetrachloroethylene (average
influent concentration of 2.8 pg/L) in ammonia stripping towers fed with
highly treated wastewater.
Adsorption
Adsorption isotherms for tetrachloroethylene in distilled water are
presented in Figure 4. If a tetrachloroethylene concentration of 100 yg/L
is assumed, the range of equilibrium capacities from these isotherms would
be 14 to 69 mg/g.
Adsorption tests using granular material on a pilot scale were conduc-
ted in Rhode Island by the Drinking Water Research Division during the
summer of 1977. A portion of a drinking water distribution system had
become contaminated with 600 yg/L to 2500 yg/L of tetrachloroethylene from
polyvinyl-toluene lined asbestos cement pipe (4). Two different adsorbents
were examined with 4-cm (1.5-in) diameter glass columns. One test column
contained Filtrasorb® 400 granular activated carbon, and a parallel column,
Ambersorb® XE-340 synthetic resin. Both columns had an 8.5-minute empty bed
contact time. The granular activated carbon maintained an effluent concen-
tration of tetrachloroethylene below 0.1 yg/L for 11 weeks, giving a break-
through loading of 46.7 mg/g (12,900 m3/m3). Because of inclement weather,
the study was stopped after 20 weeks. At that time the resin was passing an
average of 0.4 ug/L tetrachloroethylene (Table 5), giving an empirical
loading to breakthrough of 45.6 mg/g (18,800 m3/m3). Although the resin was
similar to the activated carbon in loading to breakthrough, it exhibited a
relatively flat breakthrough curve. This suggests that the rate of contami-
nant movement through this resin is slow, relative to the wavefront movement
through activated carbon.
One of the objectives of a USEPA study in New Jersey was to examine the
effectiveness of adsorption. A contaminated well was intermittently pumped
into a stainless steel tank having a floating lid. The water was then
pumped to adsorption columns and an aerator (Figure 5). In the non-aerated
water, tetrachloroethylene concentrations ranging from 60 to 205 yg/L were
reduced to less than 0.1 yg/L throughout the study (58 weeks) by the granu-
lar activated carbon (18-minute empty bed contact time), giving a loading to
breakthrough of >6 mg/g (>32,000 ir/m3). Similarly, after 58 weeks, resin
column effluent concentrations were <0.1 yg/L which yields a loading of
>17.7 mg/g ( >117,000 m3/m3). The tetrachloroethylene concentrations
remaining after aeration (see Table 4) were also removed to below detection
by both the resin and activated carbon.
18
-------
TABLE 4. REMOVAL OF TETRACHLOROETHYLENE FROM DRINKING UATER BY DIFFUSED-AIR AERATION
Location of
Average
Average effluent concentration
study influent
concentration, 1 :1
"Spiked"
Cincinnati, Ohio
tap water
Contaminated
well in New
Jersey
1,9/L
1025
636
338
114
107
17
92
698
161
139
32
32
3
Air-to-water ratios
2:1 3:1 4:1 8:1 16:1
416 304
177 46
103 47
17 7
17 7
2 1
156 16
34 8 <1
34 4 1
4 <1 <1
4 <1 <1
1 <1 <1
9
, ug/L Remarks
20:1
4-cm (1 .5-in)
-1 diameter glass
2 column, 10-min.
<1 contact time.
<1 Depth = 0.8m
<"!
Air-to-water ratios
Contaminated
well on Long
Island (36)
55
27
46
5:1
33
10:1
a -,-,c
8d
15:1
>a d
10°
20:1
0.4 m3 (16 ft3)
rectangular tank
with 4 diff users.
65
Depth = 0.6m
llf a. 10-min contact time
19 b. 15-min contact time
27-cm (10.5-in) diam-
eter column. Depth =
1.7m
c. 5-min contact time
d. 10-min contact time
e. 20-min contact time
Contaminated
we! 1 on
Island
Long
(37)
101
92
52
50
Air-to-water ratios
5:1 15:1 20:1
25
15
4
30:1
76-cm (30-in) diameter,
3-m (10-ft) deep glass
column with 5 diff users,
3 10-min contact time.
Note: Blank spaces indicate no tests conducted.
19
-------
E
O)
Z
o
CO
cc
<
o
O)
E
UJ
z
UJ
o
cc
O
I
o
UJ
Q
UJ
00
oc
o
03
Q
100 c
I I I I 11 ll{ I I I I I 11±
B
I I I I Mil I I I I I I I I
Freundlich
Parameters
Isotherm
A
K 273
l/n 0.6
B
84
0.4
C
51
0.6
I I Mil
I I I I 11 I ll
I I I I I I II
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 4. Isotherms for Tetrachloroethylene Adsorption on Activated Carbon.
20
-------
TABLE 5. REMOVAL OF TETRACHLOROETHYLENE FROM DRINKING WATER BY'ADSORPTION*
Time in c
weeks (be
mVm3)
Average concentration, yg/L
jperation, Effluent
;d volumes Influent Filtrasorb® 400 Ambersorb® XE-340
activated carbon resin
4 ( 4700) 1367 <0.1 <0.1
8 ( 9400) 1984 <0.1 0.1
12 (14,100) 1950 0.1 <0.1
16 (18,800) 906 0.2 0.2
20 (23,500) 825 2.8 0.4
*Study b}
Approach
t USEPA in Rhode Island. Empty bed contact time =8.5 min.
i velocity = 5m/hr (2 gal/min-ft2).
A B E
, , c. n
Free Storage * ,T rets -^-k . *
•*> *• 4cm o°S°
°0°0
go°o
°0°0
OT WT B T °°°°°° » r^
T r •'•] ^ I r°s 1 ^ Pi
tPump .•:•':'; o°°° :: ;
„- :•••'••: S5°o i
From 22cm ::::y;; gggg -.; ,
Well JL ii gggg ! ] -p
1 art/»m o2°2 i ' 1 §°s 9
1- Air
A and D: Ambersorb® XE— 340 resin; 5 min. Empty Bed Contact Time (EBCT)
B and C: Witcarb® 950 Granular Activated Carbon; 18 EBCT
E: Diffused-air aerator; 10 min.Contact Time; 4:1 (air: water)
Approach velocity = 2.5m/hr (1 gal/min - ft2)
Figure 5. Illustration of USEPA-DWRD Pilot Scale Treatment
Used at Contaminated Well Site in New Jersey.
21
-------
Boiling
The boiling point of tetrachloroethylene is 121°C, but it forms a nega-
tive azeotrope with water and boils below 100°C (20). Table 6 shows the
results of four separate boiling experiments. Although different quality
waters were used, only 1 to 2 percent of the initial concentration of tetra-
chloroethylene remained after 3 minutes of vigorous boiling in each experi-
ment.
TABLE 6. REMOVAL OF TETRACHLOROETHYLENE FROM WATER BY BOILING
Time of boiling,
minutes
Tetrachloroethylene concentration, yg/L
A B C
0
(Before heating)
1
2
3
5
10
300
14
6
3
2
298
29
14
5
2
120
11
7
3
9
2
A - Spiked Cincinnati, Ohio, tap water
B - Spiked distilled water
C - Contaminated well water from Pennsylvania
22
-------
CIS-1.2-DICHLOROETHYLENE* ^ H
Structure C = C;
cr a
Other Names (31, 32)
cis-acetylene dichloride; cis-l,2-dichloroethane; NC1-C51581
This isomer of dichloroethylen^ is used as a solvent and a fermentation
retardant (31).
Conventional Treatment
Wood's.group (48) has indicated that, in Miami, Florida, ground water,
the cis-l,2-dichloroethylene concentraton was 25 yg/L and that precipitative
softening and filtration ineffectively removed it.
Aeration
NKRE, an engineering firm, removed, by aeration from well water, 58
percent of an 18-ug/L to 118-yg/L (average 58 ug/L) concentration of
cis-l,2-dichloroethylene at an air-to-water ratio of 5:1. The removal could
be increased to 85 percent with a 30:1 air-to-water ratio (37). In a Drink-
ing Water Research Division aeration study in New Jersey, 80 percent removal
of this contaminant was observed at an air-to-water ratio of 4:1 and 10
minutes contact time. The diffused-air aeration devices used in both the
above studies are described in Table 2.
Adsorption
USEPA developed isotherms for the adsorption of cis-l,2-dichloroethy-
lene in distilled water on pulverized Witcarb® 950 and pulverized Filtra-
sort® 300. The estimated adsorption capacities are 2.7 and 1.4 mg/g,
respectively, for the solvent at an equilibrium concentration of 100 ug/L
(Figure 6). At a utility in New Hampshire (see pages 11 and 13 for descrip-
tion), the cis-l,2-dichloroethylene averaged 6 yg/L in the water applied to
the pilot scale adsorber (Figure 7), and the capacity for the activated
carbon at exhaustion was 0.2 mg/g. At a site in Connecticut (also described
on pages 11 and 13), the average concentration of cis-l,2-dichloroethylene
was 2 ug/L, and the adsorption capacity on activated carbon was 0.1 mg/g.
Companion adsorbers containing Ambersorb® XE-340 were also monitored at
these two New England sites. The resin maintained an effluent concentration
of cis-l,2-dichloroethylene below detection for the duration of the New
Hampshire study (20 weeks), and for more than one year, but less than 2
*See Table 1, page 6, for properties.
23
-------
E 100
05
z
o
CQ
DC
<
O
O)
E
UJ
Z
LU
LU
O
DC
O
I
5
C/3
O
Q
LU
OQ
or
8
Q
10
0.1
I I I I I III) I I I I I II l
H H
\
Cl Cl
Structure
I I I I I I l±
I I I I
I Mil
Freundlich
Parameters
Isotherms
A
K 8.4
l/n 0.5
B
6.5
0.7
I I I I 11 III I I I I 11II
0.001
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 6. Isotherms for Cis-l,2-Dich1oroethylene Adsorption on Activated
Carbon.
24
-------
UJ
"
52°
u
NF
Effluent F-400
x; \
New Hampshire groundwater
EBCT = 9 min.
Approach Velocity = 5m/hr
_L
0
0
\;
V
a
Effluent XE-340
4
4,480
8
8,960
12
13,400
16
17,920
20
22,400
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
P
O iu
*£
TO
«u
o
NF
I I
— Connecticut groundwater
EBCT = 8.5 min.
Approach Velocity = 5m/hr
Contaminant
detected in
influent after
six weeks of
service
Columns sampled
after two years
0 10 20 30 40
0 11,860 23,720 35,580 47,435
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
50 104
59,300 123,340
Figure 7. Removal of Cis-1,2-Dichloroethylene by
Activated Carbon and Polymeric Resin.
Adsorption on Granular
25
-------
years ( >5.4 mg/g loading) at the Connecticut site.
Wood and DeMarco (48) evaluated Filtrasorb® 400 granular activated car-
bon, Ambersorb® XE-340 resin, and Amberlite® IRA-904 anion exchange resin on
the organic-laden ground water in Miami, Florida. Pilot scale adsorbers
[2.5-cm (1-in) diameter glass columns] were placed on flow streams of raw,
lime-softened and chlorinated filtered water. In the untreated (raw) water,
the average concentration of cis-l,2-dichloroethylene was 25 yg/L, and this
solvent was detected in the effluent from the activated carbon between weeks
2 and 3 (0.3 mg/g loading to breakthrough). The XE-340 resin lasted approx-
imately 9 weeks (0.7 mg/g), and the anion exchange resin did not remove any
of the contaminant. The effects of placing the adsorbents at other loca-
tions within the treatment plant are shown in Table 7. The XE-340 resin
performed better on the raw water than on the treated water, which may
indicate how the high pH of lime softening affects capacity.
NKRE (37) reported nearly identical loadings to breakthrough and to
exhaustion on XE-340 resin for a 2- and 4-minute contact time; this is shown
in Table 7.
Boiling
Two samples of well water from Pennsylvania, having cis-l,2-dichloro-
ethylene as one of the contaminants, were boiled for varying times by the
Drinking Water Research Division in Cincinnati and then analyzed. The
results, given in Table 8, show that between 5 and 10 minutes of vigorous
boiling were necessary to reduce the contaminant level to 5 ug/L or less.
26
-------
TABLE 7. REMOVAL OF CIS-1,2-DICHLOROETHYLENE BY ADSORPTION
Average influent Empty bed
concentration, Bed depth, contact time,
Adsorbent vg/L m (ft) minutes
Service to breakthrough*
Time,
days
Bed volumes, Loading,
m3/m3 mg/g
[Miami, FL (48)]
Filtrasorb® 400
on raw water
Filtrasorb® 400
on filtered water
Ambersorb® XE-340
on raw water
Ambersorb® XE-340
on lime-softened
water
Ambersorb® XE-340
on filtered water
Amber! ite® IRA-904
Ambersorb® XE-340
25
18
25
22
16
27
40
0.8 (2.5)
0.8 (2.5)
1.5 (5)
2.3 (7.5)
3.1 (10)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
1.5 (5)
[Glen Cove, NY
0.3 (1)
0.6 (2)
6
6
12
18
25
6
6
6
6
12
(37)]
2
4
18
18
59
101
>122
60
30
48
Not
Not
48
102
4300
4300
7100
8000
>7000
14,400
7200
11,500
effective
effective
37,200
39,500
0.3
0.2
0.3
0.4
>0.3
0.7
0.3
0.4
1.7
1.9
Service to exhaustiont
Ambersorb® XE-340
50
45
0.3 (1)
0.6 (2)
2
4
67
153
51 ,900
59,400
4.2
4.4
*0.1 ug/L or more in effluent
tEffluent = influent
-------
TABLE 8. REMOVAL OF CIS-1.2-DICHLOROETHYLENE FROM WATER* BY BOILING
Time of boiling, Concentration, ug/L
minutes
0 (before heating)
1
2
3
5
10
Sample 1
739
168
51
31
14
<1
Sample 2
153
43
34
34
20
5
*Contaminated well water from Pennsylvania. Study by USEPA, Drinking Water
Research Division, Cincinnati, Ohio, 1979. Water depth approximately 8 cm.
28
-------
TRANS-1,2-DICHLOROETHYLENE* H
c = c
Structure /
Cl H
Other Names (31-33)
trans-acetylene dichloride; trans-dichloroethylene; trans-1,2-dichloroethene
This isomer of 1,2-dichloroethylene is a low-temperature solvent that
is sometimes used to decaffeinate coffee or as a refrigerant.
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing 217 yg/L trans-
1,2-dichloroethylene was passed through a counter-current flow, diffused-air
aerator, the Drinking Water Research Division found a 97 percent reduction
in trans-1,2-dichloroethylene concentrations at a 15-to-l air-to-water
ratio. The aerator was a glass column 10cm (2.5 in) in diameter with a
water depth of 1.2 m (4 ft). The contact time was 13 minutes. Other air-
to-water ratios and corresponding percent removals are shown in Section 4,
Figure 25.
Adsorption
Dobbs and Cohen (40) developed an adsorption isotherm for this solvent
in distilled water using pulverized Filtrasorb® 300 granular activated car-
bon. From the Freundlich isotherm shown in Figure 8, the estimated adsorp-
tion capacity for this solvent at an equilibrium concentration of 100 yg/L
is 0.9 mg/g. No field data are available on the adsorption of trans-1,2-
dichloroethylene from contaminated waters.
Boiling
See Discussion, Section 4.
*See Table 1, page 6, for properties.
29
-------
10
£
O3
•z.
o
00
cc
o
O)
E
LU
§ 1.0
LU
O
CC
O
I
O
Q
0.1
QC
I-
Q
LU
CO
or
g 0.01
i I I I I lll| I I I I I IIIJ I I I I I I ll| I \ I I I 11±
H. Cl
Cl H
Structure
0.001
I J 1 I I
Jill
*fl*
AP>
•,^°
**
t\&
Freundlich Parameters
K = 3.1
l/n = 0.5
I I I I I Mil I I 1 I I I III I I I I I I II
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 8. Isotherm for Trans-l,2-Dichloroethylene Adsorption on Activated
Carbon.
30
-------
1,1-DICHLOROETHYLENE*
Structure
ci
Other Names (31-33)
1,1-DCE; 1,1-dichloroethene; vinylidene chloride; NC11-C54262
1,1-Dichloroethylene is commercially produced by dehydrochlorination of
1,1,2-trichloroethane (CH C1CHC1 ) by sodium hydroxide or lime. This sol-
vent is used in the manufacturing of plastics and, more recently, in the
production of 1,1,1-trichloroethane (17).
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
This chlorinated solvent has a high Henry's Law Constant and should he
easily removed by aeration.** This was the case in a New Jersey study in
which 97 percent was removed at an air-to-water ratio of 4:1 and a 10-minute
contact time. The influent concentration of 1,1-dichloroethylene was 122
yg/L, and the diffused-air device used is described in Table 2.
Adsorption
The Dobbs and Cohen (40) Freundlich isotherm for adsorption of
1,1-dichloroethylene in distilled water on pulverized Filtrasorb® 300
granular activated carbon is given in Figure 9. From the isotherm, the
estimated adsorption capacity for this solvent at an equilibrium concentra-
tion of 100 yg/L is 1.2 mg/g.
A New Jersey study (see discussion of tetrachloroethylene for more
information) examined adsorption of 1,1-dichloroethylene before and after
aeration. Figure 10 illustrates the performance of Witcarb^ 950 granular
activated carbon and Ambersorb® XE-340 polymeric resin during a 60-week test
period. When the adsorption system received non-aerated water, breakthrough
(greater than 0.1 yg/L) was noted after passage of 22,400 m3/m3 (6.2 mg/g)
for the activated carbon and 80,600 m3/m3 (20 mg/g) for the resin. Both
adsorbents were still removing over 80 percent of the influent concentration
of 1,1-dichloroethylene when the test was terminated. With the exception of
the XE-340 resin for a brief period near the end of the study, both
*See Table 1, page 6, for properties.
**See Discussion, Section 4, for relationship between Henry's Law Constant
and aeration efficiency.
31
-------
E
O)
z
O
CO
DC
o>
E
UJ
2
UJ
100
10
O
oc
O
u 1-0
Q
LU
00
cc
O
CO
~l I I Mill) T I I I I II
Cl H
\
Cl H
Structure
I I I I 1 I I I
0.1
0.001
I I I I I I I 11 I
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
TTTT
Freundich Parameters
10
Figure 9. Isotherm for 1,1-Dichloroethylene Adsorption on Activated Carbon.
32
-------
600
500
300
§1
•J- li I
9S 200
100
1 I T
New Jersey groundwater
W-950 EBCT = 18 min.
XE-340 EBCT = 5 min.
o
Influent
W-950
(activated
carbon)
0 10 20 30 40 50 60
W-950 0 5,600 11,200 16,800 22,400 28,000 36,600
XE-340 0 20,160 40,320 60,480 80,640 100,800 120,960
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
New Jersey groundwater
(After 4:1 aeration)
W-950 EBCT = 18 min.
XE-340 EBCT = 5 min.
0 10 20 30 40 50 60
W-950 0 5,600 11,200 16,800 22,400 28,000 36,600
XE-340 0 20,160 40,320 60,480 80,640 100,800 120,960
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
Figure 10. Removal of 1,1-Dichloroethylene on Granular Activated Carbon or
Polymeric Resin.
33
-------
adsorbents removed the 1,1-dichloroethylene remaining after aeration to
below detection.
Boiling
See Discussion, Section 4.
34
-------
VINYL CHLORIDE* H .H
c = c
Structure
H
Other Names (31-33)
chloroethylene; chloroethene; Chlorathene; Ethylene; Chloro-; ethylene
monochloride; monochloroethene; monochloroethylene; VCM; Vinyl C monomer
Vinyl chloride is commonly produced by reacting chlorine qas with
ethylene (CH2 = CH 2) (49). Billions of kilograms of this solvent are used
annually in the United States to produce polyvinyl chloride (PVC), the most
widely used.ingredient for manufacturing plastics throughout the world (50).
Evidence is also mounting that vinyl chloride may be a biodegradation end-
product of tri- and tetrachloroethylene under certain environmental condi-
tions (16).
Special precautions are necessary to sample and analyze for vinyl chlor-
ide because of its low boiling point (high volatility). Unlike trichloro-
ethyl ene, for example, vinyl chloride escapes detection in a routine
analysis for trihalomethanes. For this reason, little definitive occurrence
or treatment information exists on this contaminant in drinking water.
In 1978, Dressman and McFarren (5) conducted tests on PVC pipe. They
sampled five water distribution systems that used PVC pipe and found vinyl
chloride concentrations in the water ranging from 0.7 to 55 ^g/L. They con-
cluded that the vinyl chloride contamination levels were related to the
vinyl chloride monomer residual in the pipe, and to whether or not the water
flowed continuously or sat idle in the pipe. The authors pointed out,
however, that producers of PVC pipe claim that changes later made in the
manufacturing process lowered residual monomer in the pipe and thus reduced
the vinyl chloride expected to leach into drinking water from new PVC pipe.
Conventional Treatment
Vinyl chloride was detected intermittently in a Southern Florida ground
water. The average concentration reduction for this contaminant through the
lime softening basins and filters was 25 to 52 percent (48). These losses
were probably to the atmosphere around the open basins.
Aeration
No data are available. See Discussion, Section 4.
*See Table 1, page 6, for properties.
35
-------
Adsorption
Finished water from a Southern Florida groundwater treatment plant was
routed to four pilot scale granular activated carbon columns connected in
series. Each column contained a 76-cm (30-in) depth of Filtrasorb® 400
activated carbon, and the empty bed contact time was approximately 6 minutes
per column. Vinyl chloride concentrations in the influent ranged from below
detection to 19 yg/L, and removal by adsorption on the activated carbon was
erratic. For example, to maintain an effluent concentration of vinyl
chloride below 0.5 pg/L, the estimated activated carbon loading was 810,
1250, 2760, and 2050 nf /m3 for empty bed contact times of 6, 12, 19, and 25
minutes, respectively (48, 51). Similarly, vinyl chloride was reported to
be poorly removed on Ambersorb®XE-340 synthetic resin (51).
Boiling
No data are available.
36
-------
1,1,1-TRICHLOROETHANE* C)
Structure
PI _ p _ p _ u
Cl H
Other Names (31-33)
methyl chloroform; Chloroethene; Aerothene TT; Chlorten; NC1-C04626; alpha-
trichloroethane; -t; Chlorothane; Chlorothene NU; Chlorothene VG; Inhibisol;
methyltrichloromethane; trichloroethane
1,1,1-Trichloroethane is commercially produced by reacting chlorine
with vinyl chloride (CH2 = CHC1) or by acidifying 1,1-dichloroethylene (also
known as vinylidene chloride, CHo = CC12 ) with hydrochloric acid. 1,1,1-
Trichloroethane has replaced trichloroethylene in many industrial and house-
hold products. It is the principal solvent in septic tank degreasers,
cutting oils, inks, shoe polishes, and many other products (17, 34, 52).
Among the volatile organics found in ground waters, 1,1,1-trichloro-
ethane and trichloroethylene are encountered most frequently and in the
highest concentrations. USEPA Region III, has investigated an industrial
well water situation in Pennsylvania, in which the wells most distant from
the pollution source contained trace quantities of trichloroethylene and the
wells nearest the pollution source(s) contained 1,1,1-trichloroethane. This
possibly reflects the previous change in industrial solvent uses.ti,i,i-
Trichloroethane has also been identified in drinking water tak^n from
surface sources. In one instance, a cleaning agent containing 1,1,1-tri-
chloroethane was being used within the water treatment plant and the con-
taminants detected in the finished water could have come from that source
(53).
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
NKRE (37) observed a 66 to 85 percent reduction in (influent concentra-
tions of 3 to 7 wg/L) 1,1,1-trichloroethane concentrations with the intro-
duction of air at air-to-water ratios ranging from 5:1 to 30:1 (see discus-
sion of trichloroethylene). The diffused-air aerator used in the USEPA1 s
New Jersey study (see Figure 5) consistently achieved approximately 90 per-
*See Table 1, page 6, for properties.
tPrivate communication, H.G. Beyer, USEPA Region III Water Supply Branch
(1979).
37
-------
cent removal of 1,1,1-trichloroethane at a 4:1 air-to-water ratio. The
influent concentration ranged from 170 to 280 yg/L. Similarly, McCarty's
group (24) obtained high removals of 1,1,1-trichloroethane with both a
packed bed degasifier and an ammonia stripping tower used for advanced
wastewater treatment at Water Factory 21. The influent concentrations of
1,1,1-trichloroethane, however, were less than 5 yg/L.
Kelleher and fellow researchers (54) reported mixed results on an aera-
tion study in Norwood, Massachusetts. They used a 10-cm (4-in) diameter
glass column packed with glass raschig rings to a depth of 63 cm (25 in).
Compressed air was blown up through the packing material as contaminated
ground water trickled downward. With water from Well #4 (see Table 9) the
removal of 1,1,1-trichloroethane ranged from 74 to 97 percent for a broad
spectrum of aeration conditions, whereas from water of Well #3, the removal
was poorer. This difference could not be explained.
TABLE 9. REMOVAL OF 1,1,1-TRICHLOROETHANE FROM DRINKING WATER
USING A PILOT SCALE FORCED DRAFT PACKED TOWER (54)
Effluent concentration of 1,1,1-trichloroethane, yg/L
Influent
Source concentration, Range of air-to-water ratios
yg/L 1:1 to 10:1 11:1 to 20:1 21:1 to 50:1 >50:1
Well
#4
Well
#3
110
90
42
850
1200
630
10
8
460
387
10
4
410
210
13
3
220
350
5
49
Blanks indicate no tests conducted.
Adsorption
USEPA developed adsorption isotherms for 1,1,1-trichloroethane (Figure
11). Calculating on the basis of these isotherms, the average adsorption
capacity for a 100 yg/L concentration of 1,1,1-trichloroethane is 1.6 mg/g.
In a full-scale study at a water treatment plant in Florida, Ervin and
Singley (55) found no difference in the removal efficiency of four powdered
activated carbons: pulverized Calgon GW; Huskey Watercarb® Plus; ICI Hydro-
darco® B; and Westvaco Aqua Nuchar® II. At a dosage of approximately 7 mg/L
and a 2-hour contact time, powdered activated carbon removed at best 15 to
20 percent of an 18 yg/L 1,1,1-trichloroethane influent concentration in a
38
-------
100
O
co
DC
o>
LU
z
LU
O
oc
g
X
O
cc
Q
LLJ
CD
OC
O
(/)
O
<
EIi i i i iiij
Cl H
Cl
10
1.0
0.1
0.001
•C—C H
I I Structure
Cl H
Freundlich
Parameters
Isotherm
A
K 9.4
l/n 0.5
B
2.5
0.3
I I I I I Mil I I L J I III! J L LJ 11 111 I I I I I I II
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 11. Isotherms for 1,1,1-Trichloroethane Adsorption on Activated Car-
bon.
39
-------
Florida ground water (39, 52).
Figure 12 illustrates some of the USEPA Drinking Water Research Divi-
sion pilot scale adsorption project results from studies in New Jersey and
Connecticut. While the amount of contaminant and the type of adsorbent
varied, the length of service to breakthrough for the granular activated
carbon only ranged from 12,000 to 15,000 m3/m3. Expressed as a loading, the
activated carbon adsorbed from 0.02 to 7.5 mg/g. In the New Jersey study
(described in discussion of tetrachloroethylene), activated carbon receiving
aerated water with an average 1,1,1-trichloroethane concentration of 23 yg/L
produced an effluent with no detectable amounts during a 58-week-long study.
This resulted in am empirical loading of at least 1.9 mg/g and a length of
service greater than 32,000 m3/m3.
Kelleher's group (54) conducted adsorption experiments at a contami-
nated well site in Massachusetts. They used four 10-cm (4-in) diameter
glass columns, each containing a 60-cm (2-ft)depth of Filtrasorb® 400
granular activated carbon in series for a total adsorbent depth of 2.5 m (8
ft). These were operated to assess the effects of contact time, and time to
breakthrough was not reported. The loadings to reach 5 wg/L of 1,1,1-tri-
chloroethane in the effluent from an applied 100 yg/L concentration, were
0.26 mg/g, 0.51 mg/g, and 0.74 mg/g for contact times of 7.5 minutes, 15
minutes, and 22.5 minutes, respectively. These results are included in the
summary portion of Figure 12. The total organic carbon (TOC) concentration
was over 2 mg/L in the Massachusetts water, yet less than 0.5 mg/L in the
Connecticut and New Jersey water; thus, competitive adsorption may have
accounted for differences in performance.
Neeley and Isacoff (42) and Isacoff and Bittner (56)compared Amber-
sorb^XE-340 resin to Filtrasorb® 400 granular activated carbon for removing
1,1,1-trichloroethane from a New Jersey well water. The experiment was
conducted using 5-cm-long columns containing 15 cc of adsorbent and water
shipped to their laboratory from the contaminated well. At a 270 liter per
minute per cubic meter (2 gpm/ft3) loading rate and 3.7-minute empty bed
contact time, 1,1,1-trichloroethane at an average applied concentration of
450 ug/L broke through both adsorbents between 5000 and 6000 m3/m3. This
produced a loading of approximately 4.2 mg/g.
A difference in adsorbent behavior was seen after contaminant break-
through. The granular activated carbon column steadily became more
exhausted, while the resin column continued to remove a large percentage of
the solvent. Rather than having an incisive slope like the granular acti-
vated carbon, the slope of the breakthrough curve for the resin was gradual.
Using water from the same contaminated source in New Jersey, the Drinking
Water Research Division found with its pilot scale columns (Figure 5) that
XE-340 removed to below detection 1,1,1-trichloroethane (average applied
concentration of 237 pg/L) for almost 83,000 m3/m3 (33 mg/g). Why the
service life found in the field study, Figure 12, was so much longer than
the service life that was predicted from the laboratory studies (56) cannot
be explained.
40
-------
400
yji 200
100
\ \
New Jersey groundwater
W-950 EBCT = 18 min.
XE-340 EBCT = 5 min.
Approach Velocity = 2.5m/hr
Influent
NFo
W-950 0
XE-340 0
Effluent
W-950
(activated carbon)
Effluent XE-340
Resin
I
10 20 30 40
5600 11,200 16,800 22,400
20,160 40,320 60,480 80,640
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
50
28,000
100,800
60
36,600
120,960
50
40
30
5« 20
10
NF
W-950
XE-340
1 I
New Jersey groundwater
(After aeration)
W-950 EBCT = 18 min.
XE-340 EBCT = 5 min.
0 10 20 30 40 50 60
0 5600 11,200 16,800 22,400 28,000 36,600
0 20,160 40,320 60,480 80,640 100,800 120,960
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
Figure 12. Removal of 1,1,1-Trichloroethane on Granular Activated Carbon or
Polymeric Resin.
41
-------
i 'T
Connecticut groundwater
EBCT = 8.5min.
Approach Velocity = Brn/hr
Columns sampled
after two years
0 10 20 30 40 50 140
0 11,860 23,720 35,580 47,435 59,300123,340
TIME IN SERVICE, Weeks
BED VOLUMES, mVm3
1.0
0.8
LJJ
0.6
LLJ
LU 0.4
0.2
1.3
1.5
Summary of Granular Activated Carbon
Adsorption Studies
Keller, et al (54)
Massachusetts
(F-400)
USEPA-DWRD
Connecticut
(F-400)
USEPA-DWRD
New Jersey
(W-950)
D
1
5,000 10,000 15,000 20,000
BED VOLUMES, mVm3
25,000 30,000
Figure 12. (Cont'd.)
42
-------
In the New Jersey study, a column containing Ambersorti^ XE-340 and
receiving aerated water (see Figure 5) with an average 1,1,1-trichloroethane
v.oncentration of 23 yg/L, had detectable quantities of the solvent in the
effluent after 52 weeks. This corresponded to a loading of 101,000 m3/m
(3.9 mg/g).
In the Connecticut project, a column containing Ambersorb® XE-340
(3.5-minute empty bed contact time) was sampled weekly for one year and then
next sampled a year later. Breakthrough was evident at the end of the first
year and after 62,000 m3/m3, or 3.3 mg/g. The adsorbent was not exhausted
even at the end of the second year.
Boiling
Lataille (44) found that, depending on depth, only 1 to 20 percent of
an initial 1,1,1-trichloroethane concentration remained after 5 minutes of
boiling. Similarly, personnel in the Rhode Island State Laboratories (57)
found an average of only 2 percent of the starting 1,1,1-trichloroethane
concentration remaining after 5 minutes of boiling contaminated drinking
water samples (Table 10).
TABLE 10. REMOVAL OF 1,1,1-TRICHLOROETHANE FROM DRINKING
WATER BY BOILING
Water sample
Time of boiling,
minutes
Concentrati on, yg/L
Lexington, MA*
tap water "spiked"
with 1,1,1-
trichloroethane
0
(before heating)
5
680 1350 2700
1900
8 23
35 5a,27b,360C
Contaminated
drinking water
in Rhode Island
0
(before heating)
5
37t
1
*After Lataille (44)
.Water depth = 2 cm
Water depth = 5 cm
Water depth = 11 cm
tAverage of 12 tests with water having 1,1,1-trichloroethane concentrations
ranging from 2 to 166 yg/L. After Reference 57.
43
-------
-------
1,2-DICHLOROETHANE* Cl Cl
I I
Structure H C C H
H H
Other Names (31-33)
1,2-dichloroethane; Borer Sol; Brocide; Destraxol Borer-Sol; Dichloroemul-
sion; Di-Chloro-Mulsion; dichloroethane; Alpha, Beta-Dichloroethane;
dichloroethylene; Dutch Liquid; EDC, ENT 1,656; ethane dichloride; ethylene
chloride; ethylene dichloride; glycol dichloride; NC1-C00511; acetylene
dichloride; Dioform
1,2-Dichloroethane is used as a solvent for fats, oils, waxes, gums,
and resins (31).
Conventional Treatment
In a Louisiana study (35, 58) 1,2-dichloroethane with a mean concentra-
tion of 8 yg/L was not removed by coagulation and filtration.
Aeration
This contaminant is not easily removed from water by aeration. For
example, Symons and fellow researchers (8) reported that air applied at an
air-to-water ratio of 4:1 removed only 40 percent of the 1,2-dichloroethane
from a contaminated well water in New Jersey.
Adsorption
The USEPA developed adsorption isotherms (Figure 13) for the removal of
1,2-dichloroethane in distilled water at a concentration of 100 yg/1 by
pulverized granular activated carbon. From these data, the estimated
carbon's capacity at equilibrium ranged from 0.5 to 1.8 mg 1,2-dichloro-
ethane/gram carbon. In a New Jersey study, Witcarb® 950 granular activated
carbon maintained the effluent concentration of 1,2-dichloroethane below 0.1
yg/L for 31 weeks when the influent concentration averaged 1.4 ug/L. This
yielded a loading of approximately 0.1 mg 1,2-dichloroethane/g carbon
(17,400 m3/m3) to breakthrough. Ambersorb® XE-340 resin showed breakthrough
after 54 weeks of service and a loading of approximately 0.3 mg
1,2-di chl oroethane/g carbon (108,860 m3/m3).
In studies by DeMarco and others (35) and DeMarco and Brodtmann (58) in
Louisiana, 1,2-dichloroethane at an average concentration of 8 yg/L was
*See Table 1, page 6, for properties.
45
-------
removed to a concentration of less than 0.1 yg/L for 39 days by a full-scale
adsorber containing a 76-cm depth (30-in) of Nuchar®WV-G granular activated
carbon (20-minute empty bed contact time). The equivalent loading was 1725
m of water per m3 of activated carbon or expressed in another way, 0.3 mg
1,2-dichloroethane per gram of activated carbon.
Boiling
See Discussion, Section 4.
10
O
00
cc
TO
1.0
LU
z
LU
O
CC
g
X
O
Q 0.1
I
CM
Q
LU
CO
QC
O
0.01
I Il±
Freundlich
Parameters
Isotherms
A
K 5.7
l/n 0.5
B
3.6
0.8
I I I I I Mil I I I I I Mil I I I I II III I I I I I I II
0.001
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 13. Isotherms for 1,2-Dichloroethane Adsorption on Activated Carbon.
46
-------
CARBON TETRACHLORIDE* Cl
I
Structure Cl C Cl
Cl
Other Names (31-33)
tetrachloromethane; perchloromethane; Necatorina; Benzinoform; methane
tetrachloride; methane, tetrachloro-; Necatorine; ENT 4,705; Halon 104;
carbon chloride; Carbona; Flukoids; RIO; Tetrafinol; Tetraform; Tetrasol;
Univerm; Vermoestricid
Carbon tetrachloride was once a popular household solvent, a frequently
used dry cleaning agent, and a charging agent for fire extinguishers. Since
1970, however, carbon tetrachloride has been banned from all use in consumer
goods in the United States, and in 1978, it was banned as an aerosol propel-
lant (59). Currently, its principal use is in the manufacture of flurocar-
bons, which are used as refrigerants and, to a lesser degree, in the making
of grain fumigants. This solvent is a known contaminant in chlorine pro-
duced by the graphite-anode method (2), and chlorinated drinking water can
become contaminated with carbon tetrachloride from this source (3, 60, 61).
The American Water Works Association (AWWA) is rewriting chlorine specifica-
tions, and this will perhaps minimize carbon tetrachloride contamination
resulting from chlorination.
Conventional Treatment
Incidental to a study on trihalomethanes, the USEPA detected carbon
tetrachloride in the Ohio River and in the City of Cincinnati drinking water
in 1976 and 1977 (Figure 14). Between July 1976, and February 1977, the
concentration of this contaminant in the untreated water was 16.3 ug/L and
in the treated water, 16.0 ug/L, indicating that no net removal resulted
from powdered activated carbon addition (2 to 4 mg/L), coagulation,
settling, and filtration.
Aeration
Laboratory studies by the Drinking Water Research Division showed that
aeration with the diffused-air aerator (discussed in the section on tri-
chloroethylene treatment and also in Table 1) at a 4:1 air-to-water ratio
could remove 91 percent of the carbon tetrachloride (8).
*See Table 1, page 6, for properties.
47
-------
CO
_l
""x.
LJJ
Q
CC
g
_J
X
i_
UJ
z
a
CO
CC
0
110
100
90
80
70
60
50
40
30
20
10
0
Treatment provided @ water works:
Powdered activated carbon, coagulation,
Settling, filtration, and chlorination
A-lce formation
B-River frozen over
C-lce broken by barges
D-lce breaking up
!
«— —
y
J
'« T i1
i°\ •!
/
/
1 .1
M
Ul ' 1
MAR. APR. MAY JUNE JULY
1976
AUG. SEPT. OCT. NOV. DEC. JAN. FEB.
1977
Figure 14. Carbon Tetrachloride in Raw and Treated Water at Cincinnati, Ohio.
-------
Adsorption
Lykins and DeMarco (61) reviewed the treatment data generated by a
water utility using Ohio River water during 1976-1977 and concluded that
consistent removals of carbon tetrachloride were not obtained with powdered
activated carbon treatment. Differences could be attributed to analytical
variation. USEPA studies showed that powdered activated carbon doses up to
30 mg/L removed only about 10 percent of this contaminant from Ohio River
water.
Dobbs and Cohen (40), Weber and Pirbazari (62), and the Drinking Water
Research Division have developed adsorption isotherms for carbon tetrachlor-
ide using different protocols and different types of granular activated
carbon (Figure 15). From these studies, it was determined that the calcu-
lated adsorption capacity for carbon tetrachloride, at an equilibrium con-
centration of 100 yg/L, on activated carbon is between 1.6 mg/g and 7.0
mg/g. It is not known whether this range reflects true differences in
adsorbents or simply differences in isotherm determination technique.
Symons (63) reported on the behavior of carbon tetrachloride in water
that was applied to pilot scale adsorbers containing Filtrasorb® 400 granu-
lar activated carbon. Two adsorbers, one with a 5-minute and the other with
a 10-minute empty bed contact time, were exposed to Cincinnati, Ohio, tap
water for 18 weeks when carbon tetrachloride was detected in the influent
water. The mean concentration of the contaminant in the water was 12 ug/L,
and this was removed to less than 0.1 ug/L for 3 weeks by the activated
carbon with a 5-minute contact time and for between 14 and 16 weeks by the
activated carbon with a 10-minute contact time. This corresponds to an
empirical loading range of approximately 6000 and 14,000 m3/m3 (0.2 and 0.4
mg/g), respectively.
In the fall of 1976, three granular activated carbons manufactured in
France were also exposed to tap water in the USEPA Drinking Water Research
Division laboratory in Cincinnati. Two of the materials, PICA-A and PICA-B,
behaved similarly to the Filtrasorb® 400, but the third, PICA-C, had no
capacity for carbon tetrachloride. Further, PICA-C had no capacity for
total organic carbon or for trihalomethanes (63), leading the investigators
to suspect that the material was either poorly activated or not activated at
all.
Symons and fellow researchers (8) reported that Ambersorb® XE-340
removed carbon tetrachloride from Cincinnati, Ohio, drinking water for about
the same length of time as the granular activated carbon did. Although the
length of service to breakthrough was similar to that for granular activated
carbon, the shape of the adsorption and desorption curves were quite differ-
ent. For activated carbon, desorption was evident when influent concentra-
tions of the contaminant declined. The resin, on the other hand, showed
some desorption, but much less than the granular activated carbon did (Fig-
ure 16).
49
-------
E
CD
O
CO
cc
S
O5
£
LU
Q
CC
O
I
O
<
CC.
O
CO
cc
Q
UJ
CO
cc
O
(f)
Q
100
I I I I I I III) I I I I I 11 Ij I I I I 11ll{ I I I I I I It
Cl
10
1.0
0.1
0.001
Structure
Cl C Cl
I
Cl
Norit & Nuchar® WV-G
B C
pulverized
activated
carbon
unpulverized
activated
carbon (62)
Freundlich
Parameters
Isotherms
A
K 14.8
l/n 0.4
B
28.5
0.8
C
25.8
0.7
D
38.1
0.7
E
14.2
0.7
F
11.1
0.8
I I I I I Mil I I I I I I III I I I I I I III I I I I I I II
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 15. Isotherms for Carbon Tetrachloride Adsorption on Activated Car-
bon.
50
-------
o>
3
z
UJ
(J
z
O
o
UJ
Q
oc
o
I
o
<
cc
UJ
O
CD
OC
<
o
Cincinnati Tap Water
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
OCT. MOV. DEC. JAN. FEB. MAR. APR. MAY JUNE
1977
Figure 16. Desorption of Carbon Tetrachloride from Granular Activated Car-
bon and Polymeric Resin.
51
-------
Boiling,
Table 11 lists some results obtained after boiling water contaminated
by carbon tetrachlorlde. About 1 percent or less remains after 5 minutes of
vigorous boiling.
TABLE 11. REMOVAL OF CARBON TETRACHLORIDE FROM DRINKING WATER BY BOILING
Sample
Time of boiling,
minutes
Concentration, yg/L
Cincinnati, Ohio
(tap water)
Rhode Island State
Health Department (57)
(tap water)
0 (before heating)
5
0 (before heating)
5
30
<0.
188
2
52
-------
METHYLENE CHLORIDE* Cl
I
Structure Cl^H
H
Other Names (31-33)
dichloromethane; Aerothene MM; methylene dichloride; Narkotil; R30;
Solaesthin; Solmethine; methane dichloride; methylene bichloride; NC1-C50102
Methylene chloride is commercially produced by reacting methane direct-
ly with chlorine at approximately 500°C, or by reacting chlorine with methyl
chlorine (CHsCl). The latter process is more predominant (17). Methylene
chloride is a common ingredient in paint and varnish strippers, is an extrac-
tion solvent for decaffeinating coffee, an extraction solvent in analytical
laboratories, and a carrier solvent in the textile industry. It is used
extensively to make flexible foams in the urethane industry, and is also
used to make pharmaceutical products such as steroids, antibiotics, and
vitamins. Its uses in aerosols and as a vapor degreasing solvent are
rapidly increasing. In 1977, the Nassau County, New York, Department of
Public Works estimated that thousands of gallons of methylene chloride were
being used annually as a cesspool cleaner and drain opener (52). Methylene
chloride has been detected sporadically by the Drinking Water Research
Division during analyses of water samples from pilot scale studies for other
volatile compounds.
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing an average of
225 ug/L methylene chloride was passed through a diffused-air aerator, the
Drinking Water Research Division found an 82 percent reduction in methylene
chloride concentrations at a 15:1 air-to-water ratio. Other aeration condi-
tions and corresponding percent removals are shown in Section 4, Figure 25.
Adsorption
Dobbs and Cohen (40) developed an adsorption isotherm for methylene
chloride in distilled water using pulverized Filtrasorb® 300 activated
carbon. Weber's group (17) used distilled water and Filtrasorb® 400. These
data are illustrated in Figure 17 as Freundlich isotherms. When methylene
*See Table 1, page 6, for properties.
53
-------
chloride has an equilibrium concentration of 100 yg/L, the capacity pre-
dicted from these isotherms is approximately 0.2 mg/g.
O'Brien and fellow researchers (64) reported a carbon usage of 3.9
lb/1000 gal to maintain an effluent concentration of less than 1 yg/L in a
situation in which methylene chloride in a ground water was typically above
20 mg/L. They used two activated carbon beds in series with an empty bed
contact time of 262 minutes.
Boiling
See Discussion, Section 4.
E
CD
z
o
CO
cc
<
u
03
E
10
LU
g
DC
O
X
u
LU
Z
LU
I
LU
Q
LU
00
o:
O
CO
Q
- Cl
; 1.0
0.1
1 I I I Illlj 1 I I I I I 14;
Cl
I
-c
unpulverized
H
•H
Structure
B
pulverized
Freundlich
Parameters
Isotherms
A
K 1.3
l/n 1 .2
B
1.6
0.7
0.01
0.001
I I
I I I I II III
I I I I 11II
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 17. Isotherms for Methylene Chloride Adsorption on Activated Carbon.
54
-------
BENZENE*
Structure
Other Names (31-33)
Benzole; Benzol; coal naphtha; carbon oil; cyclohexatriene; phene; phenyl;
hydride; pyrobenzol; pyrobenzole; mineral naphtha; motor benzol; nitration
benzene; (6) annulene; bicarburet of hydrogen
Destructive distillation of one ton of bituminous coal produces approx-
imately 3 to 4 gallons of light oil, fractional distillation of this light
oil is one commercial means of producing benzene. However, some amount of
benzene is present in nearly all crude oils, and production of benzene from
petroleum and petrochemical sources far exceeds that from coal. Other means
of producing benzene include synthesis from acetylene and hydrocarbons, such
as hexane. Benzene is used primarily in the synthesis of styrene (for
plastics), phenol (for resins), and cyclohexane (for nylon). Other uses
include the production of detergents (alkylbenzenes), drugs, dyes, and
insecticides. Benzene is still being used as a solvent and as a component
of gasoline (17).
Conventional Treatment
No data are available. See Discussion, Section 4.
Oxidation
Hoigne and Bader removed 97 percent of 80 vg/L benzene in lake water
with 2.8 mg/L ozone (46).
Aeration
No data are available. See Discussion, Section 4.
Adsorption
Dobbs and Cohen (40) developed an adsorption isotherm for benzene in
distilled water using pulverized Fitrasorb® 300 granular activated carbon.
Benzene was measured by ultraviolet absorbence, and this necessitated using
relatively high (20 mg/L) initial concentrations of benzene. Weber (62), on
the other hand, developed isotherms on several different types of activated
carbon by using gas chromatography and much lower initial benzene concentra-
*See Table 1, page 6, for properties.
55
-------
tions
Weber'
other
later
this yielded considerably higher capacities. Figure 18 compares
"s isotherm on Filtrasorb® 400 with that of Dobbs and Cohen. Weber's
Freundlich parameters for benzene are given in a figure presented
in the text (Figure 30). At an equilibrium concentration of 100
the capacity for benzene predicted from Weber's isotherms ranged from
5.6 to 12.4 mg/g; the capacity from Dobbs' and Cohen's isotherm was 0.03
mg/g. When these procedures are compared for 1,4-dichlorobenzene, however,
the resulting isotherms are in agreement.
O'Brien's group (64) reported a carbon usage of 1.1 lb/1000 gal to
reduce a typical benzene concentration of 5 mg/L to less than 10 yg/l in a
contaminated ground water.
Boiling
See Discussion, Section 4.
1,000
E
O)
zf
o
CO
or
LU
-z.
UJ
N
•z.
LU
00
O
LU
00
DC
O
C/3
Q
100
10
I I I lllll| 1 I I MIM| 1 I I I I 11±
Structure
B
Freundlich
Parameters
Isotherm
A
K 49.3
l/n 0.6
B
29.5
0.4
C
16.6
0.4
D
14.2
0.4
E
1.0
1.6
1.0
0.001
I I I MM
Mill
0.01 0.1 1-0
EQUILIBRIUM CONCENTRATION, mg/L
ilil
10
figure 18. Isotherms for Benzene Adsorption on Activated Carbon.
\
56
-------
CHLOROBENZENE*
Structure
Other Names (31-33)
benzene chloride; Chlorbenzene; Chlorbenzol; MCB; monochlorobenzene;
phenylchloride; Monochlorobenzene
Chlorobenzene is produced by reacting chlorine with benzene in the
presence of a catalyst such as ferric chloride (FeCla). Large amounts of
Chlorobenzene were produced during World War I to make picric acid, but
currently its major use is as a solvent, in the manufacturing of phenol,
DDT, insecticide, dyestuffs, and as an intermediate in the manufacturing of
other compounds (17).
Conventional Treatment
When a Chlorobenzene spill was tracked through a Louisville treatment
plant over a 4-day period, raw water concentrations ranged from 0.1 to 5.0
yg/L, and finished water concentrations ranged from 1.1 to 8.5 mg/L, sug-
gesting that conventional treatment (presedimentation, coagulation, sedi-
mentation, filtration) provided poor control (65).
Aeration
In a laboratory study where distilled water containing an average of
97 yg/L Chlorobenzene was passed through a diffused-air aerator, the Drinking
Water Research Division found a 90 percent reduction in Chlorobenzene con-
centrations at a 15:1 air-to-water ratio. Other aeration conditions and
corresponding percent removals are shown in Section 4, Figure 26.
Adsorption
Dobbs1 and Cohen's (40) adsorption isotherm for Chlorobenzene in
distilled water and pulverized FiltrasortP 300 granular activated carbon is
shown in Figure 19. Using this isotherm, at an equilibrium concentration of
100 vg/L, the predicted capacity is 9.3 mg Chlorobenzene per gram of acti-
vated carbon. These isotherm data, however, were determined by ultraviolet
absorbence and the initial Chlorobenzene concentration was 26 mg/L. No
field data are available for adsorption of Chlorobenzene from contaminated
waters.
*See Table 1, page 6, for properties.
57
-------
Boiling
See Discussion, Section 4.
10,000
- I I I I I III)
Cl
O
CO
cc
LU
2
LU
M
LU
00
O
or
O
n:
o
Q
LU
CO
or
O
CO
Q
1,000
100
Structure
10
0.001
i i i rriTF
Freundlich Parameters
K = 91
l/n = 0.99
I I I I I III! I I II I I III I I I I II III I I
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
i i i i ii
10
Figure 19. Isotherm for Chlorobenzene Adsorption on Activated Carbon.
58
-------
1,2-DICHLOROBENZENE1
Structure
Cl
Other Names (31-33)
o-dichlorobenzene; ortho-dichlorobenzene; Chloroben; Dilatin DB; Dowtherm E;
DCB; dichlorobenzene; o-Dichlorbenzol; Dizene; NC1-C54944; ODB; ODCB; two
dichlorobenzene; Orthodichlorobenzol; Special Termite Fluid; Termitkill
1,2-Dichlorobenzene can be produced by chlorinating chlorobenzene in
the presence of ferric chloride. It is used as a solvent for waxes, oils,
and asphalts, as a metal degreasing agent, and as an insecticide for ter-
mites and locust borers (17, 33).
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing an average of
151 yg/l 1,2-dichlorobenzene was passed through a diffused-air aerator, the
Drinking Water Research Division found a 74 percent reduction in the average
concentrations at a 15:1 air-to-water ratio. Other aeration conditions and
corresponding percent removals are shown in Section 4, Figure 26.
Adsorption
Isotherm data are presented
dichlorobenzene section.
Boiling
See Discussion, Section 4.
in Figure 20. For discussion, see 1,4-
*See Table 1, page 6, for properties.
59
-------
10,000
E
OJ
zf
o
00
cc.
<
o
I ] I I I I III) I I I I I IIIJ I 1 I I 11 ll( I I I I I I
Cl Cl Cl
Structure
1 ,000
LU
2
LU
N
LU
CO
O
cc
o
_J
I
o
Q
Q
LU
CO
OC
O
C/D
Q
100
14-
Filtrasorb® 300
(40)
K 226 121 129 118
l/n 0.4 0.5 0.4 0.4
10
0.001
I I I I I III! I I I I I Nil I I I I il III I I I I I I
11
0.01 0.1 1.0
EQUILIBRIUM CONCENTRATION, mg/L
10
Figure 20. Isotherms for Dichlorobenzene Adsorption on Activated Carbon.
60
-------
1,3-DICHLOROBENZENE*
Structure
Other Names (31, 33)
m-dichlorobenzene; m-Dichlorobenzol; meta-diclorobenzene; m-Phenylene
dichloride; MCDB
1,3-Dichlorobenzene is usually produced by heating 1,2-dichlorobenzene
or 1,4-dichlorobenzene under pressure in the presence of aluminum or hydro-
gen chloride (17). As a solvent, its behavior is similar to that of
1,2-di chlorobenzene.
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing an average of
229 vg/L 1,3-dichlorobenzene was passed through a diffused-air aerator, the
Drinking Water Research Division found a 79 percent reduction in
1,3-dichlorobenzene concentrations at a 15:1 air-to-water ratio. Other
aeration conditions and corresponding percent removals are shown in Section
4, Figure 26.
Adsorption
Isotherm data are presented in Figure 20.
1,4-dichlorobenzene section.
Boiling
See Discussion, Section 4.
For discussion, see
*See Table 1, page 6, for properties.
61
-------
-------
1,4-DICHLOROBENZENE*
Structure
Other Names (31-33)
p-dichlorobenzene; para-dichlorobenzene; Parazene; Di-chloricide; Paramoth;
p-chlorophenyl chloride; Evola; Paradi; Paradow; PDB; Persia-Perazol;
Santochlor
1,4-Dichlorobenzene is produced by chlorinating benzene in the presence
of ferric chloride. Unlike 1,2-dichlorobenzene or 1,3-dichlorobenzene,
1,4-dichlorobenzene has a pungent, camphoric odor. Its principal uses are
in moth control (balls, powders, etc.) and as lavoratory deodorants (17).
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing an average of
225 ug/L, 1,4-dichlorobenzene was passed through a diffused-air aerator,
the Drinking Water Research Division found a 77 percent reduction in 1,4-
dichlorobenzene concentrations at a 15:1 air-to-water ratio. Other aeration
conditions and corresponding percent removals are shown in Section 4,
Figure 26.
Adsorption
Dobbs and Cohen (40) developed adsorption isotherms for the isomers of
dichlorobenzene; Weber (62) included 1,4-dichlorobenzene in an adsorption
study. All the results are shown in Figure 20. At an equilibrium concen-
tration of 100 ug/L, 1,2-, 1,3-, and 1,4-dichlorobenzene would have an
estimated capacity of 51, 47, and 58 mg solvent per gram of activated car-
bon, respectively. Initial isotherm concentrations ranged from 17 to 28
mg/L for all four isotherms. Dobbs and Cohen used ultraviolet absorbence,
and Weber used gas chromatography to determine final concentrations. Little
difference is noticeable among the various isomers with regard to their
behavior on activated carbon. No field data are available for adsorption of
1,4-dichlorobenzene or its isomers from contaminated waters.
*See Table 1, page 6, for properties.
63
-------
Boiling
See Discussion, Section 4.
64
-------
1,2,4-TRICHLOROBENZENE*
Structure
Other Names (31-33)
Pyranol 1478; trichlorobenzene; unsym-trichlorobenzene
Chlorination of benzene yields three isomers of trichlorobenzene: 1,2,
3-trichlorobenzene, 1,2,4-trichlorobenzene, and 1,3,5-trichlorobenzene. Of
these isomers, only 1,2,4-trichlorobenzene is commercially produced in any
quantity. 'It is mainly used as a dye carrier, and an herbicide inter-
mediate, but it is also useful as a heat transfer medium, a dielectric fluid
in transformers, and a degreaser (66).
Conventional Treatment
No data are available. See Discussion, Section 4.
Aeration
In a laboratory study where distilled water containing an average of
259 yg/L 1,2,4-trichlorobenzene was passed through a diffused-air aerator,
the Drinking Water Research Division found a 68 percent reduction in concen-
tration of this compound at a 15:1 air-to-water ratio. Other aeration con-
ditions and corresponding percent removals are shown in Section 4, Figure
26.
Adsorption
Dobbs and Cohen (40) developed an adsorption isotherm for 1,2,4-
trichlorobenzene in distilled water and pulverized Filtrasorb® 300 granular
activated carbon. They used ultraviolet absorbence and an initial concen-
tration of 15 mg/L. Using the Freundlich parameters given in Figure 21 at
an equilibrium concentration of 100 u9/L, the capacity for this organic
compound on activated carbon is 77 mg 1,2,4-trichlorobenzene per gram
activated carbon. No field data are available for adsorption of trichloro-
benzene from contaminated water.
Boiling
See Discussion, Section 4.
*See Table 1, page 6, for properties.
65
-------
C 1 U,UUU
O5
Z~
O
CQ
or
CJ
c/5
E
g 1,000
LU
N
z
LU
CQ
0
rr
O
1
_J
X
0
£ 100
4
CN
*~
Q
LU
CQ
or
O
CO
Q
< 10
I I I I I I III) I I I I I 1 1 Ij 1 I II 1 1 ll( 1 1 1 1 1 ll±
: ci ^
— i __
- s^Scl
or
- i>^/j
>Y^
I Structure
- ci —
— —
—
~—
"" ^^^* —
— . ^^^^ _
u 00 ^^x
, (R) O ^^^^
^®^^
— \**Q^ -^^^ —
fxV^X*-^
^**^
— —
"™
— —
_ Freundlich Parameters
K = 157
l/n=0.31 _
I 1 1 I I (III 1 1 1 1 1 1 III 1 1 I! II III 1 1 1 II 1 II
0.001 0.01 0.1 1.0 K
EQUILIBRIUM CONCENTRATION, mg/L
21. Isotherm for 124 Trirhin, K
Carbon. ^^-Trichlorobenzene Adsorption on Activated
66
-------
SECTION 4
DISCUSSION OF TREATMENT ALTERNATIVES
CONVENTIONAL TREATMENT
In full-scale water treatment plants, tetrachloroethyl ene (7), cis-
1,2-dichloroethylene (48), 1,2-dichloroethane (35, 58), carbon tetrachlor-
ide, and chlorobenzene (65) were not removed by coagulation, sedimentation,
and filtration. In a study during which 1,2- and 1,4-dichlorobenzene and
1,2,4-trichlorobenzene were found in the raw waters of four full-scale
treatment plants, they were also found in the finished waters at concentra-
tions within the analytical variation of those in the raw waters. It can
therefore be concluded that conventional treatment was ineffective for their
control (55). It is unlikely, therefore, that other chloroethylenes,
-ethanes, -methanes, and -benzenes would be effectively controlled by con-
ventional treatment.
AERATION
Laboratory and field experimentation demonstrated that air stripping is
a means for lowering the concentration of most of these contaminants in
drinking water. In a USEPA Drinking Water Research Division experiment, tap
water samples were spiked with trichloroethylene and tetrachloroethylene
alone and in combination, and then they were aerated. No significant
difference was observed in the removal efficiency of the individual
solvents, whether they were alone or combined. This is important because
mixtures of solvents exist in contaminated water and even though the
effectiveness of the process varies for each solvent, aerating to remove one
specific contaminant will also reduce the concentration of the others. A
good example of this is given in Table 12. Although aeration was employed
to remove tetrachloroethylene, the concentrations of the other solvents were
also reduced. In this illustration, if the concentrations are simply added,
the water contains approximately 460 yg/L of volatile organics before
aeration and 40 yg/L afterwards, for about 92 percent overall removal
efficiency.
Henry's Law Constant is useful in estimating whether or not aeration
should be considered (24). The removal of a contaminant by aeration gen-
erally increases with Henry's Law Constant (Table 12). Thus, although no
empirical data were available for control of many of these volatile com-
pounds with aeration, the summary presentation of the constants in Figure 22
suggests the relative ease by which they might be removed by air stripping.
Figures 23 to 26 compare available empirical data with a theoretical optimum
67
-------
removal developed by using tha reciprocal of the Henry's Law Constants given
in Reference 22. An explanation of this concept is given in Reference 67.
TABLE 12. EFFECTS OF AERATION ON A SOLVENT-CONTAMINATED
GROUND WATER*
A v_e_r_ a_ge_ j^o n c e n t r a t i o n ,
Contaminant Before After Percent Henry's Law
___ __ er° ^ 3remoal Co n stant
1,1-Dichloroethylene 122 4 97 7.8 (22)
1,1,1-Trichloroethane 237 23 90 1.2 (22)
Tetrachloroethylene 94 9 90 1.1 (21, 22)
Trichloroethylene 3 0.4 87 0.5 (21, 22)
cis-l,2-Dichloroethylene 0.5 <0.1 >80 0.31 (22)
1,1-Dichloroethane 6 1 83 0.24 (22)
1,2-Dichloroethane 1.4 0.8 42 0.05 (21, 2?)
*USEPA Drinking Water Research Division study in New Jersey.
~f"Diffused-air aeration, 10-minute contact: 4:1 (volume) air-to-water;
Water depth = 0.3m.
Whether or not the exhaust gasses create a problem with aeration has
been questioned. In one USEPA-DWRD sponsored aeration project, the princi-
pal investigator sampled for volatile solvents in the air near the top of
the aerator and identified trichloroethylene, tetrachloroethylene, 1,1,1-
trichloroethene, and 1,2-dichloroethane. The mean concentrations were far
below allowable occupational exposures (68). This air sampling program is
continuing, but the likelihood of creating an air pollution problem by
aerating solvent contaminated drinking water is remote given existing air
quality standards. Another topic of investigation by USEPA is the potential
for water quality deterioration from air-borne particulates, oxidized inor-
ganics, and microbiological growth in the aeration device. These are not
thought to be significant problems, but are currently (1982) being investi-
gated to more fully understand the aeration process.
ADSORPTION
Like aeration, adsorption has a spectrum of effectiveness. This proc-
68
-------
l_l
0.1
Ease of stripping
1.0
_ Concentration in air, jjg/L
~~ Concentration in water,jjg/L
10
100
1000
• Carbon Tetrachloride
Tetrachloroethylene
1,1,1 -Trichloroethane
Trichloroethylene I
Chlorobenzene I
Benzene 1,1-Dichloroethylene
Cis-1,2-Dichloroethylene
Trans-1,2-Dichloroethylene
1,4-Dichlorobenzene
1,3-Dichlorobenzene
_ Methylene Chloride
1,2-Dichloroethane
1,2-Dichlorobenzene
.1,2,4-Trichlorobenzene
Vinyl Chloride
Compiled from references
17-19,32
Figure 22. Comparison of Henry's Law Constants for Selected Organics.
69
-------
TOO
10
o
Z
Z
™
<
^
«2
LU „ ~
rr 1.0
i-
•^
LU
O
QC
LU
a- 0.1
nm
^ •^^^ |- i | |
N« f D
f^ * ° -"
\
I
—
i
:«:D u°
• • °
• . Q —
8
•
;
i «
1 Trichloroethylene
1 * —Theoretical Optimum Performance* _
1 * ^ »Diffused-air, USEPA-DWRD
DDiffused-air, NKRE (36, 37)
*Based on Henry's Law Constant
• —
1 1 1
0.1:1
100
10
o
z
z
<
K 1.0
LU
O
DC
LU
0.1
0.01
0.1:1
1:1
10:1 100:1
AIR TO WATER RATIO
1000:1
I
I
Tetrachloroethylene
"—Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD
DDiffused-air, NKRE (36, 37)
*Based on Henry's Law Constant
ll
_L
_L
1:1
10:1 100:1
AIR TO WATER RATIO
1000:1
Figure 23. Comparison of Actual and Theoretical Removal of Trichloro-
ethylene and Tetrachloroethylene from Drinking Water by Aera-
tion.
70
-------
100
10
O
z
z
<
£ 1.0
z
111
(J
cc
LU
Q- 0.1
0 01
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A V AA
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1 A
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1 1
0.1:1 1:1 10:1
1 1
A
A
A A
A
1,1,1-Trichloroethane (methyl chloroform)
•"•Theoretical Optimum Performance* —
• Diffused air, USEPA-DWRD
DDiffused air, NKRE (36, 37)
Apacked Tower, Kelleher, et al (54)
*Based on Henry's Law Constant
I 1
100:1 1000:1
AIR TO WATER RATIO
1OO
10
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5
111
£ 1.0
K
z
LU
cc
LU
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1
1
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0.1:1 1:1 10:1
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Carbon Tetrachloride
—Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD ~
1,2-Dichloroethane
— —Theoretical Optimum Performance*
ODiffused-air, USEPA-DWRD
*Based on Henry's Law Constant —
, ,
100:1 1000:1
AIR TO WATER RATIO
ing Water by Aeration.
71
-------
100
o
z
z
10
£ 1.0
z
LJJ
O
QC
LU
Q- 0.1
0.01
0.1:1
1:1
Cis-1,2-Dichloroethylene
—Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD
D Diffused-air, NKRE (36,37)
Methylene Chloride
— —Theoretical Optimum Performance*
ODiffused-air, USEPA-DWRD
*Based on Henry's Law Constant
1
1
10:1 100:1
AIR TO WATER RATIO
1000:1
100
10
e?
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^
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cr 1.0
H-
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i
Trans- 1,2-Dichloroethylene
—Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD
1 , 1 -Dichloroethylene
— —Theoretical Optimum Performance*
ODiffused-air, USEPA-DWRD
*Based on Henry's Law Constant
1 1 1
0.1:1 1:1 10:1 100:1 1000:1
AIR TO WATER RATIO
Figure 25. Comparison of Actual and Theoretical Removal of Cis- and Trans-
1,2-Dichloroethylene, Methylene Chloride, and 1,1-Dichloroethy-
lene from Drinking Water by Aeration.
72
-------
100
10
01
o
rr
in
0.1
0.01
0.1:1
1:1
Chlorobenzene
Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD
1,2,4-Trichlorobenzene
• —Theoretical Optimum Performance*
a Diffused-air, USEPA-DWRD
Benzene
— —Theoretical Optimum Performance*
(No data available)
*Based on Henry's Law Constant
I
I
10:1 100:1
AIR TO WATER RATIO
1000:1
100
10
o
z
z
<
2
£ 1.0
h-
z
LU
O
cc
LU
o- 0.1
0.01
<§> I ' ^-^^ 1 1 1
Vfi-
vv ®
[ 1
1
,
1
1
1
,
1 II
1
1 1,2-Dichlorobenzene
• <— — Theoretical Optimum Performance*
• Diffused-air, USEPA-DWRD
—
1 ,4-Dichlorobenzene
— —^Theoretical Optimum Performance*
O Diffused-air, USEPA-DWRD
1,3-Dichlorobenzene ~~
-— —Theoretical Optimum Performance*
(No data available)
•Based on Henry's Law Constant
1 |
i i
0.1:1 1:1 10:1 100:1 1000:1
AIR TO WATER RATIO
Chlorobenzene from Drinking Water by Aeration
73
-------
ess, however, is more complicated than aeration and water quality can have
a definite influence on performance. Figure 27 summarizes the data from
several adsorption isotherm studies and for purooses of illustration, the
adsorption capacity for each contaminant is shown at an equilibrium concen-
tration of 500 yg/L. Table 13 incorporates this isotherm data with avail-
able empirical data (mostly from pilot scale studies), so actual can be
compared to theoretical loadings. Note, even though the isotherm capacities
represent pure compound adsorption without competition, and the empirical
capacities represent adsorption in competition with background organics, in
most cases, the actual loadings are higher than the isotherm predicts. This
was unexpected, and the difference is perhaps the result of biodegradation
or perhaps suggests a need for revision in isotherm procedures.
Concern has been expressed about having contaminants concentrate on an
adsorbent then subsequently be released abruptly because of changing condi-
tions. This has not been experienced. Researchers (8, 37, 48, 51, 62, 63,
and others) have observed, however, periods when the effluent concentrations
of an organic can exceed its influent value after passing through an
adsorbent. This phenomenon is not apparent in Figure 28, where the organic
concentrations are simply added together to assess overall performance, but
some desorption is occurring when individual organic behavior is examined.
Note Figure 12 after week 50 on the unaerated flow stream in Mew Jersey and
between weeks 40 and 50 in Connecticut. In these examples, the concentra-
tion of 1,1,1-trichloroethane in the effluent from the activated carbon
adsorber is higher than in the influent, but like others have observed, this
occurs when the influent concentration of adsorbate declines and the resul-
ting desorption or "leakage" can be explained- by adsorption equilibrium
theory.
The synthetic resin, Ambersorb® XE-340 looked very promising because it
had a high capacity for most of these contaminants (Table 14). Field data
indicated that the resin's capacity was typically two to three times that of
activated carbon (on a weight basis) for control to breakthrough. Recently
(1982), however, the manufacturer announced that this resin would not be
produced commercially, so the future of adsorption by synthetic resins is
questionable.
BOILING
Boiling is oftentimes suggested as a means for consumers to decontami-
nate drinking water. Five minutes of vigorous boiling in shallow open ves-
sels has been shown to remove an average of 99 percent or more of trichloro-
ethylene, tetrachloroethylene, 1,1,1-trichloroethane, and carbon tetrachlor-
ide (44, 57), whose boiling points or azeotropic boiling points are below
that of water. The Drinking Water Research Division developed a boil inn
protocol* to compare relative efficiencies of removal. This laboratory data
is summarized in Table 15 and in general, the spectrum of removal (i.e. the
most easily removed group to the most difficult) is:
Chloroethylenes >chloroethanes >aromatic hydrocarbons >halobenzenes
*Details on this procedure are available from the authors.
74
-------
Mean Adsorption Capacity, mg/gm @ Equilibrium Concentration = 500 /ug/L
1.0 10
'
f
1 , > 1 A A f
I Benzene— \ •— Trichloroethylene
Methylene Chloride |— ' 1
Tetrachloride
Chlorobenzene
Cis-1.2-Dichloroethylene
1,2-Dichloroethane 1 L 1.1,1-Trichloroethane
I — 1,1-Dichloroethylene
Freundlich
Parameters
K l/n
Benzene 1 .0 1 .6*
16.6 0.4**
49.3 0.6t
29.5 0.4tt
14.2 0.4§
Carbon Tetrachloride 11.1 0.8*
28.5 0.8t
38.1 0.7**
25.8 0.7tt
14.2 0.7§
14.8 0.4§§
Chlorobenzene 91.0 1.0*
1,2-dichlorobenzene 129.0 0.4*
1,3-dichlorobenzene 118.0 0.4*
1,4-dichlorobenzene 121.0 0.5*
226.0 0.4**
1,2-dichloroethane 3.6 0.8*
5.7 0.5§§
cis-1,2-dichloroethylene 8.4 0.5§§
6.5 0.7$
100
y
s
r^ \
1 ,2.4-Trichlorbenzene
1 ,4-Dichlorobenzene
r 1,2-Dichlorobenzene
H 1,3-Oichlorobenzene
L Tetrachloroethylene
Freundlich
Parameters
trans-1 ,2-dichloroethylene
1 ,1 -dichloroethylene
Methylene chloride
Tetrachloroethylene
1 ,2,4-trichlorobenzene
1,1,1 -trichloroethane
Trichloroethylene
Vinyl chloride
K l/n
3.1 0.5»
4.9 0.5*
1.3 1.2*
1.6 0.7***
50.8 0.6*
84.1 0.4§§
273.0 0.6***
157.0 0.3*
2.5 0.3*
9.4 0.5§§
28.0 0.6*
26.2 0.5J
28.2 0.4§§
Not Reported
Freundlich equation:
x/m(mg/gm) = K C.(mg/l)l/n
•Filtrasorb® 300(40) §Hydrodarco® 1030 (62) fNorit(62)
••Filtrasorb® 400(62) §§Witcarb® 950 ttNuchar® WV-G(62)
•••Filtrasorb® 400(47) JFiltrasorb® 300
Figure 27. Comparison of Isotherm Adsorption Capacities on Activated Carbon.
75
-------
TABLE 13. ADSORPTION OF VOLATILE ORGANIC COMPOUNDS BY GRANULAR ACTIVATED CARBON, SUMMARY
Loading, m3/m3(a)
Trichloroethylene
Tetrachl oroethyl ene
1 ,1 ,1-Trichloroethane
Carbon Tetrachloride
Cis-l,2-Dichloroethylene|
Vinyl Chloride
1 ,2-Dichloroethane
1 , 1-Dichloroethylene
Benzene
Methylene Chloride
Avg.
cone.,
177
4
3*
0.4**
1400
94*
9**
4
1
100
237*
23**
38
1
12
18
6
2
7
8
1.4*
0.8**
2
122*
4**
5000
20,000
Bed depth,
m (ft)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.6 (2)
1.2 (4)
1.8 (6)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
1.5 (5)
2.3 (7.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
1.5 (5)
2.3 (7.5)
3.1 (10)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.9 (3)
1.8 (6)
2.7 (9)
3.6 (12)
0.8 (2.5)
0.7 (2.4)
0.8 (2.5)
0.8 (2.5)
2.9 (9.4)
2.7 (8.8)
EBCT,
min
9
8.5
18
18
9
18
18
8.5
9
7.5
15
22.5
18
18
8.5
9
10
5
6
12
18
9
8.5
5
12
18
25
20
18
18
11
22
33
44
17.5
17
18
18
54
262
Breakthrough
0.1 pg/L
(except as noted)
>20,160
>60,900 but <123, 340
>32,500
>32,500
12,300
>32,500
>32,500
>60,900 but <123,340
>20,160
l,300f
2,700f
3,900f
15,700
>32,500
11,800
16,400
14,000
6,050
4,100
7,100
8,100
14,200
29,600
810
1,250
2,800
2,050
1,700
17,400
>32,500
3,300
3,400
4,150
?7,000
2,500
2,500
22,400
>33,600
3,030?
860
Exhaustion
(inf = eff)
>20,160
>123,340
>32,500
>32,500
33,100
>32,500
>32.500
>123,340
>20,160
not reported
not reported
not reported
30,800
>32,500
26,000
22,500
25,000
not reported
15,800
14,300
13,700
19,000
48,600
2,400
Exhaustion
capacity,
m3/m3
(b)
21,500
99,900
106,560
199,800
17,500
57,400
162,800
237,600
475,200
3,800
3,800
3,800
2,600
12,000
9,400
94,400
9,400
9,400
9,400
9,400
9,400
15,300
26,000
Isotherm
Reference
USEPA-DWRD
"
11
"
USEPA-DWRD
"
"
11
"
(54)
11
USEPA-DWRD
"
11
"
(63)
"
(48)
11
"
USEPA-DWRD
"
(48)
not reported "
-
5,011
8,640
45,900
> 32, 500
9,160
7,850
>7,000
>7,000
7,450
7,450
>33,600
>33,600
>3,030
860
3,500
5,700
5,000
4,000
4,000
4,000
4,000
4,000
4,000
5,600
31,100
4,100
600
"
"
(58)
USEPA-DWRD
"
(35)
"
11
"
"
"
USEPA-DWRD
(64)
(64)
Ta~) m3 water/m^^arbon
(b) Predicted by Freundlich isotherms. Reference 40.
* Adsorption of unaerated water; ** Adsorption after 10-minjte aeration 0 4:1 (volume) air-to-water
f 5 u9/L in effluent; (? 10 ug/L in effluent
| Isotherm capacities based on Reference 40 trans-1, 2-dichloroethylene
76
-------
1000
.- 100
y
z
o
DC
O
UJ
§
O
LL
O
Z
o
ID
C/)
- Influent
New Jersey groundwater
Aeration: 4:1 (vol. to vol.)
Adsorption on Witcarb® 950
EBCT = 18 min.
C'
t
10
Aerator Effluent
Activated Carbon Effluent
I I
\*
I
t?y
I
I
i
i
i
1
rj,
j
if
fluent T 1
Concentration, /jg/L
Time a b
A 261 118
B 20 9
C <0.1 <0.1
A' - 264 99
B' 14 5
C' 95 0.1
a-1 ,1 ,1 -trichloroethane
b-tetrachloroethylene
c-1 ,1 -dichloroethylene
1
j Adsorption Following
i
1 n1 1 1 1 1 1
c d e I
76 7 2 464
2 1 0.2 32
<0.1 <0.1 <0.1 <0.1
179 7 3 552
1 1 0.2 21
<0.1 2 <0.1 97
d-1,1 plus 1,2-dichloroethane
e-trichloroethylene
Aeration
\ ,
0
Figure 28.
10 20 30 40 50
TIME IN SERVICE, WEEKS
60
70
Removal of Volatile Organic Compounds by Aeration and Adsorp-
tion on Granular Activated Carbon (Pilot Scale Study).
77
-------
TABLE 14. ADSORPTION OF TRICHLOROETHYLENE AND RELATED SOLVENTS BY AMBERSORB® XE-340, SUMMARY
Trichloroethylene
Tetrachloroethylene
1, 1, 1-Trichloroethane
Carbon Tetrachloride
Cis-1 ,2-Dichloroethylene
1 ,2-Dichloroethane
1 , 1-Dichloroethylene
Avg. cone,
ug/L
215
210
210
177
4
3
41
51
65
70
94
1400
3
2
5
33
237
23
1
19
19
40
38
40
40
25
22
16
6
2
1
122
4
Empty bed Loading to 0.1 yg/L
Bed depth, contact time, breakthrough,
m (ft) minutes m3/m3*
0.3 (1)
0.6 (2)
1.2 (4)
0.8 (2.5)
0.8 (2.5)
0.2 (0.8)
0.3 (1)
0.6 (2)
1.2 (4)
0.3 (1)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
1.2 (4)
0.8 (2.5)
0.2 (0.8)
0.2 (0.8)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.3 (1)
0.6 (2)
1.2 (4)
0.3 (1)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.8 (2.5)
0.2 (0.8)
0.2 (0.8)
0.2 (0.8)
2
4
7.5
9
8.5
5
2
4
7.5
2
5
9
8.5
9
7.5
9
5
5
9
5
10
2
4
7.5
2
6
6
6
9
8.5
5
5
5
83,700**
78,600**
>53,300**
>20,160
>123,340
>117,000
>99,900**
78,600**
>53,300**
106,000**
112,900
17,920
>123,340
>20,160
39,300**
56,000
82,600
> 100, 800
>20,160
7560
15,120
37,200**
39,500**
19,700**
36,400**
14,400
7200
11,500
>20,160
>59,000 but<123,340
108,860
80,600
110,800
Reference
37
ii
"
8
USEPA-DWRD
"
37
11
n
11
USEPA-DWRD
"
11
8
37
8
USEPA-DWRD
11
8
8
8
37
ii
11
"
48
11
11
8
USEPA-DWRD
USEPA-DWRD
USEPA-DWRD
*m3 water/m3 carbon
**Breakthrough defined by shape of wavefront curve; generally 20 to 25
adsorbent effluent
of contaminant in
78
-------
TABLE 15. REMOVAL OF VOLATILE ORGANIC COMPOUNDS FROM DRINKING HATER
BY BOILING, SUMMARY
Percent Remaining*
Organic Compound
Trichloroethylene
Tetrachl oroethyl ene
Ci s-1 ,2-Dichloroethylene
Trans- 1,2-Di chl oroethyl ene
1,1-Dichl oroethyl ene
Vinyl chloride
1,1,1-Trichloroethane
1,2-Dichloroethane
Carbon Tetrachl oride
Methyl ene chloride
Benzene
Chlorobenzene
1 , 2-Di chl orobenzene
1,3-Di chl orobenzene
1,4-Di chl orobenzene
1,2, 4-Tri chl orobenzene
1
18
14
24
14
10
16
39
13
28
33
31
38
29
42
39
2
10
8
14
9
6
8
31
7
20
26
22
28
20
34
31
Time of boil
3 4
5
4
8
1
3
4
24
3
13
18
13
21
13
26
23
2
2
5
< 0.1 <
0.9
No data
1
16
1
8
14
8
16
8
20
17
5
0
0
2
0
0
1
12
0
5
10
5
14
5
17
12
g, mm.
10
.7 <0.1
.8 < 0.1
< 0.1
.1 < 0.1
.2 <0.1
available
< 0.1
2
.5 <0.1
0.3
O.P
< 0.1
2
< 0.1
10
2
15
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
6
0.8
*Initial concentrations ranged from 88 to 1900
79
-------
-------
SECTION 5
ESTIMATED TREATMENT COSTS
In any economic analysis, the cost data presented are dependent on the
particular design assumptions made for the treatment system. For example,
the costs associated with aeration are quite sensitive to the removal effi-
ciencies. The cost of treatment, therefore, can vary significantly depend-
ing on the design parameters selected by the cost analyst and on site-
specific considerations. For this reason, these cost estimates should be
viewed as a preliminary attempt to quantify the economics of removing vola-
tile organic chemicals, such as trichloroethylene and related solvents, from
drinking water.
The first step is to estimate the cost required in developing a treat-
ment matrix. Influent concentrations were selected, and the treatment
necessary to achieve hypothetical effluent qualities* was then determined.
For aeration, air-to-water ratios were estimated (Table 15) by developing an
envelope around the empirical data in Figures 23, 24, and 25, and extrapo-
lating for the higher removal efficiencies.
Estimating the activated carbon usage necessary to achieve hypothetical
target levels (Table 16) was more complicated. First, two ratios were
established for each contaminant: a) capacity at exhaustion observed from
field studies divided by theoretical capacity determined from Dobbs' and
Cohen's (40) isotherm data and b) capacity at actual exhaustion divided by
capacity at actual breakthrough (Table 13). Isotherm capacities at the
given contaminant concentrations (1000, 100, 10, and 1 yg/L) were then mul-
tiplied by ratio "a" to give an estimated activated carbon usage to exhaus-
tion, and that value was then divided by ratio "b" to give an estimated
activated carbon usage to breakthrough. Carbon usage for intermediate
effluent concentrations were then estimated from a semi log plot (Figure 29).
The ranges of estimated aeration requirements and activated carbon
usage shown in Tables 15 and 16 are extremely wide for certain contaminant
concentrations, so on-site, pilot scale experimentation would be prudent if
treatment by either process is contemplated. For this purpose, however, it
does allow some preliminary estimates of treatment costs using computer cost
programs developed by Gumerman and others (69).
*Maximum contaminant levels have not been established for these organic
compounds. However, the USEPA Office of Drinking Water has developed
"Health Advisories" and has suggested (1) possible ranges for lifetime
exposure to selected organic chemicals.
81
-------
TABLE 16. ESTIMATED AIR-TO-WATER RATIOS NECESSARY TO ACHIEVE DESIRED TREATMENT, SUMMARY
00
ro
Inf. cone.
Trichloroethylene
Tetrachloroethylene
1 ,1 ,1-Trichloroethane
Carbon tetrachloride
Cis-1 ,2-Dichloroethylene
1 ,2-Dichloroethane
1,1-Dichloroethylene
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
Effluent concentration, ug/L
a
2:1
2:1
2:1
2:1
1:1
1:
1:
1:
6:
6:
6:1
6:1
1:1
1:1
1:1
1:1
4:1
4:1
4:1
3:1
20:1
20:1
20:1
18:1
0.1:1
0.1:1
0.1:1
<0,:l
0.1
b
40-136:1
25-100:1
10-66:1
3-34:1
25-320:1
17-150:1
11-65:1
6-30:1
60-600:1
21-260:1
10-120:1
4-52:1
_
-
-
-
14-152:1
10-115:1
8- 76 : 1
4-38:1
_
-
-
-
_
-
-
c
76:1
54:1
32:1
11:1
96:1
72:1
45:1
18:1
198:1
90:1
35:1
8:1
19:1
15:1
10:1
6:1
104:1
77:1
52:1
26:1
56:1
42:1
28:1
14:1
10:1
8:1
5:1
3:1
a
2:1
2:1
2:1
-
1:1
1:1
1:1
-
6:1
6:1
6:1
-
1:1
1:1
1:1
-
9:1
4:1
3:1
-
20:1
20:1
18:1
-
0.1:1
0.1:1
<0. 1 :1
1
b
25-100:1
10-66:1
3-34:1
-
17-150:1
11-65:1
6-30:1
-
21-260:1
10-120:1
4-52:1
-
.
-
_
-
10-115:1
8-76:1
4-38:1
-
_
-
-
-
_
_
-
c a
54:1 2:1
32:1 2:1
11:1
-
72:1 -1:1
45:1 <1:1
18:1
-
90:1 6:1
35:1 6:1
8:1
-
15:1 1:1
10:1 1:1
6:1
-
77:1 4:1
52:1 4:1
26:1
-
42:1 20:1
28:1 18:1
14:1
-
8:1 0.1:1
5:1 <0.1:1
3:1
10
b
10-66:1
3-34:1
_
-
11-65:1
6-30:1
_
-
10-120:1
4-52:1
_
-
_
_
_
-
8-76:1
4-38:1
-
-
_
-
_
-
_
_
_
c
32:1
11:1
_
-
45:1
18:1
_
-
35:1
8:1
_
-
10:1
6:1
_
-
52:1
26:1
_
-
28:1
14:1
_
-
5:1
_
_
50 100
a b c a b
2:1 4-44:1 17:1 2:1 3-34:1
--1:1 1-10:1 1:1 <1:1
_____
_
<1:1 8-36:1 26:1 <1:1 6-30:1
<1:1 2-7:1 1:1
_____
_
6:1 5-65:1 14:1 6:1 4-52:1
4:1 1-15:1 1:1
_
-
1:1 - 6:1 <1:1
<1:1 1:1
_____
_
4:1 5-50:1 34:1 4:1 4-38:1
2:1 2-10:1 4:1
_
-
20:1 - 18:1
10:1 -
_
-
0.1:1 - 3:1 <0.1:1
_
_
c
11:1
_
_
-
10:1
_
_
-
8:1
_
_
-
4:1
_
_
-
26:1
_
_
-
14:1
_
_
-
3:1
_
_
a = Theoretical optimum air-to-water ratio based on the reciprocal of the Henry's Law Constants given in Reference 22.
An explanation of this concept is given in Reference 67. For vinyl chloride, this optimum value is «0.1:1.
b = Range of air-to-water ratios extrapolated from actual experimentation. This is estimated by developing an
envelope around the data in Figures 23, 24, and 25, for log % remaining vs. air-to-water ratio.
c = Average air-to-water ratio calculated from "b".
-------
TABLE 17. ESTIMATED CARBON USAGE NECESSARY TO ACHIEVE DESIRED TREATMENT, SUMMARY
CO
CO
Desired effluent concentration,
Trichloro-
ethylene
1 ,1 ,1-Trichloro-
ethane
Tetrachloro-
ethylene
Carbon tetra-
chloride
Cis-1 ,2-Dichloro-
ethylene
1 ,2-Dichloro-
ethane
1 ,1-Dichloro-
ethylene
Inf. cone
yg/L
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
1000
100
10
1
0.1
a
5.7-10.5
13.8-25.3
33.1-64.6
79.4-146
0.17-6.1
b
6.9 (0.50)
16.7 (0.20)
41.0 (0.08)
96.1 (0.03)
1.7 (2.0)
0.79-28.0 8.1 (0.41)
3.6-127
16.0-580
10.6-16.2
29.2-44.4
80.4-122
221-337
2.9-6.6
4.3-9.8
6.4-14.4
9.5-21.4
0.6-1.4
1.8-4.4
5.5-13.5
17.0-41.6
0.8-5.2
1.1-8.4
1.6-12.5
2.4-18.4
2.5-8.5
7.1-24.6
20.4-71
59.0-205
37.0 (0.09)
169 (0.02)
14.7 (0.23)
40.1 (0.08)
111 (0.03)
306 (o.Ol)
4.8 (0.7)
7.0 (0.48)
10.4 (0.32)
15.5 (0.22)
1.1 (3.0)
3.3 (1.0)
10.1 (0.3)
31.1 (0.1)
2.0 (1.7)
3.5 (1.0)
5.2 (0.65)
7.6 (0.45)
5.5 (0.61)
15.9 (0.21)
45 (0.07)
132 (0.03)
1
a
7.8-11.3
20.2-27.9
56.3-72.1
-
0.19-7.5
0.88-36.0
4.3-186
-
17.7-21.8
55.0-66.7
186-208
-
5.0-7.9
8.8-12.3
16-20.1
-
1.0-1.6
3.5-5.3
13.0-17.8
-
1.3-7.0
2.2-13.0
3.8-22.6
-
3.3-11.5
10.4-36.4
34.8-120
b
8.7 (0.4)
22.1 (0.15)
60.3 (0.06)
-
2.6 (1.3)
13.0 (0.26)
70.0 (0.05)
-
20.7 (0.16)
59.6 (0.06)
200 (0.02)
-
6.5 (0.51)
10.6 (0.32)
18.0 (0.19)
-
1.3 (2.6)
4.2 (0.8)
14.6 (0.2)
- *
3.1 (1.1)
5.4 (0.62)
9.3 (0.36)
-
7.4 (0.45)
23.0 (0.14)
77.4 (0.04)
10
a
9.8-12.2
26.7-30.5
-
-
0.2-8.9
0.98-45.0
-
-
24.7-27.5
80.6-83.8
-
-
7.2-9.2
13.2-14.8
-
-
1.4-1.9
4.4-6.2
_
-
1.7-9.0
3.0-17.6
-
-
4.8-14.5
13.8-47.7
-
, H9/L
50
b
10.4 (0.32)
27.7 (0.12)
-
-
3.3 (1.0)
18.0 (0.19)
-
-
26.7 (0.13)
81.2 (0.41)
-
-
8.2 (0.41)
14.0 (0.24)
-
-
1.5 (2.2)
5.2 (0.65)
-
-
4.1 (0.82)
7.3 (0.46)
-
-
9.6 (0.36)
30.8 (0.11)
-
11.
31.
0,
1,
29.
99.
8.
16,
1 ,
4.
2.
3.
4.
16,
a
,2-12.7
,2-32.3
-
-
,21-9.9
.1-51.0
-
-
,5-31 .4
.0-101
-
-
.8-10.1
,1-16.6
-
-
.4-2.0
7-6.9
-
-
,0-11.1
,6-20.8
-
-
,8-16.6
,1-55.7
-
b
11.6 (0.29)
31.5 (0.11)
-
-
3.9 (0.86)
21.0 (0.16)
-
-
30.9 (0.11)
100 (0.03)
-
-
9.5 (0.35)
16.3 (0.21)
-
-
1.7 (2.0)
5.9 (0.55)
_
-
4.9 (0.68)
8.6 (0.39)
-
-
11.0 (0.31)
35.9 (0.09)
-
100
a b
11.8-13.0 12.1 (0.28)
-
-
-
0.22-10.3 4.2 (0.80)
-
-
-
31.7-33.2 32.7 (0.10)
_
-
-
'9.3-10.5 9.9 (0.34)
-
-
-
1.5-2.1 1.8 (1.9)
-
-
-
2.2-12.0 5.2 (0.65)
-
-
-
5.1-17.5 11.3 (0.29)
-
-
-) o
m water/m carbon, estimated from Reference 40
a = Granular activated carbon loading range, 10
isotherms and empirical data in Table 15.
b = Mean loading, 103 m3 water/m3 carbon (GAC usage, Ib carbon/103 gal water)
-------
CO
1,000
§?
^ 100
2
o
oc
o
z
o
o
LU
LU
10
0.1
1,1,1 -Trichloroethane
initial concentration-1000 fjg/L
I
Estimated Activated Carbon
Usage to Exhaustion (see text)
Estimated Activated Carbon
Usage to Breakthrough
(see text)
2,000(1.7) 3,000(1.1) 4,000(0.8)
ACTIVATED CARBON USAGE, mVm3 (lb/1000 gal)
5,000 (0.7)
Figure 29. Estimated Activated Carbon Usage to Achieve Target Effluent
Qualities.
-------
The cost analysis is based on 1.3 m3/min (500,000 gal/day) flow with
the treatment system shown in Figure 30. The ground water is treated by
tower aeration, diffused-air aeration, or granular activated carbon (GAC)
followed by chlorination, clearwell storage, and high-lift pumping.
The aeration towers are rectangular with an overall height of 3m (10
ft), and an air supply of 137 sLm/m2 (52 scfm/ft2) of surface area is
assumed. They have electrically driven, induced-draft fans, fan stacks, and
drift eliminators. The tower costs do not include supply pumps or underflow
pumps. The aeration basins are rectangular with a depth of 3.5 m (12 ft).
The diffused air supply system was sized for 14 sLm/m2 (5 scfm/ft2) of basin
flow area.
Adsorption consists of three steel contactors in series with an initial
supply of granular activated carbon. Activated carbon usage is based on
six-month throwaway at a cost of $1.50/kg ($0.70/lb). Chlorination consists
of a feed system (no basin) and a building for cylinder storage. A chlorine
dose of 2 mg/L is assumed, and the cost of chlorine is $0.35/kg ($320/ton).
Clearwell storage is above ground, with a capacity equal to 10 percent of
the daily plant flow. The high lift pumping has a head of 12 m (40 ft).
The estimated treatment cost does not include expenditures for land, slime
or corrosion control, fences, off-gas handling, or carbon disposal.
Figures 31 through 36 give the total treatment cost in dollars per 1000
gallons of treated water as a function of operating flow. Each figure shows
the 90 to 99 percent removal cost range in October 1980 dollars for aeration
towers, aeration basins, and adsorption for an influent contaminant concen-
tration varying from 1 to 1000 yg/L. The required aeration basin and tower
volumes for costing purposes were computed as a function of the mean air-
to-water ratios given in Table 15. The cost bands for aeration towers are
relatively narrow because little economy-of-scale exists for operating these
units at such small hydraulic loadings.
The activated carbon requirements were the mean values given in Table
16. The adsorption cost ranges are wider than those estimated for aeration
because of the influence of contaminant concentration. For example, the
cost of 90 percent removal by aeration is theoretically the same whether the
contaminant concentration is reduced from 1000 to 10 ug/L or from 1 to 0.1
ug/L. Adsorption capacity and activated carbon usage, however, vary with
contaminant concentration; therefore, the cost of 90 percent removal by
activated carbon is higher if the influent concentration is 1000 yg/L com-
pared to 100 yg/L. The cost range for adsorption is very wide for some con-
taminants because of poor adsorbability. To achieve high percentages of
removal for the poorly adsorbed contaminants, a large amount of activated
carbon is required, and this dramatically increases the cost of treatment.
Figure 37 illustrates another way of presenting the cost information
given in Figures 31 to 36. The total treatment cost of trichloroethylene
removal is shown as a function of influent concentration at four levels of
effluent concentration for each of the three treatment modes. Similar
graphs could be generated for the other contaminants. Figure 38 gives the
total treatment cost of trichloroethylene removal versus treatment plant
85
-------
Groundwater
Source
co
Aeration
Tower
Diffused
Air
Aeration
Granular
Carbon
Adsorption
Chlorination
Clearwell
High-Lift
Pumping
Flsure 30'
-------
2.0
ro
ro
O
O
O
1.0
O
O
UJ
LU
CC
0.1
0
I I I I
Granular Activated Carbon Adsorption
*
0.1
0.2
0.3
0.4
0.5 Operating Flow, mgd
2.0
"5
O)
O
O
O
r 1.0
o
o
LLJ
1
UJ
cc.
0.1
,
1
I I
Aeration
Basin
Tower
""
0 0.1 0.2 0.3 0.4 0.5 Operating Flow, mgd
0% 20% 40% 60% 80% 100% % of Design Flow
Figure 31. Cost of Trichloroethylene Removal (90-99%) (October 1980
Dollars, Influent Concentration of 1-1000 ug/L, Design
Flow of 0.5 mgd).
87
-------
TOTAL TREATMENT COST, $71000 gal
oo
TOTAL TREATMENT COST, $71000 gal
-------
10.0
CO
0)
O
O
o
X
o
u
1-
z
LU
TOTAL TREATMENT COST, $/1 000 gal TOTAL TREAT
o r* !° o :-
o •_» o o co o
~ : fa Granular Acti\
:: : l||||||||||l|
\\ \ i n nifii 1 1 M tin M ^
D 0.1 2.0
z~ A
hi
M| 90%
l|
/ated Carbon Adsorption _
:<^'
&/£
iimuiiiii^uiiiiiiiiiii
0.3 0.4 0.5
I =
sration ~r
Basin ~
e/7j
I \\\°Va' -
e')'o^^ 'M|||, Tower
"'III
) 0.1 0.2 0.3 0.4 0.5 Operating Flow, mgd
% 20% 40% 60% 80% 100% % of Design Flow
Figure 33. Cost of 1,1,1-Trichloroethane Removal (90-99%) (October 1980
Dollars, Influent Concentration of 1-1000 ug/L, Design Flow of
0.5 mgd).
89
-------
IU.U
"ro
O3
O
8
X
H
o
CJ
(-
z
LU
^
(-
£ 1.0
1-
o
h-
0.4
£ 1 1
Granular Act
vated Carbon Adsorp
1 -
ion
L—
„
r-
,
•*•:::::
—
-
-
f%V
-J""ll
— ^
0 0.1 0.2 0.3 0.4 0.5
2.0
to
O
0
o
^ 1.0
I—"
C/3
O
CJ
1-
z
LU
5
h-
LU
QC
1-
<
O
01
E 1 =
E~ Aeration ~^
-
-
_
—
—
|
I
t
I ".,
— •
_
_
— —
99^
^s/ ~
?(0
^ f)s
Basin ~
'*°ilffi?'
e/"°W ' ' ' ' 1 1 , Tower
""n,
1 1
0 0.1 0.2 0.3 0.4 0.5 Opera
0% 20% 40% 60% 80% 1 00% % of C
Figure 34. Cost of Carbon Tetrachloride Removal (90-99%) (October 1980
Dollars, Influent Concentration of 1-1000 yg/L, Design Flow of
0.5 mgd).
90
-------
re
35
00 o
• O o
en —' 01
35T^
id -s
Q. l/>
TOTAL TREATMENT COST, $71000 gal
TOTAL TREATMENT COST, $71000 gal
of
Ci s-1, 2-Di chl oroet
Influent Concentra
ene Re
on of
oval
-1000
90-99%) (October
yg/L, Design Fl
N5
o
§p
o
os
0
*3 b b
II II
/p; liiii
1 1 1 1 1 1 |
iiiiiiiiiii'd
7 c
• - - Q)
Httttttttitttitmim > i
:::::: ::::::? 3
F S
: : : ::::::::::* o
•! o o-
• • • •! ^ D
itiimiiiiin > 1
..,,,,,.,,,. D. —
II III III II IH rn 1
o
111 • TJ
, . , ., . , Q
: . . i
\ 1 1 1 I 1 1
980
of
-------
n>
oo
o o o
-h o o
—' (/>
O —-c+
• ft!
en -s o
00 -*,
13 »*
IQ i—«
ex »
•^—TO
to
ro
Concentra
-$
o
fD
r+
3-
Ol
3
n>
^3
n>
<
eu
TOTAL TREATMENT COST, $71000 gal
o
o-
o
n>
T
1.00
to o
-1 N)
_ o b
1 '" i I i I I iniiMiiirr
TOTAL TREATMENT COST, $71000 gal
-«>
§
0
/ =
CD
o5
3,
O
g
CD
05
J—' ' ' '' I lllll
O
3
(Q
Q.
-------
5.0
CD
O)
i—i Minn r
Granular Activated Carbon Adsorption
Effluent Concentration ( )
\
O 1.0
o
LU
oc
(0.1)
(10)
(1.0)
(100) -
0.1
J—I I
10
100
1000
5.0
CO
O5
O
O
o
C/5
O 1.0
U
LU
5
LU
OC
2
O
l-
0.1
(0.1)
(0.1)
I—I I II INI—
Aeration
Effluent Concentration ( )
(1.0)
(1.0)
(10)
T 1 I I II I I |
J
Basin
(100)
Tower
(100)
JLLL
J—I I I I I
10 100
INFLUENT CONCENTRATION,
1000
Figure 37.
Cost of Trichloroethylene Removal (October 1980 Dollars,
Effluent Concentrations of 0.1-100 yg/L, Design Flow of 0,5 mqd
Operating at 60% Capacity).
93
-------
2.0
15
x 1-0
H
(/>
O
O
1-
LU
2
*<
Ul
oc
_J
O
1 1 =
r- Granular Activated Carbon Adsorption -
t"1" —
Illliii
^5»
.M
0 0.1 0.2 0.3
0.3
0.2
O)
O
8
S l-°
c/)
O
0
1—
LU
5
111
cc
i-
_j
<
O
1-
0.1
i Aeration
0.4 0.5
c
^~ 'Illi =
" I I I I i ~
': 'Hllllnp"-.
: 'ii 'HI i
r- \ °°X-J.
,"a/ Basin 2
1 II I
"""i^.^. :
so* "Minn Tower
^efh ' 1 1 1 1 1 1 1 i ~"
°"»/ 1 1 1 1 1 1 I | | |
""
-
I
0 0.1 0.2 0.3 0.4 0.5
TREATMENT PLANT DESIGN FLOW, mgd
Figure 38. Cost of Trichloroethylene Removal (90-99%) (October 1980 Dollars,
Influent Concentration of 1-1000 ug/L, Operating Flow is 50% of
Design Flow).
94
-------
size for each treatment type. Operating flow is 50 percent of design flow
for these data, with an influent concentration of 1 to 1000 ug/L. Similar
cost information can be generated for the other contaminants. Note in these
estimates that operating a small treatment system at less than design flow
has a pronounced effect on unit costs.
As in any economic analysis, the cost data presented here are dependent
on the particular design assumptions that were made for the treatment
system. For example, the costs associated with both types of aeration are
quite sensitive to the removal efficiencies. The cost of treatment, there-
fore, can vary significantly depending on the design parameters selected by
the cost analyst and on site-specific considerations. For this reason,
these cost estimates should be viewed only as a preliminary attempt to
quantify the economics of removing trichloroethylene and related solvents
from drinking water.
95
-------
-------
SECTION 6
SUMMARY
Volatile organic chemicals occur in both untreated and treated drinking
water. In general, ground waters rather than surface waters are more likely
to have significant concentrations of these compounds. Some exceptions
might be during periods when a river is frozen over and volatile organics
cannot escape into the atmosphere, when upstream "spills" occur, or when
products used to treat or transport the water have contaminants.
The seriousness of having these organics in one's drinking water and
the establishment of acceptable limits are current topics of concern at
USEPA (1) that may not be resolved for some time. In the interim, however,
research is striving to better understand the effectiveness of different
water treatment processes to see what degree of volatile organic removal is
achievable so a utility can better assess the option of seeking an alterna-
tive source or providing treatment.
Although conventional treatment (coagulation, sedimentation, and fil-
tration) has been found to be largely ineffective for their control, these
organics can, however, be removed by aeration, adsorption on granular acti-
vated carbon or synthetic resins, or combinations of these processes.
Aeration, for example, preceding adsorption, seems very encouraging (Figure
28) and may be the combination needed for treating certain problem waters.
Because treatment information is lacking for many of the organic compounds
being found in drinking water, USEPA is continuing to gather data on the
effectiveness of the aeration and adsorption processes, as well as beginning
treatment studies on the effects of strong oxidants, such as ozone, and the
process of reverse osmosis. Boiling (vigorously for five minutes) can also
be effective for removing most of these organic compounds. Where treatment
data were available, preliminary estimates of treatment costs show signifi-
cant variations between process and contaminants and amplify the need for a
thorough organic analysis and site-specific experimental data.
97
-------
-------
REFERENCES*
1. Federal Register. National Revised Primary Drinking Water Regulations,
Volatile Synthetic Organic Chemicals in Drinking Water. Vol. 47, No.
43, p. 9350, March 4, 1982.
2. Federal Register. Control of Organic Chemical Contaminants in Drinking
Water. Vol. 43, No. 28, p. 5759, Feb. 9, 1978.
3. Cairo, P.R., R.G. Lee, B.S. Aptowicz, and W.M. Blankenship. Is Your
Chlorine Safe to Drink? JAWWA, 71(8):450-453, Aug. 19?Q.
4. Larson, C.D., O.T. Love, Jr., and G.8. Reynolds. Tetrachloroethylene
Leached from Lined Asbestos Cement Pipe into Drinking Water. JAWWA, 75
(4): 184-188, Apr. 1983.
5. Dressman, R.C., and E.F. McFarren. Determination of Vinyl Chloride
Migration from Polyvinyl Chloride Pipe into Water Using Improved Gas
Chromatographic Methodology. JAWWA, 70(1):29, Jan. 1978.
6. Maddox, F.D., U.S. Environmental Protection Agency, Region V, Personal
Communication, Feb. 14, 1980, as follow-up to article entitled Fed-
eral Test Links Carcinogenic Chemical to Chlorine in The Cincinnati
Enquirer, Dec. 16, 1979.
7. Seeger, D.R., C.J. Slocum, and A.A. Stevens. GC/MS Analysis of Purge-
able Contaminants in Source and Finished Drinking Water. In: Proceed-
ings, 26th Annual Conference on Mass Spectrometry and Applied Topics,
St. Louis, Missouri, May 28-June 2, 1978.
8. Symons, J.M., J.K. Carswell, J. DeMarco, and O.T. Love, Jr. Removal
of Organic Contaminants from Drinking Water Using Techniques Other Than
Granular Activated Carbon Alone -- A Progress Report. In: Proceedings,
Practical Application of Adsorption Techniques in Drinking Water, EPA/
NATO, Challenges of Modern Society, Reston, Virginia, 1979. In Press.
^Unpublished reports and sponsored project information available from
Director, Drinking Water Research Division, Municipal Environmental
Research Laboratory, Office of Research and Development, USEPA, 26 W. St.
Clair Street, Cincinnati, OH 45268.
99
-------
9. Dunlap, W. Preliminary Laboratory Study of Transport and Fate of
Selected Organics in a Soil Profile. U.S. Environmental Protection
Agency, Groundwater Research Center, Ada, Oklahoma, 1980.
10. Roberts, P.V., J. Schreiner, and G.D. Hopkins. Field Study of Organic
Water Quality Changes During Groundwater Recharge in the Palo Alto
Baylands. Presented at Symposium on Waste Water Reuse for Ground
Water Recharge, Pomona, California, Sep. 7, 1979.
11. Chiou, C.T., L.J. Peters, and V.H. Freed. A Physical Concept of Soil-
Water Equilibria for Nonionic Organic Compounds. Science, 206:831-332,
Nov. 1979.
12. Symons, J.M., T.A. Bellar, J.K. Carswell, J. DeMarco, K.L. Kropp, G.G.
Robeck, D.R. -Seeger, C.J. Slocum, B.L. Smith, and A.A. Stevens.
National Organics Reconnaissance Survey for Halogenated Organics in
Drinking Water. JAWWA, 67(ll)PartI:634-647, Nov. 1975.
13. Jarema, R. Plainville and Plainfield's Plight with Pollution.
Connecticut State Department of Health, Hartford, Connecticut, July
1977.
14. Johnson, D., H. Kaltenthaler, P. Breault, and M. Keefe. Chemical
Contamination. The Commonwealth of Massachusetts, Special Legislative
Commission on Water Supply, 14 Beacon Street, Room 201, Boston,
Massachusetts 02108, Sep. 1979. Revised, Oct. 1981 by L. Dane,
H. Katenthaler, and M. Keefe.
15. Kim, N.K., and D.W. Stone. Organic Chemicals in Drinking Water. New
York State Department of Health, Albany, New York, 1980.
16. Lang, R.F., P.R. Wood, F.A. Parson, J. DeMarco, H.J. Harween, I.L.
Pagan, L.M. Meyer, M.L. Ruiz, and E.D. Ravelo. Introductory Study of
the Biodegradation of the Chlorinated Methane, Ethane, and Ethene
Compounds. Presented at Annual AWWA Conference, St. Louis, Missouri,
June 1981.
17. Kirk-Othmer Encyclopedia of Chemical Technology, Volume 5. John Wiley
and Sons, New York, 1979, 3rd Edition.
18. Crane, A.M., and A.F. Freeman. Water Softening and Conditioning Equip-
ment: A Potential Source of Water Contamination. EPA-600/3-77-107,
U.S. Environmental Protection Agency, Office of Research and Develop-
ment, Environmental Research Laboratory, Gulf Breeze, Florida, Mar.
1977.
19. DCI Corporation. DCI Solvent Data Sheet. Indianapolis, Indiana.
20. Azeotropic Data-II, No. 35, Advances in Chemistry Series. R.F. Gould,
editor, American Chemical Society, Washington, D.C., 1962.
100
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21. U.S. Environmental Protection Agency. Innovative and Alternative
Technology Assessment Manual (Draft). EPA-430/9-78-009, Office of
Research and Development, MERL, Cincinnati, Ohio, 1978.
22. Oilling, W.L. Interphase Transfer Processes. II. Evaporation Rates
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33. Merrick, E.T., H. Ketcham, L.J. Murphy, Jr., and K. Slika. EPA Chemi-
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35. DeMarco, J., N.V, Brodtmann, Jr., H. Russell, and G. Wood. A Compara-
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36. Nebolsine Kohl man Ruggiero Engineers, P.C. Technical Memorandum Well
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of Modern Society, Reston, Virginia, 1979. In Press.
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104
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64. O'Brien, R.R., D.M. Jordan, and W.R. Musser. Trace Organic Removal
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and J. DeMarco. Treatment Techniques for Controlling Trihalomethanes
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BIBLIOGRAPHY OF RELATED ARTICLES
Giovanardi, A. Groundwater Contamination Due to Chloro-Organic Compounds in
the Milan Metropolitan Area—Causes, Effects, and Development of a Control
Through Environmental Control. Presented at the Conference on Health
Control Through Environmental Control, Bologna, Italy, Sep. 21-22, 1978.
Zoeteman, B.C.J., K. Harmsen, J.B.H.J. Linders, C.F.H. Morra, and W. SI ooff.
1980. Persistent Organic Pollutants in River Water and Ground Water of The
Netherlands. Chemosphere. 9(4).
105
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