-------
-------
5 • Wastes from the formulation of inks 126
K086: Solvent washes and sludges, caustic washes and
sludges, or water washes and sludges from
cleaning tubs and equipment used in the
formulation of ink from pigments, driers, soaps
and stabilizers containing chromium and lead.
6. Wastes from coking operations. 148
K087: Decanter tank tar sludge from coking operations.
-------
SJ-37-U2
January 198
LISTING BACKGROUND DOCUMENT
CHLORINE PRODUCTION
K071: BRINE PURIFICATION MUDS FROM THE MERCURY CELL PROCESS
IN CHLORINE PRODUCTION WHERE SEPARATELY PREPURIFIED
BRINE IS NOT USED (T).
K106: WASTEWATER TREATMENT SLUDGE FROM THE MERCURY CELL
PROCESS IN CHLORINE PRODUCTION (T).
I. SUMMARY_OF_BASIS_FOR_LISTING
The solid wastes of concern in this document are muds
from brine purification, and wastewater treatment sludges
from the mercury cell process in chlorine production. The
constituent of concern in these wastes is the toxic heavy
metal mercury.
The Administrator has determined that mercury-bearing
sludges and muds resulting from the mercury cell process in
chlorine production 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, and which therefore should be subject to
appropriate management requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations:
1. These wastes are generated in large quantities and
contain significant concentrations of mercury. At the
present time approximately 39,500 kkg of hazardous
mercury-bearing wastes are generated each year.
These wastes are calculated to contain about 154 kkg of
mercury. Large quantities of this highly toxic pollutant
are thus available for environmental release.
2. These wastes have been involved in a number of serious
damage incidents, demonstrating empirically that improper
waste management may result in substantial environmental
hazard..
-------
SOURCESOFTHEMERCURYANDTYPICALDISPOSALPRACTICZS
Twenty-seven facilities, located in 16 states, are
engaged in chlorine and either sodium hydroxide or potassium
hydroxide manufacture using the mercury cell process .( ^t 2 , 24)
These facilities are identified in Tables 1 and 2. In 1980,
their mercury cell production capacity was reported as ranging
from 27,000 to 232,000 kkg per year. (24)
B. Manufacturing^ Process (1 > 3 , 22 , 24)
In the mercury cell process, rock or evaporated salt
is dissolved in recycled brine or in fresh water in agitated
tanks to form a saturated salt brine. In plants not using
*l
prepurified salt — most of the plants using this process--"
this brine is purified by adding soda ash and sodium hydroxide,
and in some cases barium salts, precipitating barium sulfate,
calcium carbonate and magnesium hydroxide. These filtered muds
(A in Figure 1) are removed by settling and filtration,
and constitute one of the wastes of concern. The purified
brine is then fed to the electrolytic mercury cells, where
it is decomposed by electrolysis to produce chlorine and
*7Eight~presently operating facilities (listed in Table 2)
use evaporated rock salt already purified in on-site
diaphragm cell operations; these plants do not perform
significant purification, and therefore do not generate
mercury-containing brine muds.
-2-
-------
TABLE 1
FACILITIES PRODXING MERCURY-BEARING BRINE PREPARATION/PURIFICATION MUDS. (24)
STATE
AL
DL
GA
IL .
KY
IA
ME
NJ
NY
NC
OH
TN
WA
WI
FAdLTTY
Diamond Shamrock, Mobile
Diamond Shamrock, Mus.Sho.
Stauffer Chemical, LeMcyne
Diamond Shamrock, Del. City
Olin Corporation, Augusta
Monsanto Co., Sauget
Convent Ch'l, Calvert City
Pennwalt Corp., Calvert City
Stauffer Chem. , St. Gabriel
Intl. Minerals, Orrington
Linden Chemicals, Linden
Hooker Sobin, Niag. Falls
Olin Corp. , Niag. Falls
Linden Products, Acme
International Minerals,
Ashtabula
Olin Corp., Charleston
Georgia Pacific, Bellingham
Vulcan Materials, Pt. Edwards
ROCK SALT CHLORINE HAZARDOUS BRINE MUDS
SOURCE CAPACITY TOTAL, DRY BASIS
103 kkg/yr (kkg/year)
IA
IA 1
IA
NY 1
IA
IA l
IA
IA
LA
NY '
NY
Sask.KCl2
NY
IA
Sask. KC1
TN
Prepurif. evap.
MI
38
132
70
132
100
40
116
114
170
72
145
45
84
54
33
230
76
66
17TT
981
2124
1400
4750
1818
600
29143
31473
2500
900
2900
7033
2325
540
8003
4230
3363
3360
36, 328
1. Also use KC1 for KH production.
2. New York Rock salt also used prior to 1972.
3. Brine muds combined with all other mercury-containing vastes.
-3-
-------
STATE
•Sable 2
FACILITIES WHICH DO NOT PRODUCE MERCURY-BEARING BRINE MUDS.
PACILTTY
MERCURY
CHLORINE CAPACITY
103 kkg/yr
SALT SOURCE
AL
GA
LA
LA
NC
NY
TX
TX
wv
w
Olin Corp., Mclntosh 132
Linden Chemicals, Brunswick 92
BASF Wyandotte Corp.,
PPG, Lake Charles (a) 232
Linden Chemicals, Acme 46
Linden Chemicals, Syracuse^ 27
Diamond Shamrock, Deer Park(a' 99
Alcoa, Point Comfort(d) 150
PPG, Natriun 60
Linden Chemicals, Moundsville 76
~9l4
Solution mined.
Solar purified, evaporated,
dissolved in recycle brine.
Louisiana
European evap. salt,
pre-purified.
New %rk State
Texas
Texas brine, pre-purified,
evap., diss. in recycle brine.
West Virginia
Solution-mined, evap., diss.
in recycle brine
(a) These facilities use pure salt obtained from on-site diaphragm cell operations;
no hazardous brine preparation mods are generated.
(b) Facility closed in 1979.
(c) Prior to 1970 brine purification operations were conducted in the mercury cell
circuits, therefore some of the accumulated wastes fron this site may be hazardous.
i
(d) Prior to 1970 rock salt was used, and mercury-containing brine muds were generated.
-------
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-------
sodium amalgam. The spent brine from the mercury cells is
dechlorinated and approximately 94% is returned (recycled) to
the initial brine make-up for resaturation; the remainder is
discharged to wastewater treatment.
Since some of the feed of the brine purifier is a mercury-
bearing recycle stream from the electrolytic cell, the muds (A
in Figure 1) resulting from brine purification are contaminated
with mercury. According to data provided by the Chlorine
Institute, muds contain from 13-1000 ppm, averaging about 200
ppm of mercury.(24)
In all plants, the depleted purged brines from the electro-
lytic cell, together with two other waste streams generated
from ancillary processes, are channeled to waste treatment.
.Wastewater treatment generates sludges. (B in Figure 1) in'
amounts averaging 1.4 kg of sludge per kkg of chlorine pro-
duct. (14) These wastes, contain about 0.2 to 15% of mercury, with
an average concentration of 4.2% mercury^4', and constitute
the second waste of concern.
The mercury leaving the cells in the form of sodium mercury
amalgam is sent to denuders where the amalgam is decomposed at 80*C
by the addition of deionized water. Water reacts with the sodium
mercury amalgam to produce a 50 percent solution of sodium
-6-
-------
hydroxide* essentially free of sodium chloride. This solu-
tion is filtered to recover entrained mercury. The waste
from the filtration step is sent to wastewater treatment,
where mercury precipitates into the treatment sludge (stream
B). Entrained mercury is removed from the hydrogen generated
in the denuders, and returned to the electrolytic process.
After removal of mercury, the hydrogen i* either compressed
for sale, used on-site, or used as a fuel. The chlorine gas
collected in the electrolytic cells is cooled to condense out
excess water vapor. This stream, which is essentially free
of mercury, is sent to waste treatment. The partially dried
chlorine is then scrubbed with 93 percent sulfuric acid to
remove the rest of the entrained water vapor and is collected,
-compressed and liquified.
•C. Waste Generation
The wastes of interest in this document are muds that
result from the treatment of rock salt and recycled depleted
brine, and sludges generated by the treatment of purged,
depleted brines and ancillary waste streams. Seventeen
facilities (see Table 1) generate both of these wastes.
Eight other operating facilities, (those which use prepurified
or evaporated salt - see Table 2) do not generate brine puri-
fication muds (waste A, Figure 1)
*Potassium hydroxide is produced in plants using potassium
chloride as raw material.
-7-
-------
The source of mercury in the brine purification muds is
the recycled brine from the electrolytic cell (which mercury
is removed in the purification process step).
These brine preparation muds contain substantial con-
centrations of mercury, in elemental form, and as oxides,
chlorides and the complex ion. HgCl^". Earlier data indicated
that the concentration of mercury in these muds ranges from
500(12) to 2000 ppm'13,14)^ More recent data, however, indicate
that the concentration of mercury in these muds ranges between
13-1000 ppm, with an average concentration of 200 ppra in samples
from fifteen facilities.'^4) Even at the new reported levels,
the total potential mercury loadings are substantial: using the
1980 figure (ref. 24) the 36,000 kkg of hazardous brine
preparation and purification muds generated each year (Table 1)
are .therefore estimated to contain 7 kkg of mercury.
It should be noted that the amount of muds produced
depends on the source of the salt used as raw material.(11»12)
i
Facilities using salt from the Texas-Louisiana salt dome
generate about 10 kg of brine mud per kkg of chlorine.
Plants using other salt sources generate brine muds in amounts
ranging from about 20 kg per kkg of chlorine (salt from
Kansas and New York) to 45 kg per kkg chlorine (salt from
Michigan and West Virginia deposits). All the above quoted
figures are on a dry-weight basis. (1/10,11,12)
The sludges resulting from wastewater treatment
consist mainly of mercuric sulfide. Approximately 3,500 kkg
-8-
-------
of this waste is generated annually.'24) j^ contains mercury
in concentrations ranging from 0.02 to 15%, with an average
concentration of 4.2%.(24) Therefore 147 kkg of mercury are
generated in the wastewater treatment sludges each year.
In total, therefore, of the approximately 39, 500 kkg of
hazardous mercury-bearing wastes from the mercury cell process
for the production of chlorine, approximately 154 kkg of mercury
are generated annually from the mercury cell process for the
production of chlorine. A 1965 study(^5) estimated that
846 kkg of mercury were lost to the environment from this
•
industry as both water borne and solid wastes, and air emissions.
D. Waste Management (1,11,12)
Of the seventeen plants generating both listed waste streams,
_all but five combine their wastes prior to treatment. One plant
retorts all mercury-containing wastes, eight others retort only
the mercury-rich wastes, and of these eight, four store these
wastes in drums until, decisions are made on final disposal. • One
plant sends sludges to contractors for recovery. This latter
disposal method is occasionally used by other facilities. Nine
plants now use on-site pond storage of sludges, and seven use
on-site landfill. Four plants send wastes to contractors for
secured landfilling. Several plants employ combinations of these
treatment and disposal techniques.^/
^J One plant utilizes a relatively new system for recovery of
mercury from virtually all mercury bearing wastes. Treatment of
contaminated wastes with sodium hypochlorite leaves wastes with a
residual mercury.content of less than 8 ppm.(24) The treated
waste is then disposed, of by landfilling. This waste recovery
process is in theory capable of treating brine mud and of recycling
recovered mercuric chloride. However, its applicability is limited
by cell design and water balance considerations.
-9-
-------
II. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Waste
The two listed wastes are of regulatory concern because
of their contamination with the toxic metal mercury.
Brine preparation and purification muds are reported to contain
as much as 1000 ppm of mercury, and treatment sludges contain
about 4.2% mercury. ^4) Moreover, very large amounts of these
wastes (39,500 kkg) are generated. Mercury is highly toxic
to a wide variety of organisms, including man, and can accu-
mulate in biological organisms in its various forms.
These wastes have been involved in a number of damage in-
cidents, demonstrating empirically that improper management
of these wastes may cause substantial harm. These damage
"incidents are described below.
*
0 The Olin 102nd Street Landfill, Niagara Falls, Niagara
County, New York.(4)
From mid 1948 to September, 1970 Olin Chemical Cor-
poration utilized a landfill for the disposal of chemical
wastes from its Niagara Falls plant. These wastes
include brine sludge from a mercury cell chlor-alkali
plant plus other wastes such as chlorinated organics,
lime wastes, HTH wastes, fly ash, black cake wastes
(sodium chloride, sodium chlorite, sodium chlorate,
carbon, calcium carbonate, calcium hydroxide), graphite
from electrolytic cells and concrete cell bodies, together
-10-
-------
with a limited amount of research materials. This land-
fill is located in a suburban section of Niagara Falls,
New York, contiguous to the northern shore of the Niagara
River. When it was closed, the landfill was "secured" by
covering the waste with a soil cover, establishing vegetation,
and by constructing a dike along the Niagara River.
In 1978, a surface and groundwater sampling program was
initiated at the landfill site by RECRA Research Inc. and
WEHRAN Engineering Corporation^) to provide both baseline
water quality data and sufficient information to assess the
impact of previous disposal operations at the site. The
program included the analysis of waters from the various
groundwater regimes encountered on-site, and of grab samples
of surface waters from the Niagara Piver. In view of the
fact that the EPA National Interim Primary Drinking Water
Standard for mercury is 2 ug/1, pertinent results indicated
serious mercury contamination:
1) On one of the two dates on which samples were
taken, all mercury analyses for the six Niagara River
surface grab samples (taken downstream from the
furthest upriver point where the landfill borders
the river) contravened the Drinking Water Standard
in every case, with values ranging from 4.7 to 15
ug/1. On the second date, there was no significant
-11-
-------
difference in concentrations up- and down stream
from the landfill site. On this date, stormy conditions
prevailed, and the river flow was much above normal.
2) Water samples were taken from the fourteen piezo-
meters located in the saturate^ water zone in the
landfill. Soluble mercury readings ranged from
non-detectable values to 40 ug/1, with the bulk of
the readings ranging from 3.9 ug/1 to 11 ug/1.
Out of 14 samples taken, 13 contravened the Drinking
Water Standard.
3) Contiguous to the saturated water zone of the land-
fill is a semi-confined aquifer of alluvial deposits.
Water samples were taken from piezometers located
in the alluvial deposits aquifer. Soluble mercury
readings ranged from non-detectable to 35 ug/1.
These data are believed to indicate that leachate
from the landfill has migrated to this zone.
The Newco Solid Waste Management Facility Niagara Palls,
New York (5,6)
At this disposal site, Olin is currently disposing
of brine sludges emanating from its mercury chlor-alkali
process. (This site has been used as a waste disposal
area for over 80 years.) An evaluation was performed of
the presence, movement, and quality of groundwater at
this facility, and the data were incorporated in a
Draft Environmental Impact Statement for the State of
-12-
-------
New York. (5, 6) Elevated levels of mercury (6.6 ug/1)
have been found in the leachate of mercury-contaminated
sludges that have been disposed of in the landfill.
In another damage incident (involving an inactive
chlor-alkali facility not otherwise identified in the
literature), leaching of mercury from the solid wastes
from the "facility caused elevated levels of mercury in
downstream water, suspended matter, and bottom sediment.
About 39 kg of mercury are lost to water from this
unlined lagoon each year. Concentration of mercury in
water and suspended matter immediately downstream from
the plant site are about 20 times higher than immediately
upstream. The silt-clay fraction of bottom sediment
immediately downstream of the plant site contains up to
200 times as much mercury as similar sediments collected
immediately upstream from this facility. (16)
Contamination of Surface Water from an Alkali Processing
Plant in Saltville, Virginia(2D :
In another damage incident involving the 01 in
Corporation, an alkali processing plant generating the wastes
listed in this document (and other Industrial waste) disposed
of these wastes in a series of lagoons located on the^North
Pork of the Holston River in Saltville, Virginia. Although
the site (presently owned by Olinj ceased operating in 1972,
wastes continue to leach from the disposal lagoons . Mercury
-13-
-------
continues to enter the Holston River both from the site of
the chlorine plant and from disposal lagoons used for disposal-
of chlorine production wastes. The grounds where the cell
building once stood are estimated to contain some 220,000
Ibs. of mercury. Cleanup costs are estimated at $32-$40
million.
The incidents described demonstrate that mercury will
migrate from mercury-bearing wastes in harmful concentrations
and can cause substantial environmental harm unless proper
management is assured.
There are also other factors which warrant listing these
wastes as hazardous. Transportation of these wastes to off-site
disposal facilities, a management practice utilized by several
manufacturers, increases the likelihood of mismanagement of
these hazardous wastes, for example, due to improper handling
during transport, or failure to reach the intended destination.
A transport manifest system, combined with designated standards
for the management of these wastes will greatly reduce their
availability to do harm to human beings and the environment.
The quantity of these wastes generated is an additional
factor of concern. As indicated above, these wastes are gene-
rated in large quantities (39,500 kkg of waste per year,
containing 154 kkg of mercury). Under improper disposal conditions
large amounts of mercury are thus available for environmental
release. The large quantities of this contaminant poses the
danger of polluting large areas of ground and surface waters.
-14-
-------
Contamination will also occur over long periods of time,
since elemental mercury persists indefinitely. Since large
amounts of pollutants are available for environmental loading,
the attenuative capacity of the environment surrounding the
disposal facility could also be reduced or used up due to the
large quantities of pollutants available. All of these con-
siderations increase the possibility of environmental exposure
to the harmful constituent in the wastes.
B. Health and Ecological Effects
The various forms of mercury are interconvertible under
most environmental conditions. They are toxic to a wide
variety of organisms/ including man, O) an
-------
For total recoverable mercury/ the EPA has established criteria to
protect aquatic life as 0.00057 ug/1 and 0.025 ug/1 for freshwater
and saltwater species, respectively(26)t por ^he protection of
human health from the toxic properties of mercury ingested through
waster and contaminated aquatic organisms the ambient water
criterion is 0.144 ug/1.(20) Additional information and specific
references on the adverse effects of mercury on human health and
the environment can be found in Appendix A.
-16-
-------
REFERENCES
K071, K106: Chlorine Production, Mercury Cell Process.
1. Versar, Inc. Assessment of solid waste management
problems and practices in the inorganic chemicals
industry, final report. Contract Number 68-03-2604,
Task 2. Prepared for U.S. Environmental Protection
Agency. June 13, 1979.
2. Stanford Research Institute. Directory of chemical
producers. SRI International, Menlo Park, CA. 1979.
3. Currey, J.E., and G.G. Pumpkin. Chlor-alkali.
Encyclopedia of chemical processing and design. J.J.
Mcketta, ed., John Wiley and Sons, New York.
4. Not used in text.
5. Roy F. Weston, Inc. Hydrogeologic investigation of the
Newco-Niagara recycling site. Niagara Falls, New York.
July 25, 1978.
-6. Ecological Analysis Inc. Draft environmental impact
statement. Newco Solid Waste Management Facilities,
'Niagara Falls, New York. Prepared for New York State
Department of Environmental Conservation. April, 1979.
7. Not used in text.
8. Not used in text.
9. National Academy of Sciences. An assessment of mercury
in the environment. 1978.
10. U.S. EPA. Federal guidelines: state and local pretreatment
programs. EPA No. 430/9-76-Ol7a. NTIS PB No. 266 781.
1977.
11. Versar, Inc. Assessment of solid waste management
problems and practices in the inorganic chemicals industry,
final report. Contract No. 68-03-2604. Prepared for
U.S. EPA. EPA No. SW-180c. October 1979.
12. Versar, Inc. Multi-media assessment of the inorganic
chemicals industry, draft final report, v.3. Contract
number 68-03-2604, Task 4. Prepared for U.S. EPA
Industrial Research Laboratory. October 1979.
-17
-------
13. Versar, Inc. Alternatives for hazardous waste management
in the inorganic chemicals industry, final report. Contract
No. 68-01-4190. Prepared for U.S. EPA, Office of Solid
Waste, Hazardous Waste Management Division. June, 1977.
14. Versar, Inc. Assessment of industrial hazardous waste
practices, inorganic chemicals industry. Contract
number 68-01-2246. Prepared for U.S. EPA, Office of
Solid Waste Management Programs. EPA No. SW-104c. 1975.
15. Nelson, N. Hazards of mercury. Env. Res. 4:1-69:1971.
16. Turner, R.R., and S.E. Lindberg. Behavior and transport
of mercury in a river-reservoir system downstream of an
inactive chlor-alkali plant. Envir. Sci. and Technol
12:918-923:1978.
17. Beisinger K.E., and G.M. Christensen. Effects of
various metals, on survival, growth, reproduction and
metabolism of Daphnia magna. J.Fish. Rev. Board Can.
29:1691:1972.
18. Olsen G.F., et al. Mercury residues in fathead minnows,
Pimephales promelas Rafinesque chronically exposed to
methylmercury in water. Bull. Environ. Contamin Toxicol.
14:129:1975.
19. Not used in text.
20. U.S. EPA. Ambient water quality criteria for mercury.
EPA No. 440/5-80-058. NTlS PB No. 81-117 699. October 1980.
21. U.S. EPA. Damages and threats caused by hazardous
material sites. EPA No. 430/4-80/004. 1980.
22. U.S. EPA. Development document for effluent limitations
guidelines and standards for the inorganic chemicals
manufacturing point source category. EPA No. 440/1-80-
007b. June 1980.
23. Not used in text.
24. Data provided by the Chlorine Institute: Letter to Docket
3001, September 12, 1980 (Comment No. FHWR-1B-014, 1000).
-18-
-------
Response to Comments: Chlorine Production (Mercury Process) Waste.
1. Several commenters stated that the Agency's characterization
of the industry and the quantity and quality of its
wastes was inaccurate in several respects, and provided
new data on siting, production capacity, source of raw
materials and the mercury content of wastes of concern.
The listing background document was modified to reflect
this new information. Both the original and the new data
were provided by the Chlorine Institute, thus, in both
instances, the Agency relies in large part on the accuracy
and timeliness of the trade association's figures.
2. several commenters indicated that brine muds and waste-
water treatment sludges pose "very different risks of
environmental harm, and argued that these two wastes should
be accordeddifferent regulatory treatment. In particular, it
was argued that brine muds ordinarily contain lower con-
centrations of mercury, and shonld not be considered
irremediably hazrdous. It also was suggested that any
of these wastes which pass the extraction procedure
test should automatically not be regulated under subtitle C.
The Agency agrees that the mercury content of these
two wastes differs. However, we believe that mercury
concentrations and potential mass loadings from brine
muds alone are typically high enough to warrant listing.
-19-
-------
Brine purification muds contain sufficient concentrations
(13 - 1000 .ppra by industry figures) and volumes (7kkg
annually) of mercury to result in substantial environ-
mental harm if mismanaged. Even muds containing low
concentrations of mercury would need to leach only one
hundredth to one thousandth of their total mercury to exceed
the interim primary drinking water level of 0.002 ppm.
By listing these wastes the Agency is not precluding
possible site-specific delistings if individual wastes
do not meet the criteria for listing. Thus, facilities
that treat their brine purification muds to reduce
mercury concentrations could conceivably be able to delist
their wastes. EP leachate results are certainly relevant,
although not determinative, in making a delisting deter-
mination (see 45 FR 33111 - 33112, May 19, 1980). We
reiterate however, that we believe ample evidence exists
that the brine muds are typically hazardous, and therefore
intend to retain the listing for this waste stream.
3. Two commenters argued that the listing of mercury-
bearing brine sludges as hazardous is contrary to
the purposes of RCPA, because it discourages industry
efforts to render these wastes less hazardous. We
again disagree. As the commenter and the background
document point out, these wastes can be treated
to recover mercury and reduce the mercury content.
We believe this listing strongly encourages such treatment.
-20-
-------
Should the resulting residue in fact be non-hazardous,
the delisting mechanism allows individual facilities an
opportunity to avoid regulation. Further, even if
the resulting sludges are still hazardous wastes, it
it should be much easier to obtain final management
permits, again providing economic and managerial
incentives for generators to develop or make greater
use of technologies which can render such wastes non-
hazardous .
4. One commenter argued that no environmental hazard
has been shown to be associated specifically with
mercury-bearing brine purification muds. The commenter
pointed out that many varieties of mercury-bearing
wastes were deposited at the sites for which the Agency
documented mismanagement incidents. The Agency agrees
that the several damage incidents, documenting
contamination of water with mercury from landfills
in which solid wastes from chlorine production had
been disposed does not specifically implicate any
one of these residues as being the unique cause of
such contamination. Nor does the Agency deem it
necessary to make such unique identification. The
damage incidents and the published data concerning
leaching of soluble mercury in solid wastes from a
-21-
-------
chlor-alkali plant reported in the listing background
document illustrate that water contamination from
such wastes in toto does occur. Further, it appears
probable that listed chlor-alkali wastes were responsible
for at least some of the damage caused in these incidents,
If the commenter were able to document the fact
that mercury-bearing brine purification muds, when
uniquely disposed for periods similar to those
illustrated in the damage incidents, did not cause
water contamination, this could constitute proof
that such wastes might indeed not be hazardous. In
the absence of such proof, however, the Agency will
continue to list mercury-bearing brine purification
muds as hazardous.
5. One commenter stated that, although poorly managed
mercury-bearing wastes can result in environmental
damage, such' damage has resulted from wastes which
•were improperly managed in the past. The commenter
felt it unreasonable to assume that such poor management
practices would continue in the future.
It is the Agency's position that the fact that
a waste is properly managed by particular generators
or classes of generators does not render the waste
non-hazardous. RCRA requires that EPA determine
whether a waste is hazardous if substantial hazard
-22-
-------
could result when wastes are improperly treated,
stored, transported, disposed of, or otherwise
managed. The potential of the waste to cause hazard
is the key factor. This position is more fully
explained at 45 FR 33113.
6. One comraenter suggests that the EP toxicity test
should be the sole criterion for determining whether
these wastes are hazardous. While the Agency has
determined that the EP is a valid and acceptable
test for identifying wastes likely to leach toxic
constituents into groundwater, it believes the EP to
be a somewhat less precise instrument than the
listing mechanism for determining hazard, inasmuch
as the EP fails to take into account factors such as
the concentration of toxicants in the waste, their
chemical composition, and the quantitity of waste
generated, all of which have a bearing on the
hazardousness of the waste. This position and the
grounds for its determination are more fully discussed
at 45 PR 33111. Therefore, the listing mechanism
also may be used to bring wastes within the hazardous
waste management system. Listing appears particularly
appropriate here, where the wastes contain high
concentrations of very toxic constituent, and are reliably
believed to have caused substantial damage in acutal
waste management practice.
-23-
-------
SJ-39-07
January 1981
LISTING BACKGROUND DOCUMENT
K073: CHLORINATED HYDROCARBON WASTE FROM THE PURIFICATION STEP
OF THE DIAPHRAGM CELL PROCESS USING GRAPHITE ANODES IN
CHLORINE PRODUCTION (T)
i.
Chlorinated hydrocarbons are generated during the pro-
duction of chlorine in diaphragm cells with graphite anodes.
Purification results in separation of the chlorinated
hydrocarbon waste from the product. The Administrator has
determined that this waste is a solid waste which may pose a.
substantial hazard to human health and the environment when
improperly transported, treated, stored, disposed of or
otherwise managed, and which therefore should be subject to
appropriate management requirements under Subtitle C of RCRA.
This conclusion is based on the following considerations:
1. The waste contains significant concentrations of the
toxic compounds chloroform, carbon tetrachloride ,
hexachloroethane, trlchloroethane, tetrachloroethylene,
dichloroethylene, and 1 ,1, 2 , 2-tetrachloroethane. The
Agency's Carcinogenic Assessment Group has found that
chloroform, carbon tetrachloride, tetrachloroethylene
and 1, 1 , 2, 2-tetrachloroethane exhibit substantial
evidence of carcinogenicity.
2. Typical management practices include deep well injection
and incineration. Landfilling has also been employed as
a disposal method. If these practices are unregulated,
hazardous substances could be released to the environ-
ment. Improper construction or operation of a deep
well could cause leakage of the waste from the well
into usable aquifers; inadequate incineration can result
in the generation of highly toxic combustion products
such as phosgene. Uncontrolled landfilling may result
in migration of hazardous substances to air and ground
and surface waters.
-------
3. Most of these compounds have significant migratory
potential and have proven mobile and persistent in
actual damage incidents caused by improper waste
management.
ANDTYPICALDISPOS ALPRACTICES
Chlorine is produced by electrolysis of brine. It
is used in the pulp and paper industry, plastics, water
treatment and manufacture of organic and inorganic chemicals.
About 75 percent of all chlorine manufactured in the United
States is produced by the diaphragm cell process. ( ) Approxi-
mately 32 plants use diaphragm cells; of these, six plants
that utilize graphite anodes generate chlorinated hydrocarbon
contaminants.*'^-' Locations and production capacities of the
six are given in Table l.(2)
B . Manuf ac t ur in j_Pr o ce s s ( 1 » 3 )
Brine is first purified by precipitation of metals
before being sent to the diaphragm cell. Separation of
solids during purification generates waste brine muds; the
Agency has no data at this time to indicate that the brine
muds are hazardous. The purified brine is heated, brought
to saturation by the addition of salt and acidified. The
saturated salt solution is then electrolyzed in the diaphragm
cell to form chlorine, hydrogen a.nd sodium hydroxide. Chlorine
is liberated at the anode, and hydrogen and sodium hydroxide
are produced at the cathode. Reaction of chlorine with
^Graphite anodes predominated in the past, but in recent
years most plants have replaced them with metal anodes.
-25 ~
-------
Table 1
FACILITIES GENERATING CHLORINATED HYDROCARBON BEARING WASTES(2)
ICI Americas
Baton Rouge, LA
Dow Chemical
Midland, Mich.
Vulcan Materials
Denver City, Tex.
Champion Production
Canton, N.C.
Pasadena, Tex
PPG Industries
Barberton, Ohio
PRODUCTION
CAPACITY
103 KKG/YR
156
256
121
26
20
100
-------
carbonaceous materials la the graphite anode results in
the presence of chlorinated hydrocarbon contaminants in the
chlorine product.
The hydrogen is purified and either sold, vented to the
atmosphere or burned. The salt solution, which has been
decomposed to approximately half its original concentration,
is partially evaporated to increase the sodium hydroxide
concentration. During evaporation, most of the sodium chloride
precipitates from the solution and is recovered in salt
separators. After filtration and washing, the salt is recycled
to initial brine preparation..
Chlorine is recovered from the cell and cooled to remove
water and other impurities. The condensates are discharged
or recycled to the brine purifier. After cooling, the chlorine
gas is scrubbed with acid to remove residual water vapor.
The gas is then compressed and cooled to -30°C to -45°C. At
these temperatures, the chlorine liquefies and is pumped to
steel storage tanks. Some further purification is performed
during the cooling and liquefaction process. The chlorinated
hydrocarbon waste of concern is liquefied from the chlorine
gas stream during purification. Figure 1 illustrates the
process.
The Agency is also concerned that wastewaters from
clean-out of the diaphragm cell and from caustic evaporation
and salt recovery operations and sludges resulting from
treatment of these wastewaters may also be. hazardous because
-X-
-------
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-69-
-------
they contain significant amounts of lead. The Agency currently
does not have sufficient information on the concentrations
and the migratory potential of the lead in these wastes, but
they may be listed as hazardous at some time in the future.
Generators, however, must determine whether this waste is
hazardous pursuant to §§262.11 of the Subtitle C regulations.
C. Waste Generation and_Mana|ement (4)
As mentioned previously, chlorinated hydrocarbon
contaminants arise primarily from the reaction of chlorine
with carbonaceous materials in the graphite anodes. Reaction
of chlorine with oils and greases in the equipment and other
hydrocarbons present in the system also contributes slightly
to the generation of these contaminants. Depending on such
variables as the type of liquefaction, quality of anodes and
other factors, the chlorinated hydrocarbon contaminants are
liquified from the chlorine gas stream during purification
in amounts up to 1 kg per kkg of chlorine product.
Management practices vary. Vulcan Materials Co.
disposes of the chlorinated hydrocarbon waste by deep well
injection, and ICI Americas Ltd. incinerates its waste.
Champion International Corp. and PPG Industries, Inc., which
landfilled part of their wastes in sealed drums prior to
1977, apparently do not remove the chlorinated hydrocarbon
contaminants from the chlorine product at this time. Dow
Chemical's management practices are not known.
-------
in . 2iscjssioN_oF_BASis_FOR_LisTiNG
A. Ha za rds_Pose_by_the_Waste
The constituents of the chlorinated hydrocarbon
waste include the following (1):
Compound Identified
chloroform 73.7
carbon tetrachloride 10.8
hexachloroethane 8.0
peatachloroethane 1.3
trichloroethane 1.0
tetrachloroethylene " 0.6
dichloroethylene 0.3
1,1, 2,2-tetrachloroethane 0.5
Clearly, the waste contains substantial amounts of organic
compounds believed to be toxic and carcinogenic. Thus, in
light of these constituents' high migratory potential and
their ability to persist in the environment, improper
management of this waste is likely to lead to substantial
hazard.
Many of the ' constituents of concern have high vapor
pressures and thus could pose a substantial hazard to human
health and the environment via an air exposure pathway if
the waste is improperly managed. Evidence available to
EPA's Carcinogen Assessment Group indicates that chloroform,
carbon tetrachloride, tetrachloroethylene, and 1,1, 2, 2-tetra-
chloroethane are carcinogenic. The Agency believes that the
severity of the adverse health effects associated with exposure
to these constituents provfdes a sound basis for listing the
waste as hazardous. The high concentration of chloroform
-afif-
30
-------
alone justifies the listing of this waste as hazardous, in
the Agency's judgment. EPA's decision to list the waste is
supported further by case histories which reveal that these
hazardous constituents can migrate and persist in the environment.
Carbon tetrachloride, a major component of the waste,
has been identified in school and basement air in the vicinity
of Love Canal (8) and has been implicated in groundwater
contamination incidents in Plainfield, Connecticut, where
drinking water sources were adversely affected (9).
Chloroform has been found in drinking water wells near a
Jackson Township, New Jersey landfill in which chemical wastes
were dumped, and is also known to have migrated from the
Love Canal disposal site (10). Hexachloroethane, another
major constituent of the waste of concern, has 'also migrated
from at least one chemical waste disposal site (Table 7.2,
Ref. 9). In addition, damage incidents compiled by EPA
reveal numerous instances of environmental contamination due
to migration of trichloroethane and tetrachloroethylene.(10)
An estimated 125 kkg of waste per year is disposed of
in deep wells or by incineration* (2); either method may
unfavorably affect human health and the environment by con-
taminating ground and surface waters or polluting the atmosphere.
A deep well injection system that is not properly designed
*This"number was derived by multiplying 90% of the plant
nameplate capacity by 0.5, on the assumption that, on
average, 0.5 kg of chlorinated hydrocarbon wastes are
generated per kkg of chlorine.
-X-
-%*-
-------
or operated can release hazardous constituents from the well
to aquifers used as drinking water sources. Improper inciner-
ation of chlorinated hydrocarbons can result in the generation
and emission of highly toxic combustion products such as
phosgene (5,6,7) and chronically toxic chlorinated aromatic
compounds. CIS) fhe remainder of these wastes (up to 180 kkg
per year) is disposed of by means not known to the Agency.
Landfilling of drummed waste has been practiced in the
past. This disposal method presents obvious hazards; drums
are likely to corrode in the landfill and release the waste
to the surrounding area. Waste constituents could then
volatilize and enter the atmosphere or migrate to ground and
surface waters.
Chloroform has been identified by the EPA Carcinogen
Assessment Group as exhibiting substantial evidence of being
carcinogenic. Due to its highly volatile nature, (App. B),
improper disposal of chloroform-containing wastes may pose
an air pollution hazard. Long range exposures have caused
both physical and neurological disorders in humans, with
liver and kidney toxic responses representing the most pre-
valent physical pathology. FDA prohibits the use of chloroform
in drugs, cosmetics or food contact material. Additional
information and specific references on the adverse effects
of chloroform can be found in Appendix A.
-------
Carbon tetrachloride (tetrachloromethane) has been
Identified by EPA's Carcinogen Assessment Group as exhibiting
substantial evidence of being carcinogenic* Its toxic effects
include neurological damage and damage to the kidney and
lungs. It is volatile and slightly soluble in water, and is
therefore expected to migrate readily in the environment (11).
Additional information and specific references on the adverse
effects of carbon tetrachloride can be found in Appendix A.
Hexachloroethane
Hexachloroethane is moderately toxic to humans and is
one of the more toxic chlorinated ethanes to aquatic species.
It appears to have the potential to bioaccumulate (App. B).
Humans exposed to hexachloroethane may suffer central nervous
system depression and liver, kidney and heart degeneration.
It has also been shown to be carcinogenic to laboratory
animals. Little information is available on its environmental
fate and transport, but, due to the nature of the adverse
affects associated with exposure to this compound, the Agency
believes that improper disposal of a waste containing a
significant amount of hexachloroethane may pose a hazard to
human health and the environment. Additional information and
specific references on the adverse effects of hexachloroethane
can be found in Appendix A.
-JWJ-
-------
The trichloroethanes (1,1,1-trichloroethane and 1,1,2-
trichloroethane) are toxic to humans and animals, and have
been shown or are suspected to be carcinogenic. Because of the
toxic and/or carcinogenic effects of these compounds, the
Agency believes that improper management of wastes which
contain them may pose a hazard to human health and the
environment. Additional information and specific references
on the adverse effects of trichloroethanes can be found in
Appendix A.
Dichloroethyleneg
Exposure to dichloroethylenes can result in adverse human
health effects. The three isomers appear to have similar
toxic effects, including depression of the central nervous
system and liver and kidney damage (App. A). Two isomers
are mutagenic in bacterial sytems and one isomer has been
shown to be carcinogenic in laboratory animals (App.A).
Information on environmental fate and transport is scarce
but, due to the nature of the health effects resulting from
exposure to dichloroethylenes, the Agency has determined
that improper management of wastes containing these compounds
poses a hazard to human health and the enviroment. Additional
information and specific references on the adverse effects of
dichloroethylenes can be found in Appendix A.
-------
Tetrachloroethylene has been Identified by EPA's Carcinogen
Assessment Group as exhibiting substantial evidence of being
carcinogenic. In addition, repeated exposure to tetrachloro-
ethylene is implicated in mammalian liver and kidney damage
(App.A). Additional information and specific references on
the adverse effects of tetrachloroethylene is given in
Appendix A.
1,1, 2, 2-tetrachloroethane has been identified by EPA's
Carcinogen Assessment Group a-s exhibiting substantial evidence
of being carcinogenic. Occupational exposure has produced
neurological symptoms, liver and kidney damage, pulmonary
edema and fatty degeneration of the heart muscle. 1,1,2,2-
tetrachloroe thane is soluble in water (2900 ppm) and thus
has high migratory potential (11). Although environmental
fate and transport processes are not veil-defined (microbial
degradation appears to be the only known degradation mechanism
(App. B), and this process Is not likely to occur under the
abiotic conditions prevailing in most aquifiers), the Agency
believes that, due to the severity of the health effects
associated with exposure to this compound, Improper disposal
of the wastes in which it is contained poses a substantial
hazard. Additional Information and specific references on
the adverse effects of 1 , 1 , 2 , 2-tetrachloroethane can be
found in Appendix A.
-------
The waste also contains a significant amount of pentachloro-
ethane, a toxic chlorinated organic. At this time the Agency
has not compiled data on specific health effects or environmental
persistence and mobility; when the data are obtained, a
document will be prepared for Appendix A.
-------
REFERENCES
K073: Chlorine Production: diaphragm cell process.
1* U.S. EPA. Industrial Environmental Research Laboraory.
Draft final report-multimedia assessments, of the
inorganic chemical industry, v.3. Prepared by Versar,
Inc. October 1, 1979.
2. Versar, Inc. Written communication to J. Bellin, U.S.
EPA. June 3, 1980.
3. U.S. EPA. Development document for effluent limitations
guidelines and standards for the inorganic chemicals
manufacturing point source category. EPA No. 440/1-80/
007b. June, 1980.
4. U.S. EPA. Draft background document - Chlorinated hydro-
carbon bearing wastes from the diaphragm cell process in
chlorine production. Prepared by Versar, Inc. for U.S. EPA.
Office of Water Planning and Standards. May 21, 1980.
5. Edwards, J.B. Combustion formation and emission of
trace species. Ann Arbor Science. 1977.
6. NIOSH. Criteria for a recommended standard: Occupational
exposure to phosgene. 1976. NTIS PB No. 267514.'
7. Chemical and Process Technology Encyclopedia. McGraw Hill.
1974.
8. New York State Departement of Health. Love Canal,
Public Health Bomb. A special report to the Governor
and Legislature. 1978.
9. Acurex Corporation. Chlorinated hydrocarbon manufacture:
an overview. Preliminary draft report. February 1980.
10. U.S. EPA. Damages and threats caused by hazardous material
sites. EPA No. 430/9-80/004. January 1980.
11. Verschueren, K. Handbook of environmental data on organic
chemicals. Van Nostrand Reinhold Co., New York. 1977.
-------
Res poos e_to_Comoents2
Process^
1. One commenter questioned the Agency's characterization
of 1,1,1-trichloroethane as a carcinogen* The comnenter
argues that based on their evaluation of the available
data, 1,1,1-trichloroethane has not been found to be
carcinogenic (i.e., the commenter believes that the
Agency has incorrectly assessed the data).
The Agency disagrees with the commenter's claim.
Although an NCI Bioassay Study on the carcinogenicity of
1,1,1-trichloroethane referred to in the listing background
document and an unpublished study are inconclusive,
positive responses in two in vitro systems (a rat embryo
cell transformation assay (Price et. al. 1978) and a
bacterial mutation assay (Simmon et. al. 1977; McCann
and Ames, 1976)) currently used to detect chemical'
carcinogens, indicate that 1,1,1-trichloroethane has the
potential for carcinogenicity in animals. 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.*
The listing background document on trlchloroethane
*It should be noted that the Agency recently determined
to retain the listing of 1,1,1-trichloroethane as a toxic
pollutant under §307(a) of the Clean Water Act. The
reasons for that action are Incorporated by reference
herein.
-------
production and the Health and Environmental Effects
Profile on 1,1,1-trichloroethane has been modified to
discuss these findings.
References
McCann, J. and B. Ames. Detection of Carcinogens as
Mutagens in the Salmonella Microsome Test. Assay of
300 chemicals. Proc. Nat. Acad. Sci. 78:950:1976.
Price, P.J. et al. Transforming Activities of Trichloroethylen
and Proposed Industrial Alternatives. In Vitro 14:290:1978.
Simmon, V.F. et al. Mutagenic Activity of Chemicals
Identified in Drinking Water. In: Progress in Genetic
Toxicology. I.D. Scott, B.A. Bridges and F.H. Sobels, ed.
pp.249-258. Elsevier, N.Y., 1977.
3?
-------
SJ40-04
January 1, 19
LISTING BACKGROUND DOCUMENT
NITROBENZENE/ANILINE PRODUCTION
K083: Distillation bottoas from aniline production (T)
K103: Process residues from aniline extraction from the production
of aniline (T).
K104: Combined wastewater streams generated from nitrobenzene/
aniline production (T)*
I. Summary of Basis for Lasting
The first listed waste is the bottom residue generated
from the purification of aniline by distillation. The second
listed waste results from the extraction step in aniline production
and may or may not be combined with other process waters. This
listing covers the uncombined waste streams. The third
listed waste is the combined process wastewater streans from
the co-production of nitrobenzene and aniline. These waste
streams all contain toxic nitrogenous organic materials, and the
wastewater stream is likely to contain benzene as well.
The Administrator has determined that still bottoms from
aniline distillation, process residues from aniline extraction
(when generated as a separate waste stream and not combined
with other process wastewater streams), and wastewater generated
from nitrobenzene and aniline production 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, and there-
fore should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the
following considerations:
1) The distillation bottoms contain aniline, diphenyl-
amine, nitrobenzene, and phenylenediamine while the
combined wastewater stream contains these constituents
and usually contains benzene as well. The process
residue from aniline extraction, if disposed of
separately, contains aniline, nitrobenzene and
phenylenediamine. All of these constituents are
toxic. Benzene is a known human carcinogen.
Aniline, diphenylamine and phenylenediamine are
carcinogenic to laboratory aninals. Diphenylaraine
is expected to bioaccumulate.
2) Total potential loadings of benzene and aniline in the
wastewater stream from the production of nitrobenzene and
aniline could be as high as 9.5 kkg and 150 kkg annually,
quantities believed by the Agency to be quite significant in
view of these compounds' adverse health effects.
3) Current disposal practices of these wastes are not
well documented. However, there is a high potential
for contaminating groundwater by leaching from
waste treatment lagoons or landfills that are not-
properly designed or operated, since these constituents
have high migratory potential, and some have proven
mobile and persistent in actual waste management
practice. In addition, under certain conditions,
release to the atmosphere by volatilization poses
a risk of inhalation of aniline and nitrobenzene.
4) In a damage incident involving improperly managed aniline
distillation bottoms, waste oils were contaminated with
nitrobenzene from the distillation residues and spread
over roads, posing the risk of human exposure to dangerously
high concentrations of nitrobenzene. This waste has thus
proven capable of posing a substantial hazard in actual
. waste management practice. •
-------
5) The State of Texas regulates distillation bottoms
from aniline production as a hazardous waste.
II. Sources^ofjthe_Waste and Typical Disposal Practices
A. Profile^of^the^Industry
Nitrobenzene and aniline are major chemical inter-
mediates; the actual nameplate capacity was reported as
557,000 kkg<25) and 313,000 kkg, respectively.^) The U.S.
International Trade Commission lists aniline as the sixth
largest volume intermediate in terms of 1978 production.(D
Table 1 lists the facilities producing nitrobenzene and
aniline, and their production capacities. As is indicated,
most facilities produce both nitrobenzene and aniline. In
1978 97% of nitrobenzene produced was used for the synthesis
of aniline. (^ 25) ^he balance is purified for use chiefly as a
solvent, or in the manufacture of Pharmaceuticals, dyes and
photographic chemicals.
United States production of aniline is increasing.
Production levels were 151,000 kkg in 1969, 186,000 kkg in
1972, 187,000 kkg in 1975,<3) and 270,000 kkg in 1978.C1)
Aniline production capacity is anticipated to reach 450,000
kkg in 1980. Most aniline (about 40%) is used for the production of
polymeric methylene phenylisocyanate, an intermediate used in the
manufacture of urethanes; another 35% is used in the synthesis of
rubber chemicals.(2) The remainder is mainly used in the manufacture
of dyes and drugs.
-------
Table 1
PRODUCER LOCATIONS AND PRODUCTION CAPACITIES
MANUFACTURER
American Cyanamid Co.
American Cyanamid Co.
.E. I. Dupont de Nemours
& Company, Inc.
•E. .1. Dupont de Nemours
& Company, Inc.
First Mississippi Corp.
Malli.nk.rodt Corp.
Mobay Chemical Corp.
Rubicon Chemicals, Inc.
FACILITY
Bound Brook, HJ
Willow Island
Beaumont, TX
Gibbstown, NJ
Pascagoula, MS
Raleigh, NC
New Martinsville", WV
Geismar, LA
PRODUCTION CAPACITY (103kkg)
1978 1977
Nitrobenzene^25) Aniline^2
48
33
140
90
151
0
61
34
557
27
28
104
59
45
10
45
27
340
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B.
1. Manufacture of Nitrobenzene
Nitrobenzene is made by the direct nitration of
benzene using a sulfuric-nitric acid mixture. In the most
common continuous phase process, benzene is nitrated with an
aqueous mixture of sulfuric acid (53 to 60 mole percent) and
nitric acid (32 to 39 mole percent) at atmospheric pressure
and temperatures between 45 to 90°C. Yields are typically
better than 98 percent. This process (see Figure 1) is
carried out in vented stainless steel vessels equipped with
high speed agitators and cooling coils. Average residence
time is approximately 8 to 10 minutes. Nitrobenzene is
continuously drawn from the side of the reactor and separated
in a decanter. Once separated, this "crude" nitrobenzene is
reportedly used directly in the manufacture of aniline.
If pure nitrobenzene is required, the product is washed
first with water and subsequently with an alkaline solution
(generally either a sodium carbonate or sodium hydroxide
solution) in small vessels equipped with high speed mechanical
agitators, and then distilled. The wastewater resulting
from the washing operation (stream 3 in Figure 1), is one
component of the waterborne waste stream of concern in this
document.
-------
FIGURE 1
-SIGNIFICANT POLLUTANTS FROM
NITROBENZENE/ANILINE MANUFACTURE (MODIFIED FROM (2))
iuifurle
Ac*-, 7
a r^ 2 n [ • »voi«au
i v | y /TV I"MrttlM
: J \?y 2 -*.Aoiii«,
-^ \«/ -
SK^-* =S
JL v III].- .
F"1^ X^'
e ( ' * Still loctoM
« i !
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2 3 •*» » — ^
13 1 ! Steam ^Wastes t
1 StriooinS Ineinei- =
L •*
•* To wtitrv«ter
• TnctMat
Point'1*
Benzene, Nitroalkanes, Nitrobenzene, Nitrogen Oxides
Point 2*
Benzene, Nitroalkanes, Nitrobenzene, Nitrogen Oxides
Point 3
Benzene, Benzoic Acid, Carboxylic Acids, Nitrates, Nitrites,
Nitrobenzene', Nitrophenol
Point 4**
Dinitrobenzene, Nitrobenzene, Nitrophenol, Nitrogen Containing
High Molecular Weight Polymers, Polycarboxylie Acid, Dinitro-
toluene
-------
FIGURE 1 CONTINUED
Point 5
Benzene, Nitrobenzene, Nitrophenol, Polycarboxylic Acid, Nitro-
gen Containing High Molecular Weight Polymers
Point 6* u
Aniline, Carbon Monoxide, Hydrogen, Methane* Nitrobenzene
Point 7*
Cyclohexylamine, Volatile Amines, Water
Point 8*
Aainophenols, Azepins, Diphenylamine, Nitrobenzene, ?henyl-
enediaaine, Nitrogen Containing High Molecular Weight Polymers
Point 9
Aminophenol, Aniline, Nitrobenzene, Phenylenediaoine, Water
Soluble Amines
* Emitted to air and therefore not subject to RCP.A.
**This waste was listed in the May 19, 1980 promulgation (see
"Nitrobenzene Background Document" for details).
-------
Recovery of spent acid is essential from the standpoint
of economical operation. Generally, unreacted nitric acid
is extracted from the spent acid by steam stripping (denitrating
tower). The bottom product, dilute sulfuric acid (60 percent
by weight), is then concentrated by distillation (sulfuric
acid concentrator) and recycled to the reactor as shown, or
used in other manufacturing operations. Nitric acid removed
overhead from the denitrating tower is bleached with air to
remove nitrogen oxide and subsequently recycled to the reactor.
The overhead nitrogen oxides from the bleacher are scrubbed
with water and recycled to the denitrating tower.*/ The
waste resulting from acid recovery (number 5 in Figure 1) is
another component of the aqueous waste stream of concern in
this document.
2. Production of Aniline(2»3)
In the U.S., aniline production is based almost exclusively
on vapor phase reduction of nitrobenzene in the presence of a
copper catalyst. This process is also illustrated in Figure 1.
With the exception of one facility (Mallinkrodt, Inc.), the
nitrobenzene feedstock is produced on site.(2) xhe nitrobenzene
is vaporized in a stream of hydrogen and introduced into the
reactor. The crude product mixture (aniline, hydrogen and
^Another approach to spent acid recovery uses benzene, rather
than steam, to strip nitric acid from spent acid in the de-
nitrating tower. The nitric acid is thus dissolved in the
benzene and fed to the reactor. The remaining sulfuric acid
is concentrated as before.
-------
water) leaving the reactor is condensed and separated from
the gas stream. Host of this gas stream is compressed and
recycled to the reactor, but, to prevent build-up of gaseous
impurities in the reactor, some gas is purged. The two-phase
(aqueous and organic) reactor product mixture is separated.
The lower organic phase (stream B, Figure 1), consisting
principally of aniline, up to S percent nitrobenzene, and 5
percent water,(2) is purified by two stage distillation.
In the crude still, aniline and water are removed overhead,
while higher boiling organic impurities, such as nitrobenzene,
remain in the still bottoms (noted as 8, Figure 1). In a finishing
distillation step, the overhead product from the crude still
is purified to 99% specification, and the bottoms from
.this finishing distillation step are combined with the crude
distillation bottoms. (This process is shown as a single
distillation in Figure l.)<3>
Several methods are used to recover aniline from the
aqueous phase of the separator (C in Figure 1). Aniline nay
for instance be concentrated from this stream by steam stripping.
The resulting enriched aniline/water mixture is then incinerated.
This latter waste stream is not included within the present
listing, although it may be listed in the future. The Agency
solicits information as to the compo'sition of this waste and
risks associated with its improper disposal.
At some facilities aniline is recovered by countercurrent
extraction with nitrobenzene. Recovered aniline and nitrobenzene
ft
-------
are recycled to the reactor. In either case (i.e., if either
extraction or steam stripping is used), the residual waste
stream (9 in Figure 1) ordinarily is directed to wastewater
treatment with other process wastewater streams. This is
the third component of the waterborne waste stream of concern
in this document. In some facilities, the residues from the
extraction step are not combined with other process wastewaters
In such cases, the listing includes the separate wastewater
stream from the extraction step.
c. 2i5i£-2S2£.E5li22-12fl_!l222I£2£2£
The listed wastes consist of still bottoms from the
distillation of aniline (Point 8, Figure 1) and the wastewater
streams generated from nitrobenzene/aniline manufacture
(points 3, 5 and 9 of Figure 1), which are most often combined
before wastewater treatment. (Wastes from the aniline extrac-
tion step are listed when disposed of separately, as discussed
above.)
On the basis of process chemistry assumptions set forth
in (2), the aniline distillation bottoms are expected to
contain nitrobenzene, nitrophenols, aniline, diphenylamine,
and phenylenediamine. While precise concentrations are
unknown, concentrations of nitrobenzene are expected to be
quite high, since the organic phase prior to distillation
consists of 5 percent nitrobenzene, most of which would be
expected to be (and is Intended to be) removed by distillation,
leaving wastewater with low levels of nitrobenzene to go to
-sr-
-------
treatment.
The volume of aniline still bottoms and the present
practices of the industry with regard to their disposal are
not well defined. The most common disposal method for
distillation bottoms is storage in drums in private landfills.
Some of these wastes are apparently utilized for their acid-
neutralizing capacity in drilling operations.(4)
The wastewater stream components from nitrobenzene/aniline
manufacture include: the nitrobenzene washwater (Point 3),
the acid distillation column overhead (point 5) and the
aniline recovery stream (point 9). Based on a knowledge of
process chemistry, these streams are estimated to contain
the pollutants indicated in Figure 1. Most manufacturers
combine these wastewater streams prior to treatment.^) Table 2
lists typical concentrations of selected pollutants found in
combined nitrobenzene/aniline waste streams, as reported by
two manufacturers.'2)
A variety of wastewater treatment methods are applied,
and it is not known to what extent these are successful In
removing the toxic chemicals from the listed waste. The
following treatment methods have been reported:(2) steam
stripping, carbon adsorption, aerated lagoon, biological
contact stabilization, clarification, equalization, activated
sludge, stabilization pond, land application, and subsurface
disposal.
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Table_2
Characterization of Raw Waste Loading From
Nitrobenzene/Aniline Manufacture^)
Aniline
Benzene
Nitrobenzene
A
0
0
0
Y.8.1
.067
.005
.002
kg/kkg
Ml
0.
aniline
n.
005
0
0
product
Max1
0.49
0.031
0.012
kkg/yr*
Max.^
150
9.5
3.7
*0btained by multiplying the maximal value by the 340,000
kkg by 90% of annual aniline nameplate production capacity
(since plants rarely operate at 100% of capacity).
In addition to the above pollutants whose identity was
quantitatively confirmed, animophenol, benzole acid,
nitrophenol, and phenylene diamlne as well as nitrates and
nitrites are estimated^) to occur. Of these constituents
the wastewater loading data show that at least aniline,
benzene and nitrobenzene are present in substantial
concentrations, and generated in significant quantities
annually.
-yf-
Sef
5"!
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As noted above, the wastewaters from the extraction
step of aniline production are not always combined with other
process wastewater streams.
III. Discussion_of_Basis_for_Listing
A. Hazards Posed by che_Waste
On the basis of available information, it is apparent
that the listed wastes contain toxic organic materials, including
nitrobenzene, aniline, diphenylamine and phenylenediamine, and
(for the combined wastewaters) benzene. These constituents
are all toxic, and all but nitrobenzene are experimental or
(in the case of benzene) known carcinogens. All of these
constituents are projected to have migratory potential and
to be mobile and persistent in ground and surface water
(Appendix B), so that they can create a substantial hazard
if •disposal facilities are not properly designed and operated.
Aniline, nitrobenzene and phenylenediamine are quite soluble
(solubility 34,000, - 38,000 ppm and 1900 ppm respectively),'^)
and thus can easily migrate through dry sandy soils.
Diphenylamine is also significantly soluble for purposes of
risk of chronic exposure (300 ppm (5)). Furthermore, the
solubility of amines such as aniline, diphenylanine and
phenylendiamine increases significantly under conditions
which are more acidic than their acid dissociation constant
(pKa is 6.0 for phenylenediamine). Since the pH of the
rainfall in the United States presently ranges from 4.0 -
5.0(9,22)^ residues of aniline and phenylenediamine
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can be expected to leach to surface and groundwater if these
wastes are improperly transported, treated, stored, disposed
of, or otherwise managed.
Present waste disposal practices may be inadequate to
prevent waste migration* Certainly, improper management may
result in release of harmful constituents, particularly in
view of the properties of the waste constituents as described
above. For instance, if this waste should be exposed to an
environment subject to acid rainfall, disposed residues
containing phenylenediamine contacted by acid rainfall can
be expected to leach and to migrate to surface and groundwater.
Further, if this waste is treated in a lagoon, even
under relatively mild environmental conditions, the harmful
.constituents can be expected to leach from the waste, as a
result of their moderate to extreme water solubility properties
if the lagoon is not properly designed or operated.
Once released from the matrix of the waste, these constituents
could migrate from the waste and contaminate groundwater.
Nitrobenzene, for example, has proven mobile and persistent
in two major damage incidents involving waste disposal at the
Monsanto Chemical dump in East St. Louis and at the LaBounty
dump in Charles City, lowa.^10)
Another potential hazard associated with lagoon treatment
of this waste would be the volatilization of compounds with
appreciable vapor pressure such as benzene into the atmosphere,
thus posing a hazard via inhalation. Benzene has proven
-------
capable of migration and persistence via an air exposure
pathway in many actual damage incidents, Love Canal being the
most notorious.
If the wastes are landfilled, even in plastic-lined
drums, they can create a potential hazard. All drums have a
limited life span, for the exterior metal corrodes in the
presence of even small amounts of moisture. When this occurs,
the potential for groundwater contamination is high if the
landfill is not properly designed or operated. It should be
noted that many of the subject production facilities are
located in^regions of significant rainfall (LA, NJ, WV), so
that ample percolating liquid is available for leachate
formation. (In any case, there is no reason to believe that
'wastes will be containerized at all, since, absent Subtitle C
regulation, wastes could be landfilled in a variety of improper
ways.)
A special hazard posed by the subject wastes is the
possibility of the formation over time of highly carcinogenic
nitrosamines from some of their constituents.^) Aniline and
other amines (most importantly secondary amines) as well as
nitrites are thought to be present in these wastes (Figure
1). These substances may react to form nitrosamines, especially
under acidic conditions. Such conditions might result as a
consequence of co-disposal of the listed wastes with acidic
wastes, or under conditions of continued acid rainfall.
-------
Improperly managed aniline distillation bottoms have
been involved in at least one damage incident.(23) From 1976
through November 1978, contaminated waste oils were used as
dust suppressant on roads throughout East Texas. The chief
source of contamination were aniline tars (still bottoms)
from aniline production*, generated by Dupont's Beaumont
facility. These still bottoms were sent to Browning-Ferris
Industries Chemical Services, Inc., a state permitted waste
management facility, which proceeded impermissibly to mix the
wastes with waste oil, which oil was used indiscriminately as
a road dust supressant. Nitrobenzene levels in contaminated
soil varied, and were as high as 21,000 ppm. Most of the
concentrations were deemed by state environmental officials
as more than sufficient to cause substantial harm. The danger
was discovered before occurence of known harm, and Browning-
Ferris was ordered to remove approximately 10,000 cubic yards
of contaminated material from one subdivision, and additional
amounts of material from four additional subdivisions.(^3)
This incident not only illustrates the potential for
substantial harm if this waste is disposed of improperly, but
also suggests strongly that the aniline distillation residues
may contain very high concentrations of nitrobenzene, in
light of the substantial concentrations found in the contaminated
road oil. Furthermore, aniline distillation bottoms are
* The waste oils were heavily contaminated with nitrobenzene,
and the only source of nitrobenzene in wastes accepted by
Browning-Ferris were aniline distillation wastes. (23 at p. 17.)
-------
regulated as hazardous wastes (termed 'Class I wastes' under
the state waste management system) by the State of Texas
(23), another indication of their potential for hazard.
Benzene
EPA's Carcinogen Assessment Group has designated benzene
as a human carcinogen (leukemogen) . Acute exposure to high
concentrations of benzene causes central nervous system
depression (euphoria, nausea, staggering gait and coma).
Inhalation of lower amounts produces dizziness, headache and
nausea. Benzene has demonstrated teratogenic effects in laboratory
animals. Chromosomal changes have also been demonstrated in
workers exposed to benzene. '28)
For maximum protection of human health from the potential
carcinogenic effects of exposure to benzene through ingestion
the ambient water criterion is 0.80 ug/l(29).
Because benzene is soluble in water, it could be leached
from the wastewater treatment sludge which would be generated
from treatment of the combined wastewaters, in a landfill
situation and pose a threat to groundwater supplies. Because
it is also volatile (vapor pressure » 100 mm at 26.1*C
(Appendix B.))» it may pose an inhalation hazard during
handling in transportation and disposal. Additional information
and specific references on the adverse health and environmental
effects of benzene can be found in Appendix A.
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ss
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Nitrobenzene has toxic reproductive effects: in rats it
delays embryogenesis, alters normal placentation, and produces
abnormal fetuses (14); changes in the tissues of the chorion
and placenta have been reported in women exposed to nitrobenzene
(IS). Nitrobenzene has been listed as a Priority Pollutant
in accordance with §307(a) of the Clean Water Act of 1977.
With present data, it is not possible to fully estimate .
its aquatic fate. Hydrolysis and volatilization from water
are considered unlikely (15). Adsorption onto humus and clay,
and subsequent production by weathering and biological action,
of (carcinogenic) benzidine and diphenylhydrazine could be
a major fate pathway (12) Nitrobenzene is neither stored
nor ecologically magnified, but is resistant to degradation
by soil microflora (11, 12). In mammalian systems nitrobenzene
is metabolized to aniline, nitrophenol, p-hydroxyaniline
and other metabolites, which are excreted in urine, but such
metabolism in man is slower by an order of magnitude than in
animals (13).
The criterion to protect freshwater aquatic life is 480
ug/1 (24 hour average). The occupational exposure limit
(OSHA) is 5 mg/m^ (skin, 8 hr TWA). The American Conference
of Governmental Industrial Hygienists (ACGIH) threshold
limit for industrial exposure to nitrobenzene is 1 ppm.^3)
61
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Additional information and specific references on the adverse
health effects of nitrobenzene can be found in Appendix A.
Aniline
Aniline is an experimental carcinogen (16). Its absorption
causes anoxia due to the formation of methemoglobin, but
significant chronic problems (other than animal carcinogencity)
have not been demonstrated. Human exposure to vapor
concentrations of 7-50 mm has been observed to cause slight
symptoms.(30) Rapid absorption through the intact skin is
frequently the route of entry.(18,30) Cyanosis is the most
prominent outward symptom of -aniline intoxication.(8) At
0.4 mg/1 aniline is toxic to Daphnia (8). OSHA's PEL for
aniline is 19 mg/m3 (skin, 8 hr TWA)(17). Additional information
and specific references on the adverse health effects of
aniline can be found in Appendix A.
Fhenylenediamine
Phenylenediamine is a highly toxic substance, continued
exposure to which can cause liver injury (18). It is a
suspected carcinogen and teratogen (18). Of the three isooers,
the p-substituted compound is by far the more toxic (19).
The relative concentrations of the isomers in the listed
waste are not known* The oral toxicity for human beings is
high (LDi0- 50 mg/kg (19)), which, in combination with the
high water solubility of this compound is worrisome. Phenyl-
enediamine is listed by DOT as a hazardous substance (ORM-A),
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and the OSHA PEL is 0.1 mg/m3(8 hr TWA) (17)
Diphenylamine is an experimental carcinogen and teratogen
(19). Chronic exposure to diphenylamine induces cystic lesions
in the chicken'20) an(j t^e rat.'24) T^e American Conference
of Industrial Hygienists has established 10 mg/m3 as an
acceptable TLV for occupational exposure (21). Diphenylamine
can also be expected to bioaccumulate, due to its high
octanol/water partion co-efficient of 2,200 (7).
-------
References
K083: Aniline/Nitrobenzene
1. Beck, D.B., et al. Synthetic organic chemicals: United
States production and sales, 1978. US ITC Publication 1001.
1979.
2. Lowenbach, W., and J. Schlesinger. Nitrobenzene/aniline
manufacture: pollutant prediction and abatement. Mitre
Corporation Report No. MTR-7828. May 1978.
3. Northcott, J. Aniline and its derivatives. In Kirk-Othoer
Encyclopedia of Chemical Technology, M. Grayson and D. Ekroth
.eds. 3rd. ed., v.2. John Wiley & Sons, Inc., New York. 1978
4. Arthur D. Little, Inc.: information from D. Ennis.
5. CRC Handbook of Chemistry and Physics. 47th ed. Chemical
Rubber Co. Cleveland. 1966.
6. Patty, F.A. Industrial hygiene and toxicology. Interscience
Publishers, New York. 1963.
7. Hansch, C., and A. Leo. Substituent constants for corre-
lation analysis in chemistry and biology. John Wiley
and Sons, New York. 1979.
8. Verschueren, K. Handbook of environmental data on organic
chemicals. Van Nostrand Reinhold Company, New York. 1977.
9. Likens, G.E., R.F. Wright, J.N. Galloway, and T. Butler.
Acid rain. Scientific American 241:43-51:1979.
10. U.S. EPA. Damages and threats caused by hazardous material
sites. Office of Water and Waste Management, Oil and
Special Materials Control Division. EPA No. 430/9-80/004.
January 1980.
11. 43 Federal Register 59025-59027.
12. U.S. EPA. Callahan, M.A., et al. Water-related environ-
mental fate of 129 priority pollutants, v.2. EPA No.
440/4-79-0296. December 1979.
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-------
13. U.S. DHEW. Piotrowsky, J. Exposure tests for organic
compounds in industrial toxicology. NIOSH 77-144. 1977.
14. Kazanina, S.S. Morphology and histochemistry of hemochorial
placentas of white rats during poisoning of the maternal
organism by nitrobenzene. Bull. Exp. Biol. Med. 5:93:1978.
15. U.S. EPA. Oorigan, J., and J. Hushon. Air pollution
assessment of nitrobenzene. 1976.
16. National Cancer Institute. Bioassay of aniline hydrochloride
for possible carcinogenicity. NCI-CG-TR-130. NTIS P3 No. 287 539
17. 29 CFR 1910.1000.
18. Sax, N.I. Dangerous properties of industrial materials.
Van Nostrand Reinhold Co., New York. 1979.
19. U.S. DHEW. NIOSH. Registry of toxic effects of chemical
substances 1978.
20. Sorrentino, F., A. Fella and A. Porta. Diphenylamine-
induced renal lesions in the chicken Drol. Res. 6/2:71-5.
1978.
21. American Conference of Governmental Industrial Hygienists. .
Threshold limit values for chemical substances and physical
agents in the workroom environment with intended changes
for 1979. Cincinnati, OH. 45201.
22. Cowling, E. B. Acid precipitation and its effects on terres-
trial and aquatic ecosystems. Annals, N.Y. Acad. S-ci. 338:
540-556:1980'.
23. Testimony regarding east Texas road oil incident, April and
May 1979. Texas Department of Water Resources, Austin, TX.
May 30, 1979.
24. Ganier, K.D.,Jr., S. Solomon, W.W. Fitzgerald and A.P. Evan.
Function and structure in the diphenylamlne-exposed kidney.
J. Clin. Invest. 57:796-806:1976.
25. Stanford Research Institute. Directory of Chemical
Producers. SRI International, Menlo Park, CA. 1979.
26. Not used in text.
27. Not used in text.
-------
28. Trough, I. M. and W.M. Brown. Chromosome aberrations and
exposure to ambient benzene. Lancet 1:684:1965.
29. U.S. EPA. Office of Water Regulations and- Standards. Ambient
water quality criteria for benzene. EPA No. 440/5-8-018.
NTIS PB No. 81-117293. October 1980.
30. Proctor, N., and J. Hughes. Chemical hazards of the
workplace. J.B. Lippincott Co., Philadelphia. 1978.
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Response to Comments: Distillation Bottoms, Wastewater
Treatment Streams and Process Residues from Nitrobenzene/Aniline
Production.
One commenter, a manufacturer of these chemicals, objected
to the listing of wastewater streams from nitrobenzene/
aniline production, noting that they fully pre-treat
these wastewater streams, removing nitrobenzene, benzene
and aniline to extremely low levels, apparently taking
issue with the Agency's determination that these
wastes generally contain appreciable levels of these
(and other) toxic chemicals. . The commenter went on to
state that the mismanagement incident (cited in the BD)
regarding distillation bottoms from the production of
nitrobenzene in fact involved waste nitrobenzene,rather
than the listed waste.
We are not persuaded by this comment that the listed
wastes typically and frequently contain inconsequential
levels of hazardous constituents. To the extent an individual
facility is able to remove or reduce the constituents of
concern by a treatment process, the May 19, 1980 regulations
provide explicit procedures which a generator nay employ to
petition the Administrator to amend part 261 to exclude a
listed waste produced at a particular facility. (See §§ 261.20
and 260.22). a particular facility are set forth in §§261.20
and 260.22. The commenter can use these procedures to
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-------
petition for removal of the subject streams at its
facility. However, in the absence of proof regarding
error in its- assumptions concerning the nature and concen-
tration of toxicants, and the amounts of these hazardous
wastes generated, the Agency will continue to list
these streams as hazardous wastes* It should also be noted
that two of the toxic constituents of concern (phenylene
diamine and diphenylamine) were not adressed by the
commenter, thus, no data was provided to refute their
prersence or potential for creating a hazard.
With regard to the demonstrated potential for
mismanagement of these wastes, the cited legal testimony
implicated aniline distillation wastes (ref. 23 of BD
at p. 17, citing aniline tars, not waste nitrobenzene,
as the waste mixed with the road oil).
The Agency therefore disagrees with the commenter,
and judges that, because of the toxic nature of many of
the components of these wastes, the large amount of
wastes generated, and the demonstrated potential
for mismanagement, these wastes may pose a substantial
present or potential hazard to human health or the
environment, and that they should be subject to appro-
priate management requirements.
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CON 13-02
January 1981
LISTING BACKGROUND DOCUMENT
VETERINARY PHARMACEUTICALS
K084: Wastewater treatment sludges generated during the
production of veterinary Pharmaceuticals from arsenic
or organo-arsenic compounds (T).
£101: Distillation tar residues from the distillation of aniline-
based compounds in the production of veterinary pharmaceu-
ticals from arsenic or organo-arsenic compounds (T).
K102: Residue from the use of activated carbon for decolofization
in the production of veterinary Pharmaceuticals from
arsenic or organo-arsenic compounds (T).
I. SUMMARY OF BASIS FOR LISTING.
Treatment of wastewater from the production of veterinary
Pharmaceuticals from arsenic or organo-arsenic compounds generates
a wastewater treatment sludge containing arsenic or organo-
arsenic compounds' The production of this class of veterinary
Pharmaceuticals also generates residues from the distillation
of aniline-based compounds, and from the use of activated carbon
for decolorization, which also contain arsenic or organo-arsenic
compounds, wastes which are listed in this document.
The Administrator has determined that these wastewater
treatment sludges and other arsenic-containing wastes from
the production of veterinary Pharmaceuticals are solid
wastes which 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 require-
ments under Subtitle C of RCRA. This conclusion is based on
-------
the following considerations:
1) These wastes have been shown to contain high concen-
trations of arsenic. Arsenic is highly toxic and has
been identified by the Agency as a substance which has
demonstrated substantial evidence of being carcinogenic.
It is also a bacterial mutagen, and is teratogenic to
laboratory animals.
2) Disposal of these wastes in improperly designed or operated
landfills has resulted in arsenic contamination of ground and
surface water, providing empirical proof that the arsenic in
this waste is soluble and may migrate from disposal sites into
soil, groundwater and surface wate.r in concentrations sufficient
to create a substantial hazard. Further, since arsenic is an
element, and does not degrade with time, it persists, and
any contamination caused by mismanagement of these wastes
will be long-term.
3) These wastes are generated in large quantities, so that
large amounts of arsenic are potentially available for environ-
mental release, an additional hazard posed by this waste.
II. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Profile of the Industry
Three domestic companies currently produce veterinary
Pharmaceuticals containing arsenic: Salsbury Laboratories
in Charles City, Iowa; Whitmoyer Laboratories in Heyerstown,
Pennsylvania; and Fleming Laboratories in Charlotte, North
Carolina.C1.2)
B. Manufacturing Process and Waste Generation
The manufacture of arsenic-containing Pharmaceuticals
requires the reaction of an organic compound with inorganic
arsenic to form the organic arsenical product, and generates
arsenic-containing solid wastes^/
/The Agency is aware that these wastes also contain other substances
'of concern. They contain large quantities of the toxic compounds
1,1,2 trichloroe thane, phenol and nitrophenol, as well as _o-nitro--
aniline.(1) 26 organic compounds have been identified in the
process waste water in substantial concentrations including 22
priority pollutants.(*) Upon further study and evaluation these
wastes may be amended in the future to include these toxic consti-
tuents of concern, if this is deemed to be advisable.
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Arsenic-containing solid wastes generated during the production
process include tars from the distillation of aniline-based
compounds, and residue from the use of activated carbon in the
decolorization of Pharmaceuticals•(^>5) Whitmoyer reported
that it generates these wastes in annual quantities of one
hundred 55-gallon drums and more than six. hundred 55-gallon drums,
respectively.(^) Salsbury Labs also generates arsenic-containing
tars from production processes.(5)
Production of veterinary Pharmaceuticals from arsenic
compounds generates wastewaters which contain organic and
Inorganic arsenic. Treatment of these wastewaters produce
arsenic-bearing sludges. Figure 1 is a simplified representation
of the wastewater treatment system of one manufacturer's facility:
Salsbury Laboratories, which produces organic arsenicals marketed
as feed additives for chickens, turkey and swine.(1) Process
wastewaters at Salsbury are partially segregated into two
sewer systems. The first sewer system (A in Figure 1) carries
waste acid washwater (approximately 10,000 gallons per day) from
the nitration processes; this washwater is neutralized and clarified.
Although this drain system is intended to receive non-arsenic
contaminated waste water, adequate separation of arsenic wastes has
not been achieved. The acid washwater stream contains approximately
4 kg of arsenic per day.(29) ^*/ Since waste water treatment is claimed
^/ In the July 16 version of this background document, the Agency
stated erroneously that the sludges resulting from treatment of the
acid process wastewaters were a separate waste stream, and did not
contain significant concentrations of arsenic. This error is
-------
Influent
Basin
(pH adjustment)
i
Clerifier
1
- Neutralized neutral 'n
i, addle wastes precip'n
•astew»ter
> >
Treatment
sludges
(listed
waste }-
/vacuu
-------
to be 992 ef f ective(27 ) f tne treatment sludges resulting from this
acid washwater will contain almost all of this arsenic loading.
The second sever system (B in Figure 1), collects about
25,000 to 30,000 gallons per day of arsenic-containing process
wastewaters which originate from the manufacture of Salsbury's
arsenical compounds, such as 3-nitro-4-hyd roxyphenylarsonic
acid and 4-nitrophenylar sonic acid. The treatment of this waste
stream is operated on a batch basis as a two stage process involving
neutralization with slaked lime, the addition of a flocculant,
treatment with MnSC>4, and two filtration steps. The resulting
sludges, containing about 1.6 kg of arsenic per day, are combined
with those formed from the treatment of waste stream A. The mixed
treatment sludges constitute the first listed waste of concern
In this document.
•The other manufacturers of arsenic-containing veterinary
Pharmaceuticals also produce arsenic sludges. Whitmoyer
Laboratories generates approximately 1,260 drums per year of
sludge from the evaporation, volume reduction and centri-
fugation of waste salt solutions . (^) Fleming Laboratories
reported the production of arsenic sludges, but did not
describe the process by which they are generated (24).
The wastewater treatment sludges contain large amounts
of arsenic. One sample of fresh sludge from the Salsbury
Laboratories disposal site, the LaBounty landfill contained
28,000 ppm of arsenic (see below). In addition, the fact that
significant concentrations have been released from the waste
6?
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at the LaBounty site Indicates that the contaminant is present
in these wastes in substantial amounts. Borings from soils
underlying the arsenic-containing solid waste deposits at the
landfill contain a mean arsenic concentration of 700 ppm, and
borings from surrounding soils exhibited a mean concentration
of 2200 ppm.(l) Samples obtained from a well located between
the site and the river showed an arsenic concentration of 590
ppm in groundwater.(^)
The Agency, at present, has no detailed flow process infor-
mation concerning the manner in which the other listed wastes
are generated. However the wastewater treatment sludges generated
at Whitmoyer's laboratories are reported to contain 1-7% arsenic.^)
Arsenic concentrations in the other two listed wastes are also
"substantial: distillation tars are reported to contain 10'-152
arsenic, and residues from activated carbon decolorization are
reported to contain 4-142 arsenic.(*)
C. Waste Management
From 1953 to December 1977, Salsbury Laboratories
disposed of its solid wastes in the LaBounty Dump, located
on the west bank of the Cedar River. (1) Prior to 1953,
solid wastes were disposed of across the river at the municipal
dump, but quantities are estimated to be relatively minor
compared to those at the LaBounty site. The wastewater treat-
ment sludge presently is stored in drums and shipped by rail
To
-------
Co Waste Management, Inc., a commercial disposal operation
in Livingston, Alabama.(3)
Whitmoyer Laboratories' treatment sludges were stored
in on-site lagoons until groundwater contamination was detected
(this was also the disposal practice under prior ownership).
Off-site disposal has been utilized since that time. Since
1975 Whitmoyer Laboratories has drummed all of its arsenic-
containing wastes, and has shipped them to landfills specially
designed to impede release of hazardous constituents to the
environment.(^) The Agency has no information concerning the
current disposal practices of Fleming laboratories.
III. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Waste
: These treatment sludges, distillation tars, and .
activated carbon residues contain high concentrations of
arsenic, an extremely toxic substance. Arsenic and arsenic •
compounds have been identified by the Agency as a substance
which has demonstrated substantial evidence of carcinogenicity.
Arsenic Is mutagenic to bacteria and teratogenic to laboratory
animals. See Section B (Health and Ecological Effects) of this
listing background document and Appendix A for further information.
It is quite obvious that improper management of these
wastes can result in substantial hazard, since substantial
harm has in fact occurred from their faulty management. The
.if
-------
most notorious example of this damage occured at the LaBounty
landfill.
Various wastes, including large amounts of arsenic sludges,
were disposed of at the LaBounty site. In January, 1978
approximately 7.5 cubic meters of arsenic sludge were disposed
per day. (1) At one time it was estimated that the site
contained more than six million pounds of arsenic(^). The site
is located over a major aquifer. As noted above, substan-
tial arsenic contamination of soil and groundwater resulted
when the arsenic compounds leached from the waste site. As
a result of surface run-off and groundwater discharge, the
Cedar River picked up an average load of S3 kg of arsenic
per day in the vicinity of the LaBounty Site.(l) The Iowa
Department of Environmental Quality issued an order that
required Salsbury to cease disposal of wastes at the LaBounty
landfill. (77-DQ-01, Dec. 14, 1977). A report on this damage
incident*concluded that arsenic in the wastewater treatment
sludge is "fairly easily solubilized even if it is precipitated
with calcium as the arsenate".(5) The presence of arsenic in
ground and surface waters in the vicinity of the LaBounty Site
likewise clearly Indicates that, once released from the waste,
it is highly mobile and persistent.
The migratory potential of the arsenic contained in these
wastes is also substantiated by the groundwater contamination
-------
resulting from the storage of the listed waste and similar
wastes by Whitmoyer Laboratories in holding lagoons (4).
When the groundwater contamination was discovered in the
late 1960's, the company began disposing of the sludges at a
number of different sites; presently, these wastes are transported
by truck to hazardous waste landfills or a specially designed
vault disposal operation (4). Again, this demonstrates the
potential hazard posed by the migration of waste constituents
from a disposal site and the generator's subsequent recognition
of this hazard.
An additional demonstration of the necessity for proper
management occurred when Salsbury Laboratories, as a result
of a cease order, began disposing of solid wastes in a temporary
-on-site holding basin.(1) This disposal method was quickly
terminated because leachate was detected in the underdrain
system within 24-hours after disposal.(1) The 1977 court
action, coupled with -the present management of these wastes
in chemical waste landfills, substantiates the concern by
both the state and the generator for the proper management
and disposal of this hazardous waste.
These damage incidents show that arsenic may easily
migrate from these wastes and persist in the environment
upon release. Indeed, because arsenic is an element, and
does not degrade with the passage of time, it will persist
in some form virtually indefinitely.
There are a-number of additional reasons to Impose
-------
hazardous waste status on this waste. Unregulated transpor-
tation of this waste to off-site disposal facilities increases
the likelihood of harmful exposure to human beings and the
environment. Without proper means to track the waste from
the point of generation to its ultimate destination, the
waste might not reach its designated destination at all,
thus making it available to do harm elsewhere.
Furthermore, as previously indicated, arsenic sludges
from the production of veterinary Pharmaceuticals are generated
in very substantial quantitites (in January 1978, approximately
7.5 m^/day were generated at the Salsbury plant alone (1)). Large
amounts of arsenic are thus available for potential environmental
release, posing the danger of polluting large areas of ground
or surface waters. Contamination could also occur for long
periods of time, since large amounts of this pollutant are
available for environmental loading. Attenuative capacity
of the environment surrounding the disposal facility could
also be reduced or exhausted due to the large quantities of
pollutant available. All of these considerations increase
the possibility of exposure to this harmful constituent.
B. Health and Ecological Effects
Health Effects
Arsenic is acutely toxic to animals and humans (6). Death
in humans has occurred following ingestion of very small amounts
(5mg/kg) (7). Several epidemiological studies have associated
cancers with occupational exposure to arsenic (8-10), including
-ys-
-------
those of the lung, lymphatics and blood (11,12). Skin cancer
has been associated with the presence of arsenic in drinking
water (13), while liver cancer has developed in several
cases following ingestion of arsenic (14). The human carcinogenic
potential of arsenic is supported by animal studies, arsenic and
its compounds have been identified by the Agency as demonstrating.
substantial evidence of carcinogenic! ty .
Occupational exposure to arsenic has also resulted in
chromosomal damage (15), and several different arsenic
compounds have demonstrated positive mutagenic effects in
laboratory studies (16-18). The Ceratogenicity of arsenic
and arsenic compounds is well established (19-21); observed
defects include those of the skull, brain, kidneys, gonads,
eyes, ribs and genitourinary system.
The effects of chronic arsenic exposure include skin
diseases progressing to gangrene, liver damage, neurological.
disturbances (22), disturbances in red blood cell production
and cardiovascular disease (8).
Additional information and specific reference on adverse
effects of arsenic can be found in__Apj)ejid ix A .
s
Ecological Effects
The data base for the toxicity of arsenic to aquatic
organisms is more complete for freshwater organisms; con-
centrations as low as 128 ug/1 are acutely toxic to fresh-
water fish. Based on one chronic life cycle test using
Daphnja magna, a chronic value for arsenic was estimated at
853 ug/1 (21).
15
-------
Regulatory Recognition of Hazard
OSHA has set a standard 8-hr air TWA in air of 0.5
for occupational arsenic exposure. 0.05 mg/m^ has been proposed
for arsenic trioxide (23). DOT requires a "poison" warning
label.
EFA's Office of Toxic Substances under FIFRA has issued
a pre-RPAR. Arsenic is designated as a priority pollutant
under Section 307(a) of the CWA. The Office of Drinking
Water has regulated arsenic under the Safe Drinking Water
Act and the Office of Air Quality Planning and Standards-
has begun a preregulatory assessment of arsenic based on
its suspected carcinogenic effects. The Office of Water
Planning and Standards under Section 304 (a) of the Clean
•Water Act has begun development of a regulation based on
Health effects other than oncogenicity and environmental
effects. Finally, the Office of Toxic Substances has completed a
Phase I assessment of arsenic under the Toxic Substances Control
Act.
Industrial Recognition of Hazard
Arsenic administered by either the intra-muscular or
subcutaneous routes is rated as highly toxic in Sax, Dangerous
Properties of Industrial Materials (22). Arsenic is also rated
as highly toxic through ingestion, inhalation, and percutaneous
routes in Patty, Industrial Hygiene and Toxicology.
A ten-fold reduction (to 0.005 mg/m3) of the present OSHA
standard for arsenic trioxide has been proposed (23).
-------
REFERENCES
K084: Wastes from the manufacture of veterinary Pharmaceuticals.
1. Dahi, T. 0. NPDES Compliance Monitoring and Water/Waste
Characterization. Salsbury Laboratories/ Charles City,
Iowa. (June 19-30, 1978). National Enforcement Investigations
Center-Denver and Region VII-Kansas City. EPA No.
330-2-78-019. November 1978.
2. Directory of Chemical Producers, 1978 and 1979 eds.
3. Personal communication with Martha Steincamp, Enforcement
Division. EPA Region VII. Kansas City, MO. March 2, 1980
4. Personal communication to Arthur D. Little, Inc., from
Chemical Area Manager. Whitmoyer Laboratories.
Meyerstown, PA. April 3, 1980.
5. U.S. EPA. Report of Investigation. Salsbury Laboratories, Charles
Charles City, Iowa. Region VII. Surveillance and Analysis
Division. February 1979.
6. Gleason, M.N., et al. Clinical Toxicology of Commercial
Products. Acute Poisoning. 3rd ed., 1969.
7. Lee, A.M., and J.F. Fraumeni, Jr. Arsenic and respiratory
cancer in man: an occupational study. J. Natl. Cancer
42:1045:1969.
8. Pinto, S.S. and B.M. Bennett. Effect of arsenic trioxide
exposure on mortality. Arch. Environ. Health 7:5883:1963.
9. Kwratune, M., et al• Occupational lung cancer among copper
smelters. Int. J. Cancer 13:552:1974.
10. Oh, M. G., et al. Respiratory cancer and occupational
exposure to arsenlcals. Arch. Environ. Health 29:250:1974.
11. Baetjer, A. M., et al. Cancer and occupational exposure
to inorganic arsenic. 18th Int. Cong. Occup. Health,
Brighton, England. In Abstracts, September 14-19, 1975.
-------
12. Tseng, W.P., et al. Prevalence of skin cancer in an
endemic area of chronic arsenicism in Taiwan. J. Natl.
Cancer Inst. 40:453:1968.
13. U.S. EPA Hazard Profile: Arsenic. SRC, Syracuse, N.Y. 1980.
14. Nordenson, I. et al. Occupational and environmental risks
in and around a smelter in northern Sweden. II. Chromosomal
aberrations in workers exposed to
arsenic. 88:47:1978.
15. Peters, J., et al. Zum Einfluss Anorganischen Arsens auf
die DNS-Synthese Menschlicher Lymphocyten in vitro.
Arch. Derm Forsch. 242:343:1972.
16. Paton, G. R. and A.C. Allison. Chromosome damage in human cell
cultures induced by metal salts. Mutat. Res. 16:332:1972.
17. Moutschen, J. and N. Degraeve. Influence of thiol-inhibiting.
substances on the effects of ethyl methyl sulphonate on
chromosomes. Experientia 21:200:1965.
18. Hood, R. D. and S.L. Bishop. Teratogenic effects of sodium
arsenate in mice. Arch. Environ. Health 24:62:1972.
19. Beaudoin, A. R. Teratogenicity of sodium arsenate in rats.
Teratology 10:153:1974.
t
20. Perm, V. H., et al. The teratogenic profile of sodium arsenate
in the golden hamster. Arch. Environ. Health 22:557:1971.
21. U.S. EPA. Office-of Water Regulations and Standards.
Ambient water quality criteria for arsenic. EPA 440/5-80-021.
NTIS PB No. 81-117327. October, 1980.
22. Sax, N. I. Dangerous Properties of Industrial Materials.
Materials, 4th ed. Van Nostrand Reinhold, N.Y. 1975.
23. AC6IH,Threshold limit values for chemical substances and
physical agents in the workroom environment with
intended changes for 1979. Cincinnati, OH 45201.
24. Personal Communication to Arthur D. Little from Mr. George
Fleming, Fleming Labs, April 3, 1980.
25. U.S. EPA verification sampling and analysis for priority pollu-
tants at Salsbury Laboratories (Charles City, Iowa). Acurex
project 7381, Final Report 79-26/EE. April 1980. (Confidential;
Priorietary Information).
->*-
Ti
-------
26. Vitalis, J.S. to D.F. Anderson, EPA internal memorandum,
September 29, 1980.
27. Kliever, D. to P. Fahrenthpld. Comments of Salsbury
Laboratories on Effluent Guidelines Division draft report
on wastewater treatability. June 1980.
-------
JB-07-05
JANUARY 19, 1981
HAZARDOUS WASTE LISTING BACKGROUND DOCUMENT
K085: Distillation or Fractionating Column Bottoms from the
Production of Chlorobenzenes (T).
K105: Separated Aqueous Stream from the Reactor Product Washing
Step in the Production of Chlorobenzenes (T).*/
Distillation or fractionation column bottoms from the
**/
production of Chlorobenzenes, and the separated aqueous
waste stream from the reactor product washing step in the
batch production of Chlorobenzenes, are composed of a vary-
ing mixture of Chlorobenzenes (dichlorobenzene through hexa-
chlorobenzene) and benzyl chloride, and may also contain
benzene and nonochlorobenzene• The Administrator has deter-
mined that these waste streams are solid wastes and as solid
wastes may pose a substantial present or potential hazard to
human, health or the environment when improperly treated,
stored, disposed of, transported or otherwise managed. There-
fore, these wastes sho.uld be subject to appropriate management
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1. Distillation or fractionatins column bottoms from
chlorobenzene production are likely to contain sig-
nificant concentrations of dichlorobenzenes , tri-
chlorobenzenes, tetrachlorobenzene, pentachloroben-
*7ln response to comment, we have revised this listing descrip-
tion to indicate that a wastewater stream may be generated
from both batch and continuous processes. (See response to
comment #4.)
**/Throughout this background document, the terms 'chloroben-
zene(s)1 and 'chlorinated benzene(s)1 are used synonomously
to denote the group of substituted benzene compounds in
which one to six hydrogen atoms of benzene are replaced by
chlorine atoms, with no ring substituents present other
than-chlorine or hydrogen.
-7f-
-------
zene and hexachlorobenzene . Benzyl chloride is
expected to be present in significant concen-
trations. Benzene and monochlorobenzene may also
be present in lesser concentrations depending on the
efficiency of distillation . The dichlorobenzenes ,
trichlorobenzenes and tetrachlorobenzenes are all
toxic. Pentachlo-robenzene has been reported to
induce cancers in sone animal species. Hexachloro-
benzene and benzene have been identified by EPA's
Carcinogen Assessment Group (GAG) as having substantial
evidence of carcinogenicity . Benzyl chloride is
reportedly carcinogenic. Monochlorobenzene is
toxic. All of the chlorobenzenes bioaccunulate . */
2. The separated aqueous waste stream from the batch
production of chlorobenzenes is believed to contain
significant concentrations of benzene, several chloro
benzenes, and 2 , 4, 6-trichlorophenol, all of which
present chronic toxicity hazards. Benzene and 2,4,6-
trichlorophenol have been identified by GAG as having
substantial evidence of carcinogenicity.
3. These waste constituents are capable of migration,
mobility and environmental persistence if managed
improperly, and have caused substantial hazard in
actual damage incidents. Disposal of these distil-
lation bottoms and the aqueous waste in uncontrolled
landfills, therefore, could allow migration of con-
taminants to ground and surface waters and release
of volatile toxicants to the air, while improper
incineration may result in the generation of ex-
tremely hazardous compounds such as phosgene.
I. Industry Characterization and Manufacturing Process
Twelve chlorinated benzene compounds can be formed
during the chlorination of benzene including nonochlorobenzene ,
three isomers of dichlorobenzene , three of trichlorobenzene ,
*?Certain of these wastes (particularly where the higher chlorinated
benzenes are being produced) nay contain polychlorinated biphenyls.
(See Petition for Exemption under 56(e)(3)(b) of the Toxic Substances
Control Act of Olin Corporation, dated June 28, 1979, noting concen-
trations of up to 8000 ppn PCB's in distillation residues from the
production of pentachlorobenzene). The Agency is not presently listing
PCB's as a waste constituent of concern pending integration of the
RCRA Subtitle C and TSCA PCB regulations. The regulated community
and permit writers should be aware, however, of the possibility
of hazardous levels of PCB's in these wastes.
-------
pentachlorobenzene and hexachlorobenzene; their structures
and physical properties are illustrated in Figure 1 and
Table 1. In 1979 chlorobenzene production totalled about
204,000 kkg, or about half of the available capacity (56).
Most of the production is of mono-and dichlorobenzenes.
Moaochlorobenzene is the dominant commercial product; in
1978, production was approximately 134,000 kkg.(l) Production
of ortho- and para-dichlorobenzene was estimated at 10,000
kkg each for that same year.(l) Production of 1,2,4-trichloro-
benzene was 13,000 metric tons in 1973. It is estimated
that approximately.the same amount was produced in 1977. (1)
Annual production of the commercially important tri- and
tetrachlorobenzenes and of pentachlorobenzenes ranges from
"1,000 - 50,000 kkg. Major producers of chlorobenzenes in
the United States include: Allied Chemical Corporation
(Syracuse, New York); Dow Chemical Company (Midland, Michigan);
Monsanto Company (Sauget, Illinois); Montrose Chemical
Corporation of California (Henderson, Nevada); PPG Industries,
Inc. (Natrium, West Virginia); Specialty Organics, Inc.
(Irwindale, California); and Standard Chlorine Chemical
Company, Inc. (Delaware City, Delaware).(2) Certain companies,
including the Olin Corporation, produce chlorobenzenes as
intermediates rather than as end products. /Histillation
residues and aqueous waste streams from the chlorobenzene
manufacturing phase of such processes are included in the
present listing.
-------
7igure I. Chemical Structures of the. Chlorinated Benzenes
Cl
Manocfllorobenzene
Cl
Cl
-1,2-Dich
c-Dichicrcbsnzene
ci-
Cl
Cl
Cl
Cl
Cl
Cl
1,3-Dichlcrober.zer.s
sn-Dichlorobenzene
Cl
Cl
C.I.
Cl
Cl
1,4-Dichlorcbenzena
o-Dichlorobenzene
Cl
1,2,3-Trichlorobenzene 1,2,4-TricHloroienzene 1,3,5-Ttichlorober^ene
Cl
Cl
Cl
Cl
Cl Cl
1,2,3,4-Tetrachlorober.zene 1,2,3,5-Tetrachlcrcbenzene 1,2,4,5-Tetrachlorobenzer.e
Cl
Cl
ci
ci ., ci I
Pentachlorobenzene Kexachlorobenzene
-------
TAUl.t 1., niYSICAI. I'UOPKHTIE.S OF CIM.OH INATKI) OKtUKHKS
. Nitmu
H MMX-llIf li:«lll'll/.l:||»!
l.2-lilcl.lur<.l.u,.M,.e
1 , 3-l>lclil 01 ohcnzenu.
1 . 4 -III l.'lll <>| l>l,imzitite
«' 1,2. l-'I'i Iclil oroboitzcno
1 1,2, 4- IV Iclilurohuitzoite
1 , 3, 5-Tr iclil oroltonzcite
1,2,3, 4-'l\ilri)iizcue
1 , 2 , 4 , !> -Tu I 1 iiclil 01 1>-
I'unl iicli 1 ofoUunzenc
j^
CAH No.
Kill -90 -7
•J!i-'JO-l
541-73-1
106-46-7
07-61-6
120-82-1
108-70-3
634-66-2
634-90-2
95-94-3
608-93-5
118-74-1
Empirical Hal.
f annul « . Wt .
CtM5Cl 112.56
C6n4C12 M7.III
C6II4C12 -147.01
C6II4C12 147.01
C6U3C13 101.45
C^lljClj 101.45
C6IIJC1] 101.45
C6II2C14 215.90
C6H2C14 215.90
C6II2C14 215.90
C6IIC1S 250.34
C6C16 284.79
•c
-45.6*
-I I.U*
-24.7*
53.1*
54*
17*
64*
47.5*
54.5* j
140.5*
06* (
230*
D.p.b
•c
132*
IIIO.S*
173*
174*
219*
213.5*
208*i
254T
246*
246*
277*
322*
V.i|r>r
Press.
10i»in/22*
1 mm/20*
Iffllll/l 2*
0.4wm/25*
luun/40*
lmin/30"
1 Omni/ 70*
» mm/68*
linm/50*
4 Omm/ 14 6*
lmm/99*
lmiu/114*
Water
Solubl llty
Density0 (w«j/M
1.1050 500e
1.3040 I40
-------
B. Manufacturing Process
Chlorobenzene, dichlorobenzenes, and higher chlorinated
benzenes are produced in batch and in continuous processes by
chlorination of benzene in the presence of a Friedel Crafts
catalyst, such as ferric chloride, as shown in the following
react ion*/for aonochlorobenzene:
Cl CI
a
Because higher chlorinated benzenes always result from the
direct chlorination of benzene, chlorobenzene production is a
multiple product operation, i.e. a range of chlorinated
benzenes may be produced. Product ratios are influenced by
temperature, mole ratios of the feedstocks, residence time,-
and catalyst. The crude reaction product of a continuous
process may be recycled to the process to achieve the desired
final product: mixture. Depending on the final product mixture,
chlorobenzenes are purified by fractional distillation and/or
crystallization. Continuous chlorination processes, in
contrast to batch processes, minimize the amount of higher
chlorinated products, thereby maximizing monochlorobenzene
yields.
*/ 1,3-Dichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,5-
tetrachlorobenzene are not produced by the method discussed
below.
-ff-
-------
1. Production of Monochlorobenzene
a) Continuous Process (modified from references 1,6, and 7)
As shown in Figure 2, in a typical continuous process
for the production of chlorobenzenes, anhydrous benzene and
chlorine are introduced into a reactor operating at a bottom
temperature of 90-125°C and a top temperature of about 80°C.
Benzene is introduced near the top of the column, -and an
equimolar amount of chlorine is introduced near the midpoint
of the reactor. A variety of catalysts may be used, usually
iron or ferric chloride impregnated on a suitable carrier.
The overhead reactor effluent consisting of hydrogen
chloride and benzene passes through a condenser which condenses
the benzene for recycle. Hydrogen chloride is recovered by
passing the uncondensed gas through a scrubber tower contain-
ing a chlorination catalyst, thereby removing unreacted
chlorine. The mixture is then passed through o'ne or nore
towers in which chlorobenzenes are used to .remove organic
contaminants. The resultant hydrogen chloride is then recov-
ered as either an anhydrous product or as a 30-40% aqueous
solution. (If the hydrogen chloride must meet a low organic
specifica'tion, a carbon column may be used prior to or after
che water absorption tower.)
The bottom effluent from the reactor comprises an
equilibrium mixture of benzene and mixed chlorobenzenes. To
maximize monochlorobenzene production, a high recycle rate of
benzene is maintained (20:1). Chlorobenzene is withdrawn at
-------
IUO
A
CONDENSER
BENZENE.-
DRIER
»
CHLORINE-
RECYCLE
BENZENEi
cc.
1
cc
O
_i
O
UJ
O
L
H2O-
VENT
A
SCRUBBER
•>- HCI SOLUTION
-^CHLOROBENZENE
CARBON COLUMN
(OPTIONAL) '
RECOVERED
ORGANICS
SEPARATOR
FRACTIONATING
COLUMN
DICHLOROBENZENES.
TO FRACTIONAL
...CRYSTALLIZATION
:_ ^
REACTOR
DICHLOROBENZENES
AND HIGHER
CHLORINATED BENZENES
Y
FRACTIONATING
COLUMN
SOLID WASTES
(HIGHER BOILING
CHLORINATED BENZENES AND
FEEDSTOCKl IMPURITIES)
FIGURE CL
CONTINUOUS PRODUCTION OF CHLOROBENZENE (MODIFIED FROM 7)
-------
a rate equal to that at which benzene is fed and chlorinated,
and flows to a fractionating column which operates at a bottom
temperature of aproxiraately 190°C and top temperature of
140°C. The higher boiling bottom products (mostly dichloro-
benzenes) are continuously bled at approximately 2% of the
product feed to a fractionating column for recovery of the
di- and trichlorobenzenes . The wastes of concern (waste A in
Figure 2) are the bottoms from the two fractionating columns.*/
b)
Chlorobenzenes may also be manufactured by a batch
process as shown in Figure 3. Dry benzene is charged into an
agitated glass-lined or iron (steel) reactor. Either iron
turnings or anhydrous ferric chloride are used as a catalyst
and remain in the chlorinator after each product batch is
withdrawn. The desired product mix is achieved by adjustment
of chlorine concentration and reactor temperature. If raono-
chlorobenzene is the desired product, about 60 percent of
the stoichiometeric requirement of chlorine is used, and
the reaction temperature is maintained in the range of 20°
to 30*C for 10 to 16 hours. If poly-substituted chlorobenzenes
(generally dichlorobenzenes ) are desired in addition to
monochlorobenzene , the reaction is run at a temperature of
55° to 60*C for approximately six hours.
*7~In~sone~processes, the further fractionating steps for
recovery of higher chlorobenzenes is not employed, in which
case the waste of concern is the column bottoms from the
first fractionating column.
-------
VENT
CHLOROBENZENE-
BENZENE
CHLORINE
H2O-
SCRUBBERS
REACTOR
:NEUTRALIZER
SEPARATOR
BENZENE_& WATER
BENZENE & CHLORO-
• BENZENE_
CHLOROBENZENE
FRACTIONATING
COLUMN
V
POLYCHLOROBENZENES
' 1 •"U,
TO RECOVERY OF
! HIGHER
CHLORINATED
i BENZENES
I AQUEOUS_WASTE (B)
.(CHLORINATED ORGANICS)
I TO DISPOSAL
V
DISTILLA-
TION
COLUMN
SOLID WASTE (f\)
TO DISPOSAL
FIGURE 3
'BATCH PRODUCTION OF CHLOROBENZENES (MODIFIED FROM 6)
-------
Hydrogen chloride is recovered in a manner similar to chat
of continuous processes by scrubbing with chlorobenzene to remove
organic contaminants and absorbing the product gas in water to
give hydrochloric acid. The chlorobenzene product is washed in
an agitated reactor with an aqueous solution of sodium hydroxide
(10 percent by weight). The separated aqueous layer (waste B in
Figure 3) is a separate waste, and is the second waste included
in this listing.*/
After the neutralized organic layer is separated, .it is
sent to a fractionation column for product separation. As is
the case in the continuous chlorination orocess, waste A (distillation
or fractionation column bottoms are also generated). Table 2
illustrates the estimated product distribution for a fully chlorinated
batch for which 100 percent of the theoretical amount of the
chlorine requirement for monochlorobenzene was consumed.(6)
TABLE 2
PRODUCT DISTRIBUTION OF A CHLOROBENZENE BATCH REACTION (6)
Distillate
Fraction
1
2
3
4
5
Component
Benzene and water
Benzene and chlorobenzene
Chlorobenzene
Chlorobenzene and dichlorobenzene
Tar ( trichlorobenzene and higher)
% by weight
3
in
75
10
2
*7fhis aqueous stream is not expected to be present in most
continuous processes, since during the stripping step in the
continuous process (see Fig. 2) the temperature at the bottom
of the condenser column is such that residual hydrogen chloride
and benzene are removed, making a product washing step unneces-
sary. However, comments indicated that an aqueous waste stream
is generated from at least one continuous manufacturing process.
We therefore have revised the listing description of this waste
to indicate that it is hazardous Irrespective of the type or
manufacturing process.
-------
Most batch processes include further distillation steps to
to separate higher chlorinated benzenes, particularly o- and
p-dichlorobenzene and trichlorobenzene.*/ The chlorobenzene
and dichlorobenzene fraction (No. 4) is usually further
distilled to recover p-dichlorobenzene and o-dichlorobenzene.
Trichlorobenzene may also be recovered. The tarry residue
(Table 2, Fraction 5, waste A in Figures 2 and 3, the solid
waste of concern) consists chiefly of trichloro- and higher
chlorinated benzenes.
2. ^I2^USi^on of_Polychlorobenjzenes
As noted previously, aromatic chlorination is a. multiple
product process; most polychlorobenzenes can be produced via
processes similar to those described above. Reaction conditions
are, however, likely to be soraewhat different. Higher reaction
temperatures, longer reaction times and higher chlorine to
'benzene ratios are likely modifications. A process configu-
ration for production of dichlorobenzenes is shown in Figure 4.
Dichlorobenzenes (")
o-Dichlorobenzene and p-dichlorobenzene are produced by
chlorinating benzene or monochlorobenzene at 150°C-1908C over
a ferric chloride (FeCl^) catalyst. An orienting catalyst
such as benzensulfonic acid or p-dichlorobenzene may also be
employed. The isomers can be separated by fractional distillation,
or by crystallizing the p-dichlorobenzene. Another method of
obtaining the para isoraer is by chlorination of crude dichloro-
*7Table~2~is~a~product mix prior to this second distillation
-x-
-------
CHLOROBENZENE
BENZENE
—*
^ CHLORINE.
REACTOR
H20-
VENT
A
SCRUBBERS
RECYCLE
BENZENE
CRYSTALLIZER CENTRIFUGE
MONOCHLOROBENZENE
DISTILLATION
COLUMN
SOURCE: MODIFIED FROM (8)
ORTHODICHLOROBENZENE
•>- P-DjCHLOROBENZENE
-*• DICHLOROBENZENE-
SOLID WASTE
(TRICHLpRO &
HEAVIER)"
FIGURE 4
PRODUCTION OF HIGHER CHLOROBENZENES
-------
benzene over FeCl3, whereby the more reactive ortho Isomer is
converted to 1,2,4-trlchlorobenzene. p-Dichlorobenzene can then
be separated by distillation. The purified grade of o-dichloro-
benzene is obtained by efficient redistillation of the
technical product* m-Dichlorobenzene can be prepared by
isomerization of o-dichlorobenzene and p-dichlorobenzene with
heat under pressure in the presence of a catalyst.
Trichlorobenzenes.(56)
1,2,4-Trichlorobenzene is produced along with 1,2,3-
trichlorobenzene by chlorinatlon of o-dichlorobenzene at 25 to
30 9C in the presence of ferric chloride, then separated from
the 1,2,3-trichlorobenzene by distillation. 1,3,5-Trichloro-
benzene can be produced readily only by special methods such
as by the diazotization of 2,4,6-trichloroaniline followed by
treatment with alcohol. Additional methods of synthesis for
trichlorobenzenes are reviewed in the report by Ware and Vest.(57)
Tetrachlorobenzenes.(56,57)
1,2,3,4-Tetrachlorobenzene can be produced by chlorinating
1,2,3-trichlorobenzene in the presence of a catalyst. 1,2,4,5-
Tetrachlorobenzene is manufactured by chlorination of 1,2,4-
trlchlorobenzene over aluminum amalgam. To produce 1,2,3,5-
tetrachlorobenzene, 1,3,5-trichlorobehzene can be chlorinated
over aluminum amalgam. In practice, 1,2,3,4- and 1,2,3,5-
tetrachlorobenzene are produced only as by-products in the
manufacture of 1,2,4,5-tetrachlorobenzene.
-u-
-------
Pentachlorobenzene and Hexachlorobenzene (8^9)
Pentachlorobenzenes is formed by the chlorination of
benzene in the presence of ferric or aluminum chloride at
temperatures of 150 to 200°C, or by the chlorination of any
of the lower chlorobenzenes. It may also be formed in small
amounts when trichloroethylene is heated to 700°c(56)%
Hexachlorobenzene is reported not to be produced
commercially via catalytic (ferric chloride) chlorination of
benzene. When generated as a by-product of the processes
described in this document, it is found in the fractionating
column bottoms.
C. Commerciai_Use^s_of Chlorobenzenes'56)
Most (50-70%) monochlorobenzene is used as a chemical
intermediate in the synthesis of chloronitrobenzenes,
herbicides, diphenyloxide, and silicones. The remainder is
used as a solvent for herbicides, for synthetic processes and
for degreasing operations.
Sixty-five percent of the o-dichlorobenzene produced is
used in organic synthesis, primarily as a pesticide intermediate.
Fifteen percent Is used as a solvent in the production of
toluene diisocyanate. Miscellaneous solvent uses, such as
for oxides of nonferrous metals, for soft carbon deposits,
for tars and wool oils in the textile industry, and for
degreasing leather and automobile and aircraft engine parts,
account for most of the rest of the annual production of o-
dichlorobenzene. It is also a solvent in formulated toilet
-------
bowl cleaners and drain cleaners. Other uses in natal
polishes, in industrial odor control, as a heat transfer
fluid, and in rustproofing mixtures account for 4 percent of
annual o-dichlorobenzene production. o-Dichlorobenzene is
registered as a fumigant and insecticide against termites,
beetles, bacteria, slime, and fungi.
Eighty percent of the annual production of p-dichlorobenzene
goes to home and industrial use: as a moth control agent (30
percent) and as a space odorant (50 percent), especially in
toilets and rest rooms.
Miscellaneous uses as a dye intermediate, insecticide,
extreme pressure lubricant, forming agent for grinding wheels,
disintegrating paste for molding concrete and stoneware, and
as an intermediate in the manufacture of 2,5-dichloroaniline
and polyphenylenesulfide resins account for the remaining 10-20%
of the consumption of p-dichlorobenzene. No uses were
identified for m-dichlorobenzene apart from its conversion to
higher chlorobenzenes.
The most widely used tsoner of tetrachlorobenzene is
1,2,4,5-tetrachlorobenzene, which is used primarily as an
intermediate in chemical synthesis. Of the approximately
8,000 kkg consumed in 1973, 2,700 kkg were used to produce the
fungicide and bactericide 2,4,5-trichlorophenol, 4,500 kkg
were used in the production of the herbicide 2,4,5-T (2,4,5-
trichlorophenoxyacetic acid), and the remainder went to
miscellaneous uses. 1,2,4,5-Tetrachlorobenzene may
-------
also be used as an impregnant for noisture resistance, as
electrical insulation and as temporary packing protection.
According to a recent review, 1,2,4,5-tetrachlorobenzene is
now used exclusively to make 2,4,5-T and its esters, however,
it is a component of the transformer fluid, IralecO. Thus,
the use pattern for this material appears to be in flux.
EPA has no information on uses of 1,2,3,4- and 1,2,3,5-tetra-
chlorobenzenes except that the forraer, as a mixture with the
1,2,4,5-isoner, is an intermediate in the synthesis of the
fungicide pentachloronitrobenzene.
II. Waste Composition and Management
1. Fractionation Bottoms
The distillation or fractionation bottoos from the
production of monochlorobenzene consist primarily of the
higher polychlorinated benzenes (trichlorobenzenes and higher),
*/
benzyl chloride and chlorotoluenes resulting from the chloro-
nation of toluene impurities in benzene feedstock, and lesser
concentrations of feedstock benzene, product chlorobenzene,
and dichlorobenzenes (depending on the efficiency of the
fractionating step). The relative concentrations of the
various chlorobenzenes in these wastes vary according to
reaction conditions and the efficiency of fractionation. In
general, when nonochlorobenzene is the favored by-product,
*/Both o- and p-chlorotoluene are expected to be present.
These constituents are not considered to be of regulatory
concern because of their low chronic toxicity. Further
information as to the validity of this conclusion is solicited,
however.
-------
dichlorobenzene will probably be the nost prevalent of the
chlorinated benzenes in the distillation residue (and in the
waste if there is no subsequent distillation step to recover
dichlorobenzenes as product) since benzene is being chlorinated
for less time, so that smaller concentrations of tetra- to
hexachlorobenzene are formed. If dichlorobenzenes are
recovered as product, trichlorobenzenes represent the largest
fraction in the waste. When the reaction is pushed in the
direction of polychlorinated benzenes, there will be more
trichloro through hexachlorobenzene in the waste stream.
Waste composition, and especially the concentrations of
the various chlorinated benzenes, also will vary quantitatively,
although not qualitatively, depending on whether a continuous
or batch production process is used. Batch processes would
tend to have somewhat higher concentrations of higher
chlorinated benzenes, since benzene chlorination occurs for a
longer period.
Table 2 gives an estimate of wastes resulting from a
batch reaction favoring monochlorobenzene production.
Distillation tars (Fraction 5), consisting principally of
trichlorobenzenes and isoners of higher degree of chlorination
are estimated to comprise roughly 21 by weight of the total
reaction products.
Table 3 gives a second estimate of waste composition
from a batch process favoring monochlorobenzene. Snail
amounts of unreacted benzene, hydrogen chloride and chloro-
-------
benzenes are vented to the atmosphere; small concentrations
of these constituents are expected to remain in the distilla-
tion bottoms. The distillation residues (Table 3, Fraction 6),
the first-listed waste of concern in this document, comprise
about 80% of the wastes generated in this process.
Table 3(2)
ESTIMATED LOSS OF MATERIALS DURING CHLOROBENZENE MANUFACTURE
(BATCH PROCESS)
FRACTION
1
2
3
4
5
6
COMPOUND
Hydrogen chloride
Monochlorobenzene
Dichlorobenzenes
(isomers not specified)
Monochlorobenzene
Dlchlo r obenzenes
Polychlorinated-
benzenes
SOURCE (kg/kkg
Hot scrubber vent
o-Dichlorobenzene
column
do
Fractionating
towers
n
Distillation
residues*
QUANTITY
monochlorobenzene)
1.4
.88
3.7
4.0
0.1
44.0
*waste A, Figures 2 and 3
A third reference^) (shown in Table 4) taken from the
patent literature, and involving a continuous process, shows
monochlorobenzene present in fairly substantial concentrations
in the solid waste; the estimate for the production of heavier
chlorinated benzenes (31 kg/kkg of raonochlorobenzene produced)
does not differ'greatly from the estimate given in Table 2.
-------
TABLE 4
ESTIMATED EMISSIONS FROM CHLOROBENZENE MANUFACTURE
Chlorination of Benzene, Continuous Process^)
Species^
Emission (kg/kkg)
Solid
Benzene
Monochlorobenzene
Polychlorinated
benzenes
trace
2.6
31
33.6
The solid wastes (from both continuous and batch processes)
are also expected to contain significant concentrations of
i
benzyl chloride and o- and p-chlorotoluene resulting from
chlorination of toluene impurities in benzene feedstock.*/
(As noted above, the chlorinated toluenes are not waste
constituents of concern). The specific reaction pathways for
these constituents are given below:
CK-CI
HCI
CMorid-e.
*/ Toluene is believed to be the most significant feedstock
impurity. Benzene may typically contain up to 1% toluene^)
-------
The above side reactions are believed Co be those most
likely to occur under the usual conditions of benzene chlori-
natlon. Virtually all of these substances are expected to
be present in the distillation bottons since they are high
boiling chemicals that the distillation process is designed
to eliminate.
2. Separated Aqueous Stream f rom_the_Reactor Product
The aqueous stream from the reactor product washing
step in the production of chlorinated benzenes will contain
benzene, and all of the chlorinated benzenes in solution
(along with water and caustic soda used in the washing opera-
tion). The concentrations of these constituents in the waste
will depend on their concentration in the reaction product
stream and their solubilities in the alkaline wash solution.
While the Agency does not presently have precise information
on these compounds' solubilities in basic solutions, they are
not believed to differ significantly from their solubilities
in water (if anything, solubilities would be slightly higher
in basic solutions). Thus, the most soluble component,
benzene (water solubility up to 1,780 ppm) , would probably
be the principal waste constituent, and monochlorobenzene
and o- and p-dichlorobenzene would also be present in
fairly significant levels (water solubilities from 79 ppm to
500 ppm, respectively )( See Table 1) would also be present in
significant concentrations. The remaining chlorinated benzenes
-------
are probably present at much lower levels, since their solu-
bilities (See Table 1) are quite low. Phenols could also be
formed if temperatures are sufficiently high to create hydrolysis
conditions, and a highly alkaline wash mixture is used.(58)
Chlorinated phenols could also be present from the phenolization
of the di- and tri-chlorobenzenes, although concentrations
of phenols and chlorinated phenols would probably be snail.
Table 5 below shows organic contaminants found in the waste-
water stream from chlorobenzene manufacture at a Dow plant.
TABLE 5.
PRIORITY POLLUTANTS IDENTIFIED IN AQUEOUS WASTESTREAM FROM
PRODUCT WASHING STEP IN PRODUCTION OF CHLOROBENZENES(29)
Concentration mg/1 Loading kj/day
sampling a sampling b (based on
sampling a)
*The underlined data are those obtained from proprietary reports
and data files.
/Of
-------
3. Waste Management
Waste management practices for the distillation residues
generally involve disposal in on-site and off-site landfills (1).
Incineration is also practiced (2).
The separated aqueous stream generally is sent to waste-
water treatment.(1) The most feasible treatment method is acti-
vated carbon preceded by sand filtration.(1) A wastewater treat-
ment sludge is generated which is assumed to be hazardous unless
generators show otherwise. (See §261.3(a)(2)(ii) .)
III. ]?2i2I^3_?2Jsd_by_the Waste
As noted above, the distillation wastes are expected to
contain significant concentrations of tri- through hexachloro-
benzene, and benzyl chloride, lesser concentrations of dichloro-
benzenes, and some monochlorobenzene and benzene. Hexachlorobenzene
and benzene have been identified by EPA's Carcinogen Assessment
Group .as having substantial evidence of carcinogenicity. Penta-
chlorobenzene is reported to induce cancers in some animal
•- ••" • • " ' -- ' _ i —•**
species. All the chlorobenzenes are toxic to the liver, kidney
and central nervous system, in varying degree. (56) Benzyl
chloride is reportedly carcinogenic. The remaining constituents
present acute and chronic toxicity hazards. All are priority
pollutants. In addition, all of the chlorinated benzenes are
J3Joaecurnulative (based on extremely high octanol/water partition
coefficients), and so could pose an additional hazard even if
exposure is only to small concentrations of the pollutant.
-------
The aqueous waste stream contains benzene, chloroben-
zenes through trichlorobenzene, and (under certain conditions)
high chlorinated phenols (See Table 5). 2,4,6-Trichlorophenol
has been identified by the Carcinogen Assessment Group as
having substantial evidence of carcinogenicity. In addition,
it presents other chronic toxicity hazards, and is also autagenic.
In light of the reported concentrations of these hazardous
constituents, these waste streams are clearly of regulatory
concern. Indeed, for the carcinogens in the wastes, there is no
known safe level of exposure, every exposure likely giving
rise to at least one cancer in a portion of the population,
regardless of exposure concentration.(10) The Agency thus requires
strong assurance that these waste constituents are incapable
of migration, mobility, and persistence In the event of improper
management to justify not listing this class of wastes. Such
assurance does not appear possible.
All of the waste constituents have proved capable of
migration, of mobility through soils, and of environmental
persistence in the course of actual waste management practice,
creating a substantial potential for hazard. Benzene and all
of the chlorinated benzenes through pentachlorobenzene have
been detected in air, basement sump and solid surface samples
collected in the vicinity of the Love Canal waste disposal
site in Niagara, New York.(5) Benzyl chloride has been
identified as leaching from Hooker's Hyde Park site in Niagara,
New York, (12) an(j ^as Deen shown to persist in the atmosphere
-X-
&r,
103
-------
In the New Jersey area for considerable periods of
Hexachlorobenzene has likewise been shown to migrate via
air and groundwater pathways and to persist following migration.
One damage incident involving hexachlorobenzene occured in
Louisiana in the early 1970s. Inhalation exposure to hexa-
chlorobenzene resulted from transport of hexachlorobenzene-
contaminated wastes, resulting in dangerously elevated
hexachlorobenzene concentrations in humans and animals along
the route.(12) Hexachlorobenzene has also been detected in
concentrations exceeding background levels in many groundwater
monitoring samples taken at various locations at a chemical
company dump. (Table 7.2. reference 1)
The higher chlorinated phenols present in the wastewater
stream also are capable of migration,, mobility, and per-'
•sistence.. Although they are subject to biodegradation
(id.) by specifically adapted organisms, these compounds
could persist for long periods of time in the abiotic conditions
characteristic of most aquifers.(80) Migratory potential
is thus substantial, and thus, if migration occurs, chlorinated
phenols are mobile and persistent. For example, in a damage
incident at Montebello, California, involving wastes
from 2,4 dichlorophenol manufacture, 2,4-dichlorophenol
and other phenolic compounds proved capable of passing
through soils and causing longterm pollution of groundwater.
Contamination of groundwater by 2,4-dichlorophenol and
other hazardous compounds has also been reported
lO'f
-------
in East St. Louis, 111. The source of the compounds was the
Monsanto chemical dump.(12)
Since all of the waste constituents of concern have
proven capable of migration, mobility, and environmental
persistence, and have in fact caused substantial hazard in
acutual waste management practice, the Agency believes that
the waste constituents could migrate and reach environmental
receptors if the wastes are improperly managed. Landfilllng
the waste without adequate cover could easily result in
volatilization of hexachlorobenzene and benzene. Solubilization
of hazardous compounds could occur if rainwater is allowed
to percolate through the waste or run off the surface of
exposed waste. Waste constituents could then be released if
landfills are improperly designed (built without leachate
control in areas with permeable soil or located in areas
where soils have low attenuative capacity), or managed.
Improperly designed wastewater treatment ponds pose the same
risk. In the case of improperly managed landfills, surface
run-off might also transport compounds that have adsorbed to
suspended particulates.: Contaminant-bearing leachate and
surface run-off may eventually enter ground and surface waters,
polluting valuable water supplies and adversely affecting
aquatic organisms.
Improper incineration of the distillation residues pro-
vides another means by which toxic compounds can be generated
and introduced into the environment. If incineration is inade-
to*
-------
quata (for instance, if temperatures are insufficient or resi-
dence time incomplete), inadequate combustion can result in the
formation of substances (such as phosgene) that are even more
toxic than the original waste.(1) These contaminants can be
emitted from the incinerator to the atmosphere and dispersed
in the environment.
IV. Health and Ecological Effects
Health and ecological effects and potential transport
t
mechanisms for the constituents of concern that might be found
in the distillation bottoms and the separated aquaeous waste
stream from manufacture of chloro.benzenes are described below:
Benzene
Health^Effect.! Benzene is a human carcinogen. Exposure
to benzene as a result of inhalation induces abnormalities
in the blood and causes leukemia.(31-33) Benzene administered
subcutaneously has been teratogenic in mice at extremely low
doses [3 ml/kg].(34)'Chronic inhalation of this chemical in
low doses by rats has caused both inhibition and resorption
of embryos.(35) Benzene is also mutagenic when administered
orally to mice at extremely low doses [1 rag/kg],(36)
Exposure of humans to benzene has resulted in the reduction
of blood cells, aplastic anemia, impairment of the immunologic
system, and a variety of mutagenic effects in lymphocytes
and bone narrow.(37-42) Oral ingestlon of benzene in small
amounts (50 mg/kg), or one-seventieth of the oral LDso in
rats, has proven lethal to humans.(43)
-------
set a
for benzene at 10 ppm with a ceiling level of 30 ppm for
10 minutes. EPA's Office of Air Quality Planning and
Standards and Toxic Substances are performing a pre-regulatory
assessment of benzene based on its production volume, spill
reports and health and environmental effects. Additionally,
EPA's CAG has determined that there is substantial evidence
that benzene is a carcinogen. EPA has estimated 0.66 ug/1 as
the concentration in ambient water which could result in a
10~6 additional risk for cancer from the consumption of
contaminated drinking water and contaminated aquatic organisms
(65). The Consumer Product Safety Commission requires benzene
to carry special labelling.
Benzene is a priority pollutant .in accordance with §307
•of the Clean Water Act of 1977 and is listed as a hazardous
waste or hazardous waste constituent in final or proposed
regulations of California, Maine, New Mexico and Oklahoma.
Industr^al__Recognition_of Hazard - Benzene is designated
as highly toxic in industrial handbooks, and represents a
fire and moderate exposure hazard.
Additional information on the health and ecological
effects of benzene may be found in Appendix A.
Chlorobenzenes:(^3) Chlorobenzenes have moderate acute
toxlcity but, because they bioaccumulate to a significant
degree, Chlorobenzenes may pose a substantial hazard if
chronic exposure- occurs. They are relatively mobile in the
101
-------
environment and likely to persist for long periods of time
because biodegradation is slow.
Chlorobenzene (monochlorobenzene, MCB)
Health effects - Monochlorobenzene is a central nervous
.system depressant, with the typical anesthetic effect produced
by most chlorinated benzenes (45,46); degeneration of the liver
and kidney may develop on chronic exposure. Depending on
dosage, acute inhalation produces narcosis, neuropathy and
death.(46) The metabolism of monochlorobenzene may lead to
the formation of carcinogenic active intermediates.(48)
The weighted average bioconcentra.tion factor for mono-chloro-
benzene is calculated to be 10.3.(13)
Regulatorj^Recognition^of^Hazard - The OSHA PEL for
chlorobenzene is a TWA of 75 ppm. EPA's Office of Water and
Waste Management provides technical assistance data and
regulation for chlorobenzene under Section 311 of the Clean
Water Act. They are also involved with pre-regulatory assess-
ment under the Safe Drinking Water Act. The Office of Air,
Radiation and Noise and the Office of Research and Development
are involved with preregulatory assessment under the Clean
Air Act. The Office of Toxic Substances has developed test
rule recommendations under Section 4(e) of the Toxic Substances
Control Act.(56)
Monochlorobenzene is listed as a priority pollutant
in accordance with S307 of the Clean Water Act of 1977, and
final or proposed regulations of Maine, New Mexico, Oklahoma
-------
and aarine aquatic life.
p-Dichloro benzene
Health^Ef f ects - p-dichlorobenzene is toxic in rats
(oral LDso " 500 mg/kg](53)), and is lethal to humans ingesting
similar amounts. (43) At smaller dose levels (300 rag/kg)
adverse effects are noted on liver and kidney. (43) This
chemical has induced growth depression, liver cell necrosis
and death in animals exposed by inhalation. ( 56)
Regulatory Recognition of Hazard - p-dichlorobenzene has
been designated as a priority pollutant under Section 307(a)
of the CWA. The OSHA PEL standard is 75 ppm (TWA). It is
listed as a hazardous waste or a component thereof in final
or proposed regulations of the states of California, New
Mexico, and Oklahoma. Additional information on the health and
ecological effects of dichlorobenzene can be found in Appendix A
Trichloro benzenes
Health Effects - 1 , 2, 4-Trichlorobenzenes , as are the
other chlorinated benzenes, are metabolized to phenols by the
liver microsomal enzyme systems. (60) Trichlorobenzene
produces histological changes in the liver and kidney. (59)
This compound has slight to moderate acute toxicity for
various aquatic species. (*•') Its bioconcentrat ion factor
has been estimated as 182. (13)
Regulatory_and Industrial Recognition of_Hazard - The
ACGIH TLV for 1 , 2, 4-trichlorobenzene is 5 ppm. Because of
the insufficiency of available information EPA could not
derive a water quality criterion using the guidelines in
-31-
Iff)
-------
and California list chlorobenzene as a hazardous waste or a
component of hazardous waste.
Additional information on the health and ecological effects
of monochlorobenzene may be found in Appendix A.
Dichlorobenjsenej: The bioconcentratton factors for
three dichlorobenzenes range from 60-89.(13) Their bioaccu-
mulatlve properties are therefore moderate.
o-Dichlorobenzene
Health_Effects - O-dichlorobenzene is very toxic in
rats [oral LD5Q " 500 rag/Kg].(49) Human death has also
occurred at this level.(43) Chronic occupational exposure
to this chemical and its isomer is toxic to the liver,
central nervous system and respiratory system.(13) Chronic
"feeding of ortho-dichlorobenzene to rats in small doses
causes anemia as well as liver damage and central nervous
system depression.(52)
Regulatory_Recoj»nition_of Hazard - o-dichlorobenzene
has been designated as a priority pollutant under Section
307(a) of the CWA. The OSHA PEL for o-dichlorobenzene Is 50
ppm for an 8-hour TWA. o-Dlchlorobenzene was selected by
NCI for Carclnogenesis Bioassay, September 1973, and is
listed as a hazardous waste, or a component thereof, in final
or proposed regulations of the States of California, New
Mexico and Oklahoma. The U.S. EPA ambient water quality
criterion for dichlorobenzenes (all isomers) is 400 ug/1.
(13,65). U.S. EPA has also established criteria for freshwater
-------
effect In 1980. Additional information and references on
the health and environmental effects of this substance can
be found in Appendix A.
Health Effects - Chronic exposure of rats and dogs to
tetrachlorobenzene affects the liver and the hemopoietic
system (19,56). Tetrachlorobenzene is not acutely toxic
to mammals, since its oral LD5Q in the rat is 1500 mg/kg.(56)
It is reported to be acutely toxic in varying degrees to
some fresh- and saltwater organisms, and chronically toxic
to saltwater organisms . (19) The predominant mammalian dis-
position site for tetrachlorobenzene is in the lipid tissues
(16) of the body, and its bioconcentration factor was estimated
to be 1800. <13)
Tetrachlorobenzene was designated by Congress as a
priority pollutant under §307 of the Clean Water Act of
1977.
For the protection of human health from the toxic
properties 1, 2, 4 , 5-tetrachlorobenzene ingested through water
and contaminated aquatic organisms, the ambient water criterion
is determined to be 38 ug/l.C1^)
Additional information on the health and ecological effects
of benzene can be found in Appendix A.
Pen^achlorobenzene^ 56)
Health Effects - Pentachlorobenzene is reported to be
carcinogenic in mice, although not in rats or dogs. It
HI
-------
is also reported to have caused bone defects in the offspring
of rats which were exposed to this compound during gestation.
Pentachlorobenzene is quite acutely toxic at low concen-
trations (ranging from 160 ug/1 to 6,780 ug/1) to both salt-
and freshwater organisms, including plants.
Pentachlorobenzene has an extremely high octanol/water
partition coefficient of 154,000, indicating a dangerously
high bioaccumulation potential.(14)
For the protection of human health from the toxic
properties of pentachlorobenzene ingested through water and
contaminated aquatic organisms, the ambient water criterion is
determined to be 74 ug/l.(13)
Pentachlorobenzene is designated as a priority pollutant
under §307 of the Clean Water Act.
i
Additonal information on the adverse health effects of
pentachlorobenzene can be found in. Appendix A.
Hexachlorobenzene
Health Effects - U.S. EPA's Carginogen Assessment Group
(GAG) has evaluated hexachlorobenzene and has found sufficient
evidence to indicate that it is carcinogenic. It is also
fetotoxic to rats.(23) The distribution of hexachlorobenzene
is apparently the same in the fetus and the adult, with the
highest concentration accumulating in fatty tissue. (23)
Its estimated bioconcentration factor is very high: 22,000.
-------
Chronic exposure of rats to hexachlorobenzene has caused
histologlcal changes In the liver and spleen (24), and In
humans, causes porphyrinuria and other symptoms of porphyria
cutanea tarda. (25 , 26)
For protection of human health from the potential
carcinogenic effects of exposure to hexachlorobenzene through
ingestion of contaminated water and contaminated aquatic organisms
the ambient water quality criterion was set at 72 ug/1 (10~*>
incremental cancer risk).(13)
Hexachlorobenzene is designated as a priority pollutant
under §307 of the Clean Water Act.
Additional information on the adverse health effects of
hexachlorobenzene can be found in Appendix A.
Health Effects - Benzyl chloride has been identified as
a carcinogen (18), and is also rautagenic ( 27 ) .
The OSHA TWA for benzyl chloride is 1 ppm. DOT requires
labeling as a corrosive. The Office of Water and Waste
Management, EPA, has regulated benzyl chloride under Section
311 of the Clean Water Act. Preregulatory assessment has been
completed by the Office of Air, Radiation and Noise under the
Clean Air Act. The Office of Toxic Substances has requested
additional testing under Section 4 of the Toxic Substances
Control Act.
-------
REFERENCES
K085; K105: Wastes from the Production of Chlorobenzenes.
1. U.S. EPA, Office of Solid Waste. Wastes resulting from
chlorinated aromatic hydrocarbon manufacture: chloro-
benzenes, preliminary draft report. Prepared by Lowenbach
and Schlesinger Associates, Inc. February, 1980.
2. U.S. EPA, Office of Solid Waste. Assessment of industrial
waste practices: organic chemicals, pesticides, and
explosives industries (SW-118c). NTIS PS No. 2513076. 1976.
3. Hunter, W.K., Combination reaction-fractionation. U.S.
Patent 3,366,457. January, 1968.
4. Not used in text.
5. New York State Department of Health. Office of Public Health.
Love Canal - Public Health Time Bomb. September, 1978.
6. Lowenheim and Horan. Faith, Keyes and Clark's Industrial
Chemistry, 4th ed. John Wiley and Sons, Inc., New York. 1975.
7. Kirk-Othmer. Encylcopedia of chemical technology. John Wiley
-and Sons, Inc. New York. 3rd. ed. 1979.
8. Mumma, C. E. and E.W. Lawless, E. W., Survey of industrial
processing data: Task I, hexachlorobenzene and
hexachlorobutadiene from chlorocarbon processes, NTIS PB No.
243641; 1975.
9. Mellan, I. Industrial Solvents Handbook, 2nd edition.
Noyes Data Corp. Park Ridge, N.J. 1977.
10. U.S. EPA Water Quality Criteria, 44 Fed. Reg. 15926-
15930, March 15, 1979.
11. Verschueren, K. Handbook of environmental data on organic
chemicals. Van Nostrand Reinhold Co. New York. 1977.
12. U.S. EPA Open files. Hazardous Site Control Branch.
WH-548. U.S. EPA, 401 M Street, S.W., Washington, O.C.
20460. Contact Hugh Kaufman (202) 245-3051.
13. U.S. EPA Ambient Water Quality Criteria for chlorinated
benzenes. EPA 440/5-80-028. NTIS PB 81-117392. October, 1980,
us
-------
Benzyl chloride is listed in Sax's Dangerous Properties
of Industrial Materials as highly toxic via inhalation and
moderately toxic via the oral route.
Additional information and specific references on the
adverse effects of benzyl chloride can be found in Appendix A.
2^4,6-Trichlorophenol
Health Effects - NCI has concluded that this compound is
carcinogenic in mole F344 rats (inducing lymphomes and
leukemias), and in both sexes of Bg, C$, ?]_, mice, inducing
hepatocellular carcinogens and abensomas.(61) Accordingly,
2,4,6-trichlorophenol has also been identified by EPA's
Carcinogen Assessment Group as exhibiting substantial evidence
of carcinogenicity. 2,4,6-Trichlorophenol is lethal to humans
by ingestion of 60Z of the oral LD5Q dose in rats [500 mg/kg].(43)
This chemical is reportedly nutagenic(62) and adversely affects
cell metabolism.(63,64) 2,4,6-Trichlorophenol has been
designated a priority pollutant under 307(a) of the FWPCA.
Ecological Effec^s(l^) - Very small concentrations of 2,4,6-
trichlorophenol are lethal to freshwater fish [LC5Q • 175-
426 ug/1]; it is also lethal to freshwater invertebrates at
very low concentrations.
Re§ulatorj_Recognit^on_of_Ha2ard - 2,4,6-Trichlorophenol
has been designated as a priority pollutant under Section
307(a) of the CWA. Based on carcinogenicity, EPA has recom-
mended 1.2 ug/1 as the ambient water quality criterion for
-------
the Ingestlon of fish and water (10~6 excess cancer
~ Sax, in
_ lists 2, 4, 6-trichloro-
phenol as moderately toxic via ingestion.
Additional information and specific references on the
adverse effects of 2,4,6-trichlorophenol can be found in
Appendix A.
-------
28. Simnons, P.D. et al. 1,2,4-Trichlorobenzene: biodegradable
or not? Text. Chera. Color. 9:211-213:1977.
29. Dow Chemical Company, Proprietary plant Report, Midland,
Michigan. (EPA BAT Review). 1979.
30. Reviews of the Environmental Effects of Pollutants: XI
Chlorophenols, EPA600/1-79-012. 1979.
31. Aksoy, M. et al. Acute leukemia in two generations following
chronic exposure to benzene. Hum. Hered. 24:70 1974.
32. Aksoy, M. et al. Leukemia in shoe workers exposed chronically
to benzene. Blood 44:837 1974.
33. National Academy of Sciences/National Research Council.
Health Effects of Benzene: A Review. Nat'l Acad. Sci.
Washington, D.C. 1976.
34. Watanabe, G.I. & S. Yoshida, The teratogenic effects of ben-
zene in pregnant mice. Act. Med. 3iol. 19:285:1970.
35. Gofmekler, V.A. Effect on embryonic development of benzene
and formaldehyde. Hyg. Sanit. 33:327:1968.
36. Ehllng, U.H., et al. Standard protocol for the dominant lethal
- test on aale mice set up by the work group on dominant lethal
mutations of the ad hoc committee on chemogenetics. Arch.
Toxicol. 39: 173-185:1978.
37. Goldstein, G.D. Hematoxicity in humans. J. Toxicol. Environ.
Health (Suppl). 2:69:1977.
38. Snyder, R. and J.J. Kocsis, Current concepts of chronic ben-
zene toxicity. CRC Grit. Rev. Toxicol. 3:265:1975.
39. Lange, A., et al. Serum immunoglobin levels in workers ex-
posed to benzene, toluene and xylene. Int. Arch. Arbeitsmed.
31:37:1973.
40. Wolf, M.A., et al. Toxicological studies of certain alkylated
benzenes and benzene. Arch. Ind. Health 14:387:1956.
41. Kissling, M. and B. Speck, Chromosomal aberrations in
experimental benzene intoxication. Helv. Med. Acta.
36:59:1971.
42. Pollini, G. L and R. Colombi, R. Lymphocyte chromosome damage
in benzene blood dyscrasia. Med. Lav. 55:641:1964.
1*
-------
14. U.S. EPA Ambient Water Quality Criteria for chlorinated
phenols. EPA 440/5-80-032. NTIS PB 81-117434. October, 1980.
15. Altschuller, A.P. Lifetimes of organic chemicals in the
atmosphere. Env. Sci. Technol. 1980. In Press.
16. Jondorf, W.R. at al. Studies in detoxification. 'The
metabolism of halofuorobenzenes 1,2,3,4-, 1,2,3,5- and
1,2,4,5-tetrachlorobenzenes. J. Biol. Chem. 69:189:1958.
17. Sinenson, H.A., The Montebello incident. Proc. Assoc. Waste
Treatment and Exam. 11:88:1962.
18. IARC. Monographson The evaluation of carcinogenic risk of
chemicals to aan. 11:217-222:1976.
19. Broun, W.H., et al. Pharmocokinetic and toxicological
evaluation of dogs fed 1,2,4,5-tetrachlorobenzene in the
diet for two years. J. Tox. Env. Health. 4:727-734:1978.
20. Leo, A. et al. Partition coefficients and their uses.
Chem. Rev. 71:525-616:1971.
21. Not used in text.
22. Monsanto Company. TSCA Sec 8(e) Submission 8DHQ-1078-
0221(2). Final report on Salmonella mutagenicity assay of
"m-dichlorobenzene (technical!."" U.sT EPA - OPTS.
23. khera, K. S., and D. C. Villeneuve. Teratogenicity studies
on halogenated benzenes (pentachloro-, pentachloronitro-
and hexabromo-) in rats. Toxicol. 5:117:1975.
2-4. Grant, D. L. , et. al.' Effect of hexachlorobenzene on
reproduction in the rat. Arch. Environ. Contain. Toxicol.
5:207:1977.
25. Koss, R., and W. Koransky. Studies on the toxicology of
hexachlorobenzene. I. pharmacokinetics. Arch. Toxicol. .
34:203:1975.
26. Can, C. and G. Nigogosyan. Acquired Toxic Porphyria
Cutanea Tarda due to hexachlorobenzene. J. Araer. Med.
Assoc. 183:88:1963.
27. Druckrey. H., et al. [Carcinogenic Alkylating Substances
— II. alkyl-halogenides, -sulfates, -sulfonates and
strained heterocyclic compounds.] Z. Krebsforsch.
74:241-270:1970.
-------
43. Gleason, M.N., at al. Clinical Toxicology of Commercial
products: ucts: Acute Poisoning. 3rd Edition. 1969.
44. Not used in text.
45. Sax, N. Irving, Dangerous properties of industrial materials,
Van Nostrand Reinhold Company, New York, Fifth Edition, 1979.
46. Irish, D.D. Halogenated hydrocarbons: II Cylic. In
Industrial Hygiene and Toxicology, Vol. II, 2nd EdT, (ed.
F.A. Patty), Interscience, New York. 1963.
47. Not used in text.
48. Kohli, I., et al. The metabolism of higher chlorinated benzene
isomers. Can. J. Biochen 54:203:1976.
49. Not used in text.
50. Not used in text.
51. U.S. EPA Office of Toxic Substances. An ecological study
of hexachlorobenzene (HCB). EPA 560/6-76-009. 1976.
52. Yarshavskaya, S.P. Comparative toxicoloical characteristics
of chlorobenzene and dichlorobenzene (ortho- and para- isomers)
in relation to the sanitary protection of water bodies. Gig.
Sanit. 33:17:1967.
53. Not used in text.
54. Not used in text.
55. Not used in text.
56. U.S. EPA, Assessment of testing needs: chlorinated benzenes.
Support document for proposed health effects test rule,
TSCA Section 4. EPA 560/11-80-014; July, 1980.
57. U.S. EPA (1977). Investigation of selected potential environ-
mental contaminants: halogenated benzenes. EPA 560/2-77-004.
58. Morrison, R.T. and R.N., Organic Chemistry, Allyn and Bacon
Inc. Boston. (1976).
59. Coate, W.B. et al. Chronic inhalation exposure of rats,
rabbits and monkeys to 1,2,4-trichlorobenzene. Arch. Environ.
Health. 32:249:1977.
60. Smith, C.C., et al. Subacute toxicity of 1,2,4-trichloroben-
zene (TCB) in subhuman primates. Fed. Proc. 37:248:1978.
-------
61'. National Cancer Institute (NCI) Bioassay of 2,4,6-trichloro-
phenol for carcinogenicity. NCI-CG-TR-155. NTIS PB 223159.
September, 1979.
62. Fahrig. R. , et al. Genetic activity of chlorophenols and
chlorophenol impurities. In Pentachlorophenol chemistry,
pharmacology and environmental technology. K.R. Rao, ed.
Plenum Press, N.Y. 1978.
63. Weinback, E.G. and J. Garbus, The interaction of uncoupling
phenols with mitochondria and with mitochondrial protein.
J. Biol. Chem. 210:1811:1965.
64. Mitsuda, H., et al. Effect of chlorophenol analogues on Che
oxidative phosphorylation in rat liver mitochondria. Agric.
Biol. Chem. 27:366:1963.
13.0
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and_aqueous stream from
the_production_of_chlorobenzenes (K085).
1. One comraenter characterized the Agency's use of the terms
"chlorobenzene" and "chlorinated benzene", and its
occasional general references to chlorobenzenes with
higher degree 6f chlorination as "polychlorinated benzenes"
as "shoddy and ambiguous". The comnenter went on to
remark that these isomeric compounds differ in physical
properties, production, waste management, health and
environmental effects. The Agency deems the terms
"chlorobenzene(s)" and "chlorinated benzene(s)" to be
acceptable, widely used synonymous chemical terms.
However, in order to leave no room for ambiguity as to
the chemical nature of the chlorinated benzenes which are
of concern in these wastes, and in order to facilitate a
comparison of their relevant properties, a figure
illustrating their chemical structure and a table
delineating their physical properties have been added to
the Background Document.
2. One comnenter disagreed with the listing of the separated
aqueous stream from the reactor product washing step as
hazardous. The commenter disputed the Agency's determi-
nation that phenols and chlorinated phenols will be found
in this waste stream, stating that the reported occurence
of.these compounds in the untreated wastewater is atypical.
Oil
-------
The coramenter went on to state that the aqueous waste,
in any case, contains pollutants at such low concentrations
(i.e., 3-135 ppm, averaging 56 ppm) that the waste should
be of no regulatory concern under RCHA.
The Agency disagrees with these comments. Phenol
and chlorinated phenols are likely to be found in this
waste in some concentration as stated in the background
document, because chlorinated benzenes are known to form
these compounds as a result of hydrolysis under alkaline
conditions and elevated temperatures, conditions present
during chlorobenzene manufacture.(58) The presence of
these compounds in the sampled vastewater stream confirms
this process assumption.
However, on further consideration, we have decided
that certain of these compounds are not present in
the waste in concentrations sufficient to warrant their
inclusion as toxic constituents of concern. Phenol,
2-chlorophenol, and 2,4-dichlorophenol are in this category.
Not only are the reported sampled concentrations already
low, but they may be greater than concentrations normally
present from processes involving only chlorobenzene
manufacture, since the sampled waste may have included
wastewater from chlorophenol manufacture.
We will continue to list the carcinogen 2,4,6-
trlchlorophenol as a constituent of concern. Since the
reported concentration is raany orders of magnitude above
the recently promulgated human health Ambient Water
-------
Quality Criterion for this coapound (45 FR 70329
November 7, 1980), we believe the value to indicate a
potential for hazard if the waste is mismanaged. We
also believe that benzene and chlorinated benzenes may
typically be present in substantial concentrations,
namely their limits of solubility, and so will continue
to list the waste for these constituents as well.
The coomenter further argued that these constituents
are amenable to biological treatment, and so should not
be listed. The unstated thought is that although sludges
resulting from wastewater treatment are hazardous (see
§261.3), they may not contain appreciable concentrations
of the constituents of concern if biological treatment is
succes sful.
There are a number of answers to this comment. The
Agency, in its July 16 Background Document invited
commenters to show that their wastewater treatment sludges
are not hazardous. No data on this waste were submitted •
by any commentsr. Furthermore, the delisting mechanism
remains available to any facility wishing to demonstrate
that wastewater treatment sludges resulting from treatment
of wastewater from chlorobenzene manufacture is not
hazardous. Equally important, not all plants utilize
biological treatment, so that the hazardous constituents
could be present in some wastewater treatment sludges
in much higher concentration than in others.
RrZ
-------
Even where biological treatment is used, the Agency has
no assurance that the treatment is always successful in
removing hazardous constituents from the sludge, since
organisms must be specially adapted to degrade these
toxic constituents. We thus do not believe the'comment
to be sufficiently persuasive to warrant deleting this
waste listing.
3. The same commenter also mentioned in passing that it
generates an aqueous waste stream from a continuous
chlorobenzene manufacturing process, even though the
background document indicated that this waste stream is
generated only from batch processes.
Available Information continues to indicate that in
most cases, there will be no wastewater stream generated
from the continuous production of chlorobenzenes. In
response to the comment, however, we are revising the
listing description to include wastewater streams which
arise from continuous processes. Since raw materials are
the same and reaction processes are similar for both
processes, we expect any wastewater to be similar in
composition. The constituents and their concentrations
shown in reference 29, an analysis of wastewater from a
continuous process, is comparable to that predicted for
batch processes, confirming our assumption.
-------
4. One commencer criticized the Agency's characterization
regarding the persistences, nobilities and toxicities of
several chlorophenols. The comnenter recommends that the
Agency reassess the hazard of the aqueous process stream,
since, in its view, phenols and chlorinated phenols are
not hazardous constituents. Several of the comments
raised are identical to those raised by the same manufacturer
with respect to solid waste K043 (2,6-dichlorophenol
waste from the production of 2,4-D). The Agency's reply
to these comments were published on November 15, 1980
(Response to Coaments, page 635 of the BD dated November
19, 1980). There is no need to repeat them here.
Based on the foregoing discussion, the Agency will continue
to.list wastes K085 (distillation or fractionating column
bottoms from production of chlorobenzenes) and K105 (separated
aqueous stream from the reactor product washing step in the
j* r
batch production of chlorobenzenes) as hazardous.
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SJ-39-14
January 19' 1
LISTING BACKGROUND DOCUMENT
K086: SOLVENT WASHES AND SLUDGES, CAUSTIC WASHES AND SLUDGES
AND WATER WASHES AND SLUDGES FROM THE CLEANING OF TUBS
AND EQUIPMENT USED IN THE FORMULATION OF INK FROM PIGMENTS,
DRIERS, SOAPS AND STABILIZERS CONTAINING CHROMIUM AND LEAD
LEAD (T).
I. SUMMARY_OF_BASIS_FOR_LISTING*
Tubs and equipment used in ink formulation are washed by
solvents, caustics and/or water. The Administrator has deter-
mined that the spent washes and wash sludges generated after
ink formulation in which pigments, driers, soaps and stabili-
zers containing hexavalent chromium and lead are used may pose
a present or potential hazard to human health or the environ-
ment 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 co.nclusion is based on the following considerations:
1. The washes and sludges typically contain significant
concentrations of lead and hexavalent chromium. Lead
is highly toxic to a variety of species and is reportedly
carcinogenic in laboratory animals. Hexavalent chromium
is also toxic; in addition, EPA's Cancer Assessment
Group has found that CR+6 exhibits substantial
evidence of carcinogenlcity.
*The Agency is investigating the potential hazards of organic
constituents of printing inks. We are, for instance, investi-
gating the possible conversion by heat, light or reducing agents
present in waste streams or the environment, of pigments derived
from 3,3r-dichlorobenzidlne to the parent (carcinogenic) amine.
We are also concerned about wastes from the manufacture of jet
printing inks containing direct dyes derived from benzidine,
o-dianisidine and o-tolidine: such dyes could similarly be con-
verted to the carcinogenic parent amine.
Organic solvents likely to. be used in these washes are covered
under listings F003, F004, and F005, §261.31, hazardous waste
from nonspecific sources (45 FR 74890, November 12, 1980).
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2. Present management practices may be inadequate to
prevent the migration of hexavalent chromium and
lead from a. disposal site. Disposal practices
subject to RCRA include landfilling, impoundment
and removal by contract haulers. Such practices,
if uncontrolled, can result in contamination of
ground and surface waters by lead and hexavalent
chromium.
11. INBUS TRY_DE S CRIPTI ON_ AND^MANUF ACTURING__P RO CE S S < l >
An EPA survey of the ink formulating industry indicates
that there are approximately 460 ink manufacturers in the
United States (excluding captive ink producers that manufacture
ink in a printing plant solely for use in that plant). The
distribution of ink manufacturing plants by state is given in
Table 1. In 1972, total ink production was greater than one
billion pounds*
The variety of inks used today is broad, ranging from
ordinary writing inks to specialized magnetic inks. Inks
manufactured for the printing industry, which utilizes a
major portion of ink production, fall into four aajor
categories: letterpress inks, lithographic inks, flexographic
inks, and gravure inks.
Letterpress inks are viscous, tacky pastes using vehicles
that are oil and varnish-based. They generally contain resins
and dry by the oxidation of the vehicle.
Lithographic or off-set inks are viscous inks with a
varnish-based vehicle, similar to the letterpress varnishes.
The pigment content is higher in lithographic inks than letter-
press ink because the ink is applied in thinner films.
/a?
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Table 1 (1)
DISTRIBUTION OF INK MANUFACTURING PLANTS BY STATE
State _ _ Number of_?lan£s Percent of Plant£
California 47 10.2
Illinois 46 10.0
New Jersey 39 8.5
New York 34 7.4
Ohio 28 6.1
Pennsylvania 24 5.2
Texas 22 4.8
Massachusetts 21 4.6
Georgia 20 4.3
Missouri 16 3.5
Florida 14 3.0
Wisconsin 14 3.0
Michigan 13 2.8
Tennessee -13 2.8
North Carolina 10 2.2
Louisiana 9 2.0
Maryland 9 2.0
Minnesota 9 2.0
Virginia 9 . 2.0
Indiana 7 1.5
Oregon 7 1.5
All Others 49 10.7
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Flexographic inks are liquid inks which dry by evaporation,
absorption into the substrate, and decomposition. There are
two main types of flexographic inks: water and solvent.
Water inks are used on absorbent paper and the solvent inks are
used on nonabsorbent surfaces.
Gravure inks are liquid inks which dry by solvent evapora-
tion. The inks have a variety of uses ranging from printing
publications to food package printing.
Inks are either water, oil or solvent-based. The
"average" plant produces approximately 60 percent oil base
Ink, 25 percent solvent base ink and 5 percent water base ink.
In the manufacture of inks, the major ingredients
(vehicles, pigments and driers) are mixed thoroughly
to form an even dispersion of pigments within the vehicle.
The mixing is accomplished with the use of high-speed mixers,
ball mills, three-roll mills, sand mills, shot mills, and/or
colloid mills.
Most inks are made in a batch process in tubs ranging in
sizes from 19 liters (five gallons) to over 3,750 liters (1,000
gallons). The number of steps needed to complete the
manufacture of the ink depends upon the dispersion characteristics
of the ingredients. Most inks can be completely manufactured
In one or two steps since many of the pigments used can be
obtained predispersed in a paste or wetted form.
III. GENERATION^AND_MANAGEMENT_OF_HAZARDOUS_WASTE
-------
reactions generally do not occur and no by-products are
formed. When required, production tubs and manufacturing
equipment are washed clean of residue from the formulation
process. The spent cleaning solutions become contaminated
with tank residue composed of the residual raw materials.
Four broad types of raw materials are used in ink
manufacture:
0 Pigments and dyes, flushes and dispersions
9 Chemical specialties (including driers, plasticizers,
soaps and stabilizers)
0 Resins
0 Solvents
Inorganic pigments are the primary source of (hexavalent)
chromium and lead in ink industry wastewaters; chemical
specialties are also reported to contain lead. Survey data
obtained by EPA show that the ink formulation industry relies
on inorganic pigments for about 40% of the total production.
The two most widely used lead and chromium-containing pigments
are chrome yellow and molybdate orange, although many other
pigments are sources of lead and chromium in the waste.
Chrome yellow is a compound consisting of lead, hexavalent chromium
and oxygen; molybdate organge also contains lead and hexavalent
chromium as well as molybdenum.
Particular chemical specialties are another significant
source of lead and chromium in these wastes. For example,
driers containing lead are used by approximately 30% of the
-------
industry.* Stabilizers (some containing lead and phenol),
metallic soaps, and flatting agents containing lead are also
in use and are expected to contribute significant concentrations
of lead to process wastes.**
Process wastewater from ink manufacturing plants results
primarily from the rinsing of mixing tubs, roller mills, and
other equipment. Some additional wastewater may come from
floor and spill cleaning, laboratory and plant sinks, boiler
and cooling water blowdowtx, air pollution control devices
using water, and cleanout of raw material supply tank cars or
trucks.
The ink industry commonly uses three methods of ink tub
cleaning: (1) solvent-wash; (2) caustic-wash; and (3)
water-wash.
(1) §olvent-Wash_Wastes
Solvent-wash is used exclusively to clean tubs used for
formulating solvent-based and oil-based ink. The dirty solvent
generally is handled in one of three ways:
1. used in the next compatible batch of ink as part
of the vehicle;
* Examples are Shephard-lead tallates, lead linoleates, Hexogan,
Aduasol and Catalox.'^'
**Industry survey data indicate that approximately 70% of
the manufacturers use chromium-containing raw materials, and
55% use lead-containing raw materials. Thus, use of materials
containing these pollutants is widespread in the industry.
131
-------
2. collected and redistilled, either by the plant or
by an outside contractor for subsequent resale or
reuse; or
3. reused with or without settling to clean tubs and
equipment until spent, and then drummed for
disposalt If sludge is settled out it is also
drummed. These spent solutions and sludges are
usually disposed of by contract hauling.
Water-washing techniques are used in both the solvent-
base and water-base segments of the ink industry. For solvent-
base operations, water-washing usually follows caustic
washing of solvent-base tanks. For water-base operations,
water washes often constitute the only tub cleaning operation,
although water-base ink tubs may be cleaned periodically with
caus tic.
tfastewater generated by rinsing tubs or equipment used
for manufacturing water-base ink is usually handled in one of
four ways:
1. reused in the next compatible batch of water-base
ink as part of the vehicle;
2. reused either with or without treatment to clean
tubs and equipment until spent and disposed. If
sludge is settled out it is disposed by contract
hauling ;
3. discharged with or without treatment as wastewater;
or
4. disposed of immediately by contract hauling.
The water rinse following a caustic-wash is rarely reused
in a subsequent batch of ink. The most common methods for
disposal of this rinse are:
-------
1. recycling it back into the caustic as make-up water;
2. drumming it for contract hauling;
3. discharging it as wastewater, with or without pre-
treatment. Combination with other wastewater
prior to treatment or disposal is sometimes practiced.
Discharge of this wastewater is currently prohibited
by some states and municipalities and may be prohibited
in other areas in the future.
(3) Caustic-Wash Wastes
Caustic wash techniques are used to clean both
solvent-base and water-base ink manufacturing tanks. Plants
using caustic rinse or washing systems usually rinse the
caustic residue with water, although a few plants allow the
caustic solution to evaporate in the tubs. There are several
types of caustic systems commonly used by the ink industry.
For periodic cleaning of fixed tubs two methods are popular:
1. maintaining the caustic in a holding tank (usually
heated) and pumping through fixed piping or flexible
hose to the tub to be cleaned. After cleaning,
the caustic Is returned to the holding tank; and
2. preparing the caustic solution in the tub to b.e
cleaned; and soaking the tub until clean. The
caustic solution is either transferred to the
next tub to be cleaned, stored in drums or a
tank for subsequent use, or is discarded.
For cleaning small portable tubs, three common methods are used
by the Ink industry:
1. pumping caustic from a holding tank (usually heated)
to nozzles in a fixed or portable hood which is
placed over the tub to be cleaned. The caustic
drains to a floor drain or sump and is pumped back
to the tank, or is pumped back directly from the
tub;
2. maintaining an open top caustic holding tank. Small
tubs are put into "strainers" and dipped into these
tanks until clean; and
133
-------
3. placing the tubs in a "dishwasher-like" device (which
circulates hot caustic), and a subsequent water rinse.
These devices can handle tubs up to about 1900 liters
(500 gal).
Most plants using caustic, recycle the caustic solution
until it loses some of its cleaning ability. The spent
caustic is then disposed of either by contract hauling or as
a wastewater, with or without neutralization or other treatment.
The most common methods of wastewater disposal are
discharge to a sewer, contract hauling, evaporation, and land-
fill or impoundment. Most contract haulers discharge the
sludge to a landfill, although a few incinerate or reclaim it.'^
Although precise figures on the amount of waste covered
by this listing are not available, the quantity is expected
to be significant, and, furthermore, is expected to increase
•in the future. Final regulations issued by EPA's Effluent
Guidelines Division impose zero discharge requirements for
certain pollutants on all ink manufacturers in the solvent
wash category of the industry except existing pre-treaters;
proposed regulations would impose zero discharge requirements
on existing pre-treaters in the Solvent Wash category and
all others in the Caustic and/or Water Wash category. Imple-
mementation of these regulations will increase the amount
of hazardous waste requiring disposal in accordance with the
RCRA Subtitle C regulations.
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7. BI1£H1^I2^-2I_BASIS FOR LISTING
A. §AZARDS_POSED_BY_THE_WASTE
Solvent washes and sludges, caustic washes and
sludges and water washes and sludges from cleaning equipment
used in the formulation of ink from raw materials containing
lead and hexavalent chromium are listed as hazardous because
they typically contain significant concentrations of lead
and (presumably hexavalent) chromium.*
Lead is poisonous in all forms. It is one of the
most hazardous of the toxic metals because it accumulates in
many organisms and its deleterious effects are numerous and
severe. Epidemiology studies implicate occupational exposure
to hexavalent chromium in the induction of lung tumors.
Impairment of pulmonary function is also reported to result
* Other toxic metals and various toxic organics are also
known to be present in some of the wash wastes, but sufficient
data are not yet available to list the wastes for those
contaminants. It also should be noted that the tub-cleaning
wastes can exhibit hazardous characteristics other than
toxicity; the Agency has information which indicates that
the listed wastes can be ignitable or corrosive (3,4,5,6).
In addition, a number of spent solvents are listed as hazardous
in §261.31 of the hazardous waste regulations published on
November 12, 1980 (45 FR 74890), and if these solvents are used
in ink formulation and are disposed of, they are considered
hazardous wastes under the earlier listing as well as the
present listing. Listed solvents presently in use by the
ink formulation industry include: toluene, 1,1,1-trichloroethane,
ethyl benzene methylene chloride and trichloroethylene.
Delisting petitions by ink formulators using these solvents must
address not only the presence of the spent solvent itself in the
waste, but .the presence of lead and hexavalent chromium as
well.
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from chronic exposure to hexavalent chromium. (For further
information on Health and Ecological Effects of chromium and
lead, see Section B (Health and Ecological Effects) in this
background document, and Appendix A.
The following data substantiates the presence of significant
concentrations of lead and chromium in the wash wastes:
0 EPA has determined that the average concentrations
of lead and chromium per day in ink industry caustic
wash and water-wash wastewaters are 151 mg/1 and
35 mg/1, respectively. Concentrations as high as
900 mg/1 of lead and 200 mg/1 of chromium were
reported.C1)*
0 A summary of industrial waste composition data
taken from the manifests required by the State
of California for transportation of hazardous
wastes lists the following wastes from the
manufacture of printing ink as hazardous:(^)
1. Ink wastewater which contained 1000 ppm of lead.
2. Equipment cleaning washwater which contained
10,000-20,000 ppm of lead chromate.
9 "Special Waste Disposal Applications" were submitted
to the State of Illinois for the following wastes
from ink manufactures:^)
1. Solvent waste containing 120 ppm of chromium
and 770 ppm of lead.
2. Solvent waste containing 291 ppm of lead.
* A "Hazardous Waste Disposal Request" was submitted
to the Missouri Department of Natural Resources for
disposal of printing ink sludge (wash waste) con-
taining 260 ppm of chromium and 1,340 ppm of lead.(^)
0 The "Industrial Waste Surveys" file of the State of
New Jersey contained a description of ink manufacturing
wash water with 260 ppm of lead (7^.
Clearly the concentrations of lead and chromium in the
*These figures may be conservative in light of the higher
concentrations contained in state manifests, given below.
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wastes may be very substantial.
The presence of such high concentrations of toxic metals
in a waste In and of itself raises regulatory concerns. Lead
and hexavalent chromium have proven capable of migration, mobility
and persistence in many waste management settings(28)t raising
the concern that, if these wastes are improperly managed,
the lead and hexavalent chromium may be released from the
waste in harmful concentrations and adversely effect human
health and the environment. Because lead and chromium do
not degrade with the passage of time, they will provide a
potential source of long-term contamination if they are
permitted to escape from the disposal site.
Current disposal methods do not appear adequate to
prevent migration of these toxic 'metals from the waste into
the environment. Toxic metal-bearing liquid wastes placed
in an impoundment can release those hazardous constituents
to the surrounding area if seepage and overflow are not
controlled, or measures are not taken to prevent total washout.
Without regulation, proper containment of the impounded wash
wastes cannot be assured.
Clearly, if measures to retard migration of liquids
from impoundments and landfills are not employed, ground and
surface waters could easily become contaminated. Improper
landfilling of sludges settled from the liquid wastes could
also result in release of the hazardous constituents. The
heavy metal compounds might already be solubilized or may
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&
137
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solubilize as a result of disposal conditions (co-disposal
with acids, alkalis or decomposing organic matter, for instance)
and could then migrate from the disposal site to ground and
surface waters. As a result, ground and surface drinking
water supplies may become contaminated, and wildlife and
various aquatic species could be threatened by exposure to
the toxic metals lead and hexavalent chromium.
Unregulated contract hauling of wastes by private disposal
services, scavengers or purveyors in tank trucks — a waste
management method frequently used for these wastes -- creates
additional hazards. There have been innumerable damage
incidents involving unregulated contract hauling, resulting in
substantial environmental harm. (Some examples are collected
in Reference 28.) Thirty-one percent of the ink plants
surveyed by EPA did not know what the contract hauler does
with their waste.(1) There is obvious potential for abuse in
this system since there is no way to determine whether these
wastes are properly managed during transportation, treatment
or disposal; irresponsible handling at any point could ultimately
endanger human health and the environment. Therefore, it is
essential that wastes of this nature be subject to regulation
from "cradle to grave".
B. Health and Ecological Effects
1. Lead
Health Effects
Lead is poisonous in all forms. It is one of
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the most hazardous of the toxic metals because it bioaccumulates
in many species, and its deleterious effects are numerous and
severe. Lead may enter the human system through inhalation,
ingestion or skin contact. The hematopoietic system is the
most sensitive target organ for lead in humans, although
subtle neurobehavioral effects are suspected in children at
similar levels of exposure.(8)
Lead exposure has been reported to decrease reproductive
ability in men(9) and women.(10) It has also been shown to
cause disturbances of blood chemistry, (H/ neurological
disorders,(12,13)f kidney damage(^' and adverse cardiovascular
effects.d5) Lead has been shown to be teratogenic in animals.(16)
Although certain inorganic lead compounds are carcinogenic to
some species of experimental animals, a clear association
between lead exposure and cancer development has not been
shown in human populations.
Additional information and specific references on adverse
effects of lead can be found in Appendix A.
Ecological Effects
In the aquatic environment, lead has been reported to be
acutely toxic to invertebrates at concentrations as low as
450 ug/1 and chronically toxic at less than 100 ug/1.^17)
The comparable figures for vertebrates are 900 ug/1 for acute
toxicityd**) and 7.5 ug/1 for chronic toxicity. (19)
Lead is bioconcentrated by all species tested - both marine
-------
and freshwater - including fish, invertebrates and algae.
The mussel, Mytilus edulis, concentrated lead 2,568 times
that found in ambient water. Two species of algae concentrated
lead 900-1000 fold. Algae reportedly can concentrate lead in
their tissues to levels as much as 31,000 times ambient water
concentrations.(20) Lead does not degrade with the passage
of time and may be expected to persist indefinitely in the
environment in some form.
Regulatory Recognition of Hazard
As of February 1979, the U.S. Occupational Safety and
Health Administration has set the permissible occupational
exposure limit for lead and inorganic lead compounds at 0.05
mg/m^ of air as an 8-hour time-weighted average. The U.S.
EPA (1979) has also established an ambient airborne lead
standard of 1.5 ug/m^.
The U.S. EPA's Office of Water Regulations and Standards
has recommended an ambient water quality criterion for lead
to protect freshwater aquatic life of 0.75, 3.8, and 20
micrograms lead per liter (ug/1) corresponding to a water
hardness of 50, 100, and 200 mg/1 calcium and carbonate. The
ambient water quality criterion for lead to protect human
health is recommended to be identical to the existing drinking
water standard of 50 ug/1.(21)
In addition, final or proposed regulations of the States
of California, Maine, Massachusettes, Minnesota, Missouri,
New Mexico, Oklahoma and Oregon define lead containing compounds
-------
as hazardous wastes or components thereof. (22)
Industrial Recognition of Hazard
Lead is rated as highly toxic through ingestion, inhalation
and skin absorption routes in Sax, Dangerous Properties .of
Chromium
Health Effects
Hexavalent chromium is an animal carcinogen and there is
evidence that it may be a human carcinogen as well. (23)
EPA.' s Carcinogen Assessment Group has listed it as such.
Mutagenic effects in bacteria have also been described.
Cytogenetic effects in workers using hexavalent chromium
compounds have been reported. (24)
Teratogenic effects of chromium have been reported in a
single study and have not been confirmed.
Impairment of pulmonary function has been described in
chrome electroplating workers subject to chronic chromium
exposure. (25)
Additional information and specific references on the
adverse effects of chromium can be found in Appendix A.
Ecological_Ef f ec^s
Hexavalent chromium, at low concentrations, is toxic to
many aquatic species. For the most sensitive aquatic species,
Daphnia magna, a final chronic no-effect level of less than
10 ug/1 has been derived by the U.S. EPA.
Regulatory ^ecognition_o£_Hazard
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The U.S. EPA's Office of Water Regulations and Standard
has recommended an ambient water quality criterion for
hexavalent chromium to protect freshwater aquatic life of
0.29 ug/1 as a 24-hour average. For protection of saltwater
aquatic life, the criterion for hexavalent chroaiua is 13
ug/1. The ambient water quality criterion for hexavalent
chromium to protect human health is recommended to be identical
to the existing drinking water standard which is 50 ug/1.(27)
The OSHA time-weighted average exposure criterion for
chromium (carcinogenic compounds) is 1 ug/m^; for the "non-
carcinogenic" classification of chromium compounds the cri-
terion is 25 ug/3 TWA.
For the protection of aquatic species, proposed water
criteria for both trivalent aud hexavalent chrotaiura in fresh-
water and marine environments have been prepared in accordance
with the Guidelines for Deriving Water Quality Criteria.(27)
Industrial Recognition of_Hazard
Sax, Dangerous Properties of Industrial Materials,
4th Ed. 1975, rates chromium as having a high pulmonary
toxicity.
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References
K086: INK FORMULATION
1. U.S. EPA. Effluent Guidelines Division. Development
document for proposed effluent limitations guidelines
and standards for the ink formulation point source category.
EPA No. 440/1-79/090-b. Deceaber 1979.
2. Storm, D.L. Handbook of industrial waste compositions in
California - 1978. California Department of Health Services.
Hazardous Materials Management Section. November 1978.
3. State of Illinois, Environmental Protection Agency. Special
waste disposal applications. Obtained by U.S. EPA March 13-14,
1979.
4. State of Missouri, Department of Natural Resources.
Hazardous Haste Disposal Request. Obtained by U.S. EPA
March 16, 1979.
5. U.S. EPA Effluent Guidelines Division. Development
document for proposed effluent limitations guidelines
and new source performance standards for the paint formu-
lating and the ink formulating point source categories.
EPA No. 440/1-75/050. 1975.
6. Personal Communication.' National Association of Printing
Ink Manufacturers to John P. Lehman, Office of Solid
Waste, U.S. EPA, March 15, 1979.
7. State of New Jersey, Department of Environmental Protection.
State Files of Industrial Waste Surveys. Obtained by U.S.
EPA. August - September 1979.
8. U.S. EPA. Hazard profile: lead. SRC, Syracuse, NY. 1980.
9. Lancranjan, I., et al. Reproductive ability of workmen
occupationally exposed to lead. Arch Environ Health
30:396:1975.
10. Lane, R. E. The care of the lead worker. Eur. J. Ind. Med.
6:1243:1949.
11. Roels, H. A., et al. Lead and cadmium absorption among
children near a nonferrous metal plant. A follow-up
study of a test case. Environ. Res. 15:290:1978.
12. Perlstein, M. A., and R. Atlala. Neurologic sequelae of
plumbism in children. Clin. Pediat. 6:266:1966.
13. Byers, R. K., and E. E. Lord. Late effects of lead
poisoning on mental development. Am. Jour. Child. 66:471:1943.
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14. Clarkson, T. W., and J. E. Kench. Urinary excretion
of amino acids by men absorbing heavy metals. Biochera. J.
62:361:1956.
15. Oingwall-Fordyce, J., and R. E. Lane. A follow-up
study of lead workers. Br. Jour. Ind. Med. 30:313:1963.
16. McLain, R. M., and B. A. Baker. Teratogenicity, fetal
toxicity and placental transfer of lead nitrate in rats.
Toxicol. Appl. Pharmacol. 31:72:1975.
17. Beisinger, K. E. , and G. M. Christensen. Effects of
various metals on survival, growth, reproduction and
metabolism of Daphnia Magna. J. Fish. Res. Board Can.
29:1691:1972.
18. Brown, V. .M. Calculation of the acute toxicity of mixtures
of poisons to rainbow trout. Water Res. 2:723:1968.
19. Davies, P. H. , et al. Acute and chronic toxicity of lead
to rainbow trout, Salmo Gairdneri, in hard and soft water.
Water Res. 10:199:19767
20. Trollope, D.R., and B. Evans. Concentration of copper, iron,
lead, nickel, and zinc in freshwater algae blooms. Environ.
Pollut. 11:109:1976.
21. tt.S. EPA. Office of Water Regulations and Standards. Ambient
water quality criteria for lead. EPA No. 440/5-80-57. NTIS PB
Ho. 81-117681.
22. USEPA Office of Solid Waste, States Regulations File,
January, 1980.
23. National Academy of Sciences. Medical and biological effects
of environmental pollutants: Chromium. Washington, DC. 1974.
24. Hedenstedt, A., et al. Mutagenicity of fume particles from
stailess steel welding. Scand. J. Work. Environ. Health 3:
203:1977.
25. Bovett, P., et al. Spiroraetric alterations in workers in the
chromium electroplating industry. Int. Arch. Occup. Environ.
Health 40:25:1977.
26. U.S. EPA Hazard profile: chromium. SRC Syracuse, NY. 1980.
27. U.S. EPA. Office of Water Regulations and Standards. Ambient
water quality criteria for chromium. EPA No. 440/5-80-035.
NTIS P3 No. 81-117467.
28. U.S. EPA Damages and threats caused by hazardous material sites
EPA No. 430/9-80/004. 1980.
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Response_to_Coooents^_Ink Formulation Waste Streams [Proposed
Listing, December 18, 1978 (43 FR 58959)]
1. One comiaenter stated that the proposed listing is
too broad and that all wash wastes should not be consid-
ered hazardous.
The listing of the above waste has been clarified.
After reviewing available information, the Agency has
narrowed the listing to cover wastes from the cleaning of
equipment used to formulate ink from raw materials containing
chromium and lead. Data show that raw materials containing
chromium and lead are widely used in the Industry,
and the wash wastes generated when these raw materials
are used are likely to exhibit substantial concentrations
of these toxic metals. The Agency concluded that these
wash wastes present a potential hazard to human health
and the environment because improper disposal may result
in the contamination of ground and surface waters used
as drinking water sources (see the background document
for a more detailed discussion).
2. One commenter stated that wash wastes should not
be listed as corrosive since the corrosive waste streams
can be neutralized.
The fact that the wastes can be neutralized does not
mean that they are not hazardous when generated. In
order to make sure that corrosive wastes are managed
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properly* corrosivity must be determined before treatment
by neutralization or any other means (see §261.3(b)(3).
For the final listing, the Agency has decided not to
characterize the wash wastes as corrosive because adequate
data are not available to indicate that the wastes are
typically corrosive as defined in §261.22. In addition,
the Agency believes that the corrosivity of the wastes
can easily be determined by the generator. Such a
determination is required for all wastes not Included
in this listing, and for all wastes addressed by indivi-
dual petitions for delisting. (See §§ 262.11, 260.22.)
3. The commenter stated that classification of all wash
wastes as hazardous because some might contain toxic
organic substances is arbitrary.
The Agency has narrowed its proposed listing, although
the claims of the commenter are not particularly persuasive.
The revised listing does not at this time address toxic
organic substances in the waste. As additional data
becomes available, the Agency may include such substances
as toxic constituents of concern in these wastes. The Agency
for instance, concerned with the use of phthalates
used as plasticizers in ink formulation, and use of
phenols in chemical specialties. Information is solicited
as to concentrations of these materials in ink formulation
wastes, and potential mass loadings of these pollutants.
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The Agency is particularly concerned over any potential
environmental degradation by heat, light, or chemical
reducing agents of the diarylide yellow pignents to the
parent amlne, 3,3'dichlorobenzidine. Certain solvents
used in ink formulation are listed as hazardous wastes
under F002, F003, F004, and F005 (45 FR 33123, May 19,
1980).
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CON-12-02
January 198
LISTING BACKGROUND DOCUMENT
K087: Decanter Tank Tar sludge from coking operations* (T)
I. Summary of Basis for Listing
The spray cooling of coke oven gases during the by-
product recovery process results in the generation of a de-
canter tank tar-sludge. The Administrator has determined
that decanter tank tar-sludge may pose a present or po-
tential hazard to human health or the environment when im-
properly transported, treated, stored, disposed of or other-
wise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. This con-
clusion is based on the following considerations:
1) The tank tar-sludge contains significant concentrations
•of phenol and naphthalene. Phenol and naphthalene are toxic
to humans and aquatic life.
2) Phenol has leached in significant concentration from
a waste sample tested in a distilled water extraction proce-
dure. Although no leachate data is currently available for
naphthalene, the Agency believes that, due to its presence
in the tar in high concentrations and due to its relative solu-
bility, naphthalene also may leach from the waste in harmful
concentrations if the waste is improperly managed.
3) These tar-sludges are often land disposed in on-site
landfills or dumped in the open. These methods may be inade-
quate to impede leachate migration and resulting groundwater
contamination.
*The listing description has been amended from that originally
proposed on December 18, 1978 (43 FR 53959) which included two
waste listings [i.e., Coking: Decanter tank tar and Coking: De-
canter tank pitch/sludge]
Additional information substantiating the hazards associated
with polynculear aromatic hydrocarbon constituents in this
waste will be evaluated in an expanded listing background
document for an integrated by-product coke-making process.
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II. Waste Generation, Composition and Management
Coke, the residue from the destructive distillation of
coal, serves as both a fuel and as a reducing agent in the
making of iron and steel. Some coke plants recover by-products
given off or created during the coke production process, and
the recovery of by-products generates a sludge which is the
listed waste in this document. There are 56 by-product coke
plants, which generate an estimated 72,300 tons/yr of decanter
tank tar-sludge. During the recovery of chemicals in the
by-product coke production process, tar separates by conden-
sation from coke oven gas and drains to a decanter tank.
Recoverable oil fractions are decanted off the top and the
tar sludge settles to the bottom.
Approximately 97% of this tar-sludge is elemental carbon.
The remaining 3% consists of condensed tar materials. These
condensed tar materials contain the waste constituents of con-
cern, namely phenolic compounds and naphthalene, which are
formed as a result of the destructive distillation of coal.
Based on a published reference, the condensed tar compo-
nent contains, by weight, 2.2% naphthalene and 0.1% phenolic
compounds(2). With an estimated 2,169 tons/yr of condensed
car contained in the amount of tar-sludge generated annually
(i.e.i 3% of the 72,300 tons/yr of tar-sludge), approximately
47.7 tons of naphthalene and 2.2 tons of phenolic compounds
will be contained in the waste generated each
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Of the 66 coke plants generating decanter tank tar-sludge,
30 plants use the tar-sludge as a raw material in either the
sintering process or open hearth furnace operation. The re-
maining 36 plants dispose of this waste in unsecure on-site
landfills( 1) , or by dumping in the open(^).
Ill. Hazardous Properties of the Waste
Phenol and naphthalene are present in the tar component
of this waste in significant concentrations: 0.1% by weight
(1000 ppia) and 2.27, by weight (22,000 ppm) , respectively (2).
Phenol and naphthalene are toxic to humans and aquatic life.
Thus, the Agency believes" that the concentrations of these
materials in the waste are quite significant, in light of
the constituents' known health hazards. Further, these
waste constituents appear capable of migrating in significant
i
concentrations if mismanaged, and are likely to be mobile
and persistent so that waste mismanagement could result in
a substantial human health or environmental hazard.
Phenol's potential for migration from this waste in sig-
nificant concentrations has been demonstrated empirically.
Phenol leached in significant concentration (approximately
500 ppm) from a decanter tar-sludge waste sample subjected
to distilled water extraction procedure. (•*) in addition,
phenol is extremely soluble, about 67,000 ppm (? 25*c(5),
indicating high potential for migration. Phenol biodegrades
at a moderate rate in surface water and soil but moves very
12ft
m
i CO
-------
readily (App. B). Even with a persistence of only a few day,
Che rapid spreading of phenol could cause widespread contamina-
tion of the eco-system and contamination of potable water supplies
The migratory potential of phenol and its ability to move
through soils is further confirmed by the fact that it has been
detected migrating from Hooker Corporation's S Area, Hyde Park,
and 102nd St. landfills in Niagara, New York (OSW Hazardous
Waste Division, Hazardous Waste Incidents, Open File, 1978).
The compound's persistence following migration is likewise
shown by these incidents.
Although no comparable leachate data is currently avail-
able for naphthalene, the Agency believes that this constituent
also may leach in harmful concentrations from the waste if not
properly managed. The water solubility of naphthalene has been
reported to range from 30 to 40 mg/1, depending on the salinity
of the dissolving medium (7). Naphthalene has been identified
in finished drinking water, lakes, and rivers, demonstrating its
persistence and mobility (^). This information, naphthalene's
solubility in water, and its presence in the tar in such high
concentrations (22,000 ppra) make it likely that it will leach
from the waste in potentially harmful concentrations if the
waste is mismanaged, and will then be mobile and persistent, and
so poses the potential for causing substantial hazard to human
health and the environment.
Current practices of disposing of this waste in fact ap-
pear inadequate. Disposal of decanter tank tar-sludge in un-
secured landfills or by dumping in the open makes it likely
-K-
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that the hazardous constituents in the waste will leach out
and migrate into the environment, possibly reaching and con-
taminating drinking water sources. Siting of waste manage-
ment facilities in areas with highly permeable soils could
facilitate leachate migration. As demonstrated above, the
waste constituents appear capable of migration, mobility and
persistence. Thus, if disposal sites are improperly managed
or designed (e.g., lack adequate leachate collection systems),
waste constituents could leach into soils and contaminate
groundwater.
Health and Ecological Effects
Phenol
Congress designated phenol a priority pollutant under
§307(a) of the Clean Water Act.
Phenol is readily absorbed by all routes. It is rapidly
distributed to mammalian tissues. This is illustrated by
the fact that acutely toxic doses of phenol can produce
symptoms within minutes of administration regardless of the
route of entry. Repeated exposures to phenol at high concen-
trations have resulted in chronic liver damage in humans.'^)
Chronic poisoning, following prolonged exposures to low
concentrations of the vapor or mist, results in digestive
disturbances (vomiting, difficulty in swallowing, excessive
salivation, diarrhea), nervous disorders (headache, fainting,
dizziness, mental disturbances), and skin eruptions'^'.
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Chronic poisoning nay terminate fatally in sone cases where
there has been extensive damage to the kidneys or liver.
The Office of Water Regulations and Standards, U.S.
EPA'"' has found that acute and chronic toxicity of phenol to
freshwater aquatic life occur at concentrations as low as
10,200 and 2,560 ug/1, respectively, and would occur at lower
concentrations in more sensitive species than those tested.
The available data for phenol indicate that acute toxicity to
saltwater aquatic life occurs at concentrations as low as
5,800 ug/1 and would occur a lower concentrations among
species that are more sensitive than those tested. Based on
available toxicity data, the ambient water quality criteria
level for phenol to protect human health is 3.5 rag/1. The
ambient water criteria level to control undesirable taste and
odor qualities, the estimated level is 0.3 mg/1..
OSHA has set a TLV for phenol at 5 ppm. Phenol Is listed
in Sax's T)angerous Properties of Industrial Materials as high-
ly toxic via an oral route.(*) Sax also describes phenol as
a co-carcinogen and a demonstrated carcinogen via a dermal
route in studies done with laboratory animals. Additional
information and specific references on the adverse effects
of phenol can be found in Appendix A.
Naphthalene
Naphthalene is designated as a priority pollutant under
Section 307(a) of the CWA.
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Systemic reaction to acute exposure to naphthalene in-
cludes nausea, headache, diaphoresis, henaturia, fever, anenia,
liver damage, convulsions and coma. Industrial exposure to
naphthalene appears to cause increased incidence of cataracts.
Also, hemolytic anemia with associated jaundice and occasion-
ally renal disease from precipitated hemoglobin has been des-
cribed in newborn infants, children, and adults after exposure
to naphthalene by ingestion, inhalation, or possibly by skin
contact.
The Office of Water Regulations and Standards, U.S.
EPA(?) has found that acute and chronic toxicity to freshwater
aquatic life occur at concentrations as low as 2,300 and 620
ug/1, respectively, and would occur at lower concentrations
among species that are more sensitive than those tested. The
available data for naphthalene indicate that acute toxicity
to saltwater aquatic life occurs at concentrations as low as
2,350 ug/1 and would occur at lower concentrations among
species that are more sensitive than thosa tested. Using the
present guidelines, a satisfactory criterion for ambient
water quality could not be derived at this time because of
the insufficiency of data for naphthalene.
OSHA's standard for exposure to vapor for a time-weighted
industrial exposure is 50 mg/m^.
Sax lists naphthalene as moderately toxic via the oral
route and warns that naphthalene is a demonstrated neoplastic
1*5
-------
substance via Che subcutaneous route in experiments done on
laboratory animals^'. Additional information and specific
references on the adverse effects of naphthalene can be found
in Appendix A.
-*-
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REFERENCES
£037: Coking-.Decanter Tank Car Sludge.
1. U.S. EPA. Draft Development document for proposed
effluent limitations guidelines and standards for the
iron and steel manufacturing point source category;
by-product cokemaking subcategory, v.2 EPA No. 440/1-79
024a. October 1979.
2. Desha, L. Organic chemistry. McGraw-Hill Book Company,
New York. 1946.
3. Calspan Corporation. Assessment of industrial hazardous
waste practices in the metal smelting and refining industry,
v.3. Appendices. Contract No. 68-01-2604. April 1977.
4. Sax, N.I. Dangerous properties of industrial materials,
Van Nostrand Reinhold Co., New York. 5th ed., 1979.
5. Dawson, English and Petty. Physical chemical properties of
hazardous waste constituents. Appendix C of the May 2,
1980 listing background documents. 1980
6. O.S. EPA. Ambient water quality criteria for phenol.
EPA No. 440/5-80-066. NTIS PB No. 81-117772. October 1980.
7. U.S. EPA. Ambient water quality criteria for naphthalene.
EPA No. 440/5-80-059. NTIS PB No. 81-117707. October 1980.
/sr
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Response to Comments: Coking_-_Decanter Tank Tar^Sludge.
One commenter stated that the Agency has misstated the
scientific evidence for the waste constituents phenol
and naphthalene with respect to attributing potential
carclnogenicity to these two constituents.
The Agency agrees with the commenter and has revised
the listing background document in a manner consistent
with the toxicological analyses contained in Appendix A -
Health and Environmental Effects Profiles of Subtitle 0 -
Identification and Listing of Hazardous Waste, RCRA.
However, the Agency still believes that these contaminants
exhibit sufficient toxicity to be of regulatory concern.
More specifically, prolonged exposure to low concentrations
of phenol can result in digestive disturbances, nervous
and skin disorders. Similar exposure to naphthalene can
cause liver and renal disease.
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