JB-02-Uj
LISTING BACKGROUND DOCUMENT
Wastes from Usage of Halogenated Hydrocarbon
Solvents in Degreasing Operations
The following spent halogenated solvents used in degreasing:
tetrachloroethylene , methylene chloride, trichloroethylene,
1,1,1-trichloroethane , carbon tetrachloride and the chlorinated
fluorocarbons; and sludges from the recovery of these solvents
In degreasing operations.(T)*,**,***
I. SUMMARY OF BASIS FOR LISTING
Solvent degreasing operations remove grease, wax, dirt,
oil, and other undesirable substances from various materials.
All degreasing facilities which use the halogenated hydro-
carbon solvents listed above generate spent solvent solutions
which are either discarded or processed to recover the solvent
from the spent solution. Spent solvents include those which
are no longer useful without further processing, either
because they have outlasted their shelf life or because they
have been contaminated, or so changed chemically or physically
that they are no longer useful as solvents. The recovery
operations invariably generate solvent sludges.
* In December, 1978, the Agency' proposed a generic listing
for this class of wastes.
** These solvents are often marketed under various trade
marks; the listing obviously includes all trade mark
solvents which have the generic chemical name listed
above. Another point of consideration is that different
naaes nay be used to refer to the same solvent:
tetrachloroethylene - perchloroethylene
1,1,1-trichloroethane » methyl chloroform
carbon tetrachloride » tetrachloromethane
methylene chloride » dichloromethane
trichloroethylene * 1,1, 2-trichloroethylene
*** In response to industry comments, it should be noted
that the Agency is no longer listing these wastes on
the basis of ignitability or E? toxicity. However, these
solvents nay be contaminated with metals (i.e., lead and
chromium) in the degreasing operations; therefore, the
generator will be responsible for determining whether the
asta would also meet the EP toxicity characteristic.
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The Administrator has determined that spent halogenated
solvents from degreasing and the sludges that result from
associated solvent reclamation operations are solid wastes
which may pose a substantial present or potential hazard to
human health or the environment when improperly transported,
treated, stored, disposed of, or otherwise managed; therefore,
these wastes should be subject to appropriate management
requirements under Subtitle C of RCRA.
For all of the listed waste solvents, this conclusion
is based on the following considerations:
1. The chlorinated hydrocarbons are toxic and, in some
cases, genetically harmful, while chlorofluorocarbons
may deplete the ozone layer following environmental
release.
2. Approximately 99,000 metric tons of waste halogenated
solvents from degreasing operations are generated
each year(l). There are approximately 460,000
facilities dispersed throughout the country that
use, halogenated solvents and generate these wastes(l).
It is estimated that about 30,000 metric tons per year
of halogenated hydrocarbons from these facilities are
either disposed of annually in landfills or by open-
ground dumping, either as crude spent solvents
or as sludges. The remainder of these wastes are
usually incinerated. The large quantity of wastes
generated and the large number of disposal sites
utilized increases the possibility of waste mis-
aanageraent and environmental release of harmful
cons tituents.
3. Since a large majority of the spent solvents and
sludges are in liquid form, the potential for these
wastes to migrate from land disposal facilities
is high. Further, the solubility of these solvents
is generally high, increasing their migratory
potential.
4. The spent solvent solution from degreasing operations
nay contain up to 90 percent of the original solvent.
Depending on the recovery technique, sludges that result
from reclamation processes can contain up to 50 percent
of the original solvent. Such high concentrations
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of hazardous constituents increases the chance of
waste constituents escaping in harmful concentrations.
5. Spent solvents can create an air pollution problem
via the volatilization of the solvents from the
was tas .
For the five chlorinated solvents (not including chlorofluoro-
carbons) found in the waste streams, this conclusion is
based on the following considerations:
6. Incomplete combustion of the spent chlorinated
hydrocarbon solvents during incineration can
cause emissions of the solvent and generate
toxic degradation products (e.g. phosgene).
7. These spent halogenated solvents can leach from
the waste to adversely affect human health and
the environment through the resulting contamination
o f groundwa ter.
8. Current waste management practices have resulted
in environmental damage. These incidents serve to
illustrate that the mismanagement of these wastes
does occur and can result in substantial environmental
and health hazards.
9. A number of these solvents are carcinogenic or
mutagenic, or are suspected carcinogens or rautagens,
and are lethally toxic to humans and animals.
For the chlorof1uorocarbons, the Agency is basing the listing
on the following consideration:
10. Chlorofluorocarbons, after release at the surface of
the earth, mix with the atmosphere and rise into
the stratosphere where they are decomposed by ultra
violet radiation to release chlorine atoms. These
atoms catalytically deplete the ozone, leading to ad-
verse effects, including skin cancer and climate changes
II. OVERALL DESCRIPTION OF INDUSTRY USAGE
Degreasing operations are not industry specific. Degreasing
operations are prevalent in twelve major SIC (Standard Industrial
Classification) categories, numerous subcategories , and auto-
motive maintenance shops. The pertinent industries where
halogenated hydrocarbons are used primarily are presented in
Table 1. A summary of the nunber and types of plants that
conduct degreasing operations is presented in Table 2.
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Table 1
Industries Using Halogenated Hydrocarbons
in Degreasing Operations
Source SIC Code
Metal Furniture 25
Primary Metals 33
Fabricated Products 34
Non-electric Machinery 35
Electric Equipment 36
Transportation Equipment 37
Instruments and Clocks 38
Miscellaneous Industry 39
Automotive Repair Shops 75
Automotive Dealers 55
Automotive Maintenance Shops —
Texitile Plants (Fabric Scouring) 22
Gasoline Stations 55
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Table 2 - Solvent Degreasing Source Types*(l)
Source
Material Degreasing
Metal Furniture
Primary Metals
Fabricated Products
Non-electric Machinery
Electric Equipment
Transportation Equipment
Instruments and Clocks
Miscellaneous
Automotive
Auto Repair Shops
Automotive Dealers
Gasoline Stations
Maintenance Shops
Textiles
Textile Plants (Fabric Scouring)
SIC
25
33
34
35
36
37
38
39
75
55
55
22
Estimated Number
Number of of Vapor Degreasing
Plants Operations
9,233 492
6,792 1,547
29,525 5,140
40,792 5,302
12,270 6,302
8,802 1,917
5,983 2,559
15,187 886
127,203
121,369
226,445
320,701
7,201
Estimated Number
of Cold Cleaning
Operations
22,869
17,558
76,329
105,456
31,720
22,756
15,467
39,262
141,977
135,463
277,440
252,735
Total
931,513
24,145
1,230,006
*Includes facilities which do not use halogenated solvents
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III. OVERALL PROCESS DESCRIPTION. WASTE GENERATTOM LEVELS
AND GEOGRAPHIC DISTRIBUTION OF DEGREASINCT APTT TTTF<;
1. Solvents Used in Degreasing Process
As indicated in Table 3, out of the more than 1,230.000
non-halogenated and halogenated degreasing operations
(see Table 2), approximately 460,000 use halogenated
solvents(l). Table 3 breaks down the number of plants
which use halogenated solvents to show the estimated number
of these plants using a particular halogenated solvent by
their type of degreasing operation. As the table indicates,
the largest number of these plants use cold cleaning and open
top vapor degreasing operations (see next section for more
detailed discussion of specific degreasing operations).
In both of these operations, the largest number use trichloro-
ethylene and trichlorethane. Of the industries with conveyor-
ized vapor degreasing operations, the largest number use
trichloroethylene; fabric scouring operations use principally
tetrachloroethylene (perchloroethylene). Overall, trichloro-
ethylene is the solvent used most prevalently.
2 . Process Description
Degreasing operations may be classified into
four basic categories: cold cleaning, vapor degreasing
(open top), vapor degreasing (conveyorized), and fabric
scouring.
In cold cleaning operations, the solvent is main-
tained well below its boiling point. The item to be
cleaned is either immersed in the agitated solvent
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Table 3 - Estimated Number of Plants using Halogenated
Solvents by Type of Degreasing (1974) (1)
Vapor Vapor Fabric
Solvent
Carbon tetr achloride
Fluorocarbons*
Methylene Chloride
Tetr achloroethylene
Tr ichloroethylene
IT ichloroethane
Total
(open top)
2,130
293
3,121
11,440
4,011
21,000
Cold Cleaning
10,568
66,932
21,136
45,795
149,715
137,386
431,532
Conveyor ized
319
45
467
1,713
601
3,145
Scouring
2,522
693
3,215
Note: Blanks indicate no use of specified solvent in that type
of degreasing operation.
*This refers to all fluorocarbons, some of which are chlorinated.
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or suspended above the solvent where it ls systematically
sprayed in a manner similar to that of an automatic
dish washer. Simple cold cleaning operations may
even consist of a container of solvent in which
items are manually immersed, as is the case in small
auto repair shops and in service stations.
Simple vapor degreasing (open top) is achieved by
suspending the item to be cleaned above the boiling
solvent in a vat. Condensation continues until the
temperature of the object approaches that of the solvent
vapors. Often the suspended item is sprayed with liquid
solvent to facilitate further degreasing. In order to
control vapor emissions, a layer of cold air is often
maintained above the open top degreaser.
The conveyorized vapor degreaser operates in much
the same manner, except that the objects to be cleaned
are continuously conveyed through the vapor zone.
Auxiliary solvent sprays are also used to improve the
cleaning efficiency of the operations.
Fabric scouring operations are slightly more complex.
Generally, the fabric is conveyed through the degreasing
machine, where it is sprayed with solvents. The solvents
are then removed with an aqueous solution of alcohol.
3 . Waste Generation Levels and Projected Levels
The annual *rowth rate for the use of the listed
halogenated solvents in degreasing applications is expected to
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be 4 percent(l). Growth is expected to be uniform among
the various solvents, except for trichloroethylene, which
has been banned in several states for use in occupational
settings because it is a carcinogen. (1,2,21). In Cali-
fornia, the use of trichloroethy1ene has been restricted by
legislation, but tetrachloroethylene and 1,1,1-trichloroethane
are exempt(l) from the restrictions and are still used in
degreasing operations. Rhode Island has completely banned
the use of trichloroethy 1ene(2).
4. Geographic Distribution of Degreasing Operations
The location of the vapor degreasing operations has
been determined by identifying the industries with which
the operations are associated. There are about 24,145'
vapor degreasing operations in the United States, which
consume about 52 percent of the total halogenated solvents
used(l). More than 63 percent of these operations are
found in nine states (California, Illinois, Massachusetts,
Michigan, New Jersey, New York, Ohio, Pennsylvania and
Texas). Figure 1 and the associated Table 4 present the
geographic distribution of these plants.
There are about 431,532 operations that perform
cold cleaning using about 35 percent of the total
halogenated solvent consumption, while approximately
3,125 fabric scouring operations consume about 13 percent
of the total halogenated solvent(l). Assuming an equal
distribution of halogenated solvent use among cold
cleaning and fabric scouring operations, over 59 percent
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of the total halogenated solvent used for degreasing occurs
In ten states (California, Illinois, Massachusetts, Michigan,
New Jersey, New York, Ohio, Pennsylvania, Texas and North
Car olina).
IV. WASTE STREAM SOURCES AND DESCRIPTION
The usefulness of a solvent decreases with time as contami-
nants adulterate and become concentrated in the solvent. When the
boiling point of the solution (i.e., solvent and contaminants) in-
creases to about 30 °C above that of the pure solvent, the solvent
is considered spent. Halogenated solvent use pattern by type of
degreasing operation is presented in Table 5. Approximately
527,520 metric tons of halogenated solvents are used each year for
degreasing operations(1).
Spent solvent solutions include those solvents which ate no
longer useful without further processing, either because they
have outlasted their shelf life or because they have been con-
taminated, or so changed chemically or physically that they are
no longer useful as solvents. These spent solvents are either
disposed of, reclaimed and recycled by the waste generator, or
processed by a contract solvent reclaiming operator.* Reclamation
is achieved via settling and/or batch distillation. The listed
sludge results from this reclamation process.
The composition of the spent solvent is dependent on the
application of the degreasing operation. The spent solvent
*At this time, applicable requirements of Parts 262 through
265 and 122 will apply insofar as the accumulation, storage
and transportation of hazardous wastes that are used, reused,
recycled or reclaimed. The Agency believes this regulatory
coverage is appropriate for the subject wastes. These wastes
are hazardous insofar as they are being accumulated, stored or
transported. These wastes may not pose a substantial hazard
during their recycling and, even though its listed as hazardous,
this aspect of their management is not presently being regulated.
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Table 5
USE PATEERN OF HALOGENATED SOLVENTS IN DECREASING AND
Chemical
Halogenated hydrocarbons:
Carbon tetrachlorlde
Fluorocarbons*
Methylene Chloride
Perchloroethylene
TrIchloroethyleue
Tr ichloroethane
TOTAL
FABRIC SCOURING
Total U.S.
Consumption
(103 kkg)
*"\ n c •
LMlo •
534.8
428.6
235.4
330.2
173.7
236.3
OPERATIONS IN 1974
U.S. Consumption U.S
for Degreasing for
(103 kkg) (10
Cold
0.72
6
46,2
11.4
43.8
78
Va por
5
11. 1
10
43
112.7
90
U.S. Consumption
for Fabric Scouring
54.6
15
Total U.S.
Consumption
for Degreaslng
and Scouring
(103 kkg)
1939.0
186.12
271.8
69.6
5.72
17.1
56.2
109
171.5
168
527.52
*Thls refers to all fluorocarbons, a percentage of which are chlorinated.
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solution contains up to 90 percent of the original solvent(4).
Depending on the recovery technique, sludges which result from
reclamation processes contain from 1 to 50 percent of the
original hydrocarbon solvent(S). However, because of the
economic considerations of the reclaiming process, the solvent
content of the sludge is seldom reduced below 10 percent.
Heavy metal fines and other organics are also present in
these wastes, in addition to the original solvent(3).
V. QUANTITIES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
Disposal practices include overt open ground dumping,
containerized landfilling, and incineration (3). Approximately
99,000 metric tons of waste halogenated solvents frora degreasing
operations are generated annually(l). It is estimated that
about 30,000 metric tons of these are either landfilled or
open dumped.- The remaining quantity of waste halogenated
solvents from degreasing operations are incinerated. The
rationale and derivation of this estimated quantity is presented
in Appendix I.
VI. HAZARDOUS PROPERTIES OF THE WASTES
As indicated earlier, the spent halogenated solvents and
sludges frora the reclamation of these solvents contain very
significant concentrations of the solvent itself -- the
spent solvent solution contains up to 90 percent of the original
solvent and the sludge contains a minimum of 10 percent of
the original solvent. The landfilling or open ground dumping
of these wastes in an unsecure land disposal facility nay
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result in the migration of the toxic halogenated solvents
into the surrounding environment, thus becoming a potential
contaminant of groundwater. For example, since a large ma-
jority of these wastes are in liquid form -- including all of
the spent solvents -- these wastes' physical form makes them
amenable to migration from a land disposal facility. Addi-
tionally, the solubility in water of these halogenated solvents
is appreciable (13): 1,1,1-trichloroethane - 950 mg/1, tetra-
chloroethylene 150 mg/1, methylene chloride - 20,000 mg/1,
carbon tetrachloride 800 mg/1, and trichloroethylene - 1,000
mg/l(14a). These relatively high solubilities demonstrate a
strong potential for migration of these substances from inade-
quate land disposal facilities in substantial concen tr at io'ns .
Thus, improperly constructed or managed landfills (for example,
landfills located in areas with permeable soils, or landfills
with inadequate leachate control practices) could easily
fail to impede leachata formation and migration. Haphazard
dumping of the wastes is even more likely to result in migration
of waste constituents.
Once released from the matrix of the waste, the halogenated
solvents could migrate through the soil to ground and surface
waters utilized as drinking water. In the National Organics
Monitoring Survey, the Agency detected a number of these solvents
in drinking water samples tested over the past several years, thus
demonstrating the propensity of these solvents to migrate from the
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waste disposal environment and to persist in drinking water follow-
ing migration* (14a, 14b, 14c, 14e). In addition, a number
of actual documented damage incidents show the potential for a
very common halogenated solvent, trichloroethylene , to leach
from disposal sites into groundwater. (See Damage Incidents
Resulting from the Mismanagement of Halogenated Hydrocarbons ,
p . 16 . )
These actual damage incidents confirm literature data points
indicating the environmental persistence of these compounds. Thus,
1,1,1-trichloroethane, raethylene chloride, and carbon tetrachloride
are all likely to persist in the environment long enough to reach
environmental receptors (1,1,1-trichloroethane is subject to
hydrolysis, but has a half-life in groundwater of 6 months)(37).
Another problem which could result from improper landfilling
of these wastes is the potential for the contaminants to volatilize
into the surrounding atmosphere. All of the listed chlorinated
solvents are volatile and thus could present an air pollution
problem if they are improperly managed (for example, disposed of
in the open, or without adequate cover), since they are uniformly
toxic via inhalation.
A special problem is posed by chlorofluorocarbon solvents.
These solvents are also highly volatile, but instead of posing a
direct toxicity hazard, they may be released at the surfa.ce of the
earth, mix with the atmosphere and rise slowly into the stratosphere,
*Xhespecific solvents detected in these samples were methylene
chloride, carbon tetrachloride, trichloroethylene , and tetra-
chloroethylene and trichlor ofluoromethane.
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Damage Incidents Resulting From The Mismanagement of
Trichloroethylene
1. In one incident in Michigan, an automotive parts manu-
facturing plant routinely dumped spent degreasing solu-
tions on the open ground at a rate of about 1000 gallons
per year from 1968 to 1972. Trichloroethylene was one
of the degreasing solvents present in the spent solutions.
Beginning in 1973, trichloroethylene was detected at levels
up to 20 mg/1 in neary residential wells. The dump site
was the only apparent source of possible contamination (10)
2. In a second incident, also in Michigan, an underground
storage tank leaked trichloroethylene which was detected
in local groundwater up to four miles away from the
land (ID.
3. In April of 1974, a private water well in Bay City, Michi-
gan became contaminated by trichloroethylene. The only
nearby source of this chemical was the Thomas Company
(which replaced the well with a new one). The company
claimed that, although it had discharged trichloroethylene
into the ground in the past, it had not done so since
1968. Nethertheless, in May of 1975. two more wells
were reported to be contaminated with trichloroethylene
at concentrations of 20 mg/1 and 3 tag/1, respectively
(12).
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In March, 1978, EPA banned the use of chlorofluoro-
carbons In aerosol propellants. The primary concern in the
enactment of this ban was the ozone depletion effects resulting
from chlorofluorocarbons entering the stratosphere and reaction
with ozone. In the troposphere, chlorofluorocarbons are decom-
posed by the intense ultra violet radiation to release chlorine
atoms. The chlorine atoms catalytleally remove ozone, thereby
reducing the total amount of ozone in the stratosphere, leading
to an increase in skin cancer, climatic changes and other adverse
effects.v33,34 ) ^^e Agency is therefore concerned about chloro-
fluorocarbon use and disposal. Therefore, the Agency has proposed
the regulation of non-aerosol uses of chlorofluorocarbons.(8)
The Agency also expects to propose regulations controlling
the airborne emissions of these solvents and other volatile
organics so as to reduce the air pollution problems presented
when these solvents are used or disposed. These proposed
regulations will apply certain standards to a number of the
Volatile Organic Compounds (VOC) which have been demonstrated
to be precursors of or lead to the formation of ozone and
other photochemical oxidants in the atmosphere. Ozone air
pollution endangers the public health and welfare and is
thus reflected in the Administrator's promulgation of a
National Ambient Air Quality Standard for Ozone (February 8,
1979. 44 FR 8202). Additionally, 1,1,1-trichloroethane and
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methylene chloride, which are not ozone percursors, are
being regulated under the proposed rule since under EPA's
proposed airborne carcinogen policy, a compound which shows
evidence of hunan carcinogenic i ty is a candidate for regulation
under Section 111 as a pollutant "reasonably anticipated to
endanger public health and welfare". Finally, t r i chlor of luoro-
methane, as indicated in the earlier discussion of chlorof luoro-
carbons in general, has been implicated in the depletion of
the stratospheric ozone layer, a region of the upper atmosphere
which shields the earth from harmful wavelengths of ultra
violet radiation, that would increase skin cancer risks in
humans .(33,34)
Additionally, if these wastes are incinerated, as a
large percentage are, and the wastes are not subject to
proper incineration conditions (i.e., temperature and residence
tiaes), pollution of the environment may result from the
airborne disposal of uncombus t ed halogenated organics, partially
combusted organics and newly formed organic compounds.
Phosgene is an example of a partially combusted chlorinated
organic which is produced by the decomposition or combustion
of chlorinated organics by hea t ( 1 5 , 1 6 , 1 7 ) . Phosgene has
been used as a chemical warfare agent and is recognized as
ex t rene ly toxic.
The large quantities of the spent solvent and sludges re-
sulting from the recovery of these solvents, a combined total
of 99,000 metric tons per /ear, are another area of concern.
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As previously indicated, these wastes are generated in
substantial quantities and contain very high concentrations
of the original solvent (the spent solvent solution contains
up to 90 percent and the sludges contain up to 50 percent
of the original solvent). The large quantities of these
contaminants pose the danger of polluting large areas of
ground or surface waters. Contamination could also occur
for long periods of time, since large amounts of pollutants
are available for environmental loading. All of these
considerations increase the possibility of exposure to the
harmful constituents in the wastes.
VII . HEALTH AND ECOLOGICAL EFFECTS ASSOCIATED WITH THE
CONSTITUENTS IN THE WASTES
The toxicity of tetrachloroethylene, methylene chloride,
1,1,1-trichlorethane, trichloroethylene, carbon tetrachloride
and chlor ofluorocarbons has been well docum'en ted . Capsule
descriptions of the adverse health and environmental effects
are summarized below; more detail on the adverse effects of
these solvents can be found in Appendix A.
Tetrachloroethylene has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
carcinogenicity.(^1) Repeated exposure of rats and mice
to tetrachloroethylene in air or in the diet has resulted
in fatty degeneration of the liver, increased kidney weight
and toxic nephropathy.(18,19,20). Additionally, tetrachloro-
ethylene is slightly toxic to freshwater fish.(14b»22>23)
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Methylene chloride has been shown to be rautagenic to a
bacterial strain, S. typhiraur ium. C 2 4 ) jn addition, acute
exposure to methylene chloride in humans is a central nervous
system depressant resulting in narcosis in high concentrations
and is metabolized to carbon monoxide and causes an increase
in ca rboxyheraog lobin ( 2 5 ) .
Although 1 , 1 , 1-trichloroe thane (MC) has been shown in
an NCI bioassay to induce a variety of neoplasms ( 26 ), these
data were not conclusive. A high incidence of deaths in
test animals has led to retesting of this compound by a manu-
facturer and the NCI(26). In vitro studies have indicated
that MC is slightly mutagenic in the Ames test, and can cause
mammalian cell transformation. Human toxic effects seen
after exposure to 1 , 1 , 1-trichloroe thane include changes in
several central nervous system functions, including reaction
tine, perceptual speed, manual dexterity and equilibr iura( 27 ) .
In addition, animal studies have produced toxic effects in
the central nervous system, cardiovascular system, pulmonary
system, and induced liver and kidney daraage(27).
Trichloroethylene has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
carcinogenici ty . - 21 ) Trichloroethylene has also been
shown, both through acute and chronic exposure, to produce
disturbances of the central nervous system and other neuro-
logical ef fects( 28, 29, 30) .
Carbon t e t r achlo r ide has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
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care Inogenicity.(21) in addition, toxicologleal data for
non-human mammals are extensive and show carbon tetrachloride
to cause liver and kidney damage, biochemical changes in
liver function and neurological damage(32).
The hazards associated with exposure to the above halo-
gen a ted solvents have been recognized by other regulatory
programs. Tetrachloroethylene, methylene chloride, 1,1,1-
trichloroethane, trichloroethylene, and carbon tetrachloride
and the two fluorocarbons, trichlorofluoromethane and dichloro-
difluoromethane, are listed as toxic pollutants in accordance
with §307(a) of the Clean Water Act of 1977.* Under §6 of the
Occupational Safety and Health act of 1970, final standards
for occupational exposure have been established and promulgated
in 29 CFR 1910.1000 for carbon tetrachloride, methylene chlor-
ide and 1,1,1-trichloroethane. On March 17, 1979, fully halo-
genated f1uorocarbons were banned by the Consumer Products
Safety Commission as propellants in the United States, except
for essential uses because of their threat to the ozone. In
addition, final or proposed regulations in the States of
California, Louisiana, Maryland, Massachusetts, Minnesota,
Missouri, New Mexico, Oklahoma and Vermont define compounds
containing one or more of the solvents tetrachloroethylene,
methylene chloride, 1,1,1-trichloroethane, trichloroethylene,
carbon tetrachlor ide and trichlor ofluoromethane as hazardous
wastes or coaponents thereof.35
*T'ne Agency has recently proposed to remove tr ichloro f luorome thane
and dichlorodif1uoromethane from the list of toxic pollutants
under §307(a) of the Clean Water Act (45 FR 46103, July 9, 1980).
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ATTACHMENT I
DERIVATION OF THE ESTIMATED QUANTITIES OF THE WASTE
I. ANNUAL QUANTITIES OF WASTES
Total amount of spent solvents (Halogenated and non-
halogenated)C1) = 425,560 kkg
Total amount of spent solvents from vapor degreasingC1)
= 54,560 kkg
Vapor degreasing units only use halogenated solvents so all
of the 54,560 kkg from this source are halogenated solvents.
Cold cleaners and fabric scourers use both halogenated and
non-halogenated solvents. Assume that the spent solvent
solutions contain solvents in the same proportion as their
use. About 12 percent of solvent use in applications other
than vapor degreasing is halogenated(1).
.-. (425,560 kkg - 54.560 kkg) (0.12)(1)
• 44,250 kkg of halogenated solvents contained in wastes
from sources other than vapor degreasing
54,560 kkg + 44,520 kkg = 99,000 kkg of halogenated
solvents yr
II. DISPOSITION OF WASTE
The disposition of about 30 percent of these wastes can be
derived from information which is documented in the litera-
ture. The disposition of the remaining 70 percent is based
upon extrapolations and economic consideration of waste
nanageraent alternatives.
A. DISPOSITION OF 30 PERCENT OF THE WASTE
0 Vapor degreasers only use halogenated solvents(l)
0 Virtually all metal finishing shops (SIC 35, 36,
37, and 39), and by implication vapor degreasing
operations, either reclaim their spent solvents
or sell them to solvent refiners.(1,3)
0 Between 50-99 percent of the solution is recovered(4,5)
Approximately 37 percent of the plants which recover
these solvents on-site dispose of their waste sludges
in landfills(3).
(amount of waste) (1-percent recovery)(percent of
plants with on-site recovery) x (percent of plants
that landfill) = Amount of waste landfilled.
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1. Assume 50 percent of the solution is recovered
(54,560 kkg) (0 . 50 ) (0.37)(0.70) - 7,065 kkg
-• Assume 99 percent of the solution is recovered
(54,560 kkg) (0.01) (0.37)(0.70) - 140 kkg
140 kkg to 7,065 kkg of halogenated solvents
disposed of In landfills.
About 20 percent of the solvent reclaimers which process
the remaining 63 percent of the solvents from this source
also landfill their waste. The remaining 80 percent
of the solvent reclaimers reportedly incinerate their
sludges(4,5). Therefore an additional 109 to 5,456
kkg of halogenaced solvents are landfilled by solvent
reclaimers.
3. DISPOSITION OF THE REMAINING 70 PERCENT OF THE WASTE
The wastes generated by the plants in the SIC cate-
gories delineated above represent about 60 percent
of all vapor degreasing operations and about 30
percent of all wastes generated by all degreasers.
Reportedly, a facility which generates at least 350
gallons of spent halogenated solvents anually has
economic incentive to implement a recovery strategy(4,9).
Virtually all vapor degreasers nee' this criteria.
The disposition of spent solutions from cold cleaning
and fabric scouring operations is not as well defined.
In order to account for these wastes, some economic
factors have been considered. In general, it is expected
that a plant or industry which has a high incidence
of use of a relatively expansive solvent will probably
have some kind of recovery strategy, assuming the scale
of operations permits an acceptable payback period.
In cold cleaning and fabric scouring operations, the
following factors are pertinent:
0 Cold cleaning and fabric scourers use halogenated
solvents IT conjunction with Inexpensive non-
halogenaced solvents. It has been estimated
that thes-2 operations must have six to twelve
times the solvent throughput of plants which
only use h a 1 -3 g e n a t s d solvents Ln order to
economically justify a recovery strategy.
0 Cold cleaning and fabric s._juring operations
represent i b o u r 94.7 percent of all facilities
that use h .11 33 ena ted solvents but only use about
43 percent of the total supply of these solvents
-23-
-------
that are used for degreastng. The implication is
that, on the average, the solvent throughput
rate is much lower in this segment of the
degreasing industry than that of the vapor
degreasing segment.
Although some cold cleaning and fabric scouring
operations probably operate on a scale that would
make a recovery strategy economically attractive,
it is not possible to estimate the extent of recovery
operations in this segment of the industry. The
economics seem to indicate that the incidence of
recovery from these operations is probably very low.
C. THE GROSS ESTIMATE
In estimating the disposition of all the wastes,
the best and worst cases pertaining to the portion
of the waste which cannot be documented in the
literature are considered. The ideal case is where
all of the wastes from cold cleaning and fabric
scouring operations are processed by contract re-
claimer using maximum efficiency recovery techniques
(i.e., 99 percent recovery). The worst case would
be where all of this waste is simply disposed of.
The following is the basis for the estimate.
From Section A
249 kkg Co 12,521 kkg of h alienated solvents are
land filled.
Best Case for Cold Cleaning and Fabric Scouring
(amount of waste)(percent recovered)(percent
landfilled) = amount landfilled
(44,520 kkg)(0.01)(0.2) = 90 kkg of waste land-
filled
Worst case for cold cleaning .and fabric scouring
is when all 44,520 kkg of waste is landfilled
The estimated best and worst cases for the disposition
of halogendced solvents fron all types of degreasing
operations ire 339-57,041 metric tons per year. It
is unlikely char either the besc or worst case is
representative of reality. IT this case, about half
of the waste is generated by vapor degreasers where
it is likely chat the incidence of recovery is high.
The remaining half Is generated in environments where
-------
the incidence of recovery is probably very low. A
reasonable inference and prudent estimate based on
available data would be about 30,000 metric tons
per year of halogenated solvents disposed of on land.
-------
REFERENCES
1. Hoogheem, T.J., et al. Source assessment: Solvent evaporatlor
degreasing operations. U.S. EPA No. 600/12-79-019f. NTIS
?3 No. 80 128 812.' August, 1979.
2. Mansville Chemical Products. Chemical products synopsis:
trichloroethylene. Mansville, New York. September, 1976.
3. L'.S. EPA. Hallowell, J.B., et al. Assessment of industrial
hazardous waste practices: Electroplating and metal finishing
industries - job shops". U.S. EPA. NTIS PB No. 264 349. September
1976.
4. U.S. EPA. Organic solvent cleaners-background information for
proposed standards. U.S. EPA No. 450/2-78-045 a . October, 1979.
5. U.S. EPA. Source assessment: Reclaiming of waste solvents.
State of the art. NTIS No. 232 934. April, 1978.
6. No t used in text.
7. Not used in text.
8. Federal Register, Vol. 43, Pg. 11301. March 17, 1978.-
9. U.S. EPA. Control of volatile organic emissions from solvent
metal cleaning. U.S. EPA No. 450/2-77-022. November, 1977.
10. Michigan Department of Natural Resources - Geological Survey
Division. Case history-'* 48.
11. Shellenbarger, P. New charge hits Air Force. The Detroit
News. May 17, 1979.
12. U.S. EPA. Open files. Hazardous Site Control Branch, WH-543,
U.S. EPA, 401 M St., S.W., Washington, DC. 20460.
Contact Hugh Kauffman. (202) 245-3051.
13. U.S. EPA. Section II of Appendix B of the listing background
document: Fate and transport potential of the hazardous
constituents. U.S. EPA, Office of Solid Waste. 1980.
14a. U.S. EPA. Trichloroethy 1ene: Ambient water quality criteria.
NTIS PB No. 292 443. 1979.
14b. U.S. EPA. In-depth studies on health and environmental
impacts of selected water pollutants. Work resulting f r o 3
Contract No. 63-01-4646. 1973.
-2(o-
-------
14c. U.S. EPA. Preliminary assessment of suspected carcinogens in
drinking water, and appendices. A report to Congress.
Washington, D.C. EPA No. 560-4-75-003. 1975.
lid. Not used in text.
14e. U.S. EPA. The National organic monitoring survey. Technical
Support Division, Office of Water Supply, U.S. EPA. Washington,
DC. 20460. 1978.
15. Edwards, John 3. Combustion formation and emission of trace
species. Ann Arbor Science . 1977.
16. NIOSH criteria for recommended standard: Occupational
exposure to phosgene. HEW, PHS, CDC, NIOSH. NT IS PB 267 514.
1976.
17. Chemical and Process Technology Encyclopedia. McGraw Hill.
1974.
18. National Cancer Institute. Bioassay of tetrachloroethy1ene
for possible carcinogenicity. NTIS P3 No. 272 940. NCI-CG-
TR-13. DHEW Publication No. (NIH) 77-813. 1977.
19. Rowe, V.X., et al. Vapor toxicity of tetrachloroethylene
for laboratory animals and human subjects. AMA Ar ch. Ind .
Hyg. Occu?. Med. 5:566. 1952.
20. Klaassen, C.D., and G.L. Plaa. Relative effects of chlorinated
hydrocarbons on liver and kidney function in dogs. Tox i co1.
Appl. Pharmacol. 10:119. 1967.
21. U.S. EPA. Carcinogen Assessment Group, Office of Research
and Development. List of carcinogens. April 22, 1980.
22. Alexander, H., et al. Toxicity of perchloroethylene,
trichi oroethy1ene, 1,1,1-trichi oroechane , and methylene
chloride to fathead minnows. Bull. Environ. Contam. Toxicol.
20:344. 1973.
23. U.S. EPA. Tetrachloroethylane: Ambient vater quality criteria.
NTIS PB No. 292 445. 1979.
24. Simmon, V.F., et al. Mutagenic activity of chemicals identified
in drinking water. S. Scott, et al., e d s . In: Progress in
genetic toxicology- 1977.
25. National Academy of Sciences. Chloroform, carbon tetrachloride
and other halo me thanes: Environmental assessment. Publication
Mo. 2763. 1973.
-3.7-
-------
26. National Cancer Institute. Bioassay of 1,1,1-trichloroethane
for possible carcinogenicity. NCI-CG-TR-3. NT IS PB No. 265 08,"
1977.
27. U.S. EPA. Chlorinated ethanes: Ambient water quality criteria.
NTIS PB No. 297 920. 1979.
28. N'omiyama, K., and H. Nomiyama. Metabolism of trichloroethylene
in human sex differences in urinary excretion of trichloroacetic
acid and trichloroethano1. Int. Arch. Arbeitsmed. 28:37.
1971.
29- Sardodej, A., and J. Vyskocil. The problem of trichloroethylene
in occupational medicine. AMA Arch. Ind. Health. 13:581. 1956.
30. McBirney, B.S. Trichloroethylene and dichloroethylene poisoning
AMA Arch. Ind. Hyg. 10:130. 1954.
31. No t used in text.
32. Von Oettingen, W.F. The halogenated hydrocarbon of industrial
and toxicological importance. In; Elsevier monographs on
toxic agents. E. Browning, ed. Elsevier Publishing Company.
New York. 1964.
33. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloromethane release.
Publication No. 2529. 1976.
34. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Stratospheric
ozone depletion by halocarbons: Chemistry and transport. 1979.
35. U.S. EPA. State Regulations Files. Hazardous Waste Programs,
WH-563, U.S. EPA., 401 M St., S.W., Washington, DC. 20460.
Contact Sam Morekas. (202) 755-9145.
36. Not used in text.
37. Dawson, English and Petty. Physical chemical properties of
hazardous waste constituents. 1980.
-------
SJ-31-06
WASTES FROM USAGE OF ORGANIC SOLVENTS
t
I. LISTING
The listed wastes are those major streams which result
fron usage of organic solvents. The listed solvents include
both halogenated and non-halogenated organic compounds. The
specific wastes listed are:
The following spent halogenated solvents: tatrachloroe thylene,
methylene chloride, trichloroethylene, 1,1,1-trichloroe thane,
chlorobenzene , 1,1,2-trichloro-l,2,2-1rif1uoroethane , o-di-
chlorobenzene , trichlorofluorone thane, and the still bottoms
from the recovery of these solvents (T);
The following spent non-halogenated solvents: xylene, acetone,
0O3 ec'ayl acetate, ethyl benzene, ethyl ether, n-butyl alcohol,
eyelohexanone, raethanol, methyl isobutyl ketone; and the
still bottoms frora the recovery of these solvents (I);
. The following spent non-halogeanted solvents: cresola and
00^ cresylic acid, and nitrobenzene; and the still bottoms from
the recovery of these solvents (T); and
The following soent non-halogenated solvents: toluene, methyl
e t hy 1 ketone, carbon disulfide, isobutanol, pyridine; and the
ill bottoms frora the recovery of these solvents (I,T).
Listing codes for the most widely used halogenated
organic solvents are presented in Table I-1, and codes for
v i d a 1 v - u s e d non-halogenated o r 3 a n i c solvents are in Table 1-2.
II. SUMMARY OF BASIS FOR LISTING
Wastes resulting from usage of organic solvent-; tvoically
contain significant concentrations of the solvent. Examples
of wastes from usage of organic solvents include still-bottoms
-------
from solvent recovery and spent solvents from dry cleaning
operations and maintenance and repair shops.
The Administrator has determined that waste from usage
of the 24 organic solvents listed in Tables 1-1 and 1-2 nay
be a solid waste, and as a solid waste, may pose a substantial
present or potential hazard to human health or the environment
when improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations*:
1. Of the list of 24 solvent types presented in Tables
1-1 and 1-2, each solvent exhibits one or more
properties (i.e., ignitability and/or toxicity)
which pose a potential hazard. These solvents
represent approximately 95' percent or more of
organic solvent usage in the United States (see
Table II-l)-
2. The use of organic solvents is widespread throughout
the United States, and the quantities involved are
large; according to Table IT-1 the total annual
usage of the listed materials as solvents is over
2.8 X 106 '
-------
TABLE 1-1
LISTING CODES FOR HALOGENATED ORGANIC SOLVENTS*
(in order of usage as solvent)
Solvents
Listing
Codes
Flash
Point (°F)
Perchloroethylene
Methylene chloride
Trichloroethylene
1 , 1 , 1 ,-Trichloroethane
Chlorobenzene
1,1,2-Triehloro-1,2,2-
Tri fluoroe thane
o-Dichlorobenzene
Trichlorofluorome thane
T
T
T
T
* ^ •> 1ja. c a Tn this table are based on information contained in
Reference (1). Dashes in place of data mean either the values
were not available or (in the case of flash points) not
applicable.
-y-
-1.1-
-------
TABLE 1-2
LISTING CODES FOR NON-HALOGENATED ORGANIC SOLVENTS*
(in order of usage as solvent)
Solvents
Xvle nes
Me thanol
Toluene
Methyl ethyl ketone
Acetone
Methyl isobutyl ketone
Carbon disulfide
Ethyl acetate
Ethyl benzene
Ethyl ether
a -Butyl alcohol
Isobutanol
Cresols and cresyllc acid
Cyc lohexanone
Nitrobenzene
P y r i d i n e
Listing
Codes
x* *
I,**
I,T**
I,T**
X**
I,**
I,T**
x**
I**
I**
I**
I,T**
T
I **
T
1.
I,T**
Flash
Point (°F)
84(2)
54
39
22(3)
3
61
-25
45(2)
59
-49(2)
115
82
-
111(3)
-
68
* All -data in this table are based on information contained in
Reference ' 1) e x c e T t as noted. Hashes in place of data -lean
either that the values v e r e not available or (in the case of
flash ooints) not applicable.
**3ecause the listed waste typically would contain a large
percentage of these solvents, the listed wastes would fail
the i»iitability characteristic for liquids--a flash point
less :han 60°C (140°F).
-32-
-------
The fifteen solvents listed as either toxic
or toxic and ignitable pose a further hazard to
human health and the environment. If improperly
managed, these solvents could migrate from the
disposal site into ground and surface waters,
persist in the environment for extended periods
of time, and cause substantial hazard to environ-
mental receptors.
The two fluoroc-a-rbons, l,l,2-trichloro-l,2,2-
trifluoroethane and trichlorofluororaethanes present
a different type of hazard. Due to their high
volatility, these two organics can rise into the
stratosphere and deplete the ozone, leading to
adverse healch and environmental effects.
•i. Damage incidents resulting from the mismanagement of
waste solvents have been reported. These damage
incidents are of three types:
(a) Fire/explosion damage resulting from ignition
of the solvents;
(b) Contamination of wells in the vicinity of in-
adequate waste storage or disposal (with re-
sulting illness in at least one instance); and
(c) Direct entry of solvent into a waterway, resulting
in fish kills.
5. These damage incidents show that mismanagement
occurs and that substantial hazard to human health
and the environment may result there from.
HI. SOURCES OF THE WASTE ANTD TYPICAL DISPOSAL PRACTICES
A. Overall Description of Industry Usage*
The primary solvent-using inHustri^s -ind the quantity
of solvents they use annually are as follows:-^
*Large amounts of chen i .-. a 1 s listed in Table 11 - L are used in
such non-solvent applicitisis is zhemical feedstock so that
the total production of specific solvent chemicals for all
applications is often many tines larger than the amount
used specifically as a
-------
Table II-l
RANKING AND AMOUNTS OF THE LISTED SOLVENTS^)
Amount Used As
Chemical Naae Solvent (kkg/yr)
Xylenes 489,900
Mechanol 317,500
Toluene 317,500
Parchloroethylene 255,800
Methylene chloride 213,200
Methyl ethyl ketone 202,300
Trichloroethylene 188,200
1 ,1 ,1-Trichloroethane 181,400
Acetone 86,200
Methyl isobutyl ketone 78,000
Chlorobenzene 77,100
Carbon disulfide 77,100
Ethyl acetate 69,900
Ethyl benzene 54,430
Ethyl ether 54.430
n-3utyl alcohol 45,360
l,l,2-Trichloro-l,2,2-tri-fluoroethane 24,040
Isobutanol 18,600
o-Dichlorobenzene 11,800
Cresols & cresylic acid(a) 11,800
Cyclohexanone 9,072
Nitrobenzene 9,072
Trtchlorofluoronethane 9,072
Pyridine 907
•a} Consu^p t ion a-nounts for cresol and cresylic acid were
combined .
-------
Paint & Allied Products and Industrial 1,153,500 kkg/yr
Operations
Surface Cleaning 610,600 kkg/yr
Pesticide Production 266,700 kkg/yr
Laundry and Dry Cleaning Operations 214,550 kkg/yr
Pharmaceuticals Manufacture 34,740 kkg/yr
Solvent Recovery Operatic"ns (Contract and 499,000 kkg/yr
in-house) (feedstock)
Table III-l summarizes the use pattern of the 10 most
widely used solvents in the industrial categories listed
above. These data illustrate the distinct difference between
halogenated and non-halogenated solvents in industrial usage;
the chlorinated and other halogenated solvents in Table
III-l are used almost exclusively in the surface cleaning,
laundry and dry cleaning categories, whereas t'le non-halo-
genated solvents are used primarily in the production cate-
gories (paint, pesticides and pharnaceutica1s). The ten
specific solvents included in this table are believed to
account for about 80 percent of all organic solvent usage.(D
The composition of the spent solvent* is dependent on its
application, but the spent solvent contains up to 90 percent
of the original solvent**. Depending on the recovery techniques,
*Spent solvents include those solvents which are no longer
useful without further processing either because they have
outlasted their shelf life or because they have been
contaminated, or so changed chemically or physically that
they are no longer useful as solvent.
**United States Environmental Protection Agency. 1976.
Assessment of Industrial Hazardous Waste Practices
Electroplating and Metal Finishing Industries - Job
Shops P3-264-349.
-------
(.-.LI ca-^a ir. —.its sf 10' yJ.
o
c
^
I 5 i:
o
5
j
o
p ;
c ;
292' - - !iŁ5
61
'1153
510
i i
_!..!- I
I"'! i
ir. rhe re.sp=~ive carercris^.
•zr^.- -ha solve.-- =.- issue is rr
is r.cz «r^r-r..
-------
sludges which result from reclamation processes contain from 1
to 50* of the original solvent.* However, because of the
economic considerations of the reclaiming process, the solvent
content of the sludge is seldom reduced below 10 percent.**
3• Solvent Usage in Paint & A1 _ . e d Products and
Industrial Operations
The category of Dalnt & Allied Products and Industrial
Operations Is taken here to include the following solvent-use
industrial operations:
0 Paint & Allied Products Manufacture
Roll Coatings
0 Paper Coa t ings
0 Dye Manufacture
0 Ink Manufacture
3 Adhesive Manufacture
' Printing Operations
The Paint and Allied Products and Industrial operations
category accounts for about half of all organic solvent utili-
zation by industry. The Paint and Allied Products portion
of this category is the largest solvent-use s ;i be a t ego r y , with
Printing Operations being the second largest use subcategory.
For the Paint & Allied Products Industry, there are
about 1200 paint manufacturing companies that operate more
*'."ni:ed States Environmental Protection Agency. 1979.
Organic Solvent Cleaners-background Information for
Proposed Standards. -.PA-4 5/1 2-73-04 5a .
**United States Environmental Protection Agency. 1978.
Source Assessment: ^ecla"iming of Waste Solvents. State
of the Art. P3-239-934.
-X-
-17-
-------
than 1500 plants. Solvents are important ingredients in
formulations for solvent-thinned paints, lacquers, and factory-
applied coat ings .
Solvent containing wastes arise from the use of solvents
Co clean equipment, and still bottoms from the recovery of the
solvents used in production*. It is estimated^4' that approxi-
mately one-third of the solvents used for equipment cleaning
are reclaimed, and that 7 x 10° gallons of solvent are
disposed of yearly from this source.
The total quantity of solvent-containing wastes from
the paint industry is estimated to contain 14,300 kkg/yr of
solvents.(^' These are primarily non-halogenated solvents
such as xylenes, methanol, acetone, toluene, MEK, etc.
The remaining industrial processes included in this over-
all category (manufacture of inks, adhesives, dyes, and
various types of coatings) utilize organic solvents (primarily
non-halogenatad) in much the sane manner as the paint industry;
that is, as an important component of formulations and for
equipment cleaning.(D Printing operations also use sol-
vents for cleaning operations and as dye or pigment carriers.
The types of waste generated from these industries should be
generally similar to those from the paint industry and include:
"quipment cleaning wastes;
Still bottoms from solvent recover1/.
*Additional waste streams from these industrial categories (such
as off-specification product and spills .of finished product)
are expected to be c o 7 e r 3 d b v future listings.
-Uf-
-------
Spent solvents used for equipment cleaning, if not re-
claimed, are drummed and landf i lied (*). Most paint companies
contract for waste disposal services. Solvent recovery still
bottons are incinerated, landfilled, or injected into deep
wells.(5)
C . Surface Cleaning
The Surface Cleaning category consists of two
important subcategories:
0 Industrial Degreasing
0 Re pa i r work
Industrial Maintenance and Repair
Commercial Service and Repair
Consumer-performed Maintenance and Repair
About half of the solvents used in Surface Cleaning
Operations, as shown in Table III-l, are used in Industrial
Degreasing, (see the Listing Background Document for Solvent
Degreasing Operations) with the other half being used in
various types of repair work.(l) According to Reference
(6), the total number of degreasing operations in the United
States for 1976 was over 1,300,000, of which nearly half
were associated with manufacturing operations of various
t v p e s . The major solvents used are trichloroethylene, 1,1,1-
trichloroe thane, and chlorofluorocarbons. Most of the
solvents used in surface cleaning were halogenatei, iue to
their nonflannable character; this property is especially
important in high-tanperatura degreasing operations.
-u"-
-------
Neither surface cleaning nor etcher of its two subcate-
gorles can be classified as industry specific, per se; rather,
these operations are conducted in a number of types of indus-
tries (i.e., primary metals, auto repair shops, textile
plants).
With respect to the geographic distribution, industrial
degreasing is the most concentrated source of solvent wastes
from the surface cleaning category since degreasing is asso-
ciated with manufacturing operations that involve metal
finishing (including etching, plating, priming and painting)
and electronic components manufacture. The repair
work subcategory is much more diffuse in distribution, with
both commercial service and repair and consumer-performed
maintenance and repair being generally distributed in the
same pattern as the population itself.(5)
The major types of wastes from solvent usage in the
industrial degreasing subcategory are used (spent) solvent
and solvent recovery still bottoms. Wastes from the repair
work subcategory would include both halogenated and" non-
halogenated solvents, and would take the form of relatively
small amounts of used solvent (typically up to a few gallons),
plus contaminated rags and other materials.
D. Production of Pesticides, Pharmaceuticals and
Other Organic Chemicals
Solvent qp?li:ations in the production of pesticides,
Pharmaceuticals and other organic chemicals include usage as
-------
a reaction (synthesis) medium, and usage in equipment cleaning.(
The solvents used are primarily non-halogenated and are
typically selected for compatibility with the production
process. Toluene is the most widely used solvent in pharma-
ceuticals manufacture, methanol is used as the reaction
solvent in Nylon 66 production, and acetone is used as the
solvent in the production of cellulose acetate.(*)
Wastes frora solvent usage in these industries take the
form of off-specification product material, equipment cleaning
wastes, and solvent recovery still cottons. The destination
of all solid wastes is not known, but a large percentage is
reclaimed either in-house or by contract recovery ope rat ions.(5)
Solvent-containing wastes in these industries are not as'
geographically distributed as in the other categories discussed
herein, but would be expected to follow the general geographical
pattern of the organic chemical industry.
E. Laundry and Dry Cleaning
There are about 25,000 retail dry cleaning plants
in the United States, 18,000 of which use between 167,000
k'
-------
solvents are used Co remove dirt, grease and other materials.
It is believed that 8 percent^7' -of the amount of perchloro-
ethylene used in dry cleaning is disposed of along with still-
botton and cooker residues, so that the amount of perchloro-
ethylene discarded is between 13.4 and 16.6 thousand kkg/yr.
The distribution of dry cleaning plants is uniform with
respect to population and is especially associated with popu-
lation in large urban areas.(7)
Still bottoms from retail dry cleaning consist of about
60 percent solvent and 40 percent oily residue.(7) "Cooker"*
residues are 25 percent solvent and 75 percent spent filter
(mostly diatoraaceous earth).(7)
F. Solvent Recovery Operations
Still bottoms from solvent recovery operations are
Che regaining waste streams included in this Listing. Each
of Che solvent use industry cacegories discussed above generates
feedstocks for solvent recovery operations. Recovery nay be
accomplished either in-house or by conCracC Co a recovery firm.
With regard to contract solvent recovery operaCions,
there are between 30 and 100 contract solvent recovery
operations in the 'J.S.(^) The surface cleaning caCegory,
and particularly industrial degreasing operations is one of che
largest sources of spent solvents sent Co concract reclaimers.
*A "cooker" is a type of still in which so 1vant-contaminated
diatonaceous filter powder is heated to drive off the solvent
fraction of the total liquid residue contained in the filter
po wde r-
-X-
--J2-
-------
Other important sources of spent solvents are the paint, ink,
and coatings manufacturers and manufacturing processes where
very pure solvents are used in organic synthesis (e.g., the
organic chemical and Pharmaceuticals industries).*^8) Some
contract reclaiming of solvents is also carried out on sol-
vents from commercial and industrial dry cleaning operations.
The geographic distribution, by state, of contract solvent
recovery operations is presented in Table III-2.
The volume of feedstock sent to the contract solvent
recovery industry is approximately 287,000 kkg/yr; of this
volume, about 27 percent are halogenated.(^)
Although there are approximately 100 contract solvent
recovery companies, the total number of solvent recovery
operations is much larger due to on-site recovery. Of the
total number of plants involved in "cleaning oDerations",
97.39 percent perform on-premises solvent re:)very.(8)
Excluding the dry cleaning plants, which are distributed
geographically in the same pattern as population, the geographic
distribution of all solvent recovery operations is as shown
in Table III-3.
Solvent recovery still bottoms (sludges) from contract
reclaiming operations amount to about 7 3 , 9 "• 0 -;kg/yr, of which
between 5 and 50 percent i •> solvent, or an average solvent
content of about 25 pe r c e n ~ . ' 4 } Voo-.it 2~ o-ercent of the
solvents in still-bottom slices are halogenated. ( ' ) Thus,
the total still bottom «-a-te from contract reclaiming consists
of the following components:
-------
Table III-2
GEOGRAPHIC DISTRIBUTION OF CONTRACT SOLVENT
RECOVERY OPERATIONS^4)
\T e w J e r s e y 9
California 9
Ohio 8
Illinois 3
Michigan 7
Mew York 5
Indiana 4
Massachusetts 3
Rhode Island 2
Maryland 2
South Carolina 2
Georgia 2
Kentucky 2
Tennessee 2
Missouri 2
Texas 2
Connec t icuc 1
North Carolina 1
Florida 1
Kansas 1
\rizona I
TT
--N-
-------
Table IZZ-3
—n DisT?;H-jTia; c? SCIV--ST .-^L^IXTG
C'-s-a
x T - '— - —
Arize -a
Cal i f o —r.i a
Colorado
-.^i a
C— o-c; a
'.'_J — < - C
r. e."^^ V C-*. ^
I-O u i s i .= ~a
V s i' ->a
v - - - = <--• • • c s. - - ~
•u~cr. igar.
. : =S- -i
v.- c=c.._:
>'c.~."ar.a
^va^a
N'ev r.=r~^ shire
Nev Mexico
>^ev York
^^'*>~-'"~-l •» 3. ^' 1 1. 7^. -H.
Ohio
C!-t
cf Tcral
: s
0.94
0.59
• 0 .
C.15
i —
0 *5
W . _ J
3.5
* j
E-l
2.2
1.7
2.0
0.5
2.0
j ^
-. .3
- ^
i W
2.3
0.77
.1 ~ Q
0.33
— * /
0.57
3. 9
2.5
=!i'
1.3
i . i
5.9
0.57
1.3
-------
"Jtah
.r.ia
21
5
C "7
72
41
90
Ł
0.36
0.24
2.3
1.7
O.SS
2.2
r\ * A
-------
13,250 kkg/yr solvent, including 13,320 kkg/yr non-
halogenated and 4,930 kkg/yr halogenated;
54,750 kkg/yr non-solvent contaminant, including oils, waxes,
metals and chlorinated and nonchlorinated organics.
The estimate of 25 percent average solvent content, as
presented above, can probably be applied to solvent recovery
still bottoms for all of the industries discussed herein,
since the technology used to reclaim solvents is roughlv
similar throughout U.S. industry.^3^
Waste Management Practices*
The nost widely used management practices for spent
solvents is either recovery/reclamation (either on-site
or by contract recovery operations), land disposal (which
nay include anything froo open ground dumping to landfi111ng),
or incineration. For still bottoms, about 3 "^ 3) to 36^)
percent of these bottoms from contract solvent reclaimers
*The Agency has concluded that it does have jurisdiction
under Subtitle C of RCRA to regulate waste materials that
are used, reused, recycled or reclaimed. "urthernore, it
has reasoned that such materials do not become less hazard-
ous to human health or the environment because they are
Intended to be used, reused, recycled or reclaimed in lieu
of being discarded. Therefore, at this time, applicable
requirements of Parts 2o2 through 265 and 122 will apply
to the accumulation, storage and transportation of hazardous
wastes that are used, reused, recycled or reclaimed. The
Agency believes this regulatory coverage is appropriate to
the subject wastes. These spent solvents and still bottoms
from the recovery of these solvents are hazardous in so far
is they are being accumulated or stored in drums or tanks
prior to recycling. Therefore, these wastes will be con-
sidered as hazardous whether recycled or disposed. However,
at the present time, the management of these wastes during
recycling operations will not be regulated.
.-17-
-------
are incinerated. Still bottom sludges from both contract
reclaimers and from solvent recovery operations performed
by solvent-using industries, if not incinerated, are either
Ian.drilled or injected into deep vells.f ,5) Land disposal
of still bottom sludges from contract reclaimers is mostly
in landfills that are covered d ;i i 1 y . V ^ ) A snail amount
of sludge is used as asphalt ex:ender (about 0.1 percent).(
-vf-
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IV. References to Section III
1. Lee, B.B., G.E. Wilkins and E.M. Nichols. Organic
solvent use study. Final Report. EPA No. 560/12-790-
002. NTIS PB No. 301 342. 1979.
2. Wildholz, M. (ed.). The Merck Index. 9th ed. Merck
and Company. Rahway, New Jersey. 1976.
3. Sax, N. I. Dangerous Properties of Industrial Materials.
Van Nostrand Reinhold Publishing Company, New York. 1963.
4. Scofield, F., J. Levin, G. Beeland and T. Laird. Assess-
ment of industrial hazardous waste practices, paint &
allied products industry, contract solvent reclaiming
operations, and factory application of coatings. EPA
No. 530/SW-119c. NTIS PB No. 251 669. September, 1975.
5. Levin, J., G. Beeland, J. Greenberg, and G. Peters.
Assessment of industrial hazardous waste practices:
Special machinery manufacturing industries. NTIS PB No.
262 981. March, 1977.
6. Goodwin, D. R., and D. G. Hawkins. Organic solvent
cleaners - Background information for proposed standards.
EPA No. 450/2-78-045a. NTIS PB No. 137 912. October, 1979.
7. International Fabricare Institute. Silver Spring, Maryland
Personal communication with B. Fisher. December, 1979.
8. Tierney, D.R., and T.W. Hughes. Source assessment
reclaiming of waste solvents. State of the Art. EPA
No. 600/2-7S-004f. NTIS PB No. 282 934. April, 1978.
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IV. HAZARDS POSED BY THE WASTES
A,» Hazardous Properties of the Solvents
The major halogenated solvents exhibit organic toxic
properties which make them potentially hazardous to human
health and the environment. Tn particular, the two halo-
jenated solvents, perchloroethylene and trichloroethylene
are on CAG's List of Carcinogens and 1 ,1,1-trichloroethane
is a suspect carcinogen. All of the listed halogenated
organic solvents, except 1 ,1,2-trichloro-l,2,2-trif 1uoro-
ethane, are priority pollutants under Section 307(a) of the
CWA.
A number of the non-halogenated organic solvents also
exhibit toxicity properties. For example, nitrobenzene has
been identified as a suspect carcinogen. These compounds
are toxic via one or more of the exposure routes inhalation,
ingestion and/or through the skin. Short tern human exposure
to these compounds can have numerous adverse effects. (For
more information on the adverse health effects of these
halogenated and non-halogenated solvents, see Health and
Environmental Effects, pp'. 38-45. In addition, almost all
of the non-halogenated solvents also present an ignitahility
hazard.
In light of the health hazards associated with the waste
-------
solvents — particularly those which are genetically active--
and the high concentrations of hazardous solvents contained
in the waste, the Agency believes a decision not to list
these waste solvents as hazardous would be warranted only if
the Administrator were convinced that waste solvents could not
migrate and persist, reaching 'human or environmental receptors
(if improperly managed). Such assurance does not appear possi-
ble. Not only do all of the waste solvents invarying degrees,
have significant potential for migration, mobility, and persist-
ence, but many have been implicated in actual damage incidents as
well. The Administrator thus believes the hazardous waste
listing to be warranted.
In addition, almost all non-halogenated solvents also
present an ignitability hazard. According to Table 1-2,
the fourteen most-used non-halogenated organic solvents exhi-
bit flash points of 115°F or below, and are thus well below
the limit set for defining an ignitable waste under RCRA
§261.21 (flash point below 140°F); therefore, these spent
solvents and the still bottoms from the recovery of these
solvents are defined as hazardous.
Based on the information in Section III, nost of the
wastes from usage of organic solvents are landfilled or incin-
erated. Smaller amounts of these solvent wastes are either
placed on open land (or rtunps), into storm sewers, and into
deep wells. Misnanagenent and improper disposal of these
-------
wastes by any of these methods could result in a substantial
health and environmental hazard.
Actual damage incidents (see pp. 32-35) involving"certain
of these listed wastes confirm the dangers of ignitability,
and of leaching of waste constituents from landfills to
groundwater. Improper waste incineration could also lead to
substantial hazard. Thus, inadequate incineration conditions
(temperature and residence time) can result in emission of
solvents or toxic degradation products. Where a chlorinated
solvent is involved, emissions could be more dangerous than
the waste itself. For example, phosgene is a partially
combusted chlorinated organic (halogenated solvent) which is
produced by the decomposition or combustion of chlorinated
organics by heat. ^a • ^^ »^-c ' Phosgene has been
used as a chemical warfare agent and is recognized as extremely
toxic.
3. Migratory Potential and Persistence of Halogenated And
Non-Halogenated Solvents
The following section discusses the migratory potential,
nobility, and persistence of the individual waste solvents.
In general, a_l of these solvents appear capable of sufficient
migration, mobility and persistence to create a substantial
hazard should waste mismanagement occur.
Environmental fate d * t a showing the ootential for release
of the individual halo»enat*i and non-haloge na t = d solvents is
-------
SJ-34-01
described below and summarized in Table IV-1 and Table IV-2.
Perchloroethylene
Perchloroethylene, if not properly disposed of, may
migrate from the waste into the environment via both air and
.ground water exposure pathways.
Having been detected in several sites away from the
disposal area (i.e., found in varying amounts in school
basement air, in basement sumps, and on solid surface samples
at the Love Canal site), perchloroethy1ene has indeed been
demonstrated to be quite mobile and persistent.1'
Methylene Chloride
Hethylene chloride, if not properly managed, may migrate
from the waste into the environment. It is very water-
soluble (20,000 ng/1), thus could leach into groundwater
and persist there due to its stability.1^ It is also very
volatile (350 mm Hg at 20°C) and could present an air pollu-
tion problem because of its high evaporation rate (1.8 times
the rate of ether) and its stability in air and light.10
Trichloroethylene
Trichloroethylene , if not properly managed, may migrate
from the disposal site into the environnent via air and
groundwater pathways. First, it is volatile (77 mg Hg at
20"C, 141.04 mm Hg at 40°C'S), so it nay be released from
the waste into the air; it has been detected in school and
basement air at the Love Canal site.*5
-------
TABLE IV-1
Halogenated Solvents*
Compound
Perch lor oe thy lene
Methylene chloride
Trichloroe thy lene
1, 1,1-Trichloroethane
Chlorobenzene
1
1,1,2-Trichloro-
1,2, 2-Tr if luor oe thane
1
1 , 2-D ichlor obenzene
Trichlorof luor ome thane
Vapor Pressure
(mm Hg)
19 at 25 °C5
350 at 20°C
77 at 25°C5
100 at 20 °C
10 at 22 °C
270 at 20°C
1.56 at 25°C5
687 at 20°CU
Solubility in
Water (mg/1)
150 at 25 °C5
20,000 at 25 °C5
1,000 at 20°C5
950 at 25 °C
488 at 25 °C
10 at 25°C
145 at 25 °C
1,100 at 25 o11
Octanol/Water
Partition
Coefficient
3392
20
1952
158
690
100
24002
'
3392
* Table compiled from data given in "Physical Chemical Properties of Hazardous Waste
Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
-54-
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Table IV-2
Non-Halogenated Solvents*
Compound
Me t ha no 1
Toluene
Methyl ethyl ketone
Methyl isobutyl ketone
Carbon disulfide
Isobutanol
Cresols and cresylic
acid ortho (1,2)
aeta (1,3)
para (1,4)
itrobenzene
Pyridine
Vapor Pressure
(mm Hg)
100 at 21.2°C
28.4 at 25°C
100 at 25°C
16 at 20°C
260 at 20°C
10 at 25°C
0.24 at 25°C1-1
0.04 at 20°C^
0.11 at 25°CH
1 at 44.4°C
20 at 25°C
Solubility
in Water
Miscible
470 at 25'C
100,000 at 25°C
10,000 at 25°C
2,200 at 25°C
95,000 at 18°C
31,000 at 40°C11
23,500 at 20°C11
24,000 at 40°CL1
1,900 at 25°C
Miscible
Octanol/Water
Partition Coefficient
5
117
1
1
100
8
HO2
1022
982
62
5
*Table compiled from data given in "Physical Chemical Properties of Hazardous
'Jaste Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
-------
Ic is also relatively water-soluble (1,000 mg/1), so
that it may leach into groundwaters if not adequately contained.
Trichloroethylene has been detected in a number of wells and
residue ponds near groundwater contaminated by a chemical
company dump, as well as in basement sumps at the Love Canal
site, confirming its moblity and persistence in groundwater.9
l,l,l-Trichloroet'-ine
1,1,1-Trichloroethane is a highly mobile compound, and
if not properly managed, could migrate from wastes into
the environment. It is highly volatile (100 mm Hg at 20°C;
approximately 210 mm Hg at 40°C), so that it may be released
from waste sites into the air. Once in the air, it will
only decompose at elevated temperatures. Because of this,
and the fact that 1,1 ,1-trichloroethane is reactive to sunlight
at high altitudes, while stable at low altitudes, it nay
create air-pollution problems if disposed of inadequately.^-^
It has been detected in school and basement air at the Love
Canal s i te . 9
1,1,1-trichloroethane is also relatively water-soluble
(950 mg/1) and mobile, particularly where soils are low in
inorganic content.10 Tt is also relatively persistent in
groundwater where it reacts slowly, releasing hydrochloric acid.10
Chlorobenzene
Chlorobenzene may migrate from the disposal site into the
en/ironment if inadequately disposed of. Its water solubility is
fairly high (488 mg/1) to enable its leaching into groundwater
where it would persist, since it is not amenable to hydrolys is . -[~>
-------
Chlorobenzene is also volatile so it could be released from
wastes into the alr-10 It has been detected in school
and basement air, basement sumps, and solid surface samples
at the Love Canal site.9 Because it does not biodegrade
well, Chlorobenzene is very persistent in the environment.10
l>1»2~Trichloro-l>2>2-trifluoroethane/Trlchlorofluoromethane
These two solvents, if improperly managed, can migrate from
the disposal site into the environment. They are extremely
volatile (1,1,2-trichloro-l,2,2-trifluoroethane-270 mm Hg at
20°C, to over 500 mm Hg at 40°C;10 trichlorf1uoronethane-
687 ma Hg at 20°C7) and very persistent in the environment
due to resistance to biodegradation, photodecomposition, and
chemical degradation.7 Because of their high volatility and
persistence, after release at the surface of the earth,
these solvents rise to the stratosphere where they nay release
chlorine atoms and deplete the ozone. This can lead to
various adverse health and environmental effects resulting
from an increase in the amount of ultraviolet radiation
reaching the earth, as well as possible changes in the earth's
climate induced by the "greenhouse effect".3'14
o - PiChlorobenzene
o - Dichlorobenzene, if disposed of improperly, may
migrate from the disposal site into the environment by both
air and water pathways. Having been detected at several
sites away from the disposal area (found in school and base-
nent air, in basement sumps, and in solid surface samples at
-vf-
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the Love Canal site), o-dichlorobenzene has been demonstrated
to he mobile and persistent.
o-Dichlorobenzenes has a very high octanoI/water par-
tition coefficient of 2,400, indicating a high bioaccuraulation
potential. Thus, migration, even in small concentrations,
could lead to a chronic toxicity hazard (Appendix A).
Toluene
Toluene, if improperly managed, may migrate from the
the disposal site into the environment. Tt is relatively
volatile (vapor pressure 23 mm Hg at 20°C) and so can migrate
via and air pathway. Tt can re-enter the hydrosphere in
rain.^-2 Toluene is also capable of migration via a groundwater
pathway since it is relatively soluble (470 mg/1), and persistent
in abiotic environments (such as most aquifers).
Toluene has been detected in school and basement air,
basement sumps, and solid surface samples at the Love Canal
site, demonstrating its mobility and persistence in both air
and groundwater."
Methyl Ethyl Ketone
Methyl ethyl ketone, if disposed of inadequately may
migrate from the disposal site into the environment. It is
extremely soluble in water (100,000 mg/1), and therefore could
leach into groundwater. Tt is also very volatile (185.4 mm
'-Ig at 40°C^), and could present an air pollution problem
if improperly contained. because of its high solubility
-------
it could be re-entrained from air into the hydroshpere via
rain.
Methyl ethyl ketone has been detected at several sites
near groundwater contaminated by an old chemical company
dump, as well as in school and basement air at the Love Canal
site, demonstrating both its mo-bility and persistence.9
Carbon Disulfide
Carbon disulfide, if improperly managed, may migrate
from the disposal site into the environment. It is extremely
volatile (260 mm Hg at ?. 0 ° C) and althouth subject to photo-
lysis, could present an air pollution problem if inadequately
contained. It is also quite soluble in water (2200 mg/1),
and is not known to attenuate in soils; therefore it could
leach into the groundwater, where, being unamenable to hydro-
lysis, it is likely to persist for an extended time period.1 ^
Isobutanol
Isobutanol, if improperly managed, may migrate from
the disposal site into the environment. It is extremely
water-soluble (95,000 mg/1); thus, if inadequately contained,
it may contaminate surface water and adversely affect its self-
purification ability.10 jn addition, isobutanol could leach
into groundwater if disposal is inadequate.
Cresols (and cresylic acid)
Cresols, if improperly managed, may migrate from the
disposal site into the environment. Cresols are highly
soluble (23,500 to 31,000 mg/1) and are not known to attenuate
-------
significantly in soils; thus, they could leach into groundwater
if disposal is inadequate. Once in water, cresols rapidly
form chlorinated compounds, which are more environmentally
objectionable.10 Cresols are not known to hydrolyze and so
would be likely to persist in groundwater.11
Nitrobenzene
Nitrobenzene, if disposed of inadequately, may migrate
from the disposal site into the environment. It is water-
soluble (1900 mg/1) and would be mobile where soil organic
content is low,10 and thus could leach into groundwater if
disposal is not adequate. It is likely to be highly per-
sistent in groundwater since it is not amenable to hydrolysis
and does not biodegrade well.^0
Pyridine
Pyridine, if disposed of inadequately, may migrate from
the disposal site. Because pyridine is miscible with water,
it has high migratory potential. It would be mobile as well,
unless soil has high clay content.10 Pyridine also would be
likely to persist in the abiotic environment of most ground-
waters .
C. Mismanagement of Wastes Destined for Land Disposal
Documented damage incidents resulting from the mis-
management of these wastes from usage of organic solvents
are presented below:
-yt-
-------
Damage Resulting from Ignitability of Wastes
(1) A load of used pesticide containers delivered to a
disposal site in Fresno County, California, also con-
tained several drums of an acetone-raethano1 solvent
mixture. When the load was compacted by a bulldozer,
the waste ignited, engulfing the bulldozer in flames
and dispersed pesticide wastes.(13)
(2) A large number of drums containing organic solvent wastes
were deposited in a landfill at Contra Costa, California.
In the immediate area were leaking containers of concen-
trated mineral acids and several bags of beryllium wastes
in dust forra. The operators failed to cover the wastes
at the end of the day. The combination of wastes ignited
during the night, starting a large chemical fire which
possibly dispersed toxic beryllium oxide.(13)
(3) Two serious fires at the Merl-Milara Landfill, St. Clare
County, Illinois (August, 1973 and April, 1974) were
attributed to the presence of solvent wastes from plastics
manufacture.(13 )
Contamination of Groundwaters
(1) In two separate instances in Michigan, trichloroethylene
was dumped on the ground and later found to have migrated
into groundwater. In one case, trichloroethylene dumped
at a rate of 1000 gallons per year over a four-year
period was detected in residential wells as much as
1100 feet from the site of dumping. Concentrations
ranged as high as 28 ppn.'13)
-vf-
-(0\-
-------
In the other case, the Air Force at a base near
Oscoda, Michigan, had problems with contaminated ground-
water because of a leaking tank which use to hold
trichloroethylene. The problem was compounded when
a waste hauler apparently mismanaged the trichloro-
ethylene that was hauled from the leaking tank, and
groundwater contamination up to four miles away was
considered one of the results. (H)
(2) A sump overflow in 1971 at the Superior Tube Company
allowed trichloroethylene wastes to leak into a cooling
pond. Seepage from this pond was found to contaminate
a private well 75 yards distant and a company well at
the site.(13>
(3) Open dumping of wastes, including solvent wastes, from
a chemical packing plant by U.S. Aviex Company resulted
in entry of organic solvents into the water table and
contamination of several nearby water wells in 1973.
One family reported illness resulting from use of the
contaminated well water.(13)
(4) [Mono ] c'nlorobenzenes , at concentrations of 5 mg/1 and
30 mg/1 has been detected in the water from 2 of 21 ob-
servation wells, installed at depths up to 50 feet at
varying distances from an industrial manufacturing com-
plex devoted to the development and manufacture of en-
gineering plastics.(14)
-------
The damage Incidents presented above illustrate the
following potential hazards associated with wastes from usage
of organic solvents:
(1) Ignitability hazard during mismanagement;
(2) Potential toxicity hazard to humans via groundwater
exposure pathways.
-------
IV . References to Section IV (A, B and C)
1- Jacobs, S. The handbook of solvents. D. Van
Nostrand Company, Inc. New York. 1957.
la. Edwards, J.B. Combustion formulation and emission of trace
species. Ann Arbor Science. 1977.
Ib. NIOSH. Criteria for a recommended standard: Occupational
exposure to phosgene. HEW, PHS, CDC, NIOSH. NTIS PB No.
267 514. 1976.
Ic. Chemical and Process Technology Encyclopedia. McGraw
Hill. 1974.
2. Leo, A., C. Hansch and D. Elkins. Partition coefficients
and their uses. Chem. Rev. 71:525-616. 1971 (Updated 1977).
3. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloro me thane
release. Publication No. 2529. 1976.
4. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Stratospheric
ozone depletion by halocarbons: Chemistry and transport.
1979.
5. Patty, F.A., ed. Industrial hygiene and toxicology.
Interscience Publishers, New York. 1963.
6. Sax, N. I. Dangerous properties of industrial materials,
5th ed. Van Nostrand Reinhold Company, New York.
1979.
7. U.S. EPA. Environmental hazard assessment of one- and
two-carbon f luor ocar bons . EPA No. 560/2-75-003. NTIS
P3 No. 246 419. 1975.
3. U.S. EPA. Evaluation of treatment, storage, and disposal
techniques for ignitable, volatile, and reactive wastes.
Contract Number 68-01-5160. (Draft final report). 1980.
9. "Love Canal Public Health Bomb", A Special Report to the
Governor and Legislature, New York State Department of
Health. 1973.
10. U.S. EPA. Physical chemical properties of hazardous
waste constituents. (Prepared by Southeast Environmental
Research Laboratory; Jim Falco, Project Officer). 1980.
11. Verschueren, K. Handbook of environmental data on
organic chemicals. Van Nostrand Reinhold Company, New
York. 1977.
-44-
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12. Walker, P. Air pollution assessment of toluene.
NTIS PB No. 256 735. May, 1976.
13. U.S. EPA. Open Files. Hazardous Site Control Branch,
WH-548, U.S. EPA. 401 M St., S-W., Washington, D.C. 20460
Contact Hugh Kauffman. (202) 245-3051.
14. TSCA Section 8(e) notice from General Electric Company to
U.S. EPA, Region I Permits Branch, January 23, 1980.
-(,*>--
-------
D. Health and Environmental Effects*
Perchloroethylene (Tetrachloroethylene)
Perchloroethylene (PCE) was reported carcinogenic to
mice.(^) It has also been identified by the Agency as a
chemical which has demonstrated substantial evidence of being
carcinogenic. PCE is chronically toxic to rats and mice, causing
kidney and liver damage;(l^>^°»21-) and to humans, causing impaired
liver function.(2) Subjective central nervous system complaints
were noted in workers occupationally exposed to PCE.(^' PCE
exposure is reported to cause alcohol intolerance to humans.
PCE is a priority pollutant under Section 307(a) of the
Clean Water Act.
Methylene Chloride (Dichloromethane )
EPA has found "suggestive" evidence of the carcinogenicity
of methylene chloride, therefore, methylene chloride is
considered a "suspect carcinogen" (Appendix A^; methylene
chloride was also reported as being mutagenic to a bacterial
strain, _S_. typhimurium. (24) -jt was reported to be feto- or
embryo-toxic to rats and mice.(23) Female workers had
gynecological problems after prolonged exposure to methylene
chloride.(36) Methylene chloride also causes central
nervous system depression and elevation of carboxyhemoglobin
levels.(1°) Severe contamination of food or water can
causa irreversible renal and hepatic injury.(30) Acute
toxicity values range from 147,000 to 310,000 ug/1 for aquatic
*Euhyl benzene, which is only being listed for its ignitability
hazard, is also considered a priority pollutant under Section
307(a) of the Clean Water Act.
-3X-
-------
organises (Appendix A)
Trtchloroethylene
Trichloroethylene (TCE) has been reported Co be carcino-
genic to mice.(15) It has also been identified by the Agency
as a chemical which has demonstrated substantial evidence of
being carcinogenic.H8) industrial exposure to TCE caused
some cases of central nervous system disturbances (headaches,
insomnia, tremors) as well as peripheral nervous system
impairment (neuritis, temporary loss of tactile sense, finger
pa ra lys is ) . ' •*- > 1 3 ) Rare cases of hepatic damage have been re-
ported following repeated abuse of TCE.(6)
TCE was found to be toxic in varying degrees to several
freshwater organisms. (<• 8) There was also a 50% decrease
noted in l^C uptake by a saltwater algae at a concentration
of 3,000 ng/1.(2°)(Appendix A)
1,1,1-Trichloroethane (Methyl Chloroform)
Data regarding the careinogenicity of 1,1,1-trichloroe th-
ane is inconclusive. (1?) it is mutagenic in the Ames test,
and in a mamallian cell transformation system (See Appendix
A). Chronic exposure, albeit is greter than ambient levels,
can cause central nervous system disorders in humans. Animal
studies showed toxic effects on the central nervous system,
cardiovascular system, oulmonary system, and induced liver
and kidney damage.^34) 1, 1 ,1-Trichloroethane is a priority
pollutant under Section 307(a) of the Clean Water Act.
-yf-
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Chlorobenzene (Monochlorobenzene, MCB)
Chlorobenzene has been found to produce htstopathological
changes In the lungs, liver, and kidneys following its inhalation
by rats, rabbits and guinea pigs. (7) Oral administration of
^onochlorobenzene to rats was reported to cause growth retar-
dation in males .( H) MCB also -appears to increase the activity
of some microsomal enzyme systems, wh-ich enhances the metabolism
of many drugs, pesticides, and other xenobiotics.(29)(Appendix ^ )
MCB was reported to be toxic to varying degrees to
several fresh- and salt-water organisms, including algae, (28)
has a high biomagnification factor (Appendix B), is resistant
to biodegradation and hydrolysis and is, therefore, persistent.
MCB is a priority pollutant under Section 307(a) of the
Clean Water Act, is a subject of TSCA section 4 Test Rule, and
has been selected for bioassay by NCI. These regulatory actions
point to concern regarding its toxicity.
1,1,2 Trichloro-1,2,2 trifluoroethane
The Agency's primary concern in listing this solvent is
the air pollution hazard resulting from its release at the
surface of the earth. This can have many adverse health and
environmental effects including increased incidence of skin
cancer, reduced productivity in several important agricultural
crops, and increased mortality in the larvae forms of several
important seafood species resulting from the depletion of
the ozone.(39,40) Because of these effects, EPA is currently
considering regulation of CFG production and use.
-------
1,2-Dichlorobenzene (ortho isomer)
Ortho 1,2-dichlorobenzene exhibits moderate toxicity via
inhalation and oral routes. The major toxicologica1 effect
is injury to the liver and kidneys; it is also a central ner-
vous system depressant after short periods of exposure(19»22)
(Appendix A) .
1,2-dichlorobenzene is designated a priority pollutant
under section 307(a) of the Clean Water Act.
Trichlorofluorome thane
The Agency's primary concern in listing this solvent is
the air pollution hazard resulting from its release at the
surface of the earth. This can have many adverse health and
environmental effects including skin cancer resulting from
the depletion of the ozone (Vide Sufora). ( 39»4°) However,
additional adverse health effects have been found and are
presented below.
Exposure of rabbits to trichlorofluoromethane was re-
ported to cause cardiac arrhythmias.^-"^ It induced
cardiac arrhythmias, sensitized the heart to epinephrine-
induced arrhythmias, and caused tachycardia (increased
heart rate) myocardial depression, and hypertension in the
monkey, dog, rat and mo use.(26)
Trichlorofluoromethane is a priority pollutant under
Section 307(a) of the Clean Water Act.*
*The Agency has recently proposed to remove trichlorofluoro-
-ie thane from the list of toxic pollutants under §307(a) of
the Clean Water Act (45 FR 46103, July 9, 1980).
-------
Toluene
Toluene is a toxic chemical absorbed into the body by
inhalation, ingestion, and through the skin. Data on its
tnutagenicity and carcinogenicity are inconclusive, but it
has been reported to cause chromosomal change; teratogenic
problems were also recently reported.'4'' The acute
toxic effect is central nervous system depression, (•+5;
and irritation of eye and throat. These effects occur at
low concentrations [200 ppm].(^°) Chronic occupational
exposure to toluene has led to the development of neuro-rauscular
disorders. Occupational exposure to female workers to toluene
reported to cause several reproductive problems, both to the
wonan and the offspring.(25) Chronic toluene exposure can
cause dermatitis, affect the immune system, and cause permanent
damage to the central nervous system.(4 " '
Since toluene is metabolized in the body by a protective
enzyme system which is also involved in the elimination of
other toxins, it appears that over-loading the metabolic
pathways with toluene -nay greatly reduce the clearance of
other more toxic chemicals. Additionally, the high affinity
of toluene for fatty tissue can assist in the absorption of
other toxic chemicals into the body- Thus, synergistic
effects of toluene on the toxicities of other contaminants
may render the waste stream nore hazardous (Appendix A).
Toluene is a priority pollutant under Section 307(a) of
the Clean Water Act.
-70-
-------
Methyl Ethyl Ketone
Methyl ethyl ketone Is a highly volatile ignitable liquid
of moderate toxicity via ingestion which can affect the
peripheral nervous system and is an experimental teratogen
(Appendix A ) . It is also a strong irritant of the mucous
membranes of the eyes and nose.. A lethal dose in animals
(LC5Q ~ 700 ppra) has caused marked congestion of the internal
organs and slight congestion of the br.iii. Lungs also showed
emphysema (Appendix A).
Carbon Disulfide
Short term human exposure to low atmospheric concentrations
of carbon disulfide nay result in central nervous system de-
pression, headaches, breathing difficulty and gastrointestinal
disturbances. Exposure to short term b-ut high atmospheric
concentrations can lead to narcosis and death. The symptoms
of humans subjected to repeated exposure to high concentrations
or prolonged exposure to low concentrations include insomnia,
fatigue, loss of memory, headache, melancholia, vertigo and
loss of appetite. Visual impairment, loss of reflexes, and
lung irritation has been r epo r t ed . ( *9 » 2 2 > Kats and mice exposed
3 hours per day for 20 weeks to an average concentration of 37 ppra
carbon disulfide showed evidence of toxic e f fee t s . < 19 )( Appendix A)
Isobutanol
Rats receiving isobutyl alcohol, either orally or subcu-
taneously, one to two tines a week for 495 to 643 days showed
liver carcinomas and sarcomas, spleen sarcomas and myeloid
leukemia. (43)
-71-
-------
Ingestion of one molar solution of Isobutyl alcohol in
water by rats for 4 months did not produce any inflammatory
reaction of the liver. However, rats ingesting a two molar
solution for two months developed Mallory's alcoholic hyaline
bodies in the liver and were observed to have decreases in
fat, glycogen, and R N A in the liver. (43)
Acute exposure to isobutyl alcohol causes narcotic effects,
and irritation to the eyes and throat in humans exposed to
100 ppm for repeated 3 hour periods. Formation of facuoles
in the superficial layers of the cornea and loss of appetite
and weight were reported among workers subjected to an undeter-
mined but apparently high concentration, of isobutyl alcohol.(44)
(Appendix A)
Pyridine
Pyridine exhibits moderate toxicity when absorbed into
the human body through oral, dermal, and inhalation routes.(22)
Liver and kidney damage has been produced in animals and man
after oral adrainistration.(3) in small doses, conjunctivitis,
dizziness, vomiting, diarrhea and jaundice may appear; tremors
and ataxia, irritation of the respiratory tract with asthmatic
breathing, paralysis of eye muscles, vocal cords and bladder
also have been reported.(22)
Adverse taste in fish (carp, rudd) has been reported at
5 ppm. Pyridine causes inhibition of cell multiplication in
algae and bacteria at 23 and 340 ppm respectively.(35^(Appendix A)
-72-
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Nitrobenzene
Nitrobenzene Is a suspected carcinogen.(4) When
administered to pregnant rats, it caused abnorna1ities in
some of the fetuses exanined.(^) Changes were observed
in the chorionic and placental tissues of pregnant workers
exposed to nitrobenzene,^) and menstrual disturbances
after chronic exposure have been reported. Chronic exposure
to nitrobenzene has been found to cause a variety of blood-
variety disorders.
Nitrobenzene is toxic in varying degrees to several
salt- and fresh-water organises.(31) (Appendix A), and nitro
benzene is a priority pollutant under Section 307(a) of the
Clean Water Act.
Cresols (Cresylic Acid)
Cresol is highly toxic if orally administered, and
moderately toxic if inhaled. Absorption may result in danage
to kidney and liver as well as the central nervous system.(22
Exposure to cresol can cause severe skin burns and derma-
titis .(l9»22>(Appendix A)
-73-
-------
VII. References to Section IV, D
1. Bardodej, A., and J. Vyskocil. The problem of trichloro-
ethylene in occcupational medicine. AMA Arch. Ind. Health.
13:581. 1956.
2. Coler, H.R., and H. R. Rossmiller. Tetrachloroethylene
exposure in a small industry. Ind. Hyg. Occup. Med.
3:227. 1953.
3. Deichmann, W.R. Toxicology of drugs and chemicals.
Academic Press Inc., New York. 1969.
4. Dorigan, J. and J. Hushon. Air pollution assessment
of nitrobenzene. NT IS PB No. 257 776. May, 1976.
5. Gosselin, R.E., et. al. Clinical toxicology of
commercial products, 4th ed. The Williams and
Vilkin Company, Baltimore. 1976.
6. Huff, J.E. New evidence on the old problems of trichloro-
ethylene. Ind. Med. 40:25. 1971.
7. Irish, D.D. Halogenated. hydrocarbons:II. Cyclic.
In Industrial hygiene and toxicology, V.II, 2nd ed.
F. A. Patty, ed . Interscience, New York.
p. 1333. 1963.
8. Kazanina, S.S. Morphology and histochemistry of
hemochorial placentas of white rats during poisoning of
the maternal organisms by nitrobenzene. Bull. Exp. Biol.
Med.(USSR) 65:93. 1968.
9. Not used in text.
10. Klaassen, C.D., and G.L. Plaa. Relative effects of
chlorinated hydrocarbons on liver and kidney function in
dogs. Toxicol. Appl. Pharmacol. 1967.
11. Knapp, W. K-, Jr., et al. Subacute oral toxicity of
monochlorobenzene in dogs and rats. Toxicol. Appl.
Pharmacol. 19:393. 1971.
12. Not used in text.
13. McBirney, B.S. Trichloroethylene and dichloroethylene
poisoning. AMA Arch. Ind . Hyg . 10:130. 1954.
-------
14. Medek, V., and J. Kovarik. The effects of perchloro-
ethylene on the health of workers. Pracovni Lekarstvi
25:339. 1973.
15. National Cancer Institute.- Car c inogene s i s bioassay
of trichloroethylene. NCI-CG-TR-2. NTIS PB No. 264 122.
1976.
16. National Cancer Institute. Bioassay of tetrachloro-
ethylene for possible carcinogenicity. NCI-CG-TR-13.
NTIS PB No. 272 940. 1977.
17. National Cancer Institute. Bioassay of 1,1,1-trichloro-
ethane for possible carcinogenicity- NCI-CG-TR-3.
NTIS PB No. 265 082. 1977.
18. National Institute for Occupational Safety and Health.
Criteria for a recommended standard: Occupational
exposure to methylene chloride. HEW Pub. No. 76-138.
U.S. DHEW. Cincinnati, Ohio. 1976.
19. Patty, F.A., ed. Industrial hygiene and toxicology.
Volume II. Interscience Publishers, New York. 1963.
20. Pearson, C.R., and G. McConnell. Chlorinated C^ and C2
hydrocarbons in the marine environment. P roc . R. Soc .
London B 189:302. 1975.
21. -Rowe , V. K., et al . Vapor toxicity of te tr achlor oe thyl ene
for laboratory animal and human subjects. AMA Ar ch. Ind.
Hyg. Occup. Med. 5:566. 1952.
22. Sax, N. I. Dangerous properties of industrial materials,
5th ed. Van Nostrand Reinhold Company, New York. 1979.
23. Schwetz, B. A., et al. The effects of maternally inhaled
trichloroethylene , perchloroethylene, methyl chloroform,
and methylene chloride on embryonal and fetal development
in mice and rats. Toxicol. Appl. Pharmacol. 32:84. 1975.
24. Simmon, V. F., et al. Mutagenic activity of chemicals
identified in drinking water. S. Scott, et al. eds.
In: Progress in genetic toxicology. 1977.
25. Syrovadko, 0. N. Working conditions and health status
of women handling organosiliceous varnishes containing
toluene. Gig. Tr . Prof. Zabol. 12:15. 1977.
26. U.S. EPA. Environmental hazard assessment report:
Major one- and two-carbon saturated f1uorocarbons;
review data. EPA No. 560/8-76-003. NTIS PB No.
257 371. August, 1976.
27. Not used in text.
-7.5"-
-------
28. U.S. EPA. In-depth studies on health and environmental
impacts of selected water pollutants. Contract No. 68-01-4646.
1978.
29. U.S. EPA. Chlorinated benzenes: Ambient water quality criteria
NTIS PB Mo. 297 919. 1979.
30. U.S. EPA. Halomethanes: Ambient water quality criteria.
NTTIS PB No. 296 797. 1-979.
31. U.S. EPA. Nitrobenzenes: Ambient water quality criteria.
NTIS PB No. 296 801. 1979.
32. U.S. EPA. Tetrachloroethylene: Ambient water quality
criteria. NTIS PB No. 292 445. 1979.
33. Not used in text.
34. U.S. EPA. Chlorinated ethanes: Ambient water quality
criteria. NTIS PB No. 297 920. 1979.
35. Verschueren K. Handbook of environmental data on organic
chemicals. Van Nostrand Reinhold Company, New York, 1977.
36. Vozovaya, M.A. Gynecological illnesses in workers of
major industrial rubber products plants occupations.
Gig. Tr. Sostoyanie Spetsificheskikh Funkts. Tab.
Neftekhim. Khim. Prom-Sti. (Russ.) 56. (Abstract). 1974.
37. Not used in text.
38. U.S. EPA. Office of Research and Development. Carcinogen
Assessment Group. List of Carcinogens. April 22, 1980.
39. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloromethane release.
PB No. 2529. 1976.
40. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Strato-
spheric ozone depletion by halocarbons: Chemistry
and transport. 1979.
41. Linari, F., G. Perreli, and D. Varese. Clinical observa-
tions and blood chemistry tests among workers exposed
to the effect of a complex ketone--methyl isobutyl ketone.
Arch. Sci. Med. 226-237. 1964. (Ital).
42. Specht, H., J.W. Miller, P.J. Valaer, and R.R. Sayers.
Acute response of guinea pigs to the inhalation of
ketone vapors. NIH Bulletin No. 76. Federal Security
Agency. Public Health Service, National Institute of
Health, p. 66.
-74-
-------
43. Gibel, et al. Exp. Chir. Forsch. 1:235. 1974.
44. Smith et al . Arch. Ind. Hyg. Occup. Med. 10:61. 1954.
45. U.S. EPA. Toluene: Ambient water quality criteria.
MTIS PB No. 296 805. 1979.
46. NIOSH. Registry of toxic effects of chemical substances
Toluene. 197 3.
47. Nawrot, P. S., and R. E. Stapler. Embryofetal toxicity
and teratogenicity of benzene and toluene in the mouse
(abstract). Teratology. 19:41a.
48. Cohr, K. H., and J. Stockholm. Toluene-a toxicologic
review. Scand. J. Environ, and Health. 5:71-90. 1979.
-77-
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Response to Comments (Proposed Listings (December 18, 1978))
0 One commenter objected to the listing "Waste non-
halogenated solvent (such as methanol, acetone, iso-
propyl alcohol, polyvinyl alcohol, stoddard solvent
and methyl ethyl ketone) and solvent sludges from
cleaning, compounding milling and other processes."*
The commenter argued that without indicating the con-
centration or quantity of the solvent in the waste,
the Agency would be listing wastes as hazardous even
if the solvent were present in small concentrations and
quant it ies.
In the listing promulgated today for waste solvents,
the Agency is only listing those spent solvents or
still bottoms from the recovery of these solvents
which wo'uld contain substantial quantities and con-
centrations of the solvent. ^ o r example, spent solvents
can contain up to 90% of the original solvent while
the still bottoms may contain up to 50% of the spent
solvent.
A number of comnenters objected to the listing of poly-
vinyl alcohol (PVA) as a solvent. These commenters
argued that PVA is not a solvent but is a solid and
can only be used as a solute. Therefore, they recommended
that PVA be removed from the list.
*This specific listing will not be included in the final
regulation; however, it will be covered under the generic
listing "The Spent non-halogenatad solvents
-------
The Agency agrees with Che comnenters and therefore,
has removed PVA from the listing.
A number of comnenters objected to the listing of waste
halogensted/non-halogenated solvents. They felt that
the listing was too vague and ambiguous.
In the listings promulgated today, the Agency has
specifically listed only those solvents for which data
or information are available which indicates a present
or potential hazard could be posed to human health and
the environment if improperly managed. Therefore, the
listing description promulgated today should respond
to the comraenters1 objection.
-------
Response to Comnents - Spent Halogenated and Non-Halogenated
Solvents and the Still Bottoms/SJudges From the Recovery of
These Solvents
A number of comments were received with respect to wastes
F001 to F005 (Spent halogenated and non-halogenated solvents
and the still bottoms/sludges from the recovery of these
solvents).
1. One commenter requested that the Agency clarify or
define what it means by the term "spent". For example,
the commenter questioned whether "spent" refers to the
state of the chemical which was pure initially but
now appears in the waste stream after being used, or
whether it refers to the altered or decomposed state of
a chemical which has outlasted its shelf life.
The Agency agrees with the commenter and has
thus included the following definition for "spent
solvents" in the listing background documents:
"Spent solvents include those solvents which
are no longer useful as solvents without
further processing (i.e., solvent reclamation),
either because the solvents have outlasted
their shelf life, or because the solvents
-•30-
-------
have been contaminated or chemically or
physically changed.
It should be clear from this discussion that the
wastes encompassed by this listing do not include waste
streams where the solvent is a contaninant, such tnat
the waste stream is not a spent solvent, as defined
above. Thus, wastes which contain as constituents
solvents which are used in the industrial process
are not included within the scope of this listing.
Mor are these waste streams hazardous by virtue of the
mixing rule (§ 261. 3(a)(2)(ii)), since a spent solvent is
not being mixed with another solid waste.
The Agency, however, does not believe it appropriate
to define the term "spent solvent" by using a quantity/
volume cut-off (i.e., spent solvents include those
solvents wh ich contain x percent or more of solvent).
As we have indicated in other support documents (see e.g.,
Background Document on EP toxicity), the Agency does not
presently believe sufficient information exists to
establish minimum waste concentration levels for toxic
constituents, except for those regulated by the Interim
Primary Drinking Water Standards. Ue intend to make
case-by-case determinations via the delisting raechanisn
to remove those wastes containing Tiniial concentrations
of "spent solvent".
-------
Another commenter argued that the scope of the listing
of both spent solvents and still bottons/sludges from
the recovery of solvents, is overinclusive because it
do35 not recognize that certain solvent recovery opera-
tions produce non-hazardous still bottoms.* For example,
the comnenter stated that it is possible to produce a
nonleaching, non-ignitable fused waste solid containing
as low as 5 percent solvent. Therefore, the commenter
recommends that solvent recovery still bottoms be defined
as fo11ows:
"Solvent recovery still bottoms: residue from
the disti1lation/evaporation process of re-
covered solvent which has more than 10% of
the original solvent (excluding water) re-
maining"
The Agency disagrees with the comnenter. In the
first place, the commenter has not correlated the
recommended concentration of solvent with a showing that
exposure to these levels of contaminant will not cause
substantial hazard. Nor is there documentation for the
claim that still bottoms containing 5% of the listed
solvent would be incapable of posing substantial harm if
mismanaged. Furthermore, the Agency believes that
*It should be noted that this comment was directed to waste
F004 (the following spent non-halogenated solvents: cresols
and crasylic acid, and nitrobenzene; and the still bottoms
from the recovery of these solvents). However, EPA's res-
ponse is also applicable to wastes F001, FOG2 and F005.
-------
still bottoms containing 5% of the listed solvent
nay indeed pose a substantial hazard to human health
and the environment if improperly managed.* This premise
is based on the following factors:
(1) The recommended cut-off level (50,000 ppa) is at least
an order of magnitude above that needed to cause
acute effects, and in most case orders of magnitude
higher (see Appendix A to the listing background
document). Thus, still bottoms with 5% concentration
of a listed solvent would only have to leach a
snail percentage of the contained solvent to cause
substantial hazard.
(2) Cresols, cresylic acid and nitrobenzene are all
toxic chemicals: nitrobenzene is a suspect carcino-
gen and has been found to cause a variety of blood
disorders from chronic exposure. Cresols and
cresylic acid are highly toxic if administered
orally and moderately toxic if inhaled. In addition,
cresol and cresylic acid may result in damage to the
kidney and liver as well as to the central nervous
system.
(3) Because of the toxicity of these solvents, the
concentration of solvent in the still bottoms
(five percent) is considered significant by the
Agency.
*At a 5 percent level of solvent, the waste streams may no
longer he ignitable as defined in S261.21.
-------
(4) All of these solvents have high or appreciable
water solubilities (nitrobenzene: water solubility
1^00 rag/1 (Appendix B); cresols and cresylic acid:
water solubilities 23,500 and 31,000 rag/I (Appendix
3) and therefore, could leach into groundwater under
improper disposal conditions.
(5) All of these solvents are likely to persist in
groundwater; cresols, cresylic acid and nitrobenzene
are not known to hydrolyze while nitrobenzene also
does not biode grade well.j^/
The Agency therefore, believes that still bottoms from
the recovery of cresols and cresylic acid, and nitro-
benzene may pose a substantial hazard to human health
and the environment even when five percent of solvent
is in the waste. If an individual generator believes
his still bottoms are non-hazardous, the generator
should petition the Agency to de-list his wa s t e (see
§5260.20 and 260.22).
3. One coramenter criticized EPA's generic designation of
ill spent chlorinated fluorocarbons as hazardous.
Therefore, the coramenter bel laves that the broad category
(chlorinated fluorocarbons) should be replaced by specific
compounds for which documented evidence of hazard is
•iv a 1 lab le . The comnenter also -argued more specifically
* These data are all taken from Appendix R to the listing
background document.
--3H-
-------
that trichlorofluoromethane and dich1orodifluoromethane
are not hazardous constituents^/ and that EPA's reason
for regulating these materials—that they can rise into
the stratosphere and deplete the ozone leading to adverse
health and environmental effects—has not yet been
proven. The comnenter pointed out that the most sophisticated
statistical analyses of actual ozone measurements taken
at various places around the world have consistently
failed to detect the depletion calculated to have
occured to date, despite the fact that the most recent
analyses should detect this depletion even if it were
only half the calculated amount. The conraenter also
argued that there have been growing indications that
the current ozone depletion theory as it applies to
chlorofluorocarbon depletion does not accurately describe
the present-day atmosphere, or fails to consider aspects
of atmospheric chemistry which are both significant and
important. Cited in support is the study Chlorofluoro-
carbons and Their Effects on Stratospheric Ozone (2nd Rpt.)
Pollution Paper No. 15, Department of Environment, Central
Directorate on Environmental Pollution, October 1979.
VThe coramenter cited several reasons for this statement:
(1) the Health and Environmental Effects Profile (Appendix
A) indicates that both trlchlorofluoromethane and dichloro-
'luoroaethane are non-toxic, (2) EPA's proposed action to remove
these two compounds from the Clean Water Act toxic pollutant
list indicates EPA's admission as to the innocuous nature
of these two compounds in the aquatic environment, and (3)
EPA's limited discussion of the various factors under
§261 . ll(a)(3) of RCRA indicates that wastes containing these
two compounds pose no hazard during storage, transportation,
treatment or disposal.
-------
Therefore, the coramenter requested that all chlorinated
fluorocarbons be deleted from the F001 and F002 'generic
waste list.
The Agency disagrees with the commenter on both
points. With respect to their concern regarding the
generic designation of all spent chlorinated fluorocarbons
as hazardous, the Agency believes that all chlorinated
fluorocarbons share the same physiological and photo-
chemical attributes of concern, namely depletion of
the ozone. Therefore, the Agency feels justified
in listing the broad category of chlorinated fluorocarbons
as hazardous, rather than its individual -nenbers.
As to the hazardous nature of the listed chloro-
fluororaethanes, the Agency agrees "that they pose a low
potential for adverse acute effects at anbient air
concentrations, although there is some indication that
long terra exposure to very low levels (<400 p?t) will
have chronic effects (Health Assessment Document, ^PA,
October, 1980). In the present instance, however, the
Agency's overriding concern relates to the fact that
chlorinated fluorocarbons nay indirectly cause skin
cancer due to the depletion of stratospheric ozone.
Such depletion leads to increased intensity of damaging
ultraviolet light at the earth's surface. This, in turn,
leads to increased skin cancers, reduced productivity of
several important agricultural crops and increased
-------
mortality in the larval forms of several important seafood
species. The fact that these compounds are proposed to
be deleted from the list of toxic pollutants under
Section 307(a) of the Clean Water Act does not affect
our conclusion, since Section 307 does not address
adverse effects arising from air exposure pathways.
The Agency has analyzed the British Ministry of
the Environment report and has concluded that there are
few differences in regards to the science of CFC transport
into the stratosphere and the reactions involving ozone
destruction between this report and a recent National
Academy of Sciences report which provides the basis for.
EPA's regulatory action banning the manufacturing,
processing and distribution of chlorinated fluorocarbons
for those non-essential aerosol propellant uses which
are subject to TSCA authority (43 FR 11301, March 17, 1978).
While the British Ministry of the Environmental report
concluded that ample cause for regulating CFCs does
not presently exist, the Agency strongly believes that
their is sufficient evidence to regulate and limit
chlorinated flurocarbon emissions. In the judgment of
SPA, chlorinated fluorocarbons can be a significant
component of a solvent waste stream, can migrate into
the environment (stratosphere) if improperly managed,
are persistent (remaining intact long enough to migrate
tr> the stratosphere), and may pose a substantial hazard
-------
to human health and the environment. They thus should
be regulated as hazardous wastes.V We also note that
the Food and Drug Administration (FDA) has promulgated
regulations which prohibit the use of chlorinated fluro-
carbons as propellants in containers for products subject
to the Federal Food, Drug, and Cosmetic Act.
One comraenter argued that the "T" (toxic) designation
assigned to several of the waste solvents listed under
F005, is ill-conceived in light of the information
presented in the regulations and in the background
documents; specifically, methanol, toluene, methyl
ethyl ketone, methyl isobutyl ketone, pyriderie and
carbon disulfide. More specifically the commenter
noted:
Methanol - this compound is not found to be
carcinogenic, nutagenic or tera-
togenic
Toluene - this compound is shown not to be
carcinogenic, mutagenlc nor teratogenic
Methyl Ethyl - this compound is shown to have
Ke tone
no chronic toxicity
Methyl Isobutyl - this compound is shown to have
Ketone
no chronic toxicttv
It should be noted that the Office of Toxic Substances/
'J.S. Environmental Protection Agency is currently considering
further regulation of chlorinated fluorocarbon production
and use.
-------
Pyridine - this compound is not carcinogenic
or mutagenic and the determination
of teratogenicity is questionable
Carbon disulfide - this compound is shown to have
no chronic toxicity
Therefore, the commenter recommends that these compounds
no longer be designated as toxic wastes.
The Agency continues to believe that all of these
spent solvents, with the exception of aethanol and methyl
isobutyl ketone should continue to be listed as toxic.
In reviewing the data available in the record, the
Agency believes that there is sufficient evidence to
continue to list these solvents as "toxic" wastes
(except for methanol and methyl isobutyl ketone). As
explained in the health and environmental effects section
of the listing background document, "Waste from usage of
organic solvents" as well as the respective Appendix A
health profiles for these compounds, it has been reported
that chronic low level exposure to toluene has caused
chromosome damage in humans and has led to the development
of neuro-rauscular disorders. Toluene has also been
reported to cause reproductive problems to female workers
during occupational exposure.
Methyl ethyl ketone (MEK), although only moderately
toxic via ingestion, can affect the peripheral nervous
system and is an experimental teratogen. In addition,
lethal doses in animals caused narked congestion of
the internal organs and slight congestion of the brain.
-------
Chronic exposure to pyridine has produced liver
and kidney damage in both animals and humans., In
addition, small doses of pyridine have produced tremors
and ataxia, irritation of the respiratory tract with
asthmatic breathing and paralysis of the eye muscles,
vocal cords and bladder.
Chronic exposure to carbon disulfide can affect the
cardiovascular and central nervous system, causing
personality changes. In addition, exposure to short
terra, but high atmospheric concentrations can lead to
narcosis and death. Carbon disulfide is also suspected
of being teratogenic. Therefore, these solvents will
continue to be listed as toxic.
The Agency, however, agrees with the comnenter that
both spent aethanol and methyl isobutyl ketone were im-
properly listed as toxic wastes. Methanol's oral toxicity
is rated as low_^/ and in fact is permitted in foods for
human consumption as an additive. Methyl isobutyl ketone's
principal toxic effects appears to be irritation of the
eyes and mucous membranes, and gastrointestinal upset.
Under these circumstances, we do not be Have a toxicity
listing for these solvents is appropriate, thus, the
Agency will no longer list spent aethanol and methyl
isobutyl ketone as toxic wastes. However, both -nethanol
and methyl isobutyl ketone are ignitable (flash points
Sax, V. Irving. Dangerous Properties of Industrial
Materials. 5th ed. Van \ostrand Reinhold Co.
New York. 1979
-------
of 54°F and 618F, respectively). Thus spent methanol and
methyl isobutyl ketone will continue to he listed as
ignltable hazardous wastes.
One conmenter criticized the Agency's determination
that chlorobenzene, o-dichlorobenzene, methanol, toluene,
methyl ethyl ketone, nethyl isobutyl ketone, isobutanol
and ethyl benzene are persistent and do not degrade
well. The commenter argued that this inclusion is
contrary to the published literature, including this
Agency's own studies, which shows that biodegradation is
the preferred method of treatment for these compounds
in aqueous solutions. The commenter therefore, believes
that the degradation data within the listing background
document should be reviewed and properly assessed In
listing.
We note initially that the comnenter's claims are
largely unsubstantiated. We note further that bio-
degradation plays a limited role in the environmental
persistence of the waste constituents because groundwater,
the exposure pathway of paramount concern, is abiotic.
As pointed out In the listing background document (pp.
57-61), a number of these solvents have migrated via
air and groundwater pathways, and persisted for long
oeriods of time, and caused substantial hazard in the
course of actual waste management practice. Thus,
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chlorobenzene, o-dichlorobenzene, toluene and methyl
ethyl ketone have all been detected in basement air,
sump pumps and/or in solid surface samples in the Love
Canal area._*_/ All of these solvents (chlorobenzene,
o-dichlorobenzene, toluene and methyl ethyl ketone) are
thus deraonstrably persistent enough to have migrated
from a disposal site and contaminate adjacent areas to
create a substantial hazard.
In addition, the following properties/character-
istics of these compounds indicate further the persis-
tence of these solvents:**/
chlorobenzene - this solvent is not amenable to
hydrolysis nor does it biodegrade very well
and therefore is expected to persist in the
e nvironment.
toluene - this solvent is persistent in abiotic
environments (such as most aquifers) and
therefore is expected to persist in ground water.
Toluene also is relatively soluble (water
solubility 470 mg/1 at 25°C), and thus would
be expected to migrate into grovindwater.
methyl ethyl ketone - this solvent, in addition to
being reported at Love Canal, has been de-
tected at several sites near ground water
^*7Since methanol and methyl isobutyl ketone are no longer being
considered toxic, a discussion on their persistence is no
longer appropriate.
*_*_/These data are all taken from the listing background document,
"Waste from usage of orsanic solvents".
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contaminated by an old chemical company dump,
again showing migratory potential and per-
sistence ._*/
With respect to isobutanol, the Agency has not
made any claim as to the 'persistenee of this compound;
however, due to its toxicity and extremely high water
solubility (water solubility 95.000 mg/1 at 18°C), the
Agency believes that this solvent may pose a substantial
hazard to human health and the environment if improperly
managed.
Finally, ethyl benzene is being listed because of
its ignitability hazard, not toxicity. As is indicated
in the regulations (§261.21, 45 FR 33121-33122, May 19,
1980), a liquid waste is considered ignitrable, and
therefore hazardous, if it has a flash point less than
140°F. Consequently, the persistence of ethyl benzene
is not at all relevant.
Therefore, absent any information provided by the
comraenter on the persistence and degradabi1ity of these
solvents, the Agency finds no reason to c'iaage its
original conclusions.
*/Listing background Document, "Wastes from usage of organic
~ solvents", Section IV. B. (Migratory potential and per-
sistence of halogenated and non-halogenated solvents)
pg. 31.
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6. One commanter criticized the Agency's conclusion, as stated
in the listing background document, that "the solubility of
these solvents is uniformly high " (LBD pg. 3) and "the
solubility in water of these halogenated solvents is
quite high" (LRD pg. 14) when in fact, as the comnenter
points out, their solubilities vary from 10 to 20,000 mg/1
(LBD pg. 55). The comnenter went on to argue that the
Agency's determination that "these high solubilities
demonstrate a strong propensisty to migrate from inade-
quate land disposal facilities in substantial concentrations'
(LBD pg. 15) and "all of these waste solvents have sig-
nificant potential for migration, nobility and persistence..,
(LBD pg. 52) is overstated when in fact, as the commenter
indicates, migration, nobility and persistence differ sig-
nificantly with respect to both routes of transport and
rates of degredation. Therefore, the commenter believes
that the Agency needs to reassess these listings.
The Agency agrees with the commenter that the water
solubilities of the chlorinated hydrocarbons do vary
considerably. However, in re-evaluating the data, the
Agency believes that the solubilities oc all of these
solvents except 1 ,1,2-1richloro-l,2,2-trifluoroe thane
are generally high and do indeed indicate a potential
for migration from inadequate land disposal facilities.*/
^/Although the water solubility for trichlorofluoromethane
is high, the principal concern with this solvent is its
potential to rise to the stratosphere where it may release
chlorine atoms and deplete the ozone.
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The Agency recognizes that solubility is not the sole
parameter which determines the potential of a substance
to migrate into the environment, i.e., mobility and
persistence also play a role. However, it is a key
parameter in evaluating how likely these substances
are to migrate from land disposal facilities. Indeed,
this potential to migrate has been demonstrated for all
of these solvents, except methylene chloride, in actual
damage cases, i.e., tetrachloroethylene, trichloroethylene,
1i1»1-trichloroethane , chlorobenzene and o-dichlorobenzene
have all been detected to migrate at Love Canal or other
disposal facilities. Methylene chloride, although not
detected at any disposal facilities, is highly soluble
with a water solubility of 20,000 mg/1 at 25°C, and thus
has the potential to migrate from disposal sites and create
a problem. However, the Agency has modified the listing
background documents as to the solubilities of these
solvents to better reflect the Agency's conclusions.
With respect to the solvent 1,1 , 2-trichloro-l,7,2-
trifluoroethane, the Agency has indicated clearly that
the potential to migrate and contaminate groundwater is
not of concern. The primary hazard posed by the mis-
management of this solvent, as with all chlorinated
fluorocarbons, is the potential to rise to the stratos-
phere and indirectly cause skin cancer due to the
-------
depletion of stratospheric ozone^/ (see Response to
Comments No. 3 of this document for a more detailed
discussion) .
The Agency also agrees that its conclusions regarding
migration, nobility aid persistence are overstated.
Therefore, the listing background documents have been
changed to reflect the Agency's determination that,
while the various chlorinated solvents do differ in
their migratory potential, nobility and persistence,
they all may pose a substantial present or potential
hazard to human health and the environment, if improperly
managed, when considering the routes and rates of transport
and degrees and rates of degradation.
7. One cominenter believed that the Agency's decision to
include trichloroethylene on the list of chemicals which
have demonstrated substantial evidence of carcinogenicity
was inaccurate. The comraenter indicated that according
to Elizabeth Weisberger of the National Institute of
Health, whose organization did the original studies which
classified trichloroethylene as a "merely suspicious
carcinogen", indicated that "trichloroethylene seens
not to be a carcinogen." The comnenter also argued
that nore extensive and recent researc'-i indicates that
*yi,l,2-'trichloro-l,2,2-trifluoroethane is considered to be
extreraently volatile (vapor pressure - 270 mm of Hg at 208C),
and thus is likely to rise into the atmosphere.
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trichloroethylene may not be carcinogenic after all.
The Agency disagreees with the commenter. Trichloro-
ethylene has been designated carcinogenic by EPA's Cancer
Assessment Group (CAG) after reviewing the available data
in the literature. In fact, before a chemical compound
is deemed carcinogenic by CAG, it is subject to ex-
haustive literature study and evaluation. In light of
CAG's determination, EPA will continue to include tri-
chloroethylene as a chemical which has demonstrated
substantial evidence of carcinogenicity.
8. One commenter questioned the Agency's characterization
of 1,1,1-trichloroe thane as a suspect carcinogen. The
comnenter argued that 1 , 1,1-trichloroethane has not been
found to be a carcinogen. They quote the MCI Bioassay
of 1,1,1-Trichloroethane for Possible Carcinogenicity
(January 1977), which states:
"A variety of neoplasms were represented in both
1,1,1-trichloroethane treated and matched-control
rats or mice. However, each type of neoplasm has
been encountered previously as a lesion in untreated
rats or mice. The neoplasms observed are not be-
lieved attributable to 1 , 1 ,1-trichloroe thane expo-
sure, since no relationship was established between
the dosage groups, the species, sex, type of neoplasm
or the site of occurence. Even if such a relation-
ship were infered, it would be inappropriate to
make an assessment of careinogenicity on the basis
of this test, because the abbreviated life spans
of the rats and the nice."
The commenter also argued that EPA's own Office of Drinking
Water, in their appendices to Planning Workshops to
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Development Recommendations for a Groundwater Protection
Strategy, state that methyl chloroform (1,1,1-trichloro-
ethane) Is not considered to be a carcinogen (June 1980).
Therefore, the comraenter believes chat there is no support
for the carcinogenicity of 1,1,I-trichloroethane and
argues that it be deleted from all lists of hazardous
was tes .
The Agency disagrees with the commenter's claim.
Although the MCI Bioassay Study on the carcinogenicity
of 1 ,1 , 1-trichloroethane referred to in the listing
background document (pg. 464) and an unpublished study
are inconclusive, positive responses in two in vitro
systems (a rat embryo cell transformation assay (Price
et. al. 1978, Transforming Activities of Trichloroethane
and Proposed Industrial Alternatives. In .vitro. 14:290.)
and a bacterial mutation assay (Simmon et. al. 1977.
Mutagenic activity of chemicals identified in drinking
water, In t Progress in Genetic Toxicology, ed. I.D. Scott,
B. A. Bridges and F. H. Sobels, pp. 249-253; McCann, J.
and B. Ames, 1976. Detection of carcinogens as mutagens
in the Salmonella raicrosome test: Assay of 300 chemicals.
Proc. Nat. Acad. Sci. 78:950.)) currently used to detect
chemical carcinogens, indicate that 1,1,1-trichloroethane
has the potential for carcinogenicity in animals (App. A).
Additionally, a two year carcinogenesis animal bioassay
-------
is being repeated at the National Cancer Institute.
Therefore, the Agency believes that there is ample
evidence to consider 1,1,1-trichloroethane as a suspect
carcinogen*/, and thus will continue to include
1,1,1-trichloroethane as a constituent of concern.
9. One comraenter also argued that the statements in the
background document that "methylene chloride is reported
as being nutagenic to a bacterial strain, S. typhimurium",
and "methylene chloride... is highly mutagenic" are
inaccurate. The commenter pointed out that a variety
of more detailed tests performed subsequently and not
cited in the listing background document prove otherwise.
For example, a definitive cell transformation test for
methylene chloride was found negative. Additionally,
many other tests have been run for carcinogenicity of
methylene chloride with negative results.
The Agency agrees. The current assessment on the
carcinogenicity of raethylene chloride is only based on
animal experiments which are so far incomplete. How-
ever, methylene chloride is the subject of an NCT spon-
sored bioassay. In addition, EPA has found "suggestive"
evidence of the carcinogenicity of nethylene chloride
*/It should be noted that the Agency recently determined to
~ retain the listing of 1,1,1-trichloroethane as a toxic pollu-
tant under §307(a) of the Clean Water Act. The reasons for
that action are incorporated by reference herein.
-------
(App. A). The Agency cannot ignore this information.
Therefore, the listing background document will be
revised to indicate that aethylene chloride is only a
"suspect" carcinogen.
10. One commenter questioned the Agency's characterization
of tetrachloroethylene, m-ethylene chloride, trichloro-
ethylene and 1,1,1-trichloroe thane as aquatically toxic.
The comnenter indicated that statements relative to
methylene chloride li'ce ''acute toxicity values range
from 147,000 to 310,000 mg/1 (correct units are ug./l)
for aquatic organisms" are meaningless until put into
relative significance. When compared with most common
nonhalogenatad solvents, the commenter argues, the halo-
genated solvents were less toxic to the tested fish specie's.
In addition, the commenter pointed out that EPA, in fact,
concurs with this viewpoint by stating, "aquatic organisms
tend to be fairly resistent to dichlororne thane (methylene
chloride), with acute values ranging from 193,000 to 331,000
ug/1 (EPA BD 38 at 389). Therefore, the commenter believes
that EPA has not properly assessed the relatively low
aquatic toxicities of these halogenated solvents.
In re-evaluating the aquatic toxicity of tetrachloro-
ethylene, nethylane chloride, trichloroethylene ani .1,1,1-
trichloroethane, the Agency agrees with the commenter that
all four of these halogenated solvents are not of regu-
latory concern under the hazardous waste program to
- IQO-
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warrant characterization as "aquatically toxic." In
the Registry of Toxic Effects (1975 Edition), a widely
used reference book which is published by the National
Institute for Occupational Safety and Health (NIOSH>,
a rating of the aquatic toxicity or non-toxicity of
chetnical substances if provided. In this rating,
substances with an LC50 value of between 10,000 ug/1
to 100.000 ug/1 is considered slightly toxic while
substances with an LC5Q value above 100,000 ug/1 is
practically non-toxic. Based upon this rating, raethylene
chloride is practically non-toxic while the other halo-
genated solvents are slightly toxic. Therefore, the
Agency will modify the listing background document to
reflect this change. However, it should be noted that
toxic wastes are not so designated solely on the basis
of their aquatic toxicity. \s discussed earlier, all
of these halogenated solvents exhibit other toxic effects
i.e., carcinogenicity, chronic toxicity, etc. which
are sufficient to warrant designation of these solvents
as toxic.
11. One comnenter also argued that the Agency has misinter-
preted and overstated the bioaccumulation potential for
both the halogenated and non-halogenated solvents.
arguing that most of these solvents have a low bioaccunu-
lation potential. In particular, the connenter believes
that the Agency has shown a lack of perspective by
-------
concluding that, " . . .methanol could bioaccumulate
causing numerous adverse health effects from prolonged
ind/or repeated exposure" (EPA 3D-11 at 59), despite
its reported very low Kow of 5 and readily biodegradable.
Therefore, the comnenter believes that the bioaccumulation
data should be reviewed a'nd properly assessed in listing.
As discussed in the preamble to Part 261 of the
hazardous waste regulations (45 FR 33105-33107), the
Agency in listing wastes for which a characteristic
has not been developed has adopted a flexible, multiple
factor approach to be better able to accommodate itself
to the complex determinations of hazard. These multiple
factors include the type of toxic threat posed, the
concentrations of the toxic constituents in the waste,
the migratory potential, persistence and degradation
of the toxic constituents, the degree to which the
toxic constituents bioaccumulate in ecosystems, the
plausible types of improper management to whic'h the
waste could be subjected, the quantities of waste
generated, and other factors not explicitly designated
by the Act. Thus, if a substance exhibits one or
more of these properties, the Agency may list the waste
as hazardous. The bioaccumulation potential of a sub-
stance is not considered by the Agency as a necessary
factor before a waste can be listed. Therefore, just
because a chemical substances is not bioaccuraulativa
-/oa-
-------
is no reason not to list a waste.
With respect to the comraenter's claim for methanol,
the Agency is no longer listing this solvent for toxicity,
but for ignitability. Bioaccumulative propensity of
this compound thus is no longer relevant.
12. One commenter cited some inconsistencies/errors in the
listing background documents and suggested that the
Agency make the appropriate revisions.
The Agency agrees. There were some typographical
and transcription errors, e.g., in the methylene chloride
background document, as well as sone judgmental errors.
Therefore, within the limits of its resources, the
Agency has made every effort to correct such errors.
13. One comraenter criticized the Agency's conclusion as
stated in the listing background document that, "the
chlorinated waste hydrocarbons are toxic" (EPA BD-11
at 3) when in fact, as the commenter points out, that
the oral-rat LC5Q values vary by several orders of
magnitude. Therefore, the comraenter believes that the
listing of these halogenated solvents are not fully
warranted in all cases.
The Agency strongly disagrees with the commenters
unsubstantiated claim. As discussed in the preamble
to the May 19, 1980 hazardous waste regulations (45
FR 33107), the Agency listed a number of toxic wastes
-------
as those "which have been shown inreputable scientific
studies to have toxic, carcinogenic, mutagenic or
teratogenic effects on humans or other life forms."
Toxicity is defined to include systemic effects of
chronic low level exposure, acutely toxic^/, aquatic
toxicity, phytotoxicity or the potential (as with chlori-
nated fluorocarbons) for indirectly causing harm to
human health or other life forms. Therefore, a substance
with a high LC^Q value is not necessarily non-toxic.
In reviewing the data available in the r ecord**/ ,
the Agency is convinced that these substances are properly
designated as toxic, and that improper management and
disposal of these waste solvents may pose a substantial
present or potential hazard to human health and the
environment. Since the comrnenter failed to provide
additional toxicity data except as discussed in other
parts to this section, the Agency finds no reason to
change its original conclusion to list these solvents
as toxic wastes.
^/Acutely toxic does not include those wastes which are defined
in §251 . 11(a)(2) as acutely hazardous.
^/Appendix A (Health and Environmental Effects Profiles) out-
lines the health and environmental effects exhibited by
each of these compounds.
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ADDENDUM TO SOLVENTS BACKGROUND DOCUMENT
I. Responses To Public Comments On Proposed Solvent Mixture
Rule
A. Renumbering of the F001 through F005 Spent Solvent Listings
Several comments have been received regarding the proposal
to renumber the list of solvents by deleting F002, F003, F004,
and F005 and modifying F001 to include all the solvents formerly
listed in F001 through F005. Some commenters requested that the
Agency, if renumbering the listings, should distinguish between
halogenated and non-halogenated solvents. The reasons for the
distinction were that non-halogenated solvents usually are burned
as fuel, incinerated, or reclaimed on-site, while halogenated
solvents primarily are reclaimed on-site and then reused by the
generator. In addition, the environmental impacts posed by
halogenated and non-halogenated solvents are somewhat different
(for example, biodegradation). These commenters suggested that
we assign two new waste codes to distinguish halogenated from
non-halogenated solvents. Alternatively, one commenter suggested
that the Agency renumber the solvents listings into three codes:
halogenated, non-halogenated, and ignitable non-halogenated
solvents. This commenter believed that using the three codes
will facilitate source separation by generators and, therefore,
lead to environmentally sound treatment, disposal, and recycling
of solvent wastes.
Other commenters requested that the F001 through F005
waste codes remain as originally listed, but with the addition
of solvent mixtures at 10% or greater to each code. These
commenters believed that the five categories should be retained
-------
because the solvent groups require different treatment, recycling
and handling processes and procedures, and one single classification
number would make the differentiation between the solvents
difficult.
The following are other specific concerns mentioned by the
various commenters on the issue of renumbering:
One commenter stated that renumbering would increase the
cost of compliance for recyclers, transporters, etc.,
due to the cost of re-labeling containers, retraining
hazardous waste workers, and revising hazardous waste
management plans.
" Three commenters stated that the renumbering would cause
confusion in future paperwork (i.e., annual reporting
data manifests, transportation and storage logs), when
evaluated and compared with past documents. In particular,
one commenter stated that there may be possible
inconsistancies with the new single waste code and the
DOT manifest requirements and the manner in which solvents
are segregated for recycling (i.e., halogenated, non-
halogenated, and ignitable solvents are managed
differently).
• One commenter stated that renumbering would require
facilities to perform massive waste characterization
analyses when undergoing delisting and closure procedures.
The comraenter noted an example where this might occur.
-------
In some instances, generators are being required to
perform analyses for every constituent in a waste code
reported at their facility. Under the single combined
waste code, F001, the facility would have to test for
all 27 solvents, whereas before they may have only tested
for five.
0 Three commenters were concerned that the distinction of
the solvent's hazards would be lost if all the solvents
were combined into a single waste code, rendering the
reporting, handling, etc., of the ignitables and toxic
solvents undifferentiated. For example, in handling
these chemicals, the workers would not know if a particular
waste was toxic (i.e., carbon disulfide is harmful to
human skin) or ignitable (i.e., acetone).
• One commenter requested that the F004 solvents be
separated from the single F001 waste code because of
their corrosivity to human skin. These solvents require
careful handling and worker training.
• A few comraenters stated that the single combined F001
code would cause confusion due to past use of the F001
number. The new F001 code, which would list all 27 spent
solvents, might be confused with the present F001 code,
which lists only six solvents. Computer data systems of
hazardous waste manifests is an instance where confusion
between the two definitions of the F001 code may appear.
-------
One commenter stated that many TSDs are "permitted" only
for chlorinated solvents (F001 and F002). If all 27
solvents were grouped into a single waste code, these
facilities would be forced either to become properly
equipped to store and to handle ignitable solvents or to
upgrade their waste anaylsis plans and laboratory capabi-
lities to determine whether incoming wastes may be
accepted at their facility.
* One commenter requested that if ignitable solvents are
to remain in the hazardous waste listing as spent solvent
wastes, they should be categorized under a separate
hazardous waste number. "Toxic" solvents then could be
easily distinguished from ignitable solvents.
Agency Response:
In considering the renumbering of the solvent listings,
the Agency has concluded that renumbering may, in fact, increase
compliance costs and cause confusion (i.e., re-labeling of
containers, confusion for transporters and others handling the
wastes, different management and handling practices for
halogenated solvents, and confusion in record keeping because
of past F001-F005 designation). Therefore, we are retaining the
existing hazardous waste numbers.
B. Process Wastes Containing Solvents
Two comraenters requested that the Agency delete the term
"spent solvents" from the proposed rule. These ccmmenters felt
-------
that by limiting the mixture rule to the F001 through F005 spent
solvent wastes, the Agency would be excluding a large universe
of wastes, such as process wastes containing significant quantities
of solvents. The commenters asserted that the exclusion of
process wastes leads to enforcement difficulties. They pointed
out that there is little difference in toxicity between solvent
wastes which are spent or discarded after use, and process wastes
containing solvents.
* The coramenters stated that from an enforcement standpoint,
it may not be possible to determine if a mixed solvent waste
originally was generated as a spent solvent or as a process
waste. A generator claiming that their spent solvent mixture
is a manufacturing process waste could avoid regulation.
One of the comraenters asserted that industry has used
this reasoning in past land disposal practices.
* On the other hand, several commenters requested that the
proposed rule not apply to waste products in which solvents
were used as carriers for active ingredients. The commenters
stated that these waste quantities per container are usually
small and are equivalent to household wastes. Therefore,
the comraenters requested that these wastes not be included
in the rule.
Agency Response:
The intent of the proposed solvent mixture rule is to close
a regulatory loophole in the §261.31 spent solvent listings, in
-------
which spent solvent mjxtures currently are unregulated as hazardous
wastes. The Agency agrees with the first commenters that many
process wastes, including those containing solvents and solvent
mixtures, are erroneously unregulated. However, there are also
some process wastes which should be excluded from the regulations
because of the low concentration of hazardous chemicals or their
low toxicity.
The Agency has not developed health-based standards or
regulatory thesholds for all of the listed solvents. The level
set by today's rule is an interim measure, and may be modified
or superceded when work on the Toxicity Characteristic is
completed.
C. Applicability of the Ten Percent Threshold Level for
Solvent Mixtures
Several comments have been received concerning the 10%
threshold level for solvent mixtures. Comments are as follows:
• One commenter suggested that the threshold level should
be lowered to 1% to place tighter controls on these
wastes. This commenter stated that the lower threshold
level would be more protective in prohibiting these
solvent mixtures from sanitary landfills, because they
now would be considered hazardous wastes. At 1%, the
solvent mixtures would be less likely to mobilize other
wastes from land disposal facilities. The 1% level is
based on the 1979 EPA Draft Ambient Water Criteria. The
-------
commenter further stated that the original background
document for listing solvents and the Drinking Water
Criteria promulgated in November 1980, provide data for
establishing health-based thresholds for solvent mixtures.
One commenter similarily stated that the level should be
5000 ppm since this is more protective of human health
and the environment. The 5000 ppm level coincides with
the State of Connecticut's proposed waste oil regulations
for hazardous constituents added to waste oil. The 5000
ppm level is said to be protective of human health and
the environment for burning waste oil containing solvents.
* Three commmenters expressed concern that the 10% threshold
level will not adequately protect human health and the
environment. One stated that the Agency should not
exclude mixtures which are at concentrations below 10%,
because their toxicities are still orders of magnitude
higher than the levels considered safe for human health
and the environment. Another commenter mentioned that the
10% level is adequate for an interim measure, but not
for a final one. The commenter requested that the new
hazardous waste characteristic be based on toxicity and
that it set levels which will preempt the 10% level if
necessary to protect human health and the environment.
-------
The third commenter was concerned that many of the wastes
impacting the environment contain solvents at concentrations
much lower than the 10% level.
One commenter stated that many persons in the regulated
community, the EPA, and the States interprete the F001-F005
solvent listings to include solvent mixtures at all con-
centrations. The commenter was concerned that by specifying
a threshold level for solvent mixtures, the effect will
be a relaxation of the regulations.
• One commenter stated that the 10% threshold level may
bring into regulation wastes containing de minimis
concentrations of solvents. The commenter recommended
that the 10% level apply to only the concentration of
an individual solvent in a solvent mixture, rather
than the total concentration of all the solvents in
the mixture.
Agency Response:
In establishing the threshold for solvents, the Agency was
unable to define the concentrations at which solvent mixtures
are considered hazardous waste. At this time, the Agency has not
developed health-based thresholds for all of the 27 listed solvents.
Nor does the listing background document identify levels at
which solvent mixtures would be considered hazardous waste. The
Agency, therefore, expanded the universe of wastes considered
"spent solvents" to include those solvent mixtures commonly used
8
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as industrial solvents. The ten percent threshold level will
bring the majority of these wastes into the hazardous waste
management system. This threshold level is not intended to define
the concentration at which these mixtures are considered hazardous,
rather, it defines the concentration at which these wastes are
considered spent solvents. The level applies to the total concent-
ration of listed solvents (before use) in the mixture, and not
simply the concentration of a single solvent in the mixture.
The Agency is concerned with the total solvent effect of the
mixture. Whereas a single solvent at low concentrations may not
be hazardous, the Agency is concerned with possible hazardous
additive effects the solvent might exhibit when in combination
with other solvents in a mixture. The Agency is expanding the
EP Toxicity Characteristic to establish maximum permissible
concentrations for solvents. These thresholds will override
the 10% level for solvent mixtures, in part, and bring many
wastes containing solvents (including process wastes) into the
hazardous waste management system.
The Agency believes that the proposed rule will not result
in a relaxation of regulation because solvent mixtures used in
commerce generally contain greater than ten percent solvent.
The rule will cover many of these mixtures. Data show that
solvent mixtures often contain greater than fifty percent solvent.
Specifically, the Agency believes that solvent formulators cannot
successfully reformulate below the ten percent level and retain
the desired characteristics of solvent mixtures.
-------
The EPA believes if the regulation is extended down below the
10% level, dilute mixtures or office type cleaning products will
be brought into the system. This is not the intent of the Agency.
D. Clarification of Scope and the Definition of the Rule
Several comraenters requested clarification of the scope of
the rule and definitions of certain phrases used in the rule.
' One conunenter stated that the new F001 spent solvent
listing is confusing and should be reworded. As currently
written, the rule may be interpreted such that the 10%
threshold applies to both the individual spent solvents
and the spent solvent mixtures. The commenter recommends
that a comma be inserted after the first use of the term
"spent solvents."
Agency Response:
The Agency agrees with the commenter and will redraft the
rule to clarify the scope of the listing.
\
* Another commenter requested that the 10% threshold also
should apply to still bottoms from the recovery of solvents
and solvent mixtures. The commenter stated that still
bottoms containing less than 10% solvent should not be
considered hazardous if the individual solvents and solvent
mixtures are not hazardous below 10%.
Agency Response:
The commenter has misinterpreted the proposed rule. As
discussed in the preamble to the final rule, the regulation will
10
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list as hazardous wastes certain spent solvent mixtures which
contained, before use, ten percent or more of the solvents listed
for toxicity. The ten percent threshold does not define the
concentration at which these wastes are hazardous. (Agency data
show that solvents maybe hazardous at concentrations below ten
percent). Rather, it specifies a concentration low enough to
bring the majority of commonly used toxic solvents into the
hazardous waste management system. The preamble states that
these mixtures typically and frequently contain 50 percent or
greater total listed solvents. In many cases, solvent mixtures
contain 100 percent total solvent. Since Agency data show that
still bottoms from the recovery of these solvents may contain up
to 15 percent solvents, we are including these wastes under the
listing.
0 One commenter requested clarification of the terms
"non-solvent constituents" and "any other combination
that includes a listed solvent."
Agency Response:
In defining solvent mixtures, the Agency intended the
listing to cover mixtures that are considered solvents but
contain non-solvent constituents such as pigments (which impart
desired product color), preservatives (to enhance shelf life), or
any other additives. Thus, the Agency included the terms "non-
solvent constituents" and "any other combination that includes
a listed solvents."
• One commenter requested that the phrase "used in degreasing"
not be deleted from the F001 listing. The commenter felt
that the deletion was unnecessary and unsubstantiated.
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In addition, the commenter felt that the deletion would
add confusion to waste characterization. The commenter
contended that a paint waste containing a solvent mixture
at or above 10% would be wrongly classified as a listed
F001 waste.
Agency Response:
In the proposed rule, the Agency deleted the phrase "used
in degreasing" as part of the renumbering issue. Thus, the
qualifying phrase of each waste code had to be deleted in order
for the single F001 code to apply to all the listed solvents.
Since the Agency has retained the existing solvent listings,
the phrase "used in degreasing" will remain in the F001 solvent
listing.
E. Effective Date
Several comments were received regarding the "effective
immediately" provision of the rule. One commenter stated that
the provision was appropriate, however the majority stated
that industry needs time to comply with the new rule. The
reasons cited for allowing lead time were:
• Some companies will need time to determine whether their
waste will be a newly-regulated hazardous waste under the
solvent mixture rule.
• Companies who were generating solvent mixtures, but were
not previously regulating them as hazardous will need
time to come into compliance. For example, these companies
may need to design and build hazardous waste storage and
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processing equipment. In addition, company personnel
need to be trained in hazardous waste management.
• The proposed effective date would severly stress smaller
companies.
0 EPA's justification that few generators will be newly
regulated does not justify an immediate date. These
generators should be given the necessary time to implement
proper waste management as a result of this rule.
* The Agency has not presented a convincing argument for the
immediate effective date.
* One conunenter suggested that a 60 day period after promul-
gation would be sufficient time for the generators to
come into compliance. Two commenters suggested that the
usual six month advance notice be applied to the solvent
mixture rule.
Agency Response:
On January 11, 1985, the Agency proposed to regulate hazardous
waste and used oil burned for energy recovery in boilers and
industrial furnaces (see 50 PR at 1684). These rules, signed
November 8, 1985, prohibit burning in non-industrial boilers of
hazardous waste, including used oils adulterated by mixing with
spent chlorinated solvents. The Agency believes a substantial
loophole will be created if mixtures containing chlorinated
solvents remain unregulated when these new rules become effective.
Generators may continue to commingle these solvents with waste
oils destined for energy recovery. Based on the toxicity of
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chlorinated compounds, the Agency is concerned with possible
adverse health effects posed by the burning of these wastes. In
view of these concerns, we believe it imperative to bring these
wastes into the hazardous waste management system before the
annual demands for heating oil peak.
F. Volume vs. Weight
One comment was received concerning EPA's decision to use
volume rather than weight as the determining parameter for
solvent amounts. The commenter was concerned that Material
Safety Data Sheet information is expressed in terms of weight
percentage and that laboratory analysis results are often
reported in terms of weight per volume or weight per
weight. They recommended changing the parameter from
"volume" to "weight".
Agency Response:
The majority of the commenters did not dispute the use of
volume rather than weight in the proposed rule. The spent
solvent wastes are primarily liquids or watery sludges (slurries).
Thus, the Agency felt that it would be easier to determine the
spent solvent concentration by volume. In addition, the Agency
has contacted chemical companies to determine how the constituents
of mixtures are reported on the Material Safety Data Sheet (by volume
or weight). The answers received indicated that both systems
are used. However, since most commercial solvent products are
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expressed in terms of volume, the Agency is expressing solvent
mixtures in terms of volume.
G. Regulation of Ignitable Solvents - F003
In the proposed rule, the Agency requested comments
concerning the ignitability listing for solvents. The majority
of the comments were in favor of eliminating the list of ignitable
solvents (F003) for the following reasons:
the listing is duplicative and unnecessary
• ignitables are considered "hazardous waste" under the
"characteristic of ignitability"
0 the F001-F005 numbers should be reserved for solvents
that are toxic
* One commenter favored maintaining the ignitability listing.
This commenter felt that small facilities would be less
likely to have access to flash-point testing. These
facilities needed the ignitability listing maintained for
waste classification reasons.
Agency Response:
The Agency has decided to retain the ignitable solvents in
the list of hazardous wastes. Although the commenters are correct
that these spent solvents would be caught by the ignitability
characteristic, these solvents are likely to contain other
toxic contaminants. In fact, spent solvents become spent when
they have been contaminated with other materials (i. e. , toxic
heavy metals, toxic organic compounds) and must be disposed,
reprocessed, or reclaimed. If we were to remove these solvents
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from the list of hazardous wastes, we believe such action would
conflict with the spirit of one of the new requirements under the
Hazardous and Solid Waste Amendments of 1984. In particular,
under Section 222 of HSWA, the Administrator is required, in
evaluating delisting petitions to consider factors (including
additional constituents) other than those for which the waste
was originally listed—if there is a reasonable basis to believe
that the waste may still be hazardous. (See 50 FR 28742, July
15, 1985.) Although this provision discusses site-specific
delisting petitions, we believe that it is consistent with this
provision to make the same finding for generic delisting as
well, since such action ordinarily has far more potential impacts
on the environment than a site specific listing. Thus, since the
spent solvents are likely to contain other toxicants at levels
of regulatory concern, and since we have not evaluated those
wastes for these other toxicants, we believe it is inapprop-
riate to remove these solvents from the hazardous waste list.
Rather, persons who wish to delist those wastes will need to
submit a delisting petition, pursuant to 40 CFR §§ 260.20 and
§§ 260.22, to exclude the waste from the hazardous waste category.
One commenter also asked whether the ten percent used to
define solvent mixtures includes solvents listed for ignitability
only (F003).
Agency Response:
Since we have not evaluated these (F003) solvents for their
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toxicity, then ten percent threshold does not apply. The final
rule reflects this.
H. Affect of Solvents on Liners
One comment concerned the statement in the preamble whdch
said "since solvents are known to degrade synthetic and
clay landfill liners, these toxic constituents, once
mobilized may readily migrate to ground water." The
commenter requested that the Agency mention other studies
which indicate that dilute solvents and solvent mixtures
do not degrade clay liners.
Agency Response:
The adverse effects of concentrated solvents on synthetic
and natural liners generally is accepted (Haxo e_t al. 1985;
Lord et al. 1985; Van Schaik, 1974; Schram, 1981; Anderson and
Jones, 1983.). The adverse effect of dilute solvents and their
mixtures is less widely accepted. The effect of solvents on
synthetic liners was shown in a study where toluene at 5000 ppm
was mixed in water and exposed to a high density polyethylene
liner. The toluene mixture permeated through the liner at 2
gm/m2/day- (Surprenant et al., 1984.) The Agency acknowledges
that several studies indicate little or no effect on natural
liners. But, these studies were conducted over a short-term
period (i.e., Daniel and Liljestrand, 1984). The Agency is
concerned that in the long-term (years) exposure to dilute solvent
mixtures may degrade natural liners. Some studies indicate
mechanisms by which dilute solvents could form into concentrated
solvents so that adverse effects occur (Artiola et_ a_l. , 1985;
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Anderson and Brown, 1983). The Agency acknowledges that there
is not sufficient information available to predict the effect on
soil liners from long-term exposure to dilute solutions and that
additional research is needed.
I. Human Health Effects
* One commenter stated that the rule indicates that all
spent solvents pose carcinogenic, mutagenic, terato-
genic, and neurotoxic health risks. The commenter
asserts that at least two of the solvents, trichloroethylene
and tetrachloroethylene, have been re-evaluated such that
they are not probable human carcinogens. The commenter
felt that the revisions should be incorporated into the
development of health-based thresholds.
Agency Response:
The rule does not specify that all of the 27 listed solvents
pose these health risks. The preamble clearly states that "many
(solvents) are known carcinogens, teratogens, mutagens, or neuro-
toxins. Others are associated with acute and chronic adverse
health effects." Data from a recent NTP bioassay, however,
indicate that tetrachlorethylene is carcinogenic (National Toxicology
Program, August 1985). Trichloroethylene is also a known human
carcinogen.
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J. PCB-containing Wastes
One comraenter requested that EPA exempt from regulation
electrical equipment fluids which contain PCBs and any of the
the listed solvents.
Agency response:
IT")
The commenter has misintapreted the proposed rule and the
spent solvent listings. PCB transformer fluids (i.e., dielectric
fluids containing PCBs and tetrachlorobenzene) are not covered
under the current hazardous waste regulations. Tetrachlorobenzene
is not a listed hazardous waste. (Monochlorobenzene is covered
under the listing.) Furthermore, dilectric fluids are not considered
"spent solvents" and, as such, are not regulated under RCRA. At
this time, PCBs are regulated under the Toxic Substances Control
Act.
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