LISTING BACKGROUND DOCUMENT
WOOD PRESERVING
Wastewater from wood preserving processes that use
creosote and/or pentachlorophenol (T)
Bottom sediment sludges from the treatment of wastewaters
from wood preserving processes that use creosote and/or
pentachlorophenol (T)
I. Summary of Basis for Listing*
Wood preserving processes that use creosote or penta-
chlorophenol as preserving agents generate a wastewater,
which contains toxic phenolic compounds including penta-
and tetrachlorophenol and polynuclear aromatic hydrocarbon
(PAH) components of creosote. Treatment of this wastewater
results in the generation of a number of bottom sediment sludges
that must be removed for ultimate disposal. The Administrator
has determined that wastewater from these wood preserving
processes and the resulting bottom sediment sludges from waste-
water treatment are solid wastes that may pose a substantial
present or potential hazard to human health or the environment
when improperly treated, stored, disposed of or otherwise
managed, and therefore should be subject to appropriate.
management requirements under Subtitle C of RCRA'.
*Based on available data, and in response to industry
comment on the proposed listing (44 FR 49403, August 22,
1979), the Agency has modified this listing. Waste streams
from wood preserving processes using waterborne inorganic pre-
servatives are not Included in the listings of this document.
However, the Agency plans to study the sludges generated from
these wood preserving processes (i.e., from work tanks, cycllnders
or storage tanks), to determine whether they should also be listed
In addition, the Agency intends to study sludges generated from
the periodic dredging of retorts, cyclinders, and holding tanks
In which pentachlorophenol and creosote are used In the future
to determine whether these sludges also should be listed.
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Table of Contents
Background Document
1. Wastes From Usage of Halogenated Hydrocarbon 2
Solvents in Degreasing Operations
- The spent halogenated solvents used in
degreasing, tetrachloroethylene, nethylene
chloride, trichloroethylene, 1,1,1-tri-
chloroethane, carbon tetrachloride, and
the chlorinated fluorocarbons; and sludges
resulting from the recovery of these sol-
vents in degreasing operations (T)
2. Wastes From Usage of Organic Solvents 30
The spent halogenated solvents, tetrachloro-
ethylene, methylene chloride, trichlo.roethy-
lene, 1,1,1-trichloroethane, chlorobenzene,
l,l,2-trichloro-l,2,2-trifluoroethane, o-
dichlorobenzene, trichlorofluoromethane, and
the still bottoms from the recovery of these
solvents (T)
- The spent non-halogenated solvents, xylene,
acetone, ethyl acetate, ethyl benzene,
ethyl ether, n-butyl alcohol, cyclohexanone,
and the still bottoms from the recovery of
these solvents (I)
- The spent non-halogenated solvents, cresols
and cresylic acid, nitrobenzene, and the still
bottoms from the recovery of these solvents (T)
The spent non-halogenated solvents, methanol,
toluene, methyl ethyl ketone, methyl isobutyl
ketone, carbon disulflde, isobutanol, pyridine,
and the still bottoms from the recovery of
these solvents (I,T)
3. Electroplating and Metal Finishing Operations 82
Wastevater treatment sludges from electroplating
operations
4. Spent Waste Cyanide Solutions and Sludges 102
Spent plating bath solutions from electroplating
operations (R,T)
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Paj
Wastewater treatment sludge from the pro-
duction of molybdate orange pigments (T)
Wastewater treataeat sludge from the pro-
duction of zinc yellow pigments (T)
Wastewater treatment sludge from the pro-
duction of chrome green pigments (T)
Wastewater treatment sludge from the pro-
duction of chi/ome oxide green pigments
(anhydrous and hydrated) (I)
Wastewater treatment sludge from the pro-
duction of iron blue pigments (T)
Oven residue from the production of chrome
oxide green pigments (T)
7. Acetaldehyde Production 204
Distillation bottoms from the production of
acetaldehyde from ethylene (T)
Distillation side-cuts from the production
of acetaldehy
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Page
17. Nitrobenzene Production 403
- Distillation bottoms front the production of
nitrobenzene by the nitration of benzene (T)
18. Methyl Ethyl Pyridlne Production 416
- Stripping still tails from the production
of methyl ethyl pyridine (T)
(
19. Toluene Dlisocyanate Production 431
- Centrifuge residues from toluene dilsocya-
nate production (R,T)
20. Trichloroethane Production 444
- Waste from the product stream stripper in
the production of 1,1,1-trichloroethane (T)
Spent catalyst from the hydrochlorinator
reactor in the production of 1,1,1-tri-
chloroethane_.x.ia the vitiyl chloride
process (T)
- Distillation bottoms from the production
of 1,1,1-trichloroethane (proposed) (T)
- Heavy ends from the production of 1,1,1-
trichloroethane (proposed) (T)
21. Trichloroethylene and Perchloroethylene Production .... 475
- Column bottoms or heavy ends from the com-
bined production of trlchloroethylene and
perchloroethylene (T)
22. MSMA and Cacodylic Acid Production 500
- By-product salts generated in the production
of MSMA and cacodyllc acid (T)
23. Chlordane Production 523
- Wastewater and scrub water from the chlori-
nation of cyclopentadiene in the production
of chlordane (T)
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Page
28. 2,4,5-T Production 597
Heavy ends or distillation residues from
the distillation of tetrachlorobenzene in
the productionof 2,4,S-T (T)
29. 2,4-D Production 610
2,6-DichlorophenoL waste from the produc-
tion of 2,4-D (T)
Untreated vastewater from the production
of 2,4-D (proposed) (T)
30. Methomyl Production 623
- Wastewater from the production of methomyl
(proposed) (T)
31. Explosives Industry 637
Wastewater treatment sludges from the manu-
facturing and~~'processing of explosives (R)
Spent carbon from the treatment of waste-
water containing explosives (R)
- Wastewater treatment sludges from the manu-
facture, formulation and loading of lead-
based Initiating compounds (T)
Pink/red water from TNT operations (R)
32. Petroleum Refining 671
Dissolved air flotation (DAF) float from the
petroleum refining industry (T)
- Slop oil emulsion solids from the petroleum
refining industry (T)
Heat exchanger bundle cleaning sludge from
the petroleum refining industry (T)
API separator sludge from the petroleum re-
fining industry (T)
Tank bottoms (leaded) from the petroleum re-
fining industry (T)
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Pa;
Uastewater treatment sludges from the
following subcategory of the leather
tanning and finishing Industry: hair
save/.non-chrome tan/retan/wet finish (R)
34. Coking 739
- Ammonia still lime sludge (T)
35. Electric Furnace Production of Steel 753
- Emission control dusts/sludges from the
electric furnace production of steel (T)
36. Steel Finishing 767
- Spent pickle liquor from steel finishing
operations (C,T)
- Sludge from lime treatment of spent pickle
liquor from steel finishing operations (T)
37. Primary Copper Smelting and Refining 784
- Acid plant blowdown slurry/sludge resulting
from the thickening of blowdown slurry from
primary copper production (T)
38. Primary Lead Smelting 801
Surface impoundent solids contained in and
dredged from surface impoundments at pri-
mary lead smelting facilities (T)
39. Primary Zinc Smelting and Refining 819
Sludge from treatment of process wastewater
and/or acid plant blowdown from primary
zinc production (T)
- Electrolytic anode slimes/sludges from primary
zinc production (T)
- Cadmium plant leach residue (iron oxide) from
primary zinc production (T)
-xiv-
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This conclusion is based on Che following considerations:
1) The wastewater generated from wood preserving
processes using pentachlorophenol as a preservative
and the sludge generated from the treatment of this
wastewater will contain significant concentrations
of phenolic compounds. The wastewater from wood
preserving processes that use creosote and the
sludges generated from the treatment of this waste-
water will contain significant concentrations of
polynuclear aromatic components of creosote.
Wastewater and the resulting sludges from wood preserving
operations that use both creosote and pentachlorophenol
as preservatives will generate waste streams which
contain all or most of the above contaminants.
2) Polynuclear aroma tics, as a group, are known to be
toxic, rautagenic, teratogenic and carcinogenic.
Phenollcs are toxic and, In some cases, bioaccumu-
lative and carcinogenic.
3) Approximately 200,000,000 gallons of wastewater are
generated annually from wood preserving processes
using pentachlorophenol and creosote. About 90
percent of this wastewater Is treated by treatment
methods which generate a bottom sediment sludge.
The large quantity of waste generated increases the
opportunity for exposure if waste mismanagement occurs.
4) Treatment of wastewater in evaporation ponds or
lagoons could lead to the environmental release
of hazardous constituents and result in substantial
hazard via groundwater or surface water exposure
pathways. Evaporation of wastewater In ponds,
lagoons or by other treatment methods such as spray
Irrigation, if mismanaged, could also lead to the
release of hazardous constituents Into the atmosphere
and result in substantial hazard via an air exposure
pa thway.
5) The Agency has also been informed that incineration
is another (though less frequently used) disposal
method for these sludges. If Improperly managed,
incineration could result In the release of hazardous
vapors to the atmosphere, presenting a substantial
hazard via an air exposure pathway.
6) Off-site disposal in landfills is the most commonly
used disposal method for these sludges. This
presents the possibility of the toxic components
in the sludge migrating to nearby underground
drinking water sources if the landfill is improperly
designed or operated.
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7) Several incidents of mismanagement of wood preserving
plant wastes have occurred, demonstrating empirically
that these wastes are capable of causing substantial
harm if mismanaged.
II. Sources of the Wastes and Typical Disposal Practices
A. Industry Profile and Manufacturing Process
There are more than 415 wood preserving plants
operated by about 300 companies in the United States. The
plants are concentrated in two areas, the Southeast from east
Texas to Maryland, and along the North Pacific coast.
These areas correspond to the natural ranges of the southern
pine and Douglas fir-western red cedar, respectively (2).
Approximately 250 million cubic feet of wood are treated
each year (1), principally for railroad ties, utility poles,
and lumber for construction materials. It is estimated that
approximately 85 percent is treated with creosote or penta-
chlorophenol based preservatives as shown in Table 1 (4).
The total quantity of preservative consumed in 1975 during
these treatment cycles is shown in Table 2.
B . Process Description
At plants using creosote or pentachlorophenol-based
preservatives, wood products are treated to Increase their
resistance to natural decay, attack by insects, micro-organisms,
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TABLE 1
ESTIMATED PRODUCTION OF TREATED WOOD, 1978 (43)
Treated With
All
Products Preservatives^
Creosote
Solutions
Penta
CCA/ACA/FCAP*
Crosstles and
switchtiesc
Poles
Cross arms
Piling
Lumber and timbers
Fence posts
Other products*1
All products
106,085
64,179
1,685
12,090
105,305
20,028
18,113
327,485
103,138
18,237
41.0
9,993
10,779
4,584
7,815
154,587
449
41,905
1,615
1,154
21,209
10,983
2,681
79,996
2,498
4,038
29.1
943
73,317
4,461
7,616
92,903
*CCA: chromated copper arsenate, ACA: ammoniacal copper arsenate,
FCAP: fluor-chrome-arsenate phenol
a Volume reported for 1977 (AWAP), plus volume reported by
respondents to Assessment Team Survey, plus volume estimated for
nonrespondents.
b Creosote, Penta, and CCA/ACA/FCAP only.
c Includes landscape ties.
d Includes plywood.
Note: Components may not add to totals due to rounding.
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TABLE 2
QUANTITY OF PRESERVATIVES USED IN 1978. (44)
Preservative Quantity(million Ibs/year)
Creosote & petrolatum
Creosote and coal tar
Pentachlorophenol
(solid, solution)
Inorganic Arsenic salts
178.2
910
40.8
37.2
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or fire. Briefly, the treatment consists of debarking,
forming, drying, Impregnation of preservative, and storage
(3).
The two major wood preserving processes, producing large
quantities of wastewater and sediment sludge, are called steaming
and boultonlzlng.* Both of these processes are pressure processes
and differ mainly In the way the wood Is conditioned before or
during the application of the preservative. Figures la-le present
flow diagrams for the major wood preserving processes (Source:
Reference 19).
Steaming Is used principally on southern pines. In this
process, the stock Is normally steamed for 1 to 16 hours at
about 120°C to reduce the wood's moisture content and render
It more penetrable to preservatives. After steaming, the
preservative Is added to the same retort. Condensate removed
from the retort after steaming Is contaminated with entrained
oils, organic compounds, and wood carbohydrates.
In the Boulton process, used principally on Western
Douglas fir, the wood Is Immersed In the preservative, placed
under vacuum, and then heated In the retort at approximately
100°C. The vapor removed Is composed of water, oils, organic
compounds and carbohydrates from the wood. Contaminated
vapors from both the steaming and boultonlzlng processes are
*Vapor drying Is another wood preserving process, also
generating a wastewater and sludge of concern.
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WGOCtN
WOOD 001
PRESERVATIVE*
TO WORK TANK
WORK TANK
1
TREATING CYLINDER
STEAM
PRESERVATIVES
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AND RAM WATER .
RECOVERED OILt
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SEPARATOR
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COCLMO
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AIR AND
VAPORS
VACUUM
PUMP
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Figure la OPEN STEAMING PROCESS WOOD TREATING PLANT
-------
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MODIFIED STEAMING PROCESS WOOD TREATING PLANT
-------
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WpOOOUT
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-------
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Figure le
VAPOR CONDITIONING PROCESS WOOD TREATING PLANT
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condensed and transported to an oil/water separator to reclaim
any free oils and preserving chemicals before treatment and/or
disposal of the wastewater.(H»^)
C. Generation, Composition, and Management of Listed Waste
Streams (17.18)
1. Industry Generation of Waste
Based on the quantity of wood treated with
creosote or pentachlorophenol preservatives in 1975, and
assuming that about one gallon of wastewater is generated
per cubic foot of wood treated, over 200 million gallons of
wastewater will be generated annually.
Almost all of this wastewater is treated by treatment
methods that generate a bottom sediment sludge. Over 300,000
gallons per day of wastewater is discharged to POTW's. The
listing covers both of these Instances.*
Table 3 shows estimates of the amounts of wastewater
treatment sludges generated by creosote and pentachlorophenol
preserving processes, and the amount of certain of the hazardous
constituents contained in the wastes.
*The listing does not include wastewater discharged from
a point source regulated under §402 of CWA. This listing also
does not include any wastewater which is mixed with domestic
sewage and that passes through a sewer system before it
reaches a publicly owned treatment works (POTW) . "Domestic
Sewage" means untreated sanitary wastes that pass through a
sewer system, (See §261.4(a)(1)(i) and (li)).
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TABLE 3. POTENTIALLY HAZARDOUS SOLID WASTES FROM THE
WOOD PRESERVING INDUSTRY (8)*
(Source; American Wood Preserver's Association (1979))
Total Process Total Potentially
Solid Waste Hazardous Constituents
metric tons/yr metric tons/yr
Creosote-oil emulsion Creosote
230-930 1.1-4.6
Penta-oil emulsion Pentachlorophenol
600* 3.0
Note: Although these wastes are listed in the table in
terms of amounts generated per year, many of the wastes are
generated on a periodic basis which often can be as long as
five years (8). Thus, the sludges may be allowed to sit at
the bottom of wastewater treatment ponds for five years at a
time. Sometimes the bottom sediment sludges from the biological
treatment of wood preserving wastewater are never removed.
^Estimated maximum amount.
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2. Composition
The organic components of the wastewater and bottom
sediment sludges from the wood preserving Industry results from
the different constituents In the different formulations of pent-
chlorophenol and creosote and decomposition products of the
constituents of the preservatives.
Table 4 gives typical compositions of commercial grade
pentachlorophenol.(35) The amount of chlorinated dlbenzo-
p-dloxlns and furans varies with each industrial batch, even
when produced by the same manufacturer. In addition to the
constituents present in commercial pentachlorophenol, other
phenolic compounds have been found In wood preserving sludges
and wastewater, such as unsubstltuted phenol (Table 6); 2,4-
dlmethylphenol; p-chloro-m-cresol; 2-chloropheno1; 2,4-
dichlorophenol; and 2,4-dinitrophenol (Table 7). These
additional phenolic compounds may be the result of decomposition
of the commercial pentachlorophenol.
The consitutents of creosote are highly variable,
depending on the source of the coal, the design and attendant
operating conditions of the coke ovens and still, and the
blending of various tar distillate fract Ions.(37) Several
hundred constituents have been identified, with between 11-22
percent In concentrations gr'eater than 1Z.C36) (Table 5).
Benzota]pyrene is present at 200 ppm.(38) (The presence of
benzo[a]pyrene as a constituent in creosote is further
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TABLE 4
COMPOSITION OF SOME COMMERCIAL PENTACHLOROPHENOL SAMPLES.(35)
Dowlcide EC-7 Dowiclde 7 Monsanto
Pentachlorophenol
Tetrachlorophenol
Trichlorophenol
Higher Chlor opheno Is
Caustic Insolubles (max)
90.4 + 1.0% 85-90% 84.6%
10.4 + 0.2% 4-8% 3%
< 0.1% < 0.1%
2-6%
1
2,3,7,8-Tetrachlorodlbenzo-p < 0.05 ppm < 0.1 ppm
dioxins
Pentachlorodlbenzo-p-dioxins < 0.1
Hexachlorodlbenzo-p-dioxins 1.0 + 0.1 ppm 9.27 ppm 8 (5 p
Heptachlorodlbenzo-p-dloxlns 6.5 +_ 1.0 ppm 520 ppm
Octachlorodlbenzo-p-dloxlns 15.0 + 3.0 ppm 575-2510 ppm 1380 ppm
Tetrachlorodibenzofurans < 4 ppm
Pentachlorodibenzofurans 40 ppm
Hexachlorodlbenzofurans 3.4 +0.4 ppm Detected 90 ppm
Heptachlorodibenzofurans 1.8 + 0.3 ppm Detected 400 ppm
Octachlorodibenzofur an < 1 ppm Detected 260 ppm
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TABLE 5
CONSTITUENTS OF CREOSOTE
MAJOR COMPONENTS REPORTED PRESENT IN WHOLE CREOSOTE (REF.36)
Naphthalene
2-Methy1naphthalene
1-Methylnaphthalene
Biphenyl
Dimethylnaphthalenes
Acenaphthene
Dibenzofuran
Fluorene
9 ,10-Dihydroanthr acene
Methylfluorene
Phenanthrene
Anthracene
Acr idine
Carbazol
Methylphenanthrenes
2-Phenylnaphthalene
Me thyIanthr acenea
Pyrene
Benzofluorenes
Chrysene
9,10-Benzophenanthrene
HAZARDOUS COMPONENTS PRESENT IN SMALL QUANTITIES (less than 1%)
IN CREOSOTE (Ref. 40, 41, 42)
Benzo[a]pyrene
Benz[a]anthracene
Benzo[b]fluoranthene
Dibenz[a,h]anthracene
Indeno[l,2,3-cd]pyrene
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confirmed by the detection of elevated levels of benzo[a]
pyrene is mussles growing near creosote treated timber pilings
(about 50 ug/kg; 20 times background).O9,40)j other haz-
ardous components of creosote in concentrations less than
1% are included in Table 5 based on their detection in edible
meat of lobsters maintained in commercial tidal compounds
constructed of creosote treated timber(*°»*1), their detection
in other coal tar fractions,(*2) and In part their presence
in some wood preserving sludges where creosote is used (Table
8). The constituents normally occuring in coal tar are
expected to be In the wastes of this industry, since creosote-
coal tar solutions are used more frequently than creosote-
petroleum solutions-(Table 2).
Table 6 lists of some of the typical organic compounds
found in wood treating plant wastewaters.* The absence in
this Table of certain components of the original wood preserv-
ative chemicals, particularly some of the different phenolic
compounds, probably indicates that an analysis for their
presence was not performed rather than an actual absence of
the component.
*Approximately 125 wood preserving plants use both
organic and inorganic preservatives. Although the systems
are kept separate, cross contamination of chemicals may
occur through exchange of dollies used to transport the wood
and drippage from the Inorganic into the organic operation.
Thus, wastewater from organic wood treatment processes often
contains inorganic materials.
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TABLE 6. ORGANIC COMPOUNDS FOUND IN WOOD PRESERVING
PLANT WASTEWATER.(IS)*
Analysis of toxic phenolic compounds from 20 steam processing
plant s.
Concentration (mg/1)
Average High Low
phenol
pentachlorophenol
total oil and grease
158.0 501.3 1,0
55.0 306.0 l.Z
793.8 1,902. 11.0
Analysis of toxic phenolic compounds from 5 Boulton conditioning
plants.
phenol
pentachlorophenol
total oil and grease
491.4
10.9
321.5
1272.0
27.0
1357.
0.9
0.01
12.3
Analysis of toxic polynuclear aromatic hydrocarbons from 9
steam conditioning plants.
fluoranthene
benzo[b]fluoranthene
benzo[a]pyrene
indeno [1, 2,3-cd]pyrene
benz[a]anthracene
dibenz[a,h]anthracene
naphthalene
acenaphtylene
chr ysene
total PAH's
4.1
0.69
1.12
2.0
1.53
0.43
10.5
0.79
0.48
39.89
35.0
1.68
2.70
5.50
7.70
0.43
45.0
1.21
4.70
232.86
0.63
0.03
0.007
0.006
0.07
—
0.38
0.006
0.07
7.90
Analysis of toxic polynuclear aromatic hydrocarbons from one
Boulton conditioning plant using creosote
fluoranthene
benzo[b]fluoranthene
benzo[a]pyrene
indenofl,2,3-cd]pyrene
benz[a]anthracene
dibenzfa,h]anthracene
naphthalene
acenaphthylene
chr ysene
total PAH's
0.282
0.034
3.14
2.06
0.018
8.167
*0ther relevant data for comparing these concentrations such
as total dally wastewater flow and daily production volume
may be found in the cited reference.
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Table 7 lists toxic organic compounds which have been
found in the various wood preserving wastewater treatment
sludges, such as the bottom of primary oil/water separator
treatment sludges, flocculation sediment sludges, and biological
treatment sludges. (*• 7 »26) These contain the constituents of
the wood preservatives and decomposition products. The
analyses of the wood treating plant sludges did not reveal
every constituent listed la Table 6 In every sludge. However,
pentachlorophenol and polynuclear aromatic hydrocarbons were
common to all sludges tested.
Many wood processing plants, such as the two listed
below, may use both creosote and pentachlorophenol based
processes and thus treat the wastewater generated by these
processes in a combined treatment system. Thus, sludge
samples from one plant may contain both creosote compounds
and phenolic compounds.(6 )
According to data taken from California State hazardous
waste manifests(? ), one bottom sediment sludge from a wood
preserving plant was found to contain 5-20% pentachlorophenol.
3. Disposal and Waste Treatment Practices
These plants typically send their wastewater to
a series of treatment processes, which often generate bottom
sediment sludges. The wastewater then is either completely
retained and disposed of on the facility site (i.e., by
evaporation, spray Irrigation, etc.) or discharged to publicly
owned treatment works, or navigable waterways. The wastewater
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TABLE 7. TOXIC ORGANIC COMPOUNDS FOUND IN VARIOUS WOOD PRESERVING
PLANT WASTEWATER TREATMENT SLUDGES (17,26)
Polynuclear Aromatic Hydrocarbons:
Fluoranthene
Benzo(b)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Benzo(a)anthracene
Dlbenzo(a,h)anthracene
Acenaphthene
Naphthalene
Chrysene
Phenolics
Phenol 2,4-Dlchloropheno1
2-Chlorophenol 2,4-Dlnltrophenol
Pentachlorophenol p-Chloro-m-cresol
2,A-dlraethylphenol 2,4,6-TrIchlorophenc
-20-
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is first generated at primary oil/water separation. The
wastewater treatment sludges are generated first at oil/water
primary separation and la subsequent treatment steps.
The initial wastewater treatment at most facilities is a
primary oil-water separation, where much of the wood treatment
chemicals are recovered and recycled to the preservative
work tank. Variations include the addition of secondary
oil water separators, accumulation or surge tanks prior to
the oil water separators, or dehydrators for the oil recovered
from the separators. These wastewater treatment processes
each generate sludges which are periodically removed, containing
the components of creosote and/or pentachlorophenol. An
analysis of the sludge from the bottom of a pentachlorophenol
oil-water separation pit showed concentrations of 1.84 ppm
pentachlorophenol; 1,650 ppm 2,4-dichlorophenol; 5,090 ppm
fluoranthene; A3,640 ppm naphthalene; 604 ppm pyrene; 8,410
ppm an thr acene/phenanthr ene; and 1,690 ppm p-chloro-m-cr esol .*>• ^6 *
Flocculation or adsorption of the wood preserving oils
by the addition of clays, resins, alum, lime, or polymers is
sometimes used as a secondary wastewater treatment process
after primary oil-water separation. This process also generates
bottom sediment sludges with a high oil and pentachlorophenol
content. An analysis of the sludge from treating pentachloro-
*These analytical values should be used only to indicate ranges of
concentrations. The Agency has not yet established standard pro-
tocols for these analyses
-21-
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phenol wastewater with polymeric flocculants and clay after
two oil separation steps showed concentrations of 8.2 ppm
2,4-dimethylphenol; 1,400 ppm fluoranthene; 3,000 ppm acenaph-
thene; 1,200 ppm naphthalene; 52 ppm pyrene; 45 ppm chrysene;
84 ppm benzo[ghi]perylene; 1,400 ppm fluorene; 52 ppm dibenz[ah]
anthracene; and 3,200 ppm phenanthrene .*(26).
Biological treatment of pre-processed wastewaters is
used at some facilities. Alternatively, the pretreated
wastewaters are sometimes discharged to publicly owned treat-
ment works (POTWs) which use some form of biological treatment
process.
Two plants using biological aerated lagoons as one step
in their wastewater treatment process were found to have
compounds from both creosote and pentachlorophenol as con-
stituents of their sludges (Table 8). The wastewater treatment
system for the first plant (Plant 10) generally consists of:
(1) chemical flocculation with Bentonite clay and decantatlon,
leaving a clay sludge, (2) nutrient addition and aeration of
the clarified wastewater, generating a biological sludge,
(3) spray pond evaporation, and (4) total retention of the
wastewater by evaporation from the retention pond. The
wastewater treatment system for the second plant (Plant 11)
consists of: (1) settling in a basin where collected oil Is
recycled, (2) storage for 40 days in a pond and recycling of
the water to the plant, (3) lagoon aeration with 60 days
detention time, (4) spray irrigation, and (5) runoff storage.
*These analytical values should be used only to indicate ranges of
concentrations. The Agency has not yet established standards
protocols for these analyses.
-------
TABLE 8. ORGANIC COMPOUNDS FOUND IN SLUDGES FROM AERATED
LAGOON SECTIONS OF WASTEWATER TREATMENT FACILITIES
(Ref. 6)
Plant 10
Bottom Sediment Dry Weight (ug/kg)(6)
Polynuclear Aromatic Hydrocarbons Aerated Lagoon
Benz[a]anthracene*
Chr ysetie*
Phenolics
Phenol
2,4-dimethylphenol
2-chlorophenol
2,4,6-tr ichlorophenol
Pentachlorophenol
3,700
4,500
9,030
4,398
396,000
No data
302,000
Final Pond
149
2,060
16,000
3,418
1,200
25,000
58,000
Plant 11
Polynuclear Aromatics
Benz[a]anthracene*
Benzo[a]pyrene*
Chrysene*
Bottom Sediment Dry Weight (ug/kg)(&)
Aerated Lagoon
1,250
5,980
9,280
Phenolics
Phenol
2-chlorophenol
Pentachlorophenol
4,500
300
4,800
*These were the only polynuclear aromatic hydrocarbons tested
for. These components are known to be present In creosote
in relatively small concentrations, so that a ouch higher
total polynuclear aromatic hydrocarbon concentration could
be inferred. In any case, these concentrations of these con-
stituents are significant in light of their careinogenicity.
See Table 10, showing carcinogenic risk from exposure to
these components at concentrations orders of magnitude lower
than those observed at Plant 11.
-------
After biological treatment, treatment by Irrigation may
be used. This process typically consists of (1) settling,
(2) storage, (3) aerated treatment, (4) spray Irrigation,
and (5) runoff storage as described for Plant 11 above.
The wastewater flow at this particular plant equipped with
this type of treatment system averaged approximately 50,000
gallons a day.(6)
It has been argued that many of the hazardous constituents
In wastewater are biodegradable and therefore would not be
found in wastewater treatment sludges resulting from biological
treatment. This argument first of all does not apply when
sludges are generated by non-biological treatment. Information
available to the Agency indicates that a large percentage of
wood treating plants practice either flocculation and/or sand
filtration as well as primary oil/water separation treatment
steps prior to biological treatment.(19) In any case, the Agency
continues to believe that most biological treatment sludges still
will contain significant concentrations of toxic phenols and
in some instances significant concentrations of the constituents
of creosote, since the mechanism of reduction of pentachlorophenol
and high molecular weight toxic pollutants is thought to be
that of adsorption upon the blomass rather than complete
biological degradation.(L^)*
*Some comments were received stating that a hazardous
waste designation would discourage biological treatment of
wastewater. Where biological treatment, in fact, proves
successful in adequately degrading hazardous constituents,
the delisting mechanism provides generators a means of
avoiding hazardous waste status for their treatment sludges.
-24-
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Studies on biodegradability Indicate that under specific
idealized conditions, pentachlorophenol is biodegradable
(9,10,11). Pentachlorophenol has been shown to be degradable
when composted in permeable soil at pentachlorophenol concen-
trations of 200 ppm or less. Under these conditions, at
least 98% of the PGP can be destroyed in about 200 days (12).
However, biodegradation is feasible only if the microorganisms
have been acclimated to pentachlorophenol and the pentachloro-
phenol concentration Is carefully controlled (13). Another
study found that PGP persisted in warm moist soils for a
period of 12 months (22). The sludge, therefore, would need
to be combined with non-contaminated permeable soil in a ratio
of 1:20 in order to ensure that the reported level of degradation
at the disposal site Is possible.
The viability for activated sludge to be used as a
treatment for wastewater from the wood preserving industry
containing pentachlorophenol indeed was questioned by one
study.(33) initially, the acclimated blomass would
remove large quantities of pentachlorophenol, resulting in
effluent concentrations of less than 1.0 mg/liter. However,
in all cases, a point was reached where additional pentachloro-
phenol was not removed. Decreasing the pentachlorophenol
concentrations in the influent to the bioreactor feed tended
only to postpone when the sludge became saturated. Therefore,
biodegradation of pentachlorophenol under the conditions of
this system did not appear to be occurlng.
-25-
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Furthermore, Table 8 gives sludge sample data taken at two
plants which treated wastewater with biological processes and
shows that phenols and polynculear aromatic hydrocarbons are
not completing blodegraded.
Additionally, a contractor/hauler that disposes of an
unspecified bottom sediment sludge for a wood treatment
plant has provided an analysis of the waste for EPA (3).
The analysis is as follows:
Component Concentration, mg/l(6'
Total phenols 5,043
pentachlorophenol 34
Dlnitrophenol 24
Creosote 10,000
Evaporation with or without the addition of heat is
another process used to treat wastewatera and which generates
bottom sediment sludges. Incineration of wastewaters is
another less frequently practiced treatment process for the
wastewaters. Discharge to the air of decomposition products
of pentachlorophenol, such as chlorinated dioxins and dibenzo-
furans, (23,24,25) as well as the volatilized organic consti-
tuents pentachlorophenol and creosote, is possible under
uncontrolled situations.
Ill. Discussion of Basis for Listing
A. Hazardous Properties of the Waste
As discussed earlier, the most commonly used wood
preservatives are creosote and pentachlorophenol. The principal
toxic pollutants in wastewater from plants that use these
preservatives are phenolic compounds, and polynuclear aromatic
-26-
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hydrocarbon components of creosote. Table 10 summarizes
the concentrations of these substances in ambient water
which have been found toxic to aquatic life or necessary to
protect human health by the Agency's Office of Water
Regulation and Standards.C3*) Comparison of these ambient water
criteria with the concentrations of the pollutants found in the
wood preserving industry's wastewater and wastewater treatment
sludges (Tables 6-9) clearly indicates the potential for
environmental damage or harm to human health if these wastes
are mismanaged, since the observed concentrations are many
orders of magnitude above ambient water quality criteria
levels for protection of potential adverse effects on human
health.
The World Health Organization 1970 Standards for Drinking
Water recommends a concentration of PAHs not to exceed 0.2
ug/1. This value Is greater than the ambient water quality
criteria given in Table 10, but is substantially less than
.the concentrations found in plant effluents (Table 6).
EPA's Office of Water and Waste Management, Effluent
Guidelines Division has set a maximum limit of 100 mg/1 oil
and grease for point source effluents from the wood preserving
industry, based on considerations of technology and economic
feasibility. (See 40 CFR §§429.74 and 429.84.) This 100 mg/1
oil and grease level has been found to correspond to an
approximate 1.0 mg/1 polynuclear aromatic hydrocarbon effluent
concentration and an approximate 15 mg/1 pentachlorophenol
-27-
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TABLE 10
AMBIENT WATER QUALITY CRITERIA & OBSERVED TOXICITY LEVELS FOR
CONTAMINANTS PRESENT OR LIKELY TO BE PRESENT IN THESE WASTES**
(Ref. 34)
mg/1 = milligrams per liter =• ppm •
ug/1 = micrograma per liter « ppb »
ng/1 » nanograms per liter » ppt =»
parts per million
parts per billion
parts per trillion
Freshwater
Aqua tic
Life
Saltwater
Aq uatic
Life
Human
Health
POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs)
PAHs (total)
Acenaphthene
Fluor anthene
Isophorone
Naphthalene
Benzo[a]pyrene
Dibenz[a ,h]anthracene
520 ug/1
(acute)
3980 ug/1
(acute
117,000 ug/1
(acute)
620 ug/1
300 ug/1
(acute)
500 ug/1
(acute)
16 ug/1
(acute)
12,900 ug/1
(acute)
2,350 ug/1
(acute)
2.8 ng/1*
(cancer risk
of 10-6)
.02 mg/1
(taste and odor
only)
42 ug/1
5.2 mg/1
insufficien t
data
2.8 ng/1*
(cancer risk
of 10'6)
1.3 ng/1*
*Indicates recommended criteria level to protect human health
or aquatic organisms. The cancer risk hazards given in this
table are for protection at the one 106 level. The Ambient
Water Quality Criteria give ranges for protection from cancer
risks from 0 corresponding to zero exposure level up to 10^.
**Lowest toxicity values are cited. No entry indicates insuffi-
cient data to establish a level for either acute or chronic
toxicity. See original documents for more information.
-------
PHENOLIC COMPOUNDS
Phenol
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
2,3-Dichlorophenol
2,4-Dlchlorophenol
2,5-Dichlorophenol
2,6-Dichlorophenol
3,4-Dichlorophenol
2,4,5-Tr ichlorophenol
Freshwater
Aquatic
Life
Saltwater
Aqua tic
Life
2,560 ug/1 5,800 ug/1
(acute & chronic)(acute)
4,380 ug/1
(acute)
2,000 ug/1
(flavor, fish)
29,700 ug/1
(acute)
365 ug/1
(chronic)
0.4 ug/1
(flavor, fish)
(cancer risk
of 10-6)
Human
Health
2,4,6-Trichlorophenol 970 ug/1
3.5 mg/1*
(toxicity)
0.3 mg/1 *
(taste & odor)
0/1 ug/1*
(taste & odor)
0.1 ug/1*
(taste and odor
0.1 ug/1*
(taste & OQ-.)
0.4 ug/1*
(taste & odor)
3.09 mg/1*
(toxicity)
0.3 ug/1*
(taste & odor)
0.5 ug/1*
(taste & odor)
0.2 ug/1*
(taste & odor)
0.3 ug/1*
(taste & odor)
2,600 ug/1*
(toxicity)
L.O ug/1*
(taste & o )
1.2 ug/1*
(cancer risk of
-29-
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2,3,4,6-
Tetrachlorophenol
2,3,5,6-
Tetrachlorophenol
Freshwa ter
Aquatic
Life
Saltwater
Aquatic
Life
400 ug/1
(acute)
Human
Health
1.0 ug/1*
(taste & odor)
1.0 mg/1
(toxicity)
2-Methyl-4-chlorophenol --
3-Methly-4-chlorophenol 30 ug/1
(acute)
3-Methyl-6-chlorophenol --
Nitrophenols (general)
Dinitro-o-cresol
Dinitrophenol
150 ug/1
(acute)
4,850 ug/1
(acute)
30 ug/1*
(taste & odor)
1800 ug/1*
(taste & odor)
3000 ug/1*
(taste & odor)
20 ug/1*
(taste & odor)
13.4 ug/1*
(toxicity)
70 ug/1*
(toxicity)
-30-
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concentration. Actual risk assesment calculations for protecting
the health of specific population groups were not used to calcu-
late this standard. Even so, Table 5 shows that wastewater
from this industry after primary treatment by oil/water
separation contains higher concentrations of oil and grease
than allowed by this standard and also higher concentrations
of polynuclear aromatic hydrocarbons and phenollcs than if
the 100 mg/1 oil and grease criteria were met. Further, the
concentrations of polynuclear aromatic hydrocarbons and
phenollcs that correspond to 100 mg/1 oil and grease are
much higher than the ambient water quality criteria given in
Table 10.
Phenollcs are toxic and in some cases bioaccumulatlve
and carcinogenic. Phenol, pentachlorophenol, 2,3,4,6-tetra-
chlorophenol, 2 , 4,6-trichlorophenol, and 2,4-dichlorophenol
are given highly toxic ratings in N. Irving Sax's Dangerous
Properties of Industrial Materials. 2,4,6-Trichlorophenol
has been identified by the Agency as a compound exhibiting
substantial evidence of being carcinogenic. In addition,
2,4,6-trIchorophenol has been reported to be rautagenic,
and pentachlorophenol has shown mutagenlc and teratogenic
ef fects .
Many polynuclear aromatic hydrocarbons are known to be
toxic, niutagenic, teratogenic and carcinogenic. Benz(a)-
anthracene and chrysene have been identified by the Agency
as compounds exhibiting substantial evidence of being
-31-
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carcinogenic. Additional information and specific references
on the adverse effects of the following substances can be
found in Appendix A: These substances are also designated as
priority pollutants under Section 307(a) of the Clean Water Act.
Pentachlorophenol Creosote
Phenol Chrysene
2-Chlorophenol Naphthalene
p-Chloro-m-cresol Fluoranthene
2 ,4-Dimethylphenol Benzo[b]fluoranthene
2,4-Dinltrophenol Benzo['a] pyrene
Trichlorophenols Indeno[1,2,3-cd]pyrene
Tetrachlorophenols Benz[a]anthracene
2,4-Dinitrophenol Dibenz[a]anthracene
Acenaphthalene
B . Migratory Potential of Hazardous Constituents
In light of the extreme danger posed by these waste
constituents, the Agency would require some assurance that
these waste constituents will not migrate and persist to warrant
a decision not to list these waste streams. No such assurance
appears readily available.
Many of these waste constituents, in fact, have proven
capable of migration, mobility and persistence. Chrysene,
naphthalene, benz(a)anthracene, and other polynuclear aromatic
hydrocarbons have been detected in rivers, demonstrating
ability to persist.(20) The migratory potential and
persistence of phenol, trichlorophenol and dichlorophenol
is confirmed by the fact that these constituents have been
identified in samples taken at the Love Canal site in Niagara,
Falls, New York.C28) Dichlorophenol has also been found in
-32-
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school and basement air at Love Canal, demonstrating ability
to migrate and persist in the air (See "Love Canal, Public
Health Bomb, a Special Report to the Governor and Legislature",
New York State Department of Health,1978.)
The American Wood Preservers Association examined the
leaching In soil of pentachlorophenol at concentrations that
would approximate conditions' of treated wood in contact with
the ground.(*»12) Soils containing 100 and 300 ppm penta-
chlorophenol resulted in a leachate containing less than
0.01 percent of the original concentration of the pentachloro-
phenol In the soil. However, the concentration levels in these
studies were less than those which have been found in some
wood preserving plant wastes. Additionally, the binding
ability of soil with phenols may be much greater than that
of biological treatment or other residue sludges. Thus, the
predictive ability of an experiment showing a small amount of
leaching for pentachlorophenol contaminated soils may not be
applicable to treatment plant sludges. That pentachlorophenol
will leach and migrate in actual mismanagement cases is in
any event demonstrated by the damage Incidents described
below.
Creosote compounds have also demonstrated the ability
for mobility and persistence. An actual damage incident of
surface and groundwater contamination due to improper manage-
ment of wood preserving chemicals, including creosote and
pentachlorophenol, confirms the migratory potential, mobility
-T T-
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and persistence of the waste constituents in these wastes.
In the 1950's, waste chemicals including creosote and other
types of wood preserving chemicals were injected into wells
in Delaware County, Pennsylvania. The injected wastes migrated
into groundwater, infiltrated a storm drain sewer, and discharged
Into a small stream, causing biological damage. Although
injection of the wastes into the wells ceased in the 1950's,
contamination was first observed in 1961.(21) Thus, the
waste constituents proved capable of migration via both
ground and surface waters, and were able to persist and
cause damage for long periods of time.
Two other mismanagement incidents demonstrate both the
potential for migration and persistence of wood preserving
plant wastes. In one incident, creosote was found to migrate
from wood preserving treatment into the groundwater supply
of a neighboring community (29). 'A very recent incident
(September 14, 1980) of groundwater contamination by penta-
chlorophenol from a wood preserving plant occurred in Jacksonville,
Florida. This sludge dump on the company property was allegedly
responsible for contamination levels of pentachlorophenol in
adjacent residential property groundwater at levels as high
as 0.50 ppm. Drinking water was so far not found to be
contaminated at an experimental detection limit of 12 ppm
pentachlorophenol, but nltrophenol and 2-chloropheno1 were
detected though not quantified. Soil samples at one location
adjacent to the facility contained up to 24 ppra pentachloro-
phenol. (3°) These incidents demonstrate empirically that
-34-
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these sludges, if mismanaged, may cause substantial harm to
humans or other environmental receptors.
The mobility and persistence of polynuclear aromatic
hydrocarbons also is shown by a number of damage Incidents.
Although these incidents do not involve the wood preserving
industry, they do show that PAHs may migrate from creosote-
containing wastes, and prove persistent upon release.
A company in Minnesota handled, stored, treated and
disposed of coal tar, creosote oil and other products for
over 50 years in an 80-acre site. While the operation
supposedly included discharge of waste products into a ponding
area, there were apparently numberous cases of spills, leaks,
pipeline breaks, and burial of wastes over the years. As a
result, chemicals associated with the company's process,
among these polynuclear aromatic hydrocarbons, migrated as
far as two miles. Five drinking water wells contaminated by
the toxic wastes were closed in 1978 and 1979 after operations
were stopped in 1971.(31)
A coke company in St. Paul used a 10'xl3' unlined basin
to dispose of oil, grease, various hydrocarbons and phenols.
Inspection at the time of sale of this property revealed
both soil and groundwater contamination with polynuclear
aromatic hydrocarbons as far as 1400 feet from the pit. (31)
Another reason for thinking that the hazardous constituents
in these wastes could prove sufficiently mobile to reach
groundwater is the large quantities of waste generated. We
believe the attenuative capacity of the environment surrounding
-35-
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these facilities could be reduced or used up, since large
quantities of bottom sediment sludge containing such large
concentrations of harmful constituents are disposed of In
landfills or sometimes allowed to accumulate at the bottom
of ponds and lagoons for long periods of time.
Finally, many of the constituents of concern are highly
bloaccumulatlve In environmental receptors. Benz(a)anthracene
and pentachlorophenol are extremely bloaccumulatlve with
octanol/water partition coefficients of 426,579 and 102,000,
respectively. Tetrachlorophenol, trIchlorophenol and dichlorophenol
are also highly bloaccumulatlve with octanol/water parltion
coefficients of 12,589, 4,169 and 1,380, respectively (App. B).*
Thus, the possibility that waste constituents could accumulate
in harmful concentrations if they reach a receptor further
supports a hazardous waste listing.
In light of the above damage Incidents demonstrating
migration and persistence and the extreme dangers to human
health and the environment posed by these constituents, a
failure to list this waste as hazardous is not justified.
C . Exposure Pathways
Mismanagement of these wastes, therefore, could lead
to environmental contamination since constituents are available
*An octanol/water coeflcient of 100 means that after an
aqueous solution of the tet compound is intimately mixed with
octanol and allowed to separate, there will be 100 times as
much of the test compound in the octanol than in the water.
Solubility of a substance in octanol models its solubility In
body fat tissue and Is, therefore, Indicative of bioaccumulation
po ten tial.
-36-
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for release and are likely to persist following release.
Thus, as previously noted, the wastewaters generated by wood
preserving operations are typically treated by evaporation,
combined biological and irrigation process, or incineration.
Bottom sediment sludge, generated by the treatment of the
wastewater, is typically disposed of in an off-site landfill,
after prolonged storage in holding lagoons. Incineration is
another possible disposal method.
The treatment of wastewater in ponds and/or lagoons, if
mismanaged, could lead to the release of hazardous constituents
by leaching from the resulting sludges, particularly in
light of these constituents' demonstrated propensity for
migration. These waste constituents could thus contaminate
groundwater if ponds or lagoons are unlined or lack adequate
leachate collection systems. Siting of wastewater treatment
facilites in areas with highly permeable soils could likewise
facilitate leachate migration. The bottom sediment sludges,
which form at the bottom of wastewater treatment ponds or
lagoons, could thus release harmful constituents and contaminate
groundwater. As previously noted, these sludges may be
allowed to sit at the bottom of ponds for five years or longer(8»
thus increasing the potential for release of harmful constituents
and for eventual groundwater contamination.
There is also a danger of migration into and contamination
of surface water if ponds and lagoons are improperly designed
or managed. Thus, inadequate flood control measures could
-------
result in washout or overflow of ponded wastes.
Disposal of bottom sediment sludge in off-site landfill,
if mismanaged, could also lead to release of hazardous constituents
The waste constituents of concern may migrate from improperly
designed or managed landfills and contaminate ground and
surface waters.
Transportation of these sludges off-site Increases the
likelihood of mismanagement and of their causing harm to
human health and the environment. Mismanagement of sludges
during transportation thus may result In hazard to human
and wildlife through direct exposure to harmful constituents.
Furthermore, absent proper management safeguards, the waste
might not reach the designated disposal destination at all.
The harmful constituents in the waste also present
a health hazard via an air inhalation pathway. Studies on
actual pentachlorophenol and creosote process wastewater
samples using a laboratory scale pan evaporator Indicated
that a large percentage of the constituents of pentachloro-
phenol and creosote were entrained in the vapors after several
hours of heating at temperatures up to 88°C.(^8)
A letter from the manager of Kopper's Co., Inc.
indicated that evaporation of pentachlorophenol effluent from
a pan evaporator or cooling tower or other spray device could
increase the amount of PCP discharged into the air and into
the general environment. No supporting analytical data was
provided (27). Thus, evaporation of wastewaters in poods,
lagoons, stripper/cooling towers, evaporation pans, and
-38-
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Incineration of wastewaters or sludges could lead to the
release of hazardous and volatile constituents into the air.
Disposal of sludges by incineration is another type
of management which could lead to substantial hazard. Improper
incineration might result In serious air pollution by the
release of toxic fumes occurring when incineration facilities
are operated in such a. way that combustion Is incomplete.
The formation of more toxic compounds such as polychlorinated
dibenzo-p-dioxins or dibenzo-furans during the combuslon of
pentachlorophenol mixtures is also possible.(23,24,25) These
conditions can, therefore, result in a significant opportunity
for exposure of humans, wildlife and vegetation, in the
vicinity of these operations, to potentially harmful substances
-39-
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References
1. Federal Register, Vol. 44, No. 212. Wednesday, October 31,
1979.
2. Development Document for Effluent Limitation. EPA: 440/l-74-023a.
3. Federal Register No. 202. Wednesday, October 18, 1978.
4. Ernst and Ernst. Wood Preservation Statistics. 1976. American
Wood Preservers Association.
5. Not used in text
6. Myers, L.H., et al. Indicatory Fate Study. EPA: 660/2-78-175.
August, 1979.
7. Handbook of Industrial Waste Compositions in California. 1978
8. Multimedia Pollution Assessment of the Wood Products Industries,
Edward C. Jordan Co., Inc., for Industrial Pollution Control
Division, EPA Contract No. 68-03-2605, November, 1979.
9. Hartford, W.H., "The Environmental Impact of Wood Preservation,"
American Wood Preservers Association, 1976. *4-Not—cite-4—Ln..-
docunent)—=> j> 2 ^
10. Young, A.L. et al, Fate of 2,3,7,8-tetrachlorodibenzop-dioxln
(TCDD) in the Environment: Summary and Decontamination
Recommendations, United States Air Force Academy, Colorado,
USAFA-TR-76-18, October, 1976. (-WuL cited lu J u c umTerrrtrfr- p- * *
11. Kirsch, E.J., and J.E. Etzel. Microbial Decomposition of
Pentachlorophenol, Journal of Water Pollution Control Federation,
Vol. 45, No. 2, February, 1973.
12. Arsenault, R.D., "Pentachlorophenol and Contained Chlorinated
Dibenzodloxlns In the Environment—A Study of Environmental Fate,
Stability, and Significance when Used in Wood Preservation."
American Wood Preservers Association, 1976.
13. Proceedings: Technology Transfer Seminar on the Timber Processing
Industry—March 10,11, 1977. Toronto, Ontario. EPS: 3-WP-78-1,
January, 1978.
14. Not used in text
15. Not used in text
16. Not used in text
17. Accurex Corporation, "Solid Waste from Wood Treating Processes
- a Hazardous Waste Background Document", December 20, 1979.
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18. Acurex Corporation, "Wood Treating Industry Multimedia Emission
Inventory", Draft Report, June, 1980. EPA Contract 68-02-2611.
19. Development Document for Effluent Limitations, Guidelines and
Standards for the Timber Products Processing Point Source
Category.. EPA 440/ l-79/023b.
20. Shakleford and Keith, "Frequency of organic compounds identified
in water," EPA-600/4-76-062 , Environmental Research Laboratory,
Athens, Ga., Dec. 1976.
21. U.S. EPA, Open File, unpublished data, Hazardous Site Control
Branch, WH-545, 401 M St. S.W., Washington, D.C. 20460.
Contact Hugh Kauffman 202/245-3051.
22. Harvey, W.A. and A.S. Crofts, "Toxicity of PCP and its sodium
salt in three yolo soils." Hilgardia 2±, 487 (1952).
23. Chem. Eng. News, Sept. 24, 1979, p. 27.
24. Rappe, C. and M. Stellan, "Formation of polychlorinated
dlbenzo-p-dioxlns (PCDDs) and dlbenzof urans (PCDFs) by burning
or heating chlorophenates " Chemosphere , No. 3, 269 (1978).
25. Jansson, B. and G. Sundstrom, "Formation of polychlorinated
dibenzo-p-dloxlns during combustion of chlorophenol formulations"
Sci. Total Environ. 10, 209-217 (1978).
26. Office of Water & Waste Management, Effluent Guidelines Division,
U.S. EPA, Unpublished data from ESE, Inc.) Plant sampling
reports. 1979-1980. NOTE; This data may be used to indicate
relative amounts of constituents only.
27. Arenault, R.D., Priva,te communication to D. Costle, Administrator,
U.S. EPA (February 13, 1980).
28. N.Y. State Department of Health, 1978. "Love Canal, public
health bomb, a special report to the governor and legislature"
(1978).
29. Mittelman, A. (1978) "Exposure analysis for creosote, coal
tar and coal tar neutral oils, Unpublished Data. Office of
Pesticides & Toxic Substances, U.S. EPA.
30. Private Communication, Vincent Cassidy, Water Pollution
Control, Department of Health, Welfare, and Biological Environ-
mental Services, City of Jacksonville, Florida, October 15,
1980.
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31a. U.S. EPA, "Damages and threats caused by hazardous material
sites", EPA/430/9-80/004, p. 20. Jan. 1980.
31b. U.S. EPA, Suit against Rellly Tar, St. Louis Park, Minn.,
Filed Sept. 4, 1980 In District Court, Minneapolis, Minn.
32. Not used in text
33. Industrial and Environmental Research Laboratory, Food and
Wood Products Branch. Contract No. 68-03-2605. "Evaluation
of the batch treatment of Industrial phenolic wastes."
Unpublished data. Progress Report No. 5(12) of E. C. Jordon
Co., 1979.
34. Office of Water Regulations & Standards, (1980) EPA. Ambient
Water Quality Criteria, FR (November ,1980).
*Note: No Federal REglster Citation is yet avaialble, but the
the Water Quality Criteria have been signed by the Administrator
at the time of preparation of this document.
35. Environmental Health Advisory Committee, Science Advisory
Board, U.S. EPA. Report of the Ad Hoc Study Group on Penta-
chlorophenol Contaminants. Draft Report, December, 1978.
36. Nestler, F.H.M. The characterization of wood preserving
creosote by physical and chemical methods of analysis.
Proposed USDA Forest Service Reseach Paper FPL 195. Preliminary
copy. 1974.
37. Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed.,
Vol. 6, p 302, 1973.
38. Guerin, M.R. Energy sources of polycylic aromatic hydrocarbons.
Oak Ridge National Laboratory. 1977.
39. 43 FR 48154, 1978.
40. Office of Solid Waste, U.S. EPA. Listing background documents
for Creosote, Health & Environmental Effects. Appendix A
May 19, 1980.
41. Dunn, B.P. & J Fee. Polycyclic aromatic hydrocarbon carcinogens
in commercial seafoods. J. Fish Res. Board Can. 36, 1469, 1979.
42. Office of Toxic Substances, U.S. EPA. Investigation of
selected potential environmental contaminants: Asphalt
and coal for pitch Final Report. EPA-560/2-77-005, 1978.
43. U.S. Dept. of Agriculture, State's EPA Preservative
Chemical Assessment Team. The biological and economic
assessment of pentachloropheno1, inorganic arsenic, and
creosote. Draft, May 15, 1980,.
44. American Wood Preservers Institute. Comments submitted
to the Office of Solid Waste, U.S. EPA, September 19, 1980.
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Response to Comments - Wood Preserving Industry
One commenter raised a number of questions with respect to
the hazardousness of waste K001 (Bottom sediment sludge
from the treatment of wastewaters from wood preserving
processes that use creosote and/or pentachlorophenol) and
the proposed listing (wastewater from wood preserving
processes that use creosote or pentachlorophenol).
1. The commenter first states that RCRA was not
intended to cover the treatment and disposal
activities of such facilities (i.e., at wood
preservers), but rather was designed to eliminate
abuses in waste treatment and disposal such as
at Love Canal. The commenter then argues that
these wastes are already adequately regulated
under the Clean Water Act (CWA) and that the
listing of wastewaters resulting from wood
preserving and the sludge generated when the
wastewater is treated will result in an ex-
pensive burden to the wood preserving industry
without any commensurate public benefit.
The Agency strongly disagrees with the
commenter's claims. The Resource Conservation
and Recovery Act was enacted by Congress to
control the improper management of hazardous
wastes. Although the Act has several objective*?
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(Including the promotion of resource recovery
and the proper management of non-hazardous
solid waste), Congress1 overriding concern
in enacting RCRA was to establish a national
system which would ensure the proper management
of hazardous waste. Nowhere in the Act or in the
legislative history does Congress make a distinction
between the types of treatment, storage or disposal
facilities the Act was meant to control. Tn fact,
the Act is quite clear as to the extent of coverage;
all wastes identified or listed by EPA as hazardous
will be subject to the Federal "cradle-to-grave"
management system for hazardous wastes. Therefore,
hazardous waste treatment, storage and disposal
facilities at wood preserving plants clearly may
be subject to the requirements of RCRA.
The Agency also disagrees with the commenter's
claim that these wastes, if managed in conformity
with current effluent regulations, present no
serious threat to human health and the environment.
First, the comment is not even relevant to the
listing of bottom sediment sludges. With regard to
the proposed listing of process wastewater, it
should be pointed out that under the CWA the Agency's
authority is limited to the actual point source
discharge into navigable waters, and not to the
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industrial wastewaters upstream from the point of
discharge. Environmental hazards posed by wastewaters
in treatment and holding facilities—primarily
groundwater contamination and the vaporization of
volatile organic materials — therefore is not controlled
under the CWA or other environmental statutes (See
the Part 261 preamble for more detailed discussion
of regulatory authority of wastewaters 45 FR at
3309 (May 19, 1980)).
Secondly, the fact that waste effluent is
treated prior to point source discharge does not
guarantee that human health and the environment is
protected adequately during the treatment process.
EPA believes that there is In fact a strong potential
for hazardous volatile emissions from certain
wastewater treatment processes using heat (i.e.,
pan evaporation or thermal ponds), which are currently
used by the wood preserving Industry. For example,
in a laboratory pan evaporator test*, pentachlorophenol
was detected and quantitatively recovered from
the vapor phase. In this test, large percentages
of the original pentachlorophenol in the wastewater
was recovered in the volatile emissions after 3 to
4 hours of heating at temperatures up to R8.2°C.
* Accurex Report, 1980,
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Emissions of naphthalene, acenaphthene, fluorene
and phenanthrene/anthracene —all hazardous
constituents—also were found from creosote waste-
water pan evaporator tests.* Additionally, in a
letter from the manager of Kopper's Co., Inc.**,
it was indicated that evaporation of pentachlorophenol
effluent from a pan evaporator, cooling tower, or
other spray device would increase the amount of
pentachlorophenol discharged into the air and
into the general environment.
Furthermore, incineration is also used by the
wood preserving industry as a method for managing
wastewater (although the Agency does not currently
know to what extent). Disposal by incineration,
if mismanaged, could result in the release of
toxic fumes when incineration facilities are operated
in such a way that combustion is incomplete (i.e.,
the formation of toxic compounds such as polychlor-
inated dibenzo-p-dioxins and dibenzofurans during
*The normal volatility of pentachlorophenol and of the
components of creosote and pentachlorophenol would be greatly
Increased by the common phenomenon of co-distillation, or
the additive vapor pressures of the components of the two
phase oil/water system, (see WJ Moore, Physical Chemistry,
or any similar undergraduate chemistry text.) Therefore,
the Agency cannot accept data on the volatilization temper-
ature of individual components of creosote and pentachloro-
phenol as predicting the volatilization temperature during
a steam dist1111satIon process, as exists during pan
evaporation.
**Arenault, R.D., Feb. 13, 1980, Private communication to
0. Costle, Administrator, U.S. EPA.
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the combustion of pentachlorophenol mixtures, as
well as volatilizing of pentachlorophenol and
creosote*). Therefore, the Agency strongly believes
that mismanagement of these wastewaters could lead
to a large amount of pentachlorophenol, creosote
components and other volatile organics volatilizing
into the atmosphere creating a substantial present
or potential hazard to human health and the environ-
ment. Assertion of RCRA jurisdiction provides a
logical means of dealing with this potential problem.
Finally, with respect to the commenter's concern
as to the economic Impact these regulations will have
on the wood preserving industry, the Agency has
reviewed carefully the legislative history of RCRA
and finds no indication that Congress Intended
adverse economic impact to be considered In imple-
menting Subtitle C of RCRA. Nor is there any
explicit requirement in the Act directing EPA to
consider costs in the development of its regulations,
as appear in other environmental statutes. Rather,
*Chemical Engineering News, Sept. 24, 1979, p. 27; Jansson,
B. and G. Sundstrom, 1978, "Formation of Polychlorinated
Dibenzo-p-dioxins During Combustion of Chlorophenol Formu-
lations", Science Total Environment, 10, 209-217; Rappe,
C. and M. Stellan, 1978 "Formation of Polychlorinated
Dibenzo-p-dioxins (PCDDs) and Dlbenzofurans (PCDFs) by
Burning or Heating Chloroohenates", Cheraosphere, No- 3,
p. 269.
-/i 7-
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Che Agency Is directed to protect human health and
the environment. This being the case, we do not
believe consideration of economic Impact to be
relevant in making hazardous waste listing deter-
minations .
2. The commenter then argued that the overwhelming
majority of data contained in the listing background
document on wood preserving pertains only to waste-
water treatment sludge, and not to wastewater Itself.
In fact, the commenter points out that only Table 5
on pg. 155 (May 19, i960 listing background document)
contains any indication that the hazardous constituents
may be present In wood treating wastewater, and even this
table fails to give any indication of the concentrations
of those substances. Therefore, the commenter argues that
this limited information in no way justifies the summary
conclusion that wood treating wastewater will contain
"significant" concentrations of either "toxic phenolic
compounds and volatile organic solvents such as benzene", or
"toxic polynuclear aromatic components of creosote
and volatile organic solvents such as tol«.«tie."
Thus, the commenter believes the Agency has failed
to establish any factual predicate for listing
wood preserving wastewater as hazardous.
The Agency agrees with the comraenter that the
listing background docunent on wood preserving
-48-
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contained only limited data on the composition and
concentrations of the toxic constituents present
in the wastewater. However, the Agency also believes
that sufficient Information was available in the
record (which the commenter has been known to
review) to support the listing of this waste stream.
For example, in the draft report, "Wood Treating
Industry Multimedia Emission Inventory", prepared
by the Aciurex Corp., June 1980 (cited by the
commenter), analysis of wastewaters from both the
steam and boulton conditioning processes shows
levels of phenolic compounds and polynuclear aromatic
compounds in a number of the samples which are many
times higher than the ambient water quality criteria
standards. The listing background document has
been amended by adding new data giving untreated
wastewater pollutant concentrations and the levels
of these pollutants In ambient water which may
adversely affect aquatic life and human health.
(Reference Nos. 18,19,34). We also have reopened
the comment period to receive additi-onal comment
on this new data. Additionally, if wood preserving
plant wastewater did not typically contain significant
levels of a number of toxic contaminants, then
effluent limitations would not have been placed on
this industry under the Clean Water Act.
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3. The commenter also objected to the Agency's con-
clusion that these wastes are uniform throughout
the country. The commenter believes that EPA
has failed to take Into account the various tech-
nologies and treatment methods used which would
lead to variations In the concentration of the
toxic constituents in the wastes. For example,
the commenter indicated that sludges generated by
evaporation wastewater disposal mechanisms such as
cooling towers will contain relatively high concen-
trations of pentachlorophenol and certain other
substances, whereas bottom sediment sludges from
biological wastewater treatment lagoons generally
contain markedly lower concentrations of pentachloro-
phenol. The same lack of uniformity also applies
to wastewater because of the variations In preserva-
tion technologies and wastewater treatment technologies
For example, the comraenter Indicated that the concen-
tration of pentachlorophenol in wastewater generated
in the steam conditioning process, for instance,
typically range from 1.2 mg/1 to 306 rag/1.* Therefore,
the commenter believes that due bo the wide range
in the concentrations of the hazardous constituents,
* Wood Treating Industry Multimedia Emission Inventory, Corp..
June 1980.
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wood preserving wastewaters and sludges do not
exhibit sufficient uniformity to be listed as
hazardous wastes.*
In responding to this comment, the Agency
emphasizes that listing of wood preserving waste-
water treatment sludges and wastewaters Is justified
even If these waste streams have widely varying
compositions, provided that wastes meeting this
description typically or frequently are hazardous.
More extensive review of the concentration levels
of the constituents of concern have been included
in the revised listing background document. These
are contrasted with the concentration levels found
to adversely affect aquatic organisms or human
health which have been set as ambient water quality
criteria levels found in Table 10 of the listing
background document (these ambient water quality
criteria have recently been signed by the Administrator
and are now awaiting Federal Register publication).
In all cases, the wastes contained several of the
*The commenter also included data in their comments taken from
EPA's Background Document for Effluent Limitations, Guidelines
and Standards for Timber Products Processing (October 1979)
which indicates the concentration of the toxic contaminants
in the wastewater to be low. However, this data represents
the concentration of these contaminants in the treated effluent
wastewater. The Agency believes that this data is inappro-
priate on which to make a decision on the hazardousness of
untreated wastewater.
-51-
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constituents of concern at concentration levels
many orders of magnitude greater than those in
Table 10. For example, compare the coranenter's
low range concentration of 1.2 mg/1 pentachloro-
phenol in untreated wastewater with the concentration
of 3.2 ug/1 (0.0032 mg/1) which has been found to
be acutely or chronically toxic to some freshwater
aquatic species. A hypothetical waste concentration
of 1 mg/1 polynuclear aromatic hydrocarbons should
be compared to the ambient water quality criteria
of 2.8 ng/1 (0.0000028 mg/1) necessary to prevent
a human cancer risk of one in 10*>.
Under certain conditions, a concentration of
a substance in a waste stream which is greater
than the ambient water quality criteria may not
present a threat to the environment or to human
health. An effluent containing 1 mg/1 polynuclear
aromatic hydrocarbons could be released to certain
remote navigable waters where no significant
exposure to humans or aquatic life results.
Alternatively, this same waste could potentially
be managed in such a way as to significantly
affect the quality of the environment and human
health by, for example, drinking water contam-
ination on adjacent residential property. We
believe the potential causing substantial hazard
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Is evident, and that hazardous waste regulation
therefore Is appropriate.
Therefore, the Agency will continue to list
these wastes as hazardous because of their extreme
toxicities. The Agency believes that the burden
should be on the generator to show that their
waste is non-hazardous through the de-listing
process (§§260.20 and 260.22).
4. The commenter then requested that if the Agency
decides to list the wastewater and sludge as
hazardous, a minimum cut-off level below which the
waste would be considered non-hazardous should be
set. The coomenter argued that this approach is
consistent with the factors for listing wastes as
hazardous which are enumerated in Section 261.11(a)(3)
and would provide for a more rational basis for
regulating the industry. Additionally, the conmenter
felt that setting a minimum concentration would pro-
vide owners and operators of covered facilities with
a fixed yardstick to determine whether they produce
hazardous wastes and provide significant incentives
to fall below the threshold level. As a suggestion,
the ceminenter recommended that the Agency adopt
the present effluent limitations of 100 mg/1 oil
and grease for wood treating wastewater since
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EPA's Effluent Guidelines Division has reported
that If oil and grease, as measured by Standard
Methods Is 100 rag/1 or less, then pentachloro-
phenol and total polynuclear aromatic hydrocarbon
concentrations are usually below 15 mg/1 and 1 mg/1,
respectively.
The Agency agrees with the commenter that
setting a minimum cut-off level below which the waste
would be considered non-hazardous is desirable;
however, the Agency has been unable to do this
since no chronic exposure threshold levels, ex-
cept for those toxic contaminants specified in the
National Interim Primary Drinking Water Standards
(NIPDWS), relating to drinking water have been
established. Additionally, the Agency is concerned
with the possibility of volatile emissions from
the wastes but again no chronic exposure thresh-
hold levels relating to air emission standards have
been established. Therefore, the Agency will not
set a minimum cut-off level for these wastes, but
rather will continue to evaluate the hazardous-
ness of these wastes after considering the factors
specified in § 261.11(a ) (3) .
We also note that effluent discharge levels
established by the Effluent Guidelines Division
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are not necessarily appropriate In evaluating
whether a waste is hazardous, since the effluent
limitation level is based on the pollutant reduction
achieved by Best Available Technology, which standard
not only is technology-based, but takes economic
considerations into account. The RCRA standard,
"may pose a substantial present or potential hazard
to human health or the environment when improperly
o
managed" ( § 1^04( 5) (B) ) , is much broader since it is
neither technology based, nor are economic consider-
rations relevant. We therefore do not accept the
argument that effluent guideline indicator limitation
levels should be used to gauge a waste's potential
to cause substantial harm if mismanaged.
5. The comiaenter also indicated that a number of
fundamental mistakes were made by the Agency in
characterizing these wastes. For example, both
benzene and toluene are cited as present in both
the wastewater and sludge. With respect to waste-
water, the comraenter indicates that these constituents
are likely to be found only in treating plants
which utilize vapor drying, and thus cannot be
considered as typical of the industry's wastes.
Further, the comraenter points out that these substances
are likely to be present in only minute quantities.
-55-
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Moreover, the listing background document contains
no evidence that either benzene or toluene are
ever present In wood treating wastewater sludge.
However, the commenter points out that both benzene
and toluene are listed as constituents of concern
for the wastewater treatment sludge.
In re-assessing the data, the Agency agrees
with the coramenter and has revised the listing
background document to reflect these changes.
Additionally, benzene and toluene have been removed
as constituents of concern for both the wastewater
and bottom sediment sludges.
6. The commenter also felt that data taken from the
California state hazardous waste manifests (I.e.,
concentration data of pentachlorophenol (5-20%)
in the bottom sediment sludge) was inaccurate and
refers not to the concentration of pentachlorophenol
in the sludge, but rather to the concentration of
pentachlorophenol in the original treatment solution
Therefore, the commenter requested that EPA re-
examine the accuracy of this data.
In contacting Dr. David Storm of the Depart-
ment of Health, State of California, the Agency
has confirmed the accuracy of this data. We thus
will continue to Include this data in the listing
background document to support the listing of the
bottom sediment sludge.
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7. The commenter Chen argued that the listing back-
ground document was Incorrect In Its statement that
bottom sediment sludge may accumulate In wastewater
treatment ponds for about five years prior to
removal (B.D., pp. 153 and 164). The commenter
pointed out that sludge from biologically active
lagoons may never be removed.
The Agency has amended the listing background
document to include this information.
8. The commenter then felt that EPA had severely
mischaracterlzed the biodegradablllty of penta-
chlorophenol, i.e., the commenter believes that
pentachlorophenol is "readily biodegradable."
The Agency disagrees with the commenter's
claim. In data submitted by the commenter, penta-
chlorophenol in concentrations of 200 ppm or less
did not degrade for 205 days. The Agency believes
that this period of time Is not insignificant, and
in fact, is concerned that pentachlorophenol will
volatilize into the atmosphere or migrate into
groundwater over this time period and will create
a substantial hazard to human health and the environ-
ment, especially due to the toxlcity of pentachloro-
phenol. The Agency also believes that because of
the higher concentrations of pentachlorophenol found
in some wood preserving sludges, the blodegradabllity
-57-
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of this compound would be less, as discussed in the
listing background document. Additionally, penta-
chlorophenol has been found to persist in warm moist
soils for a. period of 12 months,* and also has
been detected in human and animal tissues showing
that pentachlorophenol in its present ambient
environmental concentrations does not degrade
readily enough to prevent detectable levels in
human and animal tissues.**
The American Wood Preservers Institute itself
has acknowledged the difficulty of blodegradatlon
of sludge containing greater concentrations of
pentachlorophenol by the following statement:
"While the activated sludge in POTWs has
the capacity to blodegrade penta[-chloro-
phenol], sludge from evaporative disposal
mechanisms generally contain high concen-
trations of wood preserving materials and
consequently will not biodegrade unless
diluted."***
Finally, actual damage incidents have demon-
strated the ability of pentachlorophenol and
*Harvey, W.A. and A.S. Crafts, 1952, "Toxicity of
PCP and its Sodium Salt in Three Yolo Soils",
Hilgardia 21, 487.
**U.S. EPA, Office of Drinking Water, 1980, Penta-
chlorophenol Ambient Water Criteria Document.
***AWPI, Comments on Timber Products Processing Point
Source Category, Feb. 15, 1980.
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creosote to persist in the environment for several
years. These incidents show empirically that
pentachlorophenol can persist in concentrations
sufficient to cause substantial harm if mismanaged.
Therefore, the Agency does not consider penta-
chlorophenol "readily biodegradable" and will
continue to include pentachlorophenol as a consti-
tuent of concern in the listing of these wastes.
9. The commenter then argued that there Is no evidence
that tetrachlorodibenzoparadioxin (TCDD) is present
as a constituent of wood treating wastewater or
bottom sediment sludge as indicated in the listing
background document (footnote no. 2, pg. 155).
In re-evaluating the available data, the
Agency agrees with the commenter that current data
does not indicate the presence of tetrachlorodi-
benzoparadioxin In the listed wastes except where
these wastes are incinerated, since polychlorinated
dlbenzo-p-dioxins are formed during the incomplete
combustion of pentachlorophenol mixtures. There-
fore, the listing background document has been
modified to reflect this change. Other chlorinated
dioxins have been found in commercial pentachloro-
phenol (Table 4) and could therefore be expected
to be present in very small amounts In some wastes.
10. The comraenter also argu-ed that EPA's bibliography
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Is incomplete and often contains only one side of
the story on many issues relating to wood preserving.
For example, the coramenter pointed out that refer-
ences 15 and 16 are alarmist articles concerning
suspected diverse health effects from penta-treated
wood while the final report "Miami Epidemiologic
Studies Program,"* which found no correlation with
any regulatory used wood preserving chemical and
no connection whatsoever with wood treating wastes,
was not cited in the listing background document.
Additionally, the commenter pointed out that
several of the studies relied upon by EPA contain
inaccuracies which have not yet been corrected
although the Agency has been made aware of these
problems.
In preparing the listing background document,
the Agency has relied for the most part on data/
reports that were available to the Agency. There
may have been some studies the Agency was unaware
of which were not included in the listing background
document. The Agency agrees with the commenter
that as much data as possible should be considered
*Aldrich, T.E. and R.C. Duncan, "Investigation of
Citizen Reported Increase of Cancer Mortality and
Morbidity in Madison County, Kentucky in Relation
to Pentachlorophenol Exposure," October 24, 1979.
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In making a determination on the hazar<1ousness
of the waste. Therefore, the Agency has modified
the bibliography and will include other studies
that are pertinent, including the Miami Epldemiologic
Studies Program cited by the commenter.
The Agency would like, however, to make a few
comments with respect to this study. The commenter
characterized the study as having found no correlation
between exposure to regularly used wood preserving
chemicals (i.e., pentachlorophenol) and chronic
disease. While the Agency believes that this
study may not provide the basis for proof of a
correlation between exposure to wood treated with
pentachlorophenol and chronic disease,* the Agency
does believe It provides enough positive data to
be provocative. For example, the study concluded
that n[i]n any case, there would appear to be a
suggestion of the need for the study of a possible
risk between occupational exposure to pentachloro-
phenol treated materials and leukemia." Additionally,
in the November 16, 1979, clarification memorandum
Included in this study, the statement is made by
*Some of the reasons the Agency believes this study
does not provide the basis of proof include its
limited scope, the inadequate time span allowed
from exposure to observation of Tialignant disease,
the possibility that the pentachlorophenol used
at the tine of exposure contained greater amount
of contaminants, etc.
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the researchers "[t]hat six (five depot employees
and one community) cases from this category [chronic
lymphocytic and chronic myelocytic leukemia] would
have a common association to pentachlorophenol is
remarkable." Therefore, the Agency believes that
this study in no way conflicts with the listing
background document, or our decision to list penta-
chlorophenol as a waste constituent of concern:
With respect to the other studies the commenter
cites which contain inaccuracies, the Office of
Solid Waste has cited data only from those portions
of the report which are accurate. Therefore, the
Agency believes that it can continue to utilize
this data. It should be noted, however, that the
Agency expects to correct the Inaccuracies in these
reports as soon as possible.
11. The commenter also argued that the Agency has
failed to cite a single incident of mismanagement
of sludge from wood preserving wastewater treat-
ment or wood preserving wastewater which has
resulted in any sort of environmental problem.
The commenter pointed out that although this
criterion is listed as relevant to a hazardous
waste listing in §261.11(a)(3)(ix), the absence
of any such problems over the history of the wood
treating industry does not appear to have received
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any attention from EPA. Therefore, the commenter
believes that the Agency has failed to adequately
assess either the potential for ham from wood
preserving wastes or any actual harm which has
resulted from sludges from treatment of wood
preserving wastewater or the wastewater Itself.
The commenter mlspercelves the regulatory
mechanism adopted by the Agency for Identifying
hazardous waste through the listing process. The
factors listed In §261.11(a)(3) need not all be
present for a waste to be listed as hazardous.
While this factor Is relevant In making listing
determinations, a waste need not actually have
been aismanaged for It to be considered hazardous.
In fact, the definition of hazardous waste cited
in the Act supports this Interpretation, since a
a waste is hazardous if it "may pose a substantial
hazard. . .if improperly managed. . ." Congress
thus clearly indicated that damage did not have
to be demonstrated before designating a waste as
hazardous. If this interpretation was not taken
only those wastes which have caused environmental
insult could be designated as hazardous. The
entire rationale for enacting RCRA, to prevent the
mismanagement of hazardous waste and the resulting
potential for creating substantial harm to human
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health and the environment, would be undermined.
Therefore, the Agency believes that actual damage
does not have to be demonstrated, but only to show
that the waste, if improperly managed, may pose a
substantial hazard to human health and the environ-
ment which the Agency believes it has done for the
two wastes generated from the wood preserving
Industry.
In any case, we have considered whether these
wastes have been involved in damage incidents, and,
as shown In the listing background document, mismanage-
ment and actual damage have indeed occurred. We
believe these incidents sHow empirically that these
wastes are capable of posing substantial hazard If
mismanaged and thus warrant listing.
12. The commenter argued that the Office of Solid Waste
has failed to coordinate and take into account the
actions of other branches of EPA (i.e., Effluent
Guidelines Division and the Special Pesticide Review
Division, etc.) with respect to the wood treating
industry. More specifically, the commenter believes
that the hazardous waste regulations have the potential
to overlap or conflict with programs under the Clean
Air Act, the Clean Water Act (I.e., regulations to
be promulgated on effluent limitations applicable
to the wood treating Industry) and the Federal
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Insecticide, Fungicide and Rodenticide Act (i.e.,
the RPARs the Agency is currently considering
against the three wood preservative chemicals,
pentachlorophenol, creosote and the inorganic arsen-
icals). Therefore, the commenter believes that any
regulations promulgated under RCRA must be coor-
dinated with other parts of the Agency to avoid
confusion In the regulated community caused by
conflicting and environmental programs.
In preparing the listing background document
on the wood treating industry (May 2, 1980), the
Agency had discussed the various aspects of these
listings—wastewater and bottom sediment sludge
from the wood treating Industry—with other offices
within the Agency before promulgating these regula-
tions. Therefore, the Agency did attempt to avoid
any internal inconsistencies. However, to ensure
that any Inconsistencies that still remain are
either straightened out or fully explained, the
Office of Solid Waste has discussed these listings,
along with the comments received by the American
Wood Preservers Institute (AWPI), with both the
Effluent Guidelines Division and the Special Pesticide
Review Division. It should be noted, however,
that part of the confusion expressed by the commenter
may be due to their misunderstanding of the authorities
-65-
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and objectives on Che various pieces of environmental
legislation (e.g., see response to comments nos. 1
and 16 in this background document).
13. The coraraenter then argued that the quantities of
waste generated from wood preserving are not large,
and thus do not pose the degree of risk which would
warrant subjecting the industry to the burdensome
reporting, monitoring, recordkeeping, financial and
Insurance requirements under Parts 264 and 265.
Additionally, the commenter argued that wood
preservers do not actually accumulate significant
amounts of hazardous waste on-site since their
treatment processes renders the waste materials
Innocuous.
The Agency disagrees with the commenter.
Data presented in the listing background document
indicates that approximately 200 million gallons
of wastewater are generated annually of which approx-
imately 90 percent is treated to generate bottom
sediment sludge. Additionally, data provided by
the American Wood Preserver's Association Indicates
generation of total process solid wastes of between
830 to 1530 metric tons/yr, which in the Agency's
opinion is a significant quantity of waste, especially
in light of the extreme toxiclties of the constituents
of concern in these particular wastes. Therefore,
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the Agency believes that these wastes are generated
In sufficient quantity and do pose a risk substantial
enough to warrant control under the hazardous waste
management control system.
With respect to the coementer's claim that
the treatment processes render the waste materials
Innocuous, the Agency would like to make two points.
First, the Act requires that any process which
treats a hazardous waste requires a permit under
RCRA, thus is subject to control under Subtitle C
of RCRA. Second, the Agency believes that insuffi-
cient data has been submitted by the comraenter to
substantiate their claim that these treatment
processes render the waste materials (i.e., bottom
sediment sludge) innocuous. In this regard, we
note that the commenters supplied almost no waste
analytic data with their comments, even though the
wastes were originally proposed for listing In
August, 1979, and even though the July 1980 comment
period for comment to the May Interim final listing
was effectively extended to allow this industry
time to gather and present such data. (Industry
comments have, however, been helpful and informative
In other respects.) Third, information available
to the Agency indicates that currently practiced
wastewater treatment processes (e.g., cooling/
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stripping towers) generate sludges which in the
Agency's opinion are not Innocuous after consideration
of the concentrations of wood preserving oil residues.
Indeed, even biological treatment sludges from final
retention ponds appear to contain relatively high
concentrations of particular waste constituents
(see Table 7 to the listing background document).
14. Another comraenter argued that three chemicals
mentioned In the listing background document
(benz[a]anthracene, benzo[b]fluoranthene, and
benzo(a)pyrene) are not commonly constituents of
"modern" creosote. The comraenter further argued
that reported adverse effects may have only been
caused by certain creosote oils, e.g., those
containing benzo[a]pyrene.
The Agency accepts the evaluation conducted by
the Carcinogen Assessment Group that creosote Itself
has substantial evidence of carclnogenlclty, and
that this propensity derives In part from consti-
tuents other than benzo[a]pyrene . Another component
of creosote, chrysene, Is present In larger quanti-
ties (and was listed by the commenter as a constituent
even of "modern" creosote) than the three components
mentioned by the commenter, and has also been
evaluated by EPA's Carcinogen Assessment Group as
having substantial evidence of carcinogenic!ty.
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Thus, even if the commenter is correct, we would
not alter the waste listing.
But in any case, there is evidence that these
compounds are indeed components of creosote.
Furthermore, benzo[a]pyrene has been found to
be present in creosote by sources other than the
commenter.* It and the other components questioned
by the commenter also have been found in both
wastewater and bottom sediment sludges from wood
preserving plants(18) and has been detected in
elevated levels in mussels growing near creosote
treated timber pilings (39,40) and ln the edible
meat of lobsters maintained in commercial tidal
compounds constructed of creosote treated timber.
(40,41). We thus believe these substances are
ordinarily found in creosote and can escape into
the environment to cause substantial harm.
Therefore, the Agency will continue to include
these substances as a basis for listing creosote-
containing waste-water and bottom sediment sludges
from the wood preserving Industry.
15. The commenter argued that pentachlorophenol does
not meet RCRA's criteria for classification as an
acutely hazardous waste under section 261.ll(a)(2),
*Guerin, 1977 "Energy Sources of Polycylic Aromatic
Hydrocarbons." Oak Ridge National LaboratoTy.
-------
and submitted unpublished studies showing that
pentachloropheno1 had acute toxicity ranges outside
of the criteria limits set in section 261.ll(a)(2).
The coraraenter asserted that the Department of
Transportation (DOT), which uses the same criteria
in making determinations of "Poison B" materials
responded to the same studies by removing penta-
chlorophenol from its "Poison B list."*
First, the Department of Transportation did
not consider the toxicity in its delisting of
pentachlorophenol. The published rationale for
the DOT decision** appears Instead to consider
only the fact that pentachlorophenol is a solid,
Instead of a liquid: "This entry is listed with
quantity restrictions and packaging requirements
for a liquid, yet the material is a solid. . .,
it has therefore been deleted because of the
uncertainty of entry description." The Agency
is not able to acknowledge that the DOT either
performed a toxicological validation of the sub-
mitted studies or delisted pentachlorophenol for
reasons of its correct commercial form.
*We note in passing that this comment is actually
addressed to the §261.33 regulation. However,
since the comment was made in the course of comments
on the wood preserving industry waste listing, and
pentachlorophenol is of particular significance to
this Industry, we are responding to the comment here
**41 £fi 40618 (September 20, 1976).
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The Office of Pesticides Programs has assisted
the Office of Solid Waste by reviewing several
published acute toxicity studies on pentachlorophenol.
With this validation, the Agency is able to remove
pentachlorophenol from the acutely hazardous list.
The studies in question are summarized below.
One published study showing an oral lethal
dose of 27 mg/kg was performed as a 0.5% solution
of pentachlorophenol in fuel oil, and therefore
was not found indicative of the toxicity of penta-
chlorophenol alone without contribution of toxicity
from the vehicle. Besides this study, which was
criticized by the commenter, the Agency is aware
of two additional studies indicating the possibility
of an LD5Q value below SO mg/kg. A recent exper-
iment* resulted in an oral LDso of 36 tag/kg for
pentachlorophenol administered to C57 male mice
in 40% ethanol. One report estimated the LT)5Q for
humans to be as low as 29 mg/kg.** The Ahlborg study
may also have had toxicity contribution from the
vehicle. (This study would not have been available
to the DOT for Its 1976 decision.) The Dreisbach
*Ahlborg, U.G., and K. Larsson. "Metabolism of
Tetrachlorophenols In the Rat." Arch. Toxicology,
4j), 63 (1978).
**Dreisbach, R.H. Handbook of Poisoning, Diagnosis
and Treatment, p. 256 (1963).
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listing was found too general and without supporting
data.
The two unpublished contract studies submitted
to the Agency by the commentsr were not subjected
to validation, since published studies following
technically more defensible protocol were available.
For example, the material tested by both International
BioReseach and Wil Research Laboratories for the
commenter Is described as "49-162 Pentachlorophenol
from Reichhold Chemicals; small brown crystals
with a pungent odor." There is no way for the
Agency to determine if this substance is technical
or purified grade, or if it resembles the commercial
products of other companies such as Dow or Monsanto.
No analyses of major impurities was given. The
crystalline solid tested may have been a product
of an isolation/purification synthesis step that
never occurs in the preparation of concentrated
solutions of pentachlorophenol for major industrial
use (technical grade). Also, there exists an
inconsistency between the two studies submitted by
the commenter in its description of the administered
dose. One study describes a 1.0% suspension of
the pentachlorophenol in corn oil and the other
describes a 50% solution of pentachlorophenol in
corn oil. It is highly improbable that identical
pentachlorophenol samples would not dissolve in low
-72-
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concentrations In corn oil, but would dissolve In
high concentrations.
16. Finally, the American Wood Preservers Institute
has argued both in its comments and in other public
forums that the Agency should not promulgate hazardous
waste listings for this industry until the Rebuttable
Presumption Against Registration (RPAR) process
for pentachlorophenol and creosote is completed
by the Agency's Office of Pesticide Programs. (The
RPAR process is well underway, and is expected to
be completed within the next six months.) Indeed,
it is suggested that the Agency may be precluded
legally from listing these wastes pending completion
of RPAR review.
We disagree strongly. The RCRA hazardous waste
listing process and the Federal Insecticide, Fungi-
cide, and Rodentlcide Act (FIFRA) cancellation
process have different objectives and are governed
by different statutory standards. The FIFRA review
process balances the environmental hazards with
the benefits of use of a pesticide. Thus, under
FIFRA, the key determination for registration or
cancellation of a pesticide Is whether use or
continued use "generally causes an unreasonable
adverse effect on the environment." (FIFRA Sections
3(d), 6(b).) An 'unreasonable adverse effect on
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the environment1 Is defined as "any unreasonable
riafc to man or the environment, taking into account
the economlct social, and environmental costs and
benefits ot the use of any pesticide."* Further,
In determining whether to issue a notice of Intent
to cancel a registration, the Administrator must
take into account the proposed action's impact on
"production and prices of agricultural commodities,
retail food prices, and otherwise on the agricultural
economy." (FIFRA Section 6(b).)
No such balancing is involved in making hazardous
waste listing determinations (or in identifying
hazardous wastes by means of a characteristic) under
RCRA. Wastes are to be regulated as hazardous if
they are capable of posing a substantial threat
to human health or the environment if managed
improperly (RCRA Section 1004(5)). No weighing
of benefits is mentioned in the statute, nor is
such a consideration even germane, since the dis-
position of solid or hazardous wastes ordinarily
has little if any social or economic benefit (see
H.R. Rep. No. 94-1491, 94th Cong., 2d Sess. 4 (1976))-.
*(FIFRA,Section 2(bb), emphasis supplied; see also
40 CFR §162.11(a)(5)(iii) (authorizing consideration
in determining whether to cancel a pesticide use
of evidence of whether the "economic, social and
environmental benefits of the use -of the pesticide
subject to the presumption outweigh the risk of
use.")
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Identification and listing of hazardous wastes
thus is a significantly different type of deter-
mination than RPAR review under FIFRA. Simply put,
wastes frora manufacture of registered pesticides
may well be capable of posing a substantial threat
to human health and the environment and thereby be
listed as hazardous even if the social, economic
and environmental benefits of use of the pesticide
outweigh the respective risks and justify its
continued registration. This being so, we believe
it inadvisable to defer regulation of these wood
preserving process wastes pending completion of
RPAR review since neither determination controls
the other. Indeed, under the Integration provision
of RCRA (Section 1006(b)), the Agency is to inte-
grate Its implementation of RCRA and other environ-
mental statutes (including FIFRA) "only to the
extent that it can be done in a manner consistent
with the goals and policies expressed in (RCRA) and
in the other acts. . ." As shown above, the RCRA
listing process and the FIFRA RPAR review process
have fundamentally different goals and policies,
and fundamentally different substantive statutory
standards. We therefore will proceed with our
listings of these process wastes.
-75-
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We note as a further , and central, reason for
not deferring regulation that the RPAR process will
not consider the composition of wood preserving
manufacturing process wastes or their potential to
cause substantial harm if mismanaged. These process
wastes are not pesticides; nor are they registered
for use. Their potential to cause substantial
environmental harm if mismanaged is not at issue,
or even relevant to the RPAR proceeding. We thus
do not accept the advisability, even as a pragmatic
matter of deferring RCRA regulation pending completion
of RPAR review.
1 ' -
Protection Agency
•on V. :.ib«r.i
1- iJojrn Dt-i.-t-orn Srreet jX
C:!,cago, Illinois 60604 J-""'
a.r
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lie 015
BACKCROUN'D DOCUMENT
RESOURCE CONSERVATION A\'D RECOVERY ACT
SUBT1TLF. C - IDENTIFICATION AND LISTING 0? H»~*. - =, 00 JS
§§261.31 and 261.32 - Listing of Hazardous Wastes ( r 1 na I i z ?. i ! o
of May 19, 1980 Hazardous i.'3s:e Ms-)
T
*&ccx.*<:-d
o^r - c-L- -r
U.S. ENVIRONMENTAL PROTECTION ACEVCV
Oft LCK OF SOLID I/AS TF.
N' o v e -a b e r 1 A , 1930
1941". 26'
-------
Table of Cor.
Background Docuaent P age
1. Wastes Fron Usage of Halogenated Hydrocarbon .......... I
Solvents in Degrca&ing Operations
- The following spent halogenated solvents
used in degreaslng: te tr ac hloroe thylene ,
f- » V tr ichloroe thylene , methylene chloride
^ 1 , 1, 1-trlchloroe thane , carbon te tr achlor id e ,
and chlorinated f luo c ocar bons ; and sludgas
from the recovery of these solvents in de-
greasing operations (T)
2. Wastes From Usage of Organic Solvents ..... . ....... .... 29
- The following spent halogenated solvents:
t e tr a c hlor oe t h yl ene , methylene chloride,
trichloroethylene, 1 ,1, 1-trichloroethane,
^ c hlor obe n zene , 1 , 1 , 2- tr Ic hlor o-l , 2 , 2- tr 1-
• ^ f luo r oe t hane , or t ho- d Ichl or obenzene , and
tr Ic hloro fl uor ome thane ; and the still
bottoos froa the recovery of these solvents (T)
The following spent no n-halogena t ed solvents:
xylene, acetone, ethyl acetate, ethyl
benzene, ethyl ether, methyl isobutyl
i-- _ ^i ketone, n-butyl alcohol, eye lohexanone ,
• & 3 and raethanol; and the still bottoms from
the recovery of these solvents (I)
^
\ O f)
The following spent non-halogena t ed solvents
cresols and cresyllc acid and nitrobenzene;
and the still bottoms from the recovery of
these sol vents. (T)
The following spent non-halogena ted solvents:
toluene, methyl ethyl ketone, carbon disulflde,
O 5 isobutanol, and pyridlne; and the still.
bottoras from the recovery of these solvents
(I,T)
3. Electroplating and Metal Finishing Operations ......... 105
» ~ Wastewater treatment sludges from electroplating
operations except from the following processes:
(1) sulfurtc acid anodizing of aluminum; (2)
tin plating on carbon steel; (3) zinc plating
(segregated basis) on carbon steel; (A) aluminum
or zlnc-alusnlnun plating on carbon steel;
-vl-
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(5) cleaning/stripping assqc iated with
zinc and aluminum plating on carbon stir _
and (6) che-aical etching and milling of
aluminum (T)
W a s I e v? a t e r treatment sludges f r o n the che^uea!
conversion coating of aluminum (T)
4 . Spent Waste Cyanide Solutions and Sludges .. 144
Spent cyanide plating bath solutions f- : -
electroplating operations (except for -r = i : : _ s
QO^ metals electroplating spent cyanide pi = ~ . - z
bath solutions) (R,T)
^. - Plating bath sludges from the bottom of
^ plating baths from electroplating
operations where cyanides are used in c-i
process (except for precious metals e 1 i : : r : -
plating plating bath sludges) (R,T)
£. - Spent stripping and cleaning bath solut-._s
? ' from electroplating operations where cyi-.-ss
are used in the process (except for pre: . : _5
metals electroplating spent stripping a-.:
cleaning bath solutions) (R,T)
Quenching bath sludge froa oil baths f r : a.
O \ C* metal heat treating operations where cyiiifas
are used in the process (except for pr e c •-.-_• s
metals heat treating quenching bath sluices)
(R,T)
Spent cyanide solutions from salt bath r: -
Q I' cleaning from metal treating operations
(except for pr'ecious metal heat treat! r. g
spent cyanide solutions from salt bath
pot cleaning) (R,T)
Quenching wastewater treatment sludges :" r .-> a
.* metal heat treating operations where cya~ides
are used in the process (except for precious
netals heat treating quenching wastewater
treatment sludges) (T)
"(3 i Ll - Cyanid^tlon wastewater treatment tailing pond
sediment from mineral metals recovery opera-
tions (T)
_ ^ - Spent cyanide bath solutions fron mineral
' raetals recovery operations (R,T)
- vi i-
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5. Chromium Pigments and Iron Blues ........... —.--.-—. ...... — 188V
rX _j -N - Wastewater treatment sludge from the pro-
duction of chrome yellow and ora-,je pigments (T )
K <*>r*"3 ~ Wastewater treatment sludge from the pro-
-* duction of molybdate orange pigments (T)
Wastewater treatment sludge from the pro-
r> OO^\ duction of zinc yellow pigments (T)
Wastewater treatment sludge from the pro-
l£ OO ^ duction of chrome green pigments (T)
. t - Wastewater treatment sludge from the pro-
i^- ® ^ duction of chrome oxide green pigments
(anhydrous and hydrated) (T )
Wastewater treatment sludge from the pro-
duction of Iron blue pignents (T)
IK OO% ~ Oven residue from the production of chrome
oxide green pigments (T )
6 . Acetaldehyde Production ............................... 216
Distillation bottoms from the production of
/< O O^] acetaldehyde from ethylene (T)
K. n I fo ~ Distillation side-cuts from the production
of acetaldehyde from ethylene (T)
7. Acrylonitrile Production ............................ . . 237
i - Bottom stream from the wastewater stripper
f\ f) I' In the production of ac rylonl tr 11 e (R,T)
Bottom stream from the acetonltrile column
KO /3 ln t}^e Productlon of acrylonl tr 11 e (R,T)
- Bottoms from the acetonitrlle purification
column In the production of ac r y 1 on 1 1 r 11 e (T)
K o 1-4
8. Benzyl Chloride Production .......................... <. 259
L, .,c ~ Still bottoms from the distillation of benzyl
^ C I J chloride (T)
-vl 11-
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Page
9. Carbon Tetrachloride Production ............. ..... 273
Heavy ends or distillation residues fr.z : ;
production of carbon tetrachloride (T )
10. Epichlorohydrin Prod-jetton ................ ..... 301
Heavy ends (still bottons) from the pur.-
flcatlon column In the production of
' eplchlorohydrin (T)
L 2
11. Ethyl Chloride Production ............................ 320
Heavy ends from the f r ac t lona t io n colt-rz
ln ethy1 chloride production (T)
12. Ethylene Dlchlorlde and Vinyl Chloride Monoz=r 7r:- ... 336
d uc t ion
Ko/^f - Heavy ends from the distillation of e t - / I -i - e
dichlorlde in ethylene dlchlorlde prod'.::::-. ;7)
Is . - H e av y ends from the distillation of vlr. /I
C^"° chloride in vinyl chloride raono-aer pr oc .::-..- n (.T)
13. Fluorocarbon Production ............................... 372
. . . - Aqueous spent antimony catalyst waste frcs
rS °«^ ' fluorome thanes production (T)
14. Phenol/Acetone Production ............................. 389
- Distillation bottom tars from the prodoccic-n
O s~. <7^ of phenol/acetone from curaene (T)
15. Phthalic Anhydride Production
" Distillation light ends from the production
of phthalic anhydride from naphthalene (T)
Distillation bottoms from the production
/< O^ / of p'ichallc anhydride from naphthalene (T)
Distillation light ends from the production
of phthalic anhydride from ortho-xylene (T)
Distillation bottoms from the production
of phthalic anhydride from ortho-xylene (T)
- ix-
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Page.
16. Nitrobenzene Production ............................... 423
- A - Distillation bottoms fro a the production of
nitrobenzene by the nitration of benzene (T)
17. Methyl Ethyl Pyrldine Production ...................... 435
> - Stripping still tails from the production
oAfe of methyl ethyl pyridine (T)
18. Toluene Dlisocyanate Production ....................... 451
Centrifuge and distillation residues from
OA.~J toluene diisocyanate production (R,T)
19. Trichloroethane Production ...... ................... ••• 469
Spent catalyst from the h yd r oc hlor 1 n a t or
reactor in the production of 1,1,1-tri-
O&-.0 chloroethane via the vinyl chloride
pr oce s s (T )
Waste from the product steam stripper in
the production of 1 , 1 , 1- t r ic hlor oe t hane (T )
Distillation bottoms from the production
of 1 , 1 , 1-tr Ic hloroe thane (T)
- Heavy ends from the heavy ends column from
the production of 1 , 1 , 1- t r 1 c hlor oe t han e (T)
20. Tr ichloroe thylene and Pe r chl or oe t hy 1 ene Production .... 505
Column bottoms or heavy ends from the coa-
bined production of t r ic hi oroe t hy 1 ene and
C> 3 O perchloroethylene (T)
21. MSMA and Cacodyllc Acid Production .................... 529
By-product salts generated in the production
O3 | of MSMA and cacodyllc acid (T)
22. Chlordane Production ................ ..... ...... ....... 552
Wastewater and scrub water from the chlorl-
nation of eye lop
of chlordane (T)
y -
~* nation of eye lopen t ad lene in the production
-------
Page
~ Wastcwater treatment sludges from the rro-
doction of chlordane (T)
Filter solids fro a the f I 1 t r .« t I o ,1 of '- -. a -
/< r>3 V chlorocyclopentadiene In the production
o f chlor dan e (T)
Vacuum stripper discharge from the chlordene
chlorlnator In the production of chlorJane (T)
23. Disulfoton Production
Still bottoms from toluene reclamation
distillation in the production of disolfo-
ton (T)
Wastewater treatment sludges frora the pro-
duction of disulfoton (T)
24. Phorate Production 585
Wastewater treatment sludges from the pro-
duction of phorate (T)
Filter cake from the filtration of diethyl-
phosphorodithioic acid in the production
of phorate (T)
Wastewater fron the washing and stripping
of phorate production (T)
25. Toxaphene Production 597
Wastewater treatment sludge frora the pro-
duction of toxaphene (T)
Untreated process waste^ater from the pro-
duction of toxaphene (T)
26. 2,4,5-T Production 609
Heavy ends or distillation residues from
the distillation of tetrachlorobenzene in
- xl-
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27. 2,4-D Pra-dOT'EWTr^V.- Frv".'. ;-;-. 622
- 2,6-Dichloropheno1 waste from the produc-
/< r"/ V tion of 2,4-D (T)
Untreated wastewater from the production
of 2,4-D (T)
28. Explosives Industry 640
k^ o i-J t4 ~ Wastewater treatment sludges from the manu-
facturing and processing of explosives (R)
if - Spent carbon from the treatment of waste-
^ °9 5 water containing explosives (R)
/^ , . - Wastewater treatment sludges from the manu-
^ fc ' *> facturing, formulation and loading of lead-
based Initiating compounds (T)
'•vOl/~"7 - Pink/red water from TNT operations (R)
29. Petroleum Refinig 677
s\ - Dissolved air flotation (DAF) float from the
K C)LI o petroleum refining Industry (T)
Secondary (emulsified) oil/solids/water
separator sludge in the petroleum refining
Industry (proposed) (T)
- Slop oil emulsion solids from the petroleum
7 refining Industry (T)
Heat exchanger bundle cleaning sludge from
, the petroleum refining industry (T)
K O 5 d
API separator sludge from the petroleum re-
fining industry (T)
K.O&/
Primary o11/so 1 ids/water separation sludge In
the petroleum refining Industry (proposed) (T)
Tank bottoms (leaded) from the petroleum re-
k o ^3- fining industry (T)
-xli-
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Page
30. Coking 720
K O (&O - Air-nonla still MTG sludge from coking opera-
tions (T)
31. Electric Furnace Production of Steel 734
, - Emission control dusts/s ludges from the
i*- O w / primary production of steel In electric
furnace (T)
32. Steel Finishing 753
Spent pickle liquor from steel finishing
operations (C,T)
33. Primary Copper Smelting and Refining 775
Acid plant blc--down s 1 ur r y/s 1 udge resulting
, . from the t h IC'".P n ing of blowdown slurry from
K.OI?1-/ primary copper production (T)
34. PrimaryLead Smeltlr^. 792
Surface Inpoundent solids contained in and
N, 0 «? Q dredged from surface Impoundments at pri-
mary lead smelting facilities (T)
35. Primary Zinc Smelting and Refining 810
Sludge from treatment of process wastewater
l^ Q b (0 and/or acid plant blowdown from primary
zinc production (T)
// - Electrolytic anode si Ime s/si udge s from primary
*> Oic ~J zinc production (T)
i* Q - Cadmlun plant leach residue (Iron oxide) from
^•^ " primary zinc production (T)
36. Secondary Lead Smelting 832
Emission control dust/sludge from
secondary lead smelting (T)
Waste leaching solution from acid
leaching of emission control dust/
sludge from secondary lead smelting (T)
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BACKGROUND DOCUMENT
RESOURCE CONSERVATION AND RECOVERY ACT
SUBTITLE C - IDENTIFICATION AND LISTING OF HAZARDOUS WASTE
§§261.31 and 261.32 - Listing of Hazardous Wastes {Finalization
of Hay 19, 1980 Hazardous Waste List)
' P
A <
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF SOLID WASTE
November 14, 1980
1941.28
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Hazardous Waste Listing Background Document
INTRODUCTION
Subtitle C of the Solid Waste Disposal Act, as amended
by the Resource Conservation and Recovery Act of 1976 creates
a comprehensive "cradle-to-grave" management control system
for the disposal of hazardous wastes designed to protect the
public health and the environment from the Improper disposal
of such waste. Section 3001 of that Subtitle requires EPA Co
identify the characteristics of and list hazardous wastes.
Wastes identified or listed as hazardous will be included in
the management control system created by Sections 3002-3006
and 3010. Wastes not identified or listed will be subject to
the requirements for non-hazardous waste imposed by the States
under Subtitle D.
Hazardous Waste List
The purpose of the hazardous waste list as required by
Section 3001 of RCRA is to identify those wastes which may
present a potential hazard to human health or the environment.
The waste so identified is considered hazardous (unless it
has been excluded from the list under §5260.20 and 260.22)
and subject to the Subtitle C regulations. A solid waste,
or class of solid wastes is listed if the waste:
(1) exhibits any of the characteristics identified in
Subpart C of the final regulations; or
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(2) meets the definition of § 261.11(a)(2) of the regu-
lations (i.e., may cause or significantly contri-
bute to, an increase in mortality or an increase
in serious irreversible, or incapacitating rever-
sible, Illness) and thus, presents an acute hazard
to humans; or
(3) contains any of the toxic constituents listed in
Appendix VIII of Part 261 unless, after considering
any of a number of factors, the Administrator con-
cludes that the waste will not meet the criterion
of § 261.11(a)(3) (i.e., nay pose a substantial
present or potential hazard to human health or the
environment when it is improperly treated, stored,
transported, disposed of or otherwise managed).
The Agency considered several approaches for formulating
the list. The approaches can be broken down into three main
types :
0 Hazardous Waste from Non-Specific Sources - these
are wastes which are generated from a number of
different sources (i.e., electroplating, etc.)
0 Hazardous Waste from Specific Sources - these are
wastes which would be generated from a very specific
source (i.e., distillation bottons from the produc-
tion of acetaldehyde from ethylene, etc.)
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8 Commercial Chemical Products - these are a list of
commercial chemical products or manufacturing
chemical intermediates which if discarded either
as the commercial chemical or nanufacturing chemical
intermediate itself; off-specification commercial
chemical products or manufacturing chemical inter-
mediates; any container or inner liner removed
from a container that has been used to hold these
commercial chemical products or manufacturing
chemical intermediate unless decontaminated; or
any residue or contaminated soil, water or other
debris resulting from the clean-up of a spill
into or on any land or water, of these comnercial
chemical products or manufacturing chemical inter-
mediates are hazardous wastes.
(This listing background document will cover the first two
categories; the third category of hazardous waste is discussed
in the background document entitled, "Hazardous Waste from
Discarding of Commercial Chemical Products and the Containers
and Spill Residues Thereof."
HAZARDOUS WASTE FROM NON-SPECIFIC AND SPECIFIC SOURCES
On May 19, 1980, as part of its final and interim final
regulations implementing Sections 3001 of RCRA, EPA published
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a list of hazardous wastes which included 85 wastes from
manufacturing processes (§§261.31 and 261.32, 45 Fjl 33123-
33124). These lists were published in interim final form to allow
the public an opportunity to commen-t on additional data the
Agency had collected on these wastes since the close of the
initial public comment period on the proposed Subtitle C
regulations (43 FR. 58957-58959, December 18, 1978).
At the same time, the Agency also proposed for comment
eleven additional hazardous waste listings (45 FR 33136-33137,
May 19, 1980). All of these wastes were identified by the
Agency in the course of developing the necessary technical
data to support the May 19, 1980, interim final hazardous
waste list.
The background data used to support these listings came
primarily from two sources. The majority of this data or
information comes from studies undertaken by the Agency or
data available to the Agency (i.e., industry assessment
studies conducted by the Office of Solid Waste, effluent
guidelines studies conducted by the Office of Water Planning
and Standards, health effects and fate and transport data
compiled by the Office of Research and Development and Office
of Water Planning and Standards, damage assessments and
Incidents compiled by the Office of Solid Waste, etc.)*.
*It should be noted that a number of these documents (e.g.,
pesticide waste background documents) contain confidential
Information. This data has been removed from the document
and will not be made available to the public. This data,
however, is part of the Administrative record and is included
in the Agency's case to support the listing.
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The second source of data came from Information collected
from State Agencies (i.e., manifest data, etc .) .
The Agency received a large number of comments on both
the Interim final and proposed hazardous waste listings. We
have evaluated these comments carefully and responsed In
detail In the listing background documents. The respective
listing background documents have also been revised as
appropriate and are now "final-final" documents.
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Table of Contents
Background Document Page
1. Wastes From Usage of Halogenated Hydrocarbon 1
Solvents in Degreasing Operations
- The following spent halogenated solvents
used in degreaslng: tetrachloroethylene,
trichloroethylene, methylene chloride
1,1,1-trichloroethane, carbon tetrachloride,
and chlorinated fluorocarbons; and sludges
from the recovery of these solvents in de-
greasing operations (T)
2. Wastes From Usage of Organic Solvents 29
- The following spent halogenated solvents:
tetrachloroethylene, methylene chloride,
trichloroethylene, 1 ,1,1-trichloroethane,
chlorobenzene , 1,1,2-trichloro-l,2,2-tri-
" fluoroethane , ortho-dichlorobenzene, and
trichlorofluoromethane; and the still
bottoms from the recovery of these solvents (T)
The following spent non-halogenated solvents:
xylene, acetone, ethyl acetate, ethyl
benzene, ethyl ether, methyl isobutyl
ketone, n-butyl alcohol, eye lohexanone,
and methanol; and the still bottoms from
the recovery of these solvents (I)
The following spent non-halogenated solvents:
cresols and cresylic acid and nitrobenzene;
and the still bottoms from the recovery of
these solvents (T)
- The following spent non-halogenated solvents:
toluene, methyl ethyl ketone, carbon dlsulfide,
isobutanol, and pyridine; and the still
bottoms from the recovery of these solvents
(I.T)
3. Electroplating and Metal Finishing Operations 105
- Wastewater treatment sludges from electroplating
operations except from the following processes:
(1) sulfurlc acid anodizing of aluminum; (2)
tin plating on carbon steel; (3) zinc plating
(segregated basis) on carbon steel; (4) aluminum
or zinc-aluminum plating on carbon steel;
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(5) cleaning/stripping associated with tin,
zinc and aluminum plating on carbon steel;
and (6) chemical etching and milling of
aluminum (T)
Wastewater treatment sludges from the chemical
conversion coating of aluminum (T)
4. Spent Waste Cyanide Solutions and Sludges
Spent cyanide plating bath solutions from
electroplating operations (except for precious
metals electroplating spent cyanide plating
bath solutions) (R,T)
Plating bath sludges from the bottom of
plating baths from electroplating
operations where cyanides are used in the
process (except for precious metals electro-
plating plating bath sludges) (R,T)
Spent stripping and cleaning bath solutions
from electroplating operations where cyanides
are used in the process (except for precious
metals electroplating spent stripping and
cleaning bath solutions) (R,T)
Quenching bath sludge from oil baths from
metal heat treating operations where cyanides
are used in the process (except for precious
metals heat treating quenching bath sludges)
(R,T)
Spent cyanide solutions from salt bath pot
cleaning from metal treating operations
(except for precious metal heat treating
spent cyanide solutions from salt bath
pot cleaning) (R,T)
Quenching wastewater treatment sludges from
metal heat treating operations where cyanides
are used In the process (except for precious
metals heat treating quenching wastewater
treatment sludges) (T)
Cyanidatlon wastewater treatment tailing pond
sediment from mineral metals recovery opera-
tions (T)
Spent cyanide bath solutions from mineral
metals recovery operations (R,T)
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Page
Chromium Pigments and Iron Blues 188
Wastewater treatment sludge from the pro-
duction of chrome yellow and orange pigments (T)
Wastewater treatment sludge from the pro-
duction of molybdate orange pigments (T)
Wastewater treatment sludge from the pro-
duction of zinc yellow pigments (T)
Wastewater treatment sludge from the pro-
duction of chrome green pigments (T)
Wastewater treatment sludge from the pro-
duction of chrome oxide green pigments
(anhydrous and hydrated) (T)
Wastewater treatment sludge from the pro-
duction of iron blue pigments (T)
Oven residue from the production of chrome
oxide green pigments (T)
Acetaldehyde Production 216
- Distillation bottoms from the production of
acetaldehyde from ethylene (T)
Distillation side-cuts from the production
of acetaldehyde from ethylene (T)
Acrylonitrile Production 237
Bottom stream from the wastewater stripper
in the production of acrylonitrile (R,T)
Bottom stream from the acetonitrile column
in the production of acrylonitrile (R,T)
Bottoms from the acetonitrile purification
column in the production of acrylonitrile (T)
Benzyl Chloride Production 259
Still bottoms from the distillation of benzyl
chloride (T)
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Page
9. Carbon Tetrachloride Production 273
Heavy ends or distillation residues from the
production of carbon tetrachloride (T)
10. Epichlorohydrin Production 301
Heavy ends (still bottoms) from the puri-
fication column in the production of
epichlorohydrin (T)
11. Ethyl Chloride Production 320
Heavy ends from the fractionation column
in ethyl chloride production (T)
12. Ethylene Bichloride and Vinyl Chloride Monomer Pro- ... 336
d uc t ion
Heavy ends from the distillation of ethylene
dichloride in ethylene dichloride production (T)
Heavy ends from the distillation of vinyl
chloride in vinyl chloride monomer production (T)
13. Fluorocarbon Production • 372
Aqueous spent antimony catalyst waste from
fluoromethanes production (T)
14. Phenol/Acetone Production 389
Distillation bottom tars from the production
of phenol/acetone from curaene (T)
15. Phthalic Anhydride Production 404
Distillation light ends from the production
of phthalic anhydride from naphthalene (T)
Distillation bottoms from the production
of phthalic anhydride from naphthalene (T)
Distillation light ends from the production
of phthalic anhydride from ortho-xylene (T)
Distillation bottoms from the production
of phthalic anhydride from ortho-xylene (T)
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Page
16. Nitrobenzene Production 423
Distillation bottoms from the production of
nitrobenzene by the nitration of benzene (T)
17. Methyl Ethyl Pyriditie Production 435
Stripping still tails from the production
of methyl ethyl pyridine (T)
18. Toluene Diisocyanate Production 451
Centrifuge and distillation residues from
toluene diisocyanate production (R,T)
19. Trichloroethane Production 469
Spent catalyst from the hydrochlorinator
reactor in the production of 1,1,1-tri-
chloroethane via the vinyl chloride
process (T )
Waste from the product steam stripper in
the production of 1,1,1-trichloroethane (T)
Distillation bottoms from the production
of 1,1,1-trichloroethane (T)
- Heavy ends from the heavy ends column from
the production of 1,1,1-trichloroethane (T)
20. Trichloroethylene and Perchloroethylene Production .... 505
Column bottoms or heavy ends from Che com-
bined production of trichloroethylene and
perchloroethylene (T)
21. MSNA and Cacodyllc Acid Production 529
- By-product salts generated in the production
of MSMA and cacodyllc acid (T)
22. Chlordane Production 552
Wastewater and scrub water from the chlori-
nation of cyclopentadiene in the production
of chlordane (T)
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Page
Wastewater treatment sludges from the pro- v,'
duction of chlordane (T)
Filter solids from the filtration of hexa-
chlorocyclopentadiene In the production
o f chlor dane (T)
Vacuum stripper discharge from the chlordene
chlorinator in the production of chlordane (T)
23. Disulfoton Production 573
Still bottoms from toluene reclamation
distillation In the production of disulfo-
ton (T)
Wastewater treatment sludges frora the pro-
duction of dtsulfoton (T)
24 . Phor ate Production 585
Wastewater treatment sludges from the pro-
duction of phorate (T)
Filter cake from the filtration of dlethyl-
phosphorodlthioIc acid in the production
of phorate (T)
Wastewater froa the washing and stripping
of phorate production (T)
25. Toxaphene Production 597
Wastewater treatment sludge from the pro-
duction of toxaphene (T)
Untreated process wastewater from the pro-
duction of toxaphene (T)
26, 2,4,5-T Production 609
Heavy ends or distillation residues from
the distillation of tetrachlorobenzene in
the production of 2,4,5-T (T)
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Page
27. 2,4-D Production 622
2 , 6-Dichlorophenol waste from the produc-
tion of 2,4-D (T)
- Untreated wastewater from the production
of 2,4-D (T)
28. Explosives Industry 640
Wastewater treatment sludges from the manu-
facturing and processing of explosives (R)
Spent carbon from the treatment of waste-
water containing explosives (R)
Wastewater treatment sludges from the manu-
facturing, formulation and loading of lead-
based initiating compounds (T)
Pink/red water from TNT operations (R)
29. Petroleum Refinig 677
Dissolved air flotation (DAF) float from the
petroleum refining industry (T)
Secondary (emulsified) oil/solids/water
separator sludge in the petroleum refining
industry (proposed) (T)
Slop oil emulsion solids from the petroleum
refining Industry (T)
Heat exchanger bundle cleaning sludge from
the petroleum refining industry (T)
- API separator sludge from the petroleum re-
fining industry (T)
- Primary o11/solIds/water separation sludge in
the petroleum refining industry (proposed) (T)
Tank bottoms (leaded) from the petroleum re-
fining Industry (T)
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P age
30. Coking 720
Ammonia still lime sludge from coking opera-
tions (T)
31. Electric Furnace Production of Steel 734
Emission control dusts/sludges from the
primary production of steel in electric
furnace (T)
32. Steel Finishing 753
Spent pickle liquor from steel finishing
operations (C ,T )
33. Primary Copper Smelting and Refining 775
Acid plant blowdown slurry/sludge resulting
from the thickening of blowdown slurry from
primary copper production (T)
34. Primary Lead Smelting 792
- Surface impoundent solids contained in and
dredged from surface impoundments at pri-
mary lead smelting facilities (T)
35. Primary Zinc Smelting and Refining 810
Sludge from treatment of process wastewater
and/or acid plant blowdown from primary
zinc production (T)
Electrolytic anode slimes/sludges from primary
zinc production (T)
Cadmium plant leach residue (iron oxide) from
primary zinc production (T)
36. Secondary Lead Smelting 832
Emission control dust/sludge from
secondary lead smelting (T)
Waste leaching solution from acid
leaching of emission control dust/
sludge from secondary lead smelting (T)
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v
Generic Listings
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LISTING BACKGROUND DOCUMENT
Wastes from Usage of Halogenated Hydrocarbon
Solvents in Degreasing Operations
The following spent halogenated solvents used in degreasing:
tetrachloroethylene, methylene chloride, trichloroethylene,
1,1,1-trichloroethane, carbon tetrachloride and the chlorinated
fluorocarbons; and sludges from the recovery of these solvents
in degreasing ooerations . (T)* ,**,***
I. SUMMARY OF BASIS FOR LISTING
Solvent degreasing operations remove grease, wax, dirt,
oil, and other undesirable substances from various materials.
All degreasing facilities which use the halogenated hydro-
carbon solvents listed above generate spent solvent solutions
which are either discarded or processed to recover the solvent
from the spent solution. Spent solvents include those which
are no longer useful without further processing, either
because they have outlasted their shelf life or because they
have been contaminated, or so changed chemically or physically
that they are no longer useful as solvents. The recovery
operations invariably generate solvent sludges.
* In December, 1978, the Agency proposed a generic listing
for this class of wastes.
** These solvents are often marketed under various trade
marks; the listing obviously Includes all trade mark
solvents which have the generic chemical natae listed
above. Another point of consideration is that different
nanes raay be used to refer to the sane solvent:
tetrachloroethylene = perchloroethylene
1 ,1,1-trichloroethane = methyl chloroform
carbon tetrachloride = tetrachloromethane
methylene chloride = dichloromethane
trichloroethylene = 1,1, 2-trIchloroethylene
*** In response to industry comments, it should be noted
that the Agency is no longer listing these wastes on
the basis of ignitability or EP toxicity. However, these
solvents may be contaminated with metals (i.e., lead and
chromium) in the degreasing operations; therefore, the
generator will be responsible for determining whether the
waste would also neet the EP toxicity characteristic.
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The Administrator has determined that spent halogenated
solvents from degreasing and the sludges that result from
associated solvent reclamation operations are solid wastes
which may pose a substantial present or potential hazard to
human health or the environment when improperly transported,
treated, stored, disposed of, or otherwise managed; therefore,
these wastes should be subject to appropriate management
requirements under Subtitle C of RCRA.
For all of the listed waste solvents, this conclusion
is based on the following considerations:
1. The chlorinated hydrocarbons are toxic and, in some
cases, genetically harmful, while chlorofluorocarbons
may deplete the ozone layer following environmental
release.
2. Approximately 99,000 metric tons of waste halogenated
solvents from degreasing operations are generated
each year(l). There are approximately 460,000
facilities dispersed throughout the country that
use halogenated solvents and generate these wastes(l).
It Is estimated that about 30,000 metric tons per year
of halogenated hydrocarbons from these facilities are
either disposed of annually In landfills or by open-
ground dumping, either as crude spent solvents
or as sludges. The remainder of these wastes are
usually incinerated. The large quantity of wastes
generated and the large nunber of disposal sites
utilized Increases the possibility of waste ois-
manageraent and environmental release of harmful
cons tituents.
3. Since a large majority of the spent solvents and
sludges are In liquid form, the potential for these
wastes to migrate from land disposal facilities
is high. Further, the solubility of these solvents
is generally high, Increasing their migratory
potential.
4. The spent solvent solution from degreasing operations
may contain up to 90 percent of the original solvent.
Depending on the recovery technique, sludges that result
from reclamation processes can contain up to 50 percent
of the original solvent. Such high concentrations
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of hazardous constituents increases the chance of
waste constituents escaping in harmful concentrations.
5. Spent solvents can create an air pollution problem
via the volatilization of the solvents from the
wast es .
For the five chlorinated solvents (not including chlorofluoro-
carbons) found in the waste streans, this conclusion is
based on the following considerations:
6. Incomplete combustion of the spent chlorinated
hydrocarbon solvents during incineration can
cause emissions of the solvent and generate
toxic degradation products (e.g. phosgene).
7. These spent halogenated solvents can leach from
the waste to adversely affect human health and
the environment through the resulting contamination
of groundwater.
8. Current waste management practices have resulted
in environmental damage. These incidents serve to
illustrate that the mismanagement of these wastes
does occur and can result in substantial environmental
and health hazards.
9. A number of these solvents are carcinogenic or
mutagenlc, or are suspected carcinogens or mutagens,
and are lethally toxic to hunans and animals.
For the chlorofluorocarbons, the Agency is basing the listing
on the following consideration:
10. Chlorofluorocarbons, after release at the surface of
the earth, mix with the atmosphere and rise into
the stratosphere where they are decomposed by ultra
violet radiation to release chlorine atoms. These
atoms catalytically deplete the ozone, leading to ad-
verse effects, including skin cancer and climate changes.
II. OVERALL DESCRIPTION OF INDUSTRY USAGE
Degreasing operations are not industry specific. Degreasing
operations are prevalent in twelve najor SIC (Standard Industrial
Classification) categories, numerous subcategories, and auto-
motive maintenance shops. The pertinent Industries where
halogenated hydrocarbons are used primarily are presented in
Table 1. A sunnnry of the nunber and types of plants that
conduct degrcasing operations is presented in Table 1.
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Table 1
Industries Using Halogenated Hydrocarbons
in Degreasing Operations
Source SIC Code
Metal Furniture 25
Primary Metals 33
Fabricated Products 34
Non-electric Machinery 35
Electric Equipment 36
Transportation Equipment 37
Instruments and Clocks 38
Miscellaneous Industry 39
Automotive Repair Shops 75
Automotive Dealers 55
Automotive Maintenance Shops
Texitile Plants (Fabric Scouring) 22
Gasoline Stations 55
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Table 2 - Solvent Degreasing Source Types*(l)
Source
Material Degreasing
Metal Furniture
Primary Metals
Fabricated Products
Non-electric Machinery
Electric Equipment
Transportation Equipment
Instruments and Clocks
Miscellaneous
Automotive
Auto Repair Shops
Automotive Dealers
Gasoline Stations
Maintenance Shops
Textiles
Textile Plants (Fabric Scouring)
SIC
25
33
34
35
36
37
38
39
75
55
55
22
Number of
Plants
9,233
6,792
29,525
40,792
12,270
8,802
5,983
15,187
127,203
121,369
226,445
320,701
7,201
Estimated Number
of Vapor Degreasing
Operations
492
1,547
5,140
5,302
6,302
1,917
2,559
886
Estimated Number
of Cold Cleaning
Operations
22,669
17,558
76,329
105,456
31,720
22,756
15,467
39,262
141,977
135,463
277,440
252,735
,
Total
931,513
24,145
1,230,006
^Includes facilities which do not use halogenated solvents
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III. OVERALL PROCESS DESCRIPTION, WASTE GENERATION LEVELS
AND GEOGRAPHIC DISTRIBUTION OF DEGREASING FACILITIES
1. Solvents Used in Degreasing Process
As indicated in Table 3, out of the more than 1,230,000
non-halogenated and halogenated degreasing operations
(see Table 2), approximately 460,000 use halogenated
solvents(l). Table 3 breaks down the number of plants
which use halogenated solvents to show the estimated number
of these plants using a particular halogenated solvent by
their type of degreasing operation. As the table indicates,
the largest number of these plants use cold cleaning and open
top vapor degreasing operations (see next section for more
detailed discussion of specific degreasing operations).
In both of these operations, the largest number use trlchloro-
ethylene and trichlorethane. Of the industries with conveyor-
ized vapor degreasing operations, the largest number use
trichloroethylene ; fabric scouring operations use principally
tetrachloroethylene (perchloroethylene). Overall, trichloro-
ethylene is the solvent used most prevalently.
2. Process Description
Degreasing operations may be classified into
four basic categories: cold cleaning, vapor degreasing
(open top), vapor degreasing (conveyorized), and fabric
scouring.
In cold cleaning operations, the solvent is main-
tained well below its boiling point. The item to be
cleaned is either immersed, in the agitated solvent
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Table 3 - Estimated Number of Plants using Halogenated
Solvents by Type of Degreasing (1974) (1)
Vapor Vapor Fabric
Solvent
Carbon tetrachloride
Fluorocarbons*
Methylene Chloride
Te tr achloroe thylene
Tr ichloroethylene
Tr ichlorocthane
Total
(open top)
2,130
29S
3,121
11, 440
4,011
21,000
Cold Cleaning
10,568
66,932
21,136
45,795
149,715
137,386
431,532
Conveyor ized
319
45
467
1,713
601
3,145
Scouring
2,522
693
3,215
Note: Blanks indicate no use of specified solvent in that type
of degreaslng operation.
*This refers to all fluorocarbons, some of which are chlorinated.
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or suspended above the solvent where It is systematically
sprayed in a manner similar to that of an automatic
dish washer. Simple cold cleaning operations may
even consist of a container of solvent in which
items are manually immersed, as is the case in small
auto repair shops and in service stations.
Simple vapor degreasing (open top) is achieved by
suspending the item to be cleaned above the boiling
solvent in a vat. Condensation continues until the
temperature of the object approaches that of the solvent
vapors. Often the suspended item is sprayed with liquid
solvent to facilitate further degreasing. In order to
control vapor emissions, a layer of cold air is often
maintained above the open top degreaser.
The conveyorlzed vapor degreaser operates in much
the same manner, except that the objects to be cleaned
are continuously conveyed through the vapor zone.
Auxiliary solvent sprays are also used to improve the
cleaning efficiency of the operations.
Fabric scouring operations are slightly more complex.
Generally, the fabric is conveyed through the degreasing
machine, where it is sprayed with solvents. The solvents
are then removed with an aqueous solution of alcohol.
3. Waste Generation Levels and Projected Levels
The annual growth rate for the use of the listed
halogenated solven: s In degreasing applications is expected to
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be 4 percent(l). Growth is expected to be uniform among
the various solvents, except for trichloroethylene, which
has been banned in several states for use in occupational
settings because it is a carcinogen. (1,2,21). In Cali-
fornia, the use of trichloroethylene has been restricted by
legislation, but tetrachloroethylene and 1,1,1-trichloroethane
are exempt(l) from the restrictions and are still used in
degreasing operations. Rhode Island has completely banned
the use of trichloroethylene(2 ) .
4. Geographic Distribution of Degreasing Operations
The location of the vapor degreasing operations has
been determined by identifying the industries with which
the operations are associated. There are about 24,145
vapor degreasing operations in the United States, which
consume about 52 percent of the total halogenated solvents
used(l). More than 63 percent of these operations are
found in nine states (California, Illinois, Massachusetts,
Michigan, New Jersey, cNew York, Ohio, Pennsylvania and
Texas). Figure 1 and the associated Table 4 present the
geographic distribution of these plants.
There are about 431,532 operations that perform
cold cleaning using about 35 percent of the total
halogenated solvent consumption, while approximately
3,125 fabric scouring operations consume about 13 percent
of the total halogenated solvent(l). Assuming an equal
distribution of halogenated solvent use among cold
cleaning and fabric scouring operations, over 59 percent
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::r-tiri ^
-,-.,-•4 7-0
;:--• Xi-t shirs --£
::«- .'ersey l,:tO
..«•-• .-.•=.••: : ^s
:'<•-• Vtr n * • - -*
r.c:-r. Ctrcii.-.i •:
Ncrth 2isctt '0
C-hio 1.5"5
. i - S i S
.• i : r. e
:; - s *cr.:r * --. s
215
5
1,737
1:3
17,'
Scu;>. ~i-.c.zt
T i .•.:;-;: s fe e
Texis
i,:;fi
i 9
212
-------
of the total halogenated solvent used for degreaslng occurs
in ten states (California, Illinois, Massachusetts, Michigan,
New Jersey, New York, Ohio, Pennsylvania, Texas and North
Carolina).
IV. WASTE STREAM SOURCES AND DESCRIPTION
The usefulness of a solvent decreases with time as contami-
nants adulterate and become concentrated In the solvent. When the
boiling point of the solution (i.e., solvent and contaminants) in-
creases to about 30°C above that of the pure solvent, the solvent
Is considered spent. Halogenated solvent use pattern by type of
degreasing operation Is presented in Table 5. Approximately
527,520 metric tons of halogenated solvents are used each year for
degreasing operations( 1).
Spent solvent solutions include those solvents which are no
longer useful without further processing, either because they
have outlasted their shelf life or because they have been con-
taminated, or so changed chemically or physically that they are
no longer useful as solvents. These spent solvents are either
disposed of, reclaimed and recycled by the waste generator, or
processed by a contract solvent reclaiming operator.* Reclamation
is achieved via settling and/or batch distillation. The listed
sludge results from this reclamation process.
The composition of the spent solvent Is dependent on the
application of the degreasing operation. The spent solvent
*At this time, applicable requirements of Parts 262 through
265 and 122 will apply insofar as the accumulation, storage
and transportation of hazardous wastes that are used, reused,
recycled or reclaimed. The Agency believes this regulatory
coverage is appropriate for the subject wastes. These wastes
are hazardous insofar as they are being accumulated, stored or
transported. These wastes may not pose a substantial hazard
during their recycling and, even though its listed as hazardous,
this aspect of their management is not presently being regulated.
-II-
-------
Table 5
USE PATEERN OF HALOGENATED SOLVENTS IN DECREASING AND
Chemical
Halogens ted hydrocarbons:
Carbon tetrachlorlde
Fluorocarbons*
Methylene Chloride
Perchloroethylene
Tr Ichl or oe thy lene
Trichloroe thane
FABRIC SCOURING
Total U.S.
Consumption
<103 kkg)
534.8
428.6
235.4
330.2
173.7
236.3
OPERATIONS IN 1974
U.S. Consumption
for Degreaslng
(103 kkg)
Cold
0.72
6
46.2
11.4
43.8
78
Vapor
5
U.I
10
43
112.7
90
Total U.S.
Consumption
U.S. Consumption foe Degreaf
for Fabric Scouring and Scour ir
(103 kkg) (103 kkg)
5.72
17.1
56.2
54.6 109
15 17 1 . 5
168
TOTAL
1939.0
186.12
271.8
69.6
527.52
*Thls refers to all fLuorocarbona, a percentage of which are chlorinated.
-------
solution contains up to 90 percent of the original solvent(^).
Depending on the recovery technique, sludges which result from
reclamation processes contain from 1 to 50 percent of the
original hydrocarbon solvent(5). However, because of the
economic considerations of the reclaiming process, the solvent
content of the sludge is seldom reduced below 10 percent.
Heavy metal fines and other organics are also present in
these wastes, in addition to the original solvent(3).
V. QUANTITIES OF THE HASTE AND TYPICAL DISPOSAL PRACTICES
Disposal practices include overt open ground dumping,
containerized landfilling, and incineration (3). Approximately
99,000 metric tons of waste halo<»enated solvents fron degreasing
operations are generated annually(l). It is estimated that
about 30,000 metric tons of these are either landfilled or
open dumped. The remaining quantity of waste halogenated
solvents from degreasing operations are Incinerated. The
rationale and derivation of this estimated quantity is presented
in Appendix I.
VI. HAZARDOUS PROPERTIES OF THE WASTES
As indicated earlier, the spent halogenated solvents and
sludges from the reclamation of these solvents contain very
significant concentrations of the solvent itself -- the
spent solvent solution contains up to 90 percent of the original
solvent and the sludge contains a minimum of 10 percent of
the original solvent. The landfilling or open ground dumping
of these wastes in an unsecure land disposal facility nay
-yf-
- 13-
-------
result In the migration of the toxic halogenated solvents
into the surrounding environment, thus becoming a potential
contaminant of groundwater. For example, since a large ma-
jority of these wastes are in liquid form — including all of
the spent solvents -- these wastes' physical form makes them
amenable to migration from a land disposal facility. Addi-
tionally, the solubility in water of these halogenated solvents
is appreciable (13): 1,1,1-trichloroethane - 950 mg/1, tetra-
chloroethylene 150 mg/1, raethylene chloride - 20,000 mg/1,
carbon tetrachloride 800 mg/1, and trichloroethylene - 1,000
mg/l(14a). These relatively high solubilities demonstrate a
strong potential for migration of these substances from inade-
quate land disposal facilities in substantial concentrations.
Thus, improperly constructed or managed landfills (for example,
landfills located in areas with permeable soils, or landfills
with inadequate leachate control practices) could easily
fail to impede leachate formation and migration. Haphazard
dumping of the wastes is even more likely to result in migration
of waste constituents.
Once released from the matrix of the waste, the halogenated
solvents could migrate through the soil to ground and surface
waters utilized as drinking water. In the National Organics
Monitoring Survey, the Agency detected a number of these solvents
in drinking water samples tested over the past several years, thup
demonstrating the propensity of these solvents to migrate from the
-I/-
-------
waste disposal envlronraenc and to persist in drinking water follow-
ing migration* (14a, 14b, 14c, 14e). In addition, a number
of actual documented damage incidents show the potential for a
very conmon halogenated solvent, trichloroethylene, to leach
from disposal sites into groundwater. (See Damage Incidents
Resulting from the Mismanagement of Halogenated Hydrocarbons,
p. 16.)
These actual damage incidents confirm literature data points
indicating the environmental persistence of these compounds. Thus,
1,1,1-trichloroethane, methylene chloride, and carbon tetrachlorIde
are all likely to persist in the environment long enough to reach
environmental receptors (1,1,1-trIchloroethane is subject to
hydrolysis, but has a half-life in groundwater of 6 months)(37).
Another problem which could result from Improper landfllllng
of these wastes Is the potential for the contaminants to volatilize
into the surrounding atmosphere. All of the listed chlorinated
solvents are volatile and thus could present an air pollution
problem if they are improperly managed (for example, disposed of
in the open, or without adequate cover), since they are uniformly
toxic via inhalation.
A special problem is posed by chlorofluorocarbon solvents.
These solvents are also highly volatile, but instead of posing a
direct toxicity hazard, they may be released at the surface of the
earth, mix with the atmosphere and rise slowly into the stratosphere,
*The specific solvents detected in these samples were methylene
chloride, carbon tetrachloride, trichloroethylene, and tetra-
chloroethylene and trichi or ofluoromethane.
-------
Damage Incidents Resulting From The Mismanagement of
Trichloroethylene
1. In one incident in Michigan, an- automotive parts manu-
facturing plant routinely dumped spent degreasing solu-
tions on the open ground at a rate of about 1000 gallons
per year from 1968 to 1972. Trichloroethylene was one
of the degreasing solvents present in the spent solutions.
Beginning in 1973, trichloroethylene was detected at levels
up to 20 mg/1 in neary residential wells. The dump site
was the only apparent source of possible contamination (10)
2. In a second incident, also in Michigan, an underground
storage tank leaked trichloroethylene which was detected
in local groundwater up to four miles away from the
land C11).
3. In April of 1974, a private water well in Bay City, Michi-
gan became contaminated by trichloroethylene. The only
nearby source of this chemical was the Thomas Company
(which replaced the well with a new one). The company
claimed that, although it had discharged trichloroethylene
into the ground in the past, it had not done so since
1968. Nevertheless, in May of 1975, two more wells
were reported to be contaminated with trichloroethylene
at concentrations of 20 mg/1 and 3 mg/1, respectively
(12).
-------
In March, 1978, EPA banned Che use of chlorofluoro-
carbons in aerosol propellants. The primary concern in the
enactment: of this ban was the ozone depletion effects resulting
from chlorofluorocarbons entering the stratosphere and reaction
with ozone. In the troposphere, chlorofluorocarbons are decom-
posed by the intense ultra violet radiation to release chlorine
atoms. The chlorine atoms catalytically remove ozone, thereby
reducing the total amount of ozone in the stratosphere, leading
to an increase in skin cancer, climatic changes and other adverse
effects.'''*'^' The Agency is therefore concerned about chloro-
fluorocarbon use and disposal. Therefore, the Agency has proposed
the regulation of non-aerosol uses of chlorofluorocarbons.(8)
The Agency also expects to propose regulations controlling
the airborne emissions of these solvents and other volatile
organics so as to reduce the air pollution problems presented
when these solvents are used or disposed. These proposed
regulations will apply certain standards to a number of the
Volatile Organic Compounds (VOC) which have been demonstrated
to be precursors of or lead to the formation of ozone and
other photochemical oxidants in the atmosphere. Ozone air
pollution endangers the public health and welfare and is
thus reflected in the Administrator's promulgation of a
National Ambient Air Quality Standard for Ozone (February 8,
1979, 44 FR 8202). Additionally, 1 ,1 ,1-trichloroethane and
-17-
-------
methylene chloride, which are not ozone percursors, are
being regulated under the proposed rule since under EPA's
proposed airborne carcinogen policy, a compound which shows
evidence of human carclnogenicity is a candidate for regulation
under Section 111 as a pollutant "reasonably anticipated to
endanger public health and welfare"t Finally, trichlorof luoro-
methane, as indicated in the earlier discussion of chlorof luoro-
carbons in general, has been implicated in the depletion of
the stratospheric ozone layer, a region of the upper atmosphere
which shields the earth from harmful wavelengths of ultra
violet radiation, that would increase skin cancer risks in
humans. (33,34)
Additionally, if these wastes are Incinerated, as a
large percentage are, and the wastes are not subject to
proper incineration conditions (i.e., temperature and residence
times), pollution of the environment may result from the
airborne disposal of uncombusted halogenated organlcs, partially
combusted organlcs and newly formed organic compounds.
Phosgene is an example of a partially combusted chlorinated
organic which is produced by the decomposition or combustion
of chlorinated organics by heat (15 , 16 , 17) . Phosgene has
been used as a chemical warfare agent and Is recognized as
extremely toxic.
.The large quantities of the spent solvent and sludges re-
sulting from the recovery of these solvents, a combined total
of 99,000 metric tons per year, are another area of concern.
-13-
-------
As previously indicated, these wastes are generated in
substantial quantities and contain very high concentrations
of the original solvent (the spent solvent solution contains
up to 90 percent and the sludges contain up to 50 percent
of the original solvent). The large quantities of these
contaminants pose the danger of polluting large areas of
ground or surface waters. Contamination could also occur
for long periods of time, since large amounts of pollutants
are available for environmental loading. All of these
considerations increase the possibility of exposure to the
harmful constituents in the wastes.
VII. HEALTH AND ECOLOGICAL EFFECTS ASSOCIATED WITH THE
CONSTITUENTS IN THE WASTES
The toxicity of tetrachloroethylene, raethylene chloride,
1,1,1-trichlorethane, trichloroethylene, carbon tetrachloride
and chlorofluorocarbons has been well documented. Capsule
descriptions of the adverse health and environmental effects
are summarized below; more detail on the adverse effects of
these solvents can be found in Appendix A.
Tetrachloroethylene has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
carclnogenicity.(21) Repeated exposure of rats and mice
to tetrachloroethylene in air or in the diet has resulted
in fatty degeneration of the liver, increased kidney weight
and toxic nephropathy.(18,19,20). Additionally, tetrachloro-
ethylene is slightly toxic to freshwater fish.(14b»22»23)
-------
Methylene chloride has been shown to be rautagenic to a
bacterial strain, S. typhimurium. ( 2^ ) In addition, acute
exposure to methylene chloride in humans is a central nervous
system depressant resulting in narcosis in high concentrations
and is metabolized to carbon monoxide and causes an increase
in carboxyhemoglobin( 25) .
Although 1 , 1 ,1-trichloroe thane (MC) has been shown in
an NCI bioassay to induce a variety of neoplasms ( 26) , these
data were not conclusive. A high incidence of deaths in
test animals has led to retesting of this compound by a manu-
facturer and the NCI(26). In vitro studies have indicated
that MC is slightly nutagenic in the Ames test, and can cause
mammalian cell transformation. Hunan toxic effects seen
after exposure to 1 , 1 ,1-tr ichloroethane Include changes in
several central nervous system functions, including reaction
time, perceptual speed, manual dexterity and equilibriura( 27 ) .
In addition, animal studies have produced toxic effects in
the central nervous system, cardiovascular system, pulmonary
system, and induced liver and kidney damage(27).
Trichloroethylene has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
carcinogenicity. (21) Trichloroethylene has also been
shown, both through acute and chronic exposure, to produce
disturbances of the central nervous system and other neuro-
logical effects(28,29,30).
Carbon te trachloride has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
-20-
-------
carcinogenicity.(21) in addition, toxicological data for
non-human mammals are extensive and show carbon tetrachloride
to cause liver and kidney damage, biochemical changes in
liver function and neurological damage(32).
The hazards associated with exposure to the above halo-
genated solvents have been recognized by other regulatory
programs. Tetrachloroethylene , methylene chloride, 1,1,1-
trichloroethane, trichloroethylene, and carbon tetrachloride
and the two fluorocarbons, trichlorofluoromethane and dichloro-
difluoromethane, are listed as toxic pollutants in accordance
with §307(a) of the Clean Water Act of 1977.* Under §6 of the
Occupational Safety and Health act of 1970, final standards
for occupational exposure have been established and promulgated
in 29 CFR 1910.1000 for carbon tetrachlortde, methylene chlor-
ide and 1,1,1-trichloroethane. On March 17, 1979, fully halo-
genated fluorocarbons were banned by the Consumer Products
Safety Commission as propellants in the United States, except
for essential uses because o'f their threat to the ozone. In
addition, final or proposed regulations in the States of
California, Louisiana, Maryland, Massachusetts, Minnesota,
Missouri, New Mexico, Oklahoma and Vermont define compounds
containing one or more of the solvents tetrachloroethylene,
methylene chloride, 1,1,1-trichloroethane, trichloroethylene,
carbon tetrachloride and trichlorofluoromethane as hazardous
wastes or components thereof.35
*The Agency has recently proposed to remove trichlorofluoromethane
and dichlorodifluoromethane from the list of toxic pollutants
under §307(a) of the Clean Water Act (45 FR 46103, July 9, 1980).
-------
ATTACHMENT I
DERIVATION OF THE ESTIMATED QUANTITIES OF THE WASTE
I. ANNUAL QUANTITIES OF WASTES
Total amount of spent solvents (Halogenated and non-
halogenated)(D - 425,560 kkg
Total amount of spent solvents from vapor degreasing(l)
=• 54,560 kkg
Vapor degreasing units only use halogenated solvents so all
of the 54,560 kkg from this source are halogenated solvents.
Cold cleaners and fabric scourers use both halogenated and
non-halogenated solvents. Assume that the spent solvent
solutions contain solvents in the same proportion as their
use. About 12 percent of solvent use in applications other
than vapor degreasing is halogenated(1).
.'. (425,560 kkg - 54,560 kkg) (0.12)(1)
= 44,250 kkg of halogenated solvents contained in wastes
from sources other than vapor degreasing
54,560 kkg + 44,520 kkg = 99,000 kkg of halogenated
solvents yr
II. DISPOSITION OF WASTE
The disposition of about 30 percent of these wastes can be
derived from information which is documented in the litera-
ture. The disposition of the remaining 70 percent is based
upon extrapolations and economic consideration of waste
management alternatives.
A. DISPOSITION OF 30 PERCENT OF THE WASTE
0 Vapor degreasers only use halogenated solvents(l)
0 Virtually all metal finishing shops (SIC 35, 36,
37, and 39), and by Implication vapor degreasing
operations, either reclaim their spent solvents
or sell them to solvent refiners.(1,3)
" Between 50-99 percent of the solution is recovered(4,5)
0 Approximately 37 percent of the plants which recover
these solvents on-site dispose of their waste sludges
in landfllls(3).
(amount of waste) (1-percent recovery)(percent of
plants with on-slte recovery) x (percent of plants
that landfill) = Amount of waste landfilled.
-22-
-------
1. Assume 50 percent of the solution is recovered
(54,560 kkg) (0.50)(0.37)(0.70) = 7,065 kkg
2. Assume 99 percent of the solution is recovered
(54,560 kkg) (0.01) (0.37)(0.70) = 140 kkg
140 kkg to 7,065 kkg of halogenated solvents
disposed of in landfills.
About 20 percent of the solvent reclaimers which process
the remaining 63 percent of the solvents from this source
also landfill their waste. The remaining 80 percent
of the solvent reclaimers reportedly incinerate their
sludges(4,5). Therefore an additional 109 to 5,456
kkg of halogenated solvents are landfllled by solvent
reclaimers .
B. DISPOSITION OF THE REMAINING 70 PERCENT OF THE WASTE
The wastes generated by the plants in the SIC cate-
gories delineated above represent about 60 percent
of all vapor degreasing operations and about 30
percent of all wastes generated by all degreasers.
Reportedly, a facility which generates at least 350
gallons of spent halogenated solvents anually has
economic incentive to implement a recovery strategy(4,9).
Virtually all vapor degreasers meet this criteria.
The disposition of spent solutions from cold cleaning
and fabric scouring operations is not as well defined.
In order to account for these wastes, some economic
factors have been considered. In general, it is expected
that a plant or Industry which has a high Incidence
of use of a relatively expensive solvent will probably
have some kind of recovery strategy, assuming the scale
of operations permits an acceptable payback period.
In cold cleaning and fabric scouring operations, the
following factors are pertinent:
0 Cold cleaning and fabric scourers use halogenated
solvents in conjunction with inexpensive non-
halogenated solvents. It has been estimated
that these operations must have six to twelve
times the solvent throughput of plants which
only use halogenated solvents in order to
economically justify a recovery strategy.
Cold cleaning and fabric scouring operations
represent about 94.7 percent of all facilities
that use halogenated solvents but only use about
48 percent of the total supply of these solvents
-23-
-------
that are used for degreaslng. The implication is
that, on the average, the solvent throughput
rate is much lower in this segment of the
degreasing industry than that of the vapor
degreaslng segment.
Although some cold cleaning and fabric scouring
operations probably operate on a scale that would
make a recovery strategy economically attractive,
it Is not possible to estimate the extent of recovery
operations in this segment of the industry. The
economics seem to indicate that the incidence of
recovery from these operations is probably very low.
C. THE GROSS ESTIMATE
In estimating the disposition of all the wastes,
the best and worst cases pertaining to the portion
of the waste which cannot be documented in the
literature are considered. The ideal case is where
all of the wastes from cold cleaning and fabric
scouring operations are processed by contract re-
claimer using maximum efficiency recovery techniques
(i.e., 99 percent recovery). The worst case would
be where all of this waste is simply disposed of.
The following is the basis for the estimate.
From Section A
249 kkg to 12,521 kkg of halogenated solvents are
landfilled.
Best Case for Cold Cleaning and Fabric Scouring
(amount of waste)(percent recovered)(percent
landfilled) - amount landfilled
(44,520 kkg)(0.01)(0.2) - 90 kkg of waste land-
filled
Worst case for cold cleaning and fabric scouring
is when all 44,520 kkg of waste is landfilled
The estimated best and worst cases for the disposition
of halogenated solvents from all types of degreasing
operations are 339-57,041 metric tons per year. It
is unlikely that either the best or worst case is
representative of reality. In this case, about half
of the waste is generated by vapor degreasers where
it is likely that the incidence of recovery is high.
The remaining half is generated in environments where
-2H-
-------
the incidence of recovery is probably very low. A
reasonable inference and prudent estimate based on
available data would be about 30,000 metric tons
per year of halogenated solvents disposed of on land.
-------
REFERENCES
1. Hoogneem, T.J., et al. Source asses*m -nt: Solvent evaporation
degreasing operations. U.S. EPA No. 600 /12-79-019f. NTIS
PB No. 80 128 812.- August, 1979.
2. Mansville Chemical Products. Chemical products synopsis:
trichloroethylene. Mansville, New York. September, 1976.
3. U.S. EPA. Hallowell, J.B., et al. Assessment of Industrial
hazardous waste practices: Electroplating and metal finishing
industries - job shops. U.S. EPA. NTIS PB No. 264 349. September,
1976.
4. U.S. EPA. Organic solvent cleaners-background information for
proposed standards. U.S. EPA No. 450/2-78-045a. October, 1979.
5. U.S. EPA. Source assessment: Reclaiming of waste solvents.
State of the art. NTIS No. 282 934. April, 1978.
6. Not used in text.
7. Not used in text.
8. Federal Register, Vol. 43, Pg. 11301. March 17, 1978.
9. U.S. EPA. Control of volatile organic emissions from solvent
metal cleaning. U.S. EPA No. 450/2-77-022. November, 1977.
10. Michigan Department of Natural Resources - Geological Survey
Division. Case history #48.
11. Shellenbarger, P. New charge hits Air Force. The Detroit
News. May 17, 1979.
12. U.S. EPA. Open files. Hazardous Site Control Branch, WH-548,
U.S. EPA, 401 M St., S.W., Washington, DC. 20460.
Contact Hugh Kauffman. (202) 245-3051.
13. U.S. EPA. Section II of Appendix B of the listing background
document: Fate and transport potential of the hazardous
constituents. U.S. EPA, Office of Solid Waste. 1980.
14a. U.S. EPA. Trichloroethylene: Ambient water quality criteria.
NTIS PB No. 292 443. 1979.
14b. U.S. EPA. In-depth studies on health and environmental
impacts of selected water pollutants. Work resulting from
Contract No. 68-01-4646. 1978.
-------
14c. U.S. EPA. Preliminary assessment of suspected carcinogens in
drinking water, and appendices. A report to Congress.
Washington, D.C. EPA No. 560-4-75-003. 1975.
14d. Not used in text.
lAe. U.S. EPA. The National organic monitoring survey. Technical
Support Division, Office of Water Supply, U.S. EPA. Washington,
DC. 20460. 1978.
15. Edwards, John B. Combustion formation and emission of trace
species. Ann Arbor Science. 1977.
16. NIOSH criteria for recommended standard: Occupational
exposure to phosgene. HEW, PHS, CDC, NIOSH. NTIS PB 267 514.
1976.
17. Chemical and Process Technology Encyclopedia. McGraw Hill.
1974.
18. National Cancer Institute. Bioassay of tetrachloroethylene
for possible carcinogenlclty. NTIS PB No. 272 940. NCI-CG-
TR-13. DHEW Publication No. (NIH) 77-813. 1977.
19. Rowe, V.K., et al. Vapor toxicity of tetrachloroethylene
for laboratory animals and human subjects. AMA Arch. Ind.
Hyg. Occup. Med. 5:566. 1952.
20. Klaasserv, C.D., and G.L. Plaa. Relative effects of chlorinated
hydrocarbons on liver and kidney function in dogs. Toxlcol.
Appl. Pharmacol. 10:119. 1967.
21. U.S. EPA. Carcinogen Assessment Group, Office of Research
and Development. List of carcinogens. April 22, 1980.
22. Alexander, H., et al. Toxicity of perchloroethylene,
trichloroethy 1ene, 1,1,1-trichloroethane, and methylene
chloride to fathead minnows. Bull. Environ. Contain. Toxicol.
20:344. 1978.
23. U.S. EPA. Tetrachloroethylene: Ambient water quality criteria.
NTIS PB No. 292 445. 1979.
24. Simmon, V.F., et al. Mutagenic activity of chemicals Identified
in drinking water. S. Scott, et al., eds. In: Progress in
genetic toxicology. 1977.
25. National Academy of Sciences. Chloroform, carbon tetrachloride
and other haloraethanes: Environraental assessment. Publication
No. 2763. 1978.
-------
26. National Cancer Institute. Bioassay of 1,1,1-trichloroethane
for possible carcinogenicity. NCI-CG-TR-3. NTIS PB No. 265 082.
1977.
27. U.S. EPA. Chlorinated ethanes: Ambient water quality criteria.
NTIS PB No. 297 920. 1979.
28. Nomlyama, K. , and H. ivoraiyama. Metabolism of trichloroethylene
in human sex differences in urinary excretion of trichloroacetic
acid and trichloroethanol. Int. Arch. Arbeitsmed. 28:37.
1971.
29. Bardodej, A., and J. Vyskocll. The problem of trichloroethylene
in occupational medicine. AHA Arch. Ind. Health. 13:581. 1956.
30. McBirney, B.S. TrIchloroethylene and dichloroethylene poisoning.
AHA Arch. Ind. Hyg. 10:130. 1954.
31. Not used in text.
32. Von Oettingen, W.F. The halogenated hydrocarbon of industrial
and toxicological importance. In; Elsevier monographs on
toxic agents. E. Browning, ed. Elsevier Publishing Company.
New York. 1964.
33. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloromethane release.
Publication No. 2529. 1976.
34. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Stratospheric
ozone depletion by halocarbons: Chemistry and transport. 1979.
35. U.S. EPA. State Regulations Files. Hazardous Waste Programs,
WH-563, U.S. EPA., 401 M St., S.W., Washington, DC. 20460.
Contact Sam Morekas. (202) 755-9145.
36. Not used In text.
37. Dawson, English and Petty. Physical chemical properties of
hazardous waste constituents. 1980.
-------
ovJ J i
WASTES FROM USAGE OF ORGANIC SOLVENTS
I. LISTING
The listed wastes are those najor streams which result
from usage of organic solvents. The listed solvents Include
both halogenated and non-halogenated organic compounds. The
specific wastes listed are:
The following spent halogenated solvents: tetrachloroethylene,
.-, methylene chloride, tr ichloroethylene , 1,1,1-tr ichloroethane ,
.^ chlorobenzene, 1,1, 2-trichloro-l,2,2-trifluoroethane, o-di-
v chlorobenzene, trichlorofluororaethane, and the still bottoms
from the recovery of these solvents (T);
The following spent non-halogenated solvents: xylene, acetone,
-"/ethyl acetate, ethyl benzene, ethyl ether, n-butyl alcohol,
,', eye lohexanone, raethanol, methyl isobutyl ketone; and the
\ still bottoms from the recovery of these solvents (I);
The following spent non-halogeanted solvents: cresols and
cresylic acid, and nitrobenzene; and the still bottoms from
the recovery of these solvents (T); and
The following spent non-halogenated solvents: toluene, methyl
ethyl ketone, carbon disulfide, isobutanol, pyridine; and the
still bottoms from the recovery of these solvents (I,T).
Listing codes for the most widely used halogenated
organic solvents are presented in Table 1-1, and codes for
widely-used non-halogenated organic solvents are in Table 1-2.
II. SUMMARY OF BASIS FOR LISTING
Wastes resulting from usage of organic solvents typically
contain significant concentrations of the solvent. Examples
of wastes from usage of organic solvents include still-bottoms
-------
from solvent cec-'very and spent solvents fror !ry cleaning
operations and maintenance anr] repair shops.
The \dainistrator has deternined that waste from usage
of the 24 organic solvents listed In Tables 1-1 and 1-2 may
be a solid waste, and as a solid waste, Tray pose a substantial
present or potential hazard to human health or the environment
when improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations*:
1. Of the list of 24 solvent types presented in Tables
1-1 and 1-2, each solvent exhibits one or more
properties (I.e., ignitability and/or toxlclty)
which pose a potential hazard. These solvents
represent approximately 95 percent or more of
organic solvent usage in the United States (see
Table II-l).
2. The use of organic solvents is widespread throughout
the United States, and the quantities involved are
large; according to Table II-l the total annual
usage of the listed materials as solvents Is over
2.8 X 106 kkg.
3. Of the twenty-four solvents listed in Tables I-
1 and 1-2, nine are listed for meeting only the
ignitability characterisitc. These nine spent
solvents all have a flash point below 60°C (140°F)
and are thus considered hazardous.
*The Agency Is presently aware that these solvents may contain
concentrations of additional toxic constituents Listed In
Appendix VIII of the regulations. For purposes of this
listing, however, the Agency is only listing those wastes for
the presence of the halogenated and non-halogenated solvents.
The Agency expects to study these listings further to deter-
mine whether the waste solvent and still bottom listings
should be amended.
-30-
-------
TABLE T-l
LISTING CODES FOR HALOGENATED ORGAMIC SOLVENTS*
(in order of usage as solvent)
Solvents
Listing
Codes
Flash
Point (°F)
Perchloroethylene
Methylene chloride
Trichloroethylene
1,1,1,-Trichloroethane
Chlorobenzene
1,l,2-Trlchloro-l,2,2-
Trifluoroethane
o-Dichlorobenzene
Trichlorofluoromethane
T
T
T
T
T
T
*A11 data in this table are based on information contained in
Reference (1). Dashes in place of data mean either the values
>--ere not available or (in the case of flash points) not
applicable.
-y-
-------
TABLE 1-2
LISTING CODES FOR NON-HALOGENATED ORGANIC SOLVENTS*
(in order of usage as solvent)
Solvents
Xylenes
Methanol
Toluene
Methyl ethyl ketone
Acetone
Methyl isobutyl ketone
Carbon dlsulfide
Ethyl acetate
Ethyl benzene
Ethyl ether
n-Butyl alcohol
Isobutanol
Cresols and cresylic acid
Cyclohexanone
Nitrobenzene
Pyr idine
Listing
Codes
x**
I,**
I,T**
I,T**
I**
I,**
I,T**
I**
I**
I**
x**
I.T**
T
I**
T
I,T**
Flash
Point (°F)
84(2)
54
39
22(3)
3
61
-25
45(2)
59
-49(2)
115
82
-
111(3)
-
68
* All data in this table are based on information contained in
Reference (1) except as noted. Dashes in place of data mean
either that the values were not available or (in the case of
flash points) not applicable.
**Because the listed waste typically would contain a large
percentage of these solvents, the listed wastes would fail
the ignltability characteristic for liquids—a flash point
less than 60°C (140°F).
-32-
-------
The fifteen solvents listed as either toxic
or toxic and ignitable pose a further hazard to
human health and the environment. If improperly
nanaged, these solvents could migrate from the
disposal site into ground and surface waters,
persist in the environment for extended periods
of time, and cause substantial hazard to environ-
mental receptors.
The two fluorocarbons, 1 ,1, 2-trichloro-1,2,2-
trifluoroethane and trichlorofluororaethanes present
a different type of hazard. Due to their high
volatility, these two organics can rise into the
stratosphere and deplete the ozone, leading to
adverse health and environmental effects.
4. Damage incidents resulting from the mismanagement of
waste solvents have been reported. These damage
incidents are of three types:
(a) Fire/explosion damage resulting from ignition
of the solvents;
(b) Contamination of wells in the vicinity of in-
adequate waste storage or disposal (with re-
sulting illness in at least one instance); and
(c) Direct entry of solvent into a waterway, resulting
in fish kills.
5. These damage incidents show that mismanagement
occurs and that substantial hazard to human health
and the environment may result there from.
III. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Overall Description of Industry Usage*
The primary solvent-using industries and the quantity
of solvents they use annually are as
*Large amounts of chemicals listed in Table II-l are used in
such non-solvent applications as chemical feedstock so that
the total production of specific solvent chemicals for all
applications is often many times larger than the amount
used specifically as a solvent.
-------
Table II-l
RANKING AND AMOUNTS OF THE LISTED SOLVENTS^1)
Amount Used As
Chemical Name Solvent (kkg/yr)
Xylenes 489,900
Methanol 317,500
Toluene 317,500
Perchloroethylene 255,800
Methylene chloride 213,200
Methyl ethyl ketone 202,300
Trlchloroethylene 188,200
1,1,1-Trlchloroethane 181,400
Acetone 86,200
Methyl isobutyl ketone 78,000
Chlorobenzene 77,100
Carbon dlsulfide 77,100
Ethyl acetate 69,900
Ethyl benzene 54,430
Ethyl ether 54,430
n-Butyl alcohol 45,360
l,l,2-Trichloro-l,2,2-tri-fluoroethane 24,040
Isobutanol 18,600
o-Dichlorobenzene 11,800
Cresols & cresylic acid
-------
Paint S Allied Products and Industrial 1,153,500 kkg/yr
Operat ions
Surface Cleaning 610,600 kkg/yr
Pesticide Production 266,700 kkg/yr
Laundry and Dry Cleaning Operations 214,550 kkg/yr
Pharmaceuticals Manufacture 34,740 kkg/yr
Solvent Recovery Operations (Contract and 499,000 kkg/yr
in-house) (feedstock)
Table III-l summarizes the use pattern of the 10 most
widely used solvents in the industrial categories listed
above. These data illustrate the distinct difference between
halogenated and non-halogenated solvents in industrial usage;
the chlorinated and other halogenated solvents in Table
III-l are used almost exclusively in the surface cleaning,
laundry and dry cleaning categories, whereas the non-halo-
genated solvents are used primarily in the production cate-
gories (paint, pesticides and pharnaceuticals). The ten
specific solvents included in this table are believed to
account for about 80 percent of all organic solvent usage. CD
The composition of the spent solvent* is dependent on its
application, but the spent solvent contains up to 90 percent
of the original solvent**. Depending on the recovery techniques,
*Spent solvents Include those solvents which are no longer
useful without further processing either because they have
outlasted their shelf life or because they have been
contaminated, or so changed chemically or physically that
they are no longer useful as solvent.
**United States Environmental Protection Agency. 1976.
Asscssnent of Industrial Hazardous Waste Practices
51 ec t ropla t lnj» and Metal Finishing Industries - Job
Shops P3-264-349.
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sludges which result from reclamation processes contain from 1
to 50% of the original solvent.* However, because of the
economic considerations of the reclaiming process, the solvent
content of the sludge is seldom reduced below 10 percent.**
B. Solvent Usage in Paint & Allied Products and
Industrial Operations
The category of Paint & Allied Products and Industrial
Operations is taken here to include the following solvent-use
industrial operations:
0 Paint & Allied Products Manufacture
8 Roll Coatings
0 Paper Coatings
0 Dye Manufacture
0 Ink Manufacture
0 Adhesive Manufacture
0 Printing Operations
* The Paint and Allied Products and Industrial operations
category accounts for about half of all organic solvent utili-
zation by industry. The Paint and Allied Products portion
of this category is the largest solvent-use subcategory, with
Printing Operations being the second largest use subcategory.
For the Paint & Allied Products Industry, there are
about 1200 paint manufacturing companies that operate more
*United States Environmental Protection Agency. 1979.
Organic Solvent Cleaners-Background Information for
Proposed Standards. EPA-45/12-78-045a.
**United States Environmental Protection Agency. 1978.
Source Assessment: Reclaiming of Waste Solvents. State
of the Art. PB-289-934.
-X-
-------
than 1500 plants. Solvents are Important ingredients in
formulations for solvent-thinned paints, lacquers, and factory-
applied coatings.
Solvent containing wastes arise from the use of solvents
to clean equipment, and still bottoms fron the recovery of the
solvents used in production*. It is estiaated^^ that approxi-
mately one-third of the solvents used for equipment cleaning
are reclaimed, and that 7 x 10& gallons of solvent are
disposed of yearly from this source.
The total quantity of solvent-containing wastes from
the paint industry is estimated to contain 14,300 kkg/yr of
solvents.' ' These are primarily non-halogenated solvents
such as xylenes, methanol, acetone, toluene, MEK, etc.
The remaining Industrial processes Included In this over-
all category (manufacture of inks, adhesives, dyes, and
various types of coatings) utilize organic solvents (primarily
non-halogenated) in much the same manner as the paint industry;
that is, as an important component of formulations and for
equipment cleaning.(D Printing operations also use sol-
vents for cleaning operations and as dye or pigment carriers.
The types of waste generated from these industries should be
generally similar to those from the paint industry and include:
Equipment cleaning wastes;
Still bottoms from solvent recovery.
^Additional waste streams from these Industrial categories (such
as off-specification product and spills of finished product)
are expected to be covered by future listings.
-------
Spent solvents used for equipment cleaning, If not re-
claimed, are drummed and landfilled(*). Most paint companies
contract for waste disposal services. Solvent recovery still
bottons are incinerated, landfII led, or injected into deep
wells.<5>
C. Surface Cleaning
The Surface Cleaning category consists of two
Important subcategories:
0 Industrial Oegreasing
0 Repair work
Industrial Maintenance and Repair
Commercial Service and Repair
Consumer-performed Maintenance and Repair
About half of the solvents used in Surface Cleaning
Operations, as shown In Table III-l, are used in Industrial
Degreasing, (see the Listing Background Document for Solvent
Degreasing Operations) with the other half being used in
various types of repair work.C*) According to Reference
(61, the total number of degreasing operations in the United
States for 1976 was over 1,300,000, of which nearly half
were associated with manufacturing operations of various
types. The major solvents used are trichloroethylene, 1,1,1-
tr Ichloroe thane, and chlorofluorocarbons. Most of the
solvents used in surface cleaning were halogenated, due to
their nonflammable character; this property is especially
important in high-temperature degreasing operations.
-u'-
-------
Neither surface cleaning nor either of its two subcate-
gories can be classified as industry specific, per se; rather,
these operations are conducted in a number of types of indus-
tries (i.e., primary metals, auto repair shops, textile
plants).
With respect to the geographic distribution, industrial
degreasing is the most concentrated source of solvent wastes
from the surface cleaning category since degreasing is asso-
ciated with manufacturing operations that involve metal
finishing (including etching, plating, priming and painting)
and electronic components manufacture. The repair
work subcategory is much more diffuse in distribution, with
both commercial service and repair and consumer-performed
maintenance and repair being generally distributed in the
sane pattern as the population itself.(5)
The major types of wastes iron solvent usage in the
industrial degreasing subcategory are used (spent) solvent
and solvent recovery still bottoms. Wastes from the repair
work subcategory would include both halogenated and non-
halogenated solvents, and would take the form of relatively
small amounts of used solvent (typically up to a few gallons),
plus contaminated rags and other materials.
D. Production of Pesticides, Pharmaceuticals and
Other Organic Chemicals
Solvent applications in the production of pesticides,
Pharmaceuticals and other organic chemicals Include usage as
-------
a reaction (synthesis) medium, and usage in equipment cleaning.(
The solvents used are primarily non-halogenated and are
typically selected for compatibility with the production
process. Toluene is the most widely used solvent in pharraa-
ceuticals manufacture, methanol is used as the reaction
solvent in Nylon 66 production, and acetone is used as the
solvent in the production of cellulose acetate.(D
Wastes from solvent usage in these industries take the
form of off-specification product material, equipment cleaning
wastes, and solvent recovery still bottoms. The destination
of all solid wastes is not known, but a large percentage is
reclaimed either in-house or by contract recovery operations.(5)
Solvent-containing wastes in these industries are not as
geographically distributed as in the other categories discussed
herein, but would be expected to follow the general geographical
pattern of the organic chemical industry.
E. Laundry and Dry Cleaning
There are about 25,000 retail dry cleaning plants
in the United States, 18,000 of which use between 167,000
kkg/yrC7) and 208,000 kkg/yr^1) of perchloroethylene. Of the
other 7000 plants, 6000 use about 72,700 kkg/yr of Stoddard's
solvent*, (which is a petroleum distillate), and 1000 use tri-
chlorofluoroethane at a rate of about 900 kkg/yr.(?) The
*Stoddard solvent is not specifically included in the waste
listings, however, since this solvent has a flash point of
of 105°F (i.e., meets the ignitability characteristic),
it would also be regulated under the Subtitle C regulatory
control system.
-HJ-
-------
solvents are \tsud to remove dirt, grease and other materials.
It is believed that 8 percent^7) of the amount of perchloro-
ethylene used in dry cleaning is disposed of along with still-
botton and cooker residues, so that the amount of perchloro-
ethylene discarded is between 13.4 and 16.6 thousand kkg/yr.
The distribution of dry cleaning plants is uniform with
respect to population and is especially associated with popu-
lation in large urban areas.(7)
Still bottoms from retail dry cleaning consist of about
60 percent solvent and 40 percent oily residue.(7) "Cooker"*
residues are 25 percent solvent and 75 percent spent filter
(mostly diatomaceous earth).(?)
F. Solvent Recovery Operations
Still bottoms from solvent recovery operations are
the renalning waste streams included in this listing. Each
of the solvent use industry categories discussed above generates
feedstocks for solvent recovery operations. Recovery may be
accomplished either in-house or by contract to a recovery firm.
With regard to contract solvent recovery operations,
there are between 80 and 100 contract solvent recovery
operations in the U.S.(^) The surface cleaning category,
and particularly industrial degreaslng operations is one of the
largest sources of spent solvents sent to contract reclaimers.
*A "cooker" is a type of still in which solvent-contaminated
diatonaceous filter powder is heated to drive off the solvent
fraction of the total liquid residue contained in the filter
powde r.
-------
Other important, sources of spent solvents are the paint, ink,
and coatings nanufacturers and manufacturing processes where
very pure solvents are used in organic synthesis (e.g., the
organic chemical and Pharmaceuticals industries).^"' Some
contract reclaiming of solvents is also carried out on sol-
vents fron commercial and industrial dry cleaning operations.
The geographic distribution, by state, of contract solvent
recovery operations is presented in Table III-2.
The volume of feedstock sent to the contract solvent
recovery industry is approximately 287,000 kkg/yr; of this
volume, about 27 percent are halogenated.(*)
Although there are approximately 100 contract solvent
recovery companies, the total nunber of solvent recovery
operations is much larger due to on-site recovery. Of the
total nunber of plants involved in "cleaning operations",
97.89 percent perform on-premises solvent recovery.'**)
Excluding the dry cleaning plants, which are distributed
geographically in the sane pattern as population, the geographic
distribution of all solvent recovery operations is as shown
in Table III-3.
Solvent recovery still bottoms (sludges) from contract
reclaining operations amount to about 73,900 kkg/yr, of which
between 5 and 50 percent is solvent, or an average solvent
content of about 25 percent.(*) About 27 percent of the
solvents in still-bottom sludges are halogenated.^' Thus,
the total still bottom waste from contract reclaiming consists
of the following components:
-------
Table III-2
GEOGRAPHIC DISTRIBUTION OF CONTRACT SOLVENT
RECOVERY OPERATIONS^4)
New Jersey 9
California 9
Ohio 8
Illinois 8
Michigan 7
New York 5
Indiana 4
Massachusetts 3
Rhode Island 2
Maryland 2
South Carolina 2
Georgia 2
Kentucky 2
Tennessee 2
Missouri 2
Texas 2
Connecticut 1
North Carolina 1
Florida 1
Kansas 1
Arizona 1
74
-v#-
-------
C? SCXJvINT 5-CIAIXIN3 C?£?.-ri
State
ii^s-.a
Arizona
.irxar-sas
California
Colorado
Co-~-ac~ *'cnc
P.I
"iorica
Georgia
Illinois
Zcv£
•'.arSiS
r^--.-^-.;
L£j:siar.a
Mai^s
.".arvland
y.assacr.'jser-s
Kicr.icar.
;-;ir.-;eso-a
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KissCviri
vo—ar.a
Ke=rssx=
fevEca
Ke« Harrshire
few Jersey
New Mexico
Sew Voric
Ncrch Carclir-a
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-------
Table III-3 (cx:"'c)
cf Pisr.zs
of l
Lfc=h
Verrxj-t
Virginia
Was hi:*: ten
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-------
13,250 kkg/yr solvent, including 13,320 kkg/yr non-
halogenated and 4,930 kkg/yr halogenated;
54,750 kkg/yr non-solvent contaninant, including oils, waxes
metals and chlorinated and nonchlorinated organics.
The estimate of 25 percent average solvent content, as
presented above, can probably be applied to solvent recovery
still bottons for all of the industries discussed herein,
since the technology used to reclaim solvents is roughly
similar throughout U.S. industry.(8^
Waste Management Practices*
The most widely used management practices for spent
solvents is either recovery/reclamation (either on-site
or by contract recovery operations), land disposal (which
may Include anything from open ground dumping to landfilling),
or incineration. For still bottons, about 8()(8) to 86^)
percent of these bottons from contract solvent reclaimers
*The Agency has concluded that It does have jurisdiction
under Subtitle C of RCRA to regulate waste materials that
are used, reused, recycled or reclaimed. Furthermore, it
has reasoned that such materials do not become less hazard-
ous to human health or the environment because they are
intended to be used, reused, recycled or reclaimed in lieu
of being discarded. Therefore, at this time, applicable
requirements of Parts 262 through 265 and 122 will apply
to the accumulation, storage and transportation of hazardous
wastes that are used, reused, recycled or reclaimed. The
Agency believes this regulatory coverage is appropriate to
the subject wastes. These spent solvents and still bottoms
fron the recovery of these solvents are hazardous in so far
as t^ey are being accumulated or stored in drums or tanks
prior to recycling. Therefore, these wastes will be con-
sidered as hazardous whether recycled or disposed. However,
ac the present time, the management of these wastes during
recycling operations will not be regulated.
-------
are incinerated. Still bottom sludges from both contract
reclaimers and from solvent recovery operations performed
by solvent-using industries, if not Incinerated, are either
landfilled or injected into deep wells.C8,5) Land disposal
of still bottom sludges from contract reclaimers is mostly
in landfills that are covered daily. (**) A small amount
of sludge is used as asphalt extender (about 0.1 percent).
-Vf-
-------
IV. References to Section III
1. Lee, B.B., G.E. Wilklns and E.M. Nichols. Organic
solvent use study. Final Report. EPA No. 560/12-790-
002. NTIS PB No. 301 342. 1979.
2- Wildholz, M. (ed.). The Merck Index. 9th ed. Merck
and Company. Rahway, New Jersey. 1976.
3. Sax, N. I. Dangerous Properties of Industrial Materials.
Van Nostrand Reinhold Publishing Company, New York. 1963.
4. Scofield, F., J. Levin, G. Beeland and T. Laird. Assess-
ment of industrial hazardous waste practices, paint &
allied products industry, contract solvent reclaiming
operations, and factory application of coatings. EPA
No. 530/SW-119c. NTIS PB No. 251 669. September, 1975.
5. Levin, J., G. Beeland, J. Greenberg, and G. Peters.
Assessment of industrial hazardous waste practices:
Special machinery manufacturing industries. NTIS PB No.
262 981. March, 1977.
6. Goodwin, D. R., and D. G. Hawkins. Organic solvent
cleaners - Background information for proposed standards.
EPA No. 450/2-78-045a. NTIS PB No. 137 912. October, 1979.
7. International Fabricare Institute. Silver Spring, Maryland
Personal communication with B. Fisher. December, 1979.
8. Tierney, D.R., and T.W. Hughes. Source assessment
reclaiming of waste solvents. State of the Art. EPA
No. 600/2-78-004f. NTIS PB No. 282 934. April, 1978.
-------
IV. HAZARDS POSED BY THE WASTES
A. Hazardous Properties of the Solvents
The najor halogenated solvents exhibit organic toxic
properties which nake them potentially hazardous to human
health and the environment. In particular, the two halo-
genated solvents, perchloroethylene and trichloroethylene
are on CAG's List of Carcinogens and 1,1,1-trichloroethane
is a suspect carcinogen. All of the listed halogenated
organic solvents, except 1,1,2-trichloro-l,2,2-trifluoro-
ethane, are priority pollutants under Section 307(a) of the
CWA.
A number of the non-halogenated organic solvents also
exhibit toxicity properties. For example, nitrobenzene has
been identified as a suspect carcinogen. These compounds
are toxic via one or aore of the exposure routes inhalation,
ingestion and/or through the skin. Short tern human exposure
to these compounds can have numerous adverse effects. (For
more information on the adverse health effects of these
halogenated and non-halogenated solvents, see Health and
Environmental Effects, pp. 38-45. In addition, almost all
of the non-halogenated solvents also present an ignitability
hazard.
In light of the health hazards associated with the waste
-so-
-------
solvents—particularly those which are genetically active--
and the high concentrations of hazardous solvents contained
in the waste, the Agency believes a decision not to list
these waste solvents as hazardous would be warranted only if
the Administrator were convinced that waste solvents could not
migrate and persist, reaching human or environmental receptors
(if improperly managed). Such assurance does not appear possi-
ble. Not only do all of the waste solvents invarying degrees,
have significant potential for migration, mobility, and persist-
ence, but many have been implicated in actual damage incidents as
well. The Administrator thus believes the hazardous waste
listing to be warranted.
In addition, almost all non-halogenated solvents also
present an ignitability hazard. According to Table 1-2,
the fourteen most-used non-halogenated organic solvents exhi-
bit flash points of 115°F or below, and are thus well below
the limit set for defining an ignitable waste under RCRA
§261.21 (flash point below 140°F); therefore, these spent
solvents and the still bottoms from the recovery of these
solvents are defined as hazardous.
Based on the information in Section III, most of the
wastes from usage of organic solvents are landfilled or Incin-
erated. Smaller amounts of these solvent wastes are either
placed on open land (or rtunps),-into storm sewers, and into
deep wells. Mi snanageinent and improper disposal of these
- *»-)-
-------
wastes by any of these methods could result In a substantial
health and environmental hazard.
Actual damage Incidents (see pp. 32-35) Involving certain
of these listed wastes confirm the dangers of Ignltabllity,
and of leaching of waste constituents from landfills to
groundwater. Improper waste Incineration could also lead to
substantial hazard. Thus, inadequate incineration conditions
(temperature and residence time) can result in emission of
solvents or toxic degradation products. Where a chlorinated
solvent is involved, emissions could be more dangerous than
the waste itself. For example, phosgene Is a partially
combusted chlorinated organic (halogenated solvent) -which is
produced by the decomposition or combustion of chlorinated
organlcs by heat.(^a»^^»^c) Phosgene has been
used as a chemical warfare agent and is recognized as extremely
toxic.
B. Migratory Potential and Persistence of Haloganated And
Non-Halogenated Solvents
The following section discusses the migratory potential,
mobility, and persistence of the Individual waste solvents.
In general, all of these solvents appear capable of sufficient
migration, mobility and persistence to create a substantial
hazard should waste mismanagement occur.
Environmental fate data showing the potential for release
of the Individual halogenated and non-halogenated solvents is
-yfi-
-sz-
-------
J.J • Jt • U A
described below and summarized in Table IV-1 and Table IV-2.
Perchloroethylene
Perchloroethylene, if not properly disposed of, may
niigrate from the waste into the environment via both air and
groundwater exposure pathways.
Having been detected in several sites away from the
disposal area (i.e., found in varying anounts in school
basement air, in basement sumps, and on solid surface samples
at the Love Canal site), perchloroethylene has indeed been
demonstrated to be quite mobile and persistent.^
Methylene Chloride
Methylene chloride, if not properly managed, may migrate
from the waste into the environment. It is very water-
soluble (20,000 mg/1), thus could leach into groundwater
and persist there due to its stability.1*3 It is also very
volatile (350 mm Hg at 20°C) and could present an air pollu-
tion problem because of its high evaporation rate (1.8 times
the rate of ether) and its stability In air and light.10
Trichloroethylene
Trichloroethylene, if not properly managed, may migrate
from the disposal site into the environment via air and
groundwater pathways. First, it is volatile (77 mg Hg at
20°C, 141.04 ram Hg at 40°CS), so it nay be released from
the waste into the air; it has been detected in school and
basement air at the Love Canal site.*"*
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TABLE IV-1
Halogenated Solvents*
Compound
Perchloroethylene
Methylene chloride
Trichloroethylene
1,1,1-Trlcbloroethane
Chlorobenzene
1,1,2-Ttichloro-
1,2, 2-Tr if luoroe thane
1,2-Dichlorobenzene
Tr ichlorof luorome thane
Vapor Pressure
(mm Hg)
19 at 25 °C5
350 at 20 eC
77 at 25°C5
100 at 20°C
10 at 22 °C
270 at 20"C
1.56 at 25 "C5
687 at 20'C11
Solubility in
Water (mg/1)
150 at 25 °C5
20,000 at 25 CC5
1,000 at 20°C5
950 at 25 °C
488 at 25 "C
10 at 258C
145 at 25 CC
1,100 at 25 °u
Octanol/ Water
Partition
Coefficient
3392
20
1952
158
690
100
24002
3352
* Table compiled from data given in "Physical Chemical Properties of Hazardous Waste
Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
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Table IV-2
Non-Halogenated Solvents*
Vapor Pressure
(mm Hg)
Solubility Octanol/Water
in Water Partition Coefficient
Methanol
Toluene
Methyl ethyl ketone
Methyl isobutyl ketone
Carbon disulfide
Isobutanol
Cresols and cresylic
acid ortho (1,2)
meta (1,3)
para (1,4)
Nitrobenzene
Pyridine
100 at 21.2°C
28.4 at 25°C
100 at 25°C
16 at 20°C
260 at 20°C
10 at 25°C
0.24 at 25°C11
0.04 at 20°C11
0.11 at 25°C11
1 at 44.4°C
20 at 25°C
Miscible
470 at 25°C
100,000 at 25°C
19,000 at 25°C
2,200 at 25°C
95,000 at 18CC
31,000 at 40ecH
23,500 at 20°C11
24,000 at 40°C1:L
1,900 at 25°C
Miscible
5
117
1
1
100
8
1102
1022
982
62
5
*Table conpiled from data given in "Physical Chemical Properties of Hazardous
Constituents" (M.S. EPA, 1980) unless otherwise specified by superscript.
-5T-
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It is also relatively water-soluble (1,000 mg/1), so
that it may leach into groundwaters if not adequately contained.
Trichloroethylene has been detected in a nunber of wells and
residue ponds near groundwater contaminated by a chemical
company dump, as well as in basement sumps at the Love Canal
site, confirming its moblity and persistence in groundwater.9
1,1,1-Trlchloroethane
1,1,1-Trichloroethane is a highly mobile compound, and
if not properly managed, could migrate from wastes into
the environment. It is highly volatile (100 mm Hg at 20°C;
approximately 210 mm Hg at 40°C), so that it may be released
from waste sites into the air. Once in the air, it will
only decompose at elevated temperatures. Because of this,
and the fact that 1,1,1-trichloroethane is reactive to sunlight
at high altitudes, while stable at low altitudes., it nay
create air-pollution problems if disposed of inadequately.^
It has been detected in school and basement air at the Love
Canal site.9
1,1,1-trichloroethane is also relatively water-soluble
(950 mg/1) and mobile, particularly where soils are low in
inorganic content.10 jt ±s also relatively persistent In
groundwater where it reacts slowly, releasing hydrochloric acid.l
Chlorobenzene
Chlorobenzene may migrate from the disposal site into the
environment If inadequately disposed of. Its water solubility is
fairly high (488 mg/1) to enable its leaching into groundwater
where it would persist, since It is not anenable to hydrolysis.10
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Chlorobenzene is also volatile so it could be released from
wastes into the air.^-^ It has been detected in school
and basement air, basement sumps, and solid surface samples
at rbe Love Canal site. Because it does not biodegrade
well, chlorobenzene is very persistent in the environment.10
l,l,2-Trichloro-l,2,2-trifluoroethane/Trichlorofluoroniethane
These two solvents, if improperly managed, can migrate from
the disposal site into the environment. They are extremely
volatile (1,1, 2-trichloro-l,2,2-trifluoroethane-270 mm Hg at
20°C, to over 500 mm Hg at 40eC;10 trichlorfluororoethane-
687 mia Hg at 20°C7) and very persistent in the environment
due to resistance to biodegradation, photodecomposition, and
chemical degradation.7 Because of their high volatility and
persistence, after release at the surface of the earth,
these solvents rise to the stratosphere where they may release
chlorine atoms and deplete the ozone. This can lead to
various adverse health and environmental effects resulting
from an increase in the amount of ultraviolet radiation
reaching the earth, as well as possible changes in the earth's
climate induced by the "greenhouse effect".^»4
o - Dichlorobenzene
o - Dichlorobenzene, if disposed of improperly, may
migrate from the disposal site into the environment by both
air and water pathways. Having been detected at several
sites away from the disposal area (found in school and base-
ment air, in basement sumps, and in solid surface samples at
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-iT7-
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the Love Canal site), o-dxchlorobenzene has been demonstrated
to he mobile and persistent.
o-Dichlorobenzenes has a very high octanol/water par-
tition coefficient of 2,400, indicating a high bioaccumulation
potential. Thus, migration, even in small concentrations,
could lead to a chronic toxicity hazard (Appendix A).
Toluene
Toluene, if improperly managed, may migrate from the
the disposal site into the environment. It is relatively
volatile (vapor pressure 28 mm Hg at 20°C) and so -can migrate
via and air pathway. It can re-enter the hydrosphere in
rain.12 Toluene is also capable of migration via a groundwater
pathway since it is relatively soluble (470 mg/1), and persistent
in abiotic environments (such as most aquifers).
Toluene has been detected in school and basement air,
basement sumps, and solid surface samples at the Love Canal
site, demonstrating its mobility and persistence in both air
and groundwater.^
Methyl Ethyl Ketone
Methyl ethyl ketone, if disposed of inadequately may
migrate from the disposal site into the environment. It is
extremely soluble in water (100,000 mg/1), and therefore could
leach into groundwater. It is also very volatile (185.4 mm
Hg at 40°C^), and could present an air pollution problem
if improperly contained. Because of its high solubility
-------
it could be re-entrained from air into the hydroshpere via
rain.
Methyl ethyl ketone has been detected at several sites
near groundwater contaminated by an old chemical company
dump, as well as in school and basement air at the Love Canal
site, demonstrating both its mobility and persistence.5
Carbon Disulfide
Carbon disulfide, if improperly- managed, may migrate
from the disposal site into the environment. It is extremely
volatile (260 mm Hg at 20°C) and althouth subject to photo-
lysis, could present an air pollution problem if inadequately
contained. It is also quite solubl'e in water (2200 tag/1),
and is not known to attenuate in soils; therefore it could
leach into the groundwater, where, being unamenable to hydro-
lysis, it is likely to persist for an extended time period.1°
Isobutanol
Isobutanol, if improperly managed, may migrate from
the disposal site into the environment. It is extremely
water-soluble (95,000 mg/1); thus, if inadequately contained,
it may contaminate surface water and adversely affect its self-
purification ability.10 In addition, Isobutanol could leach
into groundwater if disposal is inadequate!
Cresols (and cresylic acid)
Cresols, if improperly managed, may migrate from the
disposal site into the environment. Cresols are highly
soluble (23,500 to 31,000 ng/1) and are not known to attenuate
-------
significantly in soils; thus, they could leach into groundwater
if disposal is inadequate. Once in water, cresols rapidly
form chlorinated compounds, which are more environmentally
objectionable.10 Cresols are not known to hydrolyze and so
would be likely to persist in groundwater.^
Nitrobenzene
Nitrobenzene, if disposed of inadequately, may migrate
from the disposal site into the environment. It is water-
soluble (1900 mg/1) and would be mobile where soil organic
content is low,10 and thus could leach into groundwater if
disposal is not adequate. It is likely to be highly per-
sistent in groundwater since it is not amenable to hydrolysis
and does not biodegrade well.l^
Pyridine
Pyrldine, if disposed of inadequately, may migrate from
the disposal site. Because pyridine Is raiscible with water,
it has high migratory potential. It would be mobile as well,
unless soil has high clay content.10 Pyridine also would be
likely to persist in the abiotic environment of most ground-
waters .
C. Mismanagement of Wastes Destined for Land Disposal
Documented damage Incidents resulting from the mis-
management of these wastes from usage of organic solvents
are presented below:
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Damage Resulting from Ignitability of Wastes
(1) A load of used pesticide containers delivered to a
disposal site in Fresno County, California, also con-
tained several drums of an acetone-raethanol solvent
mixture. When the load was compacted by a bulldozer,
the waste ignited, engulfing the bulldozer In flames
and dispersed pesticide wastes.(*3)
(2) A large number of drums containing organic solvent wastes
were deposited in a landfill at Contra Costa, California.
In the immediate area were leaking containers of concen-
trated mineral acids and several bags of beryllium wastes
in dust form. The operators failed to cover the wastes
at the end of the day. The combination of wastes ignited
during the night, starting a large chemical fire which
possibly dispersed toxic beryllium oxide.(13)
(3) Two serious fires at the Merl-Nilam Landfill, St. Clare
County, Illinois (August, 1973 and April, 1974) were
attributed to the presence of solvent wastes from plastics
manufacture.(13)
Contamination of Groundwatera
(1) In two separate instances in Michigan, trichloroethylene
was dumped on the ground and later found to have migrated
into groundwater. In one case, trichloroethylene dumped
at a rate of 1000 gallons per year over a four-year
period was detected in residential wells as much as
1100 feet from the site of dumping. Concentrations
ranged as high as 28 ppm.(13)
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In the other case, the Air Force at a base near
Oscoda, Michigan, had problems with contaminated ground-
water because of a leaking tank which use to hold
trlchloroethylene. The problem was compounded when
a waste hauler apparently mismanaged the trichloro-
ethylene that was hauled from the leaking tank, and
groundwater contamination up to four miles away was
considered one of the results. (H)
(2) A sump overflow in 1971 at the Superior Tube Company
allowed trichloroethylene wastes to leak into a cooling
pond. Seepage from this pond was found to contaminate
a private well 75 yards distant and a company well at
the site.(13)
(3) Open du-nping of wastes, including solvent wastes, from
a chemical packing plant by U.S. Avlex Company resulted
in entry of organic solvents into the water table and
contamination of several nearby water wells in 1973.
One family reported illness resulting from use of the
contaminated well water.(13)
(4) [Mono]chlorobenzenes, at concentrations of 5 mg/1 and
30 mg/1 has been detected in the water from 2 of 21 ob-
servation wells, installed at depths up to 50 feet at
varying distances from an industrial manufacturing com-
plex devoted to the development and manufacture of en-
gineering plastics•(1^)
-------
The danage incidents presented above Illustrate the
following potential hazards associated with wastes from usage
of organic solvents:
(1) Ignitability hazard during mismanagement;
(2) Potential toxicity hazard to humans via groundwater
exposure pathways.
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IV. References to Section IV (A, B and C)
1. Jacobs, S. The handbook of solvents. D. Van
Nostrand Company, Inc. New York. 1957.
la. Edwards, J.B. Combustion formulation and emission of trace
species. Ann Arbor Science. 1977.
Ib. NIOSH. Criteria for a recommended standard: Occupational
exposure to phosgene. HEW, PHS, CDC, NIOSH. NTIS PB No.
267 514. 1976.
Ic. Chemical and Process Technology Encyclopedia. McGraw
Hill. 1974.
2. Leo, A., C. Hansch and D. Elkins. Partition coefficients
and their uses. Chem. Rev. 71:525-616. 1971 (Updated 1977).
3. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloromethane
release. Publication No. 2529. 1976.
4. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Stratospheric
ozone depletion by halocarbons: Chemistry and transport.
1979.
5. Patty, F.A., ed. Industrial hygiene and toxicology.
Interscience Publishers, Hew York. 1963.
6. Sax, N. I. Dangerous properties of industrial materials,
5th ed. Van Hostrand Reinhold Company, New York.
1979.
7. U.S. EPA. Environmental hazard assessment of one- and
two-carbon fluococarbons. EPA No. 560/2-75-003. NTIS
PB No. 246 419. 1975.
8. U.S. EPA. Evaluation of treatment, storage, and disposal
techniques for ignltable, volatile, and reactive wastes.
Contract Number 68-01-5160. (Draft final report). 1980.
9. "Love Canal Public Health Bomb", A Special Report to the
Governor and Legislature, New York State Department of
Health. 1978.
10. U.S. EPA. Physical chemical properties of hazardous
waste constituents. (Prepared by Southeast Environmental
Research Laboratory; Jim Falco, Project Officer). 1980.
11. Verschueren, K. Handbook of environmental data on
organic chemicals. Van Nostrand Reinhold Company, New
York. 1977.
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12. Walker, P. Air pollution assessment of toluene.
NTIS PB No. 256 735. May, 1976.
13. U.S. EPA. Open Files. Hazardous Site Control Branch,
1:11-548, U.S. EPA. 401 M St., S.W., Washington, O.C. 20460.
Contact Hugh Kauffman. (202) 245-3051.
14. TSCA Section 8(e) notice from General Electric Company to
U.S. EPA, Region I Permits Branch, January 23, 1980.
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D. Health and Environmental Effects*
Perchloroethvlene (Tetrachloroethylene)
Perchloroethylene (PCE) was reported carcinogenic to
mice.(16) It has also been identified by the Agency as a
chemical which has demonstrated substantial evidence of being
carcinogenic. PCE is chronically toxic to rats and mice, causing
kidney and liver damage;(10»^>21) and to humans, causing impaired
liver function.(-) Subjective central nervous system complaints
were noted in workers occupationally exposed to PCE.(1^' PCE
exposure is reported to cause alcohol intolerance to humans.
PCE is a priority pollutant under Section 307(a) of the
Clean Water Act.
Methylene Chloride (Dichloromethane)
EPA has found "suggestive" evidence of the carcinogenicity
of methylene chloride, therefore, raethylene chloride is
considered a "suspect carcinogen" (Appendix A); methylene
chloride was also reported as being mutagenic to a bacterial
strain, S. typhimurium.(24) jt was reported to be feto- or
enbryo-toxic to rats and mice.(23) Female workers had
gynecological problems after prolonged exposure to methylene
chloride.(36) Methylene chloride also causes central
nervous system depression and elevation of carboxyhemoglobin
levels.d-8) Severe contamination of food or water can
cause irreversible renal and hepatic injury.(30) Acute
toxicity values range from 147,000 to 310,000 ug/1 for aquatic
*F.thyl benzene, which is only being listed for its ignitability
hazard, Is also considered a priority pollutant under Section
lf)7(a) of the Clean Water Act.
-3X-
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organisms (Appendix A)
Trichloroethylene
Trichloroethylene (TCE) has been reported to be carcino-
genic to mice.***' It has also been identified by the Agency
as a chemical which has demonstrated substantial evidence of
being carcinogenic.(38) Industrial exposure to TCE caused
some cases of central nervous system disturbances (headaches,
insomnia, tremors) as well as peripheral nervous system
impairment (neuritis, temporary loss of tactile sense, finger
paralysis).'^»^3) Rare cases of hepatic damage have been re-
ported following repeated abuse of TCE.(*>)
TCE was found to be toxic in varying degrees to several
freshwater organisms.'28) There was also a 50% decrease
noted in 14C uptake by a saltwater algae at a concentration
of 8,000 mg/1.(2°)(Appendix A)
1,1,1-Trichloroethane (Methyl Chloroform)
Data regarding the carcinogenic!ty of 1,1,1-trichloroeth-
ane is inconclusive.(17) jt is rautagenic in the Ames test,
and in a mamallian cell transformation system (See Appendix
\). Chronic exposure, albeit is greter than ambient levels,
can cause central nervous system disorders in humans. Animal
studies showed toxic effects on the central nervous system,
cardiovascular system, pulmonary system, and induced liver
and kidney damage.(34) I,1,1-Trichloroethane is a priority
pollutant under Section 307(a) of the Clean Water Act.
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Chlorobenzene (Honochlorobenzene, MCB)
Chlorobenzene has been found to produce histopathological
changes in the lungs, liver, and kidneys following its inhalation
by rats, rabbits and guinea pigs.^7^ Oral administration of
monochlorobenzene to rats was reported to cause growth retar-
dation in males. (H) MCB also appears to Increase the activity
of some microsoraa1 enzyme systems, which enhances the metabolism
of many drugs, pesticides, and other xenoblotics.(29)(Appendix A)
MCB was reported to be toxic to varying degrees to
several fresh- and salt-water organisms, including algae,(28)
has a high biomagnification factor (Appendix B), is resistant
to biodegradation and hydrolysis and is, therefore, persistent.
MCB is a priority pollutant under Section 307(a) of the
Clean Water Act, is a subject of TSCA section 4 Test Rule, and
has been selected for bioassay by NCI. These regulatory actions
point to concern regarding its toxicity.
1,1,2 Trichloro-1,2,2 trifluoroethane
The Agency's primary concern in Listing this solvent is
the air pollution hazard resulting from its release at the
surface of the earth. This can have many adverse health and
environmental effects including increased incidence of skin
cancer, reduced productivity in several important agricultural
crops, and increased mortality in the larvae forras of several
important seafood species resulting from the depletion of
the ozone. (39»*0) Because of these effects, EPA is currently
considering regulation of CFC production and use.
-------
1,2-Dichlorobenzene (ortho isomer)
Ortho 1,2-dichlorobenzene exhibits moderate toxicity via
inhalation and oral routes. The major toxicological effect
is injury to the liver and kidneys; it is also a central ner-
vous system depressant after short periods of exposure'^*»**)
(Appendix A).
1,2-dichlorobenzene is designated a priority pollutant
under section 307(a) of the Clean Water Act.
Trichlorofluoromethane
The Agency's primary concern in listing this solvent is
the air pollution hazard resulting from its release at the
surface of the earth. This can have many adverse health and
environmental effects including skin cancer resulting from
the depletion of the ozone (Vide Suf ora) . O9 > *°) However,
additional adverse health effects have been found and are
presented below.
Exposure of rabbits to trichlorofluoromethane was re-
ported to cause cardiac arrhythmias.(26) jt induced
cardiac arrhythmias, sensitized the heart to epinephrine-
induced arrhythmias, and caused tachycardia (increased
heart rate) myocardlal depression, and hypertension in the
monkey, dog, rat and mouse.(26)
Trichlorofluoromethane is a priority pollutant under
Section 307(a) of the Clean Water Act.*
*The Agency has recently proposed to remove trichlorofluoro-
methane from the list of toxic pollutants under §307(a) of
the Clean Water Act (45 FR 46103, July 9, 1980).
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Toluene
Toluene Is a toxic chemical absorbed into the body by
inhalation, Ingestion, and through the skin. Data on its
mutagenicity and carcinogenic!ty are inconclusive, but it
has been reported to cause chromosomal change; teratogenic
problems were also recently reported.'^7) The acute
toxic effect is central nervous system depression, (*5;
and irritation of eye and throat. These effects occur at
low concentrations [200 ppm].^^^ Chronic occupational
exposure to toluene has led to the development of neuro-muscular
disorders. Occupational exposure to female workers to toluene
reported to cause several reproductive problems, both to the
wonan and the offspring.(25) Chronic toluene exposure can
cause dermatitis, affect the immune system, and cause permanent
damage to the central nervous system. (^8)
Since toluene is metabolized in the body by a protective
enzyme system which is also involved in the elimination of
other toxins, it appears that over-loading the metabolic
pathways with toluene may greatly reduce the clearance of
other more toxic chemicals. Additionally, the high affinity
of toluene for fatty tissue can assist in the absorption of
other toxic chemicals Into the body. Thus, synergistic
effects of toluene on the toxicities of other contaminants
may render the waste stream more hazardous (Appendix A).
Toluene is a priority pollutant under Section 307(a) of
the Clean Water Act.
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Methyl Ethyl Ketone
Methyl ethyl ketone Is a highly volatile ignitable liquid
of moderate toxicity via ingestion which can affect the
peripheral nervous system and is an experimental teratogen
(Appendix A). It is also a strong irritant of the raucous
membranes of the i-y»s and nose. A lethal dose in animals
(LC5Q - 700 ppm) has caused marked congestion of the internal
organs and slight con^---tio: cf the brain. Lungs also showed
emphysema (Appendix A).
Carbon Disulfide
Short term human exposure to low atmospheric concentrations
of carbon disulfide may result in central nervous system de-
pression, headaches, breathing difficulty and gastrointestinal
disturbances. Exposure to short term but high atmospheric
concentrations can lead to narcosis and death. The symptoms
of humans subjected to repeated exposure to hign concentrations
or prolonged exposure to low concentrations include insomnia,
fatigue, loss of memory, headache, melancholia, vertigo and
loss of appetite. Visual impairment, loss of reflexes, and
lung irritation has been reported.C1^, 22) Rats and mice exposed
8 hours per day for 20 weeks to an average concentration of 37 ppm
carbon disulfide showed evidence of toxic effects.(19)(Appendix A)
Isobutanol
Rats receiving isobutyl alcohol, either orally or subcu-
taneously, one to two times a week ;'->r 495 to 643 days showed
liver carcinomas and sarcomas, spleen s^. omas and myelold
leukemia.<43)
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Ingestion of one molar solution of Isobutyl alcohol in
water by rats for 4 months did not produce any inflammatory
reaction of the liver. However, rats ingesting a two molar
solution for two months developed Mallory's alcoholic hyaline
bodies in the liver and were observed to have decreases in
fat, glycogen, and RNA in the liver.C43)
Acute exposure to isobutyl alcohol causes narcotic effects,
and irritation to the eyes and throat in humans exposed to
100 ppm for repeated 8 hour periods. Formation of facuoles
in the superficial layers of the cornea and loss of appetite
and weight were reported among workers subjected to an undeter-
mined but apparently high concentration, of isobutyl alcohol.(**)
(Appendix A)
Pyridlne
Pyrldine exhibits moderate toxi--.-. when absorbed into
the human body through oral, dermal, and inhalation routes.(22)
Liver and kidney damage has been produced in animals and man
after oral administration.(3) in small doses, conjunctivitis,
dizziness, vomiting, diarrhea and jaundice may appear; tremors
and ataxia, irritation of the respiratory tract with asthmatic
breathing, paralysis of eye muscles, vocal cords and bladder
also have been reported.(22)
Adverse taste in fish (carp, rudd) has been reported at
5 ppra. Pyridine causes inhibition of cell multiplication in
algae and bacteria at 28 and 340 ppm respectIvely.'^'(Appendix A)
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Nitrobenzene
Nitrobenzene is a suspected carcinogen.'^' When
administered to pregnant rats, it caused abnormalities in
some of the fetuses examined.'"' Changes were observed
in the chorionic and placental tissues of pregnant workers
exposed to nitrobenzene,^) and menstrual disturbances
after chronic exposure have been reported. Chronic exposure
to nitrobenzene has been found to cause a variety of blood-
variety disorders.
Nitrobenzene is toxic in varying degrees to several
salt- and fresh-water organisms.(3D (Appendix A), and nitro-
benzene is a priority pollutant under Section 307(a) of the
Clean Water Act.
Cresols (Cresylic Acid)
Cresol is highly toxic if orally administered, and
moderately toxic if inhaled. Absorption may result in damage
to kidney and liver as well as the central nervous system.(22)
Exposure to cresol can cause severe skin burns and derma-
titis .(19 • 22>(Appendix A)
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VII. References to Section IV, D
1. Bardodej, A., and J. Vyskocil. The problem of trichloro-
ethylene in occupational medicine. AMA Arch. Ind. Health.
13:581. 1956.
2. Coler, H.R. , and H. R. Rossmiller. Tetrachloroethylene
exposure in a small industry. Ind. Hyg. Occup. Med.
8:227. 1953.
3. Deichmann, W.R. Toxicology of drugs and chemicals.
Academic Press Inc., New York. 1969.
4. Dorigan, J. and J. Hushon. Air pollution assessment
of nitrobenzene. NTIS PB No. 257 776. May, 1976.
5. Gosselin, R.E., et. al. Clinical toxicology of
commercial products, 4th ed. The Williams and
Wilkin Company, Baltimore. 1976.
6. Huff, J.E. New evidence on the old problems of trichloro-
ethylene. Ind. Med. 40:25. 1971.
7. Irish, D.D. Ralogenated hydrocarbons:II. Cyclic.
In Industrial hygiene and toxicology, V.II, 2nd ed.
F. A. Patty, ed. Inter science, New York.
p. 1333. 1963.
8. Kazanina, S.S. Morphology and histochemistry of
hemochorial placentas of white rats during poisoning of
the maternal organisms by nitrobenzene. Bull. Exp. Biol.
Med.(USSR) 65:93. 1968.
9. Not used in text.
10. Klaassen, C.D., and G.L. Plaa. Relative effects of
chlorinated hydrocarbons on liver and kidney function in
dogs. Toxicol. Appl. Pharmacol. 1967.
11. Knapp, W. K., Jr., et al. Subacute oral toxlclty of
monochlorobenzene in dogs and rats. Toxicol. Appl.
Pharmacol. 19:393. 1971.
12. Not used in text.
13. McBirney, B.S. Trichloroethylene and dichloroethylene
poisoning. AMA Arch. Ind. Hyg. 10:130. 1954.
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14. Medek, V., and J. Kovarik. The effects of perchloro-
ethylcne on the health of workers. Pracovni Lekarstvi
25:339. 1973.
15. National Cancer Institute. CareInogenesls bloassay
of trichloroethylene. NCI-CG-TR-2. NTIS PB No. 264 122.
1976.
16. National Cancer Institute. Bioassay of tetrachloro-
ethylene for possible carcinogenicity. NCI-CG-TR-13.
NTIS PB No. 272 940. 1977.
17. National Cancer Institute. Bioassay of 1,1,1-trichloro-
ethane for possible carcinogenicity. NCI-CG-TR-3.
NTIS PB No. 265 082. 1977.
18. National Institute for Occupational Safety and Health.
Criteria for a recommended standard: Occupational
exposure to methylene chloride. HEW Pub. No. 76-138.
U.S. DHEW. Cincinnati, Ohio. 1976.
19. Patty, F.A., ed. Industrial hygiene and toxicology.
Volume II. Interscience Publishers, New York. 1963.
20. Pearson, C.R., and G. McConnell. Chlorinated CL and 0,2
hydrocarbons in the marine environment. Proc. R. Soc.
London B 189:302. 1975.
21. Rowe, V. K., et al. Vapor toxicity of tetrachloroethylene
for laboratory animal and human subjects. AMA Arch. Ind.
Hyg. Occup. Med. 5:566. 1952.
22. Sax, N. I. Dangerous properties of industrial materials,
5th ed. Van Nostrand Reinhold Company, New York. 1979.
23. Schwetz, B. A., et al. The effects of maternally inhaled
trichloroethylene, perchloroethylene, methyl chloroform,
and methylene chloride on embryonal and fetal development
in mice and rats. Toxicol. Appl. Pharmacol. 32:84. 1975.
24. Simmon, V. F., et al. Mutagenic activity of chemicals
identified in drinking water. S. Scott, et al. eds.
In; Progress in genetic toxicology. 1977.
25. Syrovadko, 0. N. Working conditions and health status
of women handling organos11iceous varnishes containing
toluene. Gig. Tr. Prof. Zabol. 12:15. 1977.
26. U.S. EPA. Environmental hazard assessment report:
Major one- and two-carbon saturated fluorocarbons;
review data. EPA No. 560/8-76-003. NTIS PB No.
257 371. August, 1976.
27. Not used in text.
- 7JT-
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28. U.S. EPA. In-depth studies on health and environmental
Impacts of selected water pollutants. Contract No. 68-01-4646.
1978.
29. U.S. EPA. Chlorinated benzenes: Ambient water quality criteria.
NTIS PB Ho. 297 919. 1979.
30. U.S. EPA. Haloraethanes: Ambient water quality criteria.
NTIS PB No. 296 797. 1979.
31. U.S. EPA. Nitrobenzenes: Ambient water quality criteria.
NTIS PB No. 296 801. 1979.
32. U.S. EPA. Tetrachloroethylene: Ambient water quality
criteria. NTIS PB No. 292 445. 1979.
33. Not used in text.
34. U.S. EPA. Chlorinated ethanes: Ambient water quality
criteria. NTIS PB No. 297 920. 1979.
35. Verschueren K. Handbook of environmental data on organic
chemicals. Van Nostrand Reinhold Company, New York, 1977.
36. Vozovaya, M.A. Gynecological illnesses in workers of
major industrial rubber products plants occupations.
Gig. Tr. Sostoyanie Spetsificheskikh Funkts. Tab.
Neftekhim. Khim. Prom-Sti. (Russ.) 56. (Abstract). 1974.
37. Not used in text.
38. U.S. EPA. Office of Research and Development. Carcinogen
Assessment Group. List of Carcinogens. April 22, 1980.
39. National Academy of Sciences, National Research Council.
Halocarbons: Environmental effects of chloromethane release.
PB Ho. 2529. 1976.
40. National Academy of Sciences, National Research Council.
Committee on Impacts of Stratospheric Change. Strato-
spheric ozone depletion by halocarbons: Chemistry
and transport. 1979.
41. Linari, F., G. Perreli, and D. Varese. Clinical observa-
tions and blood chemistry tests among workers exposed
to the effect of a complex ketone--methyl isobutyl ketone.
Arch. Sci. Med. 226-237. 1964. (Ital).
42. Specht, H., J.W. Miller, P.J. Valaer, and R.R. Sayers.
Acute response of guinea pigs to the inhalation of
ketone vapors. N1H Bulletin No. 76. Federal Security
Agency. Public Health Service, National Institute of
Health, p. 66.
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43. Gibel, et al. Exp. Chlr. Forsch. 1:235. 1974.
44. Smith et al. Arch. Ind. Hyg. Occup. Med . 10:61. 1954.
45. U.S. EPA. Toluene: Ambient water quality criteria.
NTIS PB No. 296 805. 1979-
46. NIOSH. Registry of toxic effects of chemical substances.
Toluene. 1978.
47. Nawrot, P. S., and R. E. Stapler. Embryofetal toxiclty
and teratogenlclty of benzene and toluene In the mouse
(abstract). Teratology. 19:41a.
48. Cohr, K. H., and J. Stockholm. Toluene-a toxlcologic
review. Scand. J. Environ, and Health. 5:71-90. 1979.
-4X-
-77-
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Response to ^oivmepts (Proposed Listings (December 18, 1978))
One commenter objected to the listing "Waste non-
halogenated solvent (such as raethanol, acetone, iso-
propyl alcohol, polyvlnyl alcohol, stoddard solvent
and methyl ethyl ketone) and solvent sludges from
cleaning, compounding milling and other processes."*
The commenter argued that without indicating the con-
centration or quantity of the solvent in the waste,
the Agency would be listing wastes as hazardous even
if the solvent were present in small concentrations and
quant i t ies.
In the listing promulgated today for waste solvents,
the Agency is only listing those spent solvents or
still bottoms from the recovery of these solvents
which would contain substantial quantities and con-
centrations of the solvent. For example, spent solvents
can contain up to 90% of the original solvent while
the still bottoms may contain up to 50% of the spent
solvent.
' \ number of commenters objected to the listing of poly-
vinyl alcohol (PVA) as a solvent. These commenters
argued that PVA is not a solvent but is a solid and
can only be used as a solute. Therefore, they recommended
that PVA be removed from the list.
*This specific listing will not be included in the final
regulation; however, ic will be covered under the generic
listing "The Spent non-hrilogenated solvents...."
- 1C- .
-------
The Agency agrees with the comnenters and therefore,
has removed PVA from the listing.
A number of comraenters objected to the listing of waste
halogenated/non-halogenated solvents. They felt that
the listing was too vague and ambiguous.
In the listings promulgated today, the Agency has
specifically listed only those solvents for which data
or information are available which Indicates a present
or potential hazard could be posed to human health and
the environment if improperly managed. Therefore, the
listing description promulgated today should respond
to the comraenters' objection.
-7
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Response to Connents - Spent Halogenated and Non-Halogenated
Solvents and the Still Bottoms/Sludges From the Recovery of
These Solvents
A number of comments were received with respect to wastes
F001 to F005 (Spent halogenaced and non-halogenated solvents
and the still bottoms/sludges from the recovery of these
solvents ).
1. One comnenter requested that the Agency clarify or
define what it means by the term "spent". For example,
the comnenter questioned whether "spent" refers to the
state of the chemical which was pure Initially but
now appears in the waste stream after being used, or
whether it refers to the altered or decomposed state of
a chemical which has outlasted its shelf life.
The Agency agrees with the commenter and has
thus included the following definition for "spent
solvents" in the listing background documents:
"Spent solvents include those solvents which
are no longer useful as solvents without
further processing (i.e., solvent reclamation)
either because the solvents have outlasted
their shelf life, or because the solvents
-------
have been contaminated or chemically or
physically changed.
It should be clear from this discussion that the
wastes encompassed by this listing do not include waste
streams where the solvent is a contaninant, such that
the waste stream is not a spent solvent, as defined
above* Thus, wastes which contain as constituents
solvents which are used in the industrial process
are not included within the scope of this listing.
Nor are these waste streams hazardous by virtue of the
nixing rule (§261. 3(a)(2)(ii)), since a spent solvent is
not being mixed with another solid waste.
The Agency, however, does not believe it appropriate
to define the term "spent solvent" by using a quantity/
volume cut-off (i.e., spent solvents include those
solvents which contain x percent or more of solvent).
As we have indicated in other support documents (see e.g.,
Background Document on EP toxicity), the Agency does not
presently believe sufficient information exists to
establish minimum waste concentration levels for toxic
constituents, except for those regulated by the Interim
Primary Drinking Water Standards. We intend to make
case-by-case determinations via the delisting mechanism
to remove those wastes containing minimal concentrations
of "spent solvent".
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2. Another conmenter argued that the scope of the listing
of both spent solvents and still bottoms/sludges from
the recovery of solvents, is overinclusive because it
does not recognize that certain solvent recovery opera-
tions produce non-hazardous still bottoms.* For example,
the commenter stated that it is possible to produce a
nonleaching, non-ignitable fused waste solid containing
as low as 5 percent solvent. Therefore, the comraenter
recommends that solvent recovery still bottoms be defined
as f oHows :
"Solvent recovery still bottons: residue from
the distillation/evaporation process of re-
covered solvent which has more than 10% of
the original solvent (excluding water) re-
ma ining"
The Agency disagrees with the coramenter. In the
first place, the commenter has not correlated the
recommended concentration of solvent with a showing that
exposure to these levels of contaminant will not cause
substantial hazard. Nor is there documentation for the
claim that still bottoms containing 52 of the listed
solvent would be incapable of posing substantial harm if
misnanaged. Furthermore, the Agency believes that
*It should he noted that tliis comment was directed to waste
I'004 (the following spent non-haloge n* t ed solvents: cresols
and cresylic acid, and nitrobenzene; and the still bottoms
from the recovery of these solvents). However, EPA's res-
ponse is nlso applicable to wastes FDfll, F002 and F005.
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still bottoms containing 5* of the lasted solvent
nay Indeed pose a substantial hazarr, to human health
and Che environment if improperly ma'iaget^* This premise
is based on the following factors:
(1) The reconnended cut-off level f/50,000 pp ) is at least
an order of magnitude above thit needed to\iause
acute effects, and in most cas* orders of m .nitude
higher (see Appendix A to the isting backgro .M
document). Thus, still bottom- with 5% concent"ition
of a listed solvent would only have to leach a
snail percentage of the contaMed solvent to cause
substantial hazard.
(2) Cresols, cresyllc acid and nitrobenzene are all
toxic chemicals: nitrobenzene Is a suspect carcino-
gen and has been found to cau.ie a variety of blood
disorders from chronic exposire. Cresols and
cresylic acid are highly tox z if administered
orally and moderately toxic if inhaled. In addition,
cresol and cresylic acid may result In damage to the
kidney and liver as well as :o the central nervous
system.
(3) Because of the toxicity of hese solvents, the
concentration of solvent in the still bottoms
(five percent) is considere significant by the
Agency.
*Ac
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(4) All of these solvents have high or appreciable
water solubilities (nitrobenzene: water solubility
1900 rag/1 (Appendix B); cresols and cresylic acid:
water solubilities 23,500 and 31,000 rag/1 (Appendix
B) and therefore, could leach into groundwater under
improper disposal conditions.
(5) All of these solvents are likely to persist in
groundwater; cresols, cresylic acid and nitrobenzene
are not known to hydrolyze while nitrobenzene also
does not biodegrade well.J^/
The Agency therefore, believes that still bottoms from
the recovery of cresols and cresylic acid, and nitro-
benzene raay pose a substantial hazard to hunan health
and the environment even when five percent of solvent
is in the waste. If an individual generator believes
his still bottoms are non-hazardous, the generator
should petition the Agency to de-list his waste (see
§5260.20 and 260.22).
3. One comnenter criticized EPA's generic designation of
all spent chlorinated fluorocarbons as hazardous.
Therefore, the commenter believes that the broad category
(chlorinated fluorocarbons) should be replaced by specific
conpounds for which documented evidence of hazard is
available. The comnenter also argued more specifically
*These data are all taken from Appendix B to the listing
background document.
-------
that trichlorofluoromethane and dlchlorodifLuoromethane
are not hazardous constituents^/ and that EPA's reason
for regulating these materials--that they can rise Into
the stratosphere and deplete the ozone leading to adverse
health and environmental effects—has not yet been
proven. The commenter pointed out that the most sophisticated
statistical analyses of actual ozone measurements taken
at various places around the world have consistently
failed to detect the depletion calculated to have
occured to date, despite the fact that the most recent
analyses should detect this depletion even if it were
only half the calculated amount. The comraenter also
argued that there have been growing indications that
the current ozone depletion theory as it applies to
chlorofluorocarbon depletion does not accurately describe
the present-day atmosphere, or fails to consider aspects
of atmospheric chemistry which are both significant and
important. Cited in support is the study Chlorofluoro-
carbons and Their Effects on Stratospheric Ozone (2nd Rpt.)
Pollution Paper No. 15, Department of Environment, Central
Directorate on Environmental Pollution, October 1979.
coranenter cited several reasons for this statement:
(1) the Health and Environmental Effects Profile (Appendix
A) indicates that both trichlorof1uoromethane and dichloro-
fluororaethane are non-toxic, (2) EPA's proposed action to remove
these two compounds from the Clean Water Act toxic pollutant
list Indicates EPA's admission as to the innocuous nature
oC these two compounds in the aquatic environment, and (3)
EPA's United discussion of the various factors under
§261.11(a)(3) of RCRA indicates that wastes containing these
two compounds pose no hazard during storage, transportation,
treatment or disposal.
-------
Therefore, the coramenter requested that all chlorinated
fluorocarbons be deleted from the F001 and F002 generic
waste list.
The Agency disagrees with the commenter on both
points. With respect to their concern regarding the
generic designation of all spent chlorinated f luorocarbons
as hazardous, the Agency believes that all chlorinated
fluorocarbons share the same physiological and photo-
chemical attributes of concern, namely depletion of
the ozone. Therefore, the Agency feels justified
in listing the broad categorv of chlorinated fluorocarbons
as hazardous, rather than its Individual members.
As to the hazardous nature of the listed chloro-
fluoromethanes, the Agency agrees that they pose a low
potential for adverse acute effects at ambient air
concentrations, although there Is some indication that
long terra exposure to very low levels «400 ppt) will
have chronic effects (Health Assessment Document, EPA,
October, 1980). In the present instance, however, the
Agency's overriding concern relates to the fact that
chlorinated fluorocarbons nay indirectly cause skin
cancer due to the depletion of stratospheric ozone.
^uch depletion leads to Increased Intensity of damaging
ultraviolet light at the earth's surface. This, in turn,
Leads to Increased skin cancers, reduced productivity of
several Important agricultural crops and Increased
-------
mortality in the larval forms of several important seafood
species. The fact that these compounds are proposed to
be deleted from the list of toxic pollutants under
Section 307(a) of the Clean Water Act does not affect
our conclusion, since Section 307 does not address
adverse effects arising from air exposure pathways.
The Agency has analyzed the British Ministry of
the Environment report and has concluded that there are
few differences in regards to the science of CFC transport
into the stratosphere and the reactions involving ozone
destruction between this report and a recent National
Academy of Sciences report which provides the basis for
EPA's regulatory action banning the manufacturing,
processing and distribution of chlorinated fluorocarbons
for those non-essential aerosol propellant uses which
are subject to TSCA authority (A3 FR 11301, March 17, 1978).
While the British Ministry of the Environmental report
concluded that ample cause for regulating CFCs does
not presently exist, the Agency strongly believes that
their is sufficient evidence to regulate and limit
chlorinated flurocarbon emissions. In the judgment of
F.PA, chlorinated fluorocarbons can be a significant
component of a solvent waste stream, can migrate into
the environment (stratosphere) if improperly managed,
are persistent (remaiiing intact long enough to migrate
to the stratosphere^, and nay pose ii substantial hazard
-------
to human health and the environment. They thus should
be regulated as hazardous wastes.^/ We also note that
the Food and Drug Adninistration (FDA) has promulgated
regulations which prohibit the use of chlorinated fluro-
carbons as propellants In containers for products subject
to the Federal Food, Drug, and Cosmetic Act.
One commenter argued that the "T" (toxic) designation
assigned to several of the waste solvents listed under
F005, is Ill-conceived in light of the information
presented in the regulations and in the background
documents; specifically, methanol, toluene, methyl
ethyl ketone, methyl isobutyl ketone, pyridene and
carbon disulfide. More specifically the commenter
noted:
Methanol - this compound is not found to be
carcinogenic, mutagenlc or tera-
togenic
Toluene - this compound is shown not to be
carcinogenic, mutagenic nor teratogenlc
Methyl Ethyl - this compound is shown to have
Ketone
no chronic toxiclty
Methyl Isobutyl - this compound is shown to have
Ketone
no chronic toxiclty
lt should be noted that the Office of Toxic Substances/
U.S. Environmental Protection Agency Is currently considering
further regulation of chlorinated fluorocarbon production
and use.
-------
Pyridine - this compound is not carcinogenic
or mutagenic and the determination
of teratogenicity is questionable
Carbon disulfide - this compound is shown to have
no chronic toxicity
Therefore, the commenter recommends that these compounds
no longer be designated as toxic wastes.
The Agency continues to believe that all of these
spent solvents, with the exception of methanol and methyl
isobutyl ketone should continue to be listed as toxic.
In reviewing the data available in the record, the
Agency believes that there is sufficient evidence to
continue to list these solvents as "toxic" wastes
(except for methanol and methyl isobutyl ketone). As
explained in the health and environmental effects section
of the listing background document, "Waste from usage of
organic solvents" as well as the respective Appendix A
health profiles for these compounds, it has been reported
that chronic low level exposure to toluene has caused
chromosome damage In humans and has led to the development
of neuro-muscular disorders. Toluene has also been
reported to cause reproductive problems to female workers
during occupational exposure.
Methyl ethyl ketone (MEK), although only moderately
toxic via ingestlon, can affect the peripheral nervous
system and Is an experimental teratogen. In addition,
lethal doses in animals caused marked congestion of
the internal organs and slight congestion of the brain.
-------
Chronic exposure to pyridine has produced liver
and kidney damage in both animals and humans. In
addition, snail doses of pyridine have produced tremors
and ataxia, irritation of the respiratory tract with
asthmatic breathing and paralysis of the eye muscles,
vocal cords and bladder.
Chronic exposure to carbon disulfide can affect the
cardiovascular and central nervous system, causing
personality changes. In addition, exposure to short
terra, but high atmospheric concentrations can lead to
narcosis and death. Carbon disulfide is also suspected
of being teratogenic. Therefore, these solvents will
continue to be listed as toxic.
The Agency, however, agrees with the commenter that
both spent methanol and methyl isobutyl ketone were im-
properly listed as toxic wastes. Methanol's oral toxicity
is rated as low*y and in fact is permitted in foods for
hunan consumption as an additive. Methyl isobutyl ketone's
principal toxic effects appears to be irritation of the
eyes and mucous membranes, and gastrointestinal upset.
Under these circumstances, we do not believe a toxicity
listing for these solvents is appropriate, thus, the
Agency will no longer list spent methanol and methyl
isobutyl ketone as toxic wastes. However, both methanol
Tnd methyl isobutyl ketone are ignitable (flash points
Fa-:, \". Irving. Dangerous Properties of Industrial
".iterlals. 5th ed. Van Nostrand Reinhold Co.
Vcw York. 1979
-------
of 54"F and 61°F, respectively). Thus spent nethanol and
rnethyl isobutyl ketone will continue to he listed as
ignitable hazardous wastes.
5. One conmenter criticized the Agency's determination
that chlorobenzene , o-dichlorobenzene, methanol, toluene,
methyl ethyl ketone, methyl isobutyl ketone, isobutanol
and ethyl benzene are persistent and do not degrade
well. The comnenter argued that this inclusion is
contrary to the published literature, including this
Agency's own studies, which shows that biodegradation is
the preferred method of treatment for these compounds
in aqueous solutions. The commenter therefore, believes
that the degradation data within the listing background
document should be reviewed and properly assessed in
listing.
We note Initially that the comnenter's claims are
largely unsubstantiated. We note further that bio-
degradation plays a limited role in the environmental
persistence of the waste constituents because groundwater,
the exposure pathway of paramount concern, is abiotic.
\s pointed out in the listing background document (pp.
57-61), a nunber of these solvents have migrated via
air and groundwater pathways, and persisted for long
periods of time, and caused substantial hazard in the
course of actual waste nan.i",ene nt practice. Thus,
- °\\-
-------
chlorobenzene, o-dichlorobenzene, toluene and methyl
ethyl ketone have all been detected In basement air,
sump pumps and/or in solid surface samples in the Love
Canal area.J^/ All of these solvents (chlorobenzene,
o-dichlorobenzene, toluene and methyl ethyl ketone) are
thus demonstrably persistent enough to have migrated
from a disposal site and contaminate adjacent areas to
create a substantial hazard.
In addition, the following properties/character-
istics of these compounds indicate further the persis-
tence of these solvents;**/
chlorobenzene - this solvent is not amenable to
hydrolysis nor does it biodegrade very well
and therefore is expected to persist in the
environment.
toluene - this solvent is persistent in abiotic
environments (such as most aquifers) and
therefore is expected to persist in groundwater.
Toluene also is relatively soluble (water
solubility 470 mg/1 at 25°C), and thus would
be expected to migrate into groundwater.
methyl ethyl ketone - this solvent, in addition to
being reported at Love Canal, has been de-
tected at several sites near groundwater
±1 Since raethanol and methyl isobutyl ketone are no longer being
considered toxic, a discussion on their persistence is no
longer appropriate.
*_^/These data are all taken from the listing background document,
"Waste from usage of organic solvents".
-------
contaminated by an old chemical company dump,
again showing migratory potential and per-
sis tence ,^_l
With respect to isobutanol, the Agency has not
made any claim as to the persistence of this compound;
however, due to its toxicity and extremely high water
solubility (water solubility 95,000 mg/1 at 18*C), the
Agency believes that this solvent may pose a substantial
hazard to human health and the environment if improperly
managed.
Finally, ethyl benzene is being listed because of
its ignitability hazard, not toxicity. As is indicated
in the regulations (§261.21, 45 FR 33121-33122, May 19,
1980), a liquid waste is considered ignitable, and
therefore hazardous, if it has a flash point less than
140°F. Consequently, the persistence of ethyl benzene
is not at all relevant.
Therefore, absent any Information provided by the
comraenter on the persistence and degradability of these
solvents, the Agency finds no reason to change its
original conclusions.
^/Listing Background Document, "Wastes from usage of organic
solvents", Section IV. B. (Migratory potential and per-
sistence of halogenated and non-halogenated solvents)
pg. 31.
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6. One commenter criticized the Agency's conclusion, as stated
in the listing background docunent, that "the solubility of
these solvents is uniformly high " (LED pg. 3) and "the
solubility in water of these halogenated solvents is
quite high" (LBD pg. 14) when in fact, as the comraenter
points out, their solubilities vary from 10 to 20,000 mg/1
(LBD pg. 55). The comnenter went on to argue that the
Agency's determination that "these high solubilities
demonstrate a strong propensisty to migrate from inade-
quate land disposal facilities in substantial concentrations'
(LBD pg. 15) and "all of these waste solvents have sig-
nificant potential for migration, nobility and persistence..
(LBD pg. 52) is overstated when in fact, as the coaraenter
indicates, migration, nobility and persistence differ sig-
nificantly with respect to both routes of transport and
rates of degradation. Therefore, the commenter believes
that the Agency needs to reassess these listings.
The Agency agrees with the comraenter that the water
solubilities of the chlorinated hydrocarbons do vary
considerably. However, in re-evaluating the data, the
Agency believes that the solubilities of all of these
solvents except 1,1, 2-trlchloro-1,2,2-trifluoroethane
are generally high and do indeed indicate a potential
for migration froTi Inadequate land disposal facilities.^/
^/Although the water solubility for trichlorofluoroaiethane
Is Mgh, the principal concern with this solvent is its
potential to rise to the stratosphere where it nay release
chlorine ato.ns and deplete the ozone.
-------
The Agency recognizes that solubility is not the sole
parameter which determine? the potential of a substance
to migrate into the environment, i.e., nobility and
persistence also play a role. However, it is a key
parameter in evaluating how likely these substances
are to migrate from land disposal facilities. Indeed,
this potential to migrate has been demonstrated for all
of these solvents, except methylene chloride, in actual
damage cases, i.e., tetrachloroethylene, trichloroethylene,
1,1,1-trichloroethane, chlorobenzene and o-dlchlorobenzene
have all been detected to migrate at Love Canal or other
disposal facilities. Methylene chloride, although not
detected at any disposal facilities, is highly soluble
with a water solubility of 20,000 rag/1 at 25°C, and thus
has the potential to migrate from disposal sites and create
a problem. However, the Agency has modified the listing
background documents as to the solubilities of these
solvents to better reflect the Agency's conclusions.
With respect to the solvent 1,1,2-trichloro-1,2,2-
trifluoroethane, the Agency has Indicated clearly that
the potential to migrate and contaminate groundwater is
not of concern. The primary hazard posed by the mis-
management of this solvent, as with all chlorinated
fluorocarbons, is the potential to rise to the stratos-
phere and indirectly cause skin cancer due to the
-------
depletion of stratospheric ozoneV (see Response to
Comments No. 3 of this document for a nore detailed
discussion).
The Agency also agrees that its conclusions regarding
migration, mobility and persistence are overstated.
Therefore, the listing background documents have been
changed to reflect the Agency's determination that,
while the various chlorinated solvents do differ in
their migratory potential, mobility and persistence,
they all may pose a substantial present or potential
hazard to human health and the environment, if improperly
managed, when considering the routes and rates of transport
and degrees and rates of degradation.
7. One commenter believed that the Agency's decision to
Include trlchloroethylene on the list of chemicals which
have demonstrated substantial evidence of carclnogenlclty
was inaccurate. The commenter indicated that according
to Elizabeth Weisberger of the National Institute of
Health, whose organization did the original studies which
classified trlchloroethylene as a "merely suspicious
carcinogen", Indicated that "trichloroethylene seems
not to be a carcinogen." The comnenter also argued
that more extensive and recent research indicates that
^/l,l,2-trichloro-l,2,2-trlfluoroethane is considered to be
extremently volatile (vapor pressure - 270 mm of Hg at 20°C),
and thus is likely to rise Into the atmosphere.
-------
trlchloroethylene may not be carcinogenic after all.
The Agency disagreees with the commenter. Trichloro-
ethylene has been designated carcinogenic by EPA's Cancer
Assessment Group (CAG) after reviewing the available data
in the literature. In fact, before a chemical compound
is deemed carcinogenic by CAG, it is subject to ex-
haustive literature study and evaluation. In light of
CAG's determination, EPA will continue to include tri-
chloroethylene as a chemical which has demonstrated
substantial evidence of carcinogenicity.
8. One commenter questioned the Agency's characterization
of 1,1,1-trichloroethane as a suspect carcinogen. The
commenter argued that 1,1,1-trichloroethane has not been
found to be a carcinogen. They quote the NCI Bioassay
of 1,1,1-Trichloroethane for Possible Carcinogenicity
(January 1977), which states:
"A variety of neoplasms were represented in both
1,1,1-trichloroethane treated and matched-control
rats or mice. However, each type of neoplasm has
been encountered previously as a lesion in untreated
rats or mice. The neoplasms observed are not be-
lieved attributable to 1,1,1-trichloroethane expo-
sure, since no relationship was established between
the dosage groups, the species, sex, type of neoplasm
or the site of occurence. Even if such a relation-
ship were infered, it would be inappropriate to
make an assessment of carcinogenic1ty on the basis
of this test, because the abbreviated life spans
of the rats and the mice."
The commenter also argued that EPA's own Office of Drinking
Water, in their appendices to Planning Workshops to
-97-
-------
Development Recommendations for a Groundwater Protection
Strategy, state that raethyl chloroform (1,1,1-trichloro-
ethane) Is not considered to be a carcinogen (June 1980).
Therefore, the cotnmenter believes that there is no support
for the carcinogenicity of 1,1,1-trichloroethane and
argues that it be deleted from all lists of hazardous
wa s t e s .
The Agency disagrees with the commenter's claim.
Although the NCI Bioassay Study on the carcinogenicity
of 1,1,1-trichloroetha'ne referred to in the listing
background document (pg. 464) and an unpublished study
are inconclusive, positive responses in two in vitro
systems (a rat embryo cell transformation assay (Price
et. al. 1978, Transforming Activities of Trichloroethane
and Proposed Industrial Alternatives. In vitro. 14:290.)
and a bacterial mutation assay (Simmon et. al. 1977.
Mutagenic activity of chemicals identified in drinking
water, In; Progress in Genetic Toxicology, ed. I.D. Scott,
B. A. Bridges and F. H. Sobels, pp. 249-258; McCann, J.
and B. Ames, 1976. Detection of carcinogens as mutagens
in the Salmonella nicrosome test: Assay of 300 chemicals.
Proc. Nat. Acad. Sci. 78:950.)) currently used to detect
chemical carcinogens, indicate that 1 ,1,1-trIchloroethane
has the potential for carcinogenicity in animals (App. A).
Additionally, a two year carcinogenesis aninal 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
careinogen*y, and thus will continue to include
1,I,1-trichloroethane as a constituent of concern.
9. One comnenter also argued that the statements in the
background document that "methylene chloride is"reported
as being nutagenlc to a bacterial strain, S. typhlmurium",
and "raethylene chloride... is highly rautagenic" are
inaccurate. The comnenter pointed out that a variety
of more detailed tests perforned subsequently and not
cited in the listing background document prove otherwise.
For example, a definitive cell transformation test for
nethylene chloride was found negative. Additionally,
many other tests have been run for carcinogenlcity of
raethylene chloride with negative results.
The Agency agrees. The current assessment on the
carcinogenicity of nethylene chloride is only based on
animal experiments which are so far incomplete. How-
ever, methylene chloride is the subject of an NCI spon-
sored bioassay. In addition, E?A has found "suggestive"
evidence of the carcinogenlcity of nethylene chloride
It should be noted that the Agency recently determined to
rpt.iin the listing of 1, 1 ,1-t r ichloroe thane as a toxic pollu-
tant tinder §307(a) of the Clean Water Act. The reasons for
th*t action are incorporated by reference herein.
-------
(App. A). The Agency cannot Ignore this information.
Therefore, the listing background document will be
revised to indicate that methylene chloride is only a
"suspect" carcinogen.
10. One ceminenter questioned the Agency's characterization
of tetra>chloroethylene, methylene chloride, trichloro-
ethylene and 1,1,1-trichloroethane as aquatically toxic.
The comraenter indicated that statements relative to
methylene chloride like "acute toxicity values range
from 147,000 to 310,000 mg/1 (correct units are ug/1)
for aquatic organisms" are meaningless until put into
relative significance. When compared with most common
nonhalogenated solvents, the comnenter argues, the halo-
genated solvents were less toxic to the tested fish species.
In addition, the comnenter pointed out that EPA, In fact,
concurs with this viewpoint by stating, "aquatic organisms
tend to be fairly resistent to dichloromethane (methylene
chloride), with acute values ranging from 193,000 to 331,000
ug/1 (EPA BD 38 at 389). Therefore, the commenter believes
that EPA has not properly assessed the relatively low
aquatic toxicltles of these halogenated solvents.
In re-evaluating the aquatic toxicity of tetrachloro-
ethylene, raethylene chloride, trlchloroethylene and 1,1,1-
trichloroethane, the Agency agrees with the commenter that
all four of these halogenated solvents are not of regu-
latory concern under the hazardous waste program to
-------
warrant characterization as "aquatically toxic." In
the Registry of Toxic Effects (1975 Edition), a widely
used reference book which is published by the National
Institute for Occupational Safety and Health (NIOSH),
a rating of the aquatic toxicity or non-toxicity of
chemical substances if provided. In this rating,
substances with an 1>C$Q value of between 10,000 ug/1
to 100,000 ug/1 is considered slightly toxic while
substances with an LCso value above 100,000 ug/1 is
practically non-toxic. Based upon this rating, raethylene
chloride is practically non-toxic while the other halo-
genated solvents are slightly toxic. Therefore, the
Agency will modify the listing background document to
reflect this change. However, it should be noted that
toxic wastes are not so designated solely on the basis
of their aquatic toxicity. ^s discussed earlier, all
of these halogenated solvents exhibit other toxic effects
i.e., carcinogenicity, chronic toxicity, etc* which
are sufficient to warrant designation of these solvents
as toxic.
11. One commenter also argued that the Agency has misinter-
preted and overstated the bioaccumulation potential for
both the halogenated and non-halogenated solvents,
arguing that most of these solvents have a low bioaccumu-
lation potential. In particular, the comraenter believes
that the Agency has shown a lack of perspective by
-------
concluding that, ". . .lethanol could bioaccumulate
causing numerous adverse health effects from prolonged
and/or repeated exposure" (EPA BD-11 at 59), despite
Its reported very low Kow of 5 and readily biodegradable.
Therefore, the commenter believes that the bioaccumulation
data should be reviewed and properly assessed in listing.
As discussed in the preamble to Part 261 of the
hazardous waste regulations (45 FR 33106-33107), the
Agency In listing wastes for which a characteristic
has not been developed has adopted a flexible, multiple
factor approach to be better able to accommodate itself
to the complex determinations of hazard. These multiple
factors include the type of toxic threat posed, the
concentrations of the toxic constituents in the waste,
the migratory potential, persistence and degradation
of the toxic constituents, the degree to which the
toxic constituents bioaccumulate in ecosystems, the
plausible types of improper management to which the
waste could be subjected, the quantities of waste
generated, and other factors not explicitly designated
by the Act. Thus, if a substance exhibits one or
more of these properties, the Agency may list the waste
as hazardous. The bioaccuraulation potential of a sub-
stance is not considered by the Agency as a necessary
factor before a waste can be listed. Therefore, just
because a chemical substances is not bloaccumulative
-------
is no reason not to list a waste.
With respect to the commenter's claim for methanol,
the Agency is no longer listing this solvent for toxlclty,
but for ignitability. Bioaccunulative propensity of
this compound thus is no longer relevant.
12. One commenter cited some inconsistencies/errors in the
listing background documents and suggested that the
Agency make the appropriate revisions.
The Agency agrees. There were some typographical
and transcription errors, e.?., in the methylene chloride
background document, as well as soae judgmental errors.
Therefore, within the limits of its resources, the
Agency has nade every effort to correct such errors.
13. One comraenter criticized the Agency's conclusion as
stated in the listing background document that, "the
chlorinated waste hydrocarbons are toxic" (EPA BD-11
at 3) when in fact, as the commenter points out, that
the oral-rat LC5Q values vary by several orders of
magnitude. Therefore, the comnenter believes that the
listing of these halogenated solvents are not fully
warranted in all cases.
The Agency strongly disagrees with the commenters
unsubstantiated clain. As discussed in the preamble
to the May 19, 1980 hazardous waste regulations (45
FR 33107), the Agency listed a number of toxic wastes
- /03-
-------
as those "which have been shown inreputable scientific
studies to have toxic, carcinogenic, mutagenic or
teratogenic effects on humans or other life forms."
Toxicity is defined to include systemic effects of
chronic low level exposure, acutely toxic^/, aquatic
toxlcity, phytotoxicity or the potential (as with chlori-
nated fluorocarbons) for indirectly causing harm to
human health or other life forms. Therefore, a substance
with a high LCso value is not necessarily non-toxic.
In reviewing the data available in the record**/,
the Agency is convinced that these substances are properly
designated as toxic, and that improper management and
disposal of these waste solvents may pose a substantial
present or potential hazard to human health and the
environment. Since the commenter failed to provide
additional toxlcity data except as discussed in other
parts to this section, the Agency finds no reason to
change its original conclusion to list these solvents
as toxic wastes.
^/Acutely toxic does not include those wastes which are defined
in §261 .11(a)(2) as acutely hazardous.
*_^/Appendix A (Health and Environmental Effects Profiles) out-
lines the health and environmental effects exhibited by
each of these compounds.
-------
Electroplating and Metal Finishing Operations
Wastewater Treatment Sludges From Electroplating Operations
except from the following processes: (1) sulfuric acid
anodizing of aluminum; (2) tin plating on carbon steel;
(3) zinc plating (segregated basis) on carbon steel;
(4) aluminum or zinc-aluminum plating on carbon steel;
(5) cleaning/stripping associated with tin, zinc and
aluminum plating on carbon steel; and (6) chemical etching
and milling of aluminum (T)
Wastewater Treatment Sludges from the Chemical Conversion
Coating of Aluminum (T)*
Summary of Basis for Listing
Wastewater treatment sludges from electroplating operations
are generated by a number of industry categories located nation-
wide. These wastes contain a variety of metals such as chromium,
cadmium, nickel, and also contain completed cyanides. The
Administrator has determined that solid wastes from these
processes may pose a substantial present or potential hazard
to human health and the environment when improperly transported,
treated, stored, disposed of or otherwise managed, and therefore
should be subject to appropriate management requirements under
Subtitle C of RCRA. This conclusion Is based on the following
considerations:
*In response to comments, this listing has been modified to
better define those electroplating operations which generate
hazardous waste - see Response to Comments in back of the
background document for additional details.
Chemical conversio-n coating of aluminum is included in
the general category of electroplating, however, since this
waste is being listed only for the presence of chromium and
cyanide, the waste will be listed separately.
-/OS--
-------
1. Wastewater treatment sludges from the listed electro-
plating operations contain significant concentrations
of the toxic metals chromiun, cadmium and nickel and
toxic coraplexed cyanides.
2. Wastewater treatment sludges from the chemical con-
version coating of aluminum contain significant
concentrations of chromium, a toxic metal and
complexed cyanides.
3. Leaching tests using the extraction procedure specified
in the extraction procedure toxicity characteristic
have shown that these metals leach out in significant
concentrations, with some samples falling the extraction
procedure toxicity characteristic. Therefore, the
possibility of groundwater contamination via leaching
will exist if these waste materials are improperly
dis posed.
4. A large quantity of this waste is generated annually
with amounts expected to Increase substantially
when the pretreatment standards for these sources
become effective.
5. Damage incidents (i.e., contaminated wells, destruc-
tion of animal life, etc.) that are attributable
to the improper disposal of electroplating wastes
have been reported, thus indicating that the wastes
Day be mismanaged in actual practice, and are
capable of causing substantial harm if mismanagement
occur s.
Sources of the Waste and Typical Disposal Practices
The electroplating industry consists of both job shops
and captive platers. Job shops are snail, independent
operations performing electroplating on a contract basis while
captive facilities are part of an integrated manufacturing firm
(I.e., electroplating operations carried-out In an automobile
manufacturing facility, aircraft manufacturing facility, etc.).
Of the approximately 10,000 electroplating facilities in the
- /Ofc-
-------
United States, it is estimated that 3,000 are job shops and
6,100 are captive shops including 400 printed circuit board
manufacturers. Approximately 7 percent of the job shops and
42 percent of the captive shops discharge directly to the waters
of the United States. C1)
Process Description
Electroplating, as defined in this document, includes a
wide range of production processes which utilize a large num-
ber of raw materials. Production processes include common and
precious metals electroplating, anodizing, chemical conver-
sion coating (i.e., coloring, chromating, ohosphating and
immersion plating), electroless placing, chemical etching and
milling and printed circuit board manufacturing (S). The
prl-nary purpose of electroplating operations is to apply a
surface coating, typically by electrode decomposition, to
provide protection against corrosion, to increase wear or
erosion resistance, or for decorative purposes. The operation
itself involves immersing the article to be coated/plated into
a bath consisting of acids, bases, salts, etc. A plating line
is a series of unit operations conducted in sequence in which
one or more coatings are applied or a basis material is removed.
Figure I illustrates a standard electroplating process. (For
a more detailed discussion of the electroplating process, see
the Development Document for Existing Source Pretreatment
Standards for the Electroplating Point Source Category, August
1979 (S) .)
-/07-
-------
The metals used in electroplating operation (both common
and precious metal plating) include cadmium, lead, chromium
in hexavalent form, copper, nickel, zinc, gold and silver.
Cyanides are also extensively used in plating solutions and
in some stripping and cleaning solutions. Electroless plating
often uses copper, nickel and tin complexed with cyanide.
Etching solutions are commonly made up of strong acids or
bases with spent etchants containing high concentrations of
spent metal. The solutions include ferric chloride, nitric
acid, ammonium persulfate, chromic acid, cupric chloride and
hydrochloric acid. Anodizing is usually performed on aluminum
parts using solutions of sulfuric or chromic acid often
followed by a hot water bath, however, nickel acetate or
sodium or potassium dichromate seal may also be used in the
process.
Chemical conversion coating processes apply a coating to
the previously deposited metal or basis metal for Increased
corrosion protection, lubricity, preparation of the surface
for additional coatings or formulation of a special surface
appearance. This manufacturing operation Includes chromatlng,
phosphating, metal coloring, and immersion platings.(5)
During the process of chromating, a portion of the base
metal is converted to one of the components of the surface
films by reaction with aqueous solutions containing hexavalent
chromium (CrVI). The solutions are generally acidic and
-------
niul ClP.iwlno | ul
|
[ Alkaline
Chlcu-JncU.lon
|
• ..
I
I
I
1
i
~Li
ClllMlilL.il
Prent pi LA11 on
i
i
I
_P_arU •...'.!
iUivso Hater
to
SaulUry Sc\/nr*
Tvt'!C-V. ri
-------
Immersion tin plating baths contain stannous chloride, potassium
bitartrate, ammonium aluminum sulfate, sodium cyanide or
sodium hydroxide. Typical immersion gold plating used to
gild inexpensive itens of jewelry uses solutions of gold
chloride, potassium cyanide, or pyroohosphate . Typical
process baths used in the industry are shown in Table !.(''
Waste Generation and Composition
As indicated in Figure 1, the spent plating/coating
solution and rinse water is chemically treated to precipitate
out the toxic metals and to destroy the cyanide. The extent
to which plating solution carry-over adds to the wastewater
and enters the sludge depends on the type of article being
plated and the specific plating method employed.
The composition of these sludges will vary because of
the multitude of production processing sequences that exist
in the industry. For example, printed circuit board
manufacture involves electroplating, etching, electroless
plating and conversion coating, and generate one type of
sludge. A different processing sequence, on the other hand,
generates a sludge with a differing composition. However, it
Is expected that since most platers conduct a number of different
electroplating operations, most of the sludges will contain
significant concentrations of toxic metals, and may also
contain coiplexed cyanides in high concentrations if cyanides
are not properly isolated in the treatment process.
-III-
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Table
Typical Electroplating Baths and Their Chemical Composition
1.
Plating Compound
Cadmium Cyanide
Cadmium Fluoborate
3. Chromium Electroplate
4. Copper Cyanide
5. Electroless Copper
6. Gold Cyanide
7. Acid Nickel
8. Silver Cyanide
9. Zinc Sulfate
Constituents
Cadmium oxide
Cadmium
Sodium cyanide
Sodium hydroxide
Cadmium fluoborate
Cadmium (as metal)
Ammonium fluoborate
Boric acid
Licorice
Chromic acid
Sulfate
Fluoride
Copper cyanide
Free sodium cyanide
Sodium carbonate
Rochelle salt
Copper nitrate
Sodium bicarbonate
Rochelle salt
Sodium hydroxide
Formaldehyde (37%)
Gold (as potassium
gold cyanide)
Potassium cyanide
Potassium carbonate
Depotassium phosphate
Nickel sulfate
Nickel chloride
Boric acid
Silver cyanide
Potassium cyanide
Potassium carbonate (min.)
Metallic silver
Free cyanide
Zinc sulfate
Sodium sulfate
Magnesium sulfate
Concentration (g/1)
22.5
19.5
77.9
14.2
251.2
94.4
59.9
27.0
1.1
172.3
1.3
0.7
26.2
5.6
37.4
44.9
15
10
30
20
100 ml/1
8
30
30
30
330
45
37
35.9
59.9
15.0
23.8
41.2
374.5
71.5
59.9
-117.-
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Table 2 illustrates the varying composition of these sludges
for two of the metals in twelve different plating processes.
There are a number of electroplating operations, however,
which are usually conducted separately and which are not
expected to contain significant concentrations of the toxic
metals or cyanides. These processes (tin plating on carbon
steel, zinc plating (segregated basis) on carbon steel,
aluminum or zinc-aluminum plating on carbon steel, cleaning/
stripping associated with tin, zinc and aluminum plating on
carbon steel, sulfuric acid anodizing of aluminum and chemical
etching and milling of aluminum), therefore, have been excluded
from the general category of electroplating operations.
Wastewater treatment sludges generated from these processes
are consequently not listed hazardous wastes, but may be hazardous
If they fail one of the characteristics.
The predominant type of uastewater treatment sludge
generated from this industry is metal hydroxide sludge (which
results from alkaline precipation). Those electroplating
processes using chromium all employ the hexavalent form of
this element. Consequently the raw wastes resulting from
this process contain chromium only in the hexavalent form. The
efficiency of the removal of hexavalent chromium depends on
the extent of its reduction. If reduction is incomplete, or
if neutralization and metal precipitation take place too
rapidly, hexavalent chromium is likely to be entrained in
-------
Table 2
Heavy Metal Content for Chromium, and Cadmium
in Electroplating Sludges-Dry
Primary ?lating Process
Segregated Zinc
Segregated Cadmium
Zinc Plating and Chromating
Copper-Nickel-Chromium
on Zinc
Aluminum Anodizing*
(chromic process)
Nickel-Chromium on Steel
Multi-Process Job Shop
Electroless Copper on Plastic,
Acid Copper, Nickel Chromium
Multi-Process with Barrel or
Vibratory Finishing
Printed Circuits
Nickel-Chromium on Steel
Cadmium-Nickel-Copper on
Brass and Steel
Cr
Cd
200
62,000
65,000
•iOO
1,700
14,000
25,000
137,000
<100
22,000
1,100
ND
ND
1,500
ND
570
3,500
79,200
—
<100
<100
48,900
500
-------
Che precipitation sludges, resulting in their contamination with
hexavalent chromium. Moreover, the higher the concentration
of hexavalent chrome in the wastewater, the greater is the
likelihood of its inefficient or ineffective reduction, and
the consequent likelihood of the contamination of chromium
hydroxide sludges with hexavalent chrome. Screening studies
have shown CrVl concentrations averaging 420 ppm in raw
waste streams from electroplating (metal finishing) oper at ions • (
Values as high as 12,900 ppm have been re por ted . ( ^ ) In fact,
stapling data show that concentrations of hexavalent chromium
in raw waste from metal finishing operations and chromium
concentrations in the effluent after wastewater treatment
are positively correlated (ref. 14, p. VII-27), showing that
Inefficient reduction does occur. Although not widely used,
when wastewater is treated by sulfide precipitation, metallic
sulfide sludges, are also generated.
Among those facilities which discharge to publicly
owned treatment works (POTW's), approximately 80 percent
of the job shops and 70 percent of the captive shops do not
presently treat their wastewater and, therefore, do not
currently generate water pollution control sludges. However,
compliance with the electroplate pretreatment standards for
existing job shops will be required by October 1982, and for
captives shortly thereafter. Thus, when the regulations are
implemented, virtually all elec tr opl ater s will generate a
sludge and drastically increase the quantity of wastewater
treatment sludge produced (see page 14 below).
- US'-
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Typical Disposal Practices
A recent study ^^ , surveying 48 plants, indicated
that approximately 20 percent of the electroplating facilities
dispose of their waste on-site while the remaining BO percent
haul their waste off-site to commercial or municipal disposal
facilities. The actual disposal practices utilized by the
industry vary greatly (i.e., landfilling, lagooning, drying
beds and drum burial). However, the Agency is aware that
electroplating facilities are known to be using extremely poor
hazardous waste disposal practices. For example, one printed
circuit board manufacturer is know to dispose of its waste
sludges in a dry river bed.(8) Numerous damage incidents
caused by industry waste disposal practices likewise indicates
poor waste management practices.
Hazards Posed by the Waste
As indicated earlier in Table 2 and as shown in Table 3,
wast'.'water treatment sludge from electroplating facilities
gene"ating a listed waste contain significant concentrations
of tie toxic metals cadmium, chromium and nickel (with some
levels exceeding 1,000 mg/kg (dry weight)) and cyanide.
Tablt' A provides some additional analytical data on the
comp'.sition of raw wastewater from forty-six coatings plants.
As is indicated, these toxics are present in the raw wastewater,
and t'us can be expected to be found in the treatment sludge
at si;nificant levels, particularly after implementation of the
electroplating industry pretreatment standards. In the
-------
sludges the metallic elements occur as hydroxides. As out-
lined above, chromium may be present as the entrained hexa-
valent species.
Leaching tests run by the American Electroplaters'
Society (AES) under a grant from the Industrial Environmental
Research Laboratory (IERL) U.S. Environmental Protection
Agency have shown that these metals leach out in significant
concentrations with some samples failing the extraction
procedure toxicity characteristic (Table 5). The leaching
tests used in the AES study were performed on twelve separate
samples using the proposed extraction procedure (43 FR 58956-
"5R957). A leaching test was also performed on two samples
using the ASTM distilled water leaching test; the results of
this test (Table 6) indicate that two of the contaminants of
concern (i.e., chromium and cadmium) may not solubilize in
water to the extent found in the acid leaching test. However,
since these sludges tend to be disposed of in acid environments
(i.e. sanitary landfills), the acid leach test would replicate
more closely what would be expected to happen under field
conditions, and thus Is more predictive of potential hazards
from improper management. Cyanides have also been shown to
leach from these wastes at concentrations ranging from 0.5
to 170 rag/1. (*) The Public Health Service's recommended
concentration limit for cyanide in drinking water in n.2
mg/1 (I?-), indicating that cyanide leaching may also
lead to a substantial hazard.
-in-
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Table 3
Projected Sludge Concentrations For Various Heavy
Metals and Cyanides (mg/1) (5)*
Pollutant
Cadmi urn
Nickel
Chromium, Total
Cyanide, Total
Raw Waste Cone.
(mean)
0.08
5.0
3.8
O.A
Projected Sludge Cone.
( me a n )
2% Solids 20% Solids
3.2
486.2
369.7
42.9
32.5
4862.0
3697^0
429.2
*Projections of sludge concentrations are based on mean raw waste
sampled during an effluent guidelines study. This study utilized
an 82 plant data base and the data are derived from analyses
of actual raw waste concentration, assumptions of clarifier
removal efficiencies (96-93%) and non-dewatered and dewatered
sludge solids content (2% and 20%, respectively). To estimate
pollutant concentrations in sludge, the assumption is made
that:
1. 1% of the influent flow goes to the sludge stream at
2% solids.
2. The clarifier removal efficiencies were 96-98%.
There fore,
Mass removed = influent flow x influent waste concentration •
(1-.01) x influent flow x effluent concentration
And ,
mass removed
Sludge pollutant concnetration = .01 x influent flow
-ns-
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Table 4
Composition of Raw Waste Streams From Coating
Processes (mg/l)(15)
Chromium, total .19 - 79.2
Cyanide, total .005 - 126.0
Cyanide, amenable to chlorination .004 - 67.56
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Table 5
Pr
1A
2A
3A
4A
5A
6A
7A
8A
9A
.OA
.1A
Extract Concentrations From Elec
Treatment Sludge (
imary Plating Process
Segregated Zinc
Segregated Cadmium
Zinc Plating and Chromating
Copper-Nickel-Chromium on
Zinc
Aluminum Anodizing
Nickel-Chromium on Steel
Multi-Process Job Shop**
Electroless Copper on Plastic,
Acid Copper, Nickel, Chromium
Multl-Pocess with Barrel or
Vibratory Finishing**
Printed Circuits
Nickel-Chromium on Steel
troplating
mg/1)^'
Cr*
1.22
1.89
85 .0
21.8
<0.01
25.4
0.24
400
0.32
0.12
4.22
Wastewater
Cd*
0.23
126
6.0
-
-
2.16
-
0.03
-
<0.01
12A Cadmlum-Nicke1-Copper on
Brass and Steel 4.85 268
Note: Those concentrations underlined would fail the Extraction
Procedure Toxiclty Characteristic
* These values were determined using the proposed extraction
procedure contained in the toxicity characteristic.
** The ASTM distilled water extraction procedure was run on
these samples with the following results:
Plant Cr (mg/1) Cd (mg/1)
7A 0.63 0.03
9A 0.04
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Once released from the matrix of the waste, cadmium,
hexavalent chromium, nickel, and cyanide could migrate from
the disposal site to ground and surface waters utilized as
drinking water sources. Hexavalent chromium compounds, both
chromates and dichromates have extremely high water solubility
(see Attachment II). Therefore hexavalent chrome, if present
in these wastes, will leach into groundwaters and effluent
streams, and is likely to pollute such waters in amounts
significantly exceeding the NIPDWS of .05 rag/1.
Present practices associated with the landfilling,
dumping or impounding of the waste may be inadequate to
prevent such occurrences. For instance, selection of disposal
sites in areas with permeable soils can permit contaminant-
bearing leachate from the waste to migrate to groundwater.
This is especially significant with respect to lagoon disposed
wastes because a large quantity of liquid is available to
percolate through the solids and soil beneath the fill.
Actual damage incidents involving electroplating wastes are
presented in Attachment I, again showing that actual mismanage-
ment of electroplating wastes has occurred, and has resulted
in substantial environmental hazard.
The prevalence of off-site disposal creates a further
potential for mismanagement and substantial hazard. Not only
is there a danger of mismanagement in transport, but there is
the further danger of unraanifeste4 wastes never reaching their
destination or of being disposed with Incompatible wastes.
-------
An overflow with respect to lagoon disposed wastes might
be encountered if the liquid portion of the waste is allowed
to reach too high a level in the lagoon; a heavv rainfall could
cause flooding which might reach surface waters in the vicinity
unless the facility has proper diking and other flood control
measures.
In addition to difficulties caused by improper site
selection, unsecure land disposal facilities are likely to
have insufficient leachate control practices. There may be
no leachate collection and treatment system to diminish
leachate percolation through the wastes and soil underneath
the site to groundwater and there nay be no surface run-off
diversion system to prevent contaminants from being carried
from the disposal site to nearby surface waters.
With regard to the fate of these waste constitutents
once they migrate, the heavy raetal contaminants present in
the waste are elements which persist indefinitely in some
form and therefore may contaminate drinking water sources
for long periods of time. Cyanides have been shown to be
extremely mobile in the soil environment\q) and have been
shown to move from soils to groundwater.(19) Thus cyanide
is also available for potential release and transport to
environmental receptors.
The Agency has determined to list wastewater treatment
sludges from electroplating operations as T hazardous wastes,
on the basis of chromium, cadmium, nickel and cyanide, although
-yf-
-------
chromium and cadmium are also neasurable by the (S) character-
istic. Moreover, concentrations for chromium and cadmium in
the EP extract from this waste from individual sites might be
less than inn times the national interim primary drinking water
standard as Indicated (although the Agency's own extraction
data indicates that extract concentrations have exceeded the
100 x benchmark for some generators). Nevertheless, the Agency
believes that there-are factors in addition to metal concen-
trations in leachates which justify the T listing. Some of
these factors already have been Lndentlfied, namely that
present Industry disposal practices have often proven inade-
quate; the presence of nickel and cyanide, often in high
concentrations, two constitutents not caught by the (E)
characteristic; the nondegradability of the three heavy metals
and the high concentrations of cadmium and chromium in actual
waste streams.
The quantity of these wastes generated is an additional
supporting factor. As indicated above, wastewater treatment
sludge from electroplating operations will drastically Increase
in quantity when the pre t rea t merit standards are Implemented in
October 19R2 and these sludges will contain extremely high
cadmium, chromium and nickel concentrations (see p. 11 above).
Large amounts of each of these metals are thus available for
potential environmental release. The large quantities of
t'lese contaminants pose the danger of polluting large areas
of grruinrt anrf surface waters. Contamination could also occur
-------
for long periods of time, since large amounts of pollutants
are available for environmental loading. Attenuative capacity
of the environment surrounding the disposal facility could
also be reduced or used up due to the large quantities of
pollutant available. All of these considerations increase
the possibility of exposure to the harmful constitutents in
the wastes, and in the Agency's view, support a T listing.
Health Effects Associated with Hazardous Waste Constttutents
The toxiclty of cadmium, chromium, nickel and cyanide
has been well documented. Capsule descriptions on the adverse
health and environmental effects are summarized below; more
detail on the adverse effects of cadmium, chromium, nickel,
and cyanide can be found in Appendix A.
The Carcinogenicity of various hexavalent chromium com-
pounds in humans is well documented^1">)t and E?A's CAG has
determined that there is substantial evidence that hexavalent
chromium compounds are carcinogenic to man. In one study
rats showed a weak carcinogenic response to trivalent chromium
compounds. Oral administration of trivalent chromium results
in little chromium absorption, the degree absorption is
slightly higher following administrtion of hexavalent compounds.
Chronic - toxicity problems associated with chromium include
damage to liver, kidney, skin, respiratory passages and lungs*
Allergic dermatitis can result from exposure to both tri- and
hexavalent chromium.
-------
No data for chronic toxicity trivalent chromium for
freshwater fish or algae are available. The chronic toxicity
value for the freshwater invertebrate Daphia magna, based on
a single study, is reported as 445 mg/1 (CrIII) and 10 mg/1
(CrVI). Chronic embryo-larval tests on six species of
freshwater fish exposed to CrVI resulted in values ranging
from 37 to 72 mg/l.(15)
Cadmium shows both acute, and chronic toxic effects in
humans. The LDSO (oral, rat) is 72 mg/kg. Excessive intake
leads to kidney damage. Cadmium and its compounds have also
been reported to produce oncogenic and teratogenic effects.
Aquatic toxicity has been observed at suh-ppb levels.
Nickel has been found to bring about a carcinogenic
response upon injection in a nunber of animal studies. Nickel
has also been demonstrated to present adverse effects in a
three generation study with rats at a level of 5 mg/1 (^ ppm)
in drinking water. In each of the generations, increased
number of runts and enhanced neonatal mortality were seen.
Chronic exposure to nickel has also resulted In injury to
both the upper and lower respiratory tract in man.
Ferrocyanides exhibit low toxicity, but release cyanide
ions and toxic hydrogen cyanide gas upon exposure to sunlight.
Cyanide compounds can adversely affect a wide variety of
organisms. For example, cyanide in its most toxic form can
be fatal to humans in a few minutes at a concentration of
300 ppm. Cyanide is also lethal to freshwater fish at concen-
-I2S--
-------
tratlons as low as about "ifl mg/1 and has been shown to adversely
affect invertebrates and fishes to concentrations of about
in mg/1. The hazards associated with exposure to chromium,
cadraiuTO, nickel and cyanide have been recognized by other
regulatory programs. Chromium, cadmium, nickel and cyanide
are lister! as priority pollutants in accordance with §307(a)
of the Clean Water Act. Under &6 of the Occupational Safety
and Health Act of 1970, a final standard for chromium has been
promulgated in 29 CFR 1910.1000; oermissable exposure limits
have also been established for KCN and NaCN. The U.S. Public
Health Service established a drinking water standard of 0.2
rag CV/1 as an acceptable level for water supplies. In addition,
final or proposed regulations for the State of Maine, Massa-
chusetts, Vermont, Maryland, Minnesota, New Mexico, Oklahoma,
and California define chromium, cadmium, nickel, and cyanide
containing compounds as hazardous wastes or components thereof. (
-yt.-
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References
1. U.S. EPA Economic analysis of pretreatment standards for
existing sources of the electroplating point source
category. EPA No. 440/2-79-031. NTIS PB No. 135 262.
August, 1979.
2. U.S. EPA. Assessment of industrial hazardous waste practices,
Electroplating and metal finishing industries -
job shops, EPA No. 68-01-2664. NTIS PB No. 264 349.
September, 197 6.
3. Not used in text.
4. American Electroplating Society. Interim Phase I Report:
Electroplating wastewater sludge characterization.
August 24, 1979; revised September 12, 1979.
5. U.S. EPA. Development document for existing source pretreat-
ment standards for the electroplating point source
category. EPA No. 440/1-78/085. February, 1978.
6. U.S. EPA. Composite of State Files. Special wastes disposal
applications. Result of leachate tests on cyanide
containing wastes from Illinois, Iowa, Kansas and
Pennsylvania. 1976-1979.
7. Metal Finishing Guidebook and Directory. V.77, No. 13.
Metals and Plastics Publications, Inc., Hackertsack, New
Jersey/ January, 1979.
8. U.S. EPA. Effluent Guidelines On-going BAT Study.
9. U.S. EPA. Alesii, B.A. and W.A. Fuller. The mobility of
three cyanide forms in soil. pp. 213-223. In; Residual
management by land disposal. W.H. Fuller, ed.t U.S.
EPA, Cincinnati, Ohio. NTIS PB No. 256 768. 1976.
10. U.S. EPA. The prevalence of subsurface migration of hazardous
chemical substances at selected Industrial waste land
disposal sites. EPA No. 530/SW-634. U.S. EPA, Washington,
D.C . 1977.
11. U.S. EPA. State Regulations Files. January, 1980.
12. U.S. EPA. Cyanides: Ambient water quality criteria.
NTIS PB No. 296 792. 1979.
-------
13. U.S. EPA. Open File of Hazardous Waste Incidents.
14. U.S. EPA. Development document for effluent limitations
and guidelines and standards for metal finishing point
source category. EPA No. 440-1-80-091-A. June, 1980.
15. U.S. EPA. Ambient water quality criteria for chromium.
EPA No. 440/5-80-035. October 1980.
16. U.S. EPA. Review of the environmental effects of
pollutants; III. Chromium. ORNL/EIS-80;EPA No.
600/1-78-023. May, 1980.
17. Carline, R.L., ed. Transition metal chemistry, V.I. Marcel
Dekker, New York. 1965.
18. Latimer, W.M., and J.H. Hildebrand. Reference book of
inorganic chemistry. MacMillan, New York. 1940.
19. Griffin, R.A., A.K. Au, and R.R. Frost. Effects of pU on
adsorption of chromium from landfill leachate by clay
minerals.' J. Environ. Sci. Health A12(8): 431-
449. 1977.
20. Bartlett, R.J., and J.M. Kirable. Behavior of chromium in
soils: I Trivalent forms. J. Environ. Qual. 5:379-
383. 1976.
21. National Acadmeny of Sciences. Medical and biological
effects of environmental pollutants; chromium.
Washington, D.C. 1974.
22. U.S. EPA. Application of sewage sludge to cropland;
appraisal of potential hazards of the heavy metals to
plants and animals. EPA No. 430/9-76-013. NTIS PB
No. 264 015. November, 1976.
23. Bartlett, R.J., and J.M. Kimble. Behavior of chromium in
soils'.II. Hexavalent forms. J. Environ. Qual. 5:383-
386. 1976.
24. Comments from Reynolds Aluminum. July 18, 1980.
25. Memorandum from Mike Keller and Gay Contos to Matt Straus.
Subject: Chemical conversion coating process, dated
September 17, 1980.
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Attachment I
Damage Incidents Resulting From the Mismanagement
of Electroplating WastesC13)
Columbia County, Pennsylvania (1965) - Unlined lagoons caused
contamination of a number of private wells in the area. The
lagoons contained plating wastes and were leaking such
pollutants as cyanide, copper, nickel, alkyIbenzenesulfonate
and phosphate.
Illinois - At a farm site in Illinois used for the dumping of
highly toxic industrial wastes (mostly from metal finishing
operations), three cows died as a result of cyanide oolsonlng
and extensive danger occured to wildlife, aquatic biota and
vegetation. Additionally, crops cannot be safely grown in
the area again.
Bronson. Michigan (1939) - Since 1939, electroplating industries
in Bronson, Michigan have experienced difficulty in disposing
of their electroplating wastes. Originally, the wastes were
discharged Into the city's sewer system which was subsequently
emptied into a creek. Contamination of this water resulted in
the death of fish and cattle below Uronson from cyanide
poisoning. All the plating wastes of the company were
subsequently discharged to ponds.
Lawrenceburg, Tennessee - Between 1962 and 1972 in Lawrenceburg,
Tennessee, an industry dumped up to 5,000 gallons of untreated
-------
metal plating waste daily into trenches n
-------
more years of natural attenuation and dilution before It
becomes useable again. Meanwhile, the plume is still slowly
moving, threatening a nearby creek and other wells in the
area .
Kent County, Michigan - An aquifer used for a municipal waste
supply was contaminated by chromium leachate from a sand and
gravel pit used as a landfill. The landfill had been taken
from a former dumping ground for electroplating wastes. The
fill material was removed to ameliorate the pollution problem.
Allegan County, Michigan (1947) - Wells produced yellow water
which contained high levels of chromium. About three years
before any contamination appeared, a metal-plating company
began discharging chrome-plating wastes into an infiltration
pit and the surrounding overflow area. Discharge of plating
wastes resulted in the contamination of the glacial-drift
aquifer. Health Department personnel estimated it would be
about six years before the aquifer in the vicinity of the
wells would be free of chromate. All private wells in the
village of Douglas were condemned.
Riverside County, California (1956) - Chrome plating wastes
were discharged on the ground and into a cesspool. Samples
from four wells contained concentrations of hexavalent chromium
of as much as 3 tag/I and 18 others contained trace amounts.
The National Interim Primary Drinking Water Standard for
total chroraiura is 0.05 mg/1.
-tet-
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Attachment II
Solubility and Environmental Mobility Characteristics
of Chromium Compounds
The tripositive state is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of ligands such as water,
ammonia, urea, halides, sulfates, amines and organic
aicds.f 16«17) Thousands of such compounds exist. This
complex formation underlies the tanning reactions of chromium,
and is responsible for the strong binding of trivalent chromium
by soil elements, particularly clays.
At pH values greater than about 6, trivalent chromium
forms high molecular weight, insoluble, "polynuclear" complexes
of Cr(OH>3 which ultimately precipitate as Cr203.nH2<>. This
process is favored by heat, increased chromium concentration,
salinity and time.(16) These chromium hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form,
Cr is therfore, resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubilization of
chromium hydroxide:
-132-
-------
Resulting Calculated CrIII
Reaction Keq.C18) Concentration mg/1
2.
3.
Cr(OH;3+2H+
Cr(OH),
Cr(OH),
CrOH"*" +2H20 108
Cr+3+30H" 6.7xlO~31
H++Cr02~+H20 <»xlO~17
PH5
520
35
i
pH6
5.2
0.035
i
pH7
0.052
i*
i
*i= I7) Little soluble chromium is found in
soils.'1 • ' If soluble trivalent chromium is added to
soils it rapidly disappears from solution and is transformed
Into a form that is not extracted by ammonium acetate or
complexing agents .'12113) However, It is extractable by very
strong acids, indicating the formation of insoluble
hydroxides.(19>20) Thus: above pH5, chromium(III) Is immobile
because of precipitation; below pH4, chromium (III) is immobile
because it is strongly absorbed by soil elements; between pH4
and 5 the combination of absorption and orecipi tat ion should
render trivalent chromium quite imnobile.'1^»20)
In contrast, hexavalent chromium compounds are quite
soluble, and hexavalent chromium is not as strongly bound to
-J33-
-------
soils . ( I** i 21) Hexavalent chromium remains as such in a
soluble form in soil for a short tine, and is eventually
reduced by reducing ap,ents if pre sen t. (2 2 , 2 3) ^s compared
with the trivalent forra, hexavalent chromium is less strongly
adsorbed and more readily leached from soils^19) and thus, is
expected to have nobility in soil materials.(^ ^)
ul _
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Response to Comments - Wastewater Treatment Sludges from
Electroplating Operations
A number of comments have been received with respect to waste
F006 (Wastewater treatment sludges from electroplating
operat ions).
1. One commenter pointed out that EPA's original proposal
to list "electroplating wastewater treatment sludges"
(43 FR 58958), and the background document which accompanied
this proposal, did not specifically propose to Include
anodizing operations and chemical conversion coating
operations within the electroplating wastewater treatment
sludge designation. Therefore, the commenter argues
that the May 19, 1980 listing expanded what was originally
included in the proposed listing description without
allowing for adequate public comment or clearly stating
that this designation has been expanded.
The Agency disagrees with the commenter. Although
the term "electroplating" was not specifically defined
either by the listing or appropriate background document,
the term was defined by the Agency under regulations
pronulqated by the Effluent Guidelines Division (EGO).
It has Seen Aj»ency policy to use the same definitions
for the same terms throughout the Agency to avoid
confusion among the regulated community. Only when the
•\fiency Intentionally defines terms differently would
-------
the Agency believe it has an obligation to inquire
whether a listing description --in this case "electro-
plating wastewater treatment sludges"— encompassed the
same processes as those defined under the EGD regulatory
pr ogram.
A number of commenters objected to the inclusion of the
sulfuric acid anodizing process in the general category
of electroplating operations, and the subsequent inclu-
sion of these process sludges as hazardous wastes in
§261.31. The commenters first point out that the ano-
dizing of aluminum is not-an electroplating operation.
Rather, it is an operation which etches and oxidizes the
aluminum as compared to the plating of a different metal
which occurs in electroplating. Secondly, the commenters
indicate that the two major processes used in aluminum
anodizing, chromic acid process and sulfuric acid process,
are entirely different. The chromic acid process uses
chromium rich solutions, so that chromium would be
expected in the waste, while the sulfuric acid process
does not use chromium, cadmium, nickel or cyanide-rich
solutions. Therefore, the commenters argue that wastewater
treatment sludges from the sulfuric acid anodizing
process would not be expected to contain significant
concentrations of these contaminants, and thus recommend
that wastes generated from the sulfuric acid anodizing
-------
process be excluded in the general category of electro-
plating operations and removed from the hazardous waste
list.
In reviewing the various electroplating processes,
including the two primary processes used In aluminum
anodizing, the Agency generally agrees with the commen-
ters and has modified the listing to exclude vastewater
treatment sludges generated from the sulfuric acid
anodizing processes. However, the Agency also believes
that it nay not be accurate to portray the wastes from
either process (i.e., the chromic acid and sulfuric
acid processes) as non-hazardous in all cases soley on
the basis of the anodizing solution. To improve the
corrosion resistance of anodic coatings on aluminum,
the anodized surface Is lamersed into Blightly acLdiCed
hot water. The sealing process converts the amorphous
anhydrous aluminum oxide to the crystalline monohydrate
(A1203.H20X- For sulfuric oxide anodized parts, 5-10%
by weight sodium dichromate can be added (the use of
sodium dichroraate as a sealer for uncolored sulfuric
anodizing is a recognized non-proprietary Industrial
process*). Consequently, the amount of chromium in
sulfuric acid anodizing sludges may be significant.
Additionally, unsealed anodic coatings on aluminum are
*Chuck Bent, Reynolds Aluminum, August 27, 1980. Personal
communlcation.
-------
colored by immersion in a solution of organic or inor-
ganic dyes. After rinsing, the sealing of the dye is
accomplished by immersion in a hot solution of nickel
or cobalt acetate. Therefore, the amount of nickel in
these sludges may also be significant. However, the
available information indicates that both chromium and
nickel are used infrequently as sealants in this process
(I.e., the large majority of the industry uses a plain
hot water bath in the sealing process). Therefore, the
Agency will only use the characteristics (principally
the EP toxicity characteristic)* to determine whether
these wastes are hazardous at this time. If after
further study, however, the Agency finds that both
sodium dichromate and nickel acetate are commonly used
in the sulfuric acid anodizing process and that these
toxic contaminants end up in the waste in significant
concentrations, the Agency will consider bringing these
sludges back into the hazardous waste system by listing.
3. One commenter objected to the Inclusion of wastes from
chemical conversion coating operations as hazardous
wastes, especially with respect to coating operations
of aluminum. The commenter argues that the listing
background document contains a rather unspecified scenario
*By relying on the characteristics, those sludges which con-
tain significant concentrations of nickel would not be
brought into the hazardous waste system.
-------
on the potential adverse effects of cadmium, chromium,
nickel and cyanide and that this s'cenario is clearly
not appropriate for sludges from chemical conversion
coating operations. The commenter also points out
that neither cadmium, nickel or cyanide are present
in wastes from the chemical conversion coating of
aluminum in significant concentrations (the EP was
conducted on two chemical conversion coating waste
treatment plant sludges, and showed low concentrations
of these metals). With repsect to chromium, the commenter
believes that the concentrations of this contaminant in
the EP extract from the two sludge samples (Sample A -
3.24 mg/1 Cr and Sample B - O.lfi mg/1 Cr) provides no
basis for listing these wastes as hazardous. The
commenter therefore recommends that the listing F006
(wastewater treatment sludges from electroplating opera-
tions) be revised to exclude wastes from the chemical
conversion coating of aluminum.
The Agency disagrees with the commenter. Although
the listing background document does not provide a
specific discussion on chemical conversion coating
operations and includes only limited data on the compo-
sition and concentrations of the toxic constituents In
these sludges, data contained in the references to the
background document fully support the listing of sludges
from chemical conversion coating operations. For example,
-------
in the Agency's Development document for Existing Source
Pretreatment Standards for the Electroplating Point
Source Ca tegory, (">) effluent streams from forty-six
coatings plants were sampled and analyzed for a number
of compounds including cyanide and chromium. The results
of this sampling effort are presented below:
Composition of Raw Waste Streams
from Coatings Process (mg/1)
Compound Concentration
CR (Total) .19 - 79.2
Cyanide .005 - 126.0
As is indicated, these toxic compounds are present
in the raw wastewater, thus can be expected to be
found in the treatment sludges, at much higher concen-
trations, after implementation of the electroplating
pretreatment standards. The Agency believes that
these sludges are no different (i.e, would contain toxic
metals and complex cyanides in significant concentrations)
than other electroplating sludges which have been shown
to leach. Addditionally, it should be pointed out that
conversion coating processes are usually associated with
electroplating operations and, thus, wastes from conversion
-------
coating operations are most likely to be combined with
those of other metal finishing operations of similar
waste characteristics and treated in a single treatment
plant. Therefore, the Agency will continue to include
the general category of chemical conversion coating
operations in the electroplating category, so that
these process sludges will continue to be listed as
hazardous wastes. However, the listing background
document will be revised to include a more detailed
discussion of chemical conversion coating operations.
With respect to the specific category of chemical
conversion coating of aluminum, the Agency also has de-
cided to continue to include these sludges as part of the
hazardous waste listing. This decision Is based, after
careful review of the process, on the frequent use of
chromate compounds in the various conversion coating
operations on aluminum. Thus, sodium chromate or pota-
ssium dichromate Is used in common oxide-conversion
coating solutions, potassium dichromate is used In
phosphate-conversion coating solutions, and sodium
dichromate is used in chromate-conversion coating solu-
tions. C25) Although limited analytical data is available,
the Agency believes that the chromium used in the process
will end up in the raw wastewater and subsequently
precipitate out into the treatment sludges. In data
submitted by one commenter, the level of chromium found
-------
in the EP extract from one sludge sample was 3.24 mg/1
(approximately 65 times the NIPDWS), a level considered
significant by the Agency.*^24) Additionally, cyanides
are known to be used in the coloring of anodlzed alumi-
num. C5) Therefore, the Agency will continue to list
sludges from the chemical conversion coating of aluminum.
However, since this waste is not expected to contain
significant concentrations of cadmium and nickel, the
Agency has decided to list these sludges separately for
the presence of chromium and cyanide as the only constit-
uents of concern.
Several commenters felt that the listing "Wastewater
treatment sludges from electroplating operations" was
overly broad. More specifically, the commenters indicate
that the listing will require industry to manage the
following electroplating baths, sludges and solutions as
hazardous wastes: (1) tin plating on carbon steel, (2)
zinc plating (segregated basis) on carbon steel, (3)
aluminum or zinc-aluminum plating on carbon steel (4) all
cleaning and stripping associated with tin, zinc and aluminum
plating on carbon steel and (5) chemical etching and
milling of aluminums. Commenters argue that these
*Data was also submitted by the coamenter which Indicates that
the level of chromium found in the EP extract (0.16) can be
Insignificant, However, this one data point is insufficient
to remove all sludges from this process from the hazardous
waste listing.
- i u -> _
-------
processes do not use chromium, cadmium, nickel and
cyanide solutions, and thus Chat these compounds are
not expected to be present In the sludges, and also
that no data was presented in the listing background
document to support the inclusion of these processes in
the listing. Therefore, they recommend that the Agency
revise the listing to exclude the plating of tin, zinc
(segregated basis) and aluminum on carbon steel and
chenical etching and milling of aluminum from this
listing.
In reviewing the various electroplating processes,
the Agency agrees with the commenters that the above
electroplating processes would not generate a sludge
which would contain significant concentrations of chro-
mium, cadmium, nickel and cyanide. We have consequently
modified the listing to exclude wastewater treatment
sludges generated from: (1) tin plating on carbon steel,
(2) zinc plating (segrated basis) on carbon steel,
(3) aluminum or zinc-aluminum plating on carbon steel,
(4) all cleaning/stripping associated with tin and
aluminum on carbon steel, and (5) chemical etching and
milling of aluminum from the hazardous waste listing.
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Listing Background Document
SPENT WASTE CYANIDE SOLUTIONS AND SLUDCES
1. LISTING
The listed wastes are those waste streams, from several
industry segments which specifically contain cyanide salts
or coraplexed cyanide compounds. These listing descriptions
have been modified to make it clear that only those processes
which use cyanide salts or complexed cyanide compounds are
covered by the listing. These wastes are generlcally listed
as follows:
Cyanide Salts
Electroplating
Spent cyanide plating bath solutions (except for
precious metals electroplating spent cyanide plating
bath solutions)(R,T)*
Placing bath sludges from the bottom of plating
baths where cyanides are used in the process (except
for precious metals electroplating plating bath
sludges)(R,T)
Spent stripping and cleaning bath solutions where
cyanides are used in the process (except for precious
metals electroplating spent stripping and cleaning
bath solutions)(R,T)
Metal Heat Treating
Quenching bath sludge from oil baths where cyanides
are used in the process (except for precious metals
heat-treating quenching bath sludge)(R,T)
Spent cyanide solutions from salt bath pot cleaning
(except for precious metals heat-treating spent
solutions from salt bath pot cleaning)(R,T)
*Spent plating bath solutions and plating bath sludge from the
bottom of plating baths also contain complexed cyanides, but
are more significant as sources of cyanide salts.
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Mineral Metals Recovery
Spent cyanide bath solutions (R,T)
Complexed Cyanides*
Metal Heat Treating
Quenching wastewater treatment sludges where cyanides
are used In the process (except for precious metals
heat-treating quenching wastewater treatment sludges)(T)
Mineral Metals Recovery
Cyanidation** wastewater treatment tailing pond sediment (T)
II. SUMMARY OF BASIS FOR LISTING
A number of different industry categories located nation-
wide dispose of spent or waste cyanide solutions and sludges,
the most prevalent being electroplating, metal heat treating
and mineral metals recovery operations. Cyanide is present
in these wastes in the form of either (1) alkali-metallic or
alkaline earth cyanide salts such as sodium, potassium, and
calcium cyanide or (2) as heavy metal cyanides, ferro- and
ferricyanides, and ferric ammonium ferrocyanide (iron blue)
referred to as complexed cyanides.(*)
The Administrator has determined that wastes from these
processes may be solid wastes, and as solid wastes may pose
a substantial present or potential hazard to human health and
*In response to comments, two of the listings ("Flotation
tailings from selective flotation from mineral metals recovery
operations" and "Dewatered air pollution control scrubber
sludges from coke ovens and blast furnaces") which were
promulgated on May 19, 1980 (45 FR 33123) have been deleted
from the hazardous waste list. See Response to Comments in
back of the background document for details.
**Cyanidation as described In this background document is meant
to include the recovery of gold via a caustic cyanide leach.
Cyanidation can also be used to recover silver; however, do-
mestically little if any silver Is recovered by cyanidation
except when silver is recovered as a by-product from gold re-
covery oper a t ions . ( •*• )
- 1
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the environment when Improperly transported, treated, stored,
disposed of or otherwise managed, therefore should be subject-
to appropriate management requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations:
1. Each of the wastes exhibits either reactive or
toxic properties or both due to their cyanide
content.
2. These wastes generally contain high concentrations
of cyanide. Additionally, land disposal of cyanide
wastes is widespread throughout the United States
with 769 kkg of cyanide (CN~) contained in
these wastes annually. Thus, the high cyanide
concentration levels and the large annual generation
rate, Increases the likelihood of exposure and
possibility of substantial hazard.
3. Cyanides can migrate from the waste to adversely
affect hutaan health and the environment by the
following pathways, all of which have occured in
actual management practice:
(a) generation of cyanide gas resulting from the
reactive nature of cyanide salts when mixed
with acid wastes;
(b) contamination of soil and surface waters in the
vicinity of inadequate waste disposal resulting
in destruction of livestock, wildlife, strean-
dwelling organisms, and local vegetation; and
(c) contamination of private wells and community
drinking water supplies in the vicinity of
inadequate waste disposal.
III. SOURCES OF CYANIDE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Overall De script ion of Industry Sources
Waste cyanide solutions and sludges containing both
cyanide salts and conplexed cyanides are generated by a number
of different Industries Including electroplating, metal heat
treating and mineral metals recovery operations. Approximately
- I <-J L -
-------
20,000 facilities in the United States use one or more electro-
plating or heat treating processes in manufacture of primary
raetals, fabricated metals, nachinery, and electronics equipment.^6
An additional 5 facilities use cyanide in the process of
recovering precious metals, particularly gold and silver.
(Conplexed cyanide waste solutions or sludges containing only
conplexed cyanide are generated by a number of other industrial
processes, principally iron blue manufacturing.*)
Table 1 lists the equivalent cyanide (CN~) consumed
annually by each of these processes including the specific
types of cyanide salts and complexed cyanides used. Table 2
indicates the number of facilities and types of waste associated
with these different sources. Industrial processes which
generate these waste cyanide solutions and sludges are further
described below.
B. Waste Generation, Waste Stream Description and Waste
Management Practices
The major processes which generate cyanide salt-con-
taining waste include (1) electroplating using cyanide plating
baths or cyanide stripping or cleaning baths, (2) metal heat
treating using cyanide quenching baths, and (3) mineral metals
recovery using cyanide plating baths. Complexert cyanide
wastes (primarily ferro and ferricyanides) are generated fron
*Iron blue manufacturing is discussed in the chromium pigments
background document and thus is not presented here.
-------
Table 1
Equivalent Cyanide (CN~) Consumed Annually By
Process and By Specific Type (Salts or Complexed)(*
Cyanide Salts
NaCN
KCN
CaCN2
Electro-
plating
10,292
72
Heat
Treat ing
1,428
65
Mineral
and
Metals
Recovery
unknown'
Complexed Cyanides
Heavy Metal 2,346
Ferrocyanides
Farricyanides
TOTAL 12,710
65
1,558
(a>MRI (1976) has estimated that about 650 kkg of NaCN is
used for precious metal cyanidation;'^) however, one of
the cyanidation precious metal operations uses a copper
ore and, thus, an unknown fraction of this total is not
used primarily for precious metals recovery.
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Table 2
CYANIDE WASTE SOURCES
Source
Number of Facilities
Types of Wastes(s)
Electroplating
Minerals and Metals
Recovery
13, 000(a>
Metal Heat Treatment
Cyanide salts and
complexed cyanides
(Solution and sludge)
Cyanide salts and
complexed ferro
and ferricyanlde
(solutions and
sludges in tailing
ponds)
Sodium and potassium
cyan ide (solut ion
and sludge)
(a)Based on Oct. 1979 Effluent Guidelines document estimates. (U.S.
Environmental Protection Agency. Oct., 1979. Draft Development
for Effluent Limitations Guidelines, New Source Performance Stan-
dards and Pretreatment Standards for the Photographic Processing
Point Source Category. Washington, D.C.).
-------
(1) treatment of electroplating wastewater (2) treatment of
quenching process wastewater from the metal heat treating
industry and (3) treatment of cyanldation wastewater
from mineral metals recovery operations.
1. Electroplating
a. Generation of Spent Plating, Stripping and Cleaning
Bath Solutions
Electroplating, as defined in this document, in-
cludes both common and precious metal electroplating, anodizing,
chemical conversion coating (i.e., coloring, chromating,
phosphating and Immersion plating), chemical etching and
milling, electroless plating, and printed circuit board
manufacturing. The primary purpose of electroplating opera-
tions is to apply a surface coating, typically by electrode
decomposition, to provide protection against corrosion, to
increase wear or erosion resistance, to restore worn parts
to their original dimensions, or for decoration.(7) The
operation itself involves immersing the article to be coated/
plated into a bath consisting of acids, bases, salts, etc.
A plating line consists of a series of unit operations
conducted in a sequence in which one or more coatings are
applied or a basis material is removed. (For a more detailed
discussion of the electroplating process see the Development
Document for Existing Source Pretreatment Standards for the
Electroplating Point Source Category, August 1979).'')
-------
Figure 1-1 in Appendix I illustrates a standard electro-
plating process. Cyanides may be used to make-up the various
plating/coating solutions and stripping and cleaning bath
solutions.(') For example, the electrolytic baths used
in both chromium and precious metal electroplating typically
consist of cyanide salts of sodium, potassium, cadmium,
zinc, copper, silver, and gold.C1) After extended use,
plating baths become deficient in the specific ion being
plated/coated, leaving cyanides in solution either as simple
ions or in complexes. After extended use of stripping and
cleaning solutions, metals begin to accumulate so that further
removal of metal coatings on articles becomes difficult.
At that point these solutions are either processed for metal
recovery (this is particularly true of precious metal plating
operations) or discarded. Untreated spent plating, stripping
and cleaning bath solutions, when discarded, represent the
major sources of cyanide salt containing wastes generated
in electroplating operations* (and a minor source of complexed
cyanides) .
^Another major source of cyanide salt waste is the rinse water
contaainated by the solution remaining on the article that
has been plated, stripped, or cleaned. This rinsewater is
either treated and present in wastewater treatment sludge,
In which case it is part of a listed waste, or discharged
directly to a POTW. Rinsewater which is mixed with domestic
sewage that passes through a sewer system before it reaches
a POTW for treatment is excluded from subtitle C regulation
under §261.A(a) ( 1). The Agency is in the process of developing
pre-treatment standards for the electroplating industry.
-------
b. Management of Spent Plating, Stripping and Cleaning
Bath Solutions, and Generation of Treatment Sludges
Spent plating, stripping and cleaning bath solutions
ai '• rinse waters containing cyanide compounds are chemically
treated, primarily with hypochlorite or chlorine, to convert
cyanide compounds to carbon dioxide, metal salts, nitrogen,
and wa ter . (1)
Coraplexed cyanides that are present in hypochlorite-
treated bath solutions and rinse waters are precipitated as
part of the sludge during any additional wastewater treatment
(see Figure 1-2 In Appendix I). Even though the cyanide is
treated, a certain percentage of the complexed cyanide is
not destroyed and thus may be present in the sludges.(*«8)
These sludges are typically disposed of in a sanitary
landfill. (1.8)
c. Plating bath sludge from the bottom of cleaning
baths
Additionally, cyanide plating solutions that have
been restored several times often leave a sludge in the
bottom of the bath which must be cleaned out when spent
solutions are discarded. These sludges often contain cyanide
salts and complexed cyanides when cyanide solutions are used
in the process and typically are placed in drums for chemical
landfill disposal.d)
-------
Available plant Information Indicates that nearly all
of the cyanide-containing materials discharged to the environ-
ment are treated, although It Is possible that some small
plating shops may either discharge directly to municipal
sewer systems or landfill spent solutions.(1)*
2. Metal Heat Treatment
Generation of Cyanide-Containing Quenching Bath
Sludge and Spent Solutions from Salt Bath Pot Cleaning
Case hardening by carburizing adds carbon to the
surface of steel. (^) Liquid carburizing uses cyanides as
the source of carbon. Liquid carburizing is accomplished by
submerging the metal in a molten salt bath containing sodium
cyanide (6-23%). Figure 1-3 in Appendix I Illustrates the
liquid carburizing process. Sodium cyanide is also used in
the case hardening of steel using either the liquid nitriding
or carbon!triding processes.
Cyanide salt-containing wastes from this process generally
arise from two sources: (1) quenching sludge and (2) pot
cleanout. In the quenching process, oil is used as the
quenching media. The sodium cyanide adhering to the
case hardened steel during oil quenching Is not soluble and
*However , since 60 to 80 percent of these small plating shops
have shifted to non-cyanide baths (such as zinc), the quantity
of untreated cyanide waste landfilled from electroplating
operations is getting smaller.(1)
-------
s o t 1 1 p s I o i h i' bottom of L li c> i] n <• n c h i n ft tank as a sludge. Another
•source of ryrinLde waste (.ilthontfh generated in less volume
than the quenching sludge) results from cleaning out salt bath
pots.
b. Generation of Quenching Wastewater Treatment Sludge
Where process wastewaters containing cyanides are
chemically treated, sludges from these operations are typically
disposed of in landfills.(^) During waste treatment some
of the untreated cyanide may complex with heavy metals and
precipitate in the sludge.(7)
3. Mineral and Metals Recovery
Cyanides are used extensively in the extraction and
beneficiation of gold and silver from ore.
a. Generation and Management of Cyanidation Wastewater
Tailings Pond Sediment
Use of cyanide (cyanidation) in the recovery of
gold and, to a lesser extent, silver, varies In process
complexity depending on the ore matrix. Generally, the ore
is pulverized to expose gold and silver deposits prior to
leaching by caustic cyanide solutions. (*•) The gold or
silver-laden caustic cyanide , solution Is then electrolysed,
and :he gold or silver is deposited on stainless steel wool
cathodes (see Figure 1-4 in Appendix I). The cyanide bath Is
then chemically treated with hypochlorlte or chlorine to
-------
destroy cyanide salts and complexes. The resulting wastewater
tailings pond sediment is a listed waste. Ferrocyanide and
ferricyanide complexes formed in tailings pond sediment are
periodically dredged and disposed of in landfills.'^-'
b. Generation of Spent Cyanide Bath Solutions^1)
This waste stream also arises from the cyanidation
process described above. Some minerals and metals recovery
plants, however, instead of chemically treating spent cyanide
bath solutions, discharge the waste directly to tailing ponds
where oxidation and sunlight are relied upon to convert
cyanide salts to complex cyanides which precipitate into the
pond sediment. In this case, the listed waste stream is the
spent cyanide bath solution.
C. Waste Characteristics and Quantities
Waste cyanide solutions and sludges are generated
nationwide with most disposal occuring in EPA Regions I
through IV and in Region IX.(10) The quantity and types of
wastes that result from any of these processes are variable
and depend upon operation conditions at each facility, but
significant cyanide concentrations in all of these waste
streams are anticipated.- Nearly all cyanide processes include
some form of chemical treatment which destroys most of the
cyanide prior to precipltaion of solids and heavy metals. Of
the total 14,260 kkg equivalent cyanide consumed annually,
-------
12,710 kkg is used by the electroplating industry.A large
percentage of that is either oxidized by electrolysis In the
plating bath, destroyed during alkaline chlorination or
ozonation prior to wastewater discharge.(D This means
that approximately 127 kkg of equivalent cyanide (CN~)
(probably in the salt form) is disposed of annually on land
by this industry. Of the remaining 1,557 kkg (from the
total of 14,260 kkg) equivalent cyanide (CN~) consumed
annually, about Al percent (769 kkg - 127 kkg = 642
kkg) is disposed of on land as solutions or sludges.'*'
The balance is either recovered or chemically destroyed by
alkaline chlorination, electrolysis, or ozonation. Sixty-seven
percent of this 642 kkg of CN" disposed of (by industries
other than electroplating) Is in complexed cyanide form.
Table 3 lists the types of cyanide wastes generated, the
range of quantity disposed of in solid waste streams by an
individual facility, and the total quantity of waste for each
of the contributing sources of manufacturing processes.
These quantities are considered significant in light of
cyanide's migratory potential (see p. 21-24) and high toxicity.
The fact that disposal occurs nationwide is also significant,
since the wastes are exposed to many differing environmental
conditions and management situations, increasing the possibility
of mismanagement.
-------
Cyanide is expected to be present in most of these waste
streams in high concentrations. Table 3A contains cyanide
salt and complexed cyanide concentration data from listed
electroplating and metal heat treating wastes. Concentrations
.ange from 38 ppm to 92,300 ppm, with most concentrations
exceeding 1,000 ppm. In light of the health dangers associated
with cyanide (see pp. 27-28 below), these concentrations are deemed
to be of regulatory concern.
The Agency presently lacks concentration data on the
cyanidation wastes generated by the mineral metals recovery
industry, although concentrations are believed to be high
based on the large quantity of cyanides disposed of annually.
(See Table 3)
D. Typical Disposal Practices
In general, waste management of cyanide solutions
and sludges relies primarily on disposal in municipal,
chemical, or company-owned landfills.'*-'
Facilities using only one process, sometimes find it
more cost effective to landfill spent cyanide salt solutions
(without any chemical treatment) along with cyanide sludges.(!)
Of course, as described above, most spent solutions are managed
Initially in holding ponds, which are treatment facilities
under RCRA.
Spent cyanide solutions and sludges from electroplating
operations are generally treated by alkaline chlorinatlon
prior to discharge into municipal sewer systems or landfill
disposal. Data characterizing the disposal practices In some
states indicate, however, that some small plating shops dispose
of spent plating solutions and sludges which still contain
untreated cyanide in landfi1 Is.(1)
-------
Table 3
Waste Characteristics (Ii2,7f10)
Source
Electroplating
Mineral and
Metals
Recovery
Annual Waste
Quanity/Facility
kkg
Cyanide (CN~)
Quantity Used/
Facility
Total Annual
Waste Quantity
(kkg)
Cyanide Salts
(Cn-)
Disposed
Annually
(kkg)
Type of Waste
Spent plating,
Stripping and
Cleaning bath
solutions; plating
bath sludge; plating
bath and rinse
water treatment
sludge
Cyanidation waste-
water treatment
sludge
25-l,250(a>
42,000 (1»>
20-300(d>
Complexed
Cyanides
(CN)
Disposed
Annually
(kkg)
Metal Heat
Treating
Quenching bath
sludge and spent
bath solution and
quenching waste-
water treatment
sludge
11-
6,125(10>
Quantities based on the range in number of number of employees per facility 10-500 employees(')
bTotal based on estimated 16.8 employees per facilityC1); 10,000 facilities*7); and 2.5 kkg/yr-employee (wet
basls)(10) (gee flgure 1)
cTotal based on estimated 62% of total consuption of 20,500 kkg (CN) and 1% disposal(l)
(contlnr ">
-------
Table 3 (Continued)
based cm mining capacity: estimated total consumption is 650
e50X of NaCK equivalent consuption(^)
fRauge of total annual waste for facilities included in a composite of state tfste disposal applications
assuming waste density 4kg/gallon(2) . Based on total waste disposal estimates average quantity per
facility is 3.5 kkg/yrC10*.
STotal based on estimated 25 employees per facility; 7,000 facilities of which 25% use cyanide^1';
0.14 kkg/yr-employee(10) (See figure 1)
hRange of content of waste per facility for facilities iincluded in a composite of state
waste disposal applications assuming waste density and kg/gallon'^)
f-Total based on estimate that 13% of waste are cyanide wastes and 25% of all cyanide waste is
destroyed.
JEstimate based on raw waste load data from "Development document for interim final and proposed
effluent limitations guidelines and new source performance standards for the ore mining and
dressing industry point source category." Volume 1.
-Jrf-
-------
Industry
Meral Heat TreatIns
Metal Heat TreacIr-E
Klectr-ir-Lating
Electroplating
K'eetr opiating
Electroplating
'•'J-^ctr opiating
iJectroplatlng
Electroplating
Electroplating
Metal Heat Treating
Source-'
Cyanide Salts
Quenching Bath sludge
and Spent Solution
Quenching Bath sludges
Spent Cleaning Bath
Solution
Spent Cleaning Bath
Solution
Spent Plating Bath
Solution
Plating Bath Sludge
Complexed Cyanides
Plating Bath Treatment
Sludge
Spent Plating Bath
Solution
Spent Plating Bath
Solution
Plating Bath Treatment
Sludge
Quenching Wastewater
Treating Sludge
Table 3A
Cyanide Wastes1'2'
Concentrations
Typed of
Waste/Form**
Potassium and
Sodium Cyanide/
Solid**
Potassium and
Sodium Cyanide/
Sludge
Sodium Cyanide/
Solution
Cyanide Salts/
Solution
Sodium Cyanide
Solution
Metal Salts/Sludge
Complex Metal
Cyan id e/Solut ion
Complex Metal
Cyanide/Solution
Complex Metal
Cyanide/Solution
Complex Metal
Cyanide/Sludge
Comples Metal
"vanide Solids***
Annual Disposal
in Gallons
3,000
13,200
Cyan Ide
Concentrations
PP°»
92,300
8,530
22,500
14,000
6,600
1,000
15,600
6,600
36,000
12,000
6,600
350,000
38
14,547
64
80
14 , 329
2,000
1,681
26,803
-------
Table 3A
Cyanide Wastes^2)
Concentrations
Continued
Cyanide
Type of Annual Disposal Concentrations
Industry Source* Waste/Form** in Gallons ppm
Metal Heat Treating Quenching Wastewater Complex Metal 5,500 8,400
Treatment Sludge Cyanides/Sludge
*Source descriptions included in special waste disposal applications were not always the same as those
presented in the listing'2). An attempt was made to classify the waste in its approximate category
** These descriptions were taken directly from the special waste disposal applications^2^.
*** Solid cyanide wastes are placed in drums and disposed of. Solid waste quantities are expressed in
gallons related to the size of the drum used to containerize wastp for disposal.
-Hoi-
-------
MineraL and netals recovery wastes from extraction of
gold and stiver (cyaridation) are diposed of in tailing
ponds which msy be lined with clay and are sometimes constructed
to control run-off and dam seepage.(1) The size, construction,
and location of tailing ponds and retention of waste solutions
in ponds varies from site to site. When wastes are not
alkaline chlorinated to destroy cyanide prior to disposal,
tailing pones are used as holding ponds where natural air
oxidization and sunlight destroy the cyanide or where the
cyanides are conplexed with metals in solution and by attach-
ment to gangue materials.^^'
This data suggests that cyanide-containing wastes are
soraetimes managed properly. Many danage incidents involving
cyanide-containing wastes (set forth at pp. 25-27 below)*
indicate, however, that waste mismanagement may occur and
cause substantial hazard. Furthermore, proper management of
wastes capable of causing substantial hazard if mismanaged
does not make a waste non-hazardous under the definition of
hazardous waste contained in Section 1004(5) of RCRA. In
fact, industry management practice described above suggests
strongly that industry itself regards these wastes as hazardous
and requiring careful management.
IV. HAZARDS POSZD BY THE WASTES
Cyanide salt-containing wastes exhibit both reactive
and toxic properties which nake them potentially hazardous to
*AdriiCtonal Manage incidents are described in the electroplating
waste b a c- K g r CM "i c* document.
-------
human health and the environment. If exposed to mild acid
conditions, these wastes can react to generate toxic hydrogen
cyanide gas. Cyanide wastes are land disposed and if improperly
managed, cyanide can migrate from these wastes as toxic hydrogen
cyanide gas or in a soluble form into groundwater or surface
water supplies. Adverse health effects on landfill operators
and environmental stress to avian and possibly human
populations is possible if hydrogen cyanide is generated.
This most toxic form of cyanide can be fatal to humans in a
few minutes at concentrations of 300 ppm. Soluble cyanides,
while less toxic, are also fatal to sensitive species of fish
'at levels between 0.05 and 0.10 mg/1 and are rapidly fatal for
most fish species above 0.2 mg/1.(5) Further evidence of
the potential hazard of disposed cyanide wastes is the
fact that cyanide salts and complexed cyanides may: (1)
migrate from disposal sites in substantial concentrations,
(2) may be improperly managed, and (3) have proved hazardous
to human health in actual waste management incidents.*
1. Hazards via a Groundwater Exposure Pathway
These wastes contain high concentrations of cyanide, a
highly toxic substance. As illustrated in Table 3A above,
*Additional damage incidents are described in the electroplating
waste background document.
-------
cyanide concentrations in these wastes may vary from 38 ppm
to 350,000 ppm — highly elevated concentrations in light of
cyanide's extreme toxicity (see App. A and pp. 27-28). The U.S.
lublic Health Service recommended standard for cyanide in
drinking water, for example, is 0.2 mg/1 (App. A). Thus,
these cyanide concentrations in and of themselves are of
considerable regulatory concern.
Furthermore, cyanide is present in these wastes in
soluble form. Table 4 contains simulated leachate extract
data for the waste streams contained in Table 3A. The
extraction procedure is based upon the acidic environment
utilized in the Subtitle C EP. This data indicates that the
coraplexed cyanides tend to be relatively soluble and the
cyanide salts were highly soluble In this environment. In
all cases, cyanide leached from the waste in concentrations
exceeding the U.S. Public Health Service recommended standard,
in most cases, by many orders of magnitude. Thus, cyanide is
fully capable of migrating from disposed wastes.
Cyanide would be capable of migrating from these wastes
if improperly disposed, for example, if disposal occured in
areas with permeable soils, or if adequate leachate control
measures are not adopted. The migrating cyanide is likely to
be highly mobile, since cyanides have been shown to be
extremely mobile in the soil environment. pH appears to
influence the mobility, with greater mobility at high pH.(14)
-------
Table 4
LEACHABLE CYANIDE WATES<2>
Industry
Metal Heat Treating
Metal Heat Treating
Electroplating
Electroplating
Electroplating
Electroplating
Electroplating
Electroplating
Source *
(Cyanide Salts)
Quenching Bath
Sludge and Spent
Solution
Quenching Bath
Sludge
Spent Cleaning
Bath Solution
Spent Cleaning
Bath Solution
Spent Plating
Bath Solution
Plating Bath
Sludge
Type of
Waste/Form**
Potassium and
Sodium Cyanide/
Solid***
Potassium and
Sodium Cyanide/
Sludge
Sodium Cyanide/
Solut ion
Cyanide Salts/
Solution
Cyanide Salts/
Sodium
Metal Salts/
Annual
Disposal
in Gallons
3,000
13,200
22,500
14,000
6,600
1,000
Cyan ide
Concentrat
ppm
92,300
8,530
350,000
38
14,547
64
Sludge
(Complexed Cyanides)
Plating Bath
Treatment Sludge
Spent Plating
Bath Solution
Complex Metal
CyanIde/Solution
Complex Metal
CyanIde/Solution
-vt-
15,600
6,600
80
14,329
Leachable
Cyanide/
Metals
(pH 5.5
Conditions)
Within These
Wastes (ppm)
8,530
18,000
28
9,048
49
0,5
119
-------
Table 4 (Continued)
Industry
Source *
Type of
Waste/Form**
Annual
Disposal
In Gallons
Cyanide
Concentrations
PPM
Leachable
Cyanide/
Metals
(PH 5.5
Conditlons)
Within Thes.-
Wastes (?pm;
Electroplating
Electroplating
Metal Heat Treating
Metal Heat Treating
Spent Plating
Bath Solution
Plating Bath
Treatment Sludge
Quenching Waste-
water Treatment
Sludge
Quenching Waste-
water Treatment
Sludge
Complex Metal 36,000
Cyanide/Solution
Complex Metal 12,000
Cyanide/Solution
Complex Metal 6,600
Cyanide/Solids***
Complex Metal 5,500
Cyanide/Sludge
2,000
1,681
26,803
8,400
80
170
915
9.3
*Source descriptions Included In special waste disposal applications were not always the same as
those presented In the listing^). An attempt was made to classify the waste Inlts appropriate
category.
**These descriptions vere taken directly from the special waste disposal applications^-'.
***Solid cyanide wastes are placed In drums and disposed of. Solid waste quantities are expressed
In gallons related to the size of the drum used to containerize waste for disposal.
-------
Even clay liner systems nay not adequately impede migration,
as in the presence of water, montraorillonite clays (which
have high surface areas) sorbed cyanide only weakly.(15)
Cyanide has also been shown to move through soils into
groundwater.(16) In light of the extreme toxicity of this
waste constituent in the environment, its migratory potential
in both salt and complexed form, and its environmental
persistence and mobility, it strongly appears that waste
mismanagement can result in substantial potential hazard.
Certainly the Administrator cannot with assurance state
that cyanide will not migrate from these wastes and persist
in the environment; yet such assurance is required to justify
a decision not to list these wastes.
In any case, actual damage incidents involving cyanide-
containing wastes, including some of the wastes listed here,
confirm that cyanide can migrate, persist, and contaminate
groundwater, public drinking water, soil, and vegetation.
For example, a landfill site in Gary, Indiana, In which large
quantities of cyanide electroplating wastes have been disposed,
has leached into groundwater supplies.(17)
A total of 1,511 containers (mostly 55 gallon and 30
gallon drums) of industrial waste containing cyanides, heavy
-------
metals, and miscellaneous other materials were disposed of
improperly on a farm near Bryon, Illinois. Leachate entering
nearby surface water was responsible for the death of three
-nws and substantial damage to wildlife (birds, downstream
aquatic community, stream bottom-dwelling organisms) and
local vegetation. Pathological examinations established
that the cattle died of cyanide poisoning.(12)
In 1965, unlined lagoons in Columbia County, Pennsylvania,
caused contamination of private wells In the area. The
lagoons were leaking plating wastes containing cyanide,
copper, nickel allkylbenzenesulfonate, and phosphate.(12)
A landfill In Monroe County, Pennsylvania, that accepts
plating process wastes such as hydrocyanic acid, has created
a groundwater pollution problem in the area.(12)
Between 1962 and 1972 in Lawrenceburg, Tennessee, an
industry dumped up to 5,000 gallons of untreated metal plating
waste daily into trenches near the city dump. Trace quantities
of cyanide were measured in private wells and In an adjacent
drinking water supply.(12) More recently, cyanide wastes were
disposed down boreholes in Pittston, Pennsylvania, which
discharged directly into a nearby waterway.(*-3)
2 . Reactivity Hazard
Cyanide salt-containing wastes (although not complexed
cyanide wastes) pose a reactivity hazard as well. These are
cyanide bearing wastes which when exposed to mild acidic
conditions react to release toxic hydrogen cyanide gas, and
-------
thus possess the characteristic of reactivity (see 5261.23
(a)(5)).
Documented damage incidents resulting from mismanagement
of wastes from disposal of cyanide salts are presented below:
Damage Resulting from Reactivity of Wastes
(1) A tank truck, emptied several thousand gallons of
cyanide waste onto refuse at a sanitary landfill
In Los Angeles County, California. Another truck
subsequently deposited several thousand gallons of
acid waste at the same location. Reaction between
the acid and the cyanide evolved large aqounts of
toxic hydrogen cyanide gas. A potential disaster
was averted when a local chlorine dealer was
quickly called to oxidize the cyanide with
hydrogen chlorine solution.'12) Hydrogen cyanide
gas can be fatal to humans in a few minutes at
a concentration of 300 ppm. The average fatal
dose is 50 to 60 rag.
(2) A standard procedure at a Southern California dispo-
sal site for handling liquid wastes containing
cyanides and spent caustic solutions was to Inject
these loads into covered wells dug into a completed
section of a sanitary landfill. Routine air sampling
in the vicinity of the wells detected more than
1000 ppm HCN. No cyanide was detected during
addition of the spent caustic to a new well. On
-------
che basis of these discoveries, use of the wells
was discontinued. The cyanide gas was apparently
formed in the well as a result of lowering of the
pH of the waste by C02 and organic acids produced
in the decomposition of refuse. ("/
V. HEALTH EFFECTS
The toxicity of both cyanides and hydrogen cyanide have
been well documented. Cyanide In its most toxic form can be
fatal to humans in a few minutes at a concentration of 300
ppm. Cyanide Is also lethal to freshwater fish at concen-
trations as low as about 50 ng/1 and has been shown to
adversely affect invertebrates and fish at concentrations of
about 10 mg/ 1 . Hydrogen cyanide is also extremely toxic to
humans and animals, causing interferences with respiration
processes leading to asphyxiation and damage to several organs
and systems. Toxic effects have also been reported at the
very low exposure level of less than 1 mg/kg .' 15 , 16 )
The hazards associated with exposure to cyanide and
hydrogen cyanide have also been recognized by other regulatory
programs. Congress listed cyanide as a priority pollutant
under §307(a> of the Clean Water Act of 1977. In addition, the
U.S. Public Health Service established a drinking water
standard of 0.2 mg/ 1 as an acceptable level for cyanide in
water supplies. The Occupational Safety and Health Administration
(OSHA) has established a permissible exposure limit for KCN
and NaCN at 5 ng/m^ as an eight-hour t line-we ighted average.
-no-
-------
Additionally, the OS11A permissible limit for exposure to HCN
is 10 ppm (11 rng/tn^) as an eight-hour time-weighted average.
DOT requires a label stating that HCN is a poisonous and
flammable gas.
Finally, final or proposed regulations of the states of
California, Maine, Maryland, Massachusettes, Minnesota,
Missouri, New Mexico, Oklahoma and Oregon define cyanide
containing compounds as hazardous wastes or components
thereof.C17 >
A more detailed discussion of the health effects of
cyanide Is contained in Appendix A.
-yf-
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V. REFERENCES
1. U.S. EPA., The manufacture and use of selected cyanides.
EPA. No. 560/6-76-012. NTIS PB No. 251 820. April, 1976.
2. U.S. EPA. Composite of State Regulations Files. Special
wastes disposal applications. Results of leachate
tests on cyanide containing wastes from Illinois, Iowa,
Kansas and Pennsylvania. Hazardous Haste State Programs,
WH-565, U.S. EPA., 401 M St., S.W., Wash., D.C. 20460.
3. Cotton, F. A. and G. Wilkinson. Advanced Inorganic
chemistry. John Wiley & Sons, Inc., New York. 1979.
4. U.S. EPA, Production and use of cyanide. NTIS PB No. 297 606.
1978.
5. U.S. EPA, Quality criteria for water. NTIS PB No.
263 143. July, 1976.
6. Personal communication. W. Webster, U.S. EPA, to K.
Crumvine, U.S. EPA. January 17, 1980.
7. U.S. EPA, Development document for proposed existing
source pretreatment standards for the electroplating
point source category. EPA No. 440/1-78/085. February, 1978.
8. U.S. EPA. Industrial process profiles for environmental
use: Chapter 24, The iron and steel industry. EPA No.
600/2-77-023X. NTIS PB No. 266 226. February, 1977.
9. Not used in text.
10. U.S. EPA. Assessment of industrial hazardous waste practices
special machinery manufacturing industries. EPA No. SW-141C.
NTIS PB No. 265 981. March, 1977.
11. U.S. EPA. Development document for effluent limitations
guidelines and new source performance standards for the
iron and steel foundry industry. Office of Water & Waste
Management, U.S. EPA. 401 M St., S.W., Washington, D.C.
20460. July, 1974.
12. U.S. EPA. Open Files. Hazardous Site Control Branch.
WH-548. U.S. EPA, 401 M Street S.W., Washington, D.C.
Contact Hugh Kauffman. (202) 245-3051.
13. Philadelphia Enquirer. Series of articles related to
Pittston cyanide disposal. October 15-26, 1979.
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14. Alessl, B.A., and W.H. Fuller. The mobility of three
cyanide forms in soil. In; Residual management by land
disposal. W.H. Fuller, ed. NTIS PB No. 256 768. 1976.
15. Cruz, M., et. al. Absorption and- transformation of HCN
on the surface of calcium and copper montmorillonite.
Clay Minerals. 22:417-425. 1974.
16. U.S. EPA. The prevalence of subsurface migration of
hazardous chemical substances at selected industrial waste
land disposal sites. EPA No. 520/SW-634. NTIS PB No.
272 973. 1977.
17. Chemical & Engineering News. Editors Newsletter.
November 17, 1979.
-/73-
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Response To Comments
on Proposed Listings (December 18, 1978)
1. One coranenter suggested that the listings of "Spent or waste
cyanide solutions or sludges" should be modified so as to
include solutions or sludges containing small amounts of
cyanide formed during one or more proces operations. The
following language was recommended:
"Spent or waste cyanide solutions or sludges
resulting from cyanide-based processes (R,T)"
0 The Agency agrees with the comraenter that solutions or
sludges that contain minute quantities of cyanide should
not and are not intended to be included in the above
listing. However, to limit the listing to just those
processes which result from cyanide-based processes may
leave out several waste streams from RCRA control wich
could present a problem, if improperly managed. For
example, during blast furnace operations nitrogen, water
and carbon combine to produce hydrogen cyanide. Desul-
furization scrubbers installed on many of the blast
furnace stacks scrub HCN scrubber liquor is rarely treated.
Thus, if the scrubber liquor is dewatered, the cyanide is
likely to end up in the sludge at concentrations high
enough to be of concern (see discussion under Coke Oven
and Blast Furnace, p. 15, for more details).
2. A number of comments suggested that the definition of cyanide
bearing wstes should distinguish between "free cyanide" and
"ferro cyanide", since the latter would not be available to
generate hydrogen cyanide under mild, acidic, or basic conditions
0 The Agency agrees that only cyanide salt-containing wastes
pose a reactivity hazard, and the listing descriptions
reflect this distinction, since no complex cyanide wastes
are listed for reactivity.
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Response to Comments - Spent Waste Cyanide Solutions and
Sludges [Interim Final Regulation, May 19, 1980]
A number of comnents have been received with respect to wastes
F007 to F016 (Spent plating bath solutions from electroplating
operations; Plating bath sludges from the bottom of plating baths
from electroplating operations; Spent stripping and cleaning bath
solutions from electroplating operations; Quenching bath sludge
from oil baths from metal heat treating operations; Spent solutions
from salt bath pot cleaning from metal heat treating operations;
Quenching wastewater treatment sludges from metal heat treating
operations; Flotation tailings from selective flotation from mineral
metals recovery operations; Spent cyanide bath solutions from
mineral metals recovery operations; and Dewatered air pollution
control scrubber sludges from coke ovens and blast furnaces).
1. A number of commenters have indicated that the Agency, in
listing wastes F007 to F013, has Inadvertantly Included wastes
generated by processes that do not use cyanide or cyanide
compounds and, thereby, describe wastes that do not contain
cyanide salts or complexes. Therefore, the commenters recommend
that the listing descriptions for wastes F007 to F013 to be
modified to make it clear that only those processes which use
-/7S--
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cyanide salts or complexes would be covered by the
listing.*
The Agency agrees with the commenters. In promulgating
these waste listings, the Agency only intended to describe
wastes that may contain cyanide salts or complexes. There-
fore, the Agency has redefined the subject wastes to Indicate
that only wastes from processes utilizing cyanides are
included. Specific wording changes in the listing descrip-
tion are set out below (the changes to these definitions
are underlined):
EPA Hazardous
Waste Number
F007
F008
Hazardous Waste
Spent cyanide plating bath
solutions from electro-
plating operations (except
for precious metals electro-
plating spent cyanide plating
bath solutions)
Plating bath sludges from
the bottom of plating baths
from electroplating operations
where cyanides are used in the
process (exce"p~tfor precious
metals electroplating plating
bath sludges)
*Among the processes cited as not always using cyanides are:
(1) aluminum anodizing process (electroplating), (2) chemical
conversion coating operations (electroplating), (3) tin plating
on carbon steel (electroplating), (4) zinc plating (segregated
basis) on carbon steel (electroplating), (5) aluminum or zinc-
aluminum plating carbon steel (electroplating), (6) cleaning/
stripping associated with tin, zinc and aluminum plating on
carbon steel (electroplating), (7) netal heat treating operations,
and (8) selective flotation from mineral metals recovery operations.
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-176,-
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EPA Hazardous
Waste Number
F009
F010
F011
F012
F013
Hazardous Waste
Spent stripping and cleaning
bath solutions from electro-
plating operations where
cyanides are used In the
process (except for precious
metals electroplating spent
stripping and cleaning bath
solutions)
Quenching bath sludge from
oil baths from metal heat
treating operations where
cyanides are used In the
process (except for precious
metals heat-treating quenching
bath sludge)
Spent cyanide solutions from
salt bath pot cleaning from
metal heat treating operations
(except for precious metals heat-
treating spent solutions from
salt bath pot cleaning)
Quenching wastewater treatment
sludges from metal heat treat-
Ing operations where cyanides
are used in the process (except
for precious metals heat-treating
quenching wastewater treatment
sludges)
Waste is being removed from the
list- see No. 4 of this section
for more details
2. One commenter objected to the inclusion of solutions and
sludges extracted or emanating from precious metals electro-
plating and metal heat treating operations. The comraenter pointed
out that these solutions and sludges are richly impregnated
with precious metals—gold, sliver, platinum and its deriv-
atives, or rhodium and thus are never discarded (to the
-X-
-/77-
-------
coramennet's knowledge), but are always sent to metal recovery
or reclamation. Therefore, the comraenter argues that these
solutions and sludges are not "solid wastes", as that term is
defined in §261.2 of the Subtitle C regulations.
In evaluating the comraenters arguments, the Agency agrees
with the comraenter that both the solutions and sludges extracted
from precious netals electroplating and metal heat treating
operations are not solid wastes, and therefore, have been
excluded from the hazardous waste listings F007 to F012. The
primary argument on which the Agency based its decision is
the extremely high value of the precious metals and the fact
that most if not all of these facilities could not afford to
discard these solutions and sludges. As pointed out by the
comraenters, these solutions and sludges are never discarded,
thus, these materials do not meet the current definition of
solid waste (45 FR 33119). Therefore, the Agency has excluded
solutions and sludges from precious metals electroplating and
heat treating operations from these listed waste categories.
Residues from reclamation of these solutions and sludges are
solid wastes, however, and must be tested against the
characteristics of hazardous waste to determine if they are
hazardous.
We note further that the definition of "solid waste" may
be amended in the future, and that these materials may be
solid wastes under the amended definition. In that event,
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-I7S-
-------
we do not intend to repropose this listing for comment, in
light of our earlier proposal and interim final promulgation
when the opportunity for comment was utilized fully.
3. A number of commenters argued that the Agency should differen-
tiate between the form of cyanide present in the waste (i.e.,
complex cyanides vs. free cyanides). The commenters point out
that complex cyanides are considerably less toxic than free
cyanides (the commenters do not disagree that free cyanides
are toxic). They argue in addition that complex cyanides are
generally Insoluble and environmentally stable. Therefore,
the commenters recommend that wastes listed for complexed
cyanides by removed from the hazardous waste listings.
The Agency disagrees with the commenters. First of all,
it should be pointed out that the Agency has already differen-
tiated between the form of cyanide present in the waste i.e.,
only cyanide salt-containing wastes (free cyanides) are listed
as posing a reactivity hazard.
Second, although complexed cyanides are less toxic than
free cyanides, this simple statement does not adequately
address the potential for harm posed by complexed cyanide-bearing
wastes because complexed cyanides undergo photodecomposltion
resulting in extremely toxic hydrogen cyanide and free cyanide
decomposition by-products.*/
V These toxic photodecomposition residuals (chiefly HCN) have been
shown to be resistant to naturally occurring wavelengths reaching
the earth's surface. (Frank, S.N., and D.J. Bard. 1977. Hetero-
geneous photocatalytic oxidation of cyanide ion in aqueous solution
of titanium dioxide powder. Jour. Amer. Chem. Soc. 99(1): 303-304.
Thus, these residuals will not photolyse further so that this degrada-
tion mechanism will not further affect toxicity in waste management
sett ings.
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This phenomenon is especially well documented for iron
cyanides, the most prevalent form of complexed cyanide in
the wastes listed here. (See Ecological Analysts, Inc.,
Cyanide, an Overview and Analysis of the Literature on
Chemistry, Fate, Toxicity, and Detection in Surface Waters,
prepared for the Inter-Industry Cyanide Group, and sources
there cited (June, 1979). While no photodegradation rate
constant is indicated in these sources, it has been shown
in laboratory experiments that the rate of generation of
hydrogen cyanide and free cyanide via photodecomposition of
complexed cyanides exceeds the rate of cyanidjs loss froo
solution via volatilization. Thus, we can clearly envision
situations where mismanaged wastes containing complexed
cyanides cause substantial environmental harm due to photolysis
and subsequent migration of HCN and free cyanides.
Damage incidents involving disposal of complexed cyanide-
containing wastes bear out our concern. Thus, a series of
nassive fish kills have been reported presumably caused by
the photodecomposition of iron cyanides. (See Doudoroff,
1976, Toxicity to Fish of Cyanide and Related Compounds—A
Review (prepared for U.S. EPA, EPA 600/3-76-038). In one
such incident, fish mortalities occurred in the summer of
1949 in Tulpehocken Creek, Lebanon County, Pennsylvania, and
were believed to have been due to pollution escaping from
a leaking waste-treatment lagoon accepting complexed cyanide
wastes. "Appreciable amounts of ferro- and ferrIcyanide"
-y-
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were said to have been found In the seepage from the waste-
treatment lagoon and in a heavy silt deposit in the stream
bottom. Cyanide was found in the tissues of dead fish in
amounts believed to have been sufficient to have caused
death, and local residents reported that all the fish mortal-
ities occurred at midday on bright, sunny days (emphasizing
the role of photodecomposition).
Therefore, the Agency will continue to list wastes
which contain complexed cyanides since they do have the
potential to migrate, photodecompose and generate HCN and
present a substantial hazard to human health and the
environment.
4. A large number of commenters have also objected to the
inclusion of "flotation tailings from selective flotation
from mineral metals recovery operations" on the hazardous
waste list. The commenters argue that the Agency's rationale
for listing this particular waste is objectionable both on
procedural grounds and technical grounds. With respect to
the procedural arguments, the commenters claim that this
particular listing was never proposed as a hazardous waste
prior to its listing, thus, the requirements under the
Administrative Procedure Act has not been followed.
The commenters also argued substantively that available
scientific and technical data do not support listing this
waste as hazardous. Their specific claims are:
-JSJ-
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a. Nature of the Toxicity; Flotation tailings will only
contain complex cyanides, not highly toxic free cyanides.
b. Concentration of Cyanide Waste; Concentration of cyanide
in the tailings is so low as not to pose any threat. A
number of coraraenters provided specific analytical data
on the concentration of of cyanide in the waste. These
concentrations ranged fron 10 ug of CN~/1 to 1 mg of
CN-/1
c. Potential to Migrate; Complex cyanides are generally
stable and even when they do disassociate the percent-
age of free cyanide produced from the complex cyanide
is small.
d. Persistence: Cyanides have a low degree of persistence
In the environment.
e. Potential to Degrade into Non-harmful Constituents;
Cyanide Is amenable to a number of natural treatment
methods Including air oxidation, sunlight and biode-
gradation.
f. Bioaccumulation: Cyanide does not bioaccumulate.
g. Improper Management! It is virtually impossible to
improperly manage disposal of this waste stream (no
explanation was provided concerning this statement).
h. Reported Damage; No known cases of damage to human
health or the environment caused by cyanide from
tailings are cited in the background document.
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Therefore, the commenters recoranend that the Agency
remove its classification of flotation tailings as a
hazardous waste.
The Agency strongly disagrees with the commenters
that the Agency has failed to follow the procedures required
by the Administrative Proedures Act (APA). On December 18,
1978, the Agency proposed a list of approximately 200 hazardous
wastes, including "Spent or waste cyanide solutions or sludges
(R,T)" (see proposed §250.14(a) [45 FR at 58957]. As a result
of this proposed listing, a number of comments were received
which suggested that the Agency list those specific cyanide
wastes of regulatory concern, instead of a listing solely on
a generic basis* In response to comments, the Agency therefore
listed ten (10) specific cyanide-containing wastes, including
the flotation tailings. Additionally, in promulgating this
particular waste interim final on May 19, 1980 (45 FR 33123),
the Agency allowed an additional opportunity to comment
before promulgating the listing as a "final-final" regulation.
Therefore, the Agency believes that sufficient opportunity
for comment was provided.
However, we are persuaded by the commenters technical
argunents, and therefore will remove waste F013 (flotation
tailings from selective flotation from mineral metals recovery
operations) from the hazardous waste list. We are convinced
that cyanide concentrations in this waste stream ordinarily
are too low to be of regulatory significance. Analytical
-------
data submitted by commenters and results of a study conducted
by Battelle,* Indicate that concentration of cyanides found
In this waste are very low and are present In a stable form,
so that migration of free cyanides from this waste is unlikely
to occur.** We thus do not believe that this waste would pose
a substantial hazard to human health and the environment, if
improperly managed.
5. One coramenter also argued that waste F014, "Cyanidation waste-
water treatment tailing pond sediment from mineral metals
recovery operations" is not hazardous. The commenter raised
many of the same arguments advanced to challenge the listing
of flotation tailings (F013), but provided no analytical data
in support.
After again reviewing the various processes that would
use cyanide (cyanidatlon) and generate a cyanidation wastewater
treatment tailing pond sediment, the Agency continues to
believe that this waste will contain significant concentrations
of cyanide, based on the large quantity of cyanides disposed.
For example, data provided in the listing background document
indicates that between 1-10 kkg of complexed cyanides
are disposed of by these facilities. We thus will continue
*Mezey, E.J., G.R. Smithson, and James F. Shea, Draft Final Report
on Phase II, "Treatab111ty and Alternatives for NaCn for Flotation
Control," IERL/EPA, Cincinnati, Ohio. January 31, 1980.
**Analysis of the flotation tailings for cyanides, provided by the
coramenters were <.01 ug CN~/g, .58 mg CN~/1 and 1 mg of CN~/1.
Data provided in the Battelle Report .indicated that most if not
all mines using cyanide use cyanide in "almost starvation amounts.'
-------
to Include this particular waste In Part 261.31. In addition,
the Agency believes that the conditions of disposal/storage
are ripe for the complexed cyanides to photolyze to free
cyanides which are extremely toxic and highly mobile due to
the practice in the Industry to use sunlight as part of the
treatment process for cyanides (see pg. 12).
Moreover, we note the absence of any supporting data
in the comment showing empirically that this waste typically
contains insignificant concentrations of cyanide. The Agency
will continue to list this waste until such a showing is
made .
Another commenter objected to the inclusion of waste F016,
"Dewatered air pollution control scrubber sludges from coke
ovens and blast furnaces." The commenter first argued that
the cyanide compounds present in coke oven and Iron blast
furnace scrubber sludges are iron cyanide complexes which are
"non-toxic." The commenter then pointed to several studies
commissioned by EPA to evaluate the potential hazardousness
of steel Industry wastes. The first study* concluded that
the level of heavy metals, cyanide and phenols in iron blast
furnace dust and sludge leachate, were less than 10 times the
1977 EPA Drinking Water Quality Standard. The other study**
also concluded that iron blast furnace sludge was not found
to leach toxic constituents in significant concentrations.
Furthermore, the commenter argued that while some pertinent
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leachate data for a coke oven sludge is presented, the
concentration of total cyanide found in the coke oven
leachate is relatively small (0.613 rag/1).*** Finally, a
number of steel companies analyzed the eleuate of their waste
by means of the EP test and showed an insignificant concentration
of total cyanide in the leachate.**** Therefore, the commenter
recommends that this waste be deleted from 5261.31.
After reviewing these data, it appears that these wastes
contain small concentrations of cyanide, and that the cyanide
present has very limited migratory potential. We therefore
are not listing this waste strean as hazardous. It should be
pointed out that the Agency is making this decision to de-list
all scrubber sludges from blast furnaces and coke ovens mainly
on data from iron blast furances. However, the Agency would
expect to find similar concentrations of cyanide from both
blast furnaces and coke ovens because the underlying
* Enviro Control, Inc., Hazardous Waste Listings: Fully Integrated
Steel Mills (Aug. 1978), prepared for EPA under Contract No. 68-
01-3937.
** Calspan Corp., Assessment of Industrial Hazardous Waste Practices
in the Metal Smelting and Refining Industry, Volume III, Ferrous
Smelting and Refining at 17 (April 1977), prepared for EPA,
PB 276161
*** Composite of State Files of "Special Waste Disposal Application'."
1976-1979. Results of Lechate Tests on Cyanide Wastes from
Illinois, Iowa, Kansas, and Pennsylvania.
****Analysis of the eleuate from various iron blast furnace
sludges extracted by means of the EP test were 0.091 rag/1,
0.086 mg/1 and 0.005 mg/1 of total cyanide.
-------
process is essentially similar. If the Agency identi-
fies data to contradict this assumption, we will con-
sider bringing appropriate sub-categories of these
wastes back, into the hazardous waste regulatory control
system.
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LISTING BACKGROUND DOCUMENT
Chromium Pigments and Iron Blues
Wastewater treatment sludge from the production of chrome
yellow and orange pigments (T)
Wastewater treatment sludge from the production of molybdate
orange pigments (T)
Wastewater treatment sludge from the production of zinc
yellow pigments (T)
Wastewater treatment sludge from the production of chrome
green pigments (T)
Wastewater treatment sludge from the production of chrome
oxide green pigments (anhydrous and hydrated) (T)
Wastewater treatment sludge from the production of iron blue
pigments (T)
Oven residue from the production of chrome oxide green pig-
ments (T)
Summary of Basis for Listing
The above listed wastewater treatment sludges are gen-
erated when wastewaters from chromium pigments production
are treated to remove heavy metals. Oven residue from hydrated
chromic oxide manufacture is generated when the raw materials
are heated together to form the pigment product. The Admini-
strator has determined that these wastewater treatment sludges
and oven residues 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 therefore should be subject to appropriate
-------
Inorganic Chemicals
-------
management requirements under Subtitle C of RCRA. This con-
clusion is based on the following considerations:
1. These wastewater treatment sludges contain substantial
amounts of the toxic metals lead and chromium (to some
extent in hexavalent form) and also contain ferric
ferrocyanide when iron blue pigments are produced. The
oven residue contains a substantial amount of hexavalent
chromium.
2. If these wastes are managed improperly, toxic chromium
and lead may leach from the waste and migrate to the envi-
ronment. Ferrocyanide will decompose upon exposure to
sunlight, releasing cyanides and hydrogen cyanide gas.
3. A significant quantity of these sludges is generated
annually, and the amount is expected to increase. When
Industry wastewater treatment standards based on best
practicable technology are implemented, approximately
4300 metric tons of sludge will be generated per year.
Currently 50-60% of that amount is generated.
4. These wastes are frequently disposed of in unlined lagoons
and landfills, or dumped in the open. These management
practices may not be adequate to prevent toxic constituents
from being released to the environment.
Profile of the Industry (1,2)
Chrome pigments are used extensively in paints, printing
ink, floor covering products and paper. They may also be
used in ceramics, cement and asphalt roofing. Eleven plants
currently manufacture chromium pigments; two also manufacture
iron blue pigments. Individual plant production rates range
from a low of 9 metric tons per day to a high of 79 metric
tons per day. Total yearly industry-wide production is
estimated at 64,500 metric tons; approximately 60Z of that
total is manufactured by two plants in the northeastern
United States. All other plants are located in the midwest
and south.
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Manufacturing Processes
1. Manufacture of Chrome Yellow and Orange Pigments
Chrome yellow and orange pigments are produced by reacting
sodium dichrooate, caustic soda and lead nitrate as follows (1):
(a) 2HN03 + PbO > Pb(N03}2 + H2°
(b) Na2Cr207 + 2NaOH + 2Pb(N03)2 > 2PbCr04 + 4NaN03 + H20
Lead chromate (a hexavalent chromate) is formed as a precipitate
and is recovered by filtration, then treated, dried, milled
and packaged. The filtrate, containing lead and hexavalent
chromium compounds, is sent to a wastewater treatment facility.
A process flow diagram is given in Figure 1 (3).
2. Manufacture of Molybdate Orange Pigments
Molybdate orange pigment Is made by the co-precipitation
of lead chromate (PbCrOA) and lead molybdate (PbMo04). Molybdic
oxide is first dissolved in aqueous sodium hydroxide; sodium
chromate is then added. This solution is mixed and reacted
with a solution of lead oxide in nitric acid. The reactions,
all involving hexavalent chromium compounds, are as follows (1):
a. Mo03 + 2NaOH > Na2Mo04 + H20
b. PbO + 2HN03 > Pb(N03)2+ H20
c. Na2Mo04 + Pb(N03)2 > PbMoO^ + 2NaN03
d. Na2Cr04 + Pb(N03)2 > PbCrO^ + 2NaN03
e. PbMoO^ + PbCrO^ > PbCrO^ . PbMoO$
The precipitate (lead chromate and molybdate) is filtered,
washed, dried, milled and packaged. The filtrate, containing
lead and hexavalent chromium compounds, is sent to the wastewater
-------
714
LEAD OXIDE
WATEfl
403 MlinWACIO—|
(On ACETIC ACID)
, DISSOLVING
263 60% NoOll—>*
490 SODIUM'
DICIIHOMATE
DISSOLVING
MIXING '
AND.
DEVELOPMENT
FILTRATION
AND
WASHING
DRYING,
MILLING
AND
PACKAGING
.1000 F
rnooi
WASTE
TREATMENT
• WLVES WILL DIFFE/J DUE 70 DIFFEHEHT
n£AGTAHTS USED 7D HAKE DIFFEflENT
SHADES OF CfltOME YELLOlV
SOL
T
30 PbCrO<
10.4 Cr(Oll),
2C.I CaS
2.6 PUOII)C
EFFLUENT
644 NoN03*
14.3 NOjSQf*
1.7 Co (NO,),
OR Ca(Aa)x)
WATER
FIGURE 1
CHROME YELLOW MANUFACTURE
-X- -/«)/-
-------
255 SODIUM
CIIHOMATli
WATEH
212
MOLYI1DIC
OXIDE —
WATER —
E3G 50%
CAUSTIC
SODA
G44
LEAD
OXIOE
371
NITIMC
ACID
iWATE
_J
MIX
TANK
IMPUMTY CWTAJNEO IN MOLrODIC
OXIDE HAW
I7.0 MaCI
i
MIXER
HOLDING
TANK
\
9.0 HjtSO^
9.7 SOj
12 Ca(0ll]t
FILTRATION
AND
WASHING
1?
CHEMICAL TREATMENT
SLUDGE SEPARATION
i
SOLIDS TO LAHOFII.I.
I.ZO MIOj*
ZO PbCrOrPbMoOi
10 Cr(OJt),
ZG CaSO^-211^0
2.5 Pb{OII)
17.0 NaCI •
002 NuNO,
M
1.7
WATEH
VENT
t
DRYING,
MILLING
• AND
PACKAGING
IOOO
J>bCr<
woo>
MOLYDDATE
\/ \ .
_ /
NU-. MANUrACTURU
-------
treatment facility. A flow diagram is given ia Figure 2 (3).
3. Manufacture of Zinc Yellow Pigments
Zinc yellow pigment is a complex compound of the oxides
of zinc, potassium and hexavalent chromium. It is produced
by the reaction of zinc oxide, hydrochloric acid, sodium di-
chroraate (a hexavalent chromium compound) and potassium
chloride (1):
a. 2KCL + 2HC1 + 2Na2Cr207 . H20 > K2Cr40!3 + 4NaCl + 3H20
b. 4ZnO + K2Cr4<)i3 + 3H20 > 4ZnO . K20 . 4Cr03 . 3H20
The product forms as a precipitate and is filtered, washed,
dried, milled and packaged. The filtrate, containing hexavalent
chromium compounds are sent to the wastewater treatment
facility. A flow diagram is given in Figure 3 (3).
4. Manufacture of Chrome Green Pigments
Chrome green pigments are co-precipitates of chrome
yellow and iro.a blues. They include a wide variety of hues,
from very light to very dark green. Chrome green is produced
by mechanically mixing chrome yellow and iron blue pigments
in water. The coprecipitate formation of chrome green, a hexa-
valent chromium compound, is given by the following reaction (1):
(1) PbCr04 + Fe(NH4) [Fe(CN6>] > PbCr04Fe(NH4)[Fe(CN)6]
The co-precipitate is filtered, dried, ground, blended and
packed. The filtrate, containing lead and hexavalent chromium,
is sent to wastewater treatment for removal of suspended
pigment particles. Figure 4 gives a process flow diagram
for the manufacture of chrome green (3).
-------
WATER
VAPOR
VENV
t
A n 4 7 n n -**--
iui inu - ft* DEW
103 111.1 — • •*• ncAU 1 lUM ffr v/tri I
Tin ifci a. ' TANK ' A
703 Nn.CrrOr-n.O^— .S>
71 S0t >»
IGCHaOII-: 1»
SOLID
'ATER, DRYING,
RIFUGE ^ MILLING B^4Zno-KO
NO AND pnODUCT
^^,U PACKAGING PRODUCT
v ' '
TREATMENT
I I
HESltXT: LIQUID CrFLUENT
20 ZING YELLOW 41 KCI
24 ZnO I3I NacSO4
40 CrlOllJg 433 NaCl
WATER
FIGURE 3
ZINC YELLOW MANUFACTURE
-------
WATCH
V/ATCR
203 IRON DLUE—1»-
WATCH
RESLUimY
77fi 1 TAD
NIT! I AIL
100 SODIUM
CIIIIOMAIE '
ir>7 SODIUM <
SULfAli:
nCACTDM
TAUK
V/ASM
U..
SI 1 ADI:
TANK
LIQUID
T
FILTER
DRY'
GRIND,
ULEND
AND
PACK
moo
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WILL
on
C/liCM
V/ATtn I
No/10,
5 CllllOf.lC GI1LUI
(AS susrcNocn sot.ins IN v/Aten)
3
CHROME GREEN MANUFACTURE
-------
5. Manufacture of Anhydrous and Hydrated Chrome Oxide Green
Pigments.
Anhydrous chrome oxide, a trivalent chromium pigment,
is produced by the calcination of sodium dichromate, a hexa-
valent chromate, with sulfur or carbon according to either
of the following reactions (1):
a. Na2Cr207 + S > Cr203 •*• Ha2S04
b. Na2Cr207 + 2C > Cr203 + Na2C03 + CO
The recovered trivalent chromium oxide is slurrled with
water, filtered, washed, dried, and packaged. The washwaters,
probably containing some unreacted hexavalent chromate materials,
are sent to wastewater treatment. A process flow diagram is
given in Figure S (3).
Hydrated (trivalent) chrome oxide is made by reacting sodium
dichromate with boric acid as follows (1):
2Na2Cr207 + 8H3B03 > 2Cr203 . 2H20 + 2Na2B407 + 8H20 +• 302
The raw materials are blended in a mixer, then heated in an
oven at 550" C. Oven residues, which contain hexavalent and
trivalent chromium, remain to be disposed of as wastes. The
reacted material is slurrled with water and filtered. The
filtered solids are washed, dried, ground, screened and
packaged. The filtrate and washwater are treated to recover
boric acid. The waste stream from the boric acid recovery
unit and washwaters from the filtration step, containing a
hexavalent chromium compound, are sent to wastewater treatment.
A process flow diagram is given in Figure 6 (3}>
-------
5)V1^i'.i)iHh)i^H.^i|^.:i,;i)Viiyv^/{|lils 'r'i V. *
1991 SODIUM
UlCimOMATE •
WATER
I90 SULFUR-
2Z WHEAT-
FLOUR
63 COt,CO,SOz WATEM
WATCH
VF.WT
BLENDER
KILN
SLURRY
TANK
I
FILTER
33
nco
1
DRYER
TREATMENT
50i.it> nEsiDUC uouin EFFV.UUHT
27. CrlOII)n
GRIND,
SCREEN
AMD
PACKAGE
JC
*p
0)
FIGURE S
ANHYDROUS CHROMIC OXIDE PIGMENT MANUFACTURE
-------
25
WATER
wAirn
VENT
JM
rc *• s
ni FMnrn -- m nvrM (•»
,C ACID— «*-
Jit
>LURRY _ ii/AtMi .. r-ii T
TANK -^ WAS" — ^ FIL1
SOLID WASTETO LANDFILL
10 CrtO,- ElljO
646 SULFiniC ACID
nonic ACID nrrnvrnv
nirpwi F UtOUVtUT
RECYCLE UNIT
93BNoxSOHl rf
300 HjQO, }>T\ ^*
95 NotCrpT*2H/)( ' '
31 HfSQ, »*•
'fll 30, »• . TT1EATMEN
76 NaOH ^
I
T
c*r*nfrpii 1000
rrn >. nnvm n* oi*m_i_r< >i_r. n
Ll( --^ UNTLH —•* . •••^»Crx01
' pnoou
PACKAGE
1 1
SOUP LIQUID
MS1QUC ICJILUEfil
6CCr(OH)9 >»7 NfliSO,
r MANUFACTURE-
-------
TABLE 1
Composition of Wastewater Treatment
Sludge and Oven Residue from Chromium
Pigments Productlon(3)
SOURCE OF SLUDGE
Production of Chrome
Yellow and Orange Pigments
Production of
Molyhdate Orange Pigments
Production of
Zinc Yellow Pigments
Production of
Chrome Green Pigments
Production of
Anhydrous Chromic Oxide
Pigments
Production of Hydrated
Chromic Oxide Pigments
Production of
Iron Blue Pigments
Oven Residue from
Production of Chromic
Oxide Pigments
CONTAMINANTS IN SLUDGE
Mass units/1000 mass units product.
30 PbCr04 (Lead chromate)
10.4 Cr(,OH>3 (Chromium hydroxide)
2.5 Pb(OH)2 (Lead hydroxide)
20 PbCr04 . PbMoO^ (Molybdate Orange)
10 Cr(OH)3 (Chromium hydroxide)
2.5 Pb(OH)9(Lead hydroxide)
20 47,nO.K?0.4Cr03 .3^0 (Zinc Yellow)
48 Cr (011)^ (Chromium hydroxide)
5 PbCr04Fe(NH4) f Fe(CN)fil (Chrome Green)
22 Cr(OH)3 (Chromium hydroxide)
66 Cr(OH)3 (Chromium hydroxide)
25 Fe4(Fe(CN)6)3 (Ferric Ferrocyanide)
10 CT203.2H20 (Chromium Oxide)
Cr (VI)
asZ of total Cr
48.5
23.4
21.9
100
0
0
*
0
*Iron blue wastewater treatment sludge will contain chromium compounds when sodium
chromate is used as an oxidizing agent. Generators, should they seek to dellst their
iron blue waste streams should thus address hexavalent chromium concentrations as well
as cyanide concentrations in their wastes.
-yt- -
-------
G. Manufacture of Iron Blue Pigments
Iron blue pigments are produced by the reaction of so-
dium ferrocyanide with an aqueous solution of iron sulfate
and ammonium sulfate. The precipitate formed is separated
and oxidized with sodium chlorate or sodium chrornate, a
hexavalent chromium compound, to form iron blues (FeCNH^
[Fe(CN)g]). The product is filtered, dried and packaged
as shown in Figure 7. The filtrate, containing ferric ferro-
cyanide (and hexavalent chromium when sodium chromate is used
as an oxidizing agent) is sent to wastewater treatment.
Waste Generation and Composition
Some plants produce different pigments in sequence,
while others manufacture several pigments concurrently and
combine the wastewaters for treatment at a single facility.
The wastewaters contain unreacted materials, by-products of
reaction, and unprecipitated pigment products. Uastewater
treatment generally involves reduction of metal ions (such as
chrome VI) if necessary, neutralization, and precipitation of
metals with lime or caustic soda.
The efficiency of the removal of hexavalent chromium
depends on the extent of its reduction. If reduction is
incomplete, and if neutralization and metal precipitation
take place too rapidly, hexavalent chromium is likely to be
entrained in the precipitating sludges, resulting in their
contamination with hexavalent chromium. The higher the concen-
tration of hexavalent chrome in the wastewater, the greater
-]/-
-200-
-------
Kcciclioa
Tcmk
77T
.0
Tank
. , .
0s* ^
/ /
Oxidolion
Tank
.' ,*C/
& Wo
N*
Dryer
'
Grind, Screen
& I'aclccjijc
e?
Treatment
276 Co ( OH)?.
I
ECflucnl
Solitl Rniiduc
507 CaSO^ Wolcr H-
25 Pc/i(Fc(CN)6)3 • 70 NaCl
190 Fe?O3 1016 NozSO^
32 l:c(OII)2 300
ULUL: MANui:V\ci\ji«i
-------
is the likelihood of its inefficient or ineffective reduc-
tion, and the consequent likelihood of the contamination of
chromium hydroxide sludges with hexavalent chrome. Screening
and verification data from three chrome pigment plants
show appreciable concentrations of chromium in raw waste
streams: (55-310 ppm) , presumably in hexavalent form.(l)
At one facility treated waste effluent contained 130 ppm of
chr omium.C 1)
The composition of the wastewater treatment sludge from
chromium pigments production is dependent upon the pigments
which are being manufactured, as shown in Table 1 below, and
whether wastes from multi-process plants are combined for treat-
ment. With regard to the waste constituents of regulatory con-
cern, chromium is usually present and lead may also be found.
Ferric ferrocyanide is a component of the sludge when iron
blues are produced. Table 1 lists the chromium, lead and
cyanide-containing compounds in the respective sludges, and
their amounts relative to the amount of the sludges.
The Agency lacks data on the precise total amounts of
hazardous constituents In the sludges. These amounts,
however, are believed to be substantial. Data indicates
that wastewaters from all chromium pigment plants accumulate
8,450 Ibs. of chromium, 2,538 Ibs of lead and 157 Ibs of
cyanide per day (2). Because treatment of the wastewaters
is effected by consolidation of contaminants in the sludge, the
sludge is expected to contain much higher concentrations of
-202.-
-------
those contaminants. Moreover, as shown by the material
balances indicated on Figures 1-7 above, and the data of
Table 1, compounds of hexavalent chromium and lead are
significant constituents of the treatment sludges, and are
estimated Co be present in substantial concentrations.
Except for the production of chromic oxide pigments, and
the production of iron blue pigments if sodium chromate is
not used, the untreated wastewater from chromate pigment
production contain chromium in the hexavalent form (see Table
I), the manufacture of these different products typically
occurs either in alternating or simultaneous mode at the same
production facility. Thus, even though some individual
product lines may not result in wastes containing hexavalent
chrome, the sludges in toto are expected to be contaminated.
The remaining listed hazardous waste, oven residue from
the production of hydrated chrome oxide green pigments, is
generated when sodium dichromate and boric acid are heated to
form the pigment product. A chromium containing compound
(probably containing unreacted hexavalent chrome)^®) is found
in the oven residue as a result of chromium in the feed
material.
The amount of sludge generated is quite substantial.
The Agency estimates that approximately 2,100 to 2,600 metric
tons of sludge are currently generated per year by treatment
of wastewaters from the manufacture of chromium pigments.(4)
The amount of wastewater treatment sludge is expected to
Increase significantly in the near future. Treatment standards
-V-
-------
based on Best Practicable Technology (BPT) are being developed
for the chromium pigments industry, and compliance will result
in removal of at least 95% of the chromium and lead from
wastewaters. Using current production figures, the Agency
estimates that about 4300 metric tons per year (dry weight)
of sludge will be generated by the industry when BPT standards
are implemented.(1)
The Agency emphasizes, however, that the amounts of the
hazardous constituents lead and hexavalent chromium in these
sludges appear to be sufficiently high to be of regulatory
signlf icance.
Current Waste Management Practice
A report by the Versar Corporation in 1975 indicates
that, at that time, eight companies manufacturing chromium
pigments disposed of their wastewater treatment sludge on
land. (3) Two companies disposed on-site, one by ponding and
the other using landfill after treatment. Six companies disposed
off-site, one to a municipal landfill, one to a land dump and
four to private landfills. Another company discharged to the
sewer and one claimed to recover its wastes.(3)
Hazards Posed by These Wastes
These wastes may pose a substantial threat to human
health and the environment if the hazardous constituents are
released to the environment, and environmental release may
occur as a result of waste mismanagement. In the sludges,
lead and chromium occur as pigment particles, as hydroxides,
-Vf-
-20M-
-------
and presumably, as entrained hexavalent chromium; these
compounds may be solubilized if the wastewater treatment
sludges are improperly managed. (See Attachment I to this
document.) Solubilization of lead is pH-dependent, and
increases as the pH of the solubilizing medium decreases.''/
If the sludges are exposed to acidic conditions (which might
occur due to co-disposal with waste acids, or in municipal
landfills or in areas where acid rain is prevalent), this
toxic metal could be released from the waste martrix.
Furthermore, lead hydroxide if present in sufficient quantities,
is soluble enough in water to exceed the National Interim
Primary Drinking Water Standard (NIPDWS) of 0.05 mg/l.(5)
Most hexavalent chromium compounds, both chromates and
dichromates have very high water solubility. Therefore
hexavalent chrome, if present in these wastes, will leach
into groundwaters and effluent streams, and is likely to
pollute such waters in amounts significantly exceeding the
NIPDWS of 0.05 mg/1.
Water is likely to come into contact with the waste in
several ways. Open dumping or improper management of a
landfill may permit percolation of rainwater through the
waste pile or allow surface run-off to solubilize hazardous
constituents. Placement of the waste below the water table
could result in leaching of the lead (and possibly chromium)
by groundwater. Clearly, wastes that require ponding are in
contact with a substantial amount of liquid, which could
-Wf-
-20S1-
-------
encourage leaching or form a head, facilitating leachate
migration to groundwater. If control practices are nonexistent
or inadequate, contaminant-bearing leachate, run-off or
icpoundment overflow may reach ground and surface waters,
polluting valuable water supplies for a considerable period
of time.
Wastewater treatment sludges from iron blues production
zna? release cyanides to air or groundwater and thus also
create a substantial hazard if improperly managed. Ferric
ferrocyanide itself has little migratory potential. It is
insoluble in water and has been observed to be quite immobile
in soil column studies (Appendix A). Ferrocyanides, however,
undergo decomposition upon exposure to sunlight, releasing
cyanide and hydrogen cyanide gas. Once released froa the
marrix of the waste, hydrogen cyanide gas will volatilize
and enter the atmosphere. Cyanide, once released, appears
to be fairly mobile in soils (Appendix A). Even clay liners
beneath a disposal site might not impede cyanide migration
significantly; in the presence of water, montmorillonlte
clays sorbed cyanide weakly (6). Cyanide thus is capable of
migrating from the waste disposal site to ground and surface
varers .
Since lead is an element, It does not decompose, and
will not degrade with the passage of time. If it escapes
fr am the disposal site, it will continue to provide a
potential source of long-term contamination. Lead is bio-
-1*-
-2O6-
-------
accumulated and passed along the food chain but is not biomagnifled.
The Agency has determined to list chromium pigments and iron
blues as T hazardous wastes on the basis of lead, hexavalent
chr ium, and ferrocyanide constituents (for iron blues), although
two of these constituents are also measurable by the EP extraction
procedure toxicity characteristic. There are other factors (in
addition to those measured by the EP toxicity characteristic)
which justify the T listing. Some of these factors already have
been identified, namely the non-degradability of these substances,
indications of lack of proper management of the wastes in actual
practice and the presence of ferrocyanide as a waste constituent
in iron blues. The quantity of these wastes generated is an
additional supporting factor.
As indicated above, wastes from the production of chromium
pigments and iron blues are generated in very substantial quantities
and the amounts generated are expected to increase. Each waste
contains substantial amounts of lead, chromium, or ferrocyanides,
and several wastes contain more than one of these contaminants.
Most of the chromium in the sludge will be in the trlvalent
form, but, as explained above, it is expected that regulatorily
significant concentrations of hexavalent chromium will remain.
Large amounts of each of these contaminants 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
pollutants are available for environmental loading. Attenuatlve
-yf-
-207-
-------
capacity of the environment surrounding the disposal facility
could also be reduced or exhausted by large quantities of
pollutants released from the waste.
All of these considerations increase the possibility of
exposure to the harmful constituents in the wastes, and in
the Agency's view, support a T listing.
Adverse Health Effects of Constituents of Concern
Ingestion of drinking water from ground and surface
waters contaminated by lead and hexavalent chromium threatens
human health. Aquatic species exposed to the heavy metals
may also be adversely effected.
Carcinogenicity of various hexavalent chromium compounds
in humans is well documented,(1^) and EPA's CAG has determined
that there is substantial evidence that hexavalent chromium
compounds are carcinogenic to man. In one study rats showed
a weak carcinogenic response to trivalent chromium compounds.
Oral administration of trivalent chromium results in little
chromium absorption. The degree of absorption is slightly
higher following administration of hexavalent compounds.
Chronic toxicity problems associated with chromium include
damage to liver, kidney, skin, respiratory passages and lungs.
Allergic dermatitis can result from exposure to both tr1- and
hexavalent chromium.
No data for chronic toxicity of trivalent chromium for
freshwater fish or algae are available. The chronic toxicity
-vf-
-------
value for the freshwater Invertebrate Daphnia magna; based on
a single study, is reported as 445 mg/1. (CRIII) and 10 ug/1
(CrVI). Chronic embryo-larval tests on six species of
freshwater fish exposed to Cr VI resulted in values ranging
from 37 to 72 ug/1.
Ferrocyanides exhibit low toxicity, but release cyanide
ions and toxic hydrogen cyanide gas upon exposure to sunlight.
Cyanide compounds can adversely affect a wide variety of
organisms because of their inhibition of respiratory metabolism.
Appendix A contains a more detailed discussion of the adverse
health and environmental effects of chromium and of cyanide.
The hazards associated with lead, chromium, and cyanide-
containing compounds have been recognized by other regula-
tory programs. Lead and chromium are listed as priority
pollutants in accordance with §307 of the Clean Water Act,
and National Interim Primary Drinking Water Standards (NIPDWS)
have been established pursuant to the Safe Drinking Water
Act .
The ambient water quality criterion for hexavalent
chromium is recommended to be identical to the existing
NIPDWS for total chromium, which Is 50 ug/1. For total
recoverable hexavalent chromium the criterion to protect
freshwater aquatic life is 0.29 ug/1 (24 hour average), not
to exceed 21 ug/1 at any time. To protect saltwater aquatic
life the corresponding concentrations are 18 ug/1 and 1260
ug/1.
-X-
-------
The OSHA time-weighted average exposure criterion for
chromium (carcinogenic compounds) is 1 ug/m-*; for the "non-
carcinogenic" class of chromium compounds the criterion is 25
ug, .3.(19)
-z/o-
-------
Attachment I
SOLUBILITY AND ENVIRONMENTAL MOBILITY
CHARACTERISTICS OF CHROMIUM COMPOUNDS
The tripositive state is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of ligands such as water,
ammonia, urea, halides, sulfates, amines and organic acids.(10•
Thousands of such compounds exist. This complex formation
underlies the tanning reactions of chromium, and is responsible
for the strong binding of trivalent chromium by soil elements,
particularly clays.(13,15)
At pR values greater than about 6, trivalent chromium
forms high molecular weight, insoluble, "polynuclear" complexes
of Cr(OH)3 which ultimately precipitate as C^C^.nHjO* This
process is favored by heat, increased chromium concentration,
salinity and time.(10) These chromium hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form Cr
is therefore resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubilization of
chromium hydroxide:
-------
Reaction
Or III concentration calculated from
Keq (mg/1).
Keq
(18)
1. Cr(OH)3+2H+ _ CrOH+++2H20 108
2. Cr(OH)3 Cr+3+30H~ 6.7x10
3. Cr(OH)3 H++Cr02~+H20 9xlO~19
Concentration (mg/1)
H5
520
-31 35
i
pH6
pH7
5.2 0.052
0*035 i*
i i
*i=<0.001 mg/1
It is apparent from these figures that, in theory, trivalent
chromium could leach from sludges to some extent. Such
solubilized chromium, however, is unlikely to contaminate
aquifers. It is complexed with soil materials, and tenaciously
held.(10»15) Little soluble chromium is found in soils . <10»12)
If soluble trivalent chromium is added to soils it rapidly
disappears from solution and is transformed into a form that
is not extracted by ammonium acetate or complexing agents.(12,13)
However, it is extractable by very strong acids, indicating
the formation of soluble hydroxides.(13»1^) Thus: above pH 5,
chromium (III) is immobile because of precipitation; below
pH 4 chromium (III) is immobile because it is strongly adsorbed
by soil elements; between pH 4 and 5 the combination of
adsorption and precipitation should render trivalent chromium
-312-
-------
quite immobile.(^-3 , 15)
In contrast, hexavalent chromium compounds are quite
soluble, and hexavalent chromium is not as strongly bound to
soils.(!3» 15) Hexavalent chromium remains as such in a
soluble form in soil for a short time, and is eventually
reduced by reducing agents if they are present. (12,14) ^s
compared with the trivalent form, hexavalent chromium is less
strongly adsorbed and more readily leached from soils,(15)
and thus is expected to have high mobility in soil materials.(
-J2/3-
-------
References
1. US EPA, Effluent Guidelines Division. Draft Development
Document for Inorganic Chemicals Manufacturing Point
Source Category. (Proposed). June 1980; EPA 440-11-79/007.
2. US EPA Effluent Guidelines Division. Inorganic Chemicals
BAT Review. EEM/DH. May 1979
3. US EPA, Office of Solid Waste. Assessment of Industrial
Hazardous Waste Practices Inorganic Chemicals Industry.
US EPA Contract No. 68-01-2246. March 1975. NTIS PB-244-832.
4. Undated memorandum from C. Dysinger to V. Stelner on Chromium
pigments and Iron blues document.
5. Handbook of Chemistry and Physics, 48th Ed. The Chemical-
Rubber Company. 1967-68.
6. Cruz, M., et al. 1974. Absorption and Transformation
of HCN on the Surface of Copper and Calcium Mon.tmorillonite.
Clay Minerals 22:417-425.
7. US EPA Open files. Hazardous Site Control Branch, WH-548,
US EPA, 401 M Street, S.W., Washington, D.C. 20460. Con-
tact Hugh Kaufman (202)755-3051.
8. La timer, W. M. and J. H. Hildebrand. 1940. Reference
Book of Inorganic Chemistry. MacMillan, New York.
9. Laboratory Waste Disposal Manual. Manufacturing Chemists
Association, Washington, D.C., 1970.
10. U.S. EPA, Review of the Environmental Effects of Pollutants;
III Chromium. ORNL/EIS-80; EPA-600/1-78-023; May 1980.
11. Translation Metal Chemistry, R. L. Carlin, ed. Marcel
Dekker, New York. 1965; Volume 1.
12. U.S. EPA. Application of Sewage Sludge to Cropland;
Appraisal of Potential Hazards of the Heavy Metals to Plants
and Animals. EPA 430/9-76-013. NTIS PB No. 264-015.
November, 1976.
13. Bartlett, R. J. and J. M. Kimble. Behavior of Chromium In
Soils: I Trivalent Forms. J. Environ. Qual. 5: 379-383:
1976.
-------
14. Bar tiett, R. J. and J. H. KIrable. Behavior of Chromium
in Soils: II Hexavalent Forms. Ibid. 5:383-386. 1976.
15. Griffin, R. A., A.K. Au, and R. R. Frost. Effect of
pH on adsorption of chromium from landfill leachate by
clay minerals. J. Environ. Sci. Health A12(8):
430-449:1977.
16. National Academy of Sciencee. Medical and Biological
Effects of Environmental Pollutants; Chromium.
Washington, D.C. 1974.
17. U.S. EPA. Treatability studies for the Inorganic
Chemicals Manufacturing Point Source Category. EPA-
440/1-80/103.
18. U.S. EPA. Chromium; Ambient Water Quality Criteria
EPA 440/5-80-035, October 1980.
19. 29 CFR 1910.1000
20. Cassarett, L. J. and J. Doull, 1979. Toxicology, the
Basic Science of Poisons, Second edition. MacMillan,
New York.
-2)5--
-------
Organic Chemicals
-------
ORD-F-4
LISTING BACKGROUND DOCUMENT
ACETALDEHYDE PRODUCTION
Distillation bottoms from the production of acetaldehyde from ethylene (T)
Distillation side cuts from the production of acetaldehyde from ethylene (T)
I. Summary of Basis for Listing
Distillation bottoms and distillation side cuts from acetaldehyde
production from ethylene contain suspected carcinogens such as chloroform,
and formaldehyde and contain other toxic materials as well.
The Administrator has determined that the still bottoms from
acetaldehyde production from ethylene may pose a substantial present or
potential hazard to human health or the environment when improperly trans-
ported, treated, stored, disposed of or otherwise managed, and therefore
should be subject to appropriate management requirements under Subtitle
C of RCRA. This conclusion is based on the following considerations:
1. The wastes contain chloroform and formaldehyde which have
been identified by the Agency as exhibiting substantial
evidence of carcinogenicity, as well as other toxic
materials, including methylene chloride, methyl chloride,
paraldehyde, and formic acid.
2. The wastes are held in settling ponds prior to deep well injec-
tion or they are disposed of in lagoons. While in the settling
ponds and lagoons, there is the potential for ground and surface
water contamination by leaching and flooding. Additionally,
there is risk of volatilization of the toxic waste components from
the settling ponds and human exposure via inhalation.
3. The wastes are persistent in the environment and tend to bio-
accumulate so that there is a potential for widespread ex-
posure through volatilization or drinking water contamination.
-------
II. Source of the Waste and Typical Disposal Practices
A. Profile of the Industry
Acetaldehyde (C^CHO) is a high-volume production chemical
intermediate used principally in the manufacture of acetic anhydride,
butyraldehyde, chloral, pyridines, and other chemical derivatives. Most
acetaldehyde is manufactured by the liquid-phase oxidation of ethylene.
Acetaldehyde is produced in three plants in the U.S., which utilize
ethylene for starting material.(2)
Table 1 provides a list of the ethylene-based plants, their
locations, and their production capacities.
TABLE 1
Acetaldehyde Producer Locations, Annual Production Capacities
and Raw Materials Used (2)(4)
1978
Production
Company
Celanese Corp.
Celanese Chem
Co. Div.
Facility
. Bay City,
Clear Lake
(metric
Tx.
, Tx.
Capacity
(Gg/Yr)
tons/yr x 10J)
136
277
Raw
Material
Ethylene
Ethylene
Eastman Kodak Co.
Eastman Chemical
Products, Inc.,
subsid. Texas
Eastman Co* Longview, Tx.
Total
277
690
Ethylene
(90Z); ethyl
alcohol (10Z)
-------
B. Manufacturing Process
The direct liquid-phase oxidation of ethylene is the most
widely used method for the manufacture of acetaldehyde. Ethylene is
catalytically oxidized with air in a dilute hydrochloric acid solution
containing the chlorides of palladium and copper. O,4»5)
The process involves the oxidation of ethylene by palladium chlo-
ride to form product acetaldehyde, palladium metal and hydrogen chloride:
+ PdCl2 + H2° ---- > CH3CHO + Pd + 2HC1
ethylene palladium acetaldehyde metallic hydrochloric
chloride palladium acid
Cupric chloride is used as the second component of the catalyst
system to reoxidize the palladium metal to palladium chloride:
2CuCl2 + Pd° > PdCl2 + 2CuCl
cupric chloride palladium cuprous
chloride chloride
The cuprous chloride thus formed is, in turn, reoxldized in the
second stage regeneration unit to cupric chloride:
2CuCl + 1/2 02 + 2HC1 > 2CuCl2 + H20
cuprous cupric
chloride chloride
-------
C. Waste Generation, Waste Composition and Waste Management
1. Waste Generation and Composition (3,4,5)
The process which generates the subject waste is shown in Figure 1.
Ethylene feed gas goes to a tubular reactor where it mixes with palladium
chloride and copper chloride in solution at 9 atmospheres of pressure
and a temperature of 130°C. The reaction products are flash evaporated
and the product acetaldehyde passes overhead to the crude distillation
column. The aqueous bottoms go to a reactor where the palladium catalyst
is regenerated and recycled to the acetaldehyde reactor. The overhead from
the crude distillation column is condensed; unreacted ethylene and light
hydrocarbons (including a small amount of acetaldehyde) are vented. The
crude acetaldehyde from the bottom of this column then goes to final
distillation. Purified acetaldehyde is distilled overhead. Two wastes
are obtained: the side-cuts and the bottoms. The distillation bottoms
(discharge wastewater) containing high-boiling organic impurities leaves
the still at the bottom; and the side-cut stream consists of higher boiling
organic and chlorinated organics is removed as a side stream higher up the
column. (4,7)
Table 2 shows the analytical composition of waste discharges for the
two streams.
Table 3 presents data on 1978 acetaldehyde production capacity,
estimated production, and estimated generation of still bottom and side
cut wastes for the three plants which produce acetaldehyde by direct
liquid-phase oxidation of ethylene.
-------
ETHYLENE
BLEED
BOTTOMS
WASTH
REGENERATED CATALYST
REACTOR
CATALYST
REGENERATION
PLASH
TOWER
SPENT CATALYST
CRUDE
DISTILLATION
COLUMN
PRODUCT
SCRUS3ER
LIGHT ENDS
DISTILLATION
COLUMNS
ACETALDEHYDE
PRODUCT
BOTTOMS
(SCRUBBER
MEDIUM)
SIDE CUT TO
•*• CHLOROALDEHYDE
RECOVERY OR
WASTE
Figure 1. SIMPLIFIED ACETALDEHYDE SCHEMATIC PROCESS FLOW
-------
TABLE 2
Uncontrolled Waste Discharge Ratio (4)
(g of discharge per kg of acetaldehyde)
Distillation
Bottoms
(Discharge Distillation
Formula Wastewater) Side-Cut Combined *>
Ethylene C£H4
Acetaldehyde C2H40
Acetic Acid 02^2 13.9
Chloroacetaldehyde C2H30C1
Acetyl chloride C2H30C1 4.2
Chloral C2HOC13 2.1
Paraldehyde (€2^0)3 1.6
Other organ ics (including chloro- 4.0
form, formaldehyde and methylene
and methyl chloride)
TOTAL Volatile Organics: 25.8
Water H?0 795:6
TOTAL' STREAM: 821.4
-
7.8
0.6
5.5
5.0
3.4
-
2.0
24.3
25.5
59.8
-
7.8
14.5
5.5
9.2
5.5
1.6
6.0
50.1
821.1
871.2
*>These totals are combined because combination of the two waste streams
is a known method disposal. (4)
-221-
-------
Table 3
Estimated Still Bottom Generation from Acetaldehyde Production - 1978a
Company
Celanese Chemical
Celanese Chemical
Texas Eastman
TOTAL:
Location
1978
Production
Capacity
(1000 KT/yr)
Estimated Estimated
Still-Bottom Side-Cut
Estimated Wastewater Waste
Production*1 Generated Generated0 Total
(1000 Mt/yr) (1000 Mt/yr) (1000 Mt/yr) (1000 Mt)
Bay City, TX
Clear Lake City,
TX
Long view, TX
136
277
277
690
97
197
197
491
111
227
227
565
5
10
10
25
116
237
237
590
aBased on data from reference 4.
bBased on 1976 industry average of 71% production, 1000 MT/yr.
cBased on Figures in Table 2, 1000 MT/yr.
-------
2. Waste Management
Reported disposal of the side cuts has been by deep well injec-
tion.^) Wastewater from the distillation bottoms has been disposed of both
by deep well injection and in anaerobic lagoons.(^) One of the three
domestic plants producing acetaldehyde from ethylene disposes of both
side cuts and wastewater by deep well injection.™' This plant combines
the two wastes prior to injection.(^) Deep well injection requires
waste presettling and flow equalization via ponding prior to injection
to avoid well obstruction. So that the wastes from this plant are also
managed at least for a time In holding ponds.
The waste constituents of concern are chloroacetaldehyde,
paraldehyde, chloroform, formaldehyde, methylene chloride, methyl
chloride and formic acid. Acetyl chloride and chloral, although dangerous,
are expected to hydrolise rapidly upon aqueous disposal, so that there
is little possibility of migration and exposure (App. B.) (42).
-------
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
The toxic components present in these wastes Iriclude the compounds
listed below in Table 4.
Table 4. Toxic Components in the Waste
o Chloroform o Paraldehyde
o Formaldehyde o Formic acid
o Methylene chloride o Chloroacetaldehyde
o Methyl chloride
A number of these compounds are known or suspected carcinogens or mutagens
while all exhibit toxic properties.
These waste constituents are capable of migration by leaching or by
volatilization from lagoons or holding ponds (the management method for
both waste streams, see p. 8 above), and of reaching environmental receptors
should the wastes be improperly managed.
As to the migratory potential of waste constituents, Chloroacetaldehyde,
which Is present in high concentrations (4), is highly soluble (App. B.).
Although subject to degredation, the most significant degredation mechanism
for Chloroacetaldehyde is biodegration, and thus Chloroacetaldehyde would
be expected to persist for long periods in the abiotic conditions of an
aquifer. (42) Further, Chloroacetaldehyde is highly volatile (vapor pressure
100 mm Hg), and thus could migrate via an air exposure pathway. (42) Chloro-
acetaldehyde is in fact an extremely noxious vapor, with a TLV of 1 ppm.
-------
(42) Thus, this threshold could be exceeded in areas in the vicinity of
the lagoon if chloroacetaldehyde were to volatilize at rates four levels
of magnitude less than its actual volatility potential. (42)
Paraldehyde, another waste constituent present in high concentrations
(4), is capable of migrating via ground or surface water, since it is
extremely soluble (120,000 ppm). (42) Bacterial degradation is the chief
degredation mechanism (42), so this compound would likely persist in an
abiotic environment such as that of most groundwaters.
Other contaminants of concern are likewise capable of migrating and
persisting via water or air exposure pathways. Chloroform, for example
is highly soluble (8200 ppm). Although it adsorbs to organic soil
constituents and to clay surfaces, management could occur in areas with
highly permeable soil or soils low in organic content, so that mobility
would not be significantly impeded. Chloroform hydrolisas slowly, and so
could persist for substantial periods in ground and surface waters (half
life of 18 months in dark water). (42)
Thus, virtually all chloroform emitted from a'lagoon is expected
to persist in groundwater or reach surface waters via groundwater move-
ment (App. B.). Such behavior is likely to result in exposure to humans
using such groundwater sources as drinking water supplies within adjacent
areas. Such movement and persistence of chloroform has been observed.
Chloroform has been detected in groundwater supplies in Miami, Florida.'
Movement of chloroform within surface water is likely to result
in exposure to aquatic life forms in rivers, ponds, and reservoirs (App.B.).
Similarly, potential exposure to humans is likely where water supplies are
drawn from surface waters.
-vf-
-------
Chloroform is projected to be released to the atmosphere from
surface water systems (App. B.)- Although chloroform decomposes slowly la
air when it is exposed to sunlight, the photochemical degradation products
are carboa tetrachloride, a carcinogen, (*7) and phosgene, a highly
toxic gas. In addition, photochemical degradation mechanisms result in
chlorine burden. At stratospheric levels, atomic chlorine reduces the
levels of ozone which shields the earth from harmful radiation.(20)
Formaldehyde is also capable of migrating and reaching environmental
receptors via a groundwater exposure pathway since it is mlscible.
Biodegradation is the most significant degradation mechanism, so that
formaldehyde would be likely to persist in groundwater. (33) Formaldehyde
also oxidizes to form toxic formic acid, increasing the likelihood of
exposure to that substance. (33)'
Formic acid could Itself migrate via both an air and water pathway,
being both highly volatile and aiscible. (33) Formic acid would have
high mobility so long as soils were not basic and were low in organic
content. (33)
Both methylene chloride and methyl chloride also are capable of
migrating and persisting via air and water exposure pathways, as both
waste constituents are quite soluble (although methylene chloride is
significantly more soluble than methyl chloride), and also highly volatile
(33).
>Soil attenuation would not significantly impede formaldehyde's migratory
potential in areas where soil is highly permeable or low in organic
constituents (33).
-------
Virtually all of the methylene chloride and methyl chloride
discharged from a lagoon is expected to persist in groundwater or reach
surface waters via groundwater movement (App. B.). Such behavior is
likely to result in exposure to humans who use such groundwater sources
as drinking water supplies within adjacent areas.
Both methylene chloride and methyl chloride are likely to be
released to the atmosphere from surface water systems (App. B.).
Furthermore, there may be high local concentrations of these compounds
near disposal sites due to their high volatility which could also result
in serious adverse effects to individuals residing near such sites, due
to exposure to high vapor concentrations.
The persistence of many of the contaminants of concern has been
demonstrated through analysis of leachates from actual disposal sites.
Chloroform has been found in PPM concentrations at Love Canal, while
methyl chloride levels reached 180 ppb. (43,44,45) Leachate from the
Story chemical site included methylene chloride in the ppm range. (*6)
As demonstrated above, therefore, the waste constituents of concern
are capable of migrating and persisting if these wastes are managed
Improperly. Improper management is certainly reasonably plausible or
possible. Thus, lagoons or holding ponds may be sited in areas with
highly permeable soils, and may lack adequate leachate control features.
There may be inadequate cover to impede migration of volatile waste
constituents. There may also be inadequate flood control measures to
impede waste washout in the event of heavy rainfall. Thus, mismanagement
could realistically occur, resulting in substantial hazard.
-------
The Agency Is aware Chat most of the waste constituents of concern
(with the exception of chloroacetaldehyde and paraldehyde) are likely to
be present in small concentrations. In light of the high potential for
substantial hazard associated with these materials, the concentrations
are deemed sufficient to warrant regulation as hazardous. The Agency's
policy for carcinogens in water, for example, is that any exposure to
a carcinogen will induce an oncogenlc response in a human receptor,
and that the greater the concentration of the carcinogenic substance,
the greater the likelihood of response. (See 44 FR 15926, 15940
(March 15, 1979)). In light of the carcinogenic potential of many
of these waste constituents, therefore, even small (<100 ppm) concen-
trations are considered significant.
Furthermore, the wastes are generated in significant quantities
(see Table 3 above) so that large amounts of all waste constituents
are available for environmental release, Increasing the likelihood of
exposure. There is also more chance of a major damage incident should
wastes be mismanaged. The quantity of waste generated Is thus a
further reason supporting the hazardous waste listing of these two
waste streams from production of acetaldehyde.
B. Health and Ecological Effects
1. Chloroform
Health Effects - Designated a priority pollutant by U.S.E.P.A.,
chloroform has been judged as having high carcinogenic potential in humans
on the basis of substantial evidence of its carcinogenicity. (10,11,47)
Chloroform also is considered a toxic chemical [oral rat 1*050= 800 mg/Kg].
-------
Other studies have demonstrated that chloroform can cause
a variety of teratological and other effects in animals, such as missing
ribs, delayed skull ossification, maternal toxicity, and fetotoxicity,
when it is administered orally or in a vapor phase. (12,13) Occupational
exposure situations have resulted in damage to liver and kidneys with
some signs of neurological disorder. C1^) Manifestation of the toxic
nature of chloroform is, in part, attributable to the observation that
metabolism results in toxicacion rather than detoxication.(",16)
Additional information and specific references on the adverse effects of
chloroform can be found in Appendix A.
Ecological Effects - Chloroform has been found to be acutely
toxic at high concentrations to bluegill and rainbow trout.
Industrial Recognition of Hazard - Chloroform has been given a
moderately toxic hazard rating via oral and inhalation routes by Sax in
Dangerous Properties of Industrial Materials.
Regulations - OSHA has set the TWA at 50 ppm.
2. Methylene chloride and methyl chloride
Health Effects - Methylene chloride^21) and methyl chloride
are rautagenic.(22,23) Methylene chloride was also reported to be feto-
or embryo-toxic to rats and mice.(4°)
Exposures to high vapor concentrations of methylene chloride
can produce dizziness, nausea and numbness of the extremities;(24)
prolonged exposure to concentrations near 500 ppm could result in central
nervous system depression and elevated levels of carboxyhemoglobln,
-------
levels that reduce the blood's ability to carry oxygen and thus cause
asphyxiation. Similar lexicological effects are expected with exposure
to methyl chloride* Severe contamination of food or water can result in
irreversible renal and hepatic injury.(25)
Exposure to high concentration can cause death.(26) Additional
information and specific references on the adverse effects of methylene
chloride and methyl chloride can be found in Appendix A.
Ecological Effects - In laboratory tests, high concentra-
tions of methyl chloride are acutely (96-hours) toxic to aquatic organisms,
e.g., the bluegill.(27) similarly, methylene chloride also Is actively
toxic.(28,29)
Regulations - The OSHA standard adopted for methylene chloride
Is TWA 500 ppm. The OSHA standard for methyl chloride is 100 ppm.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, designates methylene chloride as highly toxic via
inhalation and moderately toxic via oral and skin routes. Methyl chloride
is designated highly toxic via inhalation.
3. Formaldehyde
Health Effects - Formaldehyde has been reported to be car-
cinogenic, (30.31) mutagenic(32) and teratogenlc.(^3) The Agency has also
identified formaldehyde as a compound which exhibits substantial evidence
of being carcinogenic. It Is toxic [oral rat LV^Q " 600 mg/Kg] causing
Inflammatory effects in many mammalian species.(34) Additional informa-
tion and specific references on the adverse effects of formaldehyde can
be found in Appendix A.
-------
Ecological Effects - Formalin, an aqueous solution of for-
maldehyde, can cause toxic effects to exposed aquatic life.'") jt ±B
lethal to Daphnia magna.(36)
Regulations - OSHA has set a standard air TWA limit of 3 ppm
for formaldehyde.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, lists formaldehyde as highly toxic to skin, eyes
and mucous membranes.
A. Chloroacetaldehyde
Health Effects - Chloroacetaldehyde is a toxic chemical which
is mutagenlc and a proposed carcinogen.(37,38,39) jt is extremely corrosive
upon contact and can cause severe effects to the skin, eyes, and respiratory
tract. Upon decomposition, conversion to methyl chloride takes place
and, as previously discussed, methyl chloride is a known mutagen. Additional
information and specific references on the adverse effects of Chloroacetalde-
hyde can be found in Appendix A.
Regulations - The OSHA standard for Chloroacetaldehyde is
1 ppm in air.
Industrial Recognition of Hazard - Chloroacetaldehyde Is
designated as a highly toxic irritant in Sax, Dangerous Properties of
Industrial Materials.
-V-
-------
5. Paraldehyde
Health Effects - Paraldehyde is a toxic chemical [oral
rat LD50 => 1530 mg/Kg]. It has been implicated in human fatalities in
which congestion of the lungs and dilation of the right side of the
heart occurred following oral ingestion of the chemical.'**'
Additional information and specific references on the adverse effects
of paraldehyde can be found in Appendix A.
6. Formic Acid
Health Effects - Formic acid is toxic [oral rat U>$Q •
1,210 mg/Kg] and ingestion of even small amounts for short periods may
cause permanent injury or severe damage to akin, eyes, and mucosal
membranes. Because it is rapidly absorbed through the lungs, chronic
exposure to formic acid vapors can result in blood in urine. The OSHA
(1976) and ACGIH (1977) standards for the workplace are 5 ppm. Additional
information and specific references on the adverse effects of formic acid
can be found in Appendix A.
Regulations - The OSHA standard for formic acid is a TWA
of 5 ppm.
Industrial Recognition of Hazard - Formic acid is designated
as highly toxic via ingestion, moderately toxic via inhalation and moderately
toxic as a skin Irritant in Sax, Dangerous Properties of Industrial Materials.
-------
IV. References
1. Hayes, E.R. Acetaldehyde. Kirk-Othmer encyclopedia of chemical
technology. 2nd ed. V.I. Interscience Publishers, New York.
pp.77-95. 1963.
2. Stanford Research Institute. 1978 Directory of chemical producers -
U.S.A. SRI International. Menlo Park, California, pp. 1127. 1978.
3. Kirk-Othmer Encyclopedia of Chemical Technology. 2nd ed. V.I.
John Wiley and Sons, Inc., New York. pp. 86, 87. 1970.
4. Love11, R.J. Acetaldehyde product report. Emissions control
options for the synthetic organic chemicals manufacturing industry
(Draft). Prepared for the U.S. Environmental Protection Agency
under Contract No. 68-02-2577. January, 1979.
5. U.S. EPA. Industrial process profiles for environmental use:
Chapter 6. The industrial organic'chemicals industry. EPA No. 600/2-
77-023f. February, 1977.
6. Stanford Research Institute. 1979 Chemical economics handbook.
Acetaldehyde. SRI International, Menlo Park, California. March, 1979.
7. Jira, et al. Acetaldehyde via air or oxygen. Hydrocarbon Processing.
55(3):97-100. March, 1976.
8. Not used in text.
9. Not used in text.
10. U.S. EPA. Carcinogen Assessment Group. Type II risk assessment
for chloroform. 1979.
11. National Cancer Institute. Report on carcinogenesls bioassay of chloro-
form. NTIS PB No. 264 018. 1976.
12. Schwetz, B.A., et al. Embryo and feto-toxiclty of Inhaled chloroform in
rats. Toxlcol. Appl. Pharmacol. 28:442. 1974.
13. Thompson, D.J., et al. Teratology studies on orally administered chloroform
in the rat and rabbit. Toxlcol. Appl. Pharmacol. 29:348. 1974.
14. National Institute for Occupational Safety and Health. Recommended cri-
teria for . . . occupational exposure to chloroform. No. 75-114.
NTIS PB No. 246 695. 1974.
15. Ilett, K.F., et al. Chloroform toxicity In mice: Correlation of
renal and hepatic necrosis with covalent binding of metabolites to tissue
macroraolecules. Exp. Mol. Pathol. 19:215. 1973.
-------
References (cont.)
16. McLean, A.E.M. The effect of protein deficiency and raicrosomal
enzyme induction by DDT and phenobarbitone on the acute toxicity
of chloroform and pyrrolidine alkaloid retrosine. Brit. Jour. Exp.
Pathol. 51:317. 1970.
17. RCERA Research, Inc. Priority pollutant analyses. Prepared for
NUCO Chemical Waste Systems, Inc. Unpublished report. Tonawanda,
NY. 1979.
18. U.S. EPA. Preliminary assessment of selected carcinogens in drinking
water. EPA No. 560/4-75-003a. 1975.
19. Not used in text.
20. National Academy of Sciences, Committee on Impacts of Stratospheric
change. Stratospheric ozone depletion by halocarbons: Chemistry
and transport. Washington, D.C. 1979.
21a. Fillipova, L.M., et al. Chemical mutagens. IV Mutagenic activity
of germinal system. Genetika 8:134. 1967.
21b. Jongen, W.M.F., et al. Mutagenic effect of dichloronethane on
Salmonella typhimurium. Mutat. Res. 56:245. 1978.
22. Andrew, A.W., et al. A comparison of the mutagenic properties of
vinyl chloride and methyl chloride. Mutat. Res. 40:273. 1976.
23. Simmon, V.F., et al. Mutagenic activity of chemicals identified in
drinking water. S. Scott, et al., eds. In: Progress in genetic
toxicology. 1977.
24. Patty, F. Industrial handbook of toxicology. Interscience Press,
New York. 1979.
25. U.S. EPA. Methyl chloride: Ambient water quality criteria. NTIS
PB No. 296 797. 1979.
26. MacDonald, J.D.C. Methyl chloride intoxication. Jour. Occup. Med.
6:81. 1964.
27. Dawson, et al. The acute toxicity of 47 Industrial chemicals to fresh
and saltwater fishes. J. Hazard. Materials 1:303. 1977.
28. U.S. EPA. In-depth studies on health and environmental impacts of
selected water pollutants. Contract No. 68-01-4646. 1978.
29. Alexander, et al. Toxicity of perchloroethylene, trichloroethylene,
1,1,1-trichloroethane, and raethylene chloride to fathead minnows. Bull.
Environ. Contam. Toxicol. 20:344. 1978.
-------
References (rone.)
30. Nelson, N. Letter to federal agencies: A status report on
formaldehyde and HC1 Inhalation study in rats. New York University
Medical Center, letter dated October 19, 1980.
31. Katanabe, F., et al. Study on the carcinogenicity of aldehydes;
1st report. Experimentally produced rat sarcomas by repeated infections
of aqueous solutions of formaldehyde. Genn. 45:451. 1954.
32. Auerbach, C., et al. Genetic and cytogenetic effects of
formaldehyde and relative compounds. Mut. Res. 39:317. 1977.
33. Humi, H., and H. Olnder. Reproduction study with formaldehyde
and hexaraethylenetetramine in beagle dogs. Food Cosmet. Toxicol.
11:459. 1973.
34. Coon, R.S., et al. Animal inhalation studies on ammonia, ethyl-
ene glycol, formaldehyde, dimethylamine and ethanol. Tox. Appl.
Pharmacol. 16:464. 1970.
.35. U.S. EPA. Investigation of selected potential environmental
contaminants: formaldehyde. EPA No. 560/2-76-009. 1976.
36. Dowden, B.F. and M.J. Barrett. Toxicity of selected chemicals
to certain animals. Jour. Water Pollut. Control Fed. 37:1308.
1965.
37. Rannug et al. The nutagenlclty of chloroethylene oxide, chloroacefaldehyde,
2-chloroethanol and chloroacetic acid, conceivable metabolites of vinyl
chloride. Chen. Biol. Inter. 12(3-4):251-263. 1976.
38. Hussaln and Osterman-Golkar. Comment on the rautagenic effectiveness of
vinyl chloride metabolites. Chem. Biol. Interact. 12(3-4):265-267.', 1976.
39. Guengerich, et al. Biochem. 18:5177-5182. 1979.
40. Waskell, L. A study of the mutagenlcity of anesthetics and their ueta-
bolites. Mut. Res. 57(2):141-154. 1978.
41. Browning, E. Toxicity and metabolism of industrial solvents.
Elsevier, New York. 1965.
42. Dawson, English and Petty. Physical chemical properties of hazardous
waste constituents. Appendix C of the May 2, 1980 listing hackgroun:
document. 1980.
43. Barth, E.F., and J.M. Cohen. Evaluation of treatability of industrial
landfill leachate. Unpublished report. U.S. EPA, Cincinnati, Ohio.
November 30, 1978.
-------
References (cont.)
44. O'Brien, R.P. City of Niagara Falls, N.Y. Love Canal Project.
Unpublished report. Calgon Corp., Calgon Environmental Systems
Div., Pittsburgh, Pa.
45. RCERA Research, Inc. Priority pollutant analyses prepared for
NUCO Chemical Waste Systems, Inc. Unpublished report. Tonawanda,
NY. April, 1979.
46. Sturino, E. Analytical results: Samples from store chemicals,
data set others 336. Unpublished data. U.S. EPA, Region 5. Central
Regional Laboratories. Chicago, Illinois. May, 1978.
47. U.S. EPA. Carcinogen Assessment Group. Office of Research and
Development. List of Carcinogens. April 22, 1980.
48. Schwetz, B.A., et al. The effects of maternally inhaled trichloroethylene,
perchloroethylene, methyl chloroform, and raethylene chloride on
embryonal and fetal development in mice and rats. Toxlcol. Appl.
Pharmacol. 32:84.
-------
LISTING BACKGROUND DOCUMENT
ACRYLONITRILE PRODUCTION*
Bottom stream from the wastewater stripper in the production of
acrylonitrlle (R,T)
Bottom stream from the acetonitrile column in the production of
acrylonitrile (R,T)**
Bottoms from the acetonitrile purification column in the production
of acrylonitrile (T)**
I. Summary of Basis for Listing
The hazardous wastes generated in the production of acrylonitrile
contain the toxic constituents acrylonitrile, acrylanide, hydrocyanic
acid, and acetonitrile. The Administrator has determined'that the subject
waste from acrylonitrile production may pose a substantial present or
potential hazard to human health or the environment when improperly
transported, treated, stored, disposed of or otherwls.e managed, and
therefore should be subject to appropriate management requirements under
Subtitle C of RCRA. This conclusion is based on the following considerations:
1) Of the constituents present in these wastes,
acrylonitrile has been identified by the Agency as a
substance exhibiting substantial evidence of being
a carcinogen and Is extremely toxic. Acrylamide is
regulated as a carcinogen by OSHA. Hydrocyanic acid is
extremely toxic, as is HCN gas. Acetonitrile is also
toxic.
*In response to comments received by the Agency on the interim final list
of hazardous wastes (45 FR 33123, May 19, 1980), the listing of still
bottoms from final purification of acrylonitrile has been removed from
the hazardous waste list (see Response to Comments at the back of this
listing background document for details).
**These waste streams were originally proposed in a single listing
description, and are now listed separately for purposes of clarity.
-------
2) The bottom streams from the wastewater stripper and the
acetonitrlle column, and Che bottoms from the acetonl-
trile purification column are tyoically stored and settled
in ponds prior to deep well disposal. If improperly stored,
leachate from such systems could persist in groundwater,
causing potential exposure through drinking water. Volatili-
zation of toxic compounds from the pond also poses a risk to
humans.
3) The bottom streams from the wastewater stripper and the
acetonitrile column contain substantial concentrations of
hydrocyanic acid, which can be released as hydrogen
cyanide gas, an extremely toxic gas, if these wastes are
exposed to mildly acidic conditions.
4) The aqueous wastes from this process are generated in
substantial quantities, increasing the possibility of
exposure should mismanagement occur.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Acrylonitrile is produced in the U.S. by four producers oper-
ating six plants (Table 1). All six plants use the(SOHIO) Standard Oil of
Ohio process for ammoxidation of propylene. The chemical reaction
in the form of acrylonltrile may be represented by the following
equation:
2CH2 = CH - CH3 + 2NH3 + 302 > 2CH2 - CH - CN + 6^0
The reaction of propylene and ammonia results In acrylonltrile (70-80
percent), acetonitrile (3 percent), and hydrogen cyanide (HCN)
(3-13 percent).O)(4)(5) (Acetonitrile and hydrogen cyanide would
-------
TABLE 1
U.S. Producers of Acrylonitrile
Producer
Location
Capacity
American Cyanamid Go.
E.I. duPont de Nemours
& Company, Inc.
E.I. duPont de Nemours
& Company, Inc.
Monsanto Company
Monsanto Company
Vlstron Company
New Orleans, LA
Memphis, TN
Beaumont, TX
Chocolate Hayou, TX
Texas City, TX
Lima, Ohio
265 MM Ibs/year
270 MM Ibs/year
350 MM Ibs/year
440 MM Ibs/year
420 MM Ibs/year
frOO MM Ibs/year
2,145 MM Ibs/year
Source: Reference 2
-------
result from the reaction of acrylonitrile and water, forming
cyanohydrinacetaldehyde, which decomposes to form acetaldehyde and hydrogen
cyanide. The acetaldehyde reacts with ammonia and further decomposes to
iorm acetonitrile and water.)
By-product hydrogen cyanide is currently recovered by American
Cyanaraid, duPont, Monsanto, and Vistron. Acetonitrile by-product is recovered
by duPont and Vistron.(3)(*)(5)
B. Manufacturing Process
A flow sheet of a typical acrylonitrile plant is shown in
Figure 1. The hazardous waste streams of interest are described in
Section C.
C. Waste Generation and Management
1. Bottom stream from waste water stripper in acrylonitrile
production. (Stream 14, Figure 1)
Gases from the acrylonitrile reactor are cooled and neutral-
ized in a quench column with a sulfuric acid solution. Quenched product
gases then pass to the absorber where acylonitrile, acetonitrile and
hydrogen cyanide are recovered by absorption in water.
Quench column bottoms are sent to the wastewater stripper
column where volatile organlcs are stripped with steam and recycled to
the quench tower. The aqueous bottoms (Stream 14) which contain some
of the catalyst, ammonium sulfate and heavy organics, are generated at the
rate of about 3600 g/Kg. of acrylonitrile product(^). Applying this
ratio to the 1977 production figure for acrylonitrile gives a yearly pro-
duction rate of about 6000 MM Ibs/year of waste. A typical flow rate is
about 15*i gallons per minute.
-------
WASTE HEAT BOILER
/
STEAM
PROPYLENE
STORAGE
" _ " ru ACTOR ^S
FUGITIVE EMISSIONS
OVERALL PLANT
DEEP-WELL PONO
ACETONITRILE
STORAGE
ACETONITRILE
LOADING
Figure 1. FLOWSHEET FOR ACRYLONFTRiLE PRODUCTION
BY THE SOHIO PROCESSES f«)
-------
Table 2 summarizes Che composition of this waste stream. The waste
constituents of concern are acrylonitrile, acetonitrile, and hydrocyanic
acid.
TABLE 2
Typical Composition of Aqueous Bottom
Stream from Wastewater Stripper
1I mg/1
I
I
lAcrylonitrile
I
IAcetonitrile
I
IHCN
I
ISulfates
I
(Ammonia
.1
(Additional non-toxic solids
500 or less
3,000
7,000
32,000
15,000
40,000 approximately I
Wastewater stripper column bottoms are sent to a settling
pond where they are co-mingled with other process wastes. After the
solids settle, the liquid waste is injected into disposal wells.'"'
The acrylonitrile facility which deviates from this process is duPont in
Memphis. At this facility, the wastes are treated by alkaline hydrolysis.
The biodegradable effluent is disposed of in a municipal sewer.(8)
2. Bottom Stream from Acetonitrile Column (Stream 15, Figure 1).
The crude acetonitrile obtained as bottoms from the recovery
column goes to the acetonitrile column for separation of water (which
is recycled to.the absorber). This waste stream is also aqueous.
-------
This stream Is typically produced at a rate of 1003 g. per kg. acrylonltrile
product.(&) Applying this factor to the total nameplate capacity of
the acrylonltrile producers who are recovering acetonitrile results in an
upper limit estimate of 675 MM Ib. of the waste stream produced per year.
At the Vistroti plant, approximately 180 gallons per minute of column
bottoms are produced.(")
A typical composition of this waste stream is shown in Table 3.
TABLE 3
Typical Composition of Bottom Stream from
Acetonitrile Column (R)
(waste constituents of concern only)
HCN
Acrylonitrile
Acetonitrile
mg/1
225
•CIO
3S
This waste stream is combined with other process wastes (streams
14 and 16, Figure 1) and sent to a settling pond, followed by final
disposal, as previously described (see page 6).
3. Bottoms from Acetonitrile Purification Column (Stream 16, Fig. 1),
This stream is generated in the purification of crude acetonitrile
obtained as bottoms from the recovery column, after water separation in
the acetonitrile column. This waste stream is not expected to be present
in large quantities, since acetonitrile is a minor by-product of acrylonl-
trile production.
-------
The waste is expected to contain substantial concentrations of
acetonitrile (since purification would probably not be complete), and
acrylamide (which as a heavy compound would be found in the purification
residue). This waste is generally mixed with aqueous process waste and
sent to the settling pond, followed by final disposal (see page 6).
Although waste streams 14, 15, and 16 (the two aqueous bottom wastes,
and the acetonitrile purification column bottoms) are reported to be mingled
in process and co-disposed, the Agency has determined to list each waste
stream separately for purposes of clarity. There may also be situations
of which the Agency is unaware when one or another of these waste streams
is is not co-disposed, in which case the individual listing description
prevents a lapse in regulatory coverage.
III. Discussion of Basis for Listing
A. Toxicity Hazard Posed by Wastewater Stripper Stream, Acetonitrile
Column Stream, and Acetonitrile Purification Column Bottoms
These three waste streams are commonly co-minged in a single
settling pond, where solids are allowed to settle (see page 6), and
therefore are discussed together. The wastes are certainly capable of
creating a substantial hazard if improperly ponded.
As described above, these waste streams contain acrylonltrile,
a substance identified by the Agency as exhibiting substantial evidence
of being carcinogenic; acrylamide, which is regulated by OSHA as a
carcinogen; highly toxic hydrocyanic acid; and acetonitrile, which is also
toxic (see page 13 below). These waste constituents are deemed to be
present in sufficent concentrations to be of regulatory concern. Even in
-2HH-
-------
these highly diluted waste streams*, acrylonitrile is present in concentra-
tions up to 500 ppra (Table 2, p. 6).** Hydrocyanic acid may be present in
concentrations of 7000 ppm. Concentrations of these constituents in pond
sediments are likely to be slgrificantly higher, since pond sediments are
much more concentrated than aqueous waste streams.
These wastes are also generated in very substantial quantities.
Thus, the quantities of hydrocyanic acid, acrylonitrile and acetonitrile
discharged to a common holding pond annually, from just one plant, are
very substantial.(8)
Compound Amount/Year
Hydrocyanic Acid 5 million pounds
Acrylonitrile 300,000 pounds
Acetonitrile 2 million pounds
Very large amounts of hazardous waste constituents are thus potentially
available for environmental release. If mismanagement occurs, large
expanses of groundwater, surface water and soils may be contaminated.
Contamination will probably he prolonged, since large amounts of
pollutants are available for loading. Site attenuatlve capacity may
be exhausted as well, again increasing the risk of exposure. All of
these factors strongly support the listing.
Waste constituents, moreover, have high migratory potential.
Acrylonitrile, acrylaralde, and acetonitrile are all highly soluble
(App. B). (Acetonitrile, in fact, is raiscible.(*6>) In addition,
*Acetonitrile purification column bottoms are not aqueous, but probably are
mixed with other aqueous waste streams, and so are Included in the
discussion in the«text.
**The Agency policy is that carcinogens have no safe level of exposure.
See 44 FR 15926, 15930 (March 1979). Thus, minute concentrations of
carcinogens may well be of regulatory concern. In any case, the Agency
regards acrylonitrile concentrations In these wastes to be relatively
substantial for purposes of making a hazardousness determination.
-------
acrylamide and acrylonitrile tend to volatilize (46) > atl(j go COuld pose
a hazard via an air inhalation pathway. They may be highly mobile as
well, particularly in areas with highly permeable soils, or where soils
are low in organic content.(*<>) Aerylamide has in fact been documented
to have moved from a sewer grouting operation through the soil to a
private water well.(18) These waste constituents also may persist
after migrating from the waste site. The major degradation
mechanism for acrylamide and acetonltrile is biodegradatlon(^), which
would not affect these constituents in the abiotic conditions of an
aquifer. Acetonitrile also degrades (although slowly) to highly toxic
cyanide (*&), increasing the opportunity for hazard if *t Is released.
The major degradation mechanism for acrylonitrile is photodetoxification(13,14)j
which again would not affect this compound's persistence In groundwater.
Hydrocyanic acid, the other major waste constituent, Is
also highly noMle and persistent. Free cyanides, which may migrate from
these wastes, have been shown to be extremely mobile In soil; pH appears
to influence the mobility with greater mobility at high pH.(**) Also,
cyanide has been shown to move through soils into groundwater.d*) In
surface waters, cyanide often volatizes. The hydrogen cyanide vapors
pose a hazard to workers or nearby populations because of their
extreme toxlcity.
An actual damage Incident involving wastes containing hydro-
ocyanic acid confirm that cyanide can migrate, persist and contaminate
groundwater, public drinking water, and soil. A landfill In Monroe
County, Pennsylvania, that accepts plating process wastes such as hydro-
cyanic acid, has created a groundwater pollution problem In the
-------
Thus, these wastes could clearly create a substantial
hazard via a groundwater exposure pathway if improperly ponded, or
if concentrated liquid from the holding pond is improperly well
injected. Improper ponding also could result in a hazard via a surface
water pathway. If flooding occurs due to heavy rainfall, these hazard-
ous chemicals could enter surface water unless adequate waste management
methods are utilized. As most of the acrylonitrile plants are located
in Texas and Louisiana Gulf Coast area where average yearly rainfall is
heavy and the groundwater is close to the surface, the likelihood of
groundwater contamination is very high.
The Agency therefore regards these three wastes as toxic.
B. Reactivity Hazard Posed by Wastewater Stripper Stream and
Acetonitrile Column Stream
Both of these waste streams contain hydrocyanic acid, which is
hydrogen cyanide gas In liquid form. If these wastes are exposed to
relatively mild acidic conditions, hydrogen cyanide gas will be released.
The wastes thus meet the characteristic of reactivity contained in
Part 261.23(a)(b) and are listed accordingly.
IV. Health and Ecological Effects
1. Acrylonitrile
Health Effects - Industry-sponsored studies and other
studies of data on exposed workers and animal tests strongly indicate that
acrylonitrile is carcinogenic in humans.(20,24) jt hag aiso been identified
by Che Agency as a compound exhibiting substantial evidence of being a
carcinogen. Evidence has also developed from positive laboratory tests in
-V-
-------
several organisms that acrylonitrlie Is a mutagen.(25»27) i
also been reported to be teratogenlc and toxic to mothers.^")
Acrylonitrile is an extremely toxic chemical by inhalation, ingest ion, or
dermal routes following exposure to small quantities (oral rat LD5Q°82mg/kg.);
it is rapidly absorbed and distributed widely in the body, and acts by
damaging respiratory processes (causing asphyxia) and many tissues in a
manner similar to cyanide poisoning.(30,33)
Ecological Effects - The fathead minnow has an observed 96-
hour LC-50 of 10-18 mg/l.(34) A bluegill In a 28-day study bioconcentrated
acrylonitrile 48-fold(35>.
Priority Pollutant - Acrylonitrile is designated as a priority
pollutant under Section 307(a) of the CWA.
Regulations - Acrylonitrlie is regulated by the Office of
Water and Waste Management under the Clean Water Act (304(a) and 311)• The
Office of Toxic Substances has regulated acrylonitrile under FIFRA and has
requested additional testing under Section 4 of the Toxic Substances Control
Act. The OSHA TWA is 2 ppm.
Industrial Recognition - Sax, Dangerous Properties of Indus-
trial Materials designates acrylonitrile as highly toxic by oral and dermal
routes. The Handbook of Industrial Toxicology designates acrylonitrile as
extremely toxic via ingest ion, inhalation, and percutaneous routes. Addi-
tional information on the adverse effects of acrylonitrlie can be found in
Appendix A.
2. Acrylamide
Health Effects - Acrylamide is regulated by OSHA as a carcinogen
under OSHA Standard L910.1000(g). Acrylamide is a highly toxic chemical by
-yi-
-------
inhalation, ingestion or dermal routes (oral rat 1,050=170 mg/Kg).
Fatal intoxication has been reported following industrial exposure.(37)
The ability of acrylamide to alkylate tissue proteins and
nucleic acids would suggest that investigations in these areas are nec-
essary. O6)
Regulations - Acrylamide is regulated by OSHA as a carcinogen
under OSHA Standard 1910.1000(g). The Office of Toxic Substances has
requested additional information and testing under Section 4(e) of TSCA.
The OSHA TWA is 300 raicro-g/m3 (skin).
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, recognizes acrylamide as a highly toxic hazard
upon Ingestion, inhalation and skin absorption.
3. Hydrocyanic Acid/Hydrogen Cyanide (HCN)
Health Effects - Hydrocyanic acid in acrylonitrile produc-
tion wa*stes is extremely toxic to humans and animals via ingestion, causing
interference with respiration processes leading to asphyxiation and damage
to several organs and systems. Toxic effects have been reported in humans
at the very low exposure level of less than 1 mg/kg.(40,41) Human poisonings,
-------
Including several Involving deaths, have been reported since the 1920's.
HCN in gaseous state is extremely toxic (LCgg = 544 ppni.) to humans. In
addition the U.S. Public Health Service established a drinking water standard
of 0.2 mg/1 as an acceptable level for cyanide in water supplies.
Priority Pollutant - Cyanide is a priority pollutant under
Section 307(a) of the CWA.
Regulations - The OSHA permissible limit for exposure to
HCN is 10 ppm (skin) (11 rag/ra^) as an eight hour time weighted average.
DOT requires a label stating that HCN is a poisonous and flammable gas.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials lists HCN as highly toxic through Ingestlon, inhal-
ation and skin absorption. Additional Information on the adverse effects
of cyanide can be found in Appendix A.
4. Acetonitrile
Exposure to acetonltrlle occurs primarily through vapor
•
inhalation and skin absorption. "Exposure may cause liver and kidney
damage, disorders of the central nervous system, cardiovascular system and
gastrointestinal system. It is the release of the cyanide from
acetonitrile that is believed to cause these effects. Acute poisoning
and death have occured in workers Inhaling acetonitrile In industry.(4")
Acetonitrile is a component of cigarette smoke and is absorbed by the oral
tissues,C*7»50) Nltriles and their metabolic products have been
detected in the urine, blood, and tissues.^^ In a two year study
with rats, carclnogenesis was not shown for the chemical.'^ ' Mutagenic
-550-
-------
effects have not been demonstrated. Teratogenic effects In rats include
fetal abnormalities in pregnant rats^9) and skeletal abnormalities.<53)
From chronic exposure, rat developed liver and kidney lesions, and
monkeys showed poor coordination.(52) Until recently, acetonitrile
has been investigated by toxicologist chiefly because of its relationship
to thyroid metabolism.C51)
-251-
-------
IV. References
1. Not used in text.
?, Stanford Research Institute. 1979 Directory of chemical producers.
SRI International. Menlo Park, California. 1979.
3. Blackford, Judith L. Chemical conversion factors and yields. Chemical
Information Services. Stanford Research Institute. Menlo Park,
California. 1977.
4. Lowenheim, F.A. and M.K. Moran. Faith, Keyes & Clark's Industrial chemicals.
4th ed. John Wiley and Sons, New York. 1975.
5. Not used in text.
6. Hobbs, F. D. and J. A. Key. Emission control options for the synthetic
organic chemicals manufacturing industry. Acrylonltrile Product
Report. EPA Contract 68-02-2577. Hydrosctence. August, 1978. (Draft)
7. Hughes, T. W., and D. A. Horn. Source assessment: Acrylonitrlle manu-
facture (air emissions). EPA No. 600/2-77-107J. September, 1977.
8. Lowenbach, W., and J. Schlesinger. Acrylonitrile manufacture: Pollu-
tant prediction and abatement. Mitre Technical Report MTR-7752.
February, 1978.
9. Not used in text.
10. Not used in text.
11. Alessi, B.A., and W.H. Fuller. The mobility of three cyanide
forms in soil. pp. 213-223. In: Residual management by land disposal.
V.H. Fuller, ed. Environmental Protection Agency. Cincinnati, OH.
NTIS PB No. 256 768. 1976.
12. Not used in text.
13. U.S. EPA. Water-related environmental fate of 129 priority pollutants.
EPA No. 440/4-79-029a. 1979.
14. U.S. EPA. The prevalence of subsurface migration of hazardous chemical
substances at selected industrial waste land disposal sites. EPA No.
530/SW-634. 1977.
15. Not used in text.
16. Not used in text.
-------
17. Not used in text.
18. Igisu, Hideki, et al. Acrylamide encephaloneuropathy due to
well water pollution. J. of Neurology, Neurosurgery and Psychiatry
38:581-584. 1975.
\'-.. Not used in text.
20. O'Berg, M. Epideraiologic studies of workers exposed to acrylonitrile:
preliminary results. E.I. duPont de Nemours. 1977.
21. Not used in text.
22. Not used in text.
23. Not used in text.
24. Maltoni et al. Carcinogenicity bioassays on rats of acrylonitrile
administered by inhalation and by ingestion. La Medicina del Lavoro
68:401. 1977.
25. Benes and Sram. Mutagenic activity of some pesticides in Drosophila
melanogaster. Ind. Med Surg 38:442. 1969.
26. Not used in text.
27. Venitt, et al. Mutagenicity of acrylonitrile (cyanoethylene) in
Escherichia coli. Hut. Res. 45:283. 1977.
28. Not used in text.
29. Murray F.J., et al. Teratogenicity of acrylonitrile given to rats by
gavage or by inhalation. Ed. Cosmet. Toxicol. 16:547-551. 1978.
30. NIOSH. A recommended standard for occupational exposure to acrylonitrile.
NIOSH //78-166. 1978.
31. Not used in text.
32. Not used in text.
33. Sakurai, H., and M. Kusumoto. Epidemiological study of health Impairment
among acrylonitrile workers. Rod. Kagaku 48:273. 1972.
34. Henderson, et al. The effect of some organic cyanides (nitriles)
on fish. Eng. Bull. Ext. Ser. Purdue Univ. No. 106:130. 1961.
35. U.S. EPA. In-depth studies on health and environmental impacts
of selected water pollutants. U.S. EPA. Contract 68-01-4646.
1979.
-------
36. Not used in text.
37. U.S. EPA. Investigation of selected environmental contami-
nants: Acrylamides. NTIS PB No. 257 704. 1976.
38. NIOSH. Registry of toxic effects of chemical substances.
DHEW Pub. No. 79-100. p. 51. 1978.
39. Not used in text.
40. NIOSH. Criteria for recommended standard occupational exposure to
HCN and cyanide salts. #77-108. 1976.
41. Henderson, et al. The effect of some organic cyanides (nitriles) on
fish. Eng. Bull. Ext. Ser. Purdue University. No. 106:130. 1961.
42. Not used in text.
43. Not used in text.
44. U.S. EPA. Open files. Hazardous Site Control Branch, WH-548, U.S.
EPA. 401 M St., S.W., Washington, D.C. 20460. Contact Hugh Kauffman.
(202) 245-3051.
45. Not used in text.
46. Not used in text.
47. Dalhamn, T., et al. Mouth absorption of various compounds in cigarette
smoke. Arch. Environ. Health 16:831. 1968.
48. Dequidt, J., et al. Intoxication with acetonitrile with a report on
a fatal case. Eur. J. Toxicol. 7:91. 1974.
49. Not used in text.
50. McKee, H.C., et al. Acetonitrile in body fluids related to
smoking. Public Health Rep. 77:553. 1962.
51. Patty, p. A., ed. Industrial hygiene and toxicology. V.II.
Interscience Publishers, New York. 1963.
52. Pozzani, V.C., et al. An investigation of the mammalian toxicity of
acetonitrile. J. Occup. Med. 1:634. 1959.
53. Schmidt, W., et al. Formation of skeletal abnormalities after treatment
with aminoacetonitrile and cycylophosphamide during rat fetogenesis.
Verh. Anat. 71:635-638(Ger.) Chera. Abst. 1515w. 1976.
-------
Response to Comments - Bottom Stream from the Wastewater Stripper, Still
Bottoms from the Final Purification of Acrylonitrile, Bottom Stream from
the Acetronitrile Column and Bottoms from the Acetronltrlle Purification
Column in the Production of Acrylonitrile
A number of comments were received with respect to wastes K011 to K014
(wastes generated in the production of acrylonltrile).
1. One commenter felt that the Agency has improperly placed the
responsibility for determining the degradability of aerylonitrlie
and acrylamide for these particular wastes in the de-listing
process rather than in the listing process (i.e., the comraenter
believes that acrylonltrile and acrylamide, two of the constituents
of concern in these listings are "readily degradable" in the
environment). The commenter also disagrees with the Agency that
acrylonitrile and acrylamide are toxic to fish. The commenter,
therefore recommends that both acrylonitrile and acrylamide be
deleted as a basis for listing wastes K011 to K014. Further, the
commenter notes that both the Health and Environmental Effects
profile for acrylamide and the CAG carcinogen report for acrylonitrile
were unavailable for comment.
The Agency disagrees with the commenter'a unsubstantiated
claims as to degradability. In the listing background document,
the Agency has clearly discussed the degradability or non- degrad-
ability of these compounds in the environment. In summary,
the major degradation mechanisms for acrylonitrile and acrylamide
are biodegradation and photodetoxification, respectively, neither
of which would be strongly operative in the abiotic conditions of
an aquifer.
-------
Acrylaraide has in fact been documented to contaminate groundwater
(a private water well). If these wastes were improperly managed,
they could clearly create a substantial hazard via a groundwater
exposure pathway. This ooint is especially true for thesa wastes
since most of the acrylonitrile plants are located on the Texas
and Lousiana Gulf Coast area where the average yearly rainfall is
heavy and the groundwater is close to the surface. Therefore, the
probability that these toxic constituents will migrate and reach
an abiotic environment and not degrade is high.
With respect to the aquatic toxlclty of the two constituents,
the Agency argrees with the commenter that both acrylonitrile and
acrylamide are not toxic to fish. In the Registry of Toxic Effects
(1975 Edition), a widely used reference book which is published by
the National Institute for Occupational Safety and Health (NIOSH),
a rating of the aquatic toxiclty or non-toxicity of chemical
substances is provided. In this rating, substances with an LCgg of
between 10,000 ug/1 to 100,000 ug/1 are considered slightly toxic
[acrylonitrile (96-hr LC$Q 10-18 mg/1) and acrylamide (89-100
tag/1)]. Therefore, the Agency will modify the listing background
and delete all reference to both acrylonitrile and acralanide as
being toxic to fish.> However, both these compounds are recognized
as carcinogens: acrylamide is regulated by OSHA as carcinogenic
while acrylonitrile has been recognized by the Cancer Assessment
Group to be carcinogenic. Consequently, the Agency believes that
both of these compounds are sufficiently toxic to present potential
harm to human health and the environment, and will continue to
-------
include both acrylcmitrile and acryliraide as constituents of
concern in these particular listings.
Finally, the Agency admits that the Healt'. -"-id Environmental
Effects profile for acrylamide and the CAG carcinogen report for
acrylonitrile were unavailable for comment when the regulations
were promulgated. However, the Agency strongly believes that
sufficient information on the toxiclty/carclnogenlclty of these
two compounds were presented in the listing background document
for acrylonitrile production and the Health and Envlronmc. '.il
Effects profile on acrylonitrile to support the inclusion or
these toxic constituents. It should be noted that the CAG carci-
nogen report for acrylonitrile has been available for review since
June, 19BO.
2. One commenter requested that the Agency reassess the listing of
"Still bottoms from the final purification of acrylonitrile In
the production of acrylonitrile" (K102) as hazardous In Section
2^1.32. The comraenter pointed out that this particular stream
is an Integral part of the acrylonitrile manufacturing process
and does not meet the "sometimes discarded" provision of Section
261.2(b)(3); therefore, they argued that waste K012 should be
removed from the list of hazardous wastes.
In re-assessing the ultimate disposition of this particular
waste, the Agency agrees with the comraenter and, therefore, has
removed waste K012 from the hazardous waste list. In contacting
all the producers of acrylonitrile, the Agency has learned that
this stream meets the provision in Section 261.2(c)(3), "an inter-
-------
mediate manufacturing or mining product which results from one of
the steps in a manufacturing or raining process and is typically
processed through the next step of the process within a short
time." More specifically:
American Cyanimid Co. (New Orleans, La.) - still bottoms from the
final purification of acrylonitrile are recycled hack into the
quench neutralizer which then flows into the wastewater column.
E.I. DuPont de Nemours and Co., Inc. (Memphis, Tenn. and Beaumont, TX.)-
still bottoms from the final purification of acrylonitrile are
routed directly to the wastewater column.
Monsanto Co. (Cholocate Bayou and Texas City; TX) - still bottoms
from the final purification of acrylonitrile are routed directly to
the wastewater column.
Vitron Corp. (Lima, Ohio) - still bottoms from the final purification
of acrylonitrile are routed directly to the wastewater column.
-------
LISTING BACKGROUND DOCUMENT
BENZYL CHLORIDE
Still Bottoms from the Distillation of Benzyl Chloride (T)
1. Summary of Basis for Listing
Production of benzyl chloride results in the generation of still bottoms
which contain hazardous aromatic compounds that Include toxic organic sub-
stances, carcinogens and suspected carcinogens. The waste constituents of
concern are benzyl chloride, toluene, chlorobenzene, and benzotrIchloride.
The Administrator has determined that the still bottoms from benzyl chlo-
ride production may pose a substantial present or potential hazard to human
health or the environment when improperly transported, treated, stored, dis-
posed of or otherwise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of SCRA- This conclusion is based on
the following considerations:
1. Still bottoms from the distillation of benzyl chloride contain benzyl
chloride, benzotrichloride (when the dark chlorination, (i.e.,
catalytic light process is used), toluene, and chlorobenzene isomers.
Benzyl chloride has been identified as a carcinogen and a mutagen;
the other compounds are toxic.
2. Total quantities of benzyl chloride and benzotrIchloride generated
per year in this waste equal approximately 90,000 pounds.
3. Disposal of waste in improperly designed or operated landfills could
result in substantial hazard via groundwater or surface water exposure
pathways. Disposal by incineration, if mismanaged, can also result
in serious air pollution through release of hazardous vapors, due
to incomplete combustion. Storage of the wastes before incineration
presents a potential for contamination of surface or groundwater.
4. The hazardous waste constituents such as chlorobenzene are likely
to persist in the environment and to bloaccumulate in environmental
receptors.
-------
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Lenzyl chloride (C^Cf^Cl) is used as a raw material for Pharmaceuticals
and as an intermediate in the preparation of p-benzylphenol and benzyl alco-
hol. (^) The major use for the chemical, however, is in the production of butyl
benzyl phthalate, which is a plasticizer used in the manufacture of vinyl
products.(2)
Significant production of benzyl chloride is reported by two plants re-
sponding to the Clean Water Act Section 308 BAT questionnaire of 1979. These
plants reported only one process route: toluene chlorination. Total reported
production was 223,000 Ib/day (100,000 kg/day), which is equivalent to 73.6
million Ib/yr (33.4 million kg/yr).(5) Both plants that reported production
of benzyl chloride also provided data on average production per day. Indi-
vidual plant production ranges from 25,000 to 198,000 Ib/day (11,400 to 89,900
kg/day), and averages 112,000 Ib/day (50,600 kg/day).(5>
B. Manufacturing Process (1»2)
Benzyl chloride is produced from the chlorination of toluene. Chlorina-
tion may either be by UV light (photochlorination) or by the catalytic process.
Catalytic chlorination requires more severe reaction conditions. There are
certain differences in waste composition depending on which type of chlorina-
tion is used. These differences are described more fully below. The overall
process, however, may be generally described.
Chlorine is fed to a heated reactor containing boiling toluene (see Figure
1). For production of benzyl chloride, the reaction is allowed to continue
until there is a 37.5% Increase in weight; at this point, a mild alkali is
added to neutralize the acid formed. The by-product hydrogen chloride vapors
-------
CHLORINE
TOLUENE
To Hydrochloric Acid PlnnL
REACTOR
t
VENT
VENT
X
TOLUENE RECOVERY
COLUMN
^_,x
He
/• ^
Crude
nzyl Clilor
de
XX""^~"*
-------
from the reactor may be passed to a hydrochloric acid plant or recovered as
compressed gas.
The following equation shows the main reactions:
C6H5CU3 -t- C12 > C6H5CH2C1 + HC1
Toluene Chlorine Benzyl Chloride Hydrogen
Chloride
One side reaction is as follows:
C6H5CHC12 + C12 > C6H5CCl3 + HC1
Benzyl Chlorine Benzotrichloride Hydrogen
Dichloride Chloride
Reactor products are passed to a toluene-removal vacuum distillation
column, where unreacted toluene is removed overhead and recycled to the re-
actor. Crude benzyl chloride from the bottom of the toluene column is then
purified under vacuum in the product-fractionatlon column. Here, benzyl
chloride product is drawn off as a sidestream and the listed waste stream,
the still bottom stream, is generated.
C. Waste Composition, Generation and Management
1. Waste Composition and Generation
The still bottoms waste consists predominantly of chlorinated benzene
molecules. If the photochlorination process is used, waste constituents will
be benzal chloride (not a waste constituent of concern), and smaller concen-
trations of benzyl chloride (the product), a range of chlorinated benzenes
(from toluene feed stock impurities), and some residual feedstock toluene.(2)
The chlorinated benzenes in the still "bottoms will probably be chiefly the
heavier chlorinated benzenes (tri, tetra, penta, and hexa) since lighter
chlorobenzenes will go overhead with the product.
It is estimated that benzal chloride will be present in concentrations
of .02 kg/kg product, and additional constituents will be present in concen-
trations of .005 kg/kg product. (Modified from 2, 23)
-------
If the liquid uhast* catalytic chlorination process is used, these same
waste constituents will be present.(2) in addition, benzotrichloride will be
formed due to the severer reaction conditions.(2) (The reaction pathway for
benzotrichloride is indicated on p. 3 above.) Benzotrichloride and benzal
chloride are expected to be present in the still bottoms in the amount of
0.01 kg/kg and 0.1 kg/kg respectively. (Modified from 2, 23)
Waste quantities are expected to be significant. To gain a rough idea of
waste loading, one can assume that half the industry uses the photochlorination
process while the other half uses the catalytic process. Therefore, based
on total industry annual production of 33.4 million kg (p.2), waste loads
from the catalytic process will be over 2 million kg annually (assuming
benzal chloride is not recovered) with hazardous waste constituent loading
exceeding 200,000 kg a year. Wastes from the photochlorination process
would he generated in quantities of approximately 3.3 million kg annually
(assuming benzal chloride is not recovered), with hazardous waste loadings
of approximately 80,000 kg annually.
2. Waste Management
Two operating benzyl chloride plants reported that incineration of the
waste was their usual practice.(24) ^ third company is temporarily using
landfills until incineration equipment can be obtained.(24) Because of the
high chlorine content of the waste, an incinerator with alkali scrubbing of
off-gases is necessary for proper environmental control.
During incineration, supplemental fuel is usually necessary because of
the small heat content of the waste. Flame-out and consequent release of un-
burned toxic chlorinated hydrocarbons is not uncommon in such situations.
-------
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
As noted above, the principal waste components are benzyl chloride and
benzotrichloride. Toluene and chlorobenzene are also reported to be present,
since they are present as feedstock materials. Benzyl chloride has been
identified as a carcinogen and benzotrichloride is structurally similar to
other demonstrated carcinogens. (See pp. 9-11 following.) Chlorobenzene
and toluene are toxic chemicals.
1. Exposure Pathways
As noted, the typical disposal method for these wastes is discharge to a
holding pond or other temporary storage area prior to incineration. One com-
pany currently landfills these toxic wastes.
The waste constituents of concern may migrate from improperly designed or
managed holding ponds or landfills and contaminate ground and surface waters.
First of all, the waste constituents are soluble in significant concentrations.
Benzyl chloride is extremely soluble in water (solubility 330,000 mg/1), while
toluene and chlorobenzene are also very soluble (470 mg/1 and 488 mg/1 respec-
tively). (Appendix B.) Toluene would also tend to promote solubilizing of
other waste constituents, since it is a widely-used commercial solvent.
Thus, these waste constituents could leach into groundwater if holding
ponds or landfills are inadequatedly designed and constructed, or lack
adequate leachate collection systems.* Siting of waste management facilities
in areas with highly permeable soils could likewise facilitate leachate
migration. Disposal or storage in improperly designed or managed ponds
*Some of these waste constituents' mobility are effected by certain soil
attenuation mechanisms. (App. B) Pollutant mobility could be high, however,
where soil attenuation would be slight; for example, where soil is low in
organic content, highly permeable, or where attenuative capacity is exhausted.
-------
could similarly promote leachate formation and migration (indeed, the large
quantity of percolating liquid available could facilitate environmental
release by acting as a hydraulic head).
There is also a danger of migration Into and contamination of surface
water if holding ponds are improperly designed or managed. Inadequate
flood control measures could result in washout or overflow of ponded wastes.
The migratory potential of chlorobenzenes and toluene is confirmed by
the fact that chlorobenzenes (mono, dl, tri, tetra, and penta) and toluene
have all been detected migrating from the Love Canal site into surrounding resi-
dential basements and solid surfaces, demonstrating ability to migrate through
and persist in soils. ("Love Canal Public Health Bomb", A Special Report to
the Governor and Legislature, New York State Department of Health (1978)).
Benzyl chloride, although subject to hydrolyzation (App. B), has also been
identified as leaching from the Hyde Park Site. (OSW Hazardous Waste Divi-
sion, Hazardous Waste Incidents, Open rile, 197*.)
Once these three contaminants migrate from the matrix of the waste, they
are likely to persist in groundwater (see App. B). Chlorobenzene, toluene,
and benzyl chloride have in fact been shown to persist in soil and ground-
water, as demonstrated by the above-described damage incidents.*
*The above discussion does not consider benzotrichloride, another waste constit-
uent of concern. This waste constituent is relatively insoluble, not very vo-
latile, and tends to degrade in water. It is, however, relatively bloaccumula-
tlve (App. B). Thus, this waste constituent shows a lesser propensity to migrate
and reach environmental receptors, but could accumulate in harmful concentrations
if it reached a receptor. Furthermore, benzotrichloride has been identified as
migrating from the Love Canal site (OSW Hazardous Waste Division, Hazardous Waste
Incidents, supra), demonstrating some ability to migrate and persist if im-
properly managed.
-------
There also may be a danger of migration and exposure via an air inhalation
pathway if disposal sites lack adequate cover. Toluene is relatively volatile
(App. B), and is mobile and persistent in air, having been found in school and
basement air at Love Canal ("Love Canal Public Health Bomb", supra). Chloro-
benzenes and benzyl chloride, while less volatile (App. B), are also mobile and
persistent in air. Chlorobenzene (mono through penta) have been identified
in school and basement air at Love Canal ("Love Canal Public Health Bomb,"
supra), while benzyl chloride has been shown to persist in the atmosphere in
the New Jersey area for considerable periods of time.(6) Thus, these hazard-
ous constituents could migrate from uncovered landfills or holding ponds
and persisit for long periods in the environment.
Disposal by incineration, If mismanaged, also can result In serious air
pollution through the release of toxic fumes. This may occur when incinera-
tion facilities are operated in such a way that combustion Is incomplete (i.e.,
inadequate conditions of temperature, nixing, and residence time) resulting In
airborne dispersion of hazardous vapors containing undestroyed waste constit-
uents. This could present a significant opportunity for exposure of humans,
wildlife and vegetation in the vicinity of these operations to hazardous
constituents through direct contact and also through pollution of surface
waters.
The waste constituents in the still bottoms from benzyl chloride produc-
tion are oF the highest regulatory concern. For example, there is no known
safe level of exposure for carcinogens (see 44 Fed. Reg. 15926, 15940,
(March 15, 1979).). The Administrator would require assurance that these
waste constituents could not migrate and persist to justify a determination
not to list this waste stream. These waste constituents, to the contrary,
-------
have migrated and persisted to cause substantial hazard In actual instances.
The waste is therefore deemed hazardous.4
B. Health and Ecological Effects
1. Benzyl Chloride
Health Effects - Benzyl chloride has been identified as a
carcinogen^), and is also mutagenic^). Additional information and specific
references on the adverse effects of benzyl chloride can be found in Appendix A.
Regulatory Recognition of Hazard - 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. ^reregulatory 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 Con-
trol Act.
Industrial Recognition of Hazard - Benzyl chloride is listed in
Sax's Dangerous Properties of Industrial Materials as highly toxic via inhala-
tion and moderately toxic via the oral route.
2. Chlorobenzene
Health Effects - Chlorobenzene is a toxic chemical absorbed Into
the body by Inhalation, ingestion, and through the skin. Doses of Chloroben-
zene have been reported to cause liver damage in animals, abnormal dumping of
porphyoin pigments from the liver, weakness and stupor. Additional information
*Furthertnore, the waste constituents are generated in large annual quantities,
thus increasing the possibility of exposure if the wastes are managed
improperly. These large quantities of hazardous constituents potentially
available for release further justify a hazardous listing.
-J2C.7-
-------
and specific references on the adverse effects of chlorobenzene can be found
in Appendix A.
Environmental Effects - Chlorobenzenes are toxic to lower order
organisms and aquatic toxlcity of chlorobenzene La Indicated from studies
with saltwater shrimp species. Chlorobenzene has been shown to bioaccumulate
in fish(15).
Regulations - The OSHA TWA in air is 75 ppm. Chlorobenzene Is
designated as a priority pollutant under Section 307(a) of the CWA. (10, 11,
12, 13, 14)
Industrial Recognition of Hazard - Chlorobenzene Is listed in
Sax's Dangerous Properties of Industrial Materials as a dangerous chlorine
compound.
3. Toluene
Health Effects - Toluene is a toxic chemical absorbed Into the
body by inhalation, ingestIon, and through the skin. The acute toxic ef-
fect of toluene in humans is primarily depression of the central nervous
system(16). Chronic occupational exposure In shoe workers was reported to
lead to the development of neuro-muscular disorders, such as abnormal ten-
don reflexes and decreased grasping strength^), in animal studies, pre-
liminary evidence of bone marrow chromosomal abnormalities was report-
ed^. 19).
Since toluene is metabolized in the body by a protective enzyme
system which is also involved in the elimination of other toxins, it appears
that overloading the metabolic pathways with toluene will greatly reduce the
clearance of other, more toxic chemicals. Additionally, the high affinity of
toluene for fatty tissue can assist in the absorption of other toxic chemi-
-VtS-
-------
cale into the body. Thus, synergistic effects of toluene on the toxici-
tles of other contaminants may render the waste stream more hazardous. Be-
yond these considerations, toluene, by virtue of Its solvent properties, can
facilitate mobility and dispersion of other toxic substances, assisting
their movement toward ground or surface waters. Toluene Is designated as
a priority pollutant under Section 307(a) of the CWA. Additions! informa-
tion and specific references on the adverse effects of toluene can be found
in Appendix A.
Ecological Effects - Toluene has been shown to be acutely toxic
to freshwater fish and to marine fish. Chronic toxlcity la also reported
for marine fish(2°). The USEPA recommended criterion levels to protect
aquatic life are: freshwater, 2.3 mg/1, and marine, 100 mg/l(2°).
Regulations - Toluene has an OSHA standard for air (TWA) of 200
ppm. The Department of Transportation requires a "ClamabLe liquid" label.
Industrial Recognition of Hazard - Toluene .is listed as having a
moderate toxic hazard rating via oral and inhalation routes (Sax, Dangerous
Properties of Industrial Materials).
4. Benzotrichloride
Health Effects - Benzotrichloride is toxic with vapors that are
highly irritating to the skin and mucous membranes. In addition, large doses
have caused central nervous system depression in experimental animals^l). in-
halation of L25 ppn for 4 hours was lethal to ratsf22). Benzotrichloride has
been designated as a priority pollutant under Section 307(a) of the CWA.
Additional information and specific references on the adverse effects of benzo-
trichloride can be found in Appendix A.
-------
Industrial Recognition of Hazard - Benzotrichloride has a high
toxicity rating via inhalation (Sax, Dangerous Properties of Industrial Ma-
terials).
-------
IV. References
1. Rirk-Othmer. Encyclopedia of chemical technology. 5. John Wiley and
Sons, Inc., New York. 1964.
2. Lowenheim, 7, A. and M. K. Moran. Faith, Keyes and Clark's Industrial
chemistry. 4th ed. John Wiley and Sons, Inc., New York. 1975.
3. Not used in text.
4. Not used in text.
5. Individual Plants' Responses to EPA's 308 questionnaire.
6. Altshuller, A. P. Lifetimes of organic molecules in the troposphere
and lower stratosphere. Environmental Science and Technology. 1980.
In press.
7. Not used in text.
8. Druckrey, H., H. Druse, R. Pruessmann, S. Ivankovic, C. Landschutz.
Carcinogenic alkylating substances III. Alkyl-halogenides, -sul-
fates, -sulfonates and strained heterocyclic compounds. Z. Krbsforach
74:241-70. 1970. (Ger).
9. HcCann, J., E. Choi, E. Yamasaki, 3. N. Ames. Detection of carcinogens
as mutagens in the Salmonella/mlcrosorae test - Assay of 300 chemicals.
»roc. National Academy of Sciences VSA 72:5135-39. 1975.
10. U.S. EPA. Investigation of selected potential environmental contaminants:
Halogenated benzenes. EPA No. 560/1-77-004. 1977.
11. Lu, A.Y.H., et al. Liver mtcrosomal electron transport systems.
III. Involvement of cytochrome 35 in the KADH-supported cytochrome
p5-450 dependent hydroxylation of chlorobenzene. Biochem. Biphys.
Res. Comm. 61:1348. 1974.
12. Brodie, B. B., et al. Possible mechanism of liver necrosis caused
by aromatic organic compounds. Proc. Matl. Acad. Sci. 68:160. 1971.
13. Knapp, W. R., Jr., et al. Subacute oral toxicity of monochloro-
benzene in dogs arid rats. Toxieol. Appl. Pharnacol. 19:393. 1971.
14. Irish, D. D. Halogenated hydrocarbons: II. Cyclic. Jn Indus-
trial hygiene and toxicology. V.II, 2nd ed. F. A. Patty, ed.
Interscience. New York. p. 1333. 1963.
15. Lu, P., and Metcalf. Environmental fate and biodegradability of
benzene derivatives as studied in a nodel aquatic ecosystem.
Environ. Health Perspect. 10:269-285. 1975.
16. U.S. EPA. Toluene: Ambient water quality criteria. NTIS PB No.
296 B05/5BE. 1979.
-------
17. Matsushita, T., et al. Hereatological and neuro-muscular response of
workers exposed to low concentration of toluene vapor. Ind. Health*
13:115. 1975.
18. Dobrokhotov, V. B., and M. I. Enikeev. Mutagenic effect of ben-
zene, toluene, and a .mixture of these hydrocarbons in a chronic experi-
ment. Gig. Sanit. 1:32. 1977.
19. Lyapkalo, A. A. Genetic activity of benzene and toluene. Gig. Tr.
Prof. Zabol. 17:24. 1973.
20. U.S. EPA. Toluene: Hazard profile. Environmental Criteria and Assessment
Office, U.S. EPA. Cincinnati, Ohio. 1979.
21. Windholz, M., ed. 1976 Merck Index, 9th ed. Merck and Co., Inc.,
Rahway, NJ. 1976.
22. Sax, N. I. Dangerous properties of industrial materials, 5th ed. Van
Nostrand Tteinhold Co., New York. 1979.
23. Groggins. Unit processes on organic synthesis, 2nd ed. 1938.
24. U.S. Department of Health, Education, and Welfare. Criteria for a recom-
mended standard - Occupational exposure to benzyl chloride. Washington,
D.C. 1978.
-------
LISTING BACKGROUND DOCUMENT
CARBON TETRACHLORIDE PRODUCTION
Heavy ends or distillation residues from the production of
tetrachloride (T)
I. Summary of Basis for Listing
Heavy ends or distillation residues from carbon tetrachloride produc-
tion contain carcinogenic and toxic organic substances. These include
carbon tetrachloride, hexachlorobutadiene, hexachlorobenzene,
perchloroethylene and hexachloroethane.
The Administrator has determined that the solid waste from carbon
tetrachloride production may pose a substantial present or potential hazard to
human health or the environment when improperly transported, treated,
stored, disposed of or otherwise managed, and therefore should be subject
to appropriate management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations:
1. The heavy ends or distillation residues from the various carbon
tetrachloride production processes contain some or all of the
following constituents: perchloroethylene, carbon tetrachloride,
hexachlorobutadiene, hexachlorobenzene, and hexachloroethane.
All of these substances except hexachloroethane have been
identified by the Agency as compounds which have exhibited
substantial evidence of being carcinogenic; hexachloroethane is
a suspect carcinogen. Hexachlorobenzene Is also a teratogen. All
of these compounds are very toxic as well.
2. Approximately fl.6 million pounds/year of waste containing these
hazardous compounds are generated in the United States by six
manufacturers at 10 plants.
3. Disposal of these wastes in drums in improperly designed or
operated landfills represents a potential hazard due to the
probable corrosion of drums and the resulting leaching into
groundwater of these hazardous compounds.
-273-
-------
4. Mismanagement of Incineration operations and volatilization from
landfills could result in the release of hazardous vapors to
the atmosphere, and present a significant opportunity for
exposure of humans, wildlife and vegetation in the vicinity of
these operations to potentially harmful substances.
5. The components of concern are persistent in the environment,
thus increasing the chance for exposure.
6. The components of concern have been implicated in actual
damage incidents.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
There are six major corporations involved in the production of
carbon tetrachloride. The locations and annual capacity for each plant
are listed in Table 1.
The current principle use of carbon tetrachloride is in the
manufacture of chlorofluoromethanes used in refrigeration and aerosols.
Other uses include grain fumigation and a variety of solvent and chemical-
manufacturing applications.(^)
B. Manufacturing Process
Carbon tetrachloride is produced principally via four processes:
direct chlorination of methane, pyrolysis or chlorinolysls of hexachloro-
ethane with simultaneous chlorination of perchloroethylene, direct
chlorination of propane (in which perchloroethylene is produced as a
co-product), and direct chlorination of carbon disulfide. These processes,
and the listed waste streams generated thereby, are discussed below.*(
* These processes generally involve production of a range of chlorinated
organic products as well as carbon tetrachloride
-------
TABLE 1
Plant Sites for Carbon Tetrachloride Production''*'
Company
Location
Annual Capacity
(Millions of Pounds)
Allied Chemical Corp.
Specialty Chemicals
Division
Youndsville, WV
8
Dow Chemical, U.S.A.
Treeport, TX
Pittsburg, CA
Plaquemine, LA
135
80
125
E.I. duPont de
Nemours & Co., Inc.
Pe t r ochercs De p t.
Freon® Prod. Div.
Corpus Christ!, TX
500
Stauffer Chemical Co.
Ind. Chems. Div.
Le Mogne, AL
Louisville, XY
200
70
Vulcan Material Co.
Chemical Div.
Geisraar, LA
Vichita, KA
90
60
FMC Corporation
S. Charleston, WV
Total
300
1,568
-275"-
-------
1. Direct Chlorination of Methane (31)
The sequence of reactions for production of carbon
tetrachloride from the direct chlorination of methane is:
CH4+C12 > CH3C1+HC1
CH3C1+C12 > CH2C12+HC1
CH2C12+C12 > CHC13+HC1
CHC13+C12 > CCl^+HCl
The reaction is conducted adiabatically at temperatures ranging from
350° - 370°C and at approximately atmospheric pressure. In this process,
methyl chloride, raethylene chloride and chloroform are usually
co-produced with carbon tetrachloride. The ratio of formation of
these reaction products may be controlled to favor production of higher
chlorinated products (e.g., carbon tetrachloride) by recycle of less
chlorinated products (e.g., methyl chloride). Typical yields range from
85% to 95% based on methane.
Figure 1 represents a simplified process for production of carbon
tetrachloride via direct chlorination of methane. Methane is mixed with
chlorine, preheated and fed to a reactor fitted with mercury arc lamps
to enhance disassociation of chlorine. Chlorine is the limiting
reactant and about 65% of the methane reacts. A typical range of
products leaving the reactor is: methyl chloride - 58.5%; methylene
chloride - 29.3%; chloroform - 9.7%; and carbon tetrachloride - 2.3%.
The effluent gases from the reactor also contain unreacted methane
and hydrogen chloride which are separated by scrubbing the reacted
gases with a mixture of liquid chlororaethanes, usually a refrigerated
-276-
-------
ift
r
METHYL CHLORIDE CARBON TETRACHLOR"*
MET HYUNE CHLORIDE
RECYCLED
METHANE
METHANE-
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THRACHLORIDC
COLUMN
HEAVY ENDS
METHYL CHLORIDE METHYlENc CHLORIDE
CHLOROFORM
CARBON TTTRACHLORIOE
Figure 1.
Methyl chloride, roethylene chloride, chloroform and carbon
tetrachloride by the direct chlorination of methane.
(Modified from 31)
-------
mixture of chloroform and carbon tetrachloride. Methane and hydrogen
chloride are not absorbed and go overhead. Hydrogen chloride is
removed by scrubbing with water and methane is recycled. The enriched
chloromethane solvent absorber effluent is stripped of methyl chloride
and some methylene dichloride. The stripped solvent bottoms are
recycled to the absorber. The overhead product is condensed and
purified successively by a hot water wash (to remove residual hydrogen
chloride), an alkali wash, and a strong sulfuric acid wash (to dry the
chlorinated organic stream). The stripped methyl chloride, methylene
chloride and any heavy ends are separated by fractional distillation.
A portion of the bottoms from the stripping column together with
some or all of the recovered methyl chloride and methylene chloride
is then fed to a secondary reactor where chlorination is again carried out
photocheraically, but this time in the liquid phase. Hydrogen chloride is
vented from the reactor. The reaction products are purified and separated
by a sequence similar to that used for methyl chloride and methylene
chloride, except that any product less chlorinated than chloroform may
be recycled. Desired quantities of chloroform are removed by distillation,
and the remaining material is chlorinated in a third reactor to produce
carbon tetrachloride. The effluent from the third reactor is distilled
to recover carbon tetrachloride. The heavy bottoms from this tower is
the process waste.
Waste constituents predicted to be present in heavy ends from this
process in substantial concentrations are hexachloroethane, hexachlorobuta-
diene, perchloroetYiylene (tetrachloroethylene), and carbon tetrachloride.*
*As presented in Table 2, little or no carbon tetrachloride was recorded
found in the air, aqueous and solid emissions. However, based on industry
process, this constituent Is predicted to be present in the waste. Further,
the presence of even very small concentrations of this very potent carcinogen
are of concern to the Agency.
-------
Hexachloroethane would result from chlorination of G£ molecules, which
could be formed from methyl radicals. The same general type of reaction
would also result in formation of hexachlorobutadienes, except that C$
molecules (rather than €2 molecules) would be chlorinated. Perchloro-
ethylene is expected to result from the dechlorination of hexachloroethane.
A literature source estimating emissions from direct chlorination
of methane is set forth in Table 2.
2. Chlorinolysis of Hydrocarbon Feedstocks
Chlorinolysis* processes, in fact, make up the bulk of carbon
tetrachloride (perchloroethylene is a co-product) capacity in the United
States. Feedstocks for this process include aliphatic hydrocarbons
(e.g.,.propane), chlorinated aliphatic hydrocarbons, and chlorinated
aromatic hydrocarbons. Use of chlorinated feedstocks is particularly
valuable for control of residues from other chlorination processes,
which otherwise would pose a difficult disposal problem.
The conditions necessary for Chlorinolysis of hydrocarbon feedstocks
are somewhat more severe than those of direct chlorination of methane;
both higher temperatures and higher molar ratios of chlorine to hydrocarbon
are used. The product distribution is quite dependent on the feedstock used
and varies from over 90% carbon tetrachloride (propane) to over 90%
perchloroethylene (propene).
*Chlorlnolysis reactions refer to those chlorination reactions which
result in extensive rupture of carbon-carbon bonds.
-271-
-------
TABLE 2 ESTIMATED EMISSIONS FROM THERMAL CHLORINATION OF METHANE -
Species
EMISSIONS kg/Mg of product1
Air
Aqueous
Solid
Methane
Methyl chloride
Carbon tetrachloride
Perchloroethylene
Hexachloroethane
Sodium chloride
Sodium hydroxide
2R
trace
0.3
39
16
0.6
17
16
33
>urce: Wasselle, "Chlorinated Hydrocarbons", Process Economics Program Report No. 126, Stanford Research Institute,
1enlo Park, CA, August, 1978.
iased on hydrogen chloride product* To convert from hydrogen chloride product to a specific chlolorinated
lydrocarbon product, the following factors are used: 0.72 Ihs HCl/lb Ch^Cl
0.86 Ibs HCl/lb CH3C12
0.92 Ibs HCl/lh CH2C13
0.95 Ibs HCl/lb CC14
If
-a&o-
-------
In basic terms, the chlorinolysis involves the fracturing of carbon
bonds (at severe reaction conditions), followed by rechlorination of the
fractured portions. Waste residvies result from incomplete chlorina-
':"'on of the cracked hydrocarbon; , Hydrocarbon chlorinolysis reactions
thus tend to produce similarly-composed residual wastes. Waste con-
stituents predicted to be generally present are hexachlorobenzene,
hexachloroethane, perchloroethylene, hexachlorobutadiene, and carbon
tetrachloride. Two principal chlorinolysis processes for the
production of carbon tetrachloride are described more fully below.
a. Chlorinolysis of Propane (3D
The basic chemical equation representing the direct chlorinatlon of
propane to produce carbon tetrachloride and perchloroethylene is:
C3Rg +8C12 ------ > C2C14+C12
------ > C2C16
Figure 2 is a simple block flow diagram for the production of carbon tetra-
chloride and perchloroethylene by the direct chlorination of propane.
Feedstock chlorine, together with recycled chlorine, and propane are introduced
into a vaporizer where they are mixed with recycled chlorocarbons . Chlorine
is used in approximately 10% to 25X excess. The nixed gases react adiabatl-
cally at atmospheric pressure in a refractory-lined reactor at temperatures
ranging from 550°C and 700"C (controlled by the diluent action of
recycled streams). The recycle ratio also affects the product distribution.
Effluent from the rector (nainly carbon tetrachloride, perchlorethylene,
hydrogen chloride, chlorine, and unreacted hydrocarbon) is quenched with
perchloroethylene to minimize formation of by-products.
Carbon tetrachlortde , separated by fractionation, is condensed and
-------
Cl,
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*Motliried from 31
CARBON TETRACHLORIDE AND PERCIIl OROETUY1.FNE MANUFACTURE VIA Chionnnlyt is of
-------
withdrawn. Hydrogen chloride and chlorine are separated and scrubbed with
water In a hydrogen chloride absorber to remove HC1 as hydrochloric acid
by-product. The carbon tetrachloride column returns bottom liquid that is
rich in perchloroethene to the heavy ends colunn. Light ends from this
column are recycled to the reactor. In the heavy ends column, the
perchloroethylene-rlch stream is distilled to remove the heavy ends that
are returned for recycle. Overhead from the heavy ends column is
fractionated in the perchloroethylene column where the desired
quantity of perchlorethylene is removed as bottoms and the overhead,
containing largely carbon tetrachloride, is sent to recycle. The final
product mix is controlled by the amounts of product recycled to the
reactor. Estimated emissions from this process are shown in Table 3.*
The reaction pathways for these waste constituents are as follows:
Hexachloroethane results from the chlotination of product perchloroethylene.
Free radical reactions will result in the formation of hexachlorobutadiene
(see p. 9 where the reaction chemistry is described). Hexachlorobutadiene
could also be formed by chlorination of ethylene radicals under chlorinolysis
conditions. Hexachlorohenzene would result from the cyclization and
chlorination of C2 molecules under the high temperature reaction conditions
via a Diels-Alder reaction, whereby a cyclic compound is formed from
double bond systems.
*As presented in Table T, little or no carbon tetrachloride was recorded
found tn the air, aqueous and solid emissions. However, based on
industry process, this constituent is predicted to be present In the
waste. Further, the presence of even very snail concentrations of
this very potent carcinogen are of concern to the Agency.
-------
TABLE 3
ESTIMATED EMISSIONS FROM CARBON TETRACHLORIDE MANUFACTURE: Chlorinolysis of Propane
Species
EMISSIONS kg/Mg
Air
Aqueous
Solid
Carbon tetrachloride
Hexachloroethane
Hexachlorobutadiene
Hexachlorobenzene
Tars
Sodium hydroxide
trace
1.1
trace
3.3
3.3
3.0
10
Source: Elkin, "Chlorinated Solvents," Process Economics Program Report No. 48, Stanford Research
Institute, Menlo Park, CA, 1969
-------
b. Chlorinolysis of hexachloroethane with simultaneous
chlorination of perchloroethylene (A,2)
Expected waste constituents of concern from this process (Figure A)
aca hexachLorobenzene, hexachlorotnitadiene, hexachloroethane, and carbon
tetrachloride.* Some carbon tetrachloride is expected to be present in
distillation bottoms since it is the product and would not be completely
removed from the bottoms. Kexachloroethane is a feedstock and thus is
also expected to be found in the waste. Hexachlorobenzene will result
from the cyclization and chlorlnation of C2 molecules under high tempera-
ture pyrolysis conditions.
The final production process considered is the production of carbon
tetrachloride by chlorination of carbon disulfide.
3. Carbon Tetrachloride by Chlorination of Carbon Disulfide (3)
Direct chlorination of carbon disulfide to carbon tetra-
chloride is a long-established process which, until challenged by
chlorination of methane and chlorinolysis of hydrocarbons, was the sole
source of carbon tetrachloride. Chlorination of carbon disulfide does
have certain advantages: hydrocarbon co-products or by-products and
hydrogen chloride are not formed. Because sulfur must be recovered and
recycled however, this process is presumed to be integrated with a carbon
disulfide production facility.
The overall chemistry of this process is represented by the following
equations:
2CS24«C12 > 2CC14+2S2C12
*Additional heavy chlorinated hydrocarbons will probably also be
present, but their existence is more speculative since they would probably
"crack" into lower molecular weight compounds under chlorinolysis conditions.
14
-------
CHLORINE
PUHCE ON nCCYCLEO CIILOHINE (OAS|
CARDON
TETflACHLORIDE
CARBON
TETRACIILORIDE
COLUMN
—*
1EACTC
QUUNCH
TOWEH
HEAVIES
|lEAVYENDS[[
JL WATI
WATER .
11C)
ADSOnDEH
T
H.SO.
T
HCI SPENT
AGIO AGIO
HEAVY ENDS
COtUM
IOLUMN
y
pen
T
;HLOnO£THYLENE
COLUMN
T
- PERCHLOROETHYLENE
RECYCLE
tVAl
f
ION
M
H
OHI;
en
Figure^. CARBON TETRACI ILORIDE BY THE PYROLYSIS OF
1 HEXACHLOROETHANE & PERCHLOROETHYLENE
(Modified from 4,2)
-------
The sulfur monochlorlde formed reacts with a fresh feed of carbon disulfide
to form additional carbon tetrachloride:
2S2C12+CS2 > CC14+3S2
This reaction, In contrast to the first reaction, goes only to about 75%
completion. The sulfur formed Is recyled to carbon disulfide production.
Reaction yield Is about 95% based on carbon disulfide.
Carbon disulfide, a recycle stream of carbon dlsulfIde/carbon tetra-
chloride/sulfIde monochlorlde from dechlorlnation, and chlorine (approx.
1% wt over the stolchiometrlc requirement) react In the chlorlnator at
an approximate temperature and pressure of 100°C and 1 atm., respectively.
The reaction goes to near completion and the crude product consists
principally of carbon tetrachloride and sulfur monochlorlde, and a small
amount of carbon disulfide (>0.1£ wt ). Sulfur dichloride formation is
minimized by the presence of the carbon disulfide.
The crude product is fractionated into an overhead stream of carbon
tetrachloride and a bottom stream of sulfur monochlorlde and carbon
tetrachloride. Chlorine is added to the bottom stream to form small
amounts of sulfur dichloride which catalyzes the subsequent dechlorination
reaction. The dechlorination reactor operates under reflux conditions
using the bottom stream as a feedstock. After dechlorination, the reaction
product is separated: the overhead stream (CC14/CS2/S2C12) Is recycled
to the chlorinatlon reactor; the bottom stream, which is largely sulfur,
Is purified and recycled to carbon disulfide production. Crude carbon
tetrachloride, separated as an overhead stream from the distillation of
the chlorination mixture, Is washed with either a dilute solution of
sodium hydroxide or a suspension of calcium hydroxide to decompose sulfur
-------
monochlorlde and dlchloride. This stream is distilled and water, carbon
tetrachloride, and carbon disulfide are removed as an overhead stream.
Water is decanted, and the organic layer distilled. The bottom stream
irom this column is sent to carbon tetrachloride storage.
When properly conducted, this process would probably be waste free.
However, if conducted inefficiently, heavy ends could be generated consist-
ing of sulfur monochloride and carbon tetrachloride, probably in equal
concentrations. Obviously, the Agency is only listing this process when
waste heavy ends are actually-generated.
C. Waste Generation and Management
The distillation residue waste from the direct chlorination
or chorinolysis of hydrocarbons thus consist of heavy chlorinated hydro-
carbons, such as hexachlorobenzene, perchloroethylene, hexachlorobutadiene,
carbon tetrachloride, and hexachloroethane. These wastes are generated
in large quantities. Based on U.S.I.T.C 1978 production figures of
334,000 metric tons of carbon tetrachloride^^) an(j the waste emission
factors set forth above, an estimated 3200 metric tons of waste is
generated each year. This estimate may be conservative, since waste
emission factors were not calculated for wastes from carbon tetrachloride
production by pyrolysis of hexachloroethane. In any case, this Is a
significant annual quantity of waste generated, and it must further be
remembered that this waste will accumulate in greater quantities over
time.
Heavy ends from carbon tetrachloride production have typically
been disposed of in drums in land disposal facilities, or have been
Incinerated.
-I QO -
-------
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
The waste constituents of concern, which as shown above are
present in these wastes in substantial concentrations, are:
o Hexachlorobenzene
o Hexachlorobutadiene
o Carbon Tetrachloride
o Hexachloroethane
o Perchloroethylene
All of these substances except hexachloroethane have been identified
by the Agency as being carcinogenic and they are all very toxic.
Hexachlorobenzene is also a teratogen. Generation and accumulation of
large quantities (over 3000 MT annually, see p. 16) of wastes containing
these constituents is itself a reason for imposition of hazardous status.
The large quantities of these contaminants pose the danger of polluting
large areas of ground or surface waters. Contamination could also
occur for long periods of time, since large amounts of pollutants are
available for environmental loading. Attenuative capacity of the environment
surrounding the disposal facility could also be reduced or used up due
to the large quantities of pollutant available. All of these considerations
increase the possibility of exposure to the harmful constituents in the
wastes, and in the Agency's view, support a hazardous listing.
In light of the extreme danger posed by these waste constituents,
and the large quantities of waste generated, a decision not to list
these waste would be justified, if at all, only if waste constituents
were detnonstrably unable to migrate and persist. This is not the
case, however, since most of these waste constituents have migrated
and persisted in actual damage incidents, via both groundwater and air
-------
exposure pathways.
Carbon tetrachloride, for example, has been identified as present
in school and basement air at Love Canal, as has hexachlorbutadiene and
perchloroethlyene . (Source: "Love Canal, Public Health Bomb", a Special
Report to the Governor and Legislature, New York State Department of
Health, 1978.) Carbon tetrachloride has also been implicated in two
groundwater contamination incidents in Plainfield, Connecticut, where
drinking water sources were adversely affected (Table 1, Reference 31).
Heaxchlorobutadiene, hexachlorbenzene and hexachlorethane also have
been shown to migrate from waste disposal sites to groundwater. EPA
conducted groundwater monitoring in the vicinity of an (unnamed) chemical
waste disposal site in an effort to quantify migrating organic waste
constituents. These waste constituents were all found to have migrated
(Table 7.2, Reference 31).
Another incident illustrates even more dramatically the migraory
potential of these waste constituents. Chemical wastes from Hooker
Chemical's disposal sites at Montague, Michigan have migrated from
landfills and underground injection wells, moved through and contaminated
groundwater supplies, and contaminated a recreational lake. The contaminated
plume is 2,000 ft. wide and extends for over 1 mile. Among waste
constituents present in the plume are hexachlorobutadiene, hexachlorbenzene
and carbon tetrachloride. ^)
Hexachlorobenzene may also pose a hazard through volatilization.
A case history of environmental damage in which air, soil, and vege-
-------
tation over an area of 100 square miles was contaminated by hexachloro-
benzene (HCB) occurred in 1972. (7) There was volatilization of HCB
from landfilled wastes and subsequent bioaccumulation in cattle grazing
in the eventually contaminated areas. Accumulation in tissues of cattle
occurred, so that the potential risk to humans from eating contaminated
meat and other foodstuffs is significant.
These waste constituents thus have proven capable of migration,
mobility and persistence, and are demonstratably capable of causing
substantial hazard via groundwater, surface water and air exposure
routes, if improperly managed. Disposal by incineration is another type
of management which could lead to substantial hazard. Improper incinera-
tion can result in serious air pollution by the release of toxic fumes
occuring when incineration facilities are operated in such a way that
combustion is incomplete. In the incineration of wastes containing
carbon tetrachloride, phosgene (a highly toxic gas) is likely
to be emitted under incomplete combusion conditions.(32,33,34)
These conditions can, therefore, result in a signifcant opportun-
ity for exposure of humans, wildlife and vegetation, in the vicinity
of these operations, to potentially harmful substances.
B. Health and Ecological Effects
1. Hexachlorobenzene
Health Effects - Hexachlorobenzene has been found to be
carcinogenic in animals.(8,9) it has also been identified by the Agency
as a compound which exhibits substantial evidence of being carcinogenic.
vf
-------
This chemical is reportedly teratogenic, known to pass through placental
barriers, producing toxic and lethal effects In the fetus.(10) Chronic
exposure to HCB In rats has been shown to result In damage to the liver
and spleen.(11) It has been lethal In humans when Ingested at one-twentieth
the known oral LD^Q dose for rats. ' It has also been demonstrated
that at doses far below those which are lethal, HCB enhances the body's
capability to toxify rather than detoxify other foreign organic compounds
present in the body through its metabolism.(13) Hexachlorobenzene is
designated a priority pollutant under Section 307(a) of the CWA.
Additional information and specific references on the adverse effects of
hexachlorobenzene can be found in Appendix A.
Ecological Effects - Hexachlorobenzene Is likely to contaminate
accumulated bottom sediments within surface water systems and bloaccumulate
In fish and other aquatic organisms.(6)
Regulations - Hexachlorobenzene is a chemical evaluated by
CAC as having substantial evidence of carcinogenic!ty. Ocean dumping of
of hexachlorobenzene is prohibited. An interim food contamination toler-
ance of 0.5 ppm has been established by FDA.
Industrial Recognition of Hazard - According to Sax, Danger-
ous Properties of Industrial Chemicals, HCB is a fire hazard and, when
heated, emits toxic fumes.
2. Hexachlorobutadiene (HCBD)
Health Effects - Hexachlorobutadiene (HCBD) has been found
to be carcinogenic in animals(1*). It has also been identified by the
-------
Agency as a. compound which exhibits substantial evidence of being
carcinogenic. It is an extremely toxic chemical [W$Q (rat)- 90 mg/kg]
via ingestion. Upon chronic exposure of animals in tests conducted by
the Dow Chemical Company and others, the kidney appears to be the organ
most sensitive to HCBDt1^15'1^). Effluents from industrial
plants have been found to have HCBD concentrations as high as 240 g/l,
more than 200 times the recommended criterion level. HCBD is considered
a priority pollutant under Section 307(a) of the CWA. Additional In-
formation and specific references on the adverse effects of hexachloro-
butadiene can be found in Appendix A.
Ecological Effects - HCBD is likely to contaminate accumu-
lated bottom sediments within surface water systems and is likely to
bioaccumulate in fish and other aquatic organisms^).
The USEPA (1979) has estimated the BCF at 870 for the edible
portion of fish and shellfish consumed by Americans. Hexachlorobutadiene
is persistent in the environment(18).
Industrial Recognition of Hazard - Hexachlorobutadiene is con-
sidered to have a high toxic hazard rating via both oral and inhalation
routes (Sax, Dangerous Properties of Industrial Materials).
3. Carbon Tetrachloride
Health Effects - Carbon tetrachloride is a very potent carcin-
ogen^9) and has been identified by the Agency as a compound which exhibits
substantial evidence of being carcinogenic. It has also been shown to
be teratogenic in rats when inhaled at low concentrations.(20)
-------
Chronic effects of this chemical in the human central nervous system
have occurred following inhalation of extremely low concentrations [20
ppm](21) with death at 1000 ppm.^2) Adverse effects of carbon
tetrachloride on liver and kidney functions^23) and on respiratory
and gastrointestinal tracts(23,24) have also been reported. Death has
been caused in humans through small doses.(2^) The toxic effects of
carbon tetrachloride are amplified by both the habitual and occasional
ingestion of alcohol.(26) Especially sensitive to the toxic effects
of carbon tetrachloride are obese individuals because the compound
accumulates in body fat.(16) It also causes harmful effects in
undernourished humans, those suffering from pulmonary diseases, gastric
ulcers, liver or kidney diseases, diabetes, or glandular disturbances.^?)
Carbon tetrachloride is a priority pollutant under Section 307(a) of the
CWA. Additional information and specific references on the adverse
effects of carbon tetrachloride can be found in Appendix A.
Ecological Effects - In measurements made during the National
Organlcs Monitoring Survey of 113 public water systems sampled, 11 of
these systems had carbon tetrachloride at levels at or exceeding the
recommended safe limit.(28)
Regulations - OSHA has set a TWA for carbon tetrachloride
at 10 ppra. Carbon tetrachloride has been banned under the Hazardous Sub-
stances Act by the Consumer Product Safety Commission.
Industrial Recognition of Hazard - According to Sax, Danger-
ous Properties of Industrial Materials, carbon tetrachloride Is considered
a high systemic poison through ingestion and inhalation.
-29H-
-------
4. Hexachloroethane
Health Effects - Hexachloroe.thane has been reported to be
carcinogenic to animals, meaning that humans may be similarly affected^S).
Humans exposed to vapors at low concentrations for long periods have had
liver, kidney and heart degeneration and central nervous system damage(26),
Hexachloroethane is slightly toxic via Ingestion. It is a priority
pollutant under Section 307(a) of the CWA. Additional information and
specific references on the adverse effects of hexachloroethane can be
found in Appendix A.
Regulations - OSHA has set a TWA foe hexachloroethane at 1
ppm (skin).
Industrial Recognition of Hazard - According to Sax, Danger-
ous Properties of Industrial Materials, hexachloroethane has a moderate
toxic hazard rating.
5. Perchloroethylene (Tetrachloroethylene)
Health Effects - Perchlocoethylene (PCE) was reported
carcinogenic to nice (36). It has also been identified by the Agency
as a compound which exhibits substantial evidence of being carcinogenic.
PCE is chronically toxic to rats and mice, causing kidney and liver damage
(36,37,38), and to humans, causing impaired liver function (39).
Subjective central nervous system complaints were noted in workers occupa-
tionally exposed to FCE (40). PCE is also reported acutely toxic in
varying degrees to several fresh and salt water organisms, and chronically
toxic to salt wraCer organisms (41,42).
-------
IV. References
1. Not used In text
2. Kirk Othmer. Encyclopedia of chemical technology. 2d ed. New York.
Interscience Publishers, Hew York. 1963.
3. Stanford Research Institute. 1979 Directory of chemical producers -
U.S.A. SRI International, Menlo Park, CA. 1979.
4. Kahn, Z.S., and T.W. Hughes. Source Assessment: Chlorinated hydro-
carbons. EPA No. 600/2-79-019g. August, 1979.
5. Not used in text.
6. U.S. EPA. Technical support document for aquatic fate and transport
estimates for hazardous chemical exposure assessments. U.S. EPA
Environmental Research Lab., Athens, GA. 1980.
7. U.S. EPA. Hazardous waste disposal reports. No. 3. EPA No. 530/SW 151.3.
1976.
8. Cabral, J. R. P., et al. Carcinogenic activity of hexachlorobenzene
in hamsters. Tox. Appl. Pharmacol. 41:155. 1977.
9. Cabral, J. R. P., et al. Carcinogenesis study in mice with hexachloro-
benzene. Toxicol. Appl. Pharmacol. 45:323. 1978.
10. Grant, D. L., et al. Effect of hexachlorobenzene on reproduction
in the rat. Arch. Environ. Contain. Toxicol. 5:207. 1977.
11. Koss, G., et al. Studies on the toxicology of hexachlorobenzene.
III. Observations in a long-term experiment. Arch. Toxicol.
40:285. 1978.
12. Gleason, M.N., et al. Clinical toxicology of commercial products -
Acute poisoning. 3rd ed., p. 76. 1969.
13. Carlson, G. P. Induction of cytochrome P-450 by halogensted
benzenes. Biochem. Pharmacol. 27:361. 1978.
14. Kociba et al. Toxicologic study of female rats administered hex-
achlorobutadiene or hexachlorobenzene for 30 days. Dow Chemical
Company. 1971.
15. Kociba, R.J. Results of a two-year chronic toxiclty study with
hexachlorobutadiene In rats. Amer. Ind. Hyg. Assoc. 38:589. 1977.
16. Schwetz, et. al. Results of a reproduction study In rats fed diets
containing hexachlorobutadiene. Toxicol. Appl. Pharmacol. 42:387.
1977.
-------
17. Not useu in text.
18. U.S. EPA. Water-related environmental fate of 129 priority
pollutants. EPA No. 440/4-79-029b. 1979.
19- IARC Monographs on the evaluation of carcinogenic risk of chemicals
to man. V. I and V. XX. World Health Organization. 1972.
20. Schwetz, B. A., B. K. J. Leong and P. H. Gehring. Embryo- and
fetotoxicity of inhaled carbon tetrachloride, 1,1-dichloroethane
and methyl ethyl ketone in rats. Toxicol. Appl. Pharmacol.
28(3):452-464. 1974.
21. Elkins, Harvey B. The chemistry of industrial toxicology.
2nd ed. John Wiley & Sons, New York. p. 136. 1966.
22. Association of American Pesticide Control Officials, Inc.
Pesticide chemical official compendium. 1966.
23. Texas Medical Association. Texas Medicine 69:86. 1973.
24. Davis, Paul A. Carbon tetrachloride as an industrial hazard.
JAMA 103:962-966. 1934.
25. Dreisbach, Robert H. Handbook of poisoning: Diagnosis and
treatment, 8th ed. Lange Medical Publications, Los Altos, CA.
p. 128. 1974.
26. U.S. EPA. Carbon tetrachloride: Ambient water quality criteria
document. NTIS PB No. 292 424. 1979.
27. Von Oettlngen, W.F. The halogenated hydrocarbons of industrial and
toxicological importance. In; Elsevier monographs on toxic agents.
E. Browning, ed. Elsevier Publishing Co., NY. 1964.
28. U.S. EPA. The National Organic Monitoring Survey. Technical Support
Division, Office of Water Supply, U.S. EPA. Washington, DC. 20460. 1978.
29. Not used in text.
30. Not used in text.
31. Accurex Corp. Preliminary draft report: Chlorinated hydrocarbon
manufacture: An overview. Contract No. 68-02-2567. February 29, 1980.
32. Edward, J.B. Combustion formation and emission of trace species.
Ann Arbor Science. 1977.
-------
33. NIOSH. Criteria for recommended standard: Occupational exposure
to phosgene. HEW, PHS, CDC, NIOSH. 1976.
34. Chemical and Process Technology Encyclopedia. McGraw Hill. 1974.
35. U.S. International Trade Commission. Synthetic Organic Chemical.
1979.
36. National Cancer Institute. Biossay of tetrachloroethylene for
possible carcinogenicity. CAS No. 177-18-4. Nc I-C6-TR-13. DREW
Publication No.(NIH) 77-813. NTIS PB No. 112 940. 1977.
37. Rowe, V.K., et al. Vapor toxicity of tetrachloroethylene for
laboratory animal and human subjects. AMA Arch. Ind. Hyg. Occup.
Med. 5:566. 1952.
38. Klaasen, C.D., and G.L. Plaa. Relative effects of chlorinated hydro-
carbons on liver and kidney function in dogs. Toxicol. Appl.
Pharmocol. 10:119. 1967.
39. Coler, H. R., and H. R. Rossniller. Tetrachloroethylene exposure
in a small industry. Ind. Hyg. Med. 8:227. 1953.
40. Medek, V., and J. Kavarik. The effects of perchloroethylene on
the health of workers. Pracovni Lekarstvi. 25:339. 1973.
41. U. S. EPA. In-depth studies on health and environmental impacts
of selected water pollutants. Contract No. 68-01-4646. 1978.
42. U. S. EPA. Tetrachloroethylene: Ambient water quality criteria
NTIS PB No. 292 445. 1979.
-------
Response Co Cocnents - Heav; Ends or Distillation Rsjidues from
the Production of Carbon Te1 achloride
One commenter requestet chat the Agency reassess its interpretation
of what materials actually c nstitute waste in the production of carbon
tetrachloride. The comment* pointed out that many of these materials
are not discarded and never econe wastes; that instead, they are further
processed within a short tir to other products and manufacturing interme-
diates.
In reviewing the avaiL le information, the Agency has evidence to in-
dicate that these wastes ha- typically been disposed of in drums in land
disposal facilities, or hawi been incinerated. Therefore, these wastes are
"discarded and, thus, meet : e definition of a solid waste ($261.2) and will
continue to be listed as ha- rdous. However, this waste is not always discarded,
as evidenced by the comment' received (i.e., these wastes nay be used,
reused, recycled or reclaim ). As discussed in the preanble to the Part
261 regulations promulgated n May 19, 1980 (45 FR 33091 - 33095), the
Agency has concluded that i does have jurisdiction under Subtitle C of
RCRA to regulate waste mate als that are used, reused, recycled or
reclaimed. A large number > comments have been received, however, which
challenge this conclusion. he Agency is giving these caonents serious
consideration but has not p sently finalized this portion of the
regulations. Therefore, un la final decision is reached with respect
to r.aterials which are used reused, recycled or reclaimed, the following
guidance is offerer! to indi dual plants to assist then in determining
-------
their responsibilities under the hazardous waste regulations:
0 If the listed waste is always discarded at the individual
plant, the waste is always subject to :he full set of hazardous
waste regulations.
0 If the listed waste is sometimes discarded at a particular
plant, but is sometimes used, reused, recycled oc reclaimed,
(not used as an intermediate), the waste would only be subject
to the full set of hazardous waste regulations when discarded.
"Then used, reused, recycled or reclaimed the waste would be
subject to the special requirements for listed wastes contained
in §261.6(b) of the hazardous waste regulations (45 FR 33120).
" If the listed waste is typically processed through the
next step of the process within a short time, the material
does not meet the definition of a solid waste, i.e., is
an Intermediate product, and Is therefore not subject
to the hazardous waste regulations (45 FR 33119, and see
discussion at 45 FR 33093-33094).
-------
ORD-A-02
LISTING BACKGROUND DOCUMENT
EP;c;jLOROHYDRIN PRODUCTION
Heavj (_nds (still bottoms) from the purification column in the production of
epichlorohydrin. (T)
I. Summary of Basis for Listing
Heavy ends from the fraotionator column in the production of epichlorohydrin
contain carcinogens, mutagens, and toxic organic substances. These Include
epichlorohydrin, trichloropropane and dichloropropanol, and the chloroethers,
as pollutants of concern.
The Administrator has determined that the solid waste from epichlorohydrin
production may pose a substantial present or potential hazard to human health
or the environment when Improperly transported, treated, stored, disposed of
or otherwise managed, and therefore should be subject to appropriate management
requirements under Subtitle C of RCRA. This conclusion is based on the
following considerations:
1. The heavy ends from the production of epichlorohydrin
contain epichlorohydrin and chloroethers which have been
identified by EPA's Cancer Assessment Group as substances
exhibiting substantial evidence of carcinogenicity.
These compounds have also been reported in the literature
to show mutagenic potential. The waste also contains
trichloropropane and dichloropropanols which are very
toxic.
2. Approxinately 12,500 tons of the heavy bottoms were
generated in 1978 by two manufacturers at three
locations along the Gulf Coast.
3. The heavy wastes are stored in holding ponds prior to
incineration; during storage there is the potential for
ground and surface water contamination by leaching.
Epichlorohydrin in the waste also would tend to volatilize
and could present an air pollution hazard. If incineration
-30J -
-------
is incomplete, airborne dispersion of hazardous vapors presents
a potential of human risk.
4. Incidents o: epichlorohydrin contamination of water supplies
have occurred.
II. Sources of Wastes and Typical Disposal Practices
A. Industry Profile
Epichlorohydrin is manufactured by Dow, U.S.A. at Freeport,
Tex. and by Shell Chemical Co. at Deer Park, Tex., and Norco, La.(25)
The capacities of these plants range from 55 to 275 million pounds per
year. About 470 million pounds of epichlorohydrin were produced in
1978. (26, 27)
Epichlorohydrin is used mainly as an intermediate for the manufacture
of glycerin and epoxy resins. (25) It is also used In the manufacture
of plasticizers, surfactants, stabilizers, and ion exchange resins.
Growth is expected at 6 to 7% per year.C25)
B. Manufacturing Process
Epichlorohydrin is produced by the following reaction sequence:
Step 1:
C12 + H2<> ---------- > HOC1 + HC1
(Chlorine) (Water) (Hypochlorous (Hydrochloric
Acid) Acid)
Step 2:
CH2 - CH-CH2C1 + HOC1 ----- > CH2OHCHC1CH2C1 (65-70%) + CH2C1CHOHCH2C1(3P
(allyl chloride) HC1 1,2-dichloropropanol-l) (1,3-dichloroprop -2
hypochlorous acid
and hydrochloric
acid
-------
Step 3:
CH2OHCHC1CH2C1 + CH2C1CHOHCH2C1 +NaOH > CH2-CH-CH2Cl+NaCl+H20
(1,2-dichloropropanol-l) (1,3-dichloropropanol-2) (Epichlorohydrin)
By-products produced in small quantities are 1,2,3-trlchloro-
propane (CH2C1 CHC1CH2C1) and chloro-ethers such as:
(CH2C1-CHC1-CH2)2 - 0 [fCH2Cl)2 - CH]2 - 0
bis-2,3-dichloropropyl ether bis-l,3-dichloropropyl ether
A process flow diagram is shown in Figure 1 attached.
The mixture of hypochlorous acid and hydrochloric acid react-
ants is produced by absorbing chlorine in water. This acid mixture
plus allyl chloride are then fed to the reactor. After chlorination,
the reaction mixture (containing the dichloropropanols, some feed
materials and reaction by products) is sent to the separator. The top
aqueous layer containing hydrochloric and hypochlorous acids is then
recycled to the absorber; the bottom organic layer is sent to the
dehydrochlorinator where the dichloropropanols are dehydrochlorinated
using sodium hydroxide.
The reactant mixture from the dehydrochlorinator is steam
stripped. An azeotropic mixture is formed consisting of water and
crude epichlorohydrin. This mixture is taken overhead, condensed, and
sent to a liquid/liquid separator.
-303-
-------
WATER
I IVI -OCI ILOnOUS ACID RECYCLE
AQUEOUS PHASE
CHIORINE
REACTOR
CHLORINE
At IYI
IIYPOU ILOnOUS ACID FEED
(.IILOniNATION
REACTOR
CRUDE CHLOROIIYDRJN
SEPARATOR
©
Y I AQUEOUS PHASE
Q SEPARATOR D
SI niPI'l-n ORGANIC PHASE
—.STEAM
AQUEOUS
PHASE
STRIPPER
<5
STEAM
WASTEWATER WASTCWA7L-M
ORGANIC PWSE
WASTE STRIPPER
ffO AQUEOUS
PHASE
CHUDE
EPICHl.OnOIIYDPIN
H- CALCIUM CHLORIDE.
[ORGANIC PHASE
SODIUM
HYDROXIDE
EPICHLOMQHYORIN
7o!>V. PHOOUCTJ"""
PURinCATlON
COLUMN
DEHYOROCHLORINATION
REACTOR
1 1
rr
HAZARDOUS
WASTE STREAM
(TRICHLOROPROPAN
Figure 11
AULYU C»L°n»>l: VIA DEHYOBOCHLORINATION
-------
The waste water from the bottom of the steam stripper^-) Is stripped
in the aqueous phase stripper where small amounts of eplchlorohydrln
are recovered overhead and recycled to the steam-stripper condenser;
tiie bottom stream is discharged as water waste.*
The bottom organic phase from the liquid/liquid separator Is fed
to the organic phase stripper where residual water is removed overhead.(2)
The bottom stream of crude eplchlorohydrln is fed Co the purification column
where It is purified by fractionation^) Purified epichlorohydrin is
distilled overhead. The bottom stream from the purification column
is the waste stream of concern in this document.
C. Waste Generation and Management
The waste stream from this process Is the heavy organic
bottoms (stream 3) from the product purification column. Three plants
(two in Texas, one in Louisiana) generated 12,500 tons of heavy ends (still
bottoms) In the production of 469.6 million Ibs. of epichlorohydrin
In 1978(26*27). xhe primary disposal technique (1979) was reported to be
incineration. It is assumed, based on usual waste management practice, that
the heavy ends are stored in holding ponds or other temporary storage
facilities prior to incineration.
III. Discussion of Basis for listing
A. Hazards Posed by the Waste
Epichlorohydrin purification column bottoms typically contain the following
contaminants in the Indicated concentrations:(27)
*Thls water stream Is not presently Hsted as hazardous.
-------
Percent
Eplchlorohydrln 2
Chloroethers 14
Trichloropropane 70
Dlchloropropanol 10
Chlorinated aliphatlcs 4
100
The waste constituents of concern are epichlorohydrin, the chloroethers,
trich.lorpropane and dichloropropanol. Epichlorhydrin has been identified
as a substance exhibiting substantial evidence of carcinogenlcity by
EPA's Carcinogen Assessnent Group. It is also an animal mutagen and
is very toxic. The chloroethers are likewise recognized by the
Agency as known animal and likely human carcinogens. Their toxiclty
is likewise high. (See pp. 9-13 following.) Trichloropropane and
dichloropropanol are very toxic. Large quantities are therefore available
for environmental release in high concentrations.
These waste constituents are present in very substantial
concentrations and are generated in large quantities (12,500 tons in
1978). There is thus a strong likelihood that the waste constituents
will reach environmental receptors and cause substantial hazard if
waste constituents are mismanaged.
-------
Waste mlsraanagraent may certainly occur. As noted above, the
primary disposal for this waste is by incineration prior to which
the waste nay be stored in holding ponds or other temporary storage
containers. Disposal by incineration, if mismanaged, could result in
serious air pollution through release of toxic fumes. This may occur
when incineration facilities are operated in such a way that combustion
is incomplete (i.e. inadequate conditions of temperature, mixing and
residence time) resulting in airborne dispersion of hazardous vapors
containing waste constituents of concern, as well as other newly formed
harmful organic substances. Phosgene is an example of a partially
combusted chlorinated organic which is produced by the decomposition
of chlorinated organics by heat.(32»33»3*) This could present a significant
opportunity for exposure of humans, wildlife and vegetation In the
vicinity of these operations to risk through direct contact and also
through pollution of surface waters.
Temporary storage, if not properly managed, may also lead to the
release of harmful constituents. Thus, if holding ponds lack proper
flood control design features, there is a danger that the organics,
during periods of heavy precipitation could be emitted due to flooding
of the ponds. Should flooding occur, epichlorohydrln is stable enough
to be transported to surface waters. (Appendix B) This eventually
could result in drinking water contamination. Actual contamination of
-7-
-307-
-------
a public water supply by epichlorohydrin occured on January 23, 1978,
when a tank car derailed, spilling 197,000 pounds of epichlorohydrin in
West Virginia.* Nearby wells at a depth of 25 feet were heavily contaminated,
demonstrating'ability to be mobil in soils. A similar hazard could result
If epichlorohydrin-containing wastes were disposed in an uncontrolled
pond or lagoon.
The chloroethers are also capable of significant migration via
surface water pathways.(*) They have been found in surface and groundwaters
at concentrations exceeding the USEPA recommended maximum allowable concen-
tration levels in drinking water of 0.42mg/l, demonstrating a propensity
to migrate and persist.'**)**
Waste constituents might also escape from the holding pond via
a groundwater pathway if storage is improper (for instance using ponds In
locations with permeable soils). Epichlorhydrin is highly soluble (66,000
ppra), and is thus capable of migration. It absorbs to organic constituents
in soil, and so mobility would be high where organic content is low.(28)
The chloroethers are also highly soluble (Appendix B) and, although tending
to absorb to soils, have been shown to be mobile and persistent enough to
be found in groundwater at concentrations exceeding the proposed human
health water quality criteria, as noted above.**
* OSW Hazardous Waste Division, Hazardous Waste Incidents, unpublished,
open file, 1978.
** The Agency is not using these standards as quantitative benchmarks, but
is citing them to give some indication that very low concentrations of
these contaminants may give rise to substantial hazard.
-------
From the holding ponds or in surface water, most of the chlorin-
ated propanols would undergo hydrolysis and biodegradation. The dissolved
portion, however, could move wltfc a water front through the soil profile.
Under some conditions, the chlorinated propanols could reach a ground
water aquifer (Appendix B). Degradation of chlorinated propanols in
groundwaters would be much slower as evidenced by the observance of
many related chlorinated ethanes, ethylenes, in Love Canal leachate,
methanol, ethanol and isopropyl alcohol some 30 years after disposal.
(29,30,31)
Data show that chemical analogs, dichloroethane^ ' and
dibromochloropropane,(8) have permeated the soil mantle to contaminate
groundwater, again suggesting a similar behavior for propanols. In
addition the chloropropanols tend to bioaccumulate in aquatic
organisms,(9) thus increasing potential exposure to higher levels of
the food chain, including man.
Spichlorohydrin could also pose a threat via an inhalation exposure
pathway due to its relatively high volatility. C2^) Thus, lack of adequate
cover could result in air pollution to surrounding areas.
-------
B. Health and Ecological Effects
1. Eptchlorohydrin
Health Effects - Epichlorohydrin has been demonstrated to
be carcinogenic in animals^^ upon inhalation of vapors. This compound
has also been recognized by the Agency as a chemical compound which has
exhibited substantial evidence of carcinogenicity. (35) Epichlorohydrin
is very toxic [oral rat LD5o=90mg/Kgl. Both respiratory cancers and
leukemia are in excess among some exposed worker populations.-10,11)
Epichlorohydrin vapor also has been demonstrated to induce aberrations in
humans and animal chromosomes^^»!•*) and has induced birth defects in
animal studies conducted by the Dow Chemical Company. It is a known mutagen
to non-mammalian species.(^) Several investigators have found that epichloro-
hydrin possesses anti-fertility properties^10). Altered reproductive
function has been reported for workers occupationally exposed to eplchloro-
hydrin. Dow Chemical Company researchers have observed degenerative changes
in nasal tissue; severe kidney and liver damage has also been found in
animals exposed to vapors of epichlorohydrin.(l«il') Additional
Information and specific references on the adverse effects of epichlorohydrin
can be found in Appendix A.
Regulatory Recognition of Hazards - The OSHA time weighted
average for skin contact with epichlorohydrin in air is 5 ppra. DOT
requires a label warning that this chemical is a poison and a flammable
liquid.
- ~*. ir\ _
-------
Industrial Recognition of Hazards - Eplchlorohydrin is Intensely
Irritating and moderately toxic by the oral, percutaneous and subcutaneous
routes as well as by inhalation of the vapors (Fassett and Irish, Industrial
Hygiene and Toxicology). Plunkett considers it highly toxic in his
Handbook of Industrial Toxicology.
2. Chloroethers - bis (chloromethyl) ether and bis (2-chloroethyl)
ethers
Health Effects Both bis (chloromethyl) ether and bis (2-
chloroethyl) ethers are identified as carcinogens in animals^"'19)
under laboratory conditions. These chemicals have also been recognized
by the Agency as demonstrating substantial evidence of carcinogenicity.
Bis (chloromethyl) ether is very toxic {oral rat LD5o=210 mg/Kg; Inhalation
rat LD50=7ppm/7hl. Bis (2chloroethyl) ether is also very toxic (oral
rat Ln50=75og/Kg]. Epidemiological studies of workers in the United
States, Germany and Japan who were occupatlonally exposed to both ethers
indicate that they are human carcinogens.(20) They have also been
shown to be mutagens in bacterial screening systems.f20) Additional
Information and specific references on the adverse effects of chloroethers
can be found in Appendix A.
Regulatory Recognition of Hazard - Chloroethers are designated
as priority pollutants under Section 307(a) of the CWA. Bis (chloroethyl)
ether has a designated OSRA celling of 15 ppra. Bis (chloromethyl) ether
is designated by OSHA as a carcinogen and is required by DOT to carry
labels that say "flammable liquid" and "poison".
-------
Industrial Recognition of Hazard - Sax (Dangerous Properties
of Industrial Materials) states that bis (chloromethyl) ether has an
unknown systemic toxic hazard rating but it is a carcinogen. Bis 2
(chloroethyl) ether is highly toxic via ingestion, inhalation and skin
absorption. Both chemicals are listed as priority pollutants by the EPA.
3. Trichloropropane
Health Effects - 1,2,3-Trichloropropane Is a strong irritant
and can be toxic by oral Ingestion, inhalation, or dermal application.(21,22)
Trichloropropane is very toxic [oral rat LD5Q=320 mg/Kg]. Tsulaya et al^23^
observed significant changes in central nervous system function, as well as
enzyme changes in blood, liver, and lungs. Additional information and specific
references on the adverse effect of trichloropropane can be found in Appendix A.
Regulations - The OSHA TWA for trichloropropane in air is 50 ppa.
Industrial Recognition of Hazard - Trichloropropane is designated
in Sax, Dangerous Properties of Industrial Materials, as a highly toxic
skin irritant, moderately toxic systemic poison via oral, inhalation and
skin absorption routes and as a cumulative toxin.
4. Dichloropropanols
Health Effects - Both industrially occurring isomers, 1,3-dichloro-
propanol-2 [oral rat LD5Q=90 mg/Kg] and l,2-dlchloropropanol-3 [oral rat 1.050=
490 rag/Kg] are very toxic to laboratory animals, causing systemic as well
as local toxic effects. The toxic symptoms caused by the 1,3 Isotner have
-V*-
_ -3 n _
-------
been compared to that of the liver toxin carbon tetrachloride which causes
acute and often irreversible hepatic failure. Both compounds are potent
suln and lung irritants, absorbed by all routes of exposure and tend to accum-
ulate in the organism.(2*) Additional information and specific references
on the adverse effects of dichloropropanols can be found in Appendix A.
Industrial Recognition of Hazard - Dichloropropanol is desig-
nated in Sax, Dangerous Properties of Industrial Materials as moderately
toxic via inhalation and highly toxic via ingestion^2^.
-•*>}?>-
-------
IV. References
1. Nelson, N. Communication to the regulatory agencies of preliminary
findings of a carcinogenic effect in the nasal cavity of rats exposed
to eplchlorohydrin. New York University Medical Center, letter dated
28 March 1977.
2. Nelson, N. Updated communication to the regulatory agencies of pre-
liminary findings of a carcinogenic effect in the nasal cavity of rats
exposed to epichlorohydrin. New York University Medical Center, letter
dated 23 June 1978.
3. Peterson, C.A., Jr. Emission control options for the synthetic organic
chemicals manufacturing industry. Glycerin and its intermediates.
Abbreviated product report. EPA Contract No. 68-02-2577. March, 1979.
4. Zoeteman, B. C. J., et al. Persistent organic pollutants in river water
and groundwater of the Netherlands. In; Proceedings; 3rd Int'l Symposium
on Aquatic Pollutants. Jekyll Island, GA. October 15-17, 1979.
5. Not used in text.
6. U.S. EPA. Preliminary assessment of suspected carcinogens in drinking
water. Report to Congress. EPA No. 560/4-75-003. U.S. EPA. Washington,
DC. 20460. 1975.
7. De Walle, F. P., and E.S.K. Chian. Detection of trace organics in well
water near a solid waste landfill. _In Proceedings: 34th Industrial Waste
Conference. Lafayette. May 8-10, 1979. Purdue University. Ann Arbor
Science p. 742-52. 1980.
8. Weisser, P. News Release, Department of Health Services. Sacramento,
CA. August 23, 1979.
9. 'Clement Associates, Inc. Dossier on chloropropanes (Draft).
Contract No. EA8AC013, prepared for TSCA Interagency Testing
Committee. Washington, D.C. August, 1978.
10. Enterline, P. E. Mortality experience of workers exposed to epichloro-
hydrin. In press: Jour. Occup. Medicine. 1979.
11. Enterline, P. E., and V. L. Henderson. Communication to Medical Direc-
tor of the Shell Oil Company: Preliminary finding of the updated
mortality study among workers exposed to epichlorohydrin. Letter dated
July 31, 1978. Distributed to Document Control Office, Office of Toxic
Substances, WH-557. U.S. EPA. 1978.
12. Syracuse Research Corporation. Summarization of recent literature per-
taining to an occupational health standard for epichlorohydrin. Report
prepared by Syracuse Research Corporation for NIOSH. 1980.
-------
IV. References (Continued)
13. .Santodonat-o, et al. Investigation of selected potential environmental
contaminants: Epichlorohydrin and epibromohydrin. Syracuse Research
Corporation. Prepared for the Office of Toxic Substances, US. EPA.
EPA No. 560/11-80-006. NTIS PB No. 197 585. 1979.
14. Not used in text.
15. Not used in text.
16. Quast, J. F. et al. Epichlorohydrin - subchronic studies I. A 90-day
inhalation study in laboratory rodents. Unpublished report from
Dow Chemical Company, Freeport, Texas. January 12, 1979.
17. Quast, J. F. et al. Epichlorohydrin - subchronic studies. I. A 12-day
study in laboratory rodents. Unpublished report from Dow Chemical
Company, Freeport, Texas. January 12, 1979.
18. Innes, et al. Bioassay of pesticides and industrial chemicals for
tumorigenicity in mice, a preliminary note. J. Natl. Cancer Inst.
42:1101. 1969.
19. Juschner, et al. Inhalation carcinogenicity of alpha haloethers III.
Lifetime and limited period inhalation studies with bis(chloromethyl)
ether at 0.1 ppm. Archives of Environmental Health 30:73. 1975.
20. U.S. EPA. Chloroalkyl ethers: Ambient water quality criteria.
NTIS PB No. 297 921. 1979.
21. Hawley, G. G. Condensed chemical dictionary, 9th ed. Van Nostrand
Reinhold Co., New York. 1977.
22. NIOSH. Registry of toxic effects of chemical substances. U.S. DHEW,
PHS, CDC, DHEW (NIOSH) No. 78-104-A and No. 78-104-B. 1978.
23. Tsulaya, V. R., et al. Toxicology features of certain chlorine
derivatives of hydrocarbons. Gig. Sanit. 8:50-53. 1977.
24. Sax, N. I. Dangerous properties of industrial materials, 5th ed.
Van Nostrand Reinhold Co., Mew York. 1979.
25. Kirk-Othmer. Encyclopedia of chemical technology. 2nd ed. V.I.
John Wiley and Sons, New York. 1970.
26. Peterson, C. A. Emission control options for the synthetic organic
chemicals manufacturing industry: Glycerin and its intermediates.
Abbreviated product report. EPA Contract No. 68-02-2577. March, 1979.
-------
27. U.S. EPA. Assessment of Industrial hazardous waste practices:
Organic chemicals, pesticides and explosives industries. EPA
No. SW 118c. p. 5-20. NTIS PB No. 251 307. January, 1976.
28. Dawson, English and Petty. Physical chemical properties of hazardous
waste constituents. 1980.
29. Barth, E.F., and Cohen, J.M. Evaluation of treatability of industrial
landfill leachate. Unpublished report. U.S. EPA. Cincinattl, Ohio.
November, 1978.
30. O'Brien, R.P. City of Niagara Falls, N.Y., Love Canal Project.
Unpublished Report. Calgon Corp. Calgon Environmental Systems
Division. Pittsburgh, Pa.
31. RCERA Research, Inc. Priority pollutant analyses prepared for NUCO
Chemical Waste Systems, Inc. Unpublished report. Tonauanda, N.Y.
1979.
32. Edwards, John B. Combustion formation and emission of trace species.
Ann Arbor Science. 1977.
33. NIOSH Criteria for recommended standard: Occupational exposure
to phosgene. HEW, PHS, CDC, NIOSH. NTIS PB No. 267 514. 1976.
34. Chemical and process technology encyclopedia. McGraw Hill. 1974.
35. U.S. EPA. Office of Research and Development. Carcinogen Assessment
Group. List of Carcinogens. April 22, 1980.
-------
Response to Comments - Heavy Ends (Still Bottoms) from
the Purification Column in the Production of Epichlorohydrin
Heavy ends (still bottoms) from the purification
column in the production of epichlorohydrin (K017) are listed
as hazardous because they contain a number of toxic constituents,
including epichlorohydrin. One commenter objected to the
Inclusion of epichlorohydrin as a constituent of concern in
this particular listing. The commenter argued that since
there are only two manufacturers at a total of only three
sites in the U.S., the likelihood that the waste constituents,
especially epichlorohydrin, will reach environmental receptors
and cause substantial hazard is small especially since the
commenter believes that epichlorohydrin is "readily degradable"
(i.e., the commenter believes that the statement In the
listing background document that "epichlorohydrin Is stable
enough to be transported to surface waters" (EPA BD-11 at
302) is unsupported by the absence of any hydrolysis rates,
microbial degradation rates, photolysis rates or oxidation
rates). Further, the coomenter believes that the Agency may
have misinterpreted the toxicological studies of epichlorohydrin
conducted by the Dow Chemical Co. The commenter therefore
recommends that epichlorohydrin be deleted as a basis for
listing waste K017.
The Agency strongly disagrees with the commenter's
unsubstantiated conclusion. While manufactured at only three
sites, these plants are all located on the Texas/Louisiana
-------
Gulf Coast area where the average yearly rainfall is heavy
and the groundwater is close to the surface. The waste
constituents, including epichlorohydrin, are also present in
substantial concentrations and are generated in large quanti-
ties. Therefore, should the large amounts of waste constituents
be exposed to a leaching media and be released as a result of
mismanagement, large areas of ground and surface waters may
be affected in the Texas/Louisiana Gulf Coast area. Additionally,
while information may be limited on hydrolysis rates, microbial
degradation rates, photolysis rates and oxidation rates,
epichlorohydrin has In fact been documented to migrate and
contaminate drinking water. Further, as noted in the back-
ground document, the primary disposal for this waste is by
Incineration prior to which the waste may be stored in holding
ponds or other temporary storage containers. Disposal by
incineration, if mismanaged, could result In the release of
toxic fumes when incineration facilities are operated in
such a way that combustion is incomplete; phosgene is an
example of a partially combusted chlorinated organic which
is produced by the decomposition of chlorinated organics by
heat.
finally, the Agency, in assessing the toxicity/carcino-
genicity of epichlorohydrin, used a number of studies,
including some conducted by the Dow Chemical Co. In arriving
at the conclusion that epichlorohydrin is toxic/carcinogenic.
Tn fact, before a chemical compound is deemed carcinogenic
-------
by CAG, it is subject to much detailed study of the literature,
thus, is unlikely that the Agency has misinterpreted the
coramenter's data. The Agency, therefore, will continue to
include epichlorohydrin as a constituent of concern in this
particular listing.
-------
LB:37-2
LISTING BACKGROUND DOCUMENTS
ETHYL CHLORIDE PRODUCTION
Heavy Ends from the Fractionation Column in Ethyl Chloride Production (T)
I. SUMMARY OF BASIS FOR LISTING
The heavy ends or bottoms from the fractionatlon column used in
the production of ethyl chloride contains 1,2-dichloroethane, trichlor-
ethylene and many other heavy chlorinated organics. The Administrator
has determined that these sludges are solid wastes which may pose a
present or potential hazard to human health and the environment when
improperly transported, treated, stored, disposed of or otherwise managed
and therefore should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the following
considerations:
(1) The fractionatlon column bottoms or heavy end sludges contain
3% ethyl chloride*, 22% dichloroethanes, 32Z trichloroethylen*,
and 43% heavy chlorinated organics. 1,2-Dichloroethane is a
suspected carcinogen and trichloroethylene and many of the
heavy chlorinated organics in the wastes have been Identified
by the Agency as exhibiting substantial evidence of being
carcinogenic.
(2) The wastes traditionally have been managed by land disposal.
Information obtained from telephone contacts with manufacturers**
indicates that some of the wastes are also incinerated in
thermal destruction facilities. The substances in the wastes,
if not managed properly, could be emitted to the air if the
wastes are inadequately Incinerated or Improperly land disposed,
or could leach from Improperly managed or designed landfills
and injection wells to reach humans and other environmental
receptors. Hexachlorobenzene (a typical heavy chlorinated
organic in column bottoms) has been shown to bioaccumulate in
animal and human tissues through inhalation following mismanagement
*The Agency is aware that ethyl chloride is highly ignitable, with a flash
point of -58°F. Generators are, of course, responsible for determining
if these wastes are ignitable, even though listed for toxlcity only.
**Those manufacturers requested to remain anonymous.
-------
during transportation and improper disposal. Trichloroethylene
(another waste component) has shown to have leached into well
water from waste disposal sites.
(3) A large quantity (a combined total of about 35,000 metric
tons per year) of these wastes are generated annually.
II. INDUSTRY PROFILE
In 1979, there were reported to be six plants in the U.S. with capacity
to produce about 330,000 metric tons/year of ethyl chloride.(x> Two of the
plants are located in Texas, two in Louisiana, one in New Jersey and one in
California. The average plant produces about 64,000 metric tons/year. The
range for individual plants is about 35,000 to 100,000 metric tons/year.
Since most of the ethyl chloride produced is used for the manufacturing of
tetraethyl lead, production is on the decline.
III. MANUFACTURING PROCESS DESCRIPTION
Most of the ethyl chloride produced is manufactured by catalytic
hydrochlorlnation of ethylene.^1) A process flow diagram is given in
Figure 1. Ethylene and anhydrous hydrogen chloride gases are mixed and
reacted at 35-40°C in the presence of an aluminum chloride catalyst. The
reaction is exothermic. The vaporized products are fed into a column or
"flash drum" where crude ethyl chloride is separated from heavier
polymers. The polymer bottoms are a salable by-product. Finally, the
crude ethyl chloride is refined by fractionation. The fractionation waste
(on figure 1), or heavy ends, is composed of 3% ethyl chloride, 22% dichloro-
ethanes, 32% trichloroethylene, and 43% heavy chlorinated organlcs.^2) This
is the waste stream listed in this document.
IV. WASTE GENERATION AND MANAGEMENT
The heavy ends from the fractionating column are generated at a rate
-------
OASIS: 1 KG ETHYL CHLORIDE
ETHTLENE 0.100
HYDROGEN 0.625
ClltOR10£
©
MIXER
ALUMINUM CHLORIDE (^.001)
REACTOR
SPCIIT
CATALYST
(TO RCGtritRATIOII)
SEPARATOR
ETHYL CHLORIDE 1.0
POLYHEH
BOTTOMS 0.0?
(HYDROrOUMtR OIL)
CTHYLCItt OICHLORtOC
FRACTlOflAriHG COLUMN
WASTE',
WASTE nun roAcTiorjATinc COLUMN-LIO.UIO
ETHYL CHLORIDE 0,003
DiCHLOnOETUAMES 0.02
TRlCHLOROtTHYLE.'lE 0.03
HEAVY CHLORINATED ORCAIIICS 0.04
Source i Reference _(Z)
I Echyl Chloride MnnuCocLuro
-------
of about .093 cons per con of ethyl chloride produced.The total
quantity of waste produced is, therefore, approximately 35,000 metric
tons per year (based on the 1979 production figures).
The wastes from ethyl chloride manufacture are usually combined for
disposal with chlorinated hydrocarbon wastes of similar composition
generated in the manufacture of chlorinated solvents (chloromethanes) at
the same plant site. In 1973, it was reported that the combined wastes
were sent to land disposal.C^) More recent information indicates that
some wastes are being incinerated in thermal destruction facilities
(see p. 1, above).
VI. DISCUSSIOM OF BASIS FDR LISTING
A. HAZARDS POSED BY THE WASTE
As indicated earlier, the heavy ends from fractlonation in
ethyl chloride production contain 22% d1chloroethanes, 321 trichloro-
ethylene, and 43% heavy chlorinated organics (such as hexachlorobutadlene,
and hexa.chlorobenzene(2}) many of which have been Identified by the Agency
as substances which exhibit substantial evidence of carcinogenicity.
Further, all of the chlorinated organic constituents in the waste
demonstrate acute aquatic toxiclty, generally showing increasing
toxlcity with increasing chlorination. Should these compounds reach
environmental recepters, the potential for resulting adverse effects
would be extremely high.
These waste constituents are capable of migration. The solubility
in water of these chlorinated compounds is quite high: dichloroethane -
8700 ppn(4), trichloroethylene - 1000 ppm(5)t and hexachlorobenzene -
500 ppa(4). -[he high solubilities of these constituents indicate a
-------
strong propensity to migrate from inadequate land disposal facilities.
Thus, improperly constructed or mangaged landfills (for example, landfills
located in areas with permeable soils, or with inadequate leachate control
practices) could easily fail to impede leachate formation and migration.
Once released from the matrix of the waste, these constitutents
could migrate through the soil to ground and surface waters utilized as
drinking water sources. A number of actual damage incidents documenting
the leaching of constituents from waste sites and subsequent to ground-
water contamination (see Damage Incidents pp. 6-8) have occurred. These
damage incidents also confirm that many of these chlorinated compounds
are environmentally persistent, since they obviously persist in the
environment long enough to reach environmental receptors.
Another problem which could result from Improper landfilling of
these wastes is the potential for contaminants to volatilize into the
surrounding atmosphere. Volatilized waste constituents, hexachlorobenzene
in particular, have caused actual damage (see Damage Incidents, 1-3, pp.
6-7). 1,2-Dichloroethane (60 mm Hg at 20"C)(4) is also highly volatile,
and therefore, could volatilize and thus present an air pollution problem
if improperly managed (for example, if landfilled without adequate cover).
More recent Information Indicates that some wastes are being
Incinerated in thermal destruction facilities. Inadequate incineration
conditions (temperature plus residence time) can result in incomplete
combustion and air emission of the harmful chemical substances contained
in the wastes as well as degradation products.
The large quantities (a combined total of about 35,000 metric tons
per year) of this waste disposed of annually is another area of concern
to the Agency. As previously indicated, there are substantial concentrations
-------
of these toxic constltutents (22% dichloroethanes, 32% trlchloroethylene,
43% heavy chlorinated organics) in the waste stream. The large quantities
of these contaminants pose the danger of polluting large areas of
ground and surface waters. Contamination could also occur for long
periods of time, since large amounts of pollutants are available
for environmental loading. All of these considerations increase the
possibility of exposure to the harmful constituents in the wastes.
B. DAMAGE INCIDENTS
The constituents found in the ethyl chloride fractionation column
wastes have been implicated in a number of past damage incidents.
There have been three damage incidents caused by one of the
substances present in the heavy ends, hexachlorobenzeneO):
(1) In Louisiana, hexachlorbenzene (HCB), a toxic industrial
by-product, was dumped in a rural landfill where it sublimated. Cattle
absorbed HCB in their tissues and 20,000 animals were quarantined by the
State Department of Agriculture (Lazar, 1975). This Incident illustrates
the ability of HCB to bioaccumulate.
(2) In Southern Louisiana, industrial wastes containing
hexachlorobenzene (HCB), a relatively volatile material, were transported
over a period of time to municipal landfills in uncovered trucks. High
levels of HCB have since been reported in the blood plasma of Individuals
along the route of transport. In a sampling of 29 households along the
truck route, the average plasma level of HCB was 3.6 ppb with a high of
23 ppb. The average plasma1 level of HCB in a control group was 0.5 ppb
with a high of 1.8 ppb (Farmer et al., 1976). This incident illustrates
the ability of HCB to get into the blood stream from inhalation.
-------
(3) Hexachlorobenzene wastes were disposed in landfill sites
in southern Louisiana. Some of the waste was covered following disposal,
and some was not. Soil and plant samples taken near the landfill area
showed a decreasing HCB content as distance from the landfill increased.
The HCB levels in the plasma of landfill workers was reported to range
from 2 to 345 ppb; the average level in a control group was 0.5 ppb with
a high of 1.8 ppb. A study of the land disposal of the hexachlorobenzene
wastes indicated that uncovered wastes released 317 kilograms per hectare
per year (kg/ha/yr). This incident further illustrates the ability of
HCB to present a hazard due to improper landfill management and inhalation.
There have also been three damage incidents resulting from the
mismanagement of trlchloroethylene, another waste constituent.
(1) In one incident in Michigan, an automotive parts manu-
facturing plant routinely dumped spent degreasing solutions on the open
ground at a rate of about 1000 gallons per year from 1968 to 1972.
Trichloroethylene was one of the degreasing solvents present in the spent
solutions. Beginning in 1973, trlchloroethylene in nearby residential
wells was detected at levels up to 20 mg/1. The dump site was the only
apparent source of possible contamination (*>). This Illustrates the
migratory potential and persistence of Improperly disposed trichloro-
ethylene.
(2) In a second incident, also in Michigan, an underground
storage tank leaked trIchloroethylene which was detected in local ground-
water up to four miles away from the land(^). This also Illustrates the
migratory potential of trichloroethylene.
(3) In April of 1974, a private water well in Bay City, Michigan
became contaminated by trichloroethylene. The only nearby source of this
-------
chemical was Che Thomas Company (which replaced the well with a new one).
The company claimed that, although It had discharged trlchloroethylene
Into the ground in the past, it had not done so since 1968. Nevertheless,
in May, 1975, two more wells were reported to be contaminated with tri-
chloroethylene at concentrations of 20 mg/1 and 3 mg/1, respectively.(3)
This further Illustrates the migratory potential and persistence of this
compound.
C. Health and Ecological Effects
1. 1,2-Dichloroethane
Health Effects - 1,2-Dichloroethane is a carcinogen.(9) In
addition, this compound and several of its metabolites are highly mutagenic
(10, 11). l,2-Dichloroethane crosses the placental barrier and is embryo-
toxic and teratogenic ^^ - 16) } an
-------
u, EPA's Office of Water and Waste Management under the Safe Drinking
Water Act and by the Office of Toxic Substances under the Toxic Substances
Control Act.
Industrial Recognition of Hazard - Sax, In Dangerous Properties
at Industrial Materials, rates 1,2-dichloroethane as highly toxic upon
ingestion and inhalation.
2. Tricoloroethylene
Priority Pollutant - Trichloroethylene is listed as a
priority pollutant in accordance with §307(a) of the Clean Water Act of
1977.(20)
Health Effects - Trichloroethylene is identified as a
carcinogen.(39) It has also been identified by the Agency as a compound
exhibiting substantial evidence of carcinogenicity. Trichloroethylene
has been shown, both through acute and chronic exposure, to produce
disturbances of the central nervous system and other neurological
ef fects(",23, 24). Tr Ichloroethylene has been found to cause
heptacellcer cancinoma in mice. Additional information on the adverse
effects of trichloroethylene can be found in Appendix A.
3. Hexachlorobenzene (HCB)
Priority Pollutant - HCB is listed as a priority pollu-
tant under Section 307(a) of the Clean Water Act.
Health Effects - Hexachlorobenzene (HCB) has produced cancers
in animal species(^5,26) an^ has been recognized by the Agency to be
carcinogenic.(39) Other animal studies have shown that HCB crosses
the placental barrier to produce toxic effects and was lethal to fetuses.(27)
Hexachlorobenzene is stored for long periods in body fat. Chronic exposure
-y-
-------
to HCB has been shown to result in damage to the liver and spleen.(28)
It has also been demonstrated that at doses far below those which are lethal,
HCB enhances the body's capability to toxify, rather than detoxify, other
foreign organic compounds present in the body through its metabolism.(29)
The recommended ambient criterion^31) level for HCB in wastes
is 1.25 nanograms per liter. Actual measurements, on the other hand, of
finished drinking water in certain geographic areas have been measured
at levels up to six times the recommended criterion designed to protect
human health, demonstrating the mobility and persistence of the material.(38)
Ecological Effects - Hexachlorobenzene is very persistent.(32)
It has been reported to move through the soil into the groundwater.(21)
Movement of hexachlorobenzene within surface water systems is projected
to be widespread.(30) Movement to this degree will likely result in
exposure to aquatic life forms in rivers, ponds, and reservoirs.
Similarly, potential exposure to humans Is likely where water supplies
are drawn from surface waters.
Hexachlorobenzene is likely to contaminate accumulated bottom
sediments within surface water systems and bioaccumule in fish and other
aquatic organisms.(30)
Regulatory Regulation of Hazard - Ocean dumping of hexa-
chlorobenzene is prohibited. An interim food contamination tolerance of
0.5 ppm has been established by FDA.
Additional Information on the adverse effects of hexachlorobenzene
can be found in Appendix A.
4. Hexaclorobutadiene(HCBD)
Priority Pollutant - Hexachlorobutadiene is considered a priority
pollutant under Section 307(a) of the CWA.
-------
Routes of Exposure - oral-very toxic
Health Effects - Hexachlorobutadiene (HCBD) has been found
to be carcinogenic in animals.(23,39) Upon chronic exposure of animals
by the DOW Chemical Company and others, the kidney appears to be the
organ most sensititve to HCBD.(34,35>36«37)
The proposed human health criterion level for this compound
in water is .77 ppb.
Ecological Effects - Movement of HCBD within surface water
systems is projected to be widespread.(30)
HCBD is likely to contaminate accumulated bottom sediments
within surface water systems and is likely to bioaccumulate in fish and
other aquatic organisms.C3^)
The USEPA (1979) has estimated that the BCF Is 870 for the
edible portion of fish and shellfish consumed by Americans.
Hexachlorobutadiene is persistent In the environment.(32) it
has been reported to move through soil into groundwater.
Industrial Recognition of Hazard - Hexachlorobutadiene is considered
to have a high toxic hazard rating via both oral and Inhalation routes (Sax,
Dangerous Properltles of Industrial Material).
Additional information on the adverse effects of hexachlorabutadiene
can be found in Appendix A.
-330-
-------
REFERENCES
1. Stanford Research Institute. 1979 Directory of chemical producers -
U.S.
-------
14. Vozovaya, M. The effect of low concentrations of gasoline,
chloroethane and their combination on the generative function
of animals and on the development of progeny. Gig. Tr. Prof.
Zabo. 7:20-23. 1975,
15. Vozovaya, M. Effect of low concentrations of gasoline, dichloro-
ethane and their combination on the reproduction function of
animals. Gig. Sanlt. 6:100-102. 1976.
16. Vozovaya, M.A. The effect of dichloroethane on the sexual cycle
and embryogenesis of experimental animals. Akush. Genecol.
(Moscow) 2:57-59. 1977.
17. Urusova, T.P. (About a possibility of dichloroethane absorption
Into milk of nursing women when contacted under Industrial
conditions.) Gig. Sanit. 18(3):36-37. 1953. (Rus.)
18. Parker, J.C., et al. Chloroethanes: A review of toxlcity.
Amer. Indus. Hyg. Assoc. J. 40:A 46-60. March, 1979.
19. U.S. EPA. Chlorinated ethanes: Ambient water quality criteria.
NTIS PB No. 297 920. 1979.
20. U.S. EPA. State Regulations Files. Hazardous Waste State Programs,
WH-565, U.S. EPA, 401 M St., S.W., Washington, D.C. 20460. Contact
Sam Morekas. (202) 755-9145. January, 1980.
21. Not used in text.
22. Nomiyama, K., and H. Nomiyama. Metabolism of trichloroethylene
in human sex differences in urinary excretion of trichloroacetic
acid and trlchloroethanol. Int. Arch. Arbeitsmed. 28:37. 1971.
23. Bardodej, A., and J. Vyskocil. The problem of trichloroethylene
in occupational medicine. AMA Arch. Ind. Health 13:581. 1956.
24. McBirney, B.S. Trichloroethylene and dichloroethylene poisoning.
AMA Arch. Ind. Hyg. 10:130. 1954.
25. Cabral, J. R. P., et al. Carcinogenic activity of hexachlorobenzene
in hamsters. Nature (London) 269:510. 1977.
26. Cabral, J. R. P., et al. Carcinogensis study in mice with hexachloro-
benzene. Tox. Appl. Paramacol. 45:323. 1978.
27. Grant, D. L., et al. Effect of hexachlorobenzene on reproduction
in the rat. Arch. Environ. Contam. Toxic. 5:207. 1977.
28. Koss, G., et al. Studies on the toxicology of hexachlorobenzene.
III. Observation in a long-term experiment. Arch. Toxicol.
40:285. 1978.
-------
29. Carlson, G. P. Induction of cytochrome P-450 by halogenated
benzenes. Blochem. Pharmacol. 27:361. 1978.
30. U.S. EPA. Technical support document for aquatic fate and transport.
U.S. EPA Environmental Research Lab. Athens, GA. 1980.
31. U.S. EPA. Chlorinated benzenes: Ambient water quality criteria.
NTIS PB No. 297 919. 1979.
32. U.S. EPA. Water-related environmental fate of 129 priority
pollutants. EPA No. 440/4-79-029b. 1979.
33. Kociba, R. J. Results of a two-year chronic toxicity study with
hexachlorobutadiene in rats. Amer. Ind. Hyg. Assoc. 38:589. 1977.
34. Kociba, R.J., et. al. Toxicologic study of female rats administered
hexachlorabutadiene or hexachlorobenzene for 30 days. Dow Chemical
Company. 1971.
35. Schwetz, et al. Results of a reproduction study in rats fed diets
containing hexachlorobutadiene. Toxicol. Appl. Pharmacol. 42:387.
1977.
36. Schroit, et. al. Kidney lesions under experimental hexachlorobutadiene
poisoning. Aktual. Vpo. Gig. Epidemiol. 73. CA:81:73128F (translation),
1972.
37. Hobbs, F.D., and C.W. Stuewe. Emission control options for the
synthetic organic chemicals manufacturing industry: Carbon tetra-
chloride and perchloroethylene, (hydrocarbon chlorinolysis process),
abbreviated product report. EPA Contract No. 68-02-2577. March, 1979.
38. U.S. EPA. Preliminary assessment of suspected carcinogens in
drinking water. Report to Congress. U.S. EPA. Washington, D.C.
EPA No. 560/4-75-003. 1975.
39. U.S. EPA. Office of Research and Development, Carcinogen Assessment
Group List of Carcinogens. April 22, 1980.
-------
Response to Cnsrsents - Heavy Ends or Distillation Residues from the
Production of Ethyl Chloride
One coramentar requested that the Agency reassess Its interpretation of
what materials actually constitute waste in the production of ethyl chloride.
The commenter pointed out that many of these materials are not discarded and
never become wastes; instead, they are further processed within a short
time to other products and manufacturing intermediates.
In reviewing the available information, the Agency has evidence to
indicate that these wastes traditionally have been managed by land
disposal. Additionally, information obtained from telephone contacts
with manufacturers of ethyl chloride indicates that some of these wastes
are also incinerated in thermal destruction facilities. Therefore, these
wastes are "discarded" and, thus, meet the definition of a solid waste
(§261.2) and will continue to be listed as hazardous. However, this
waste is not always discarded, as evidenced by the comments received
(i.e., these wastes may be used, reused, recycled or reclaimed). As
discussed in the preamble to the Part 261 regulations promulgated on Hay
19, 1980 (45 FR 33091 - 33095), the Agency has concluded that it does
have Jurisdiction under Subtitle C of RCRA to regulate waste materials
that are used, reused, recycled or reclaimed. A large number of comments
have been received, however, which challenge this conclusion. The Agency
is giving these comments serious consideration, but has not presently
finalized this portion of the regulations. Therefore, until a final
decision is reached with respect to materials which are used, reused,
recycled or reclaimed, the following guidance is offered to individual
plants to assist them in determining their responsibilities under the
hazardous waste regulations:
-l*.
-33V-
-------
o If the listed waste is always discarded at the individual
plant, the waste always is subject to the full set of
hazardous waste regulations.
o If the listed waste Is sometimes discarded at a particular
plant, but sometimes used, reused, recycled or reclaimed,
(not used as an intermediate) the waste would only be subject to
the full set of hazardous waste regulations when discarded.
When used, reused, recycled or reclaimed the waste would be
subject to the special requirements for listed wastes contained
in §261.6(b) of the hazardous waste regulations (45 FR 33120).
o If the listed waste is typically processed through the next step
of the process within a short time, the material does not meet
the definition of a solid waste (i.e., is an intermediate product),
and is therefore not subject to the hazardous waste regulations
(45 FR 33119, and see discussion at 45 FR 33093-094).
-335--
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ORD-A-4
LISTING BACKGRO'. NO DOCUMENT
ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER PRODUCTION
Heavy ends from the distillation of ethylene dichlorlde in
ethylene dichloride production. (T)
Heavy ends from the distillition of vinyl chloride in vinyl
chloride monomer production. (T)
I. Summary of Basis for Listin;
The heavy ends from the disDilation of ethylene dichloride in
ethylene dichloride (EDC) production, ind the distillation of vinyl chloride
in production of vinyl chloride monome (VCM) contain toxic chemicals
and chemicals that are carcinogenic, mi:agenic, or teratogenic. The
waste constituents of concern are ethyl-ne dichloride, trichloroethanes
(1,1,1/1,1,2), tetrachloroethanes (1,1,'.,2/1,1,1,2), vinyl chloride,
vinylidene chloride, chloroform, and ca ion tetrachloride.
The Administrator has deterraiiid that the heavy ends generated
during the purification (distillation) c: crude EOC and VCM Is a solid
waste stream which may pose a substanti ' present or potential hazard to
human health or the environment when in.;operly transported, treated,
stored, disposed of, or otherwise manag-5, and therefore should be subject
to appropriate management requirements nder Subtitle C of RCRA. This
conclusion Is based on the following crsiderations:
-------
1. Of the compounds present in the ethylene dlchloride
and vinyl chloride monomer wastes, many are known or
suspected carcinogens, and several are mutagenic and/or
teratogenic.
2. Disposal of these wastes is accomplished partially by use
of landfills, which, if Improperly designed or operated,
could result in leaching of hazardous substances Into
ground or surface water and subsequent risk of human
exposure to the dangerous components of the waste*
3. Hydrocarbons, such as those predominating in this waste,
are highly mobile and persistent in the soil profile
and saturated subsurface, and have been responsible for
many reported cases of ground water pollution. Enhancing
this potential for ground and surface water pollution is
the fact that most of this waste is produced and disposed
of in Gulf coastal areas where water tables and rainfall
are generally high.
4. The total combined waste generation for the balanced EDC/VCM
process is estimated to be 170-370 million Ib./yr. Such a
large volume of waste containing dangerous constituents
justifies imposition of strict controls.
II. Source of the Wastes and Typical Disposal Practices
A. Profile of the Industry (1,2)
Ethylene dichloride (EDC) and vinyl chloride monomer (VCM)
are produced at 20 plants within the United States. Table 1 presents a
list of EDC and VCM producers. EDC is produced by both the direct
chlorination of ethylene and the oxychlorination of ethylene. VCM is
produced by the thermal cracking (dehydrochlorination) of EDC. The waste
streams listed in this document thus arise in many cases out of a common
production process. Figure L presents a summary of the chemical reactions
involved in producing EDC and VCM.
'reduction in 1978 was 6.346 million metric tons for EDC
and 3.776 million metric tons for VCM (Table 1).
-y-
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TABLE 1. PRODUCERS AND 1978 PRODUCTION CAPACITIES OF
ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER
(metric totis/yr) (1, 2)
Company
Allied
Borden
Conoco
Diamond Shamrock
Dow
Ethyl
Goodrich
PPG
Monochem
Shell
Stauffer
Union Carbide
Vulcan
Plant location
Baton Rouge, Louisiana
Gelsraer, Louisiana
Lake Charles, Louisiana
Deer Park, Texas
LaPorte, Texas
Freeport, Texas
Oyster Creek, Texas
Plaqueraine, Louisiana
Baton Rouge, Louisiana
Pasadena, Texas
Calvert City, Kentucky
Lake Charles, Louisiana
Guayanilla, Puerto Rico
Gelsmar, Louisiana
Deer Park, Texas
Norco, Louisiana
Long Reach, California
Taft, Louisiana
Texas City, Texas
Geismar, Louisiana
Ethylene Vinyl chloride
dichloride monomer
272,000
-
544,000
145,000
-
726,000
499,000
590,000
318,000
113,000
454,000
585,000
485,000
-
635,000
544,000
141,000
68,000
68,000
159,000
136,000
136,000
318,000
-
454,000
91,000
318,000
363,000
136,000
-
454,000
181,000
277,000
136,000
381,000
318,000
77,000
-
-
—
TOTALS
6,346,000
3,776,000
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ETHYLENE DICHLORIDE VIA DIRECT CHLORINATION OF ETHYLENE
CH2=CH2 + C12 -> CH2C1CH2C1 (1)
ETHYLENE DICHLORIDE VIA OXYCHLORINATION OF ETHYLENE
CH2=CH2 + 1/202 + 2HC1 -> CH2C1CH2C1 + H2n (2)
VINYL CHLORIDE MONOMER VIA THERMAL CRACKING OF ETHYLENE DICHLORIDE
CH2C1CH2C1 -> CH2=CHC1 + HC1 (3)
ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER
VIA THE BALANCED PROCESS
2CH2=CH2 + 2C12 -> 2CH2C1CH2C1 (4)
I
4CH2C1CH2C1 -> 4CH2=CHC1 + 4HC1 (5)
I I
I I "
I T
2CH2=CH2 + 02 + 4HC1 -> 2CH2C1CH2C1 + 2H20 (6)
Figure 1. Alternative methods of producing ethylene
dichloride and vinyl chloride monomer.
-------
Manufacturing Process, Waste Composition and Waste Management (1, 65, 66)
As noted above, ethylene dlchloride (EDO) is produced by two
processes: Che direct chlorination of ethylene and the oxychlorination of
ethylene. Vinyl chloride monomer (VCM) is produced by the thermal cracking
of EDC yielding hydrogen chloride (HCL) as a by-product. In the "balanced
process", ethylene is converted to EDC in two equally sized production
units utilizing direct chlorination and oxychlorination of ethylene. The
HC1 by-product produced by the thermal cracking of EDC to form VCH and by
•direct ethylene chlorination is used as feed for the oxychlorination
unit. The flow diagram for the balanced process is given in Figure 2.
For those VCM plants that purchase EDC, the by-product HCL is recovered
and sold or used in other hydrochlorlnation processes.
1. EDC Production by Direct Chlorination of Ethylene
The chemical reaction for the direct chlorination of ethylene
to produce ethylene dichloride is equation (1) in Figure 1. Ethylene is
chlorinated catalytically in a vapor- or liquid-phase reaction, in the
presence of ethylene dibroznide to prevent polychlorination, at temperatures
ranging between 50°C and 150°C and at 10 to 20 psig pressure. The catalysts
used are metallic chlorides; e.g., ferric, aluminum, copper, or antimony.
Commercially, ferric chloride is employed as a catalyst in the liquid-phase
system. Yields are reported at approximately 90% based on ethylene.(3)
Chlorine is mixed with ethylene and fed to a reactor where the
reaction takes place in the liquid phase with an excess of EDC. The
reaction is exothermic (217.6 MJ/mole or 52 kcal/mole), and heat Is
removed by jacketed walls, internal cooling coils, or external heat
-3*0-
-------
CHLORINE ETHYLENE
DILUTE
NaOH
VEN5
AIR
CHLORINAT10N
REACTOR
VENT SCRUSBE3
OXYCHLORINATION
REACTOR
i
v —
D
6 TO 8%
NaOH
AQUEOUS
WASTE
" T\
CAUSTIC WASH
1
i
ALtO
n
W3UEOU
M.INS W
S
ASTc
X
EDC DISTILLATION
HEAVY
EN2S
TO
SHIPPING
VCM DISTILLATION
HEAVY
ENDS
HEAVY
WASTES
LIGHT ENDS AND
WATER COL.
LIGHT ENDS TO w/TER
RECYCLE WATCR
2ND DISTILLATION
COLUMN
PURIRED EDC
VCM
DISTILLATION
VCM
RECYCLE HCI
Figure 2. PRODUCTION OF EDC & VCM
Modified frora references 1, 65, 66
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exchange. A liquid and a vapor stream are obtained from the reactor.
The overhead vapor effluent from the reactor is condensed in a
water-cooled or refrigerated heat exchanger to condense any ethylene
dichloride present in the vapor stream. Noncondensables are sent through
a scrubber fed with diluted sodium hydroxide to remove small amounts of
hydrogen chloride and chlorine gas before venting to the atmosphere.
Liquid effluent from the reactor, consisting mainly of crude
ethylene dichloride, is cooled, then washed with a 6% to 8% caustic solution.
Water is removed either by coalescing and phase separation, or by phase
separation and light ends distillation. Ethylene dichloride is obtained
as overhead in a heavy ends distillation column. Based on common practice
in the chlorinated hydrocarbon industry, these distillation bottoms, consist-
ing of heavy ends, are sent to disposal or used as a feedstock in another
process; this is the first waste stream of concern in this document.
A list of the pollutants found in the distillation column heavy
ends in the direct chlorination process are presented in Table 2, along
with their amounts.
Table 2. HEAVY ENDS FROM DIRECT CHLORINATION [1]
Ethylene dichloride - 3.3 Ib/ton of ethylene dichloride
1,1,2 Trichloroethane - 5.39 Ib/ton of ethylene dichloride
Tetrachloroethane - 5.39 Ib/ton of ethylend dichloride
Tars - trace
-------
2. EDC Production by Oxychlorination of Ethylene
The chemical reaction for the oxychlorination of ethylene to pro-
duce ethylene dichloride follows is presented as equation (2) in Figure 1.
Air and hydrogen chloride react with ethylene in a fluidlzed-
or fixed-bed catalytic process to produce ethylene dichloride. The
catalyst used is a mixture of copper chloride and other chlorides.
Reactor temperature varies between 1RO°C and 280°C, and pressure ranges
from 340 to 680 kPa gauge (50 to 100 psig). Yields are over 90% based
on ethylene, depending on the presence of excess ethylene or hydrogen
chloride. Excess hydrogen chloride favors the reaction.
i
Stoichioraetric amounts of ethylene, anhydrous hydrogen chloride,
and .atr'ac'g'-'f^d to a catalytic reactor. The air is compressed and preheated
prior, to eiygejring the reactor as a means of initiating the reaction. Con-
verstxjjh.'of ^thylene is virtually complete in one pass through the reactor.
The reaction is highly exothermic, and heat is recovered as steam, with
internal cooling, using coils or fixed-bed multitube reactors which resemble
a heat exchanger, with the catalyst contained inside the tubes, while
coolant flows through the shell.(3)
Effluent from the reactor is cooled by either direct water quench
or indirect heat exchange. Condensed effluent is sent to a phase separator.
Noncondensable gases consisting mainly of nitrogen are contacted in an
absorber with either water or aromatic solvent for removal of HC1 and
recovery of ethylene dichloride before venting to the atmosphere. The
organic liquid product obtained in the phase separator joins the stream
of Che product from direct chlorlnatlon and is contacted with aqueous
-------
caustic soda to neutralize any remaining hydrogen chloride.
Effluent from the neutralizer is distilled for removal of light
ends consisting of water and light chlorinated hydrocarbon impurities. The
light ends are recovered as overhead and sent to waste disposal. Bottoms
from the distillation column, which consist mainly (96% to 98%) of ethylene
dichloride, are sent to the final products purification or distillation
column. Pure ethylene dichloride is obtained as overhead and sent to storage.
The heavy ends from the EDC purification (or distillation) column are the
waste stream at issue here. Table 3 indicates pollutants contained in the
EDC heavy ends from the oxychlorination process.
Table 3. HEAVY ENDS FROM OXYCHLORINATION [2]
Ethylene dichloride -4.6 Ib/ton of ethylene dichloride
Trichloroethane - 4.6 Ib/ton of ethylene dichloride
Heavy chlorinated compounds - 5.8 Ib/ton of ethylene dichloride
Disposal of these wastes is expected to be by incineration or landfllling,
based on common practice in the chlorinated hydrocarbon Industry or used
as a feedstock In another process.
3. VCM Production
Vinyl chloride is produced from purified EDC. The purified
EDC is thermally cracked to yield crude VCM and hydrochloric acid (HC1).
The HC1 is recovered and used as feed to the oxychlorination reactor.
* This waste stream is not presently listed as hazardous.
-------
VCM is distilled to yield pure VCM. Heavy ends from VCM distillatioa
are disposed of as waste or are recycled for additional thermal cracking
and/or further chLorination to form other chlorinated organic products.
It should be noted that the balanced process generates both EDO
heavy ends and VCM heavy ends. In an integrated plant some heavy ends
from the VCM plant are cycled to the ethylene dichlorlde still. In a
non-Integrated plant, they are stripped of the ethylene dichlorlde,
which is to be recycled to the VCM unit. In either case, the ultimate
residue when wasted is expected to be disposed of by incineration or
landfill, based on common practice in this industry (i.e., the chlorinated
hydrocarbon industry).
The bottoms from the ethylene dichloride plant are partially
cycled to a downstream chlorination unit where-vth'4/iss.ldual heavy ends
are partially retained and partially s£nt toJ^SJJH^E 'Based on common
industry practice, disposal is expected to be by incineration or land-
fill.
The heavy ends waste discharge (for both EDC heavy ends and VCM
heavy ends) for a plant producing ethylene dichlorlde and vinyl chloride
monomer by the balanced process is estimated to consist principally of
the components listed in Table 4 below:
Table 4 Estimated Heavy Ends Waste Discharge for EDC
and VCM Production by the Balanced Process
Ethylene Dichlorlde 3-5 Ib/ton of EDC
Trichloroethane 4-5 Ib/ton of EDC
Tetrachloroethane 2-5 Ib/ton of EDC
Heavy Chlorinated Compounds (Tars) 3-6 Ib/ton of EDC
-------
This estimate assumes that the major constituents of EDO heavy
ends and VCM heavy ends will be the same - a reasonable supposition since
not all the carbon bonds in the EDC feedstock will be cracked by
dehydrochlorination, so that these waste constituents will remain to be
separated as heavy ends in the VCM distillation step.
The quantities shown in Table 4 are averages derived from the heavy
end composition data shown in Tables 2 and 3. Relative concentrations of
major waste constituents may be determined from the amounts of constituents
shown in Tables 2-4.
In addition to the major components listed in Table 4, the combined
ethylene dichloride - vinyl chloride monomer heavy ends waste discharge also
is expected to contain lesser quantities of the following compounds:
Vinyl Chloride
Vinylidene Chloride
Trichloroethylene
Tetrachloroethylene
Chloroform
Carbon Tetrachloride
The postulated reaction pathways for these constituents (briefly
stated) are as follows. Vinyl chloride is likely to be present since it
is the product and would not be removed completely in the distillation step.
Vinylidene chloride would result from the dehydrochlorination of trichloro-
ethylene (a major constituent of EDC heavy ends) trichloroethylene would
result from the dehydrochlorination of tetrachloroethane (another major
-------
constituent of EDC heavy ends). Trtchloroethylene could in turn be
chlorinated to form tetrachloroethylene. Chloroform could result from
the dehydrochlorination of feedstock EDC, and could in turn be chlorinated
to form carbon tetrachloride.
III. Discussion of Basts for Listing
A. Hazards Posed by the Waste
1. Quantities of Wastes Generated
Based on annual production capacities of approximately 14
billion pounds (6.35 million metric tons) for ethylene dichloride inter-
mediate and 8.3 billion pounds (3.78 metric tons) for vinyl chloride
monomer end product, as much as 30 million pounds of ethylene dichloride
and 30 million pounds each of trichloroethane and tetrachloroethane may
be present in the heavy ends waste generated from the production of these
substances each year. Very large quantities of other waste constituents
will also be generated. Thus, extremely large quantities of waste consti-
tuents are available for environmental release. Additionally, ethylene
dichloride, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane—also
present in high concentrations—are known carcinogens, while 1,1,1-tri-
chloroethane and 1,1,1,2-tetrachloroethane, also present in high concen-
trations, are suspected carcinogens. In addition, the waste also contains
lesser quantities or vinyl chloride, vinylidene chloride, tetrachloroethylene,
trichloroethylene, and chloroform, all of which are known carcinogens. A
number of the compounds found in this waste also exhibit mutagenic or
tetraogenic effects, including 1,1,1,-trichloroethane, 1,1,2-trichloroethane,
and the tetrachloroethanes. Should release occur, large-scale contamination
of the environment is likely. Moreover, contamination will be prolonged,
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-BH7-
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since large amounts of the pollutants are available for environmental loading,
Attenuative capacity of individual disposal sites also could be exhausted
due to the large quantities of pollutants available. These considerations
themselves justify hazardous waste listing status.
Further, as shown below, the waste constituents are capable of
migration, mobility, and persistence if improperly managed. Indeed, numer-
ous damage incidents involving these waste constituents have actually
occurred.
2. Exposure Pathways of Concern
Based on common industry practice, current methods for disposal
of this waste are by incineration or landfilling. Improper management
of either method can result in substantial hazard. Improper incineration
could result in serious air pollution through release of toxic fumes.
This may occur when Incineration facilities are operated in such a way
that combustion is incomplete (i.e., inadequate conditions of temperature,
mixing and residence time) resulting in airborne dispersion of hazardous
vapors containing partially combusted organlcs, newly formed organic
compounds, and hydrogen chloride. Phosgene is an example of a partially
chlorinated organic which is produced by the decomposition or combustion
of chlorinated organics by heat.(6^1 62) phosgene has been used as a
chemical warfare agent, and is extremely toxic. Improper incineration
thus could present a significant opportunity for exposure of humans,
wildlife and vegetation in the vicinity of these operations to risk
through direct contact.
Improper disposal in landfills can also lead to substantial
environmental hazard. Migration to and subsequent contamination of ground
-vf-
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and surface waters Is a particular danger. All of Che waste constituents
of concern tend to be highly soluble in water (with the exception of
vinyl chloride, which Is a gas), with solubilities ranging from 800 mg/1
(carbon tetrachloride) to 8700 mg/1 (ethylene dichloride (Appendix B).
Thus, these waste constituents will tend to migrate in high concentrations
under even relatively mild environmental conditions. Improperly sited
landfills (for example, in areas with highly permeable soils, or in areas
where soil is low In attenuative capacity) or improperly managed (for
instance, landfills with Inadequate leachate collection or monitoring
systems) could easily prove inadequate to prevent waste migration.
Once these waste constituents migrate from the waste, they are
likely to persist In groundwater for long periods of time (App. B).
Thus, Improperly designed landfills could well lead to human and
environmental exposure, and attendant substantial hazard in light of the
hazardous nature of the waste constituents.
An air inhalation pathway is an additional exposure route of
concern. Of the waste constituents, ethylene dichloride, the trichloro-
ethanes, the tetrachloroethanes, chloroform, and carbon tetrachloride all
tend to be relatively to highly volatile, with vapor pressures ranging
from 5mm Hg. (tetrachloroethanes) to 116 mm Hg. (chloroform) (App. B.).
Vinyl chloride is already a gas, so it also poses a substantial air pollu-
tion hazard. Inadequate site cover could therefore lead to escape of
volatile waste constituents and resulting contamination of air In the
vicinity surrounding the site.
There is, therefore, a strong potential that landfilling of
these wastes will ultimately result in pollution of nearby groundwater
-------
by ethylene dlchloride, the trichloroethanes, the tetrachloroethanes,
and other similar waste components. This is enhanced by the fact that
most of this waste is produced and, presumably, disposed of in Gulf
coast areas (see Table 1) where water tables are generally shallow and
rainfall is relatively high.
There is also the possibility that components of this waste
could enter surface waters, either by mishandling of the waste prior to
disposal or by migration of individual compounds through groundwater to
points of discharge to surface waters.
In surface waters, the chlorinated ethanes and ethylenes will
tend to volatize due to their high vapor pressures. However, traces will
probably remain for extended periods of time. Chloroform, one of the
waste components, in fact, has been shown to persist almost indefinitely
in surface water. (App. B)
3. Actual Damage Incidents
Actual damage incidents confirm these waste constituents'
ability to migrate and persist and cause substantial hazard if improperly
managed. The chlorinated ethanes and ethylenes-such as those which
predominate In this waste-are the classes of organic pollutants being
identified far more often than any other pollutant types in current
groundwater pollution incidents. For example, ethylene dichloride,
(1,2-dichloroethane) has been found in groundwater from public water
supply wells at Bedford, Massachusetts, where the source is believed to
be industrial operations upstream.(4)
At the Llangollen landfill in Delaware, dichloroethane (ethylene
-yi-
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dichloride and/or 1,1-dichloroethane) has been found migrating from the
landfill through nearby ground water.(5) In Hew Jersey, seepage from
landfllled wastes near the CPS chemical company resulted in contamination
of nearby ground water by trichloroethane and tetrachloroethane.(6)
1,1,1-Trichloroethane was detected in ground water at Acton, Massachusetts,
where the source is believed to be a settling lagoon at a nearby manufacturing
plant.(4) Extensive contamination of ground water by trichloroethylene
has also been reported in southeast Pennsylvania.(7) Trichloroethylene
has also been found in school and basement air, and in residential
basements in Love Canal.(64)
Field reports such as these clearly indicate that the release of
low molecular weight chlorinated hydrocarbons into the soil will result
in pollution of groundwater with the potential risk of substantial adverse
health effects. This is further substantiated by recent laboratory studies
in which 1,1,2-trichloroethane, chloroform, and similar compounds were
observed to move through a four foot profile of sandy soil with little
retardation relative to water and no apparent degradation.(8) Also,
field studies in the Netherlands and California have shown that low
molecular weight chlorinated hydrocarbons, such as those occurring
in this waste, are highly mobile and persistent in the saturated ground
water environment.(9, 10)
In light of the highly dangerous character of the constituents of
concern in the waste, some of which are likely to be present in high
concentrations, the Agency would require strong assurance that these
constituents will not migrate and persist if improperly landfilled or
Incinerated. Data In fact indicate that these constituents may well
migrate and persist via a number of exposure pathways. Thus, these
-------
wastes clearly should be listed as hazardous.
B. Health and Ecological Effects
1. Ethylene Dichloride
Health Effects - Ethylene dichloride (1,2-dlchloroethane)
has been shown to cause cancer In laboratory animals.(11) Ethylene
dichloride is extremely toxic (oral rat LD5Q » 12 mg/Kg). In addition,
this compound and several of its metabolites are highly mutagenic.(12)
1,2-Dichloroethane crosses the placental barrier and is embryo toxic and
teratogenic.(13-17) It has also been shown to concentrate in milk.(18)
Exposure to this compound can cause a variety of adverse health effects
including damage to the liver, kidneys and other organs. It can also
cause internal hemorrhaging and blood clots.(19) Ethylene dichloride
(1,2-dlchloroethane) is designated as a priority pollutant under section
307(a) of the CWA. Additional information and specific references on
adverse effects of ethylene dichloride can be found In Appendix A.
Ecological Effects - Values for a 96 hour static LCsg
for bluegills range from 256 to 300 mg/l.(2°)
Regulatory Recognition of Hazard - OSHA has set the
TWA at 50 ppm. DOT requires the containers for this chemical to carry a
warning that it is a flammable liquid. The Office of Air Pollution and
Noise has completed the preregulatory assessment of 1,2-dichloroethane
under sections 111 and 112 of the Clear Air Act. Preregulatory assessments
are also being conducted by EFA's Office of Water and Waste Management
under the Safe Drinking Water Act and by the Office of Toxic Substances
under the Toxic Substances Control Act. Ethylene dichloride is currently
being studied by the Consumer Product Safety Commission under the Consumer
Product Safety Act.
-V-
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Industrial Recognition of Hazard - Sax in Dangerous Properties
of Industrial Materials rates 1,2-dichioroethane as highly toxic upon
ingestion and inhalation.
2. 1,1,1-Trlchloroethane (Methyl Chloroform)*
Health Effects - The area of greatest health concern
regarding 1,1,1-trichloroethane exposure involves its potential for
rautagenlc, teratogenic and carcinogenic effects. In vitro studies
have Indicated that 1,1,1-trichloroethane is slightly nutagenlc with or
without activation.(20,57,58) These studies were performed using the
Ames system which is characteristically insensitive to chlorinated
hydrocarbons. 1,1,1-Trlchloroethane was also positive in an in vitro
mammalian cell transformation assay.(*•*) However, the results of two
animal carcinogen hloassay studies were Inconclusive due to design and
experimental problems.(IB,20,56) The NCI is currently re-evaluating
the carcinogenic potential of 1,1,1-trichloroethane. Studies of the
teratogenic potential of 1,1,1-trichloroethane are also suggestive;
however, more studies are needed to make a conclusive statement.(56)
Other than pschophysiologlcal effects, 1,1,1-trichloroethane
exposure at or below the OSHA-PEL (350 ppm) does not result in either
acute or chronic toxic complications. At very high concentrations
(710,000 ppm), however, 1,1,1-trichloroethane produces cardiovascular
and CNS narcotic effects, and can cause death from cardiac failure.
Animal studies as well as accidental human exposure, have shown that,
*The discussion on the health and environmental effects of 1,1,1-trichloro-
ethane has been modified as a result of comments received on the hazard-
oueness of 1,1,1-trichloroethane on other listings.
-------
at these high Inhalation concentrations, 1,1,1-tvirhloroethane produces
a "chlorinated hydrocarbon" type of microscopic pathology liver and
kidneys (fatty infiltration, cellular necrosis) which is characterized
as being much less severe than that produced by carbon tetrachloride
or trichlorethylene. Additional information and specific references
on the adversion effects of 1,1,1-trichlorethane can be found in
Appendix A.
Ecological Effects - Lethal concentrations (LCso, 96
hour values) are reported ranging from 33 zng/1 (Dab), and 70 ng/1
(Sheepshead minnow) to 69.7 mg/1 (Bluegill) and 105 mg/1 (Flathead
minnow).(24,56)
1,1,1-Trichloroethane in common with other volatile hydrocarbons,
volatilizes from water to an appreciable extent. However, retrans-
port to water from the atmosphere and decreased volatilization rates
from stagnant water render the aquatic compartment an important sink
for 1,1,1-trichloroethane. The major ecological concern, however,
is its possible role as an ozone depleter. In recent years there has
been considerable concern over human activities appreciably altering
the levels of ozone in the stratosphere. The tropospheric lifetime of
1,1,1-trichloroethane is believed to be in the range of 4-12 years, and
it has been estimated that 10-20 percent of the 1,1,1-trichloroethane
molecules released at the earth's surface will eventually reach the
stratosphere.(59^ Studies simulating conditions obtained at high
altitudes have shown(6°) that the lax resident time of 1,1,1-trichloro-
ethane In the stratosphere and the high solar uv intensity will result
in its eventual total destruction yielding free Cl atoms which are known
to destroy stratospheric ozone.
-------
Regulations - 1,1,1-Trichloroethane Is designated as a priority pollutant
under Section 307(a) of Che CWA. OSHA has set the TWA at 350 ppra. EPA
has recommended an ambient water quality criterion at 15.7 mg/1. Because
of wide use and exposure, and the inadequacy of currently available
information, the TSCA Interagency Testing Committee has recommended <55)
further evaluation to establish the carcinogenicity, mutagenicity and
teratogenicity and other chronic effects of 1,1,1-trichloroethane.
Industrial Recognition of Hazard - Sax Dangerous Properties
of Industrial Matrials lists 1,1,1-trichloroethane as carcinogenic and
moderately toxic.
3. 1,1,2-Trichloroethane
Health Effects - 1,1,2-Trichloroethane has been
shown to cause cancer in raice.C27) It has also been identified by the
Agency as a compound exhibiting substantial evidence of carcinogenicity.
(67) There is evidence that 1,1,2-trichloroethane is mutagenic and
may be embryo toxic or cause teratogenic effects.(l3~17,28-30)
1,1,2-Trichloroethane is considered toxic [oral rat LD50 = 1140 mg/Kg].
Like the other compounds of this type, the trichloro-
ethanes are narcotics, produce central nervous system effects, and can
damage the liver, kidney and other organs.(19> 1,1,2-Trichloroethane is
designated as a priority pollutant under Section 307(a) of the CWA.
Additional information and specific references on the adverse effects of
1,1,2-trichloroethane can be found in Appendix A.
geological Effects - Aquatic toxicity data are limited
with only three acute studies in freshwater fish and invertebrates with
-•555"-
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doses ranging from 10,700 to 22,000 mg/l.<20)
Regulations - OSHA has set the TWA at 10 ppn (skin).
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists 1,1,2-trichloroethane as being
moderately toxic by inhalation, ingestion and skin absorption.
4. Tetrachloroethanes
Health Effects - 1,1,2,2-Tetrachloroethane has been
shown to produce liver cancer tn laboratory mice.(31) it has also been
Identified by the Agency as a compound exhibiting substantial evidence of
being carcinogenic. {67) It is also shown to be very toxic [oral rat
LD5Q = 200 mg/Kg]. In addition, passage of 1,1,1,2-tetrachloroethane
across the placental barrier has been reported.(29) jn Ames Salmonella
bioassay 1,1,2,2-tetrachloroethane was shown to be rautagenic.'3*'
Occupational exposure of workers to 1,1,2,2-tetrachloroethane produced
neurological damage, liver and kidney ailments, edema, and fatty degeneration
of the heart muscle.<33) Both 1,1,1,2-tetrachloroethane and 1,1,2,2-
tetrachloroethane are designated as priority pollutants under Section
307(a) of the CWA. Additional information and specific references on
the adverse effects of the tetrachloroethanes can be found in Apendix A.
Ecological Effects - Freshwater invertebrates are
sensitive to 1,1,2,2-tetrachloroethane with a lethal concentration of
7-8 mg/1 being reported.<2°) USEPA estimates the BCF to be 18.
Regulations - OSHA has set the TWA at 5 ppo (skin) for
1,1,2,2-tetrachoroethane.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists 1,1,2,2-tetrachloroethane as
-------
being highly toxic via ingestion, inhalation and skin absorption.
5. Trichloroethylene
Health Effects - Trichloroethylene has been demonstrated
to induce liver cancer in mice.(34) xt has also been identified by the
Agency as a compound exhbitlng substantial evidence of carcinogenicity.(67)
This compound may be absorbed into the body by inhalation, by ingestion,
or by absorption through the skin.(34)
An excess of lung, cervical, and skin cancers and a
slight excess of leukemias and liver cancers were observed in a study of
330 deceased laundry and dry-cleaning workers who had been exposed to
carbon tetrachloride, trichloroethylene, and tetrachloroethylene.(35)
Trichloroethylene is mutagenic In bacteria and yeast
and in spot tests for somatic mutations in mice.(36)
Numerous fatalities resulting from anesthesia with tri-
chloroethylene and from Industrial intoxications have been reported.(3*)
Acute and chronic inhalation of trIchloroethylene effects the central
nervous system. Toxic effects on the liver and other organs can occur
from exposure by any route, and there is an indication that the hepa-
totoxic effect of trichloroethylene is enhanced by concomitant exposure
to ethanol or isopropyl alcohol.(34,36) Additional information and
sepclfic references on the adverse effects of trichloroethylene can be
found in Appendix A.
Ecological Effects - Freshwater fish (bluegill) are
poisoned by trichloroethylene during a 96 hour exposure to 40-60 mg/1
concentration range.(37)
Regulations - OSHA has set a TWA at 100 ppm.
-------
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists trichloroethylene as a high
systemic toxicant via inhalation and moderate via ingestion.
6. Tetrachloroethylene
Health Effects - Tetrachloroethylene is a carcinogen
in laboratory mice.(38) jt y,as aiso been identified by the Agency as a
compound exhibiting substantial evidence of carcinogenlcity.(67) The
compound can be absorbed into the body via inhalation, by ingestion,
and through the skin to increase its toxic effects.''^)
It has also been reported to be mutagenic and to cause
transformation of mammalian cells.OO) An excess of lung, cervical and
skin cancers and a slight excess of leukemias and liver cancers were observed
in a study of 330 deceased laundry and dry-cleaning workers who had been ex-
posed to carbon tetrachloride, trlchloroethylene, and tetrachloroethylene.(35)
There Is some evidence that tetrachloroethylene may be
teratogenic. Repeated exposures to tetrachloroethylene vapors produced a
variety of pathological change in the liver ranging from fatty degeneration
to neurosis in rats, rabbits and guinea pigs. Exposure to this compound
may also effect the kidneys and other organs. It also causes central
nervous system effects and gastrointestinal symptoms.(30)
A case of "obstructive jaundice" in a six week old
infant has been attributed to tetrachloroethylene In breast mllk.^0)
Additional information and specific references on the adverse effects of
tetrachloroethylene can be found in Appendix A.
7. Vinyl Chloride (VCM)
Health Effects - Vinyl Chloride has been shown to be
-------
a carcinoger In 1 -'-oratory studies. (41,42) jt has -ilso been Identified
by the Agency as a compound exhibiting substantial evidence of carcino-
genlclty. (67) This finding has subsequently been supported by epidemological
findings. (43, 44) vinyl chloride Is very toxic [oral rat LD5Q
= 500 ing/Kg). Acute exposure to vinyl chloride results in anaesthetic
effects as well as uncoordinated muscular activities of the extremeties,
cardiac arrythmias(45) anj sensltlzation of the myocardium. (46) jn severe
poisoning, the lungs are congested and liver and kidney damage occur. (47)
A decrease in white blood cells and an increase in red blood cells was
also observed and a decrease in blood clotting ability. (48) vinyl chloride
is designated as a priority pollutant under Section 307 (a) of the CWA.
Additional information and specific references on the adverse effects of
vinyl chloride can be found in Appendix A.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists vinyl chloride as having a
moderate toxic hazard rating via inhalation.
8. Vinylidene Chloride
Health Effects - Vinylidene chloride has been shown to
cause cancer in laboratory animals. (49, 50) xt has also been identified
by the Agency as a compound exhibiting substantial evidence of carcinogencity .
(67) It ig very toxic [orai rat W^Q » 200 mg/Kg]^9^. Chronic exposure
to vlnylidene chloride can cause damage to the liver and other vital
organs as well as causing central nervous system effects. Additional
information and specific references on the adverse effects of Vinylidene
chloride can be found in Appendix A.
Regulations - OSHA has set the TWA at 10 ppm.
-35*)-
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Industrial Recognition of Hazard - DOT requires containers
to be labeled "flammable liquid".
The toxic hazard of vinylidene chloride is suspected of
being similar to vinyl chloride which is moderately toxic via inhalation,
Sax, Dangerous Properties of Industrial Materials.
9. Chloroform
Health Effects - Chloroform has been shown to be carcinogenic
in animals and is recognized as a suspect human carcinogen.(51) it has also
been identified by the Agency as a compound exhibiting substantial evidence
of carcinogenicity(67). Tangential evidence links human cancer epidemiology
with chloroform contamination of drinking water.(52,53) chloroform has
also been shown to induce fetal toxicity and skeletal malformation in
rat embryos.(54,55) chronic exposure causes liver and kidney damage and
neurological disorders.(52) Additional information and specific references
on the adverse effects of chloroform can be found in Appendix A.
Ecological Effects - USEPA has estimated that chloroform
accumulates fourteenfold in the edible portion of fish and shellfish.(52)
The USEPA has recommended that contamination by chloroform not exceed
500 mg/1 in freshwater and 620 mg/1 in marine environment.(52)
Regulations - OSHA has set the TWA at 2 ppm. FDA pro-
hibits use of chloroform in drugs, cosmetics, and food contact materials.
The Office of Water and Waste Management has proposed regulation of
chloroform under Clean Water Act 311 and is in the process of developing
regulations under Clean Water Act 304(a). The Office of Air, Radiation,
and Noise is conducting preregulatory assessment of chloroform under the
Clean Air Act. The Office of Toxic Substances has requested additional
-------
testing of chloroform under Section 4 and is conducting a preregulatory
assessment under the Federal Insecticide, Fungicide and Rodenticide
Act.
Industrial Recognition of Hazard - Chloroform has been
given a. moderate toxic hazard rating for oral and inhalation exposures,
Sax, Dangerous Properties of Industrial Materials.
10. Carbon Tetrachloride
Health Effects - Carbon tetrachloride is estimated to
occur in this waste stream in low concentrations, but is a very potent
carcinogen.(56) it has been identified by the Agency as a compound
exhibiting substantial evidence of carcinogenic!ty.(67) The toxic effects
[oral rat 1.050 = 2800 mg/Kg] of carbon tetrachloride are amplified by
both the habitual and occasional ingestion of alcohol.(57)
Obese individuals are especially sensitive to the
toxic effects of carbon tetrachloride because the compound accumulates
in body fat.(^) It also causes harmful effects in humans as the
undernourished, those suffering from pulmonary diseases, gastric ulcers,
liver and kidney diseases, diabetes, or glandular disturbances.(59)
The recommended criterion level in water designed to
protect humans from the toxic effects of carbon tetrachloride Is 2.6
mg/l.(57) in measurements made during the National Organics Monitoring
Survey of 113 public water systems sampled, 11'of these systems had carbon
tetrachloride at levels at or exceeding the recommended safe limit.f6^)
Carbon tetrachloride is a priority pollutant under Section 307fa) of the
CWA. Additional information and specific references on the adverse
-3C.J-
-------
effects of carbon cetrachloride can be found in Appendix A.
Ecological Effects - Movement of carbon tetrachloride
within surface water systems is projected to be widespread. (See App. B)
Movement to this degree will likely result in exposure to aquatic life
forms in rivers, ponds and reservoirs.
Carbon tetrachloride is likely to be released to the
atmosphere from surface water systems. In the atmosphere, carbon tetra-
chloride is slowly decomposed to phosgene, a highly toxic gas. In the
incineration of carbon tetrachloride-containing wastes, phosgene is
likely to be emitted under Incomplete combustion conditions.
Regulations - OSHA has set a TWA for carbon tetrachloride
at 10 ppm. Carbon tetrachloride has been banned by the Consumer Product
Safety Commission under the Hazardous Substances Act.
Industrial Recognition of Hazard - According to Sax,
Dangerous Properties of Industrial Materials, the oral toxicity rating is
high.
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IV. References
1. U.S. EPA. Industrial process profiles for environmental use: Chapter 6,
The Industrial organic chemicals industry. EPA No. 600/2-77-023f.
February, 1977.
2. U.S. EPA. Engineering and cost study of air pollution control for
petrochemical industry-V.3. Ethylene dichloride manufacture by
oxychlorinatlon. EPA No. 450/3-73-006-c. November 1974.
3. U.S. EPA. Source assessment: Chlorinated hydrocarbons manufacture.
EPA No. 600/2-79-019g. August, 1979.
4. Water quality issues in Massachusetts. Chemical contamination,
special legislative commission on water supply. September, 1979.
5. DeWalle, P.P., and E.S.K. Chian. Detection of trace organlcs
in well water near a solid waste landfill. In Proceedings; 34th
Industrial Waste Conference, Layfayette. May 8-10, 1979.
Purdue University. Ann Arbor Science, 1980. pp. 742-752.
6. Memo from Roy Albert to E.C. Beck, Administrator EPA Region II,
Drinking Water Contamination of New Jersey Well Water. March 31, 1978.
7. Buller, R.D. Trichloroethylene contamination of ground water
case history and mitigative technology. Presented at American
Geophysical Union Fall Meeting, December 3-7, San Francisco, CA.
1979.
8. Wilson, J.T., and C.G. Enfleld. Transport of organic pollutants
through unsaturated soil. Presented at American Geophysical Union
Fall Meeting, December 3-7, San Francisco, CA. 1979.
9. Zoeteman, B.C.J. Persistent organic pollutants in river water and
ground water of the Netherlands. I_n Proceedings; Third International
Symposium on Aquatic Pollutants. October 15-17. Jekyll Island, Ga.
1979.
10. Roberts, P.V., P.L. KcCarty, Mr. Reinhard, and J. Schriener.
Organic contaminant behavior during ground water recharge. ^n_
Proceedings; The 51st Annual Conference of the Water Pollution
Control Federation. October 1-6. Anaheim, CA. 1978.
11. National Cancer Institute. Bioassay of 1,2-dichloroethane for
possible carcinogenicity. U.S. Department of Health, Education and
Welfare, Public Health Service, National Institutes of Health,
National Cancer Institute, DHEW Publication No. (NIH) 78-827. 1978.
NTIS PB No. 285 968. 1978.
-------
IV. References (Continued)
12a. McCann, J., E. Choi, E. Yamasaki, and B. Ames. Detection of carcin-
ogens as mutagenic in the Salmonella/microsome test: Assay of 300
chemicals. Proc. Nat. Acad. Sci. USA 72(2): 5135-5139, 1975a.
12b. McCann, J., V. Simmon, L. Streitwieser, and B. Ames. Mutagenicity
of chloroacetaldehyde, a possible metabolic product of 1,2-dichloro-
ethane (ethylene dichloride), chloroethanol (ethylene chlorohydrin),
vinyl chloride, and cyclophosphamide. Proc. Nat. Acad. Set. 72(8):
3190-3193. 1975.
13. Vozovaya, M. Changes In the estrous cycle of white rats chronically
exposed to the combined action of gasoline and dichloroethane vapors.
Akush. Geneko. (Kiev) 47(12): 65-66. 1971.
14. Vozovaya, M. Development of offspring of two generations obtained
from females subjected to the action of dichloroethane. Gig. Sanit.
7:25-28. 1974.
15. Vozovaya, M. The effect of low concentrations of gasoline, dichloro-
ethane and their combination on the generative function of animals.
Gig. Sanit. 6:100-102. 1976.
16. Vozovaya, M. Effect of low concentrations of gasoline, dichloro-
ethane and their combination on the reproductive function of
animals. Gig. Sanit. 6:100-102. 1976.
17. Vozovaya, M.A. The effect of dichloroethane on the sexual cycle
and embryogenesis of experimental animals. Akusk. Glnekol.
(Moscow) 2:57-59. 1977.
18. Urusova, T.P. (About a possibility of dichloroethane absorption
into milk of nursing women when contacted under industrial conditions.)
Gig. Sanit. 18(3):36-37. 1953. (Rus)
19. Parker, J.C., et al. Chloroethanes: A review of toxiclty.
Amer. Ind. Hyg. Assoc. J., 40:46-60. March, 1979.
20. U.S. EPA. Chlorinated ethanes: Ambient water quality criteria
(Draft). NTIS PB No. 297 920. 1979.
21. NCI. Bioassay of 1,1,1-trichloroethane for possible carcinogen-
icity. Carcinog. Tech. Rep. Ser. NCI-CG-TR-3. NTIS PB No. 265 082.
22. Price, P.J., et al. Transforming activities of trichloroethylene
and proposed industrial alternatives. In Vitro 14:290. 1978.
23. U.S. EPA. In vitro microbiological mutagenicity of 81
compounds. In Vitro 14:290. 1980.
-------
IV. References (Continued)
24. Schwetz, B.A., et al. Embryo- and feto-toxicity of inhaled
carbon tetrachloride, 1,1-dichloroethane and methyl ethyl ketone
in rats. Toxicol. Appl. Pharmacol. 28:452. 1974.
25. Walter, P., et al. Chlorinated hydrocarbon toxicity (1,1,1-tri-
chloroethane, trichloroethylene, and tetrachloroethylene): A monograph.
NTIS PB No. 257 185. 1976.
26. U.S. EPA. In-depth studies on health and environment impact of
selected water pollutants. Contract No. 68-01-4646. 1979.
27. National Cancer Institute. Bioassay of 1,1,2-trichloroethane for
possible carcinogenicity. U.S. Department of Health, Education, and
Welfare, Public Health Service, National Institutes of Health,
National Cancer Institute, DHEW Publication No. (NIH) 78-1324.
NTIS PB No. 283 337. 1978.
28. Elovaara, E., et al. Effects of CH2C12, CH3Cl3, TCE, PERC and
Toluene in the development of chick embryos. Toxicology 12: 111-119.
1979.
29. Truhaut, R., N.P. Lich, H. Dutertre-Catella, G. Molaa, V.N. Huyen.
Toxicologlcal study of 1,1,1,2-tetrachloroethane. Archives
des Maladies Professionnelles, de Medicine du Travail et de Securite
35(6):593608. 1974.
30. Parker, J.C., et al. Health assessment document for 1,2-dichloroethane
(ethylene dlchlorlde). Review draft report. EPA Environmental
Criteria and Assessment Office, Research Triangle Park. November,
1979.
31. National Cancer Institute. Bioassay of 1,1,2,2-tetrachloroethane
for possible carcinogenlcity. U.S. Department of Health, Education,
and Welfare, Public Health Service, National Institutes of Health,
National Cancer Institute, DHEW Publication No. (NIH) 78-627.
NTIS PB No. 277 453. 1978.
32. Brem H., et al. The mutagenlclty and DNA-modlfying effect
of haloalkanes. Cancer. Res. 34:2576. 1974.
33. National Institute for Occupational Safety and Health. Criteria
for a recommended standard...occupational exposure to 1,1,2,2-
tetrachloroethane. U.S. DHEW, Public Health Service, Center
for Disease Control, National Institute for Occupational Safety and
Health, DHEW (NIOSH) Publication No. 77-121. NTIS PB No. 273 802.
December, 1976.
-------
IV. References(Continued)
34. Page, Norbert P., and J. L. Arthur. TrichLoroethylene. Special
occupational hazard review with control recommendations. DHEW
Publication No. (NIOSH) 78-130. January, 1978.
35. Blair, et al. Causes of death among laundry and dry cleaning
workers. Am. J. Publ. Health 69;508-5U. 1979.
36. IARC Monographs. Evaluation of carcinogenic risk of chemicals to
man. Trichloroethylene. Interagency for Research on Cancer• Lyon,
France. World Health Organization. Vol. 20:545. 1979
37. U.S. EPA. Trichloroethylene: Ambient water quality criteria.
NTIS PB No. 292 443. 1979.
38. National Cancer Institute. Bioassay of tetrachloroethylene
for possible carcinogenIdty. CAS No. 127-18-4, NCI-CG-TR-13,
DHEW PB No. (NIH) 77-813. NTIS PB No. 272 940. 1977.
39. Not used in text.
40. Bignell, P.C., and H.A. Ellenberger. Obstructive Jaundice
due to a chlorinated hydrocarbon in breast nilk. Con. Med. Assoc.
J_., 117:1047-1048.
41. Viola, P.L., et al. Oncogenlc response of cat skin, lungs, and
liver to vinyl chloride. Cancer Res. 31:516. 1971.
42. Maltoni, C., and G. Lefemine. Carcinogenicity bioassays of vinyl
chloride. Am. N.Y.. Acad. Sci. 246:195. 1975.
43. Creech and Johnson. Angiosarcoma of the liver in the manufacture
of polyvinyl chloride. J. Occup. Med. 161:150. 1974.
44. Tabershaw, I.R., and Gaffey, W.R. Mortality study of workers
in the manufacture of vinyl chloride and Its polymers. J. Occup.
Med. 16:509. 1974.
45. Oster, R.H., et al. Anesthesia XXVII narcosis with vinyl chloride.
Anesthesiology 8:359. 1947.
46. Cair, J., et al. Anesthesia XXIV. Chemical constitution of
hydrocarbons and cardiac automaticity. J. Pharmaceut. 97:1. 1949.
47. Torkerson, T.R., et al. The toxicology of vinyl chloride
by repeated experience of laboratory animals. Amer. Ind.
Hyg. Assoc. J. 22:304. 1961.
48. Lester D., et al. Effects of single and repeated exposures of
humans and rats to vinyl chloride. Amer. Ind. Hyg. Assoc. J.
24:265. 1963.
-------
IV. References (Continued)
49. Environmental Health Perspectives, 1977. Vol. 21, pp. 333.
50. U.S. EPA. Vinylidene chloride hazard profile. USEPA/ECAO
Cincinnati, Ohio 45268. 1979.
51. National Cancer Institute. Report on carcinogenesls bioassay
of chloroform. NTIS PB No. 264 018. 1976.
52. U.S. EPA. Trichlorome thane (chloroform) hazard profile. US EPA/
ECAO Cincinnati, Ohio 45268. 1979.
53. McCabe, L.J. Association between trihalomethanes in drinking
water (NORS data) and mortality. Draft report. 1979.
54. Thompson, D.J., et al. Teratology studies on orally admin-
istered chloroform in the rat and rabbit. Toxicol. Appl. Pharmacol.
29:348. 1974.
55. Schwetz, B.A., et al. Embryo and fetotoxicity of inhaled
chloroform in rats. Toxicol. Appl. Pharmacol. 28:442. 1974.
56. IARC monographs on the evaluation of carcinogenic risk of chemicals
to man, Vs. 1, 20. World Health Organization. 1972.
57. U.S. EPA. Carbon tetrachloride: Ambient water quality criteria
document. NTIS PB No. 292 424. 1979.
58. U.S. EPA. Water-related environmental fate of 129 priority
pollutants. EPA No. 440/4-79-029b. 1979.
59. Von Oettingen, W.F. The halogenated hydrocarbons of industrial
and toxicological importance. In; Elsevier Monographs on Toxic
Agents. E. Browning, Ed. 1964.
60. U.S. EPA. The national organic monitoring survey. Technical
Support Division, Office of Water Supply, Washington, D.C. 20460.
1978
61. Edwards, J.B. Combustion formation and emission of trace species.
Ann Arbor Science 1977.
62. NIOSH. Criteria for recommended standard: Occupational exposure
to phosgene. HEW, PHS, CDC, NIOSH. NTIS PB No. 267 514. 1976.
63. Not used in text.
-367-
-------
IV. References (Continued)
64. "Love Canal Public Health Bomb." A Special Report to the Governor
and Legislature, New York State Dept. of Health. 1978.
65. Lowenheim and Moran. Faith, Keyes, and Clark's Industrial Chemicals.
4th ed., John Wiley and Sons, Inc. 1975.
66. Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, Inc. 1979
67. U.S. EPA. Cancer Assessment Group, Office of Research and Development.
List of carcinogens. April 22, 1980.
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Response to Comments - Heavy Ends from the Distillation of Ethylene
Dichloride in Ethylene Dichloride Production and Heavy Ends from the
Distillation of Vinyl Chloride in Vinyl Chloride Monomer Production
One commenter raised several questions with respect to wastes K019 and
K020 (Heavy ends from the distillation of ethylene dichloride in ethylene
dichloride production and heavy ends from the distillation of vinyl
chloride in vinyl chloride monomer production).
1. The commenter first requested that the Agency reassess its
interpretation of what materials actually constitute waste
in the production of ethylene dichloride and vinyl chloride
monomer. The commenter pointed out that many of these materials
are not discarded and never become wastes; instead they are further
processed within a short time to other products and manufacturing
intermediates.
In reviewing the available information, the Agency has evidence
that these wastes traditionally have been managed by incineration
or landfilling. Therefore, these wastes are "discarded" and,
thus, meet the definition of a solid waste (§261.2) and will continue
to be listed as hazardous. However, this waste is not always
discarded, as evidenced by the comments received (i.e., these
wastes may be used, reused, recycled or reclaimed). As discussed
in the preamble to the Part 261 regulations promulgated on May 19,
1980 (45 FR 33091-33095), the Agency has concluded that it does
have jurisdiction under Subtitle C of RCRA to regulate waste materials
that are used, reused, recycled or reclaimed. A large number of
-36,1-
-------
comments have been received, however, which challenge this conclusion.
The Agency is giving these comments serious consideration but has
not presently finalized this portion of the regulations. Therefore,
until a final decision is reached with resepct to materials which
are used, reused, recycled or reclaimed, the following guidance is
offered to individual plants to assist them In determining their
responsibilities under the hazardous waste regulations:
0 If the listed waste is always discarded at the individual
4
plant, the waste always is subject to the full set of hazardous
waste regulations.
0 If the listed waste is sometimes discarded at a particular
plant, but sometimes used, reused, recycled or reclaimed
(not used as an intermediate), the waste would only be subject
to the full set of hazardous waste regulations when discarded.
When used, reused, recycled or reclaimed the waste would be
subject to the special requirements for listed wastes contained
in §261.6(b) of the hazardous waste regulations (45 FR 33120).
0 If the listed waste is typically processed through the next
step of the process within a short time, the material does
not meet the definition of a solid waste (i.e., is an inter-
mediate product), and is therefore not subject to the
hazardous waste regulations (45 FR 33119, and see discussion
at 45 FR 33093-094).
2. The commenter then questioned the Agency's assessment of the
toxlcity of chloroform and objects to the inclusion of chloroform
-------
as a constituent of concern in this particular listing. Also, the
commenter believes that EPA has no perspective of the significance
of the aquatic toxiclty data.
The Agency strongly disagrees with the commenter. Chloroform
has been designated carcinogenic by the Cancer Assessment Group
(CAG) after much detailed study of the literature, including the
National Cancer Institute bioassay test results (see reference
material on CAG assessment for more details). Additionally, chloro-
form has been shown to Induce fetal toxicity and skeletal malforma-
tion in rat embryos. Although research regarding other types of
toxicity are still being conducted, the Agency believes that there
is sufficient justification so as not to remove chloroform as a
basis for listing wastes K019 and K020.
The comment regarding EPA's lack of perspective on aquatic
toxicity data is unclear and lacks supporting data, thus, no
further comment will be made.
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PS:13-1
LISTING BACKGROUND DOCUMENT
FLUOROCARBON PRODUCTION
Aqueous spent antimony catalyst waste from fluoromethanes
production. (T)
I. Summary of Basis for Listing
The production of chlorofluoromethanes via the liquid phase
fluorination process results in the generation of an aqueous
spent antimony catalyst waste which contains both toxic organic
and Inorganic substances, two of which are carcinogenic. The
waste constituents of concern are antimony compounds, chloro-
form and/or carbon tetrachloride.
The Administrator has determined that the wastevater from
the production of chlorofluoromethanes via the liquid phase
fluorination process is a solid waste which nay pose a sub-
stantial present or potential hazard to human health or the
environment when improperly transported, treated, stored, dis-
posed of or otherwise managed, and therefore should be subject
to appropriate management requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations:
(1) The waste stream contains significant quantities of antimony
compounds, chloroform and/or carbon tetrachloride.*
*Depending on the type of fluorocarbon being produced, either
chloroform or carbon tetrachloride will be used as a raw material
and appear in the waste stream as an excess reactant (see dis-
cussion, "Industry Profile and Process Description," below).
-------
(2) Chloroform, carbon tetrachloride, and antimony compounds are
highly toxic. Chloroform and carbon tetrachloride has been
evaluated by EPA as substances exhibiting substantial evidence
of carcinogenicity. Carbon tetrachloride has been shown to be
teratogenic.
I ~.) Chloroform and carbon te tr achlor ide are resistant to water
treatment methods and are therefore likely to appear in drink-
ing water if allowed to migrate from the waste into drinking
water sources. These two constituents are also volatile and
may pose a threat to human health via an air exposure pathway
if not properly managed. Antimony compounds will persist in
the environment (in some form) vitually indefinitely; therefore,
if allowed to migrate from the waste may contaminate drinking
water sources for long periods of time.
(4) It is estimated that approximately 30,000 to 60,000 Ibs. of
spent catalyst is generated annually by the two plants using
liquid phase fluorinatlon and will be in the aqueous waste
stream. The substantial quantity of waste generated Increases
the possibility of exposure should mismanagement occur.
(S) Damage incidents involving the contamination of groundwater
by antimony compounds, chloroform and carbon tetrachloride
confirm the ability of these waste constituents to be mobile,
persistent, and cause substantial harm.*
II. Industry Profile and Process Description (29,30)
Chlorofluororoethanes are manufactured by the fluorlnation of
chlorocarbons. Two different fluorination processes may be used:
liquid phase or vapor phase. This document is concerned solely with
the aqueous spent catalyst waste from the manufacture of the
^Although no data on the corroslvity of spent antimony
catalyst is currently available, the Agency believes that
this waste stream may have a pH greater than 12.5 and may
therefore be corrosive. Under §§261.22 and 262.11, generators
of this waste stream are responsible for testing their wastes
in order to determine whether their waste is corrosive.
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chlorofluoromethanes Chat are produced via liquid phase
fluorination.* The commercial products produced by this
segment of the fluorocarbon industry include chlorotrifluoro-
methane (CC1F3>, dichlorodifluoromethane (CCl2?2)> trichloro-
fluororaethane (CCljF), and chlorodifluoromethane (CHC1F2). Of
the five (S) companies that manufacture these products, it is
believed that two have plants that use the liquid phase fluorina-
tion process and generate the waste stream of concern:
Plant Size - Million
Company Location
(1)
(2)
(3)
(*)
Company
DuPont
Allied Chemical
Kaiser Aluminum
& Chemical
Pennwalt
Racon, Inc.
Location
Antioch, CA
Deepwater, NJ
East Chicago, IN
** Louisville, KY
Matague, MI
Baton Rouge, LA
Danville, IL
Elizabeth, NJ
'El Segundo, CA
Gramercey, LA
Calvert City, KY
Throughfare, NJ
** Wichita, KS
Pounds Per Year
500
190
80
60
50
Total: 880
(Source: reference 31)
*In the vapor phase fluorination process, a proprietary,
largely insoluble, metallic catalyst is used in place of the
antimony catalyst. The vapor phase catalyst will tend to last
longer and have lower concentrations of the constituents of con-
cern than the antimony catalyst used In liquid phase fluorination
**These two plants use liquid phase fluorination and generate
spent antimony chloride catalyst waste.
-------
The chlorof luorornethanes in the product family of concern are
manufactured by fluorlnating either carbon tetrachloride (CC14) or
chloroform (CHC13) using hydrogen fluoride (HF) and antimony penta-
chloride (SbClj) as a catalyst (see Figure 1). Carbon tetrachloride
is used as a starting material when trichlorofluoromethane (CC1*F),
dichlorodifluorornethane (CCl2F2), and chlorotrifluoromethane (CC1F3)
are the desired products. (Tetrafluoromethane (CF^) is also formed
as a co-product waste.) Chloroform is used as feedstock when
chlorodifluoromethane (CHC1F2) and dichlorofluoromethane 'CHC12F)
are the desired products. (A. small amount of trichlorotrifluoroethane
(C2Cl3?3) and trifluoromethane (CHF3> are formed as co-product wastes.)
In both processes, the chlorine (Cl) in the starting materials Is
successively replaced with fluorine (F). For example, starting with
carbon tetrachloride (CC14), and hydrogen fluoride, the reaction is
carried out continuously to produce the product mix desired, usually
a 50/50 blend of trichlorof luor omethane (CC^F) and dichlorodif luoro-
raethane (CC12F2) as illustrated by the following equations:
(1) CC14 + HF > C13C-F + HC1
(2) C13C-F + HF > CC12F2 + HC1
The main features of the process are shown In Figure 1.
During the process, the antimony pentachloride catalyst
) is reduced to antimony trichloride (SbC^). A slip
-------
HEAT
TO LANDFILL
TO IIP PLANT
Figure 1. FLOWSHEET FOR PRODUCTION OF FLUOROCARBONS
BY LIQUID PHASE FLUOFUNATION
(Danccl on information in Reference? 29 and 30.'
-------
stream is taken from (F) (see Figure 1.) to remove an aliquot
portion of the spent catalyst. After washing, the aqueous
L.-ant catalyst wastes (G) are sent to pits (H) where they are
either disposed of or stored until further treatment. (The
bulk of the antimony trichloride is recovered by the catalyst
filter and dried and reactivated by chlorination to form antimony
pentachloride, which is recycled to the fluorinator .)
III. Waste Composition, Generation and Management
Based on knowledge of process chemistry and best engineering
judgment, the spent catalyst wastewater from liquid phase
fluorination is expected to contain significant concentrations
of the following constituents:
(1) Spent antimony chloride catalyst not recovered by the
catalyst filter. This spent catalyst wastewater will contain
antimony trichloride as a metallic ion and other antimony
compounds.
(2) Organic residues from feedstock materials. These
will include either carbon tetrachloride or chloroform,
depending on which fluorocarbons are being produced.
Based on an estimated production of 100 million Ib/yr
(at the Dupont, Louisville, and Racon plants), it is estimated
-------
that 30-60 thousand Ibs. of spent catalyst are generated annually
and will be contained in the spent catalyst wastewater.* The
vastewater will also contain dissolved chloroform and carbon
tetrachlorlde in maximum concentrations of about 0.8 gms/100 gms
of vastevater (based on these constituents water solubilities).
Undissolved chloroform and carbon tetrachloride will also be
entrained in the wastewater unless the organic layer of the
aqueous wastestream has been separated prior to disposal.
These wastes are typ'cally discharged to clay-lined pits
(26) either for disposal or storage until further treatment.
IV. Discussion of Basis for Listing
A. Hazards Posed by Waste
As noted above, the waste components of concern are
antimony compounds, carbon tetrachloride and/or chloroform.
Antimony compounds, chloroform and carbon tetrachloride are
highly toxic. Chloroform Is a suspected carcinogen. Carbon
tetrachloride is a very potent carcinogen and has also been
shown to be teratogenic.
*This estimate is also based on data in "Fluorocarbon
Hydrogen Fluoride Industry", EPA-600/2-77-023 February 1977.
This quantity is believed significant, since large quantities
of hazardous waste constituents are available for environmental
release, increasing the risk of exposure should mismanagement
occur.
/
-------
B. Exposure pathways and migratory potential
The waste constituents of concern may migrate from
lopttl? iaslgtied or -savaged disposal OT ^toragfe sitsa ana
contaminate ground and surface waters. Antimony trichloride
is extremely soluble (601.6 gn/100 gm 1^0 (? 0"C), chloroform
Is highly soluble (2200 mg/1 @ 25°C), and carbon tetrachloride
is quite soluble (800 mg/1 I? 20"C) . Chloroform and carbon
tetrachloride are also highly volatile: 160 mm Hg @ 20°C and
91 mm Hg @ 20°C, respectively (water hae a volatility of about
17.5 mm Hg @ 20°C).(28>
Storage or disposal In clay-lined pits is the most usual
management method for these wastes. This practice may be
adequate to prevent soil and/or groundwater contamination If
pits ate pta^erly caa&tcucted and managed. Howe vet , if these
pits are not properly constructed, they can develop cracks or
leaks through thin points in the wall with subsequent release
of the waste Into the environment, in light of the waste con-
stituents' migratory potential* In any case, wastes are hazard-
ous under RCRA even if they are properly managed in fact. The
potential of the waste to cause substantial harm Is the key
factor, and these wastes are believed to have ample potential
to cause substantial hazard.
These wastes also nay cause liarm via additional exposure
pathways. There Is also a danger of migration Into or contamina-
tion of surface vat-era LF the fits are Improperly designed.
or managed. Thus inadequate flood control measures could
result in washout or overflow of the wastes. If the wastes
-------
are allowed to reach too high a level in the pits, the pits
may overflow during periods of heavy rain, releasing their
contents which may find their way into and contaminate
surface water.
There is also a danger of migration into the atmosphere
if the disposal sites are inadequately designed or managed.
Since chloroform and carbon tetrachloride are highly volatile,
they may escape into the air and present a hazard to human
health via an air Inhalation pathway. Thus, these hazardous
constituents could migrate from disposal sites with inadequate
cover .
Actual damage incidents confirm that these waste
constituents are mobile, persistent and cause substantial
hazard if improperly managed. The migratory potential of
antimony compounds is confirmed by the fact that groundwater
contamination from disposed antimony sludges has been observed
in an Iowa incident (2).
The migratory potential via an air pathway of chloroform
and carbon tetrachloride is confirmed by the fact that both
constituents have been identified as air contaminants in both
schools and basements of homes located at Love Canal,
New York ("Love Canal Public Health Bomb", A Special Report
to the Governor and Legislature, New York State Department
of Health, 1978). Chloroform has also migrated from the
-390-
-------
Love Canal site into surrounding basement sumps, demonstrating
ability to migrate through soils. (Id.) Other incidents of
groundwater contamination due to improper storage and burial
of chloroform-containing wastes further confirm chloroform's
ability to migrate through soils and contaminate groundwater.
In one incident, chloroform was detected in a well at
Dartmouth, MA. In a similar incident at Woburn, MA., chloro-
form migrated from an underground burial site to contaminate
a municipal well in the vicinity (4).
Antimony, since it is an elemental metal, will persist
indefinitely in some form in the environment. Antimony
trichloride also reacts vigorously with moisture, generating
heat and highly irritating hydrogen chloride gas. The antimony
component which results from this reaction can also cause
systemic effects (27).
The carbon tetrachloride and chloroform in the waste are
volatile and if stored in an open clay pit will tend to slowly
evaporate. Should the chloroform or carbon tetrachloride reach
ground or surface water prior to evaporation, as both have been
known to do (see above and p. 12), they could travel significant
distances due to their resistance to microbial degradation
(3). In addition, carbon tetrachloride and chloroform are
resistant to water treatment and, if they are present in
drinking water sources, are likely to appear in drinking
water.(19»18) The incidents of the migration of these harm-
ful constituents previously mentioned (see p. 9) demonstrate
-------
that they may persist long enough to reach and cause harm to
a receptor, via either a water (ground or surface) or air
pathway .
C. Health and Ecological Effects
1. Chloroform
Health Effects - Chloroform has been recognized
and regulated as a suspected carcinogen (32). It is also con-
sidered toxic [oral rat LD5Q=ROO mg/kg] and has been evaluated
by CAG as having substantial evidence of carcinogenicity.
Tangential evidence links human cancer epidemiology with chloro-
form contamination (6) of drinking water. In laboratory studies,
chloroform induces liver cancers in nice and causes kidney tumors
in experimental rats (7). Chloroform was shown to Induce fetal
toxicity and skeletal malformation In rat embryos (8,9). Chloro-
form is a priority pollutant under Section 307(a) fo the CWA.
Additionaly information on the adverse health effexts of chloro-
form can be found in Appendix A.
Ecological Effects - The U.S. EPA has determined
that chloroform accumulates fourteen-fold in the edible
portion of fish and shellfish (10).
Regualtions - OSHA has set the time weighted average
at 50 ppra.
Industrial Recognition of Hazard - Chlorofrom has
been given a toxic hazard rating via oral routes by Sax in
Dangerous Properties of Industrial Materials.
Vf
•XQI _
-------
2. Carbon Tetrachloride
Health Effects - Carbon tetrachloride is a very
potent carcinogen (11) and has also been shown to be teratogenic
in rats when inhaled at low concentrations (12). It has also
been evaluated by CAG as having substantial evidence of carcino-
genicity. Chronic effects of this chemical on the human central
nervous system have occurred following inhalation of extremely
low concentrations (20 ppm), with death at 1000 ppm (13).
Adverse effects of carbon tetrachlorIde on liver and kidney
function (acute and often irreversible hepatic failure), and on
respiratory and gastrointestinal tracts (14,15) have also been
reported. The toxic effects of carbon tetrachloride are ampli-
fied by both the habitual and occasional ingestion of alcohol
(16). Especially sensitive to the toxic effects of carbon
tetrachloride are obese individuals because the compound
accumulates in body fat (17). It also causes harmful effects
in undernourished humans, those suffering from pulmonary
diseases, gastric ulcers, liver or kidney diseases, diabetes,
or glandular disturbances (18). Carbon tetrachloride is a
priority pollutant under Section 307(a) of the CVA. Additional
information and specific references on the adverse effects of
carbon tetrachloride can be found in Appendix A.
Ecological Effects - In measurements made during the
National Organics Monitoring Survey of 113 public water systems
sampled, 11 of these systems hart carbon tetrachloride at levels
at or exceeding the rero-t»ended safe limit (19).
V-
-------
13. Association of American Pesticide Control Officials,
Inc. Pesticide chemical official compendium. 1966 ed.
p. 198. 1966.
14. Texas Medical Association. Texas Medicine 69:86.
1973.
15. Davis, Paul A. Carbon tetrachloride as an industrial
hazard. JAMA 103:963-966. Jul.-Dec. 1934.
16. U.S. EPA. Carbon tetrachloride: Ambient water quality
criteria document. NTIS PB No. 292 424. 1979.
17. U.S. EPA. Water-related environmental fate of 129 priority
pollutants. EPA No. 440/4-79-0296. 1979.
18. Von Oettingen, W.F. The halogenated hydrocarbons of
industrial and toxlcological importance. In; Elsevier
monographs on toxic agents. E. Browning, ed. 1964.
19. U.S. EPA. The National Organic Monitoring Survey.
Technical Support Division, Office of Water Supply. U.S.
EPA. Washington, D.C. 20460. 197S.
20. Brieger, H. , et al. Industrial antimony poisoning.
Ind. Med. Surg. 23:521. 1954.
21. Belyaeva, A.P. The effect of antimony on reproduction.
Gig. Truda. Prof. Zabel. 11:32. 1967.
22. Gross, H. Toxicological study of calcium halophosphate
phosphorus and antimony trloxlde in acute and chronic
toxlclty and some pharmacological aspects. Arch. Ind.
Health 11:473. 1955.
23. Schroeder, H.A. A sensible look at air pollution by
metals. Arch. Environ. Health 21:798. 1970.
24. Schroeder, H.A., and L.A. Kraemer. Cardiovascular
mortality, municipal water, and corrosion. Arch. Environ.
Health 28:303. 1974.
25. Not used In text.
26. Personal Communication from Richard Deutsch of E.I.
Dupont de Nemours and Company, Louisville, KY, December
1979.
27. Sax, M.I. Dangerous properties of industrial materials.
4th ed. Litton Education Publishing, Inc. 1975.
-------
28. Dawson, English, and Petty. Physical chemical .properties
of~hazardous*waste constituents. 1980.
29. Kirk-Othmer. Encyclopedia of chemical technoJHIy. V.5.
John Wiley and Sons, Inc., New York. 1964.
30. Lowenhelm, F.A. and M.K. Moran. Faith, Keyes and Clark's
Industrial chemistry, 4th ed. John Wiley and Sons, Inc.,
New York. 1975.
31. Stanford Research Institute. Directory of chemical
producers-United States. SRI International, Menlo
Park, CA. 1979.
32. U.S. EPA. Office of Research and Development, Carcinogen
Assessment Group. List of Carcinogens. April 22, 1980.
-------
Response to Comments - Aqueous Spent Catalyst Waste from
Fluoromethanes Production
Aqueous spent catalyst waste from fluoromethanes production
(K021) is listed as hazardous because it contains a number of
toxic constituents, including chloroform. One commenter
objected to the inclusion of chloroform as a constituent of
concern in this particular listing. Also, the commenter
believes that EPA has no perspective of the significance of
the aquatic toxicity data.
The Agency strongly disagrees with the commenter.
Chloroform has been designated carcinogenic by the Cancer
Assessment Group (GAG) after much detailed study of the
literature, including the National Cancer Institute bioassay
test results (see reference material on CAG assessment for
more details). Additionally, chloroform has been shown to
induce fetal toxicity and skeletal malformation in rat
embryos. Although research regarding other types of toxicity
are still being conducted, the Agency believes that there is
sufficient justification to continue to Include chloroform
as a basis for listing waste K021.
The comment regarding EPA's lack of perspective on
aquatic toxicity data Is unclear and lacks supporting data,
thus, no further comment will be made.
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LISTING BACKGROUND DOCUMENT
PHENOL/ACETONE PRODUCTION
* Distillation Bottom Tars from the Production of Phenol/
Acetone from Cumene. (T)*
I. Summary of Baals for Listing
Distillation bottom tars from the production of phenol/acetone from
cumene contains toxic and potentially carcinogenic organic substances.
These include phenol and polycyclic aromatic hydrocarbons (PAH) as
the pollutants of concern.
The Administrator has determined that the solid waste from phenol/
acetone production may pose a substantial present or potential hazard
to human health or the environment when Improperly transported, treated,
stored, disposed of or otherwise managed, and therefore should be sub-
ject to appropriate management requirements under Subtitle C of RCRA.
This conclusion is based on the following considerations:
1. Approximately 100-220 million pounds of these wastes containing
phenol and polycyclic aromatic hydrocarbons from tars are
generated per year at 11 plants in the United States.
2. Tars containing polycyclic aromatic hydrocarbons are demon-
strated carcinogens and mutagens, as well as being toxic.
Phenol is toxic.
3. There is potential for mismanagement of the waste by leakage
during transport or storage, by improper disposal allowing
leaching, or by incomplete incineration or combustion.
*The Agency believes that the listing description "distillation
bottom tars" is more accurate than the originally proposed descrip-
tion "heavy tars". The stream listed in this document does not, how-
ever, differ from the one initially proposed.
-------
4. The waste tars persist In the environment, and phenol can spread
rapidly In ground or surface water, posing a risk of exposure
to these hazardous compounds to humans.
II. Sources of Waste and Typical Disposal Practices
A. Profile of the Industry
Phenol/acetone is produced from cumene in eleven manufacturing
plants scattered throughout-nine states. Production data from 1978
have been reported to be 1,915 MM* Ib phenol and 1,171 MM Ib acetoncC1).
B. Manufacturing Processes,14)
There are two steps in the manufacturing process: (1) oxida-
tion of cumene to cumene hydroperoxide, and (2) cleavage of the hydro-
peroxide to form phenol and acetone. (A process flow chart is contained
as Figure I below.) Cumene hydroperoxide is the first main reaction
product when cumene is oxidized with air at 130°C in an aqueous sodium
carbonate medium. The reaction mix is circulated to a vacuum column
where unreacted cumene is separated from the mix and a cumene hydroper-
oxide concentration of about 80% is obtained in the bottoms product.
Recovered cumene is recycled to the reactor. Any alpha methyl styrene
contained in the recovered cumene is separated by distillation and
sold or incinerated. However, not all of the alpha methyl styrene
may be separated at this point. The 80% cumene hydroperoxide cumene
mixture is then reacted with 10-25% sulfuric acid at 60°C and co-mixed
with an inert solvent (such as benzene) to extract organic material
from the aqueous acid. The mixture is allowed to settle. The acid
phase Is separated out and recycled to the process. The organic
layer remaining is neutralized with dilute sodium hydroxide. The
*MM - one million
-------
GIIM6NE
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SODIUM STEARATE
CUMENE
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Ain
ACETONE
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SODIUM i (YonoxinE
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a
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0
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ujO
^
a
CUMENE
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ACETOPIIENONE
fr
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H
Z
i*
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^1
TAHS
PI IENOL. ACE IOPI IbNONE. TARS
Figure 1. FLOW DIAGRAM-PHENOL/ACETONE FROM CUMENE
(MODIFIED FI1OM REFERENCE 13)
-------
resultant aqueous waste stream containing sodium sulfate, sodium
phenate, phenol, acetone, and sodium stearate is separated and sent
to wastewater treatment.* The crude, neutralized organic layer is
r.hen sent to a series of distillation columns where acetone, cumene,
phenol and acetophenone and the solvent are recovered. The first
column separates a crude acetone product overhead that is further
purified by distillation. The bottoms from the acetone distillation
column pass through a water scrubber to remove residual acetone and
inorganic salts. They then pass to a series of columns where the
lower boiling hydrocarbons, solvents, cumene, and alphamethyl styrene
are successively removed, recovered and sold, or recycled or disposed.
The bottoms from the last of the series of columns is crude phenol.
It goes to a crude phenol surge where any remaining water is settled
out. The crude phenol is refined in the next distillation column
from which the purified phenol is removed overhead.
The bottoms from the phenol still contain phenol, acetophenone,
cumyl phenol, phenyl di-methyl carbinol, higher boiling phenolic
compounds, and polymers. This mixture may be further distilled to
recover the acetophenone. The still bottoms remaining at the comple-
tion of distillation are the waste streams of concern in this document.
C. Waste Generation and Management
The distillation bottoms are a tarry solid in physical
*The Agency is not listing this wastewater stream at the present time,
but solicits data regarding waste composition and quantity, waste con-
stituent concentrations, and waste management practices.
-------
form. An EPA study (Monsanto Research Study Vol. 6) states that
these wastes (i.e, the tars generated at the bottom of the aceto-
phenone distillation column) amount to 50 - 110 g tar/Kg (100-220
Ib tar/ton of phenol) of phenol product. The reported analysis and
quantification breakdown of this residue is:
Acetophenone 1.9 g/Kg (3.8 Ib/ton) phenol
Phenol 0.75 g/Kg <1.5 Ib/ton) phenol
Cumyl phenol 0.85 g/Kg (1.7 Ib/ton) phenol
Total tars 50 - 110 g/Kg (100-220 Ib/ton) phenol
The relative concentrations of the various waste constituents can
thus be calculated from these production figures.
As is shown above, the waste tars are expected to contain
large concentrations of polycyclic aromatic hydrocarbons for the
following reasons. Cumene (the essential feedstock material) is
Itself an aromatic. In the successive steps of hydroperoxidation
and acid cleavage, the aromatic ring can open, and polyarooatic ring
structures formed. These are high-boiling substances and will be
found in the distillation bottom tars.
The subject bottom tar residue Is generally Incinerated in combined
organic wastes incinerators within plant limits.(2) Plants which do
not have Incinerators hire contract waste haulers/landfillers.(2)
III. Discussion of Basis for Listing
A. Hazards posed by the Wastes
Based on 1977 product production levels (p. 2), the U.S. prod-
uction of phenol/acetone from cumene generates an estimated 100-220
million Ibs of the subject waste annually. The principal waste
-------
components of concern are phenol and tars.'-'' Phenol is toxic.
The tars are suspect carcinogens due to the presence of polycyclic
aromatic hydrocarbons (PAH). These waste constituents are capable
of migration from the waste to groundwater. Phenol is extremely
soluble (67,000 ppo in water) (App B). PAH's contained in tars are
less subject to migration, but are highly persistent. (See p. 8
below.) Actual damage incidents and field measurements confirm pre-
dictions that waste constituents are capable of migration, mobility,
and persistence. Phenol has been found in ppb and ppm concentrations
in leachate from sites such as Love Canal, Story Chemical and La
Bounty in Charles City, lowaX1^) Levels some eight times above
the proposed water quality criteria were found in runoff 1.5 miles
from a disposal site near Byron, Illinois.(l3)* Residuals and
ppb levels of PAH's have been found In leachate samples from the
Wade Site (Chester, PA), Reilly Tar and Chemical Co. (St. Louis
Park, MN), and Kln-Buc Landfill (Middlesex, NJ)(13>.
The primary means of disposal of residue are landfllllng or In-
cineration, (2) prior to which the wastes are held temporarily in stor-
age containers. Mismanagement by leakage during transport or storage,
Improper disposal allowing leaching, or incomplete incinerator com-
bustion may all realistically occur, with resulting high potential to
cause serious human health effects and exposure of animals in the area
through direct contact and through, pollution of surface and groundwater.
*The reference to the proposed water quality criteria in the text is
not meant to use the proposed standard as a regulatory benchmark,
but to indicate qualitatively that phenol may cause a potential
hazard if It migrates from the waste in small concentrations.
-------
Thus, disposal in a landfill, even if plastic-lined drums are used,
represents a potential hazard due to the leaching of toxic compounds
if the landfill is improperly designed or operated (i.e., drums
corrode in the presence of even small amounts of water). Landfills
may, for example, be sited in areas with highly permeable soils,
allowing leachate to migrate to groundwater. Proper leachate control
and monitoring may not be in current use, again facilitating leachate
migration to groundwater, and resulting in migration to environmental
receptors. Storage prior to incineration or off-site disposal could
lead to similar hazards as improper landfilling, since improperly
stored wastes are capable of leaking and contaminating soil and ground-
water.
Transport to off-site disposal sites by contract haulers also
could result in mismanagement and environmental insult. Not only
could these wastes be mishandled in transit, but (absent of proper
regulatory control) there is no assurance that these wastes will
arrive at their Intended destination. As a. result, they may become
available to do harm elsewhere.
Mismanagement of incineration operations resulting from
improper combustion conditions related to temperature, residence time
and mixing, could lead to the release into the atmosphere of vapors
containing hazardous products of Incomplete combustion, including
the waste constituents of concern.
Should waste constituents be released from the management envi-
ronment, they are likely to persist and reach environmental receptors,
as shown by the data presented on p. 6 above. Degradative processes
-------
do not appear to appreciably reduce dangers of exposure. Phenol
blodegrades at a moderate rate in surface water and soil, but moves
readily (App. B.). Even with persistence of only a few days, the
-apid spreading of phenol (due to its very high solubility) could
cause widespread damage of the ecosystem and contamination of potable
water supplies. A phenol spill accident in Wisconsin resulted in the
movement of phenol into groundwater and contamination of well water
for more than 1000 ft. from the spill. Phenol poisoning symptoms in
hunans developed from consumption of the well water.(5) phenols
were also Implicated in one of the damage incidents mentioned in
the principal Congressional report on RCRA, again indicating their
likelihood to migrate and persist If mismanaged. (See H. Rep. No.
94-1491, 94th Cong., 2nd Sees., 21.) High local concentrations from
indiscriminate dumping could easily exceed the limit. If phenol
were to migrate to its limit of solubility, concentration levels
would be over 10,000 times the proposed human health water quality
criteria, indicating a potential chronic toxictty hazard.*(*•&)
Tar substances of the subject type generally contain polycyclic
aromatic hydrocarbons (PAH) which are classified as priority pollutants.
The PAH's are limited in movement, but persistent in the environment.
*The reference to the proposed water quality criteria in the text is
not meant to use the proposed standard as a regulatory benchmark, but
to indicate qualitativly that phenol may cause a substantial hazard
If it migrates from the waste in small concentrations.
-------
PAH's are tightly absorbed by fine particles, and so are most likely
associated with stream, river, and lake sediments.C15) Aquatic animal
and plant species living In these media could suffer serious adverse
effects. Furthermore, substantial hazard is associated with exposure
to extremely small PAH concentrations (concentrations of PAH estimated
to result in additional lifetime cancer risks of 1 in 100,000 at 9.7
ng/l(15)) so that only minute concentrations need migrate to create
substantial harm.(15)*
B. Health and Ecological Effects
1. Tars
Health Effects - Tars containing polycyclic aromatic hydro
carbona-^PAH) are suspected carcinogens and mutagens, as well as being
toxic.(15)
Tars, in an oily waste containing petroleum lubricants,
are very toxic chemicals. They are absorbed into the body by Inhala-
tion, Ingestion, and through the skin. The oral 1059 in animals (dog,
rabbit) is 600 mg/kg(*>). Long term dermal exposure (1-43 years) to
coal tar has been reported to cause malignant tumors on hands, face,
and neck of briquette factory workers(^). The U.S.E.P.A. Cancer As-
sessment Group has recommended 9.7 ng/1 total PAH limit for water cri-
teria. The limit was based on animal test data and designed to mini-
mize lifetime cancer risk at a rate below 1 in 100,000(8). The limit
might reasonably be expected to be exceeded in cases of inadequate
*The reference to the proposed water quality criteria in the text
is not meant to use the proposed standard as a regulatory benchmark,
but to indicate qualitatively that PAH's may cause a potential hazard
If they migrate from the waste in small concentrations.
-y-
-------
industrial waste disposal. Polycyclic aromatic hydrocarbons are desig-
nated as priority pollutants (acenaphthylene, anthracene, benzo(a)
anthracene, benzo(a)pyrene, benzofluoranthene, benzo perylene, chry-
sene, dibenzo(a, h) anthracene, fluorene, indenopyrene, phenathrene,
pyrene) under section 307(a) of the CWA. Additional information and
specific references on the adverse effects of PAH tars can be found in
Appendix A.
Ecological Effects - When small amounts of coal tar were
mixed with food and fed to ducks, the toxicologic effect was anemia
and extensive liver damage.O
Regulations - The NIOSI1 recommended standard for occupa-
tional exposure to tar products shall be controlled so employees are
not exposed to substances at a concentration greater than 0.1 mg/m3 for
a ten-hour work shift. PAH's are regulated by the Office of Water and
Waste Management of EPA under the Clean Water Act.
Industrial Recognition of Hazard - According to handbook
used by industry Sax, Dangerous Properties of Industrial Chemicals,
petroleum tar is a recognized carcinogen.
2. Phenol
Health Effects - Prolonged exposure to phenol vapors
has resulted in human digestive disturbances and skin eruptions
Damage to liver and kidneys from this exposure can lead to death.
Exposure to phenol can result in chronic and acute poisoning. It
can be absorbed into the body by inhalation, ingestion, or through
the skin. Phenol is very toxic [oral LD5Q in rats is 414 mg/kg].(H'
Additional information "and specific references on the adverse effects
-------
of phenol can be found in Appendix A.
Ecological Effects - 5 mg/1 phenol is the median lethal
toxiclty (LC5Q) value for the rainbow trout.^ '
Regulatory Recognition of Hazard - OSHA has set a TLV for
phenol at 5 ppm. EPA's draft criterion for phenol in ambient water is
3.4 mg/1, and 1.0 mg for those waters which may be subject to chlori-
nation.(^) The interim drinking water standard for phenol is 1 ug/1.
The aquatic draft criterion for protecting freshwater organisms Is
600 ug/1, not to exceed 3,400 ug/l.(*)
Industrial Recognition of Hazard - Phenol Is listed as a
dangerous disaster hazard, according to the handbook, Dangerous Proper-
ties of Industrial Chemicals^10).
-------
IV. References
1. U.S. Trade Commission. Synthetic organic chemicals. United
States production and sales. Washington, DC. 1978.
2. U.S. EPA. Survey reports on atmospheric emissions from the petro-
chemical industry. V.III. EPA No. 450/337/005C. Research Triangle
Park, NC. April, 197A.
3. U.S. EPA. Stuewe, C. Emission control options for the synthetic
organic chemicals manufacturing industry, trip report - Allied
Chemical Cor poration, Frankford, PA. EPA Contract No. 68-02-2577.
March, 1977.
4. U.S. EPA. Phenol: Ambient water quality criteria. NTIS PB No.
296 787. 1979
5. Baker, E.L, et al. Phenol poisoning due to contaminated drinking
water. Arch. Env. Health pp. 89-94. March-April, 1978.
6. NIOSH. Registry of toxic effects of chemical substances. U.S.
Dept. of Health, Education and Welfare, p. 370. January, 1979.
7. Pierre, F., J. Robillard, and A. Mouchel. Skin tumors in workers
exposed to coal tar. Arch. Mai. Prof. Med. Trav. Secure. Soc.
26:475-82. 1965.
8. U.S. EPA. Carcinogen Assessment Group. Derivation of the water quality
criterion for polycyclic aromatic hydrocarbons. July, 1979.
9. Carlton, W. W. Experimental coal tar poisoning in the white Peking
duck. Avian Pis. 10:484-502. 1966.
10. Sax, N. I. Dangerous properties of Industrial materials, 4th ed.
Van Nostrand Reinhold Co., New York. p. 1008. 1975.
11. U.S. EPA. Multimedia environmental goals for environmental assessment.
V.II. EPA No. 600/7-77-1366. November, 1977.
12. National Academy of Sciences, National Academy of Engineering.
Water quality criteria 1972. A report, National Academy of Sci-
ences. Washington, DC. EPA No. R3-73-033. 1973.
13. Lowenhelm F.A.., and M. K. Moran. Faith, Keyes, and darks's
industrial chemicals, 4th ed. John Wiley and Sons, Inc., New
York. 1975.
14. U.S. EPA. Industrial process profiles for environmental use: Chapter 6,
The industrial organic chemicals industry. Ralmond Llepins, Forest
Mixon, Charles Hudak, and Terry Parsons. EPA No. 600/277-023f. 1977.
15. U.S. EPA. Water quality criteria document, polynuclear aromatic
hydrocarbons. NTIS PB No. 297 926.
-------
16. Dawson, English and Petty. Physical chemical properties of
hazardous waste constituents. 1980.
-------
Response to Comments - Distillation Bottom Tars from the
Production of Phenol/Acetone from Cumene
Distillation bottom tars from the production of phenol/acetone
from curaene (K022) are listed as hazardous because they contain both
phenol and polycyclic aromatic hydrocarbons (PAHs). One commenter
objected to the inclusion of phenol as a constituent of concern in
this particular listing. The commenter argued that since phenol has
not been established as a carcinogen, the compound is not of significant
toxicity to be included as a basis for listing. The commenter also
pointed out some inconsistencies between the aformentioned listing
background document and the Health and Environmental Effects Profile
on phenol.
The Agency strongly disagrees with the commenter. While the
carcinogenicity of phenol has not been firmly established, both liver
and kidney damage to humans will result from the chronic exposure to
phenol with death a potential consequence. In addition, the acute
toxicity of phenol results in central nervous system (CNS) depression
with symptoms severe enough to earn phenol an acute toxicity rating
of "high" in Sax.C10) This widely accepted reference indicates
that "death or permanent injury may occur due to exposure at normal
use..." Therefore, the Agency will continue to include phenol as a
constituent of concern in this particular listing.*
*It should be noted that the Agency recently determined to retain
the listing of phenol as a toxic pollutant under $307(a) of the Clean
Water Act. The reasons for that action are incorporated by reference
herein.
-------
PS-15-01
HAZARDOUS WASTE BACKGROUND DOCUMENT
PHTHALIC ANHYDRIDE PRODUCTION
Distillation light ends from the production of phthalic
anhydride from naphthalene (T)
Distillation bottoms from the production of phthalic
anhydride from naphthalene (T)*
Distillation light ends from the production of phthalic
anhydride from ortho-xylene (T)
Distillation bottoms from the production of phthalic
anhydride from ortho-xylene (T)**
I. Summary of Basis for Listing
The production of phthalic anhydride via vapor
phase oxidation of naphthalene or ortho-xylene results in the
generation of distillation residues which contain carcinogens
and toxic organic compounds. The residues of concern are
the light ends and bottoms which result from the distillation
step in which crude phthalic anhydride is purified. The
waste constituents of concern are phthalic anhydride, maleic
anhydride, and 1,4-naphthoquinone.
*0n May 19, 1980, EPA promulgated in interim final form,
"Distillation bottoms from the production of phthalic
anhydride from naphthalene" as hazardous because It contains
among other things naphthoquinones. In re-evaluating the
process chemistry, however, the Agency believes that 1,4-
naphthoquinone will be the predominant isomer found in
this waste and, thus is modifying the constituent of concern
to refer to 1,4-naphthoquinone rather than the general class
of napthoquinones.
**The Agency listed quinones as a hazardous constituent of
concern for hazardous waste listing No. K094 (Distillation
bottoms from the production of phthalic anhydride from orth-
xylene). In re-evaluating the toxicity of these compounds,
the Agency believes that Insufficient data is currently
available regarding the acute and chronic effects of the
higher molecular weight quinones and their derivatives to
support designating them as toxic constituents of a waste.
The Agency would only expect to find the higher molecular
weight quinones ir this waste, based on the process chemistry
Therefore, the Agency has removed quinones as a constituent
of concern for this waste stream.
-------
With respect to the commenter's concern as to inconsistencies
between the listing background document and the Health and Environmental
Effects Profile on phenol, the Agency will make the appropriate
corrections.
-------
The Administrator has determined that these distill-
ation residues 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 therefore should be subject to appro-
priate management requirements under Subtitle C of RCRA.
This conclusion Is based on the following considerations:
(1) The light ends from both processes contain phthalic
anhydride and maleic anhydride while the heavy ends from both
processes will contain phthalic anhydride. The heavy
bottoms from the naphthalene-based process will also contain
1,4-naphthoquinone .
(2) Phthalic anhydride, maleic anhydride and 1,4-naphthoqulnone
are organic toxicants. 1,4-Naphthoquinone and maleic anhydride
are also animal carcinogens.
(3) More than 16 million pounds of the constituents of
concern will be generated annually and require disposal a*
a result of phthalic anhydride production (assuming plants
are operating at production capacity).
(4) Disposal of these wastes in improperly designed or operated
landfills could result in substantial hazard via groundwater
or surface water exposure pathways. Disposal by incineration,
if mismanaged, can result in serious air pollution through
release of hazardous vapors, due to incomplete combustion.
Transportation of wastes off-site by contract haulers
Increases the possibility of mismanagement.*
11. Sources of Waste and Typical Disposal Practices
A. Industry Profile
The major use of phthalic anhydride is in the
manufacture of plastics, plasclcizers, paints and synthetic
^Although no data on the corroslvlty of these waste
streams are currently available, the Agency believes that
phthalic anhydride, maleic anhydride and 1,4-naphthoqulnone
are highly corrosive materials, and that these waste streams
may therefore be corrosive. Under-§262.11, generators of
these waste streams are responsible for determining whether
their wastes meet any of the characteristics.
-------
resins (3). Producers of phthalic anhydride from ortho-xylene
or naphthalene and the production capacities of these plants
are listed in Table 1. About 70% of industry capacity is
ortho-xylene-based.
Manufacturing Process
Phthalic anhydride is manufactured by the vapor phase
oxidation of ortho-xylene or naphthalene (see Figures 1 and
2 for flow diagrams). The primary naphthalene-based processes
use fluidized bed reactors. All xylene-based processes incor-
porate tubular fixed bed reactors. Except for the reactors
and catalyst handling and recovery facilities required for
the fluid unit, these vapor phase processes are similar (3).
The two basic reactions are as follows:
Napthalene-based
O
I]
c.
Ortho-xylene based
0
— ^\
-3 V205
o
fTITttJJC ANHYDRIDE
In the naphthalene-based process, naphthalene is introduced
Into a fluidized bed reactor near the catalyst bed. In the
xylene-based process, o-xylene is mixed with air and introduced
Into a fixed bed tubular reactor (in which the catalyst is con-
tained in the tubps). Both processes typically use a vanadium
-------
Table 1. Producers of phthallc anhydride
Producer
Allied Chem. Corp.
Specialty Chems. Olv.
BASF Wyandotta Corp.
Colors and Intermediate Group
Intermediates Dlv.
Exxon Corp.
Exxon Chem. Co., div.
Exxon Chem. Co. U.S.A>
Koppers Co., Inc.
Organic Materials Group
Monsanto Co.
Monsanto Chem. Intermediates Co.
Occidental Petroleum Corp.
Hooker Chem. Corp., subs id.
Hooker Chems. and Plastics Corp.
subsid.
Puerto Rico Chem. Co., subsId.
Standard Oil Co. of California
Chevron Chem. Co., subsid.
Petrochem. Div.
Stepan Chem. Co.
Surfactant Dept.
United States Steel Corp.
USS Chems., div.
Location
El Segundo, Callf<
Kearny, N.J.
Baton Rouge, La.
Bridgevllle, Pa.
Cicero, 111.
Bridgeport, N.J.
Texas City, Tex.
Arecibo, P.R.
Richmond, Calif.
Millsdale, 111.
Neville Island, Pa.
Annual Capacity
(Millions of Pounds)
36
150
130
90
235
85
150
TOTAL
87
50
100
205
1318
Raw Material
o-xylene
o-xylene
o-xylene
Desulfurized coal-tar
naphthalene
o-xylene or
naphthalene
Petroleum naphthalene
o—xylene
o-xylene
o-xylene
o-xylene
Desulfurized coal tar
naphthalene
Source: Reference 1
-------
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-------
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-------
The r.iactor effluent from both processes will contain
phthalic anhydride, maleic anhydride*, and miscellaneous organ-
ics (including iused-ring compounds). The ortho-xylene based
process will generate quinones** as part of its waste stream. The
naphthalene-based process will generate naphthoquinones.(^)
Crude phthalic anhydride is condensed by passing through
a series of switch condensers. (The condenser effluent gases
are normally water scrubbed and/or sent to an incinerator
before being released to the atmosphere.) As part of the puri-
fication process, the crude product is first distilled to
remove light ends. The stripped crude phthalic anhydride is
then distilled in a second column where heavy bottoms will
remain once the pure product is removed.(3) These distillation
residues are the waste streams of concern.
II. Waste Generation and Management
Some actual plant data describing light ends and bottoms
generation are available. One naphthalene-based plant, with a
published production capacity of 125 million pounds/year
phthalic anhydride, reported to dispose of 58,000 pounds/month
of light ends and 400,000 pounds/month of bottoms. This plant had
these wastes hauled off-site by a contractor (3), probably for
disposal by landfill.
*Process chemistry indicates that maleic anhydride will
be present in lower concentrations in the effluent generated
from ortho-xylene based phthalic anhydride production.
**A3 indicated earlier, the Agency would only expect to find
the higher molecular weight quinones in this waste based on the
process chemistry. In re-evaluating the toxicity of these higher
molecular weight quinones, we believe that insufficient data is
currently available regarding the acute and chronic effects of
these compounds; therefore, quinones will not be included as a
constituent of concern.
-------
A second naphthalene-based plant, with nominal capacity
of 90 million pounds/year, reported a combined total waste
load of 45,000 pounds/month. This plant utilized an on-site
landfill for solid waste disposal.(3)
One plant using ortho-xylene as a raw material reported
a light and heavy ends generation rate of 0.02 tons/ton of
phthalic anhydride produced. Another ortho-xylene plant
reported that it generated 0.002 tons of distillation bottoms
per ton of phthalic anhydride produced. Both plants reported
that these wastes are sent off-site for disposal'-*'.
Based on typical material balance data(3)*, it can be
estimated that the following amounts of the constituents of
concern will be contained in the distillation residues
generated as a result of total phthalic anhydride production
(assuming all plants are operating at production capacity):
Constituent
phthalic
anhydride
maleic
anhydride
1,4-naphthoquinone
Amount from xylene-based production
(million Ibs./yr.)
light ends heavy bottoms
>0.9
**
Amount from Napthalene-based
(million Ibs./yr.)
light ends heavy bottoms
>0.2
>2.5
>2.5
*Estimates based on typical material balance data for average plants
producing 130 million Ibs./yr of phthalic anhydride from ortho-xylene
and from naphthalene. Source: reference 3.
**Process chemistry indicates that maleic anhydride will be present
in lower concentrations in the light ends generated from phthalic
anhydride production from ortho-xylene than from naphthalene, due to
the nature of the basic chemical reactions.
-«-) II -
-------
Disposal practices for distillation residues will
vary. Light ends, either in a vapor or liquid state, are
usually incinerated. However, as noted above, one plant
reported having this waste, along with the heavy ends, hauled
off-site by a contractor^), probably to a landfill disposal site.
Distillation bottoms may also be incinerated, but are typically
disposed of in landfills either on or off-site. O)
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
As noted above, distillation residues (light ends
and heavy bottoms) from phthallc anhydride production contain
the following components as they are discharged from the
plant distillation units:
Phthalic anhydride
Haleic anhydride *
1,4-Naphthoquinone
All of the above waste constituents are toxic. 1,4-Naphthoquinone
and maleic anhydride are also demonstrated carcinogens.
These waste constituents appear capable of migration,
mobility and persistence if mismanaged, creating the potential
for substantial hazard in light of the dangers associated with
contact with the waste constituents. As previously noted, dis-
posal of these wastes may be by incineration, on-site landfllllng,
*Malelc anhydride, while an animal carcinogen, hydrolizes
and photolyses rapidly to non-toxic maleic acid and thus is not
expected to pose a hazard via a water or air exposure pathway.
It may, however, prove hazardous during waste transport to
off-site disposal.
-------
or off-site,disposal (probably a landfill). Improper design and
management of land disposal facilities could lead to the release
of hazardous constituents and pose a hazard via a groundwater
exposure pathway. Some of the waste constituents have in fact
proved capable of migration, mobility and persistence via this
pathway. For example, phthalic anhydride has been identified in
finished drinking water.C14)
1,4-Naphthoquinone is relatively soluble (about 200 mg/1),
and thus may also migrate from the matrix of the waste.
Disposal by incineration, if mismanaged, can present a
health hazard via an air inhalation pathway. Incomplete
combustion of the distillation residues from phthalic anhydride
production can result in the formation of various phthalate
esters which will be released from the incinerator into the
air. (These esters would be formed from the reaction of
phthalic acid with alcohols.) Certain phthalates have shown
mutagenic effects. Phthalates have also been shown to produce
teratogenic effects in rats. Chronic toxicity Includes toxic
polyneurltis in workers exposed primarily to dibutyl phthalate
(see Appendix A).
Contract hauling, in particular, presents an additional
potential for mismanagement in the transportation and handling
operations. Transportation of these wastes off-site, if not
properly managed, increases the likelihood of their causing harm
to human health and the environment. The mismanagement of wastes
during transportation thus may result in hazard to human health
-------
and wild'.ife throi-gii direct exposure Co the harmful constituents
listed above (either by direct contact with the waste or through
wind-carried particulate matter and vapors). Furthermore, absent
proper management safeguards, the wastes might not reach the
designated destination at all, thus making them available to do
harm elsewhere. It should be noted that maleic anhydride, which
is not otherwise a constituent of concern due to its lack of
persistence, could prove hazardous during transport and handling,
since the possibility of immediate exposure exists.
The large quantity of waste generated and requiring disposal
is another factor which increases the likelihood of exposure to
the harmful constituents in the waste via the various exposure
pathways. Should the large amounts of waste constituents exposed
to leaching activity be released as a result of mismanagement,
large areas of ground and surface waters may be affected. Contam-
ination could also occur for long periods of time, since large
amounts of pollutants are available for environmental loading.
Attenuative capacity of the environment surrounding the disposal
facility could also be reduced or used up due to the large quan-
tities of pollutants available over long periods of time. All
of these considerations, in the Agency's view, strongly support
a hazardous waste listing.
-------
B. Health and Ecological Effects
1. Maleic Anhydride
Health Effects - Maleic anhydride can produce
cancers following subcutaneous injections in rats.($) Maleic
anhydride is also highly toxic [ORAL rat LD50 - 481 mg/Kg] and
is known to cause acute irritation of the eyes, skin and upper
respiratory tract. There is also evidence that this compound may
cause reproductive impairment in male rats (4). Additional infor-
mation and specific references on the adverse health effects of
maleic anhydride can be found in Appendix A.
Regulations - OSHA has set a standard for air of
TWA at 0.25 ppm for an 8-hour day.(7)
Industrial Recognition of Hazard - In Sax, Dangerous
Properties of Industrial Materials, Maleic anhydride is desig-
nated as highly toxic by ingestion, and also as an irritant.
Fassett and Irish in Industrial Hygiene and Toxicology state
that maleic anhydride can produce severe eye and skin burns.
Plunkett, in his Handbook of Industrial Toxicology designates
maleic anhydride as a causal agent of severe eye and skin
burns.
2. Phthalic Anhydride
Health Effects - There is evidence that phthalic
anhydride may act as a teratogen in chick embryos'"'. It is
a potent irritant of the skin, eyes, and upper respiratory
tract. Exposure has been reported to produce progressive
respiratory damage, Including fibroses of the lungs^»').
In addition, degeneration of liver, kidney and myocardium
-------
occured(6). There is also evidence that this compound may
cause reproductive impairment in male rats'*'. Additional
information and specific references on the adverse effects of
phthalic anhydride can be found in Appendix A.
Regulations - OSHA has set a TWA for an 8-hour
exposure at 2 ppm.(')
Industrial Recognition of Hazard - Sax (Dangerous
Properties of Industrial Materials) lists phthalic anhydride
as having a moderate toxic hazard rating via oral routes.
3. 1,4-Naphthoquinone
Health Effects - 1,4-Naphthoquinone has been demonstrated
to be a carcinogen when applied to the skin of test animals'^).
This chemical is extremely irritating to the skin, mucous mem-
branes and respiratory tract. It can cause skin and pulmonary
sensitization resulting in asthmatic and allergic responses.
Changes in the blood that reduce its oxygen carrying capacity
have also been demonstrated following 1,4-naphthoqulnone exposure
which may develop into hemolytic anemia. 1,4-Naphtoquinone is also
suspected of causing adverse reproductive effects. Additional
information and specific references on the adverse effects
of 1,4-napthoquinone can be found in Appendix A.
Ecological Effects - Naphthoquinone, at a concentration
of 1.0 mg/1 will cause death within 3 hours for bluegill and
trout, and 14 hours for larval lamprey (10).
Industrial Recognition of Hazard - 1,4-Naphthoquinone
is designated in Sax's Dangerous Properties of Industrial Materials
as a moderately toxic irritant to skin, eyes, and the upper
respiratory tract.
-------
IV. References
1. Stanford Research Institute. Directory of chemical
producers-United States. SRI International, Menlo
Park, CA. 1979.
2. Not used in text.
3. U.S. EPA. Office of Air Quality Planning and Standards.
Engineering and cost study of air pollution control for
the petrochemical industry, V.7: Phthalic anhydride
manufacture from ortho-xylene. Research Triangle Park,
North Carolina. EPA No. 450/3-73-006g. NTIS PB No. 245
277. July, 1975.
4. Protsenko, E.I. Gonadotropic action of phthalic anhydride,
Gig. Sanit. 35:105. 1970.
5*. NIOSH. Registry of toxic effects of chemical substances.
U.S. Dept. of Health, Education, and Welfare. 1979.
6. U.S. EPA. Preliminary environmental hazard assessment
of chlorinated naphthalenes, silicones, fluorocarbons,
benzenepolycarboxylates and chlorophenols. Syracuse
University Research Corporation, NTIS PB No. 238 074.
1973.
7. American Conference of Governmental Industrial Hygienists.
Documentation of threshold limit values for substances
in workroom air, 3rd Edition. 1971.
8. Markroan and Savinkina. The condition of the lungs of
workers in phthalic anhydride production (an X-ray study).
Kemerovo 35. 1964.
9. Plunkett, E.R. Handbook of industrial toxicology, pg. 338,
10. Applegate, V.C., J.H. Howell, and A.E. Hall, Jr.
Toxicity of 4,346 chemicals to larval lampreys and
fishes. Department of Interior, Special Scientific
Report Number 207. 1957.
11. Not used in text.
12. Not used in text.
13. Not used in text.
14. U.S. EPA. Shackelford and Keith. Frequency of organic
compounds identified in water. Environmental Research
Laboratory. Athens, GA. EPA No. 600/4-76-062. NTIS PB
No. 265 470. December, 1976.
-------
Response ti Coangats - Distillation Light Ends and Bottoms
from the Production of Phthalic Anhydride fron Naphthalene
One commentec raised several questions with respect to
wastes K023 and K024 (Distillation light ends and bottoms
from the production of phthalic anhydride from naphthalene).
1. The commenter first argued that inclusion of wastes
from the production of phthalic anhydride appear to
be based generally on the nature of known acute
hazards from the pure or technical grade components
of chemicals found in the waste rather than the toxlcity
of the waste itself, i.e., the commenter indicated that
the actual waste contains considerable amounts of inert
materials rejected from the process. Additionally, the
commenter felt that the listing background document
did not adequately address the solubility and actual
hazards of the waste. Needing an explanation of this
particular comment, the Agency contacted the commenter
and requested further clarification. The commenter
indicated that the hazardousness of the waste should be
determined by taking a. representative sample of the
waste, applying the extraction procedure (EP), and the
decision as to whether the waste is hazardous be based
on the results of the EP test".
The commenter quite simply mispercelves the sepa-
rate regulatory mechanisms of identifying hazardous
wastes through individual listings or through charac-
teristics. (This distinction is explained in detail
-------
in th.c preamble to Part 261 and In Che Background Docu-
ments concerning the Criteria for Listing and the EP
Toxlcity Characteristic.) In initially developing the
'. oxlclty characteristic, the Agency Intended the extrac-
tion procedure (EP) to Identify toxic contaminants
other than those specified In the National Interim
Primary Drinking Water Standards (N1PDWS). However,
the Agency was unable to do this, because no other
chronic exposure threshold levels relating to drinking
water consumption have been established for other contami-
nants. More Importantly, the Agency was not fully
confident that It could suitably define and construct
testing protocols to accurately assess the hazards
presented by these other toxic contaminants. Therefore,
the Agency presently has decided to regulate wastes
containing non-drinking water standard contaminants
through the listing process.
The criteria for listing toxic wastes are intended
by EPA to Identify all those wastes which are toxic,
carcinogenic, mutagenic, teratogenic, phytotoxlc or
toxic to aquatic species. These criteria provide that
a waste will be listed where it contains any of a number
of designated toxic constituents-unless, after consideration
of certain specified factors (see §26L.11(a)(3) for list
of factors), the Agency concludes that the waste does not
meet Part B of the statutory definition of hazardous waste.
-------
The Agciii_y has adopted this flexible, multiple factor
approach to listing toxic wastes rather than the formulaic
approach embodied in the characteristics because it
considers this approach to be better able to accoraodate
itself to complex determinations of hazard. EPA further
believes that this multiple factor approach was to some
extent contemplated by Congress (see the preamble to the
Part 261 regulations for a more detailed discussion).
In using this approach, the Agency has listed
both distillation light ends and bottoms from the pro-
duction of phthalic anhydride from naphthalene as
hazardous because: (1) these wastes contain a number
of toxic constituents which have been identified by the
Agency (i.e., phthalic anhydride, raaleic anhydride and
1, A-naphthoquinones. and (2) after considering a number
of the factors specified in §261.11(a)(3) including
the toxicity presented by the constituents, the capability
of the toxic constituents in the waste to migrate from
the waste and be mobile and persistent in the environment,
the quantities of toxic contaminants generated in the
waste, plausible types of improper management to which
the waste could be subjected, etc., the Agency believes
that these wastes, if improperly managed, could present
a substantial hazard to human health or the environment.
However, it should be noted that one of the constituents
of concern, tars, has been removed as a basis for listing.
-------
In re-evaluating -he coxlclty of these chemical tars,
the Agency belif . :- that Insufficient data is currently
available t-> con^id'-r -'leraical tars as suspect carcinogens
(I.e., alL the data on the carclnogenicity of these
tars is on coal tars not chemical tars). Therefore,
the listings distillation light ends and bottoms from
the production of phthalic anhydride from napthalene
have been amended to remove tars as a constituent
of concern.
(2) The commenter then argued that wastes which are
properly managed (i.e., by incineration) should not
be classified as hazardous because, incineration is
a proper management technique. In defining a hazardous
waste, the Agency has attempted to reach those wastes
which are hazardous if mismanaged under some likely
mismanagement scenario. This of course is what the
statute requires, see Section 1004(5) of RCRA. The
purpose of this definition is to bring these wastes
into the hazardous waste management system set up by
Sections 3002 through 3005 of RCRA—not to specify
management practices. If management practices were
made part of the definition so that properly managed
wastes were excluded from the definition, the effective-
ness of the management system created under Sections
3002 through 3005 might well be vitiated, since properly
managed wastes would be excluded at the outset from the
-------
continuing supervision and control provided by the
management system thus prejudicing the Agency's ability
to ensure continued compliance with these proper manage-
ment practices. The regulations promulgated under
§§3004 and 3005 on May 19, 1980 (45 FR 33154-33588),
and those to be promulgated in the future will be
sufficiently flexible to accommodate wastes which are
properly managed and allow these facilities to continue
their present operations.
Based on the foregoing discussion, the Agency will
continue to list wastes K023 and K024 (Distillation light
ends and bottoms from the production of phthalic anhydride
from naphthalene) as hazardous.
-------
LISTING BACKGROUND DOCUMENT
NITROBENZENE PRODUCTION
0 Distillation bottoms from the production of nitrobenzene
by the nitration of benzene (T)
I. Summary of Basis for Listing
Distillation bottoms from the production of purified nitrobenzene by
the nitration of benzene contain carcinogenic, mutagenic, and toxic organic
substances. These include meta-dinitrobenzene and 2,4-dinitrotoluene as
the pollutants of concern.
The Administrator has determined that the distillation bottoms
from nitrobenzene production by the nitration of benzene may pose a
substantial present or potential hazard to hunan health or the environ-
ment when improperly transported, treated, stored, disposed of or
otherwise mismanaged, and 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 meta-dinitrobenzene which is extremely
toxic and 2,4-dinitrotoluene, a carcinogen and mutagen.
2) The distillation bottoms from the distillation of nitro-
benzene are currently disposed of in drums in private land-
fills. However, these drums have a limited life-time and
eventual rupture is likely. When this occurs, the potential
for ground water contamination is high if the landfill is
not properly designed or operated. Such nitrobenzene accidents
have actually occurred.
3) The wastes in this stream biodegrade very slowly, thereby in-
creasing the chances for exposure and posing a risk to humans.
II. Sources of Waste and Typical Disposal Practices
A. Profile of the Industry
The major use of nitrobenzene (CgH5N02) (about 97%)
is as an Intermediate In the manufacture of aniline dyes.O
The balance is purified for use chiefly as a solvent or in the manufac-
-------
cure of Pharmaceuticals. Nitrobenzene is manufactured in seven
plants, all located In the eastern and southern regions of the
U.S. Table 1 lists these plants and their production capacities.
TABLE 1. Nitrobenzene Producer Locations and Production Capacities^2)
Company
American Cyanamid Co.
Organic Chema Div.
E.I. DuPont deNemours
& Co., Inc.
Chems. Dyes and
Pigments Dept.
Indust. Chems. Dept.
First Mississippi Corp.
First Chem. Corp.,
Subsid.
Mobay Chem. Corp.
Polyurethane Div.
Rubicon Chema., Inc.
Facility
Bound Brook, NJ
Willow Island, WV
Beaumont, TX
Gibbstown, NJ
Pascagoula, MS
New Martinsville, WV
Geismar, LA.
TOTAL
1978
production
Capacity
(Gg)*
48
33
140
90
151
61
34
557**
*Gg = billion grams or 1000 metric tons (mt).
mt = 2,200 pounds.
**The 1978 U.S. production of nitrobenzene by the nitration of benzene
vas 260 (103) mt.<2>
-------
The production of nitrobenzene has been fairly stoble and can
be expected to grow in relation to the growth in demand for aniline
production that requires nitrobenzene as a feedstock.
Based on a total nitrobenzene production of 260 Gg/yr (286,000
tons), the amount of nitrobenzene subject to purification by distillation
is 31 of production, or 7.8 Gg/yr (8580 tons).(22)
B. Manufacturing Process (21)
Nitrobenzene is made by the direct nitration of benzene using
a sulfuric-nitric acid mixture (Fig. 1). Commercial specification for
the benzene raw material is:
Benzene 99.8%
Toluene 0.1% Maximum
Saturated hydrocarbons 0.1% Maximum
Thiophene 1 ppm
Benzene is added to a slight excess of the sulfuric-nitric
acid mixture (53-60% sulf uric acid; 32-392 nitric acid; 8% water;
a stochiometrlc excess of nitric acid is used) slowly with agitation
and heat removal. The reaction residence time is 2-4 hours. At
the end of this time, the mixture is allowed to settle and the crude
nitrobenzene is withdrawn; the separated, mixed acids (mostly sulfuric)
are then sent to acid recovery and reused. The small amount of
organic material contained in this stream is recovered from the acid
concentration plant and recycled. The crude nitrobenzene is first
washed with dilute sodium carbonate solution to neutralize acids,
then distilled. The nitrobenzene is recovered as an overhead product.
Distillation bottoms, the listed waste stream, are then disposed of
as waste.
-------
MIXED SULFUniC
NITRIC AGIO
DENZENE
^
0
TO 'ANILINE'
MANUFACTURE
^X
D
S^
t
UTC-O
i
SPENT MIXED
ACIDS TO
WASI
Na,C6»
HiO NITROBENZENE
UNO
NTER
C
1
WASTE
WATER
1
ISTILLATIO
1
ORGANIC
WASTES
M
RECOVERY
Figure 1. FLOW DIAGRAM
NITRATION OF BENZENE
(Modified Erom (21))
-------
C. Waste Generation and Management
The distillation bottoms are deemed to consist primarily of
nitrobenzene, meta-dinitrobenzene, and 2,4-dinitrotoluene. Meta-
dinitrobenzene and 2,4-dinitrotoluene are the waste constituents of
concern.
2,4-Dinitrotoluene is predicted to be present from the nitra-
tion of impurities in feedstock benzene, chiefly toluene (0.17.) and
paraffinlc hydrocarbons of the 05 to Cg range (0.1Z). (See p. 3,
above).
Meta-dinitrobenzene is predicted to result from the dinitra-
tion of benzene feedstock. Based upon reaction and equilibrium chemis-
try, it is estimated that approximately 2-3% of the benzene feedstock
will produce dinitrobenzene.
The potential amounts of carcinogenic and/or toxic chemicals
that will be in the waste from the distillation of 7.8 Gg/yr of crude
nitrobenzene (p. 3) are estimated to be:
meta-dinitrobenzene 156-195 mt/yr
2,4-dinitrotoluene 10 mt/yr
Total 166-205 mt/yr*
The usual disposal method of the subject distillation bottoms that
cannot be recovered or used directly as a chemical intermediate is
disposal in drums in private landfills.
*These estimates assume that all contaminants will be separated from
the product by distillation, and consequently will all be present in
the waste.
X
-------
III. Discussion of Basis for Listing
A. Hazards Posed by Waste
As stated above, the constituents of concern in this waste are
roeta-dinitrobenzene, an acutely toxic compound, and 2-4-dinitrotoluene
a carcinogen and mutagen. Both of these constituents are estimated
to be present in substantial concentrations, and to be generated
in large quantities annually. This information itself is sufficient
to warrant hazardous waste listing, in light of the danger posed by
the waste constituents*, unless it can be demonstrated that the waste
constituents will not migrate and cone in contact with environmental
receptors.
No such assurance appears possible, as both waste constituents
are projected to have migratory potential and to be mobile and persistent
in ground and surface water (App. B), so that they can create a
substantial hazard if disposal landfills are not properly designed
and operated. Thus, meta-dinitrobenzene, which is highly water
soluble (3000 ppm), can migrate without degradation through unsaturated
sandy soils, and resist degradation in ground and surface waters
(App. B).** 2,4-Dinitrotoluene is also highly soluble (2000 ppm In
water), and has been demonstrated to migrate through unsaturated
sandy soil, and to be persistent in the environment. (App B).
*For example, it is Agency policy that there is no safe exposure level
for carcinogens, i.e., a single dose in any concentration being suffi-
cient to cause cancer in some part of the exposed population.
**For example, msta-dinltrobenzene has been demonstrated to be only
slowly biodegradable in a synthetically prepared sewage effluent.(*»5»
-------
If Che wastes are landftiled, even in plastic-lined drums, they
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 all of the subject production facilities are located in regions of
significant rainfall (Gulf Coast, 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.)
Nitrobenzenes have in fact migrated from landfills, persisted
in and contaminated ground water In actual waste management practice.
Nitrobenzenes and other wastes from a Monsanto Chemical dump migrated
into and caused contamination of groundwater in E. St. Louis, Illinois.*
At the La Bounty dump along the Cedar River in Charles City, Iowa,
130,000 kg of nitrobenzenes were disposed of along with several
other chemicals. Groundwater collected between the La Bounty dump
and the Cedar River contained considerable concentrations of the
chemicals including nitrobenzenes.*
These waste constituents, therefore, are capable of migrating
from Improperly designed and operated landfills, and reaching environ-
mental receptors. Drumming of these wastes, as occurs in actual prac-
*OSW Hazardous Waste Division, Hazardous Waste Incidents, Unpublished,
Open File, 1978.
/
-------
tice, is not an adequate precaution as demonstrated by the Love
Canal incident, among others.
These wastes may also create a substantial hazard via a sur-
face water exposure pathway. Should the disposal site be flooded and
the wastes come Into contact with the surface water, the nitrobenzenes
and nltrotolueaes will resist evaporation due to their weight relative
to air and their low vapor pressure. As they are also soluble and
only slowly degradable (App. B), they have the potential for wide-
spread exposure should surface waters become contaminated.
B. Health and Ecological Effects
1. Meta-dlnitrobenzene
Health Effects - Meta-dlnltrobenzene Is extremely toxic
[LD5Q rat 30ng/Kg.] acting as a potent methemoglobln-forming agent,
I.e., an agent that reduces the oxygen-carrying capacity of the blood,
a condition that can rapidly lead to death.O Meta-dlnitrobenzene
can also cause liver damage, serious visual disturbances, and severe
anemia, as well as a variety of central nervous system and gastrointes-
tinal symptoms.(7)(8) Meta-dinltrobenzene can be stored in body fat.
Exposure to sunlight or ingestlon of alcohol may potentiate or increase
the adverse effects of poisoning.(*) Meta-dinitrobenzene IB designated
as a priority pollutant under Section 307(a) of the CWA. Additional
Information on the adverse effects of meta-dinltrobenzene can be found
in Appendix A.
Ecological Effects - Concentrations of from 2 to 12 mg/1
of unspecified isomers of dinitrobenzene have been reported lethal to
fish.(9X1Q) Meta-dinltrobenzene has been shown to inhibit photosyn-
thesis in
-------
Regulatory Recognition of Hazard - OSHA has set Che TWA
For dinitrobenzen* at 0.15 ppm. DInitrobenzene Is regulated by the
Office of Hater and Waste Manageraent of EPA under the Clean Water Act,
Section 311. Technical assistance has been requested to obtain data
on environmental effects* high-volume producttonv and spill reports.
Industrial Recognition of Hazard - According to handbooks
used by industry such as, Sax, Dangerous Properties of Industrial
OieTOYcalB/1^ the oral toxic "nazard rating is high for dinltro-
benzene. When heated, it is dangerous, decomposing to emit toxic
fumes; It also posseses an explosion hazard. According to Plunkett,
Handbook of Industrial Toxicology, ^ ) m-dinitrobenzene is extremely
toxic by oral, inhalation, and percutaneous routes. According to
Patty, Industrial Toxicology, ^^) m-dinitrobenzene is highly toxic.
2. 2,4-Pinltrotoluene
Health Effects This compound has been shown Co be a
carcinogen'^)(15) ami a tnutagen. (16,17) 2,4-Dlnitrotoluene
also causes a decrease in sperffl production and atrophy of the testes.
2,4-Dinitrotoluene is very toxic [1059 (rat) - 268 mg/Kgl.
Effects of exposure Include metheoQglablaet&ia followed by cyanosis,
liver damage, anemia and other abnormalities of the blood and effects
on the central nervous system and digestive tract. Linitrotoluene is
also an irritant an& an allergen. Alcohol produces a synergistic or
aggravated effect on the toxicity.(18,19) 2,4-Dlnitrotoluene
Is designated as a priority pollutant under Section 3Q7{a) of the
CWA. Additional information on the adverse effects of 2,4-dlni-
trotoluene can be found in Appendix A.
-------
Ecological Effects - An aquatic toxicity for 2,4-dinltrotoluene
of 10-100 ppm has beea establlshedC20).
Regulatory Recognition of Hazard OSHA has aet the TWA foe
2,4-dinitrotoluene in air at 1500 micro-g/m^ (skin).
Industrial Recognition of Hazard - According to handbooks used
by industry, such as Sax, Dangerous Properties of Industrial Materials^12),
the oral toxic hazard rating for 2,4-dinltrotoluene is very high.
-------
IV. References
1. U.S. EPA. Assessment of industrial hazardous waste practices:
Organic chemicals, pesticides, and explosives industries.
EPA No. 530/SW-118C. NTIS PB No. 251 307. January, 1976.
2. Stanford Research Institute. 1979 Directory of chemical producers-
U.S.A. SRI International, Menlo Park, CA. 1979.
3. U.S. EPA. Recommended methods of reduction, neutralization,
recovery, or disposal of hazardous wastes, V. XI: Industrial
and municipal disposal candidate waste stream constituent
profile reports, organic compounds (continued). EPA No. 670/2-
73-053-k. NTIS PB No. 224 590. August 1973.
4. U.S. EPA. Bernhard, E.L., and G.R. Campbell. The effects of
chlorination on selected organic chemicals* U.S. Environmental
Protection Agency. NTIS PB No. 211 160. 1972.
5. G. Bringmann and R. Kuehn. Biological decomposition of nitrotoluenes
and nitrobenzenes by Azotobacter agilis. Gesundh. Ing. 92(9):273-276.
L971.
6. Allen, L.A. The effect of nitre-compounds and some other sub-
stances on production of hydrogen sulfhide by sulfate-reducing
bacteria In sewage. Prec. Soe. Appl. Bact. (2):26-38. 1949.
7. U.S. EPA. Investigation of selected potential environmental
contaminants: Nitroaromatics. NTIS PB Ho. 275 078. 1976.
8. Plunkett, E.R. Handbook of Industrial Toxicology.
9. McKee and Wolf. Water quality criteria. The Resource Agency of
of California, State Water Quality Control Board. Publication
No. 3-4. 1963.
10. Meinck, et al. Industrial waste water, 2nd ed. Gustav Fisher
Verlag Stugart. p. 536. 1956.
11. Not used in text.
12. Sax, N.I. Dangerous properties of industrial materials, 4th ed.
Van Nostrant Reinhold Company, New York. 1975.
13. Patty, T.A. Industrial hygiene and toxicology. G.D. Clayton and
F.E. Clayton, eds. 3rd rev. Wiley Publications, New York. 1978.
14, Purchase, I.F.H,, et al. An evaluation of 6 short-term tests for
detecting organic chemical carcinogens. Br. J. Cancer 37:873-958.
1978.
-------
15. National Cancer Institute. Bloassay of 2,4-dinitrotoluene for
possible carcinogeniclty. U.S. Department of Health, Education
and Welfare, Public Health Service, National Institute of Health.
•4TIS PB No. 280 990. 1978.
16. Won, W.D., et al. Mutagenlcity studies on 2,4-dinitrotoluene.
Mutat. Res. 38:387. 1976.
17. Hodgson, J.R., et al. Mutagenlcity studies on 2,4-dinitrotoluene.
Mutat. Res. 38:387. 1976.
18. Frledlander, A. On the clinical picture of poisoning with
benzene and toluene derivatives with special reference to the so-
called anilinisn. Neurol. Zentrabl. 19:155. 1900.
t
19. McGee, L.C., et al. Metabolic disturbances in workers ex-
posed to dinitrotoluene. An. Jour. Dig. Pis. 9:329. 1942.
20. NIOSH. Registry of toxic effects of chemical substances. 1976 ed.
21. Lowenheim F. A., and M. K. Moran. Faith, Keyes and Clark's
industrial chemicals, 4th ed. New York. 1975.
22. U.S. International Tariff Commission. Synthetic organic chemicals
U.S. production and sale. 1978.
-------
JB-04-01
LISTING BACKGROUND DOCUMENT
METHYL ETHYL PYRIDINE PRODUCTION
Stripping Still Tails from the Production of Methyl
Ethyl Pyridine (T)
I. SUMMARY OF BASIS FOR LISTING
This waste consists of the stripping still tails generated
in the production of methyl ethyl pyridine. The waste is
expected to contain toxic organic materials — paraldehyde,
pyridine(s), and plcoline(s) — based on a review of the
process involved. The Administrator has determined that
this is a solid waste which may pose a substantial present or
potential hazard to human health or the environment when impro-
perly transported, treated, stored, disposed of or otherwise
managed, and therefore should be subject to management controls
under Subtitle C of RCRA. This conclusion is based on the
following considerations:
1) The waste is expected to contain the following
toxic organic chemicals: paraldehyde, pyridines,
and plcollnes. Paraldehyde is Included on the
NIOSH list of suspected carcinogens. The constit-
uents also exhibit human and aquatic toxlclty.
2) The constituents in the waste could migrate to
groundwater by leaching from improperly managed
lagoons or landfills, due to their high solubilities.
Release to the atmosphere is also probable due to the
high volatility of these compounds; volatization
poses the risk of direct inhalation of these toxic
organic chemicals.
3) An appreciable amount of the waste is produced
(calculated to be 720 metric tons in 1973). Approxi-
mately 75Z of the total generated is paraldehyde.
-------
II. INDUSTRY AND PROCESS DESCRIPTION
A. Profile of the Industry
Methyl ethyl pyridine (MEP) is a cyclic intermediate
produced commercially by synthesis. Only limited infor-
mation is available from which to draw an industry
profile. A 1976 studyC1) indicated that the 1973
U.S. production capacity was about 18,000 metric tons
(40 million pounds). A more recent statistical review
of the cyclic intermediates industry(2) does not include
methyl ethyl pyridine among the cyclic intermediates
for which production and sales data are available.
The TRW study C1) identified Union Carbide
as a major producer of 2-methyl-5-ethyl pyridine
(Diagram I, below). This appears to be the isomer of
major commercial importance . (*» 3) Koppers Company,
Inc., Nepara Chemical Company, Inc., and Reilly Tar and
Chemical were cited as other producers. Chem Sources-USA,
1980 editionC*) lists RIT-Chem Company, Inc. as a
producer of 4-methyl-3-ethyl pryrldlne.
•N
(T-) • (ID i
No important commercial end uses of MEP have been
identified. (3.5> 2-Me thyl-'i-ethyl pyridine is a raw
material used for the industrial production of
nicotinlc acid (3-pyrIdien-3-carhoxy1Ic acid) by
-------
nitric acid oxidation and decarboxylation.(3) it is
also a precursor for 2-methyl-5-vinyl pyridine (MVP),
which is used in acrylic fiber manufacture and in some
styrene/butadine polymer formulations. Producers
of HEP end products identified in Chem Sources-USA^)
are Vitamins, Inc. (nicotinic acid) and Philips Chemical
Company (methyl vinyl pyridine).
B. Manufacturing Process
Methyl ethyl pyridine is among the pyridine bases
that are produced commercially by synthesis (1,3,5),
rather than by isolation from coal tar.
Figure 1 Is the process diagram for MEP production.
In the initial steps of MEP production, paraldehyde is
usually generated at the plant site by reacting acetalde-
hyde with sulfuric acid to produce crude paraldehyde.
A portion of the crude paraldehyde is used in the
production of MEP, while the remaining portion is used
for the production of refined paraldehyde. The batch
still tails from paraldehyde production are sent to a
wastewater treatment sytem.*
*This waste stream is sent, along with the listed waste stream,
to a lagoon. At this time, data Is not available on the
constituents in this waste stream. However, since the waste
stream is mixed with the listed waste stream, the resulting
mixture is defined by the Agency as being a hazardous waste,
unless generators demonstrate otherwise.
-------
OASIS: I KG HtllUL-lTIIYl PYfttOlHt
1.14
LIJLH1UI.
1C AcitT""
REACTOR
i
1
AiJK'jnjA
SUWU
ArWNIA
ijim_r.ri>ATiofi
RCCTCLt K9«
ATOIIA
5.1R1CJUMG
kULk
"* lU[CA/lHHL-_
DMCM STILL
ncFiiitb pARAinruroc
»
r-»- 'STILL TAILS —
I f
CBIIDE PARALOCinrVr
1
RCACTOfl
\
1 \
)
\
• "- *
I AWITHIA 0.31
ACE'riC AC 10
HATCH STiiL
WASTE WATER
WATNCNT
SLUOCC
LIGHTS TO STOR'GC
"- ron ruT..n
PROCESS ING 0.4
: UftTjH L/UCR
0 5MLL TAILS
I (CUTS VJ
STOHAGC
PICOLINCS 0.044
prnioirn ;
. PICOLIHIS
PHENOL 0.0000003
SULfURIC ACID 0.003
ciiLoniocs o.ooois
SOLUOLE /V'IDES 0.00000*
4
ACETATES 0.0025
PAnALDEIIYDC 0.03
PICOLINES O.OHS
UATtR
Sotirco: Uefcrencu 1.
WASTE MATER TALATMENT
! 1
. LWIO
DISPOSAL
WATER
Fiourn I: Pyrldi.ics (2-Mcthyl, 5-Ethyl Pyridinc and a-PlcolInc) Manufacture.
-------
After the production of the crude paraldehyde,
2-methyl-5-ethyl pyridine is synthesized in high yield
from the liquid phase reaction of paraldehyde and
ammonia acetate, aluminum oxide, ammonium fluoride
or cobalt chloride cayalyst.(^) This process which takes
place in the reactor is shown by equation (1).'^'
v HH20 1>)
As shown in the equation, an identified by-product
in the reaction is 2-methyl pyridine ( 4. -picoline) .
The resulting process fluid is then transferred to an
ammonia stripping still for ammonia recovery. The
remaining fraction goes to a cleaner (decanter). The
cleaned MEP fraction residue is further refined by a
batch still.* The residue from the cleaner is processed
by a water layer stripping still. The stripping still
tails from this process are labelled (1) in Figure 1.
III. WASTE GENERATION AND MANAGEMENT
The stripping still tails are generated at a rate of
approximately 0.04 Kg/Kg of refined MFP.^1) This amounts
*The process effluent stream indicated as "MEP residues" from
the batch still is not included in the waste listing because
data is not yet available on the constitut ents in this waste
stream.
-X-
-------
to 720 metric tons of waste in 1973.
The TRW Studyt1' identifies the following as the major
contaminants in the listed waste stream:
paraldehyde 0.03 Kg/Kg KEP
sulfuric acid 0.003 Kg/Kg HEP
pryldines and pLcollnes 0.0025 Kg/Kg HEP
soluble acetates 0.0025 Kg/Kg ME?
phenol 0.0000003 Kg/Kg HEP*
This data Indicates that approximately 75 percent of the
total waste accounted for is paraldehyde.
According to the 1976 study, industry practice is to
manage the process effluent waste stream by sending it Co
wastewater treatment. As part of the wastewater treatment
system, the waste is most likely stored/treated in lagoons.
IV. HAZARDOUS PROPERTIES OP THE WASTE
The waste is considered to pose a potential hazard to
human health or the environment because of the presence of
toxic organics.
All of these waste constituents are acutely or chroni-
cally toxic, and paraldehyde Is included in the NIOSH list
of suspect carcinogens (see pp. 11-16 for further health
*Phenol, while a hazardous waste constituent, is not deemed
to be present in sufficient concentration to be of regulatory
concern.
-------
effects). The Waste constituents are present in the wastes
in high concentrations (see p. 6), and are also generated in
fairly substantial quantities annually, so that there is a
greater possibility of the hazardous constituents reaching
environmental receptors should improper management occur.
Exposure should also take place over longer periods of time,
since substantial quantities of pollutants are available for
environmental loading. Thus, the Agency would require some
assurance that waste components will not -migrate and persist
to warrant a decision not to list this waste stream. No
such assurance appears possible.
Each of the identified waste constituents has extremely
high water solubility (indeed, pyridene and 2-picollne are
infinitely water-soluble). (See Table 1.)
As a result of this high constituent solubility, this
waste is likely to leach harmful constituents even under
relatively mild environmental conditions, and to be highly
mobile in ground and surface waters* (App. 3). If these
wastes are exposed to more acidic environments, such as
environments subject to acidic rainfall, the potential for
waste migration increases. (See Table 1.)
Current waste management practices involve wastewater
treatment in lagoons* The potential for environmental
*Moblltty through soil is expected to be high in light of
these waste constituents' high solubilities. Further,
disposal could occur in areas with permeable soils, so
that mobility of waste constituents would not be
substantially affected.
-------
Table 1
Physical/Chemical Properties of Organlcs Identified
In Stripping Still Tails3
Compound:
Structure:
paraldehyde
CH3
pyridlne
0
2-plcollneb
jf,J.
^N"
,,c
Formula:
NW:
B • P • y C •
Vp, mm, 25°C:
Sat'd. vapord
conc'n, 25°C, g/m^:
Water solubility6:
Octanol/water^
partition co-
efficient:
Acid dissociation
constantS:
C6H1203
132
128
10
71
V
2.8(est.)
C5H5M
79
115
22
93
Inf.
4.5
C6H7N
93
129(143
10
50
v (inf.
13
5.2
5.9
(5.7; 6.0)
a Except as noted, data are from Weast, Ref. 6
b Most data are available for 2-plcoline. This Is also the
Identified by-product of MEP production and therefore the
isomer most likely present In the waste. Values in paren-
theses are for 3- and 4-picoline which have the same B.P.
solubility
c Calculated from data in WeastC6) pD-123.
VP MW
d Calculated from vapor pressure data: g/m3 760 x RT
-------
Table 1 (Continued)
e v = very soluble (probably > 1%)
Inf =• infinitely soluble
s = soluble (probably > 0.1%)
^ Source, Reference 7.
8 For pyridine and plcoline, value indicated is pka of the
conjugate acid. Source, References 8,9.
-------
contamination exists from Improper lagooning, or through
subsequent improper disposal of wastewater treatment sludges.
Thus, improperly designed or managed lagoons - for example,
thoie located in areas with permeable soils, or those lacking
leachate control features — could fail to prevent leachate
migration into the environment in light of the solubility of
the waste constituents, and the large amounts of available
percolating liquid in the lagoon. Exposure via a surface
water pathway is also possible if lagoons are constructed
without proper flood control or wash out measures
If waste sludges are Improperly landfilled they present
a similar potential hazard. Lack of leachate control or improper
siting thus could lead to waste migration.
Another pathway of concern is through airborne exposure
to these volatile organics present in the stripping still
tails. Some physical/chemical properties of the organic
species that are relevant to their potential for adverse
environmental impact are indicated in Table 1. Each of the
organic species listed is highly volatile, with vapor pressures
corresponding to saturation concentrations in the range of
grams per cubic meter at 25°C (1 ppm (v/v) corresponds to
about 1 milligram per cubic meter). Pyridine and 2-picoline
are particularly volatile. Substantial fractions of contam-
inants present in the waste could thus volatilize to the
atmosphere from lagoons and landfills that are not properly
designed and operated, increasing the risk of inhalation of
waste contaminants.
-------
Once released from the matrix of the waste these constituents
can persist and reach environmental receptors. Available data
(21) Indicates Chat biodegradatIon Is the chief degradation
mechanism with respect of paraldehyde and pyridine. Thus,
these constituents could persist In the abiotic conditions of
an aquifer similarly, persistence in air may occur.
V. HEALTH AND ENVIRONMENTAL EFFECTS
There is substantial evidence concerning the toxic
effects of the organic species of. concern. Table 2 summarizes
some data from the Registry of Toxic Effects of Chemical
Substances.C11) "araldehyde is included in the NIOSH List
of Suspected Carcinogens.(1^)
1 . Paraldehyde
Paraldehyde exhibits moderate toxicity when injested
and low toxicity when applied to the skin.(13) signs and
symptoms of paraldehyde poisoning are uncoordlnation and
drowsiness, followed by sleep. With larger doses, the
pupils will dilate and reflexes will be lost; comotosis
will follow. The symptoms of chronic intoxication from
this material are disturbances of digestion, continued
thirst, general emaciation, muscular weakness and mental
fatigue.(13) Sax also warns that paraldehyde is dangerous
and should be kept away from heat and open flames,
because when heated, it emits toxic flames.(13)
-------
Table 2
Summary of Data on Toxiclty of Organlcs
Identified in Stripping Still
PARAMETER
LDLo» oral-human
ng/kg
Compound
Paraldehyde
L4
Pyrldlne 2-Picoline
500
LD50, oral-rat
mg/kg
1530
891
790
OSHA standard
(TLV) ppm/(v/v)
Aquatic Toxlcity
96 hr TLm,
ppm(w/v)
100-1000
-------
2. Pyrines
Pyrines exhibit moderate toxlclty when introduced
to the human through oral, dermal and inhalation routes.'*^)
Liver and kidney damage have been produced in animals and
in man, after oral administration.(14) In smaller doses,
conjunctivitis, dizziness, vomiting, diarrhea and Jaundice
may appear;(15) also tremors and atoxia (deffectlve control
of muscles), Irritation of the respiratory tract with
asthemic breathing, parlysis of eye muscles, paralysis
of vocal chords and paralysis of bladder have been
reported.(15) Threshold limit values (TLV) have been
established by a number of countries for the protection
of employees* These values should not be exceeded for
an 8-hour shift of a 40-hour week:
USSR: 1.5 ppm » 5 mg/cum
USA: 5 ppm - 15 mg/cum
BRD*: 5 ppm « 15 mg/cum
Sweden: 5 ppm =• 15 mg/cum
In drinking water pyridene produces a faint odor at
0.0037 ppm and is a taste and odor problem at 0.8 ppm.(16)
Adverse taste in fish (carp, rudd) is reported at 5 ppm.(16)
Pyridine causes inhibition of cell multiplication algae
* Federal Republic of Germany
-------
(MIchrocystis aeruginosa) and bacteria (Pseudomas
ptitida) at 2R and 3AO ppn, respectively. Sax^11^
reports a number of other hazards assolated with pyridines:
(1) fire hazard, that Is dangerous when It Is exposed
to beat,: flame or oxidlzer; (2) explosive hazard, that is
severe when It Is in the form of a vapor and Is exposed to
flame or spark; and (3) disaster hazard, that Is dangerous
when heated to decomposition, the pyrldlne emits highly
toxic fumes of cyanides.
An EPA report^20) suggests that, based on health
criteria, the ambient level of pyridines in water should
not exceed 207 mg/L. On an ecological basis, it should not
exceed 500n mg/L.
3. Picollnes
Picollnes as a class exhibit high toxlclty via
dermal route and moderate toxlcity via oral and inhalation
routes. (13) £ -plcolines, X, -picolines andyS -picolines
are dangerous when heated to decomposition because
of the emission of toxic fumes of NOX. The USSR has
established a threshold limit value at 5 mg/m^ for
mixed isomers.(^ )
An EPA report^O) suggests that, based on a health
criteria, the ambient levels of picolines In water should
not exceed 316 mg/1.
-------
REFERENCES
1. U.S. EPA. Assessment of Industrial hazardous waste prac-
tices: Organic chemical, pesticides and explosives indus-
tries. EPA No. SW-118C. pp. 5-26 to 5-28 NTIS P3 No.
251 307. 1976.
2. United States International Trade Commission. Synthetic
organic chemicals: United States production and sales.
USITC Publication 1001. pp. 33-80. 1979.
3. Abramovltch, R. A. Pyrldlne and pyrldine derivatives.
In; E. P. Dukes, C. Coleman, P. Hlrsch, G. Joyce,
P. Van Reyen and G. C. Wronker, eds. Kirk-Othner
Encyclopedia of Chemical Technology. 2nd ed., V. 16.
John Wiley and Sons, New York. pp. 780-803. 1968.
4. Baker, M. J., B. D. Bradley, C. L. Gandenberger, E. M.
Giordano, J. B. Mertz, L. E. Nash and M. S. Nash, eds.
Chera-Sources-USA, 1980 ed. Directories Publishing
Co., Orraond Beach, FLorlda. pp. 296. 1980.
5. Astle, M. J. Industrial organic nitrogen compounds, ACS
monograph series. Relnhold Publishing Corporation, New
York. pp. 134-145. 1961.
6. West, R. C., ed.-in-chief. Handbook of chemistry and
physics. 47th Ed. Chemical Rubber Company. Cleveland,
Ohio. 1966.
7. Hansch, C., and A. J. Leo. Substltuent constants or correla-
tion analysis in chemistry and biology. John Wiley and
Sons, New York. 1979.
8. Perrin, D. D. Dissociation constants of organic bases in
aqueous solution. Butterworths, London. 1965.
9. Kortum, G., W. Vogel and K. Andrussow. Dissociation of
organic acids in aqueous solution. Butterworths, London.
1961.
10. Not used in text.
11. Lewis, R. J., Sr., and R. L. Tatked, eds. NIOSH. Registry
of toxic effects of chemical substances. U.S. Department
of Health, Education and Welfare. 1978.
-------
12. U.S. EPA. An ordering of the NIOSH suspected carcinogens
list. EPA No. 660/1-76-003. NTIS PB No. 251 851. 1976.
13. Sax, N. I. Dangerous properties of Industrial materials,
5th ed. Van Nostrand Relnhold Company, New York. 1979.
14. Deichmann, W. R. Toxicology of drugs and chemicals.
Academic Press, Inc., New York. 1969.
15. The International Technical Information Institute.
Toxic and Hazardous Industial Chemical Safety Manual
for Handling and Disposal with Toxicity and Hazard Data.
Toranomon-Tachikawa Bldg., 6-5. 1 Chome, Nishi-Shirabashi,
Minato-ku. Tokyo, Japan. 1976.
16. Verschueren, K. Handbook of environmental data on
organic chemicals. Van Nostrand Relnhold Company, New York.
1977.
IB. Not used in text.
19. Not used in text.
20. Cleveland, J. G., and G. L. Klngsbury. Multimedia environmental
goals for environmental assessment, V. 2. EPA No. 600/7-77-136b.
November, 1977.
21. Dawson, English and Petty. Physical cheminal
properties of hazardous waste constituents. 1980.
-------
oRD-E-oa
LISTING BACKGROUND DOCUMENT
TOLUENE DIISOCYANATE PRODUCTION
Centrifuge and distillation residues from toluene diisocyanate production (R,T)*
I. Summary of Basis for Listing
The centrifuge and distillation residues from the production of
toluene diisocyanate (TDI)** contain toxic organic substances, rautagenic
substances, and substances that are probably carcinogenic. The wastes
are also highly reactive upon contact vith water. These wastes result
from the production of toluene diisocyanate through the coupling of
toluene diamines and phosgene.
The Administrator has determined that toluene diisocyanate wastes
may pose a substantial present or potential hazard to human health or the
environment when improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appropriate manage-
ment requirements under Subtitle C of RCRA. This conclusion is based on
the following considerations:
1) The TDI centrifuge and vacuum distillation wastes consist of
toluene diisocyanates which are toxic and toluene diamines
which are suspected carcinogens.
2) More than 6000 metric tons of TDT production wastes are
produced per year.
3) Storage in drums in a landfill, a past management method
for this waste, poses a risk because toluene diisocyanate
(TDI) is a highly reactive, pressure-generating compound
which has caused explosion of drums. Several such damage
*Thls listing description has been clarified, In response to comments, to
indicate that wastes from both centrifuge and distillation processes
are included.
**This compound is also referred to as tolylene diisocyanate or Colyl
dlisocvanate,
ui «r i _
-------
incidents have occurred demonstrating the potential for
improper disposal of diisocyanate wastes.
4) In addition to the reactivity hazard, this waste could leach
toxic toluene diamine Into groundwater, if improperly managed,
posing a human health risk.'
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Toluene diisocyanate (TDI) production in the United States
in 1973C1) was 330,000 metric tons (661 million pounds). The major
producers of mixed toluene diisocyanate isomers(1) In 1979 were
Allied Chemical Corporation (Specialty Chemicals Division), BASF
Wyandotte Corporation, E. I. duPont de Nemours and Company, Inc., Dow
Chemical, U.S.A., Mobay Chemical Company, Olln Corporation, Rubicon
Chemicals Inc., and Union Carbide Corporation. Toluene diisocyanate
is the major intermediate for the production of polyurethanes. A
typical TDI continuous process plant capacity is 27,500 metric tons
(60 million pounds per year). The process Is Illustrated In Figure 1.
B. Manufacturing Process (9,10)
The starting raw materials for a continuous process plant are
a solution of toluene-2,4-diamine, 2,6-toluene-diamine, or an 80:20
mixture of the two, an inert solvent (o-dichlorobenzene) and gaseous
phosgene. These compounds are fed to two jacketed, agitator-equipped
reactor kettles, In series, along with recycled solvent where the
-------
DKGASSER
STEAM EJECTOR
I I *. TO WASTE WATCR
TOLUtNEUIAMINi; r- •> "IVVO
REACTORS
PHOSGENE — f *-f (!;tM!t:S)
RCCYra I:
WAST E GAS
SCnuniMzR
TO A
WASTE wAran ^y
— <
. ... .
VENT KETTLE j
nios«P.Nr£&
HCI
RIICOVKIIY
NrtOll^-.
-r- rS
. ^ "
"^C\ 81 ILL
\ EVAPOFATOR
TO
WASTE
WATER
SOLVENT RECOVERY
VENT COMPRESSOR ^«
RECYCLE
VCN1 GAS
HYPROIIUCT 37 5%
"""' "' i IYDROO-ILURK; AUIU
_ REflNm TOLUENE
"~"^ ""*" UHUOCYANA1L 1.0
4 VENf
I TO AiR
EVAPORATOR — { ]•*— WATER
•• nrsujui- r
CENllilVut',11 TO
OR WAST E
VAC. oisi ii i . vwvrr.R
\
CENTRIFUGE OR DISTILLATION
RESIDUE
STCAM EJECTOR
©
WASni GAJi r>CIUHU)ER
nc:i
WAlimWAlt.d
•^^
CKMTnil'tmn/fJISTILLAlION RESIDUtE
POI.YMI-.nS AND 1AI1IW MAT FER
n.RnicuiiiORiDi:
WAS 11: IGOCYANAfES
& SOLID)
\ANO
Flyuro 1. TOLUHMC DIISOCYANATE MANUFACTURE
(MQDlf IED FI1OM REFERENCE 9)
-X-
-------
following reactions shown in Figures 2 and 3 take place. An excess of phosgene
Is used In this process step. The unreacted phosgene and hydrogen chloride
formed by the reaction constitute the major components of the gas stream
exiting the second reactor. The reactor exit gas goes to a phosgene
recovery/by-product hydrochloric acid recovery system. All equipment
Is vented to scrubbers. The phosgene and hydrogen chloride are recovered
In the scrubbers.
The recovered phosgene Is recycled as a solution In the recovered
solvent to the first reactor. The by-product hydrochloric acid (2.32 Kg
of 37.5 percent HCl/Kg TDI product) Is recovered from the gas stream
after removal of the phosgene and Is stored or sold. The waste gas
scrubber effluent, containing residual hydrogen chloride (0.025 Kg/Kg
TDI product) dissolved In water, Is neutralized and then sent to the
plant industrial outfall.
The dehydrochlorlnatlon to form TDI takes place after the reactor
liquid (from Reactor 2) has been fed to the degasser. The reaction
products from the second reactor are dehydrochlorlnated by blowing an
inert gas such as natural gas through the solution to remove HC1. The
degasser gas is then sent to the phosgene and HCl recovery system, where
the HCl and phosgene are recovered as noted above and the inert gas is
recyled.
The crude TDI solution from the degassers is fed to the stills
and evaporators to recover o-dichlorobenzene solvent and purify the TDI.
The purified TDI Is sent to storage. The recovered solvent Is recycled
for use in recovery of phosgene and as a solvent for the toluenediarcine
-------
- COCi,
PHOSGENE
CHj
25-27C
j- HCI
NH.CC.Ct
(F.EACTCR 1)
CK3
•rZKCl
{nEACTOR 2)
Fscj'O 2. F.2AC7:Cr:30F2,4 A. :D 2.5-TOLUE.p:EDi.-\S::W= (S)
CHj
NCO
NrCOCl
NCO
Fir-.- 3. bZr.-^SGCKLCSI.'.-ATSCN REACTION TO FORM
-y-
-------
feed. The liquid evaporator residue containing some TDI and waste products
is then further processed by either centrifugation or vacuum distillation
to recover additional TDI product. The remaining centrifugation or vacuum
distillation residue is the waste stream listed In this document.
C. Waste Generation and Management
Approximately 0.021 Kg of waste are generated per Kg of TDI pro-
duced. (11) Based on 1973 production, this results In an excess of
6000 metric tons of centrifuge and distillation residues requiring disposal.
The material contains 90 percent polymers and tarllke matter, 6 percent
ferric chloride (largely from process impurities) and 3 percent waste
isocyanates. (H)
The wastes have been known to be disposed of In both on- and
off-site landfills, and on occasion to be containerized In drums prior
to landfilling. (See pp. 437-438 following.) Current industry practice,
however, as determined through a poll of its member companies by the
International Isocyanate Institute, Inc. Indicates that storage of residues
in drums In landfills is not a known management method.O*)
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
As shown above, the 6000 metric tons of TDI production wastes
that are generated annually are expected to contain the following comp-
onents:
o Polymers and tarlike materials - 90%
o Ferric chloride - 67,
o Waste isocyanates (Including TDI) - 3*
-------
The waste isocyanates are toxic and the fre* Isocyanates
are potentially highly reactive with other materials, including water.
1. Reactivity Hazard
Toluene diisocyanate, and other free Isocyanates present In
TDI waste, are known to react violently upon contact with water. The
reaction of free Isocyanate groups with water usually occurs very rapidly,
is exothermic, and results in the violent formation of aromatic diamines
and carbon dioxide gas. The disposal of these residues is potentially
hazardous to the people handling them, since, should water come in
contact with the waste, there could be explosive release of toxic and
potentially carcinogenic aromatic chemicals over a wide area. A simlliar
danger exists even if the wastes are drummed, since if water enters,
dangerously high pressures can result in rupture of the drum, followed
by explosive release of the contaminants. For this reason, long-term
storage of these wastes in steel drums at waste disposal sites is
considered extremely hazardous if containment is breached and water
infiltrates the drum.
There have been several damage Incidents associated with
improper disposal of toluene diisocyanate wastes, which confirm that this
waste stream is reactive. In California in 1978, a drum containing TDI
waste was picked up by a scavenger waste hauler and placed In an unprotected
storage area. After having been exposed to rain, the drum was then removed
-------
to a Class 1 landfill where 1C exploded, requiring the hospitalization of
several people.* Ir, Decrolt in May of 1978, a cank truck waiting to
dispose of a quantity of TDI waste experienced a boil-over. As a result
nine people exposed to the toxic fumes were hospitalized.*
These damage incidents illustrate the hazards created by impro-
per treatment, storage or disposal of TDI production waste. In view of
the above information, it is apparent that the waste meets the standard
for reactivity set In §261.23(a) (2) and (4).
2. Toxicity Hazard Via Ground and Surface Water Exposure Pathways
These wastes also pose a hazard via ground and surface water
pathways due Co their toxicity and potential for genetic harm. The
principal component of concern for this route of exposure is toluene-2,4-
diamine, which is produced by the reaction of diisocyanates with water,
and Is a suspect carcinogen.** (See pp. 8-10 following.)
This substance is capable of migrating from improperly designed
and managed waste disposal sices. Toluene-2,4-dlamine, produced by the reaction
of the dilsocyantes with water (12) t is very soluble (13).
Thus, if waste disposal sites are designed Improperly or are
improperly managed—for example sited in areas with highly permeable
*OSW Hazardous Waste Division, Hazardous Waste Incidents, unpublished,
open file, 1978.
**Toluene dlisocyanate, while toxic, is too reactive to persist in water,
and so probably would not pose a toxicity hazard via water. It may,
however, pose a toxicity hazard in direct handling of the waste.
-------
soils, or constructed without natural or artificial liners—there Is a
possibility of escape of waste constituents to groundwater. A further
possibility of substantial hazard arises during transport of these wastes
to off-site disposal facilities. This Increases the likelihood of their
being mismanaged, and may result either In their not being properly
handled during transport or -In their not reaching their destination at
all, thus raaking then available to do harm elsewhere. A transport mani-
fest system combined with designated standards for the management of
these wastes will thus greatly reduce their availability to do harm to
human beings and the environment. The damage incidents described above
in fact demonstrate hazards which may arise during off-site transpor-
tation and management.
The Agency presently lacks reliable data as to the environmental
persistence of the waste constituents of concern. It is assumed however,
that waste constituents are persistent enough to remain In the environment
long enough to cause substantial hazard, a conclusion supported by the
actual damage incidents involving these wastes.
A final reason for listing these wastes as hazardous is the
quantity of wastes generated. The wastes are generated In fairly sub-
stantial quantity—6,000 MT annually. Thus, large quantities of hazardous
constituents are available for environmental release, increasing the
likelihood of exposure if the wastes are mismanaged. Large expanses
of groandwater could similarly be polluted. Contaminant migration
also may occur for long periods of time, since large amounts of pollutants
-------
are available for environmental loading. All of these considerations
increase the possibility of exposure, and support a hazardous waste
listing.
B. Health and Ecological Effects
1. Toluene Diisocyanate
Health Effects - TDI is toxic [inhalation rat L05o=600ppm/6hr.]
and is an irritating material, both in its liquid and airborne forms,
because of its high reactivity. It can produce skin and respiratory
tract irritation, and can cause sensitizatlon so that sensitized individuals
are subject to asthmatic attacks upon re-exposure to extremely low concen-
trations of TDI. Additional information and specific references on the
adverse effects of TDI can be found in Appendix A.
Regulations - The OSHA standard for toluene dilsocyanate is 5
ppb, with a ceiling of 20 ppb in 10 minutes.
Industrial Recognition of Hazard - Sax's Dangerous Properties of
Industrial Materials^) designates toluene diisocyanate as an emitter of
highly toxic fumes containing hydrogen cyanide when heated to decomposition.
2. Toluene-2,A-diamine
Health Effects - Toluene-2,4-dlamine is a suspect carcino-
gen(3). Although it did not cause cancer in animals upon skin painting,(*)
it Increased the Incidence of lung cancer In the test animals. Toluene
diamine was also shown to induce liver tumors^) in rats,(*") morphological
-------
aberrations in mammalian cells^), and causes bacterial mutation in the
Ames test.(3) Additional information and specific references on the ad-
verse effects of toluene 2,4-diaraine can be found In Appendix A.
Industrial Recognition of Hazard - Toluene-2,4-diamine Is
designated in Dangerous Properties of Industrial Materials (Sax)<2) as
moderately toxic when Inhaled.
-------
IV. References
1. U.S. Tariff Commission (U.S. International Trade Commission) Synthetic
Organic Chemicals, United States Production and Sales. 1974 Prelim-
inary Reports. Washington, U.S. Government Printing Office.
2. Sax, N. Irving. Dangerous Properties of Industrial Materials, Fourth
Edition, Van Nostrand Reinhold Co., New York, 1975.
3. USEPA. Report 1980 Contract 9 68-02-2773. Potential Atmospheric
Carcinogens. Phase I - Identification and Classification, pp. 204.
4. Giles, A.L., et al. Dermal Carcinogenicity Study by Mouse-Skin
Painting with 2,4-Toluenediamlne Alone or in Representative Hair
Dye Formulations. J. Toxicol. Environ. Health, 1(3):433-440, 1976.
5. Bridges, B.A., and M.H. Green. Carcinogenicity of Hair Dyes by
Skin Painting in Mice (letter to editor). J. Toxicol. Environ.
Health, 2(l):251-252, 1976.
6. Shah, M.J., et al. Comparative Studies of Bacterial Mutation
and Hamster Cell Transformation Induced by 2,4-Toluenedlamine
(Meeting Abstract). Proc. Am. Assoc. Cancer Res., 18:22, 1977.
7. Cancer Research, 29:1137, 1969.
8. Plenta, R.J., et al. Correlation of Bacterial Mutagenlcity and
Hamster Cell Transformations with Tumorigeniclty Induced by 2,4-
Toluenediamine. Cancer Lett. (Amsterdam), 3(1/2): 45-52, 1977.
9. Lowenheim and Moran. Faith, Keyes, and Clark's Industrial Chemicals,
4th ed., John Wiley and Sons, 1975.
10. Kirk-Othmer. Encyclopedia of Chemical Technology. 3rd ed.,
John Wiley and Sons, Inc., Vew York, 1979.
11. Industrial Process Profiles for Environmental Use: Chapter 6, The
Industrial Organic Chemicals Industry. Reimond Lieplns, Forest Mixon,
Charles Hudals, and Terry Parsons, February 1977, EPA-600/2-77-023f.
12. "Criteria for a Recommended Standard Occupational Exposure to TDI,"
U.S. Dept. of HEW, Public Health Service and National Institute of
Occupational Safety and Health, HSM 73-110-22 (1973).
13. Handbook of Chemistry and Physics, 56th ed., Cleveland, CRC Press
(1975).
14. Telephone communications between Rebecca Fields of EPA and Mr. Lee Hughes
of the Mobay Chemical Corp., August 11, 1980.
15. Health and Environmental Effects Profile, Appendix A, 2,4-
Toluenediamine, No. 161, April 30, 1980.
-------
Response to Comments - Centrifuge Residue from Toluene Diisocyanate
Production
Several comments were received with respect to waste K027 (Centrifuge
residue from toluene dlisocyanate production).
1. One commenter requested a clarification on the scope of waste
listing K027. The commenter pointed out that the listing
background document included both centrifuge and distillation
residues as hazardous wastes, while the regulations specified
only centrifuge residues. Therefore, the commenter felt it was
unclear as to whether the Agency intended to limit the scope of
the listed material to only wastes generated via a centrifuge
unit operation.
In reviewing both the waste listing description as cited in
the hazardous waste regulations (45 FR 33123) and the listing
background document on toluene diisocyanate production, the
Agency agrees that clarifiction is needed on the scope of
waste listing K027. The Agency Relieves, however, it is quite
clear from the listing background document that the listing
was meant to include residues from both the centrifuge and
distillation column since the composition/hazardousness of
the waste when using either the centrifuge or distillation
unit will not differ significantly (see listing background
document TDI production: pg. 3, Figure 1 and pg. 6, 1st
paragraph). This latter point was confirmed by Mr. Lee Hughes
of the Mobay Chemical Corp., who explained that wastes from
both a centrifuge and distillation column are comparable and
that the type of waste generated depends on the type of
-------
equipment used at the particular plant.The final-final listing
description, therefore, will be amended to include wastes
generated from both the centrifuge and distillation column in
the production of toluene dlisocyanate.
2. The coramenter also requested clarification as to whether the
listing "centrifuge residue from toluene dilsocyanate production"
is limited to the undeactivated material as it is directly
discharged from the distillation or centrifuge unit or whether
it also would apply to de-activated material that results from
any treatment of the waste (viz., the coomenter indicated that
each TDI producer de-activates TDI residues differently i.e.,
by wet quenching or aging, after generation of the final dis-
tillation or centrifuge bottoms).
The listing of waste from TDI production is limited to those
undeactivated residues which are directly discharged from the
centrifuge or distillation unit operation. Any deactivation
of these residues would be considered a treatment process and
would require a permit. Any producer which believes the treat-
ment of these residues would render the waste non-hazardous
non-reactive (i.e., no longer meeting the characteristic of
reactivity) should submit a de-llating petition under 55260.20
and 260.22. It should be noted, however, that to de-list
sucessfully residues which are generated from the centrifuge
or distillation unit from the hazardous waste system, a
generator must demonstrate that the waste is both non-reactive
and non-toxic.
-------
3. The listing "Centrifuge residue from toluene dilsocyanate
production" is listed as hazardous because it contains
a number of toxic constituents, including toluene diisocyanate,
toluene-2,4-dlamine and tars (benzidimidazapone). A number of
commenters objected to the inclusion of these compounds as
constituents of concern in this particular listing or had
specific questions with respect to these toxic constituents.
More specifically:
-Toluene-2,4-diamlne- The commenter indicates, that this com-
pound is either not present in the waste or, if present, is
only there in low concentrations (i.e., low ppm concentrations).
Mr. Lee Hughes of the Mobay Chemical Co. indicated in conversa-
tion that most waste streams would not contain toluene-2,4-diaralne
since, among other things, it is not economical for the producer
to waste the starting material. Additionally, the commenter
indicated that analytical techniques used to conduct this
determination are subject to variability.
-Toluene ditsocyanate - The comraenter Indicates, that this com-
pound is not a suspect carcinogen; the commenter also asserts
that recent study results show that TDI is not carcinogenic
and not mutagenic (it should be noted that the commenter did
not provide any data or reference to any specific tests to
support its claim).
- Tars (benzidimidazapene) - the commenter indicated that although
benzidiraidazapene is cited as the principal component in these
tars, the commenter Is not aware of the existence of this substance
or any data to substantiate the claim that it is mutagenic or
carcinogenic.
-------
Therefore, the commenters recommend that all three of these toxic
constituents be deleted as a basis for listing this waste.
The Agency disagrees with the cotnmenter's first two points.
Toluene-2,4-diaralne has produced carcinogenic effects in rats and
mice in a long-term feeding study (i.e., a suspect carcinogen)
and was found to be mutagenic.'^) Additionally, it was
found to be hepatotoxic to rats and mice and also hastened the
development of chronic renal disease and accelerated animal
morbidity.(15) Therefore, toluene-2,4-diaraine is considered
very toxic by the Agency, even at minimal levels. This is parti-
cularly true where the waste constituent is a suspect or proven
carcinogen. As the Agency has stated, "There Is no scientific
basis for estimating 'safe' levels of carcinogens. The draft
criteria for carcinogens therefore state that the recommended
concentration for maximum protection of human health is zero"*.
Consequently, even if toluene-2,4-diaraine is present at low con-
centrations (low ppm) as claimed by the Industry, the waste may
well present a substantial hazard to human health and the environ-
ment should this waste constituent migrate and reach a receptor.
With respect to the coramenter's concern on the variability of
the analytical technique for toluene-2,4-diaraine, the Agency has
provided an analytical procedure for analyzing toluene-2,4-diamlne
(45 FR 33131: Appendix III, Table 1), and we will (necessarily)
accept results obtained from use of this method. If an equivalent
*EPA Water Quality Criteria, 44 FR 15Q26, 1S930 (March IS, 1979)).
-------
ui. superior method is developed by the industry, a petition for
equivalent testing or analytical methods can be submitted under
SS260.20 and 260.21.
Toluene diisocyanate, while not a proven carcinogen (although it
is still being evaluated), is nevertheless sufficiently toxic to
present a substantial present or potential hazard to human health
and the environment should it migrate from the waste (i.e., toluene
diisocyanate exposure produces respiratory sensltization, decreased
lung function, and exposure to high concentrations can result in
pulmonary edema or death). Additionally, the reaction of free
isocyanate groups with water usually occurs very rapidly, is exo-
thermic, and results in a possible explosive release of toxic and
potentially carcinogenic aromatic chemicals. In talking with Mr. Lee
Hughes of the Mohay Chemical Corp.,(^) he indicated that toluene
diisocyanate although present In the waste, is generally encapsu-
lated or otherwise not available for human exposure, however, no
data was submitted to support their contention. Therefore, the
Agency believes that toluene diisocyanate is of regulatory concern,
especially in light of past damage Incidents, and will continue to
include It as a constituent of concern in this particular listing.
However, the Agency, will delete all reference to toluene diisocya-
nate as being a suspect carcinogen in the background document
until a more definitive determination is made.
The listing of this waste stream for the presence of tars and the
existence of "benzidtmldazapene" cannot be confirmed. Additionally,
background information on chemical tars does not exist at this
-------
time. Tars (benzldlmidazapene) therefore, will be removed
ae a constituent of concern in this particular listing.
. Finally, one commenter argued that disposition of raw centrifuge
residue in drums in a landfill Is generally not practiced as a
"known management method for this waste." This point was
confirmed by the International Isocyanate Institute through a
poll of its member companies (see ex parte communication from
Rebecca Fields with Mr. Lee Hughes of the Mobay Chemical Co.,
August llth, 11HQ.) therefore, the commenter believes that the
background document needs to be amended to reflect this
information.
While disposal of these residues in drums In a landfill
may not reflect current industry practice, the fact that past
damage has occured from this disposal method is evidence that
improper management of these wastes in a probable mismanagement
scenario may present a substantial present or potential hazard
to human health and the environment (i.e., if these wastes are
not controlled as hazardous, centrifuge residues may be sent
to a sanitary landfill with no controls). Therefore, the
Agency will continue to cite disposal of these residues in
drums In a landfill as a possible mismanagement scenario.
However, the Agency will amend the listing background document
to indicate that disposal of these centrifuge residues in
drums in a landfill is not a current disposal option, but has
been practiced in the past.
-------
LISTING BACKGROUND DOCUMENT
TRICHLOROETHANE PRODUCTION
0 Waste from the product steam stripper in the production of
1,1,1-trichloroethane (T)
0 Spent catalyst from the hydrochlorinator reactor in the pro-
duction of 1,1,1-trichloroethane via the vinyl chloride
process (T)
0 Distillation bottoms from the production of 1,1,1-trichloro-
ethane (T)
0 Heavy ends from the production of 1,1,1-trichloroethane (T)
I. Summary of Basis for Listing
Waste from the heavy ends column, distillation column, and
product steam stripper, and spent catalyst from the hydrochlorinator
reactor in the production of 1,1,1-trichloroethane contain carcinogenic,
mutagenic, teratogenic or toxic organic substances. The waste stream
constituents of concern are 1,2-dichloroethane, 1,1,1-trichloroethane,
1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, and 1,1,2,2-tetra-
chloroethane, vinyl chloride, vinylidene chloride, and (possibly)
chloroform.
The Administrator has determined that these solid wastes from 1,1,1-
trichloroethane production may pose a substantial hazard to human health
or the environment when improperly transported, treated, stored, dis-
posed of or otherwise managed, and therefore should be subject to ap-
propriate management requirements under Subtitle C of RCRA. This con-
clusion is based on the following considerations:
1) These wastes are listed as hazardous because they are likely to
-------
contain 1,2-dichloroethane; 1,1,1-trlchloroethane; 1,1,2-trl-
chloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane;
vlnylldene chloride; vinyl chloride and chloroform.. Of these
substances, 1,2-dichloroethane, 1,1,2-trichloroethane, vinyl-
idene chloride, vinyl chloride and chloroform are recognized
carcinogens and 1,1,1-trlchloroethane is a suspected car-
cinogen; also a number of these chemicals have been found to
be mutagenic in laboratory studies; the chlorinated ethanes
also pass the placental barrier and several have been docu-
mented to produce teratogenic effects.
1) Significant quantities of wastes containing these hazardous
compounds may be generated each year, increasing the possi-
bility of exposure should mismanagement occur.
3) Mismanagement of incineration operations could result in
the release of hazardous vapors to the atmosphere and
present a significant opportunity for exposure of humans,
wildlife and vegetation in the vicinity of these operations
to potentially harmful substances through direct contact
and also through pollution of surface waters. Disposal of
these wastes in improperly designed or operated landfills
could create a substantial hazard due to the potential of
waste constituents to migrate and persist in aqueous
environments.
4) Damage incidents Illustrating the mobility and persistence of
chloroethanes have occurred which resulted In surface and
groundwater contamination.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Currently, there are three producers of 1,1,1-trichloroethane
In the United States. Table 1 lists the producers, sites, and esti-
mated capacities of each plant. Actual production of this compound In
1978 was 644,475,000 pounds^3).
The production of 1,1,1-trlchloroethane has shown a steady in-
crease in production as shown In Table 2. It is mainly used (92%) for
metal degreaslng and for electrical, electronic and Instrument cleaning.
Growth In the use of 1,1,1-trlchloroethane Is being accelerated because
of the potentially greater health hazard exhibited by trlchloroethylene.
-------
TABLE 1
1,1,1-Trichloroethane Producers, 8ie«s. Capacities and Processes
Conpeny
Dow Chemical
U.S.A.
PPG Indus-
tries
Vulcan
Materials
TOTAL
Location
Freeaport. TX
Plaqueolne, LA
Lake Charles,
LA
Gelsaar. LA
1
Annual Capacity
(Millions of Pounds)
450
300
ISO
*5
1.1*5
1
Process I
1
1
Via Vinyl I
Chloride 1
1
1
Via Vinyl 1
Chloride j
1
1
Via Chloro-|
nation of 1
ethane I
1
-------
TABLE 2
U.S. International Trade Commission
1,1,1,-Trichloroethane Production
Year
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
(Millions of Pounds)
29<».4
324.3
366.3
374.6
440.7
548.4
590.8
631.2
634.8
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Other solvent uses are in formulating a variety of products Including
adhesives, spot cleaners and printing inks*
B. Manufacturing and Waste Generation Process*
The bulk, of 1,1,1-trlchloroethane production In the United States
is based upon the vinyl chloride process; minor amounts (— 10%) are
made by the ethane process. In the vinyl chloride process, vinyl
chloride reacts with hydrogen chloride to form 1,\-dichloroethane,
which is then thermally chlorinated to produce 1,1,1-trichloroethane.
The yields based on vinyl chloride are approximately 95X.
1,1,1-Trichloroethane is also produced by the noncatalytic
chlorination of ethane. Ethyl chloride, vinyl chloride, vinylidene
chloride, and 1,1-dichloroethane are produced as co-products. When
1,1,1-trlchloroethane is the only desired product, vinyl chloride and
vinylidene chloride are hydrochlorinated to 1,1-dichloroethane and
1,1,1-trlchloroethane respectively; ethyl chloride and 1,1-dichloroe-
thane are recycled to the chlorination step (Kahn and Hughes, Monsanto
Research Corp., Source Assessment: Chlorinated Hydrocarbons Manufac-
ture, EPA 600/2-78-004, 1978).
Vinyl Chloride Process
The chemical reaction for the hydrochlorltiation of vinyl chloride is:
Fed 3
H2C-CHC1+HC1 > CH3HC1?
35-40*C
*Based on the process description in Key, J.A. and Standifer, R.L.,
Emissions Control Options for the Synthetic Organic Chemicals
Manufacturing Industry," U.S. Environmental Protection Agency,
EPA 68-02-2577, July 1979
-------
ChlorlnaCicn of 1,1-dichloroethane Is represented as:
CH3-CHC12+C12 > CH3CC13+HCI
Figure 1 represents a simplified process for production of *l,l,l-tri-
chloroethane via the vinyl chloride process. Vinyl chloride and hy-
drogen chloride* (and the recycled overhead stream from the light ends
column) react at 3S-40°C in the presence of ferric chloride. The re-
actor effluent Is neutralized with ammonia. The resulting solid com-
plex (residual ammonium chloride, ferric chloride, and ammonia) is
removed by the spent catalyst filter as a semisolid waste stream
(Stream G, Fig. 1). The filtered hydrocarbon stream is then distilled
in the heavy ends column and high-boiling chlorinated hydrocarbons
(tars) are removed as a waste stream (Stream H, Fig. 1). The
overhead from this column is further fractionated in the light
ends column into two streams: 1,1-dichloroethane and the lighter
components (primarily unreacted vinyl chloride). The lighter components
are recycled to the hydrochlorination reactor. The 1,1-dichloroethane
product is removed as the bottom stream and is then reacted with
chlorine in the chlorinatlon reactor at a temperature of about 400°C.
The products from this reaction are distilled, and hydrogen chloride
*The hydrogen chloride (HC1) used for vinyl chloride hydrochlorination
is often a by-product from the chlorination of 1,2 dichloroethane
or from other processes in the plant complex. .If by-product HCl Is
used, it can contain as much as 3.5% of 1,2-trlchloroethane which
will carry forward to the product stream stripper waste streams.
-------
MCI
CO'.UMU
^-
. EtUApc
COLUI
fk
f
ri
... • T o /v
Figure 1. Flow Dlngram for 1,1,1-Trlchlorocthnno from Vinyl Chloride
-------
and low boiling organic hydrocarbons are taken overhead in the HC1
column. (This stream may be recycled to supply the hydrogen chloride
required in the hydrochlorination step, or used for other chlorinated
organic processes directly (e.g., oxy-chlorination processes)). The
bottom stream from the hydrogen chloride column is further fractionated
to recover 1,1,1-trichloroethane as the overhead product, which,
after the addition of a stabilizer, is stored. The bottom stream
from the 1,1,1-trichloroethane column is comprised largely of 1,1,2-
trichloroethane, tetrachloroethanes, and pentachloroethanes (stream
14, Fig. 1). (These bottoms may be used as a feedstock for produc-
tion of other chlorinated hydrocarbons (e.g., perchloroethylene-tri-
chloroethylene, vlnylidene chloride), in which case they will not be
discarded.) Estimated emissions from this process are shown in Table
3. The listed waste streams are shown in Figure 1 as follows:
spent catalyst wastes are noted as stream 6, heavy ends
as stream H, and distillation bottoms as stream 14.
Certain 1,1,1-trichloroethane production processes use a steam
stripper prior to final distillation and recovery of 1,1,1 trichloro-
ethane, in which case a separate waste stream is generated. The
attached Figure 2 shows a process where a steam stripper is used.
Chlorination of Ethane
The main sequence of reactions occurring during the free radical
Chlorination of ethane is:
C2H6 + C12 > CH3CH2C1 + CH3CHCl2 + CH3CCl3 + HC1
C12 > CH2HC1 + CH2CC12 + HC1
-------
TABLE
ESTIMATED EMISSIONS FROM 1 , 1 , 1-TRICHLOROETHAME MANUFACTURE: Vinyl Chloride Process
Species
Hydrogen chloride
Ethane
Ethene
NH4-FeCl3~3 Complex
1 , 1-Dichloroethane
1 , 1-Dlchloroethene
1 , 2-Dichloroethane
1,1, 1-Trlchloroethane
1,1,2-TGrichloroe thane
1,1,1, 2-Tetrachloroethane
1,1,2 ,2-Tetrachloroethane
Pentachloroe thane
Sodium hydroxide
Sodium chloride
EMISSIONS kg/Mg
Air Aqueous Solid
1.6
I. ft
2.2
2.2
9.9 0.8
0.8
3.5 3.9
2.6 51.2
35.3
40.8
1.8
33.7
449.
Source: Elkin, L.M. "Chlorinated Solvents," Process Economic Program Report No. 48,
Stanford Research Institute, Menlo Park, California, February, 1969.
-------
Small amou,.:s of l,?-<3ichloroe thane and 1 ,1 ,2-trichloroethane are also
formed in minor amour ts. The product mix, however, can be varied some-
what by operating conditions. Furthermore, to maximize 1,1,1-trlchloro-
ethane production, ethyl chloride and 1,1-dichloroethane are recycled
to the chlorination reactor; vinyl chloride and vinylidene chloride
are catalytlcally hydrochlorlnated to 1,1-dichloroethane and 1,1,1-
trichloroethane respectively:
H2C=CHC1 + HC1 _ CH3CHC12
FeCl3
CH2=CC12 + HC1 _ CH3CC13
Figure 3 represents a simplified process for production of 1,1,1-trlchloro-
e thane via direct chlorination of ethane. Chlorine and ethane react in
an adiabatic reactor at an approximate temperature of 400°C and a pres-
sure of 6 atmospheres with a residence time of approximately 15 seconds.
The reactor effluent (containing unreacted ethane, ethylene together
with vinyl chloride, ethyl chloride, vinylidene chloride, 1,1-dichloro-
ethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane,
a small amount of higher chlorinated hydrocarbons, and hydrogen chloride)
is quenched and cooled. The bottom stream from the quench column, consisting
primarily of tetrachloroethane and hexachloroethane, is removed. The
overhead product from the quench column is fractionated into a chlorin-
ated hydrocarbon stream and light products — ethane, ethylene, and
hydrogen chloride. A portion of the crude hydrogen chloride stream
is used In subsequent hydrochlorlnation reactions; excess hydrogen
chloride Is purified for reuse or resale. The bottom stream from
-------
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TIllCIILOnOGMIANE I OICIII.OnOflTMAMn
HYDROGEN
CMLORIDP.
A—— - » fcoNIH
L- (^
VINYL • v -J
CMLOHIOE ^-^
IIYOnOCI ILOntNATOR
ntACTOR
REACTOR SPENT
CATALYST
WASTE
r-+* TO ATMOSPI IEHE
•«— NnOII iMiO
G>
V ^^
[ scRuoncn
*" WASTEWATER
i
i
MSPn) Old ILOROETI IANE
C± I
^NTCR) f |
] I'URiriCAllOM
COLUMN ^~
CIILOf
REA
Y
STEAM STRIPPER
GAS ErrLUENTS
t 1 — »- i,i,i-Tnic»
CIMOIllNG 1 I
^\ 1 r^ r^
+J \ \
STEAM
— -, «JTrAU^rIPPQn . ^ DISTILLATION
_^/ STHAM-* f COLUMN
HNATOR _v
CTOR
1 x^ \* • ^ HEAVY EW
STEAM STRIPPER WASTE
Figure 2. 1,1,1-TniCMLOnOETMAHIE 0V THE IIVDnOCIILOniNATION AND DinECT
CIILORINATION OF VINYL CIILORIDE. (51)
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AUG-24-2006 THU 03:54 PM FAX NO. P. 07
the hydrogen chloride column is further separated by distillation
into various products. The lower boiling hydrocarbons are removed
as an overhead product in the first column. The bottoms contain
substantially .til the heavy waste materials (tetrachlorinated ethanes
and higher). The bottoms may be disposed of as waste or used in
other chlorinated hydrocarbon processes as a feedstock. These
bottoms are the waste stream of concern from the ethane chlorination
process. (The remaining process description Is provided for informa-
tional purposes.)]
The overhead product (principally 1,1,1-tricholroethane, vinyl
chloride, vinylidene chloride, ethyl chloride, and 1,1-dichloroechane)
is fractionated and 1,1,1-trichloroethane removed as a bottom produce.
The overhead stream from the 1,1,1-trichloroethane column is fed to
the 1,1-dichloroechane column, where 1,1-diehldroethane is separated
as the bottoms stream and is recycled as a feedstock to the chlorinatioo
reactor. Vinyl chloride, vinylidene chloride, and ethyl chloride
(the overhead stream) are fed to the hydrochlorination reactor,
where vinyl chloride and vinylidene chloride react with hydrogen
chloride to form 1,1-dichloroethane and 1,1,1-trichloroethane
respectively. Approximate hydrochlorination reaction conditions
are at a temperature of 65°C and 4 atm.
The reactor effluent stream from the hydrochlorination reactor
is neutralized with ammonia. The resulting complex (ammonium chloride-
ferric chloride - ammonia) is removed by the spent catalyst filter
as a semisolid waste. (This is the analogous stream to the spent
catalyst waste in the vinyl chloride process (see Fig. 1), but is not
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AUG-24-2006 THU 03:54 PM FAX NO. P. 08
listed as hazardous when arising in the ethane chlorination process
since it cooslate principally of iron chloride and hydrogen chloride
(see Table 4)). The filtered hydrocarbon stream is fractionated
further: the bottom fraction (primarily 1,1,1-trichloroethane) ia
recycled to the trichloroethane column. The overhead stream (primarily
ethyl chloride and 1,1-dichloroethane) is recycled to the chlorination
reactor. Table 4 summarizes the estimated emissions from this process.
As shown, predicted waste constituents are Ij2-dichloroethane, 1,1,1-
trichloroethane and higher boiling ethanes which are expected to
comprise the major percentage of the waste.
Table 5 summarizes waste consituents and estimated waste
constituent amounts in waste streams generated by each process.
C. Waste Management Practices
The Agency presently lacks reliable information as to the manage'
uent practices for these vastes, but based on typical waste management
practices in the chlorinated organic manufacturing Industry it is
likely that distillation bottoms and heavy ends are landfJlled
(perhaps in drums). Aqueous wastes are probably stored on site in
pits that equalize surges in the waste flow to landfill operations*
Some wastes also may be incinerated.
III. Discussion of Basis for Listing
A. Hazarda Posed by the Waste
The various waste streams from the production of 1,1,1-
trichloroethane are likely to be generated in large quantities, as
indicated by a comparison of the waste emission factors contained in
Tables 3, 4, and 5 and the production data in Table 2. Such substantial
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TABLE 4
KSTIMATED EMISSIONS FROM I,1,1-TRICULOROBTHANE MANUFACTURE: Chlorlnatlon of Ethane
Species
F.thene
1,l-Dlchloroethane
1,2-nichloroethane
1,1,l-Trlchloroethane
1,1,2-Trichloroethane
Tetrachloroethanes
HexachIn roethanes
Iron (III) chloride
Hydrogen Chloride
Air
EMISSIONS kg/Mg
Aqueous
2.4
Solid
trace
30.7
39.0
49.7
51.4
2.8
173.6
Source: Elkln, 1969
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TABLE 5
Via Vinyl Chloride Process
Waste Stream
Distillation bottoms and
heavy ends
Compound
1,1,2-trichloroethane
1,1,1,2-tetrachloroethane
1,1,2,2-tetrachloroethane
Pentachloroethane
kg/Mg of
1,1,1-Trichloroethane
51.2
35.3
40.8
1.8
Waste from product stream
stripper*
1,2-dichloroethane
1,1,1-trichloroethane*
0.8
3.9*
Spent catalyst
**
complex
**
2.2
**
Via Chlorination of Ethane
Waste Stream
Heavy ends
Compound
1,1-dichloroethane
1,2-dichloroethane
1,1,1-trichloroethane
1,1,2-trichloroethane
tetrachloroethanes)
hexachloroethanes )
kg/Mg of
1,1,1-trichloroethane
trace
30.7
49.7
49.7
51.4
*The spent steam stripper waste is also expected to contain small concentrations
of vinyl chloride, vinylidene chloride and chloroform. Vinyl chloride is expected
to be present since it is a feedstock constituent. Vinylidene chloride Is a
by-product from the dehydrochlorinatlon of 1,1,2-trichloroethane. Chloroform
is another predicted reaction by-product, and is expected to be formed from
the splitting off of vinyl chloride monomer and ethane into single carbons,
which are subsequently chlorinated.
**The spent catalyst waste is also expected to contain small concentrations of
vinyl chloride feedstock, 1,1,1-trichloroethane product and some polymeric
materials.
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waste quantities are themselves of regulatory concern In light of
the hazardous constituents present. Thus, waste mismanagement
poses the threat of contaminating large expanses of groundwater,
surface water and air, and of reaching large numbers of environmental
receptors.
Of the chemicals potentially present in the wastes, 1,2-dichloro-
ethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, vinylidene
chloride, vinyl chloride and chloroform are on the CAG carcinogen
list; 1,1,1-trichloroethane is a suspected carcinogen and 1,1,1-
tetrachloroethane is toxic.* Some of these chemicals are also
suspected mutagens and teratogens. Should these compounds reach
human receptors, the potential for resulting adverse health effects
would be extremely high. These constituents are capable of migration.
For example, 1,2 dichloroethane, the trichloroethanes, and the
tetrachloroethanes all are relatively soluble in water (solubility
ranging from 200 ppm - 8700 ppm) (App. B), and thus, these compounds
are capable of causing chronic toxicity via a water exposure pathway.
Indeed, if they solubillze these compounds could pose a substantial
hazard at a level many orders of magnitude less than their solubility
limits. In addition, 1,2-dichloroethane and 1,1,2-trichloroethane
are fairly volatile as well (vapor pressure 60 mm Rg.)**; thus, 1,1,2-
trichloroethane and the tetrachloroethanes may pose a chronic toxicity
*Pentachloroethane poses some threat of chronic exposure via an
inhalation pathway, but is not presently considered to pose
sufficient danger to be listed as a waste constituent of concern.
**!,!,! trichloroethane is also volatile, but is expected to photolyse
rapidly so probably would not pose a substantial hazard via air in-
halation beyond the immediate disposal site (App. B.).
-V-
-------
problem via inhalation as wel!.
These waste constituents are capable of mobility and persistence
as well, as shown by numerous damage incidents Involving these waste
constituents. Chlorinated ethane and ethylene contamination of
groundwater in areas adjacent to disposal sites in fact is not uncommon.
For example, 1,1,1-trichloroethane has been detected in groundwater
in Acton, MA, where residents believe the source is a disposal site
at a nearby manufacturing facility.(*) In New Jersey, seepage
from landfilled wastes near the CPS Chemical Company also resulted
in well contamination by trichloroethylene, tetrachloroethane, and
methylene chloride^). 1,2-dichloroethane has also been detected
in groundwater supplies in Bedford, MA, where the source of contam-
ination has not been positively identified but is believed to be due
to industrial uses upstream.(*) Dichloroethanes are among the waste
constituents which have migrated from Hooker Chemical's facility at
Montague, Mich., contaminating large expanses of ground and surface
water.(^8) Trichloroethane has also nlgraged and contaminated
private drinking wells in Canton, Connecticut.(**)
Thus, these wastes are capable of causing substantial hazard un-
less properly managed, and the possibility of mismanagement and en-
vironmental release of contaminants is certainly plausible. Some
portion of these wastes are expected to be landfilled, while other
residues are expected to be incinerated. Improper landfilllng —
siting in areas with permeable soils, inadequate leachate control or
monitoring, lack of landfill cover, and the like — could allow
waste constituents to leach into groundwater, or escape via volatilization.
-------
Even if plastic lined drums are used for disposal, they represent a
potential hazard if the landfill is improperly designed or operated
(i.e., drums corrode in the presence of even small amounts of water).
The current disposal sites (the Gulf Coast) receive considerable
rainfall and have a high ground water table creating a potential for
drum corrosion.
Given the presence of the chlorinated ethanes and ethylenes and
the potential for drum degradation, it is likely that these wastes,
if improperly landfilled (i.e., improperly designed or operated
landfill), would come into contact with ground water. This is par-
ticularly true of deeper deposits or those in cooler climates where
vapor losses will be mlmimlzed. In these two cases, the waste con-
stituents will readily move with the groundwater, Just as they have
have been observed to do at sites such as Love Canal, the Kin-Rue
Landfill, and Story Chemical in Michigan County, Michigan.(49,50,51,52)
The above damage incidents support laboratory findings that any
released 1,1,2-trichloroethane and 1,2-dichloroethane will pass
through sandy soils with less than a 50 percent loss due to volatl-
llzatlon(*>).
In addition to landfllllng, the 1,1,1-trlchloroethane steam strip-
per bottoms which are recycled or incinerated is often stored temporarily
at the production site. Should leaks occur, similar problems to
those from landfills could be expected.
Mismanagement of Incinerating operations could result in the re-
lease of Hazardous vapors, containing among other substances the
waste constituents of concern, to the atmosphere and present a signifi-
-------
cant opportunity for exposure of humans, wildlife and vegetation In
the vicinity of these operations to potentially harmful substances
through direct contact and also through pollution of surface waters.
Finally, should these waste constituents migrate Into the environ-
ment they can be expected to persist, thus increasing the likelihood
of reaching environmental receptors and causing substantial harm.
The damage incidents above demonstrate environmental persistence of the
released constituents. All of these waste constituents are expected,
on the basis of literature degradation values, to persist in groundvater.
(1,1,2-Trlehloroethane is subject to hydrolysis, but haa a hydrolysis
half-life of 6 months. 1,1,2-Trichloroethane may also persist la air as
well (App. B)). Again, the persistence of these constituents is
evidenced by the measurable concentrations of these chemicals In Love
Canal leachate some thirty years after disposal^49.50.51) ^n aay
case, in light of the hazardous character of these waste constituents,
the Agency could not Justify a decision not to list these wastes
absent assurance that waste constituents are incapable of migration
and persistence. As demonstrated above, such assurance is not possible.
B. Health and Ecological Effects
1. 1,2-Dichloroethane
Health Effects - 1,2-Dichloroethane is a carcinogen;?')
it has also been identified by the Agency as demonstrating substantial
evidence of carcinogenicity.(^4) jn addition, this compound and
several of its metabolites are highly mutagenic (^»9). 1,2-Dichloro-
ethane crosses the placental barrier and is embryotoxlc and terato-
genic'l *•*' , and has been shown to concentrate in the milk of
-------
nursing mothers.(l^ Exposure to this compound can cause a
variety of adverse health effects Including damage to the liver,
kidneys and other organs, Internal henorrhaglng and blood clots^1**).
1,2-Dichloroethane Is designated a priority pollutant under Section
307(a) of the CWA. Additional Information and specific references
on-the adverse health effects of 1,2-dlchloroethane can be found In
Appendix A.
Ecological Effects - Values for a 96-hour static
Regulations - OSHA has set the TWA at 50 ppm. DOT re-
quires the containers for this chemical to carry a warning that it is a
flammable liquid.
The Office of Air, Radiation and Noise has completed pre-
regulatory assessment of 1,2-dichloroethane under Sections 111 and 112
of the Clean Air Act. Pre-regulatory assessments are also being con-
ducted by EPA's Office of Water and Waste Management under the Safe
Drinking Water Act and by the Office of Toxic Substances under the
Toxic Substances Control Act.
Industrial Recognition of Hazard - Sax, In Dangerous Proper-
ties of Industrial Materials, rates 1,2-dichloroethane as highly toxic
upon ingestlon and inhalation.
2. 1,1,1-Trichloroethane (Methyl Chloroform)
Health Effects - The area of greatest health concern
regarding 1,1,1-trichloroethane exposure Involves its potential for
rautagenlc, terarogenlc and carcinogenic effects. In vitro studies
have indicated that 1,1,1-trichloroethane is slightly mutagenic with
-------
or without activation.(20,57,58) These studies were performed
using the Ames system which is characterically insensitive to
chlorinated hydrocarbons. 1,1,1-Trichloroethane was also positive in
an in vitro mammalian cell transformation assay.(19) However, the
results of two animal carcinogen bioassay studies were inconclusive
due to design and experimental problems.(1*,20,56) The NCI is
currently re-evaluating the carcinogenic potential of 1,1,1-tri-
chloroethane. Studies of the teratogenic potential of 1,1,1-tri-
chloroethane are also suggestive; however, more studies are needed to
make a conclusive statement.^6)
Other than psychophysiological effects, 1,1,1-trlchloroethane
exposure at or below the OSHA-PEL (350 ppm) does not result in
either acute or chronic toxic complications. At very high concentrations
(710,000 ppm), however, 1,1,1-trichloroethane produces cardiovascular
and CNS narcotic effets, and can cause death from cardiac failure.
Animal studies as well as accidental human exposure, have shown that,
at these high Inhalation concentrations, 1,1,1-trlchloroethane produces
a "chlorinated hydrocarbon" type of microscopic pathology liver and
kidneys (fatty infiltration, cellular necrosis) which is characterized
as being much less severe than that produced by carbon tetrachlorlde
or trichloroethylene. Additional information and specific references
on the adverslon effects of 1,1,1-trichloroethane can be found in
Appendix A.
Ecological Effects - Lethal concentrations (LC5Q, 96
hour values) are reported ranging from 33 mg/1 (Dab), and 70 mg/1
(Sheepshead minnow) to 69.7 mg/1 (Blueglll) and 10") mg/1 (Flathead
-------
minnow).(24,56)
1,1,1-Trlchloroethane in common with other volatile hydrocarbons,
volatilizes from water to an appreciable extent. However, retrans-
port to water from the atmosphere and decreased volatilization rates
from stagnant water render the aquatic compartment an important sink
for 1,1,1-trichloroethane. The major ecological concern, however,
is its possible role as an ozone depleter. In recent years there
has been considerable concern over human activities appreciably
altering the levels of ozone in the stratosphere. The tropospheric
lifetime of 1,1,1-trichloroethane is believed to be in the range of
4-12 years, and it has been estimated that 10-20 percent of the 1,1,1-
trichloroethane molecules released at the earth's surface will
eventually reach the stratosphere.(59) Studies simulating conditions
obtained at high altitudes have shown^60) that the lax resident time
of 1,1,1-trichloroethane in the stratosphere and the high solar uv
Intensity will result in its eventual total destruction yielding free
Cl atoms which are known to destroy stratospheric ozone.
Regulations - 1,1,1-Trichloroethane Is designated as a
priority pollutant under Section 307(a) of the CWA. OSHA has set the
TWA at 350 ppm. EPA has recommended an ambient water quality criterion
at 15.7 mg/1. Because of wide use and exposure, and the Inadequacy
of currently available information, the TSCA Interagency Testing
Committee has recommended'") further evaluation to establish the
carcinogenlcity, mutagenlcity and teratogeniclty and other chronic
effects of 1,1,1-trichloroethane.
-------
Industrial Recognition of Hazard - Sax (Dangerous Propertlea
of Industrial Materials) lists 1,1,1-trichloroethane as moderately toxic
via inhalation.
3. 1,1,2-Trichloroethane
Health Effects - 1,1,2-Trlchloroethane has been shown to
cause cancer in mice;(25) it has also been identified by the Agency
as demonstrating substantial evidence of carcinogenicity.^*' There
is evidence that 1,1,2-trichloroethane is mutagenie and may be embryo-
toxic or cause teratogenic effects.(26,27)
Like the other compounds of this type, the trichloroethanes are
narcotics that produce central nervous system effects, and can damage
the liver, kidney and other organs.(15)
1,1,2-Trichloroethane is designated as a priority pollu-
tant under Section 307(a) of the CWA. Additional Information and
specific references on the adverse effects of 1,1,2-trichloroethane
can be found in Appendix A.
Ecological Effects - Aquatic toxlclty data are limited
with only three acute studies in freshwater fish and invertebrates,
with doses ranging from 10,700 to 22,000 ug/l.f17'
Regulations - OSHA has set the TWA at 10 ppm (skin).
4. Vinylidene Chloride
Health Effects - Vinylidene chloride has been shown to
cause cancer in laboratory animals (28,29) amj to be mutagenie.™8)
It has also been Identified by the Agency as demonstrating substan-
tial evidence of carcinogenicity.'5^ It is very toxic [LDj0
(rat) = 200 mg/kg] and chronic exposure can cause damage to the
-------
liver and other vital organs as well as causing central nervous
system effects. Additional information and specific references on
the adverse effects of vlnylldene chloride can be found in Appendix
A.
Regulations - DOT requires containers to be labeled "flam-
mable liquid." OSHA has set the TWA at 10 ppm.
Industrial Recognition of Hazard - The toxic hazard of vinyll-
dene chloride la suspected of being similar to vinyl chloride which is
moderately toxic via inhalation (Sax, Dangerous Properties of Industrial
Materials)(3°).
5. Vinyl Chloride
Health Effects - Vinyl chloride has been shown to be a
carcinogen In laboratory studies;(31i32,33) ic nas aiso been Identi-
fied by the Agency as demonstrating substantial evidence of carcino-
genlcity.^5*) This finding has subsequently been supported by
epidemlological findings.(33-37)
Vinyl chloride is very toxic [LD5Q (rat) = 500 mg/kgl and
acute exposure results in anaesthetic effects as well as uncoordinated
muscular activities of the extremities, cardiac arrythmlas(38) and
sensitization of the myocardium.(39) jn severe poisoning, the lungs
are congested and liver and kidney damage also occur*(*0) A decrease
in white blood cells and an Increase in red blood cells was also
observed, as well as a decrease in blood clotting ability.f*^-)
Vinyl chloride is designated as a priority pollutant under Section
307(a) of the CWA. Additional information and specific references
on the adverse effects of vinyl chloride can be found In Appendix A.
-yf-
-•-m-
-------
Regulations - OSHA has set the TWA at 1 ppm with a 5 ppm
ceiling ovef 15 minutes. DOT requires this to be labeled "flammable
gas."
Industrial Recognition of Hazard - Vinyl chloride has a
moderate toxic hazard rating via inhalation (Sax, Dangerous Properties
of Industrial Materials).
6. Chloroform
Health Effects - Chloroform has been shown to be carcino-
genic(42»5*) and tangential evidence links human cancer epidemiology
with chloroform contamination of drinking water.(43«**) Chloroform
has also been shown to Induce fetal toxicity and skeletal malforma-
tion in rat embryos.^, 46) Chronic exposure causes liver and kidney
damage and neurological disorders.^3) Additional information and
specific references on the adverse effects of chloroform can be found
in Appendix A.
Ecological Effects - The U.S. EPA has estimated that
chloroform accumulates fourteen-fold in the edible portion of fish
and shell flsh.(*3) The U.S. EPA has also recommended that
contamination by chloroform not exceed 500 ug/1 in freshwater and
620 ug/1 in marine environments.(*3)
Regulations - Chloroform has been designated as a priority
pollutant under Section 307(a) of the CWA. OSHA has set the TWA at
2 ppm. FDA prohibits use of chloroform in drugs, cosmetics and food
contact material. The Office of Water and Waste Management has pro-
posed regulation of chloroform under Clean Water Act Section 311 and is
In the process of developing regulations under Clean Water Act 304(a).
-------
The Office of Air, Radiation and Noise is conducting preregulatory
assessment of chloroform under the Clean Air Act. The Office of Toxic
Substances has requested additional testing of chloroform under Section
4 of the Toxic Substances Control Act and Is conducting pre-regulatory
assessment under the federal Insecticide, Fungicide and Rodenticide Act.
Industrial Recognition of Hazard - Chloroform has been
given a moderate toxic hazard rating for oral and inhalation exposures
(Sax, Dangerous Properties of Industrial Materials).t30)
7. Tetrachloroethanes
Health Effects - 1,1,2,2-Tetrachloroethane has been
shown to produce liver cancer in laboratory mice;(31) it has also
been identified by the Agency as demonstrating substantial evidence
of carcinogenlclty.C5*) It is also shown to be very toxic [oral rat
1.1)59 •> 200 mg/Kg.]. In addition, passage of 1,1,1,2-tetrachloroethane
across the placental barrier has been reported,(**) In Ames Salmonella
bioassay 1,1,2,2-tetrachloroethane was shown to be mutagenlc.(32)
Occupational exposure of workers to 1,1,2,2-tetrachloroethane produced
neurological damage, liver and kidney ailments, edema, and fatty de-
generation of the hear muscle.O3) Both 1,1,1,2-tetrachloroethane
and 1,1,2,2-tetrachloroethane are designated as priority pollutants
under Section 307(a) of the CWA. Additional information and specific
references on the adverse effects of tetrachloroethanes can be found
in Appendix A.
Ecological Effects - Freshwater invertebrates are
sensitive to 1,1,2,2-tetrachloroethatie *ith a lethal concentration
of 7-8 rag/1 being reported.(20) USEPA estimates the BCF to be 18.
-------
Regulations - OSHA has set the TWA at 5 ppm (skin) for
1,1,2,2-tetrachloroethane.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists 1,1,2,2-tetrachloroethane
as being highly toxic via ingestlon, inhalation and skin absorption.
-------
IV. References
1. 1979 Director of Chemical Producers United-States.
2. Chemical Economics Handbook, Memlo Park, California. December
1978. (May be purchased fromm SRI.)
3. Synthetic Organic Chemicals, U.S. Production and Sales, U.S.
International Trade Commission.
4. Water Quality Issues in Massachusetts, Chemical Contamination,
Special Legislative Commission on Water
5. Memo from Roy Albert to E. C. Bekc, Administrator, EPA Region
II, Drinking Water Contamination of Hew Jersey Well Water.
March 31, 1978.
6. Wilson, J. T., and C. G. Enfield, 1979, Transport of Organic
Pollutants Through Unsaturated Soil. Presented American Geo-
physical Union. December 3-7, San Francisco, CA.
7. National Cancer Institute. Bioassay of 1,2-Dichloroethane for
Possible Carcinogenic!ty. U.S. Department of Health, Education
and Welfare, Public Health Service, National Institutes of
Health, National Cancer Institute, Carcinogenesis Testing Program,
DHEW Publication No. (NIH) 78-1305, January 10, 1978.
8. McCann, J., E. Choi, E. Taasaki, and B. Ames. Detection of Car-
cinogens as Mutagenic in the Salmonella/Mlcrosome Test: Assay
of 300 Chemicals. Proc. Nat. Acad. Sci. USA 72(2): 5135-5139,
1975a.
9. McCann, J., V. Simmon, D. Streitwlese-r, and B. Ames. Mutageniclty
of Chloracetaldehyde, a Possible Metabolic Product of 1,2-Dichloro-
ethanes (ethylene dichloride), Chloroethanol (ethylene chlorohydrin),
Vinyl chloride, and Cyclophosphamide. Proc. Nat. Acad. Sci. ^2_
(8):3190-319 3.
10. Vozovaya, M., Changes in the Esterous Cycle of White Rats Chronically
Exposed to the Combined Action of Gasoline and Dichloroethane Vapors.
Akush. Genecol. (Kiev) 47 (12): 65-66, 1971.
11. Vozovaya, M., Development of Offspring of Two Generations Obtained
from Femals Subjected to the Actionof Dichloroethane. Gig. Sanit.
_7:25-28, 1974.
12. Vozovaya, M., The Effect of Low Concentrations of Gasoline, Di-
chloroethane and Their Combination on the Generative Function of
Animals and on the Development of Progeny. Gig. Tr. Prof. Zabol.
7:20-23, 1975.
-------
"*. Vozovaya, M., Effect of Low Concentrations of Gasoline, Dichloro-
ethane and Their Combination on the Reproductive Function of
Animals. Gig. Sanit. 6:100-102. 1976.
14. Vozovaya, M. A., The Effect of Dichloroethane on the Sexual Cycle
and Embryogenesis of Experimental Animals. Akush. Genecol. (Mos-
cos) 2:57-59, 1977.
15. Urusova, T. P. (About a possibility of dichloroe thane absorption
into milk of nursing women when contacted under industrial con-
ditions.)
16. Parker, J. C. , et al. 1979. Chloroethanes: A Review of Toxicity.
Amer. Indus. Hyg. Assoc! J., 40.: A 46-60, March 1979!
17. U.S. EPA, 1979. Chlorinated Ethanes: Ambient Water Quality Cri-
teria (Draft).
18. NCI, 1977. Bioassay of 1,1,1-Trichloroethane for Possible Car-
cinogenicity. Carcing. Tech. Rep. Ser. NCI-CG-TR-3.
19. Price, P. J., et al. 1978. Transforming Activities of Trichloro-
ethane and Proposed Industrial Alternatives. In vitro. 14:290.
20. U.S. EPA Report, In Vitro Microbiological Mutagenicity of 81
Compounds .
21. Schwetz, B. A., et al. 1974. Embryo and Fetal Toxicity of In-
haled Carbon Tetrachloridem kmkODlchloroethane and Methyl Chloro-
form in Rats. Toxtcol. Appl. Pharmacol. 28:452.
22. Stahl, C. J., et al. 1£69. Trichloroethane Poisoning. Observa-
tions on the Pathology annd Toxicology of Six Fatal Cases. Jour.
Forensic Sci., 14:393.
23. Walter P., Chlorinated Hydrocarbon Toxicity, a Monograph. PB-257185.
National Technical Information Service, Springfield, Virginia.
24. U.S. EPA, 1979. In-Depth Studies on Health and Environmental Impact
of Selected Water Pollutants. Contract No. 68-01-4646.
25. Chlorinated Solvents, Lloyd Elkin. February 1969. (May be purchased
from SRI.)
26. Elovaara, E., et al. Effects of O^C^, 0130.3, TCE, Perc and Tol-
uene In the Development of Chick Embryos, Toxicology 12; 111-119,
1979.
27. Parker, J. C. , I. W. F. Davidson and M. M. Greenberg, EPA Health
Assessment Report of 1,2-Dlchloroe thane (Ethylene Dichloride).
In preparation.
-------
28. Environmental Health Perspectives, 1977, Vol. 21, 333 pp.
29. Van Duuren, B. L., et al. 1979. Car ci.no geniclty of Halogenated
Olefinic and Aliphatic Hydrocarbons in Mic. J. Nat. Cancer Inst.
63(6): 1433-1439.
30. Sax, N. I. Dangerous Properties of Industrial Materials.
31. Viola, P. L., et al., Oncogenic Response of Rat Skin, Lungs, and
Bones to Vinyl Chloride. Cancer Res. 31; 516, 1971.
32. Maltonl, C., and G. Lefemine, Carcinogenlcity Bioassays of Vinyl
Chloride. Am. NY Acad. Sci. 2A6: 195 (1975).
33. Lee, F. I., and Harry D. S., Angiosarcoma of the Liver in a
Vinyl Chloride Worker. Lancet 1; 1316 (1974).
34. Creech & Johnson, Anglosarcona of the Liver in the Manufacture
of Polyvinyl Chloride. Jour. Occup. Med. 16; 150, 1974.
35. Falk. H., et al. Hepatic disease among workers at a Vinyl
Chloride Polymerization Plant. Jour. Amer. Med. ABSOC. 230; 59
(1974).
36. Hakk, L., et al. Liver Damage and Liver Angiosarcona in Vinyl
Chloride Workers. Jour. Amer. Med. Assoc. 230; 64 (1974).
37. Tabershaw, I. R. , and Gaffey, W. R. , Mortality Study of Workers
in the Manufacture of Vinyl Chloride and its Polymers. Jour.
Occup. Med. 16; 509 (1974).
38. Oster, R. H., et al. Anes thesis, XXVII, Narcosis with Vinyl
Chloride Anestheslology 8; 359, 1947.
39. Carr, J., et al . Anesthesis XXIV. Chemical Constitution of
Hydrocarbons and Cardiac Automatlclty. J. Pharmacol. 97 ;1 (1949).
40. Torkerson, T. R., et al. The Toxlclty of Vinyl Chloride by Re-
pe.pred Exposure of Laboratory Animals - Amer. Ind. Hyg. Assoc.
22:354 1961.
41. Lesttc, D., et al. Effects of Single and Repeated Exposures of
"unsays and Rats to Vinyl Chloride. Amer. Ind. Hyg. Assoc. Jour.
2-L: -u5, 1963.
42. National Cancer Institute, 1976. Report on Carcir«. -genesis Bio-
assav of Chloroform. National Technical Information Service,
PB-2-. »013. Springfield, Vlrg'frTiz.
43. U.S. :PA, 19'9.. Trlchlororaethane (Chloroform 1 Hazard Profile,
, Cincinnati, Ohio 45268. 39?9.
-------
44. McCabe, L. J., 1975. Assocatlon Between Trihalomethanes in
Drinking Water (NORS Data) and Mortality. Draft Report.
U.S. EPA.
45. Schuetz, B. A., et al. The effect of maternally inhaled trl-
chloroethylene, perchloroethylene, methyl chloroform and methylene
chloride on embryonal and fetal development in mice and rats.
Toxicol. Appl. Pharmacol. 32; 84-96.
46. Thompson, D. J., et al. 1974. Teratology Studies on Orally Ad-
ministered Chloroform in the Rat and Rabbit. Toxicol. Appl.
Pharmacol. 29: 348.
47. Dawson, English, and Petty, 1980. "Physical Chemical Properties
of Hazardous Waste Constituents", Table 1.
48. EPA, Hazardous Waste Division, Technology and Management Assessment
Branch, "Animal Study of Personal Injury, Economic Damage or Fa-
talities from Hazardous Haste", 1978.
49. Barth, E. F., Cohen, J. M., "Evaluation of Treatability of Indus-
trial Landfill Leachate", unpublished report, U.S. EPA, Cincinnati,
November 30, 1978.
50. O'Brien, R. P., City of Niagara Falls, New York, Love Canal Project,
unpublished report. Calgon Corp., Calgon Environmental Systems
Division, Pittsburgh, Pennsylvania.
51. Rcera Research, Inc. Priority Pollutant Analyses prepared for Nuco
Chemical Waste Systems, Inc., unpublished report, Tonawanda New
York, April, 1979.
52. Sturino, E., Analytical Results: Samples From Story Chemicals, Data
Set Others 336", unpublished data, U.S. EPA Region 5, Central Re-
gional Laboratories, Chicago, Illinois, May, 1978.
53. Source Assessment Chlorinated Hydrocarbons Manufacture. EPA-600/2-
78-004.
54. CAG List of Carcinogens, April 22, 1980.
55. U.S. EPA. Second Report of the TSA Interagency Testing Committee
to the Administrator, EPA, OTS, April 1979.
56. 44 FR 34685-34692 (June , 1979).
57. Simmon, V. F., K. Kauchaven, and R. G. Tardiff. 1977. "Mutagenic
activity of chemicals identified in drinking water" in: Progress
in Genetic Toxicology, ed. I. D. Scott, B. A. Bridges and F. R.
Sobels. pp. 249-258, Elsevier, N.Y.
-------
58. McCann, J. and B. Axes, 1976. Detection of carcinogens as
rautagens in the Salmonella raicrosome test: assay of 300
chemicals. Proc. Nat. Acad. Sci. 78: 950.
59. National Academy of Science, 1979. Stratospheric ozone de-
pletion by halocarbons: chemistry and transport. NRC, NAS.
Washington, D.C.
60. U.S. EPA. i960. Final Report on Risk Assessment of 1,1,1-
trichloroethane. Contract Number 68-01-0543. Batelle Columbus
Laboratories, Columbus, Ohio 43201.
-------
Response to Comments - Waste from the Product Steam Stripper
and Spent Catalyst from the Hydrochlorinator Reactor in the Production
of 1,1,1-Trichloroethane
One commenter raised several questions with respect to wastes
K028 and K029 (Waste from the product steam stripper and Spent catalyst
from the hydrochlorinator reactor in the production of 1,1,1-tri-
chloroethane).
1. The commenter first questioned the Agency's characterization
of 1,1,1-trichloroethane as a suspect carcinogen. The
commenter argues that based on their evaluation of the avail-
able 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
the NCI Bioassay Study on the carcinogenicity of 1,1,1-tri-
chloroethane referred to in the listing background document
(pg. 464) and an unpublished study are inconclusive, positive
responses in two iti vitro systems (a rat embryo cell trans-
formation 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 chat there is ample evidence
-------
to consider 1,1,1-trichloroethane as a suspect carcinogen.*
The listing background document on trichloroethane production
and the Health and Environmental Effects Profile on 1,1,1-
Trichloroethane will be modified to discuss these findings.
2. The commenter then criticized the Agency's characterization
of 1,1,1-trichloroethane as "very toxic to aquatic life" and
noted that the toxicity levels reported do not warrant this
characterization.
In re-evaluating the aquatic toxicity of 1,1,1-trichloro-
ethane, the Agency agrees with the commenter that 1,1,1-tri-
chloroethane is not sufficiently toxic to fish to warrant
characterization as "very toxic ...". In the Registry of Toxic
Effects (1975 Edition), a widely used reference book which is
published by the National Institute for Occupational Safety and
Health (NIOSH), a rating of the aquatic toxicity or non-toxicity
of chemical substances is provided. In this rating, substances
with an LC5Q of between 10,000 ug/1 to 100,000 ug/1 is considered
slightly toxic [1,1,1-trichloroethane (96 hour LC5Q 26-58
mg/1)]. Therefore, the Agency will modify the listing background
document to reflect this change.
The Agency will, however, continue to Include 1,1,1-trichloroethane
as a constituent of concern in this particular listing.
*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 ror that action are
incorporated by reference herein.
-------
References
McCarm, J. and B. Anes. 1976. Detection of Carcinogens as Mutagens
in the Salmonella Mlcrosome Test* Assay of 300 chemicals:
Discussion Proc. Hat. Acad. Sci. 78:950.
Price, P. J. et. al. 1978. Transforming Activities of Trichloro-
ethylene are Proposed Industrial Alternatives. In Vitro 14:290.
Simmon, V. F. et. al. 1^77. Mutagenic Activity of Chemicals
Identified in Drinking Water in: Progress in Genetic Toxicology,
ed. I. D. Scott, B. A. Rridges and V. H. Sobels. pp. 24Q-258.
Elsevier.
-------
SJ-28-01
LISTING BACKGROUND DOCUMENT
TRICHLOROETHYLENE AND PERCHLOROETHYLENE PRODUCTION
Column bottoms or heavy ends from the combined
production of trichloroethylene and perchloroethylene (T)
Summary of Basis for Listing
The column bottoms or heavy ends from the combined pro-
duction of tr-lchloroethylene and perchloroethylene are generated
when recycling streams from the chlorination and oxychlorination
processes become contaminated and must be removed and disposed.
The Administrator has determined that these heavy ends are
solid wastes which may pose a present or potential hazard to
human health and the environment when improperly transported,
treated, stored, disposed of or otherwise managed and therefore
should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the
following consideration:
(1) The column bottoms or heavy ends from combined
trichloroethylene and perchloroethylene production
contain significant concentrations of 1,1,2,2-tetra-
chloroethane , hexachlorobutadlene, and hexachloro-
benzene, each of which are carcinogenic. Also,
1,1,2,2-tetrachloroethane is a known mutagen. All
of these substances are also toxic to aquatic life
and bioaccuraulate in living tissues. In addition,
the waste contains smaller amounts of ethylene di-
chloride, hexachloroethane and 1,1,1,2 tetrachloro-
ethane, all substances with carcinogenic and/or
rautagenic properties.
(2) A large quantity (a combined estimated total of at
least 15,000 metric tons) of these wastes is generated
annually.
-------
(3) The wastes are disposed of primarily through
incineration or landfilling. Smaller amounts are
deep well injected into limestone formations. If
not managed properly, these hazardous contaminants
could be emitted to the air from inadequate incinera-
tion or improper land disposal or leach from landfills
and injection wells to expose humans and other life.
The chlorinated organics 1,1,2,2-tetrachloroethane,
hexachlorobutadiene, and hexachlorobenzene, as well
as ethylene dichloride, are water soluble and there-
fore could migrate from the wastes to contaminate
groundwater in concentrations sufficient to cause
substantial hazard.
Industry Profile^11 2,3,4}
Perchloroethylene and trichloroethylene are produced in
a combined process by seven companies at ten manufacturing
locations primarily situated in the Texas and Louisiana Gulf
area. The location of the facilities, their annual production
capacity, and estimated 1979 production are shown in Tab'le 1
and Figure 1. As shown in Table 1, the estimated 1979 production
for perchloroethylene and trIchloroethylene are 367,500 and
125,300 MT, respectively. The annual production levels for
each individual plant are variable and range from 12,600 to
63,700 MT for perchloroethylene producers and 14,000 - 63,700
MT for manufacturers of trichloroethylene. Average annual
per plant production figures are 36,750 MT for perchloroethylene
and 41,400 MT for trichloroethylene .
There currently is excess capacity within this industry
for both the production of perchloroethylene and trichloroethylene
Increased regulatory pressures from both the Environmental
Protection Agency (EPA) and the Occupational Safety and Health
-------
TABLE 1
COMPANY
Diamond Shamrock
Dow
Dupont
Ethyl
PPG
Stauffer
Vulcan
ESTIMATED CAPACITY AND PRODUCTION
PERCHLOROETHYLENE AND TRICHLOROETHYLENE
1979 CAPACITY (MT/YR)8
LOCATION VERCH.LORQETtWLENE IRICHLOROETWLENE
Deer Park, TX 75,000 A
Freeport, TX 68,000 68,000
Pittsburg, CA 18,000
Plaqueraine, LA 54,000
Corpus Christ!, TX 73,000
Baton Rouge, LA 23,000 20,000
Lake Charles, LA 91,000 91,000
Louisville, KY 32,000
Gels mar, LA 68,000
Wichita, KS 23,000
TOTAL 525,000 179,000
1979 PRODUCTION (MT/YR)
PERCtfLOROETHYLENE TRICULOROETUf LEN E
52,500
47 , 600
12,600
37,800
51,100
16, 100
63,700
22,400
47,600
16,100
367 , 500
47,600
14,000
63,700
125,300
£23,OQO-MT/yr. capacity unit placed on standby in early 1978
BMT =» Metric tons
SOURCE: References 1, 2, 3, 4
-------
FIGURE 1
LOCATIONS OF PLANTS MANUFACTURING
PERCHLOROETHYLENE AND TRICHLOROETHYLENE
1) Diamond Shamrock Corp., Deer Park,
2) Dow Chemical Co., Freeport, TX
3) Dow Chenical Co., Pittsburg, CA
4) Dow Chemical Co., Plaquemine, LA
5) DuPont, Corpus Christi, TX
6) Ethyl Corp., Baton Rougii, LA
7) PPG Industries, Inc., Lake Charles,
8) Stauffer Chemical Co., Louisville,
9) Vulcan Materials Co., Ceisnar, LA
10) Vulcan Materials Co., Wichita, KS
LA
KY
Chemicals Produced
A
A,B
A
A
A
A,B
A.B
A
A
A
A = perchloroethylene, B - trichloroethylenc
SOURCE: Reference 9
-------
Administration (OSHA) are serving to inhibit future growth in
demand for these chemicals. It is anticipated that short-
and long-term growth will average 1-2? and that the industry
output can be represented by a flat growth curve.
Manufacturing Process^' )
Perchloroethylene and trichloroethylene are produced
either separately or as co-products by either the chlorination
or oxychlor inatlon of ethylene dichloride or other C.2~
chlorinated hydrocarbons. The ratio of raw material feed
determines the relative yields of perchloroethylene and
trichloroethylene. Perchloroethylene is also produced by the
chlorinolysis of light hydrocarbons with by-product production
of carbon tetrachloride.
This listing document covers wastes generated by the
co-production process.
0 Direct Chlorination of Ethylene Dichloride (See Figure 2)
Perchloroethylene and trichloroethylene are produced by
a single-stage oxychlorination process from ethylene dichloride
and chlorine. Ethylene dichloride, chlorine, oxygen, and
recycled chlorinated organics are fed to a fluid bed reactor.
An inexpensive oxychlorination catalyst (e.g., copper chloride)
is used and the reactor is maintained under pressure at
ahov.it 425°C. Feed adjustments may he employed to vary product
-y-
- SO0!-
-------
FIGURE 2
DIRECT aiLORINATlOH OF ETHYLEN
DICHLORIDE
i.2o
o
o
o
•rl
£
rt
r
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O
a
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Vf
Trichloroethylene
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ro
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en
en
tl-0
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ygen
earn
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.ne- " >
i' >
Reactor
^
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i
Vane Scrubber J
Phase
'Separator
L
»
Dehydtaeor
L
r+
I
Percblor-crichlor
J
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3
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L
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^
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0
Perchlor Scill
!
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w^»
n
Flash
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M
01
(4
id
Vi
u
P ercUloro echylene
Waste
Reaction
5UCJ
C2"CI3 * 21'C1 *
c2n2ciA + «
7HC1 •»• 1.7502 -«• 3.5H20 + 3.5C12 (Deacon)
3.51120
65 to 90Z yield
SOURCB: Reference 3.
-------
ratios, depending upon producer requirements*
The condensed crude and weak acid are then phase-separated
wii.' the crude, being dried by azeotropic distillation. In
the perchlor-trichlor column, the crude is split into two streams,
one trichlor-rich and the other perchlor-rich. The perchlor-
rich stream, containing midboilers and heavies, is fed to the
heavies column where high boilers (1,1,2,2- and 1,1,1,2-
tetrachloroethane, pentachloroethane, hexachloroethane, dimers,
tar and carbon) are removed as bottoms and flashed to remove
tars and carbon. Midboilers are concentrated in the overheads
and recycled. Perchlor recovered from the bottoms of the
still Is neutralized with ammonia, washed, and dried.
The crude trichlor stream is fed to the trichlor product
still, where low boilers, such as dichloroethylenes, are
removed overhead and recycled to the reactor. Trichlor is
removed from che bottom, neutralized with ammonia, washed,
and drled .
This process description is an example of one of several
processes for the manufacture of perchloroethylene and tri-
chlor oethylene from ethylene dichloride. Similar waste con-
stituents (i.e., a range of chlorinated organic hydrocarbons,
including 1,1, 2,2-tetrachloroethane, hexachlorobutadiene,
and hexachlorobenzene), are expected regardless of the
process.
-------
Waste Generation and Management
1. Waste Generation
The column bottoms or heavy ends from the combined pro-
duction of perchloroethylene and ttichlocoethylene can contain
a wide variety of chlorinated hydrocarbons. A typical chemical
composition for the waste stream, often referred as hex waste,
is shown in Table 2 with composition presented in terms of
weight and mole percent.(2»') This information indicates
that the primary constituents of the waste stream are 1,1,2,2-
tetrachloroethane, hexachlorobutadlenef and hexachlorobenzene•
(Table 2 also includes solubilities of the waste stream
constituents.)C2»9i20)
The information presented in Table 2 was employed to cal-
culate the expected quantities of each hazardous component which
Is generated on an annual basis. Personal coramunlcationsCS,6,7)
with selected chemical manufacturers and a review of the
available literature indicate that the quantity of still
bottoms which becomes contaminated and must be disposed can
approach 3-5 percent of production. Assuming that these wastes
are generated at a rate of 32 of production, the estimated
quantity of each component is presented in Table 3. The
estimated annual generation rates are shown to range from
88-4996 metric tons for the individual waste components.
2. Waste Management (5,6,7)
Additional information was collected to assess the current
practices employed for handling these waste streams on an
-------
TABLE 2
TYPICAL COMPOSITION OF HEX-WASTES
Ethylene Bichloride
beta-Tr tchloroe thane
Perchloroethylene
1,1,1 , 2-Tetrachloroethane
1,1, 2 , 2-Tetrachloroethane
Petitachloroethatve
Hexachlorobutadiene
Hexachlorobenzene
Hexachloroethane
TOTAL
SOURCE: References 2,9
* Converted to PPM, Value
SOLUBILITY OF
Ethylene Dichloride
beta-Trichloroethane
Perchloroethylene
HOLE % WEIGHT % SOLUBILITY g/lOOg
distilled water
1.4 0.6 .80
7.2 4.5 .50
5.7 4.5 -01
7.9 6.3 .01
29.1 23.0 .29
2.7 3.3 <.05
27.5 33.8 .0000005
14.9 20.0 <-05
3.6 4.0
100.0 100.0
= g/lOOg it 104
PARTICULAR HEX WASTE CONSTITUENTS
IN PPM (DISTILLED WATER)
8,690
4,500
150 - 200
In
PPM*
8,000
5,000
100
100
2,900
<500
0.005
<500
Very low
L,L,2,2-Tetrachloroethane 2,900
Hexachlorobutadlene 2
Hexachlorobenzene 0.006 - 0-020
Hexachloroethane 50
SOL'RCE: Reference 20
-y-
-------
Table 3
PROJECTED QUANTITIES OF
Hexachlorobutadiene
1,1, 2,2-Tetrachloroethane
Hexachlorobenzene
1,1,1, 2-Tetrachloroe thane
Hexachloroethane
Ethylene Dichloride
Perchloroethylene
beta-Trichloroethane
Fentachloroethane
INDIVIDUAL
MOLE %
27.5
29.1
14.9
7.9
3.6
1.4
5.7
7.2
2.7
TOTAL 100.0
HEX-WASTE COMPONENTS
WEIGHT % ANNUAL PRODUCTION (MT)
33.8 4,996
23.0 3,400
20.0 2,956
6.3 931
4.0 591
0.6 88
4.5 665
4.5 665
3.3 448
100.0 14,780
SOURCE: Estimate based on Table 2 and waste generation
rate of 3% of production. (Waste streams are,
however, subject to variation in terms of both
composition and rate of generation.)
-------
AUG-24-2006 THU 03:55 PM FAX NO. P, n
Individual baais. The available information indicates that
these wastes are either being incinerated or disposed of
through landfill or deep well injection Into limestone for-
IT 'ions. Table
-------
ro
Company
Diamond Shamrock Corporation
Dow Chorales! U.S.A.
j. niMdO *
WASTE GENERATION RATES AND
Location
Deer Park, TX
Free port, TX
Pittaburg, CA
Plaquemtne , IA
•
MANAGEMENT PROCEDURES
Uaflte Production
MT
1.570
2,650
370
1,130
Current Disposal
Practice
LF
I
I
I
i
ro
8
o>
|
o
CO
tn
tn
-o
E.I. DuPoul de Nenours
Company, I tie.
Corpus ChristL, TX
1,530
Ethyl Corporation
PPG Induatrlee
Baton Rouge, LA
Lake Charlea, LA
940
3,620
Dtfl
-n
Stauffer Chemical Cospaay
Louisville, KY
670
LF
Vulcan Material Company
1 - Incineration
DWI - Deep Well Injection
LF - Landf111
SOURCE: References 5, 6, 7
Celsoar, LA.
Wichita, KS
1.420
A80
TOTAL 14,780
i
i
ro
-------
from the waste. The remaining chlorinated organics in the waste
stream are also water soluble to some extent (see Table 2).
These compounds also have demonstrated potential for mobility
through soils and persistence in groundwater.(17) (See
also information summarized at pp. 15-20 below.) Thus, it
appears likely that hazardous constituents may escape from
this waste stream and contaminate groundwater. There clearly
is insufficient Justification to warrant finding that waste
constituents will not migrate Into groundwater if improperly
managed. It should be noted that many facilities generating
these wastes are located in the Texas and Louisiana Gulf
area (see Figure 1) where rainfall precipitation is heavy,
so that the wastes are exposed regularly to solubilizing media.
Another problem with the landfilllng of these wastes is
the potential for these contaminants, particularly hexachloro-
benzene, to volatilize into the surrounding atmosphere. An
actual damage incident confirms this risk. In the Louisiana
area in the early 1970's, hex wastes containing hexachlorobenzene
(HCB), a relatively volatile material, were transported over
a period of time to municipal landfills in uncovered trucks.
High levels of HCB have since been reported in the blood
plasma of individuals along the route of transport(8).
In a sampling of 29 households along the truck route, the
average plasma level of HCB was 3.6 ppb with a high of 23 ppb,
while the average plasma level of HCB in a control group was
0.5 ppb with a high of 1.8 ppb (Farmer et. al., 1976).
-Vt-
-sn-
-------
Additionally, cattle in the surrounding area absorbed UCB in
their tissue and 20,000 animals were quarantined by the State
Department of Agriculture (Lazar 1975)(8).
The deep well injection of these wastes in permeable
limestone formations is also practiced by the industry and
could result in the migration of the hazardous constituents
from the waste and present the same type of problems presented
when these wastes are insecurely landfilled.
An additional reason for listing these wastes as hazardous
are the large volumes generated annually. The estimated
quantities of hex wastes disposed of by each producer range
from 370 to 3,820 metric tons per year (Table 4). This is a
significant quantity of waste disposal by individual generators
in the same area. It is expected that producers will use the
same disposal facility for long periods of time, causing more
exposure over longer time periods to populations in the same
disposal facility areas if wastes are improperly managed.
Also, more exposure would be expected along prevalent migration
and transport routes.
Additional health and environmental fate information on
the listed constituents of concern is presented in the following
section of this document. In general, this information indicates
qualitatively that these constituents are sufficiently mobile and
persistent to reach environmental receptors. In light of the ex-
treme dangers to human health and the environment posed by these
constituents, there Is insufficient indication of environmental
degredation to justify a failure to list this waste as hazardous.
-------
Health and Ecological Effects
1. Hexachlorobenzene (HCB)
Priority Pollutant - HCB is currently listed as a pri-
ority pollutant under Section 307(a) of the Clean Water Act.
Health Effects - Hexachlorobeazene (HCB) has produced
cancers in animal species.(13,14) other animal studies have
shown that HCB crosses the placental barrier to produce toxic
effects and fetal mortality.C15) Hexachlorobenzene Is stored
for long periods in body fat. Chronic exposure to HCB has
been shown to result in damage to the liver and spleen.(16)
It has also been demonstrated that at doses far below those
which are lethal, HCB enhances the body's capability to
toxify, rather than detoxify, other foreign organic compounds
present in the body.fl?)
Virtually all hexachlorobenzene emitted from an uncontrolled
landfill is expected to persist in groundwater or reach
surface waters via groundwater movement.(18) Such behavior
is likely to result in exposure to humans using potable
water supplies within the exposed adjacent areas.
The recommended ambient criterion(*9) level for HCB in
water is 1.25 nanograms per liter. Actual measurements, on the
other hand, of finished drinking water in certain geographic
areas have been measured at levels six times the recommended
criterion designed to protect human health, demonstrating the
mobility and persistence of the material (See Appendix A.)
-------
Ecological Effects - Hexachlorobenzene Is very persistent.^20)
It has been reported to move through the soil into the ground-
water. (21) Movement of hexachlorobenzene within surface
water systems is projected to be widespread." ' Movement to
this degree will likely result in exposure to aquatic life
forms In rivers, ponds, and reservoirs. Similarly, potential
exposure to humans is likely where water supplies are drawn
from surface waters.
Hexachlorobenzene is likely to contaminate accumulated
bottom sediments within surface water systems and bioaccumulate
In fish and other aquatic organisms.(1*)
Regulatory Recognition of Hazard - As indicated in Appendix
A, hexachlorobenzene is a chemical evaluated by CAG as having
substantial evidence of careinogeniclty. Ocean dumping of
hexachlorobenzene Is prohibited. An interim food contamination
tolerance of 0.5 ppm has been established by FDA.
Additional information on the adverse effects of
hexachlorobenzene can be found in Appendix A.
2. Hexachlorobutadiene (HCBD)
Priority Pollutant - Hexachlorobutadiene is a priority
pollutant under Section 307(a) of the CWA.
Health Effects - Hexachlorobutadiene (HCBD) has been found
to be carcinogenic In animals.(22) Upon chronic exposure to
animals by the DOW Chemical Company and others, the kidney
appears to be the organ most sensitive to HCBD . (-^»23 , 24 , 25)
The recommended human health criterion level for this compound
-------
in waLc-r, is .77 ppb. (See 44 Fed. Reg. 15926, 15954 (March
15, 1979).)
Virtually all HCBD emitted from the waste management
scenario described previously Is expected to persist in
groundwater or reach surface waters via groun^dwa ter movement .(1
Such behavior is likely to result in exposure to humans
using such groundwater sources as drinking water supplies
within adjacent areas.
Ecological Effects - Movement of HCBD within surface water
systems is projected to be widespread.^**)
HCBD Is likely to contaminate accumulated bottom sediments
within surface water systems and Is likely to bioaccumulate In
fish and other aquatic organisms.(18)
The USEPA (1979) has estimated that the BCF is at 870 for
the edible portion of fish and shellfish consumed by Americans.
Hexachlorobutadiene Is persistent In the environment.(20)
It has been reported to move through soil into groundwater
from Hooker Chemical's Hyde Park waste disposal site,* and
thus is mobile enough to migrate from Improperly managed
landfills into the environment.
Industrial Recognition of Hazard - Hexachlorobutadiene is
considered to have a high toxic hazard rating via both oral
and inhalation routes (Sax, Dangerous Properties of Industrial
Materials) .
Additional information on the adverse effects of hexa-
*OSW Hazardous Waste Division, Hazardous Waste Incidents, Un-
published, Open File, 1978.
-VI-
-------
chlorobutadiene can be found in Appendix A.
3. Hexachloroethane
Priority Pollutant - Hexachloroethane is a priority
po.lutant under Section 307(a) of the CWA.
Health Effects - Hexachloroethane has been reported to be
carcinogenic to animals, meaning that humans may be similarly
affected . (27) Humans exposed to vapors at low concentrations
for short periods have had liver, kidney and heart degeneration
and central nervous system damage.(28)
Virtually all hexachloroethane emitted from a landfill
is expected to persist in groundwater or reach surface waters
via groundwater movement.C-") Such behavior is likely to
result in exposure to humans using such groundwater sources as
drinking water supplies within adjacent areas.
Ecological Effects - Movement of hexachloroethane within
surface water systems is projected to be widespread.(*")
Movement to this degree will likely result in exposure to
aquatic life forms in rivers, ponds, and reserv,oirs.
Hexachloroethane is likely to be released to the atmosphere
from surface water systems. (18)
Regulatory Recognition of Hazard - OSHA has set a TWA for
hexachloroethane at 1 ppm (skin). Measurements of this
compound in finished drinking water have shown that hexachloro-
ethane occurs at least at the recommended water criterion
level,(28) confirming that this compound may persist in
-------
dangerous concentrations.
Additional information on the adverse effects of hexa-
chloroethane can be found in Appendix A.
4. Tetrachloroethanes
Priority Pollutant - Both 1,1,1,2-tetrachloroethane and
1,1,2,2-tetrachloroethane are designated as priority pollutants
under Section 307(a) of the CWA-
Health Effects - 1,1,2 , 2-Tetrachloroethane has been shown
to produce liver cancer in laboratory mice.(29) ^n addition,
passage of 1,1,1,2-tetrachloroethane across the placental
barrier has been reported. (3°) In an Ames Salmonella bioassay,
1,1,2,2-tetrachloroethane was shown to be mutagenic.'31)
Occupational exposure of workers to 1,1,2,2-tetrachloroethane
produced neurological damage, liver and kidney ailments, lung
edema and fatty degeneration of the heart muscle.(32)
Ecological Effects - Freshwater invertabrates are sensitive
to 1,1, 2 , 2-tetrachloroethane with a lethal concentration of 7-
8 mg/1 being reported.(33) USSPA estimates the BC? to be lfl.(33)
Regulations - OSHA has set the TWA at 5 ppm (skin) for
1,1,2,2-tetrachloroethane.
Additional information on the adverse effects of tetra-
chloroethanes can be found in Appendix A.
6 . Ethylene Dichloride
Priority Pollutants - Ethylene dichloride (1,2-dlchloroethane)
is designated as a priority pollutant under Section 307(a) of
-------
the CWA.
Health Effects - Ethylene dlchloride has been shown to
cause cancer In laboratory animals.(-*M jn addition, this
compound and several of its metabolites are highly mutagenic.(35)
Ethylene dichloride crosses the placental barrier and is
erabryotoxic and teratogenic . '^6 » 37 , 38 , 39 , 40) Ic nas aiso
been shown to concentrate in milk.(^l) Exposure to this
compound can cause a variety of adverse health effects
including damage to the liver, kidnevs and other organs. It
can also cause internal hemorrhaging and bloo'd clots. (*2)
Regulatory Recognition of Hazard - OSHA has set the
TWA at 50 ppm. The Office of Air, Pollution and Noise has
completed a preregulatory assessment for ethylene dichloride
under Sections 111 and 112 of the Clean Air Act. Preregulatory
assessments are also being conducted by EPA's Office of
Water and Waste Management under the Safe Drinking Water Act
and by the Office of Toxic Substances under the Toxic Sub-
stances Control Act.
Industrial Recognition of Hazard - Sax in Dangerous
Properties of Industrial Materials rates ethylene dichloride
as highly toxic upon ingestion and inhalation.
Additional information on the adverse effects of ethylene
dichloride can be found in Appendix A.
-------
Re ferences
1. Chemical Profiles. Schnell Publishing Company, Inc.,
New York.. 19? 9.
2. U.S. EPA. Emission control options for the synthetic
organic chemicals manufacturing industy: carbon tetra-
chloride and perchloroethylene. U.S. EPA, Office of Air
Quality Planning and Standards. Contract Number 68-02-2257
March, 1979.
3. Lowenheira, F. A., and M.K. Moran. Faith, Keyes, and
Clark's industrial chemicals, 4th Ed. Wiley Inter-
science, New York. 1975.
4. U.S. EPA. Assessment of Industrial hazardous waste
practice: organic chemicals, pesticides, and explosives-
EPA No. SW-llBc, NTIS PB No. 251 307. January, 1976.
5. Personal communication with Dr. H. Farber, Dow Chemical
Company, Midland, Michigan, February 1980.
6. Personal communication with Mr. Perry Norling, DuPont Co.,
Wilmington, Delaware, February, 1980.
7. Personal communication with Dr. Frederick C. Dehn, PPG
Industries, Pittsburgh, Pennsylvania, February, 1980.
8. U.S. EPA. Open files. Hazardous Site Control Branch,
WII-548. U.S. EPA, 401 M St., S.W., Washington, D.C. 20460-.
Contact Hugh Kaufman. (202) 245-3051.
9. U-S. EPA. Emission control options for the synthetic
organic chemical manufacturing industry: 1,1,1-trichloro-
ethane product report. U.S. EPA, Office of Air Quality
planning and Standards, Contract Number 68-02-2577.
July, 1979.
10. Edwards, J.B. Combustion formation and emission of
traces species. Ann Arbor Science. 1977.
11. NIOSK. Criteria for a recommended standard: Occupational
exposure to phosgene. HEW, PHS, CDC, MIOSH. NTIS PB
No. 267 514. 1976.
12. Cabral, J. R. P., et al. Carcinogenic activity of hexa-
c lilor obe n zene In hamsters. Tox . Appl. Pharmacol. 41:155
1977.
-------
13. Cabral, J.R.P., et al. Carcinogenesis study in mice
with hexachlorobenzene . Toxicol. Appl. Pharmacol.
45:323. 1978.
14. Grant, D.L., et al. Effect of hexachlorobenzene on
reproduction in the rat. Arch. Environ. Contam. Toxicol.
5:207. 1977.
15. Grant, D.L., et al. Effect of hexachlorobenzene on
reproduction in the rat. Arch. Environ. Contam. Toxicol.
5:207. 1977.
16. Koss, G., et al. 1978. Studies on the toxicology of
hexachlorobenzene. III. Observations in a long-term
experiment. Arch. Toxicol. 40:285. 1978.
17. Carlson, G.P. Induction of cytochrome P-450 by halogenated
benzenes. Biochem. Pharmacol. 27:361. 1978.
18. U.S. EPA. Technical support document for aquatic fate
and transport estimates for hazardous chemical exposure
assessments. U.S. EPA. Environmental Research Lab.
Athens, Georgia. 1980.
19. U.S. EPA. Chlorinated benzenes: Ambient water quality
criteria. NTIS PB No. 297 919. 1979.
20. U.S. EPA. Water-related environmental fate.of 129
priority pollutants. EPA No. 440/4-79-029b. 1979.
21. Zoeteman, B.C.J. Persistent organic pollutants in
river water and ground water in the Netherlands.
In Proceedings; Third International Symposium on Aquatic
Pollutants. Jekyll Island, Georgia. October 15-17, 1979.
22. Kociba, R.J. Results of a two-year chronic toxicity study
with hexachlorobutadiene in rats. Amer. Ind. Hyg. Assoc.
38:589. 1977.
23. Kociba R.J., et. al. Toxicologic study of female rats
administered hexachlorobutadiene or hexachlorobenzene
for 30 days. DOW Chemical Company. 1971.
24. Schwetz, et. al. Results of a reproduction study in rats
fed diets containing hexachlorobutadiene. Toxicol. Appl.
Pharmacol. 42:387. 1977.
25. Schroit, et. al. Kidney lesions under experimental hexa-
chlor obut adiene poisoning. Aktual, Vpo. Gig. Eptdemiol.
73. CA:81:73128F (translation). 1972.
26. Not used in text.
-------
27. National Cancer Institute. Bioassay or nexacruoroe tnane ror
possible carcinogenicity. No. 78-1318. NTIS PB No. 282 6C8/AS.
1978.
28. U.S. EPA. Chlorinated ethanes: Ambient water quality criteria.
NTIS PB No. 297 920. 1979.
29. National Cancer Institute. Bioassay of 1,1,2,2-tetrachloro-
ethane for possible carcinogenicity. U.S. Department of
Health, Education and Welfare, Public Health Service,
National Institutes of Health, National Cancer Institute,
DHEW Publication No. (NIH) 78-827. NTIS PB No. 277 453/AS.
1978.
30. Truhaut, R., N.P. Lich., H.T. Outertre-Catella, G. Molas,
and V.N. Huyen. Toxicological study of 1,1,1,2-tetrachloro-
ethane. Archives des Maladies Professionnelles, de Hedeclne
du Travail et de Securite 35 ( 6 ) : 593608 . 1974.
31. Breta, H. , et al. The rautagenicity and DNA-modifying
effect of haloalkanes. Cancer Res. 34:2576. 1974.
32. National Institute for Occupational Safety and Health.
Criteria for a recommended standard...occupational
exposure to 1,1,2,2-tetrachloroethane. U.S. Department
of Public Health Service, Center for Disease Control,
National Institute for Occupational Safety and Health,
DHEW (NIOSH) Publication No. 77-121. NTIS PB No. 273 602.
December, 1976.
33. U.S. EPA. Chlorinated ethanes: Ambient water quality
criteria. NTIS PB No. 297 920. 1979.
34. National Cancer Institute. Bioasay of 1,2-dichloroethane
for possible carcinogenicity• U.S. Department of Health,
Education and Welfare, Public Health Service, National
Institutes of Health, National Cancer Institute, Carclno-
genesis Testing Program, DHEW Publication No. (NIH) 78-1305.
NTIS PB No. 285 968. January, 1978.
35a. McCann, J., E. Choi, E. Yamasaki, and B. Ames. Detection
of carcinogens as mutagenic in the Salmone1la/microsome
»:est: Assay of 300 chemicals. Proc. Natl. Acad. Scl.
USA 72(2):5135-5139. 1975.
35b. McCann, J., V. Simmon, D. Stre 1 twieser, and B. Ames.
Mutageniclty of chloroacetaldehyde, a possible metabolic
product of 1,2-dlchloroethane (ethylene dichloride),
chloroethanol (ethylene chlorohydrin), vinyl chloride,
and eyelophosphamide. Proc. Nat. Acad. Sci. 72(8):
3190-3193. 1975.
-------
36. Vozovay.?, , M. Changes in the estrous cycle of
chronically exposed to the combined action of
and dichloroethane vapors. Akush. Genekol.
47(12):65-66. 1971.
38.
39.
40
41,
42,
white rats
gasoline
(Kiev)
37. Vozovaya, M. Development of offspring of two generations
obtained from females subjected to the action of dichloro-
ethane. Gig. Sanit. 7:25-28. 1974.
Vozovaya, M. The effect of low concentrations of gasoline,
dichloroethane and their combination on the generative
function of animals and on the development of progeny.
Gig. Tr. Prof. Zabol. 7:20-23. 1975.
Vozovaya, M. The effect
gasoline, dichloroethane
reproductive function of
100-102. 1976.
of low concentration6 of
and their combination on
animals. Gig. Sanit. 6:
the
Vozovaya, M. The effect of dichloroethane on the
sexual cycle and embryogenesis of experimental animals.
Akusk. Ginekol. (Moscow) 2:57-59. 1977.
Urosova, T.P. (About a possibility of dichloroethane
absorption into milk of nursing women when contacted
under industrial conditions.) Gig. Sanit. 18(3 ) :36-37.
1953 (Rus).
Parker, J.C., et al. Chloroethanes: A review of toxlcity.
Amer . Ind. Hyg. Assoc. J. 40.-A46-60. March, 1979.
43. Not used in text.
-------
Pesticides
-------
ORD-F
LISTING BACKGROUND DOCUMENT
MSMA AND CACODYLIC ACID PRODUCTION
By-producc Salts Generated in the Production of MSMA and Cacodylic Acid. (T)
I. Summary of Basis for Listing
The hazardous waste generated in the production of ItSMA (monosodlum
raethanearsonate) and cacodylic acid Is an arsenic-contaminated salt by-product.
The Administrator has determined that the solid waste from MSMA and cacodylic
acid production nay pose a substantial present or potential hazard to hunan
health or tlie environment when improperly transported, treated, stored,
disposed of or otherwise managed, and therefore should be subject to appro-
priate management requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1. These wastes contain very substantial concentrations of
arsenic, which is an extremely toxic heavy metal* Arsenic
has also been shown to be carcinogenic, mutagenic, and
tetatoge-nic. The waste generated at one plant was con-
taminated with arsenic at a concentration of 5300 mg/1.
2. Large quantities of arsenic-contaminated wastes are generated
annually in the production of MSMA and cacodylic acid. Further-
more, large quantities are often disposed of at individual sites.
Approximately 190,000,000 Ibs of arsenic-contaminated salt
have been stored in an open, uncovered pile in Wisconsin.
3. In mildly reducing environments, prevailing in most shallow
groundwaters, arsenic is most likely to be present as the
very toxic arsenice, to be relatively mobile, and to persist
virtually indefinitely.
4. Several Incidents of environmental contamination have occurred
6ue to the leaching of ttSflA/cacodylic acid wastes disposed of
in landfills, resulting in adverse human health effects.
-------
IT. Sources of the Haste
A. Profile of the Industry - MSMA is used primarily as a
herbicide, and is also an intermediate in the production of cacodylic acid.
MStlA is produced in the U.S. by Dianond Shamrock (Green Bayou, Texas);
Crystal Chemical (Houston, Texas); and Vineland Chemical (Vineland, New
Jersey). Estimated production of MSMA in 1974 was 35 million pounds.(I)
Both Crystal Chemical and Vineland Chemical also manufacture cacodylic
acid which results in a similar arsenic-contaminated salt by-product.
Combination of the salt by-products from both the manufacture of MSMA and
cacodylic acid probably occurs at most manufacturing sites, a supposition
could not be confirmed for all sites.*
B. Manufacturing Process and Waste Composition - The manufacture
of MSMA involves the reaction of arsenic trioxide and liquid caustic
soda to form sodium arsenite. This solution of arsenite is then reacted
with methyl chloride to form a disodium raethylarsenate (DSMA) slurry.
This slurry is concentrated, cooled and centrifuged with the DSMA cake
going to acidifying tanks and the liquid going to storage for reuse.
The DSMA cake is then acidified to form monosodium raethylarsenate (MSMA).
This slurry is concentrated, cooled and centrifuged, with the monosodium
methylarsenate in the liquid phase being transferred to a formulating
tank, and the resulting salt cake being collected for disposal. The
final '1VIA product is formulated to various strengths and is shipped in
either bulk fom or containers. Arsenic is persent in the salt by-product
Chemical eviHentlv conbines its two waste streams, since its
scate dtspo^.il permit provides for disposal of the combined waste
st r^ans.
-------
in substantial concentrations, since It is a prevalent feedstock con-
stituent. The production scheme for MS'IA is depicted in Figure 1.
The manufacture of cacodylic acid involves the reduction of MSMA
using sulfur dioxide. This reduced MSMA Is neutralized with caustic soda
and then reacted with methyl chloride to form cacodylic acid. The cacodylic
acid is concentrated, cooled and centrifuged. The cacodylic acid in the
liquid phase goes to a formulating tank and the salt cake is collected for
disposal. Again, it is reasonable to expect that arsenic is heavily
concentrated in the waste because it is a dominant feedstock constituent.
The presence of arsenic in the waste in high concentrations is
confirmed by an analysis of MSHA salt cake waste generated by Crystal
Chemical and provided to the Texas Departnent of Water Resources. This
analysis indicates that the waste contains arsenic concentrations of 6,300
mg/1 (6). The National Interim Primary Drinking Water Standard for
arsenic, a standard regulatory benchmark for measuring arsenic contamination
in drinking water, is .05 mg/1, demonstrating the significant concentration
level of arsenic in the waste strean.*
The Agency does not presently possess waste concentration data
for cacodylic acid waste, but arsenic concentrations are similarly believed
to be high, in light of arsenic presence as an essential feedstock material.
Further, it is believed that the MSMA and cacodylic acid wastes are often
conbined for disposal (see page 2), again suggesting that the waste streams
will contain substantial concentrations of arsenic.
*With regard to the comparison of waste concentrations and the Drinking
Vatiir Standards, wlilch assune environmental release, although not all
the arsenic contained in the uviste is likelv to be released fron the
-.viste Into the environncnt, .irscnic in these wastes may well be released
in c.inceritrrft ions well above .15 ng/1. (see p. 2 following).
-------
As.O,-
N.iOI-l-
H,O-
cn,cv
n,so..
DUST
COLLECTOR
VENT
SODIUM
APSENITE
UNIT
25%
NfljAsO,
STORAGE
METIIYLARSONIC
AGIO UNIT
CRUDE
DSMA
Y
MGMA
REACTOR
PURIFICATION
EVAPORATOR
STRIPPER
\
CM.OH
finCOVERED
II.O-
U.AOUEOU
~ -
EOUS
"t
• DSMA SALES
CENTRIFUGE
50% MSMA
BY-PnODUCT SALTS
WASHER
LIQUID
I
-*- Na,SO.
NaCI
fJ)
TO
APPROVED
LANDFILL
Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR MSMA.
-------
C. Waste Generation and Management Practices and Quantites of Wastes
Managed
There are a number of waste management practices in current
industry use, which are discussed below. In addition to these described
practices, however, there is a history of waste mismanagement resulting
in environmental harra. Descriptions of damage incidents resulting from
mismanagement of these wastes are set forth at pp. 6-7 following.
Vlneland Chemical has disposed of its solid waste in several
landfills in Pennsylvania. In May, 1979, Vineland received a permit
from the State of Pennsylvania to dispose of 3,000 tons of arsenic con-
taminated waste.(*)
Diamond Shamrock has a permit from the Texas Department of Water
Resources to dispose a monthly average of 481 tons of solid waste from
the production of various compounds.
* (2)
Crystal Chemical has a state permit for deepwell injection of
MSMA-cacodylic acid solid wastes which are slurried with liquid wastes
and rainwater and are injected 3500 to 4500 feet below the surface in
the Frio Formation (Attachment I). Prior to obtaining this permit, the
company utilized unlined earthen holding ponds for waste management in
combination with an off-site disposal program in commercial facilities.
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
The Agency has a number of reasons for listing these wastes
*The underlined daa are those obtained from proprietary reports and data
files
-------
as hazardous. First, tnese waste streams have been implicated in a number
of actual damage incidents, demonstrating the potential for substantial
hazard if these wastes are improperly managed.
Second, the concentrations of arsenic contained in these wastes
are very significant, so that if even a small percentage of the arsenic
escapes from the waste, it will enter the environment in high enough
concentrations to cause substantial harm. Further, arsenic is likely to
be mobile, and will be highly persistent upon escaping from the waste,
thus increasing the likelihood of it reaching receptors in concentrations
sufficient to cause a substantial hazard. Certainly, there is insufficient
evidence to indicate that arsenic will not migrate from the waste, and
in light of the known dangers of this contaminant and its high concentra-
tions in the waste, such assurance is necessary to justify not listing
these wastes.
Finally, these wastes contain large quantities of arsenic
(as well as high concentrations), and wastes containing large quantities
of arsenic are often disposed of at individual sites, thus Increasing
Che likelihood of a major damage Incident.
1. Incidents Involving Mismanagement of These Wastes.
A history of mismanagement of solid waste from the manufacture
of MSMA and cacodylic acid has been documented. It has been reported
that Ansul Company, a former manufacturer of MSMA and other arsenical
compounds, has stored 95,000 tons of arsenic-contaminated salt on
company property in Marinette, Wisconsin. Until recently, this stockpile
-------
was left open to the weather with no containment of runoff^ The State
of Wisconsin Ue[Jartr.ent of Itatucal Itesources has ordered AnsuL to cover
the pile as an interim measure and to truck the waste to & landfill in
Illinois.<28)
A report from the files of the Texas Department of Water
Resources (Attachment I) Indicates that a landfill containing these waste
streams was subject to overflow conditions during high rainfall periods,
causing waste washout, soil contamination, and potential leaching hazard.
The report indicates that elevated levels of arsenic were detected to
"depths of several feet" in soil surrounding the landfill. This could
result in the leaching of arsenic into groundwater and potable water
supplies.
2. Hazards "Based on Arsenic Concentrations in These Wastes
and Likely Environmental Fate of Released Wastes
As noted above, arsenic is present in these waste streams In
very high concentrations. Thus, improper management of these wastes, for
example in unlined landfills, could easily result in a substantial hazard
to human health and the environment, in light of the health hazards
posed by arsenic (see pp. 1-11 following).
Two likely exposure pathways for the leaching of arsenic are
into grounduater and surface water. The potential for this to occur from
a waste/soil «iatrix depends on the concentration of arsenic in the soil,
soil tyae (clay, sand, loam, etc.), the soil pH, as well as the concen-
trations of cadnium, magnesium, iron, and aluminum in the soil. Arsenic
is not easily leached in fine-textured soils (clay materials] but may
he lejched downward in sandy or loan
-------
Once arsenic escapes from these wastes and migrates to groundwater,
it can be expected to be both mobile and persistent. Thus, in mildly reducing
'ivironments present in most shallow groundwaters, arsenic is most likely to
be present in the form of arsenite, a mobile and highly toxic compound.(^)
As an elemental heavy metal, arsenic will persist in some form virtually
indefinitely.
The propensity for arsenic to migrate through soil and groundwater
and to persist is illustrated by an arsenic poisoning incident occurring in
Minnesota in 1972.^°' In this case, eleven persons became seriously ill
by drinking water from a well 31 feet deep. Water from this well was found
to contain up to 21,000 mg/1 of arsenic. The source of the arsenic was
established to be some 50 pounds of arsenic-containing grasshopper bait
buried in a seven foot trench near the well about 40 years previously.
Significant pollution of groundwater by arsenic moving from the
La Bounty landfill in Iowa has also been noted recently'^', and the potential
for movement of this element through the soil profile has been illustrated by
its appearance in increased concentration in groundwater at a land treatment
site for municipal wastewater. '^)
A second exposure pathway of concern is surface water. These
wastes, unless properly managed to prevent washout or runoff, could easily
contaminate surface waters. Indeed, two of the incidents described above
illustrate potential surface water contamination as a result of improper
management of these wastes (Attachments I and II).
3. Quantities of the Waste Generated
MS'IA and cacodylic acid by-product salts are generated in large
-------
concentrations, and also are disposed of in large quantites at individual
sites. The above described damage incident from Marinette, Wise., indicates
that 95,000 tons of these wastes were stored (improperly) at a single site.
Similarly, Vineyard disposes of 3,000 tons of these wastes each year.(4)
Obviously, such large quantities of this hazardous constituent has the pro-
pensity for large-scale environmental harm—for instance, there is a greater
chance of exposure, and that environmental leaching will continue for longer
periods. The large quantities of waste generated is thus a further reason
for listing these wastes.
B. Health and Ecological Effects
1. Arsenic
Health Effects - Arsenic is extremely toxic in animals and
humans(ll). Death in humans has occurred following ingestion of very
small amounts (5mg/Kg) of this chemical(12). Several epidemiological
studies have associated cancers with occupational exposure to arsenic^3-15)
including those of the lung, lymphatics and blood^, 17). Certain
cases involving a high prevalence of skin cancer have been associated
with arsenic in drinking water(l8)f while liver cancer has developed in
several cases following ingestion of arsenic^1^). Results from the
administration of arsenic to animals in drinking water or by injection
supports the carcinogenic potential of arsenic.
Occupational exposure to arsenic has resulted in chromosomal
damage(20)f while several different arsenic compounds have demonstrated
positive mutagenic effects in laboratory studies'^ l~-3).
The teratogenicity of arsenic and arsenic conpounds is
well established (--4~26) anff includes defects of the skull, brain, kidneys,
-X-
-------
gonads, eyes, ribs and genito-urinarv system.
The effects of chronic arsenic exposure Include skin diseases
progressing to gangrene, liver damage, neurological disturbances"''
and cardiovascular disease*^).
Arsenic is designated as a priority pollutant under Section
307(a) of the OTA. Additional information and specific references on the
adverse effects of arsenic can be found in Appendix A.
Ecological Effects - The data base for the toxicity of
arsenic to aquatic organisms is more complete for freshwater organisms,
where concentrations as low as 128 ng/1 have been acutely toxic to freshwater
fish. A single marine species produced an acute value in excess of 8,000
ng'l. Based on one chronic life cycle test using flaphnia nagna, a chronic
value for arsenic was estimated at 853 ng/1.(28)
Bioaccunulation factors can reach 11,000 in oysters, 8,600
in lobsters, and 23,000 in mussels.(2R)
Regulations - OSHA has set a standard air TWA of 500 mg/'O
for arsenic. DOT requires a "poison" warning label.
The Office of Toxic Substances under FIFRA has issued a
pre-RPAR. The Carcinogen Assessment Group has identified arsenic as a com-
pound which exhibits substantial evidence of carcinogeniclty. The Office of
Drinking Water has regulated arsenic under the Safe Drinking Water Act due to
its toxicity and the Office of Air Quality Planning and Standards has begun a
oraregulatory assessment of arsenic based on its suspected carcinogenic
effects. The Office of Water Planning and Standards under Section 304(a)
of the Clean ''ater Act has hep,un development of a regulation based on
-------
health effects other than on carcinogeniclty and environmental effects.
Finally, the Office of Toxic Substances has completed Phase 1 assessment
of arsenic under TSCA.
In addition, the states of Pennsylvania, Texas, and Wisconsin
obviously deem this waste to require careful management to prevent
substantial environmental harm (see attachment I and II).
Industrial Recognition of Hazard - Arsenic Is rated as
highly toxic through intra-muscular and subcutaneous routes In Sax,
Dangerous Properties of Industrial Materials.(29) Arsenic is also rated
as highly toxic through ingestion, Inhalation, and percutaneous routes
in Patty, Industrial Hygiene and Toxicology.
-------
V. References
1* U.S. EPA. Kelso, G., R. Wilkinson, J. Malon, Jr., and T. Ferguson.
Development of information on pesticides manufacturing for source
assessment. EPA No. 600/2-78-100. Environmental Protection Agency,
Research Triangle Park, NC. NTIS PB No. 283 051/1BE. 1978.
2. Not used in text.
3. Sittig, M. Pesticides process encyclopedia. Noyes Data Corporation,
Park Ridge, New Jersey. 1977.
4. Personal Communication, Kirti Shah, Pennsylvania Department of
Environmental Resources (717-787-7381), 1/31/80. See Appendix D.
5. Personal Communication, David Barker, Texas Department of Water
Resources. (512-475-5633), 12/18/79. See Appendix D.
6. Personal communication, David Jeffrey, Texas Department of Water
Resources (512-475-7097), 12/31/79. See Appendix D.
7. NIOSH. Registry of toxic effects of chemical substances. U.S.
Government Printing Office. Washington, D.C. 1978.
8. U.S. EPA. The Report to Congress: Waste disposal practices and
their effect on groundwater. U.S. EPA, Office of Water Supply,
Office of Solid Waste Management Programs. NTIS PB No. 265 081.
January 1977.
9. Koerner, E. L., and D. A. Haws. Long-term effects of land
application of domestic wastewater. EPA No. 600/2-79-072.
U.S. EPA, Washington, D.C. NTIS PB No. 297 501/9BE. 1979.
10. Hounslow, A. W. Ground-water geochemistry: arsenic in land-
fills. Ground Water 18:331. July-August 1980.
11. Gleason, M. N., et al. Clinical toxicology of commercial products.
Acute poisoning, 3rd ed., p. 76. The Williams and Wilkins Company,
Baltimore. 1969.
12. Lee, A. M. and Fraumeni, J. F., Jr. Arsenic and respiratory cancer
in man: An occupational study. Jour. Natl. Cancer Inst. 42:1045.
1969.
13. Pinto, S. S. and B.M. Bennett. Effect of arsenic trloxide exposure
on mortality. Arch. Envlronmen. Health 7:5883. 1963.
14. Kwratune, M., et al. Occupational lung cancer among copper smelters.
Int. Jour. Cancer 13:552. 1974.
-------
15. Ohn, M. G., et al. Respiratory cancer and occupational exposure to
arsenicals. Arch. Environ. Health 29:250. 1974.
16. Baetjer, A. M., et al. Cancer and occupational exposure to inorganic
arsenic. 18th Int. Cong. Occup. Health. Brighton, England, p. 393.
In: Abstracts, September 14-19. 1975.
17. Tseng, W. P., et al. Prevalence of skin cancer in an endemic area
of chronic arsenicism In Taiwan. Jour. Natl. Cancer Inst. 40:453.
1968.
18. ECAO Hazard Profile: Arsenic. SRC, Syracuse, NY. 1980.
19. Nordenson, I., et al. Occupational and environmental risks in and
around a smelter in northern Sweden. II. Chromosomal aberrations
in workers exposed to arsenic. Hereditas 88:47. 1978.
20. Petres, J., et al. Zum Einfluss a norgan ischen Arsens auf die
DNS-Synthese menschlicher Lymphocyten In vitro. Arch. Derm forsch.
242:343. 1972.
21. Paton, G. R. and A.C. Allison. Chromosome damage in human cell
cultures induced by metal salts. Mutat. Res. 16:332. 1972.
22. Moutshcen, J. and N. Degraeve. Influence of thiol-inhtbitlng
substances on the effects of ethyl methyl sulphonate on chromosomes.
Expecientta 21:200. 1965.
23. Hood, R. D. and S.L. Bishop. Teratogenic effects of sodium
arsenate in mice. Arch. Environ. Health 24:62. 1972.
24. Beandoin, A. R. Teratogenicity of sodium arsenate in rats.
Teratology 10:153. 1974.
25. Ferm, V. H., et al. The teratogenic profile of sodium arsenate in
the golden haaster. Arch. Environ. Health 22:557. 1971.
26. U.S. EPA. Arsenic: Ambient water quality criteria. NTIS PB No.
292 420/7BE. 1979.
27. WHO. Environmental health criteria: arsenic. World Health
Organization. Geneva. 1979.
28. Sperling, L. Wisconsin's Hazardous Waste Line, Wisconsin Natural
Resources. 4 (1): 14-16. 1980. '
29. Sax, N. Irving. Dangerous properties of Industrial materials.
4th ed. Van Nostrand Reinhold, New York. 1975.
30. National Academy of Science, National Research Council. Arsenic.
PB No. 2604. 1977.
-------
ATTACHMENT I
Plant located in West Harris County. Crystal manufactures arsenic-
based pesticide chemicals for sale. The proposed well will be used to
dispose of water which has been contaminated as a result of these
manufacturing processes. To the present time, the Company has utilized
only unlined earthen holding ponds for wastewater management, in combination
with a program of off-site disposal in commercial waste facilities.
Efforts to minimize the volume of contaminated waste water in the Company's
ponds by evaporation, are thwarted by the heavy rainfalls which occur in
the Houston area. Site inspection after such rainfall typically reveals
that water, tinged an orange-brown color, covers much of the site, and in
some instances, slowly drains off-site. Analyses of soil samples from
the plant indicate elevated levels of arsenic compounds in the soil to
depths of several feet. To prevent further soil and water pollution, the
Company has undertaken the waste disposal well project as the most
environmentally safe method of plant waste disposal. Along with the
implementation of the proposed injection operations, it will be necessary
to correct the existing pollution by closing the ponds, and diking and
paving the plant area. Effective control of rainfall runoff will prevent
off-site discharge of arsenic-contaminated waters. Evaluation of the
disposal well project plans follow.
CHARACTERISTICS AND COMPOSITION OF THE WASTE WATER
Manufacturing Process - Listed below is a summary of operations at Crystal's
RogerJale Roan facility.
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MSMA - Arsenic trioxide and liquid caustic soda are reacted to
forn sodium arsenite. This solution of sodium arsenite is then reacted
with methyl chloride to form a DSMA (disodium methylarsenate) slurry.
This slurry Is concentrated, cooled and centrifuged with the DSMA cake
going to acidizing tanks and the liquid going to storage for reuse. The
DSMA cake is acidized to form monosodium methylarsenate. This slurry is
concentrated, cooled and centrifuged with the monosodiura methylarsenate
in the liquid phase being transferred to a formulating tank, and the
resulting salt cake being collected for disposal. The final MSMA product
Is formulated to various strengths and is shipped in either bulk form or
containers.
Dinitro General - Dinoseb (2-Sec-Butyl-4, 6-Dinitrophenol) is
dissolved in a solvent, an emulsifier is added, and the product is shipped
in either bulk or containers.
Dinitro 3 - Dinoseb is reacted with triethanolamine to form the
triethanolamine salt of Dinoseb. A surfactant is added and the material
is shipped in bulk or containers.
Naptalam - Alphanaphthyl amine and phthalic anhydride are reacted
in a closed system to form sodium naphthylphthalamate. This material is
one of the ingredients of a product produced under the trade name NAPTRO.
Naptro - Naptalam, caustic soda, and Dinoseb are mixed to form
NAPTRO. This material is solid in 5 gallon and in 30 gallon containers.
-------
Dimethoate 267 - Technical dimethoate Is dissolved in a solvent
and emulsifiers are added. The product is then either drummed at the
plant or shipped in bulk form to a packager.
Cacodylic Acid - HSMA is reduced using sulfur dioxide. This
reduced MSMA is neutralized with caustic soda and then reacted with methyl
chloride to form cacodylic acid. The cacodyllc acid is concentrated,
cooled and centrifuged with the cacodylic acid in the liquid phase going
to a formulating tank and the salt cake collected for disposal.
Chemical Analysis - Samples
water holding
PH
Total Residue
Alkalinity, as
Hydroxyl
Bicarbonate
Carbonate
Chlor ide
Nitrate N
Sulfate
Total Organic
Metals
Arsenic
Barium
Boron
Cadmium
Calcium
Chromium
from the Company's existing waste
ponds have yielded the following analysis.
MSMA
Salt Cake
7.9
(105 °C) 30%
CaC03
0 tag/1
1,800
3,920
78,000
0.60
103,000
Carbon 2,400
6,300
<0.5
<0.02
4.6
116
26
Wastewater
(Pond)
9.8
7.7%
3,000 mg/1
0
8,000
20,800
0.26
11,600
2,000
6,900
<0.5
0.08
0.13
85
5
Wastewater
(Sump)
9.4
5,100 mg/1
0 mg/1
220
1,080
850
0.16
564
180
1,500
<0.5
0.08
<0.01
24
0.6
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Treatability Studies - Various alternative methods of disposal and treat-
ment of the waste streams have been investigated. While some of these
various methods could be marginally successful in eliminating the waste,
each produces contaminated sludge or residue. Therefore, deep well
injection is judged to be the most practical and economic solution for
disposal of this waste stream.
The following methods were investigated as an alternative to
injection:
1. Solar evaporation - The efficiency of solar evaporation is
related to temperature, humidity and rainfall rate, among other factors.
The annual rainfall rate at the plant site is in excess of 50" per year
while the evaporation rate is approximately 43" per year. Evaporation
would also produce a concentrated, contaminated precipitate which would
pose additional disposal problems.
2. Stream stripping - Little, if any, of the contaminants would
be removed and an extremely high level of energy consumption would be
required.
3. Spray evaporation - Spray evaporation, while more effective
than solar ponds, will also be inefficient because of the humid climatic
conditions. Spray evaporation has a potential for air pollution and will
produce a contaminated sludge. Large surface areas would be required for
this type of system and these areas are not available at the plant site.
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ATTACHMENT II
PHONE LOG
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MEMORANDUM OF ORAL ADVICE
Bureau of Solid Waste Management Date; January 31, 1980
Division of Hazardous Waste Management
State of Pennsylvania
Department of Environmental Resources
Name; Kurti Shah, 717-787-73&1
Re; Vineland Chemical Solid Waste Telephone |XX| Conference \1
(MSMA & Cacodyltc Acid)
Facts and Query:
Quantity, Composition and Present and Past Disposal Practices for
Disposal of MSMA and Cacodylic Acid Waste in Pennsylvania.
Is this information Public Record? Yes.
Answer; Disposed of in past at Grove Sanitary Landfill (used a process
developed by Stobatrol Corporation to encapsulate waste. Monitoring
wells in area show high sulfates and chlorides. No arsenic yet.
State may order recovery of waste) and at Lyncott Landfill (uses
terra-tite system).
By; E.G. Monnig
Comments; Waste is said to be 60% Nad, 40% Na?SO& and less than IX
arsenic (according to Vineland). Vineland permitted to dispose of
1,000 tons (850 yd3) in August. 1977. May 1979 - permit to dump 2.000-
3,000 pounds of solid waste from MSMA and Cacodyltc Acid production.
-------
MEMORANDUM OF ORAL ADVICE
Date: December 18, 1979
Name; David Barker. TDWR 512-475-5633
Re; MSMA Waste - Diamond Shamrock Telephone |XX| Conference ||
Facts and Query; Quantity, Composition and Disposal practices of MSMA
solid waste — Diamond Shamrockt
Answer: Waste contains NaCl-Na9SOA and arsenic. Relative concentration
unknown. Diamond Shamrock permitted to dispose on-site and off-site.
Off-site permit allows 481 tons on a monthly average.
By; B.C. Monnig
Comments:
-------
MEMORANDUM OF ORAL ADVICE
Date: December 31. 1979
Name: David Jeffrey TDWQ
Re: Cacodylic Acid and MSMA Waste Telephone |XX| Conference | I
Facts and Query; 1) Is the Crystal Chemical Solid waste report a natter
of public record? Yes.
2) Does MSMA salt also contain Caeodylic Acid by-
products? Probably.
Answer:
By; E.G. Monnig
Comments:
-ss-i-
-------
LISTING BACKGROUND DOCUMENT
CHLORDANE PRODUCTION
Wastewater and Scrub Water from the Chlorination of
Cyclopentadlene In the Production of Chlordane (T)
Hastewater Treatment Sludges from the Production of Chlordane (T)
Filter Solids from the Filtration of Hexachlorocyclopentadiene
in the Production of Chlordane (T)
Vacuum stripper discharges from chlordene chlorinator in
the production of chlordane (T)
I. SUMMARY OF BASIS FOR LISTING
The hazardous waste streams generated from chlordane
production include process wastewater and scrubwater, waste-
water treatment sludge, filter solids, and vacuum stripper
discharges. These waste streams contain hexachlorocyclopenta-
diene, chlordane, heptachlor, and other chlorinated organics.
The Administrator has determined that the solid waste
from chlordane production may pose a substantial present or
potential hazard to human health or the environment when
improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appro-
priate management requirements under Subtitle C of RCRA.
This conclusion is based on the following considerations:
1. Wastewater and scrubwater from the chlorinatlon of
cyclopentadiene, wastewater treatment sludge and
filter solids from hexachlorocyclopentadiene
filtration contain hexachlorocyclopentadiene.
Hexachlorocyclopentadiene is very toxic.
2. The vacuum stripper discharges from chlordene
chlorinator waste is expected to contain chlordane,
heptachlor, and other chlorinated organics.
Chlordane and heptachlor have been reported to
be carcinogenic and/or mutagenlc.
-------
3' *
4. If the wastes are mismanaged, the toxic constituents
in the waste could migrate from the waste and
contaminate groundwater. Certain constituents
of the waste (e.g., chlordane and heptachlor) are
projected to be persistant in groundwater.
II. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Profile of the Industry
According to SRI Directory of Chemical ProducersC1)
and two other sources(2»3), chlordane is produced by
only one company, Velsicol Chemical Company (a subsidiary of
Northwest Industries) at a plant in Marshall, Illinois. The
chlordane industry production capacity is estimated at 13,600
metric tons/yr (15,000 tons/yr).(3)
(4)
Chlordane is a versatile, broad-spectrum insecticide
which has been in commercial use for more than 20 years.O
It is used to protect a large variety of food crops, lawns,
turf, ornamental and shade trees, and the like from parasitic
insect life. In 1972, nonagricultural uses of chlordane
accounted for an estimated 80 percent of total U.S. consumption
of chlordane in that year.(3)
B. Manufacturing Process
Figure 1 presents a generalized production and waste
schematic for chlordane. As shown in Figure 1, the first
production step involves chlorination of cyclopentadiene to
* All underlined information is from properietary reports
and data files.
-SS3-
-------
CYCL'OPf^NTADlGNE"
+ CHLORINE
Cn WATIIR
} •
SCRUDOER
\
VE
|
Cl ILOR
WASTE
>ff
'
NATOR
•
WATER
f
f VENT" "
CY
SOLIDS
DECANTER
WASTE
WATER
POND
" i
""FILTER"
F
"b't'E'p
WELL
, | SO*C
{ III )
1 FILTER CAKE L
TO CLAY PIT
OR LANDFILL
WASTE WATER
•TREATMENT
SLUDGE
TOOFF-SITE
LANDFILL
CLOPCNTAD'IENE
- — r*riMnr
(OrDiELS" '
*" ' ALDER
1
CMLOROENG
... 1
(C) —\it
•^ CrlLORINATOR - -
.CHLORDANE
"MOr~fl "!•!" 1^^ i V/V\^U\.I
.NJU» »~ . oin||,,,
'"'WATER
1 HOLDING
INf ^ / VACLH
1 " ' "' * SIlllHi
}
IV
1 STRIPF
• WATl
1 TO
' HOLDI
PON
M A MI I~PA rT( miNG PROCESS AND WASTE SCHEMATIC"!MODIFIED FROM REFEREN 3"J~
-------
to obtain hexachlorocyclopentadiene. The hexachlorocyclopen-
tadlene la then condensed with cyclopentadiene to form chlor-
dene via the Diels Alder reaction. The chlordene is chlori-
nated to form chlordane. The main process reactions are as
follows:(3)
(A)
-r Cl,
CYCLOPENTADIENE
(B)
KSXACKLGSOCYCLOrENTADlENE
(O
a
CHLORDENE
Cl,or
SO,CU
HEXACHLOROCYCLOPENTADIENE
Cl
DIELS
ALDEn
CONDENSATION'
Cl
Cl
CKLOHDANE
a
ci
-------
These process reactions Indicate the sources of the
hazardous constituents in the wastes. They are marked A,
B and C in Figure 1 to illustrate precisely where the
reactions take place in the process.
C. Waste Generation and Management
1. Waste Streams
The four waste streams from the production of chlor-
dane which are listed as hazardous are:
0 Wastewater and scrub water from the chlorination
of cyclopentadiene
0 Wastewater treatment sludges
0 Filter solids from the filtration of hexachlorocyclo-
pentadiene
0 Vacuum stripper discharges from chlordene chlorlnator
in the production of chlordane
Hexachlorocyclopentadiene is the constituent of concern
in the first three listed wastes; chlordane, heptachlor, and
other chlorinated organlcs are the constituents in the last
listed waste.
Bach of the wastes—wastewater and scrubwater, wastewater
sludges, filter solids and vacuum stripper discharges—are
marked I, II, III and IV respectively, in Figure 1.
Wastewater and scrubwater (I) are generated during the
chlorination of cyclopentadiene and subsequent separation
steps.
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AUG-24-2006 THU 03:55 PH
FAX NO. P. 13
(4). The cyelopentadiene contains
numerous cyclic compounds, which when chlorinated result In
a multiplicity of toxic chlorinated cyclic compounds, among
which hexaehlorocyclopeatadlene predominates, aince it la the
jriocipal reaction product. Wastevater from reactor cleanup,
decanting and vent scrubbing thus contain significant amounts
of these components. As shown in Figure 1, this waste 10
sent to a settling pond.
The second listed waste (II) is a result of the treatment
Of the wastewat«r which contains hexachlorocyclopentadiene and
other toxic chlorinated organica. Since, hexachlorocyclopent-
adiene is relatively inaoluable (25ng/l) (29) and la amenable
Co blodegradatlon due to its physical chemical form, the Agency
expects this tovie organic to be present in the sludge.
Furthermore, concentrations of hexachlorocyclopentadiene in
the sludge would be expected to he significantly higher than
In wastevaters due to the undiluted composition of this waste.
Wastewater treatment sludge is
sent to an off-site landfill for disposal.
The third waste, namely filter solids from the filtration
of hexachlorocyclopentadiene (lit) results when the crude
hexachlorocyclopentadiene is filtered before it la reacted to
form chlordene (before reaction B). The filtration process la
intended to remove organic impurities, including hexachloro-
cyclopentadiene. It is thus expected that this constituent
-SS 7-
-------
AUG-24-2006 THU 03:56 PM FAX NO. P. 14
will be present In this waste, probably in significant concen-
trations. This solid waste is sent to a commercial landfill
for disposal. (3)
Vacuum stripper wastewater (IV) from the chlordene
chlorinator vent vacuum scrubber contains chlordane (which
would not be completely stripped) and heptachlor (the
principal reaction product) in dissolved or suspended states.
This waste goes to a holding pond prior to treatment.O>
While the precise concentration of waste constituents
In these waste streams are not presently available, even
very small concentrations are of concern due to these compounds'
extreme toxiclty and capacity for genetic harm, as well as the
history of wanta mismanagement associated with the sole
producer of chlorodane (see pp. 12-13 below). In any case,
concentration!) of these waste constituents are probably
quite substantial, since the identified waste constituents
are either principal reaction by products (hexachloro-
cyclopentadiene, heptachlor), or the end produr.t (chlordane).
III. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Wastes
As previously mentioned, the Hated wastes contain
one or more of the hazardous constituents hexachlorocyclopenta-
diene, chlordane and heptachlor.
Chlordane! and heptachlor have been well documented as
having lethal effects in humans when Ingested in small amounts,
and hexachloropentadlene has been documented to alter kidney
-------
AUG-24-2006 THU 03:56 PM FAX NO. P. 15
functions, and cause eye and throat irritation and headache
In humans. (For further Information, see Health and geological
gffeet of Constituents pp. 14-1R.)
1. Risks in Waste Management
As previously Indicated, (Figure 1), the wastewaters
from chlordane manufacture are discharged to a holding pond and
filtered prior to disposal.C3) Sludges from this holding pond
and filter solids from hexachlorocyclopentadlene filtration
are taken off-site for disposal.O) Disposal of the latter in
landfills, even if plastic-lined drums are used, represents a
potential hazard if the landfill Is improperly designed or
operated (i.e., drums corrode in the presence o-f even small
amounts of water). This can result In the leaching of hazardous
compounds and the subsequent contamination of groundwater. The
holding pond presents a comparable risk if not properly managed.
Further, damage incidents indicate (see D am age Incidents.
pp. 10-16) that hexachlorocyclopentadiene and heptachlor
contaminated wastes have been disposed of in improperly
designed and managed disposal facilities, which resulted in the
contamination of the air and drinking water in the area. The
possibility of improper management of these wastes and the
resulting associated hazard, is thus highly realistic.
A further consideration is the actual transportation of
these wastes to off-site disposal facilities. This increases
the likelihood of their being mismanaged, and may result
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AUG-24-2006 THU 03:56 PM FAX NO. P. 16
either la their not being properly handled during transport
or In their not reaching their destination at all (thua
making then available for harm elsewhere). 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. In reference
to this particular consideration, there was a damage Incident
In Memphis, Tennessee (discussed In detail on p. 12), due to
similar, unmanlfested waste being Illegally transported and
disposed.
2. Fate of Constituents In Waste stream
Ihe waste constituents appear to be fully able to
migrate, pass through soils, and persist In the environment
to an extent which could cause substantial harm to human
health and the environment. Although heptachlor and chlordanct
are relatively insoluble, their ability to migrate haa been
demonstrated by documented damage Incidents (see pp. 10-14)*
Based upon estimates by EPA,^) the constituents chlordane
and heptachlor in these waste streams are projected to be
persistent in ground water, and exposure to humans using
drinking water drawn from ground water in areas adjacent to
disposal sices Is Likely. Movement of all the constituents
Identified in the waste stream Is projected to be widespread
within surface water systems, resulting in likely exposure
to aquatic life forms in rivers, ponds, and reservoirs.
Concentrations up to 0.8 mg/1 and 0.04 mg/1 of chlordane and
-SfcO-
-------
heptachlor respectively, have been observed in surface waters,
confirming these compounds' mobility and persistence .(7»8)
Chlordatie is a persistent chlorinated hydrocarbon
insecticide. It persists in the soil for more than one year,
sometimes for many years. Its overall rate of degradation
is low.(29)
Further damage incidents (see Damage Incidents, below)
illustrate that hexachlorocyclopentadiene and heptachlor have
posed a hazard via air exposure to workers in contaminated
areas; they have also migrated from disposal sites to surface
and ground waters resulting in the contamination of drinking
water sources in the vicinity.
3. Damage Incidents
The most serious wastewater and solid waste disposal
problems from the manufacture of chlordane result from the
synthesis of the hexachlorocyclopentadiene intermediate.
The wastes from this process step contain highly toxic hesa-
chlorocyclopentadiene reaction product. The link between
disposal and management of heptachlorocyclopentadlene contam-
inated wastes and the hazardous implications of the leaching
of the toxic organic Into drinking water and/or air is well
documented by the damage incident described below. Further,
the vacuum stripper discharges from the chlordene chlorlnator
are of particular concern to the Agency because there also
have been documented damage incidents which show the mis-
-su-
-------
management, mobility and persistence of heptachlor contaminated
waste streams (also described below).
Sometime during March, 1977, an unknown toxic substance
began entering the Morris Forman waste treatment plant in
Louisville Kentucky. As a result, employees on sight suffered
from eye, nose, throat, lung, and skin irritation. It was
found that many wastewaters from this plant contained con-
stituents that are toxic. One of the predominant contaminants
identified was hexachlorocyclopentadiene. Upon an investiga-
tion to determine the point of entry of these contaminants
into the sewer system, it was found that a local waste handler
had storage facilities for industrial wastes in the Louisville
area. An investigation of five sights suspected to be used
by the local disposal company confirmed the existence of
hexachlorocyclopentadiene at one or more of the locations.
Drums out in the open, buried drums and barrel storage were
some of the implemented storage facilities and thus the points
of release of these contaminants. As a result, towns whose
water comes directly from the Ohio River had been alerted to
the flow of raw sewage containing the contaminant hexachloro-
cyclopentadiene into the river at Louisville. Many of these
toxic constituents were thus available for release due to
Improper management and disposal practices and even in minimal
concentrations, may cause a potential health or environmental
hazard via air exposure or contamination of drinking water
sources.(2 *)
-------
Further, the same type of waste as the toxic heptachlor
reaction by-products from chlordane production was generated
by Velsicol in Memphis, Tennessee in the production of hepta-
chlor. This vaste material from the Memphis plant was one
of the Industrial wastes which was illegally dumped into the
Louisville, Kentucky sewer by a contract waste disposal
company. Again, the specific results were the killing of
all sewage treatment plant biota and a resulting water con-
tamination problem. The cost of decontamination was in
excess of one million dollars and many workers were exposed
to this toxic material.*
Velsicol1s Memphis plant has also created groundwater
contamination problems resulting in several wells becoming
contaminated following disposal of highly toxic heptachlor
containing waste.* Disposal of this waste in either deep
wells or even in clay-lined pits can, and has, resulted in
contamination problems.
In another serious Instance of waste mismanagement
involving both hexachlorocyclopentadlene containing wastes
and Vellsicol. Velsicol buried chlorinated pesticide waste
containing hexachlorocyclopentadiene in drums at a Hardenman
County site beginning in 1964. A U.S.G.S. Study (1966-1967)
revealed that the wastes had migrated vertically to a depth
of 90 feet and laterally to a distance of 25 feet. Hexachloro-
cyclopentadiene and other chlorinated hydrocarbons were also
OSW Hazardous Waste Division, Hazardous Waste Damage
Incidents, unpublished, open file 1978.
-yt-
-S&3-
-------
detected In surface runoff. Samples of adjacent water wells
taken in April-May of 1978 showed contamination by the wastes.
The contamination was sufficient to advise the well owners
not to drink the water. At the time of the report a line
was being laid to connect these owners with the Town County
Water Supply. The cost of cleaning up the damage was $741,000
plus an outlay of $120,000 to supply water for the residents.
(Source: United State Geological Survey (1966-1967); OSW
Hazardous Waste Division, Hazardous Waste Incidents, unpublished,
open file, 1978). This damage incident again illustrates the
hazardousness of the waste, since upon mismanagement, waste con-
stituents (including hexachlorocyclopentadiene) proved capable
of migrating, persisting, and causing substantial hazard.
Past waste management practices of waste containing the
constituents of concern have presented special problems. (For
a more detailed discussion, see the report on Hazardous Waste
Disposal, Subcommittee on Oversight and Interstate and Foreign
Commerce, 96th Congress 1st sess. 4,10,17). As stated there,
16.5 million gallons of waste contaminated with heptachlor,
endrin, benzene, and aldrin was dumped at a Hardenman County
dump site. The dump site was ordered closed by the State of
Tennessee in 1972, but local drinking is contaminated and
unusable. This further indication of waste mismanagement by
the sole producer of chlordane production wastes confirms
the need for hazardous waste designation of these wastes.
Thus, these damage Incidents illustrates the potential
-------
environmental and health hazard resulting from leaching
contaminants from these Improperly disposed and managed
wastes.
B. Health and Ecological Effects of Constituents
1. Chlordane
Health Effects - Chlordane Is a very toxic chemical
[oral rat LD5Q - 283 mg/Kg] with lethal effects In humans
when Ingested In small amounts.(') Chlordane administered
orally in mice is carcinogenic causing liver cancers In both
sexes.(10) Chlordane has also been evaluated by CAG as having
substantial evidence of carcinogenicity. Chlordane has been
mutagenic in certain human cell assays. (H) Repeated doses
of chlordane have altered blood protein, blood glucose and
certain enzymes in gerbils.(12)
Chlordane is designated as a priority pollutant under
Section 307(a) of the CWA. Additional information and
specific references on adverse effects of chlordane can be
found in Appendix A.
Ecological Effects - Chlordane is acutely toxic to most
aquatic animal life. Lethal concentrations to freshwater
fish are in the microgram/liter range. Invertebrates appear
to be more sensitive to chlordane.(13) Similarly, salt
water fish and invertebrates have been shown to be very
sensitive to chlordane. (14) Chronic aquatic toxlclty of
this compound is even more severe across all freshwater and
-------
marine aniraal life.d*) In particular, fish embroyos appear
to suffer devastating damage from as little as a tenth of a
raicrogram of chlordane.<14) The aquatic damage is amplified
by the bioaccumulation factor of chlordane, i.e., scuds
bioaccumulate chlordane 7,400 fold, freshwater algae bioaccumulate
133,000 fold. Chlordane is slightly toxic to birds, moderately
toxic to wild mammals, highly toxic to soil insects, and
moderately toxic to some soil bacteria and to earthworms.
Regulations - The OSHA standard for amounts of chlordane
in air is a TWA of 600 n/ra3 (skin), based on the "one hit"
model of chemical carcinogenesis. The IISUPA has estimated
levels of chlordane in ambient water which will result in a
risk of 10~6 cancer incidence of 0.17. nanograms/liter.
Presently, a limit of 3 nanograms/liter for chlordane has
been suggested under the Interim Primary Drinking Water
Standard. The Canadian Drinking Water Standard is also 3
nanograms/liter. To protect freshwater life, the 24-hour
average is 0.24 micrograms/liter and may not exceed n.36
micrograms/liter. For saltwater species, the draft criterion
is 0.0091 micrograms/liter for a 24-hour average, not to exceed
0.18 raicrograms/liter. (15)*
*The Agency is not using the proposed water quality cri-
teria as a regulatory benchmark, but is referring to them here
to illustrate a potential substantial hazard if it migrates from
the waste at small concentrations.
-------
Industrial Recognition of Hazard - Sax, Dangerous Proper-
ties of Industrial Materials, designates chlordane as highly
toxic systematically via oral, skin absorption and inhalation
routes of exposure'
2. Heptachlor
Health Effects - Heptachlor is extremely toxic in
animals [oral rat L1>5Q = 40 mg/Kg] , also causing deaths in
humans following ingestion of very small amountstO")
Heptachlor is carcinogenic, causing liver cancer in mice.C17)
Heptachlor has also been evaluated by CAG as having substantial
evidence of carcinogenicity.
This chemical is outagenic and teratogenic in animals,
causing resorbtion of fetuses^^), chromosomal abnormalities
in bone marrow cells in adults, and cataracts in offspring.(19)
Heptachlor has caused a marked decrease in litter size and
lifespan in newborn rats.(2°) It also causes abnormal
DNA synthesis in human cell cultures.(32)
Heptachlor is a convulsant(21) and also interferes with
glucose metabolism when administered in chronic studies.(22)
Additional information and specific references on adverse
effects of heptachlor can be found in Appendix A.
Regulations - The OSHA standard for heptachlor is TWA
(air) 500mg/m3.
Industrial Recognition of Hazard - Sax, Dangerous Proper-
ties of Industrial Materials, designates heptachlor as highly
toxic via oral and dermal routes.
-------
IV. References
1. Stanford Research Institute. 1977 Directory of Chemical
Producers. SRI International, Menlo Park, California.
1977.
2. Farms Chemical Magazine. Farms Chemical Handbook.
Meister Publishing Company, Willoughby, Ohio. 1977.
3. Von Ruraker, et al. Production, distribution, use and
environmental Impact potential of selected pesticides.
U.S. EPA Office of Pesticide Programs. EPA No. 540/1-74-001.
1975.
4. Proprietary information submitted to EPA by Velsicol
Chemical Company through 1978 response to "308" letter.
5. Clement Associates, Inc. Dossier on hexachlorocyclo-
pentadiene. Contract No. EA8AC013, prepared for TSCA
Interagency Testing Committee. Washington, D.C.
August, 1978.
6. U.S. EPA. Aquatic fate and transport estimates for hazardous
chemical exposure assessments. U.S. Environmental
protection Agency, Environmental Research Laboratory.
Athens, Georgia. February, 1980.
7. Pesticide Monitoring Journal. 8:33. 1974.
8. Pesticide Monitoring Journal. 3:124. 1969.
9. U.S. DHEV. Clinical Handbook on Economic Poisons.
HEW, PHS, CDC. Atlanta, GA. NTIS PB No. 218 287. 1963.
10. National Cancer Institute. Bioassay of chlordane for
possible carcinogenlcity. NCI-CG-TR-8. NTIS PB No. 271 977.
1977.
11. Ahmed, F. E., et al. Pesticide-induced DNA damage and
its repair in cultured human cells. Mutat. Res. 42:161.
1977.
12. Karel, A. K. and S.C. Saxena. Chronic chlordane toxicity:
Effect on blood biochemistry of Meriones hurrianae Jerdon,
the Indian desert gerbil. Pestle. Biochem. Physiol. 6:111.
1976.
13. U.S. EPA. Chlordane hazard profile (Draft). 1979.
14. Kats, M. Acute toxicity of some organic insecticides
to three species of salmonlds and to the Chreesplne
stickleback. Trans. An. Fish. Soc. 90:264. 1961.
-------
15. U.S. EPA. Chlordane: Ambient water quality criteria
(draft). NTIS PB No. 292 425. 1979.
16. Gleason, M.N., et al. Clinical toxicology of commercial
products. Acute Poisoning. 3rd ed. Williams and Wilkins
Co. Baltimore. 1969.
17. U.S. EPA. Risk assessment of chlordane and hepta-
chlor. Carcinogen Assessment Group. U.S. Environmental
Protection Agency. Washington, D.C. 1977.
18. Cerey, K., et al. Effect of heptachlor on dominant
lethality and bone marrow in rats. Mutat. Res. 21:26.
1973.
19. Mestitzova, M. On reproduction studies on the occurrence
of cataracts in rats after long-term feeding of the
Insecticide heptachlor. Experlentla 23:42. 1967.
20. Ahmed, F. E., et al. Pesticide-induced DNA damage and
its repair in cultured human cells. Mutat. Res. 42:161.
1977.
21. St. Omer, V. Investigations into mechanisms responsible
for seizures Induced by chlorinated hydrocarbon insecti-
cides: The role of braim ammonia and glutamlne In con-
vulsions in the rat and cockeral. Jour. Neuroceue.
18:365. 1971.
22. Kacev, S. and R.L. Singhal. The influence of p.p^-DDT,
and chlordane, heptachlor and endrln on hepatic and
renal carboxyhydrate metabolism and cyclic AMP-adenyl
eyclase system. Life Scl. 13:1363. 1973.
23. NIOSH. Registry of toxic effects of chemical substances.
1978.
24. Morse, D. H. et al. Occupation exposure to hexachloro-
cyclopentadiene: How safe is sewage? JAMA 241:2177-2179.
1979.
25. Goggelman, W., et al. Mutagenicity of chlorinated cyclo-
pentadlene due to metabolic activation. Blochem. Pharmacol.
27:2927-2930.
26. Winteringham, P. Chemical residues and pollution program
of the Joint Division of the International Atomic
Energy Agency and the Food and Agriculture Organization
of the United Nations. Ecotoxicol. Environ. Safety
1:407-25. 1977.
27. Spechar, R. L., et al. Toxlclty and bio-accumulation of
hexachlorocyclopentadlene, hexachloronorbornadiene,
and heptachlorobornene in larval and early juvenile
fathead minnows. Bull. Environ. Contam. Toxicol. 21:576-83.
-------
28. Control of Hazardous Material Spills. la Proceedings;
The 1978 National Conference on Control of Hazardous
Material Spills. Miami Beach, Florida. April 11-13, 1978.
29. Dawson^ English, Petty. Physical chemical properties
of hazardous waste constituents. 1980.
-------
ORD-F
LISTING BACKGROUND DOCUMENT
DISULFOTON PRODUCTION
Wastewater Treatment Sludges from the Production of Dlsulfotoa (T)
Still Bottoms from Toluene Reclamation Distillation in the Production
of Diaulfotoo
-------
3. Disposal of these wastes, even in drums, in improperly designed.
or operated, landfills represents a potential hazard due to the
migratory potential of these hazardous compounds.
II. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Profile of the Industry
Disulfoton is produced in this country by only one manufac-
turer, Mobay Chemical Corporation, at its Chemagro Agricultural Division
in Kansas City, Missouri. (*) Production for 197A was estimated at 10 mil-
lion pounds. (2) _ ______ _ __ _
_ *.
Disulfoton is a systemic insecticide, primarily used to control
sucking insects, especially aphid s and plant-feeding mites. It was de-
veloped in the 1950' s and has been in commercial use for about 15 years.
Agricultural uses accounted for almost all of the estimated U.S. consump-
tion in 1972. Small quantities are used on ornamentals in the home and
garden market in the form of dry granules of very low active ingredient
content.
B. Manufacturing Process
Disulfoton is produced according to the following three-step
scheme'*);
Toluene
(A) P2S5 + 4C2H5OH + 2NaOH ---------- > 2(C2H50)2P(S)SNa + H2S + 2H20
Solvent
Ethanol "Diethyl Salt" (DES)
* The underlined data are those obtained from proprietary reports and
data files.
-------
(B) PCL3 + 3HOC2H4-S-C2H5 > 3C1C2H4-S-C2H5 + H3P03
"Thlo-AlcohoL" "Chloro Thio Alcohol" (CTA)
(C) (C2H50)2P(S)SNa + C1C2H4-S-C2H5 —> (C^O^CSj-S-C^-S-C^s + NaCl
DES CTA Disulfoton
A process flow diagram and waste schematic is shown in Figure 1.
The reaction between F2S5 and ethanol in toluene solvent occurs and
produces the dlethyl phosphorodithioic acid. The major side product of
the reaction is the o,o,o-trlethylester of the phosphorodithioic acid*.
The dlthloic acid is next converted on the dlethyl salt (OB'S) with caustic
soda. These two substeps are summarized in reaction (A) (see equation
on page 2 and corresponding (A) in Figure 1).
The DES is separated in the toluene recovery unit while the remaining
mixture of toluene, triester, and other organic residues is sent to a
toluene recovery unit. The toluene is recycled to the salt production process
and the still bottoms (Waste Stream II in Figure 1) containing o,0,0-triethy1
ester of phosphorodithioic acid go to disposal. ^
PC13 and thio alcohol are then reacted to form the chloroethyl
thloethyl ester ("chloroethyl thioethyl alcohol, CTA") and phosphorous
acid {Reaction 8, above, and corresponding (B) in Figure !)•
The third step of the production process, reaction C above, involves
the reaction between the diethyl salt (DES) and chlorothio-alcohol
(CTA) to form disulfoton and sodium chloride. This is shown in Figure 1
as the disyston unit, and marked (C).
*Also referred co in this document as o,o,o-triester,
i
-5-7.5--
-------
RECOVERED TOLUKNE
MAKEUP
.1OLUENE
!SOLVENT
ETHANOL
OES
UNIT (A)
CnUDE
OES
TOLUENE
nccovenv
UNIT
HaOH
PCI,
oi-s
WASTE
SOLIDS
(ii) 0.0.0 TruesiQT
TOOURIAt
WASTE WATL-H
•Tl BO-ALCOHOL
CTA
UNIT (0)
CFA
CHSYSTON
UNIT
(Cl
DISYJ5TON
KOLVIiNT
necovenv
UNIT
WASTE
WATER
TniiATMENT
OISULFOTON
PRODUCT
WASTE
WATER
TREATMENT SLUDGE
Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR DISULFOTON
[ADAPTED FROM CHEMAGRO DRAWING (3)]
-------
Treatment of waste water from the manufacturing process results
in a sludge (Waste Stream I In Figure 1).
C. Waste Generation and Management
As indicated in Figure 1, the dlethyl salt from the DBS unit Is
separated for further processing and the toluene, triester and other
waste solids are sent to a toluene recovery unit. The recovered toluene is
recycled back to the production process; the waste stream from this process
(Stream II, Figure 1) is composed of the unrecovered toluene, o,o,o-triester
of phosphorodithioic acid and associated organic residues. This waste
is combined with waste solids from the downstream dlsyston recovery unit
and sent for burial in landfills.^)
The dlsyston unit process water, along with wastewater from the
toluene recovery unit, is sent to the disyston solvent recovery unit where
some disulfoton is recovered and recycled to the disyston unit.
The sludge from wastewater treatment (Waste Stream I in Figure 1) is
disposed of by landfill;
(11)
*J The waste stream from the disyston recovery unit is not specif ideally
listed as hazardous, but the combined waste stream is deemed hazardous
under the 'mixing' provision of §261.3.
-•5"? 7-
-------
AUG-24-2006 THU 03:57 PM FAX NO, P. 19
III. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Waste*
There are two solid waste streams which ate considered in
this document. As previously mentioned, both waste streams contain
toxic constituents which pose a potential hazard If Improperly managed
and disposed'
The still bottoms from the toluene recovery unit (Waste Scream II)
are expected to contain triesters and unreacted toluene. There is
little Information on the toxlclty of the trlesters; however, the
compound i> structurally similar to o,o,s-triethylester( a member of
a family of compound which is very toxic (LD5Q • 80 ng/kg after 8
days)(22). Toluene is a toxic cheaicul with such acute toxic effects
in humans exposed to low concentrations (200 ppm) as excessive depression
of the nervous system.(16)
The westewater treatment sludges (Waste Stream I) also contain
toluene solvent and o,o,o-triethylester of phosphorodithloic acid,
which is a process intermediary. (For Information on the toxic effects
of these compounds, see Section III BO
1. Exposure Pathways
As noted above, the typical disposal method for both of these
wastes is in landfills. Disposal of these wastes in landfills', even if
If
-------
AUG-24-2006 THU 03:57 PM
un P. 20
NUl
lined drums ate used, represents a potential hazard if the landfill
is improperly designed or operated (the drums corrode in the presence of
even small amounts of vater). This can result In leaching of hazardous
compounds and subsequent contamination of ground water.
As A result, the waste constituents of concern nay migrate from
improperly designed and managed landfills and contaminate ground and
surface waters. Toluene is highly soluble (470 ppm)<2*> and by
virtue of its solvent properties, can facilitate mobility and
dispersion of other toxic eonstltutenea assisting their movement coward
ground and surface waters. The migratory potential of toluene is confirmed
by the fact thac toluene haa been detected migrating from the Love Canal
site into Bufroiiadiog residential basement* and solid surfaces, demon-
Btre.titig ability to migrate through B&HB ("Love Canal Public Helath
Bomb1*, A Special Report to the Government and Legislature, New York
State Department of Health (1978)). Thus, once toluene migrates from
the matrix of the waste, it IB likely to persist ID soil and groundvater.
There also may be a danger of toluene migration and exposure via an
air Inhalation pathway if disposal sites lack adequate cover* Toluene
is relatively volatile (28.4 mm Rg (24)) and is mobile and persistent
in air, having been found in school and baseoent air at Love Canal
("Love Canal Public Health Bomb", supra)*
Although very little information is available on the characteristics
of o,o,c*-trlethyle6terSp the Agency la aware of the hazardous characteristics
of the same family of compounds as this particular triester. The Agency
-------
AUG-24-2006 THU 03:58 PM FAX NO, P- 21
would require some assurance chat Che waste components will not migrate
end persist to warrant a decision not to list the mate. No such assurance,
appears readily available.
Thus, these waste constituent* could leach into groundwater If
landfills are 'itnlined, or have inadequate leachate collection systems.
Waste management facilities located in areas with highly permeable
Boils would likewise facilitate Uachate migration.
There also may be a danger of toluene migration and exposure via an
air Inhalation pathway if disposal sites lack adequate cover. Toluene
is relatively volatile (28.4 mm Kg (24)) and is mobile and persistent
in air, having been found In school and basement air at Love Canal
("Love Canal Public Health Boob," supra).
B. Health and Ecological Effects
1. Toluene
Health Effects - Toluene is a toxic chemical absorbed into
the body by inhalation, Ingestion, and through the akin. The acute toxic
effect In humans is excessive depression of the central nervous system,(15)
and this occurs at low concentrations [200 ppm].(l&) Chronic occupational
exposure to toluene'has led to the development of neuro-muscular disorders.
Since toluene is metabolized in the body by a protective
enzyme system Which is also Involved in the elimination of other toxins,
It appears that over-loading the metabolic pathways with toluene will greatly
reduce the clearance of other, more toxic chemicals. Additionally, the high
affinity of toluene for fatty tissue can assist in the absorption of other
-------
AUG-24-2006 THU 03:58 PM FAX NO. P. 22
toxic chemicals Into che body. Thus, synergistic effects of toluene on the
eoxlcicles of other contaminants may render the wastes more hazardous.
Toluene is designated as a priority pollutant under Section 307(a) of the
CWA. Additional information and specific references on the adverse
effects of toluene can be found in Appendix A.
Ecological Effects - Toluene has been shown to be acutely
toxic to freshwater fish and to marine fish. Chronic toxlclty is also
reported for marine fieh.C18)
Regulations - Toluene haa an OSHA standard for air TWA of
200 ppm. The Department of Transportation requires a "flammable liquid"
label.
Industrial Recognition of Hazard - Toluene Is listed as
having a moderate toxic hazard rating via oral and Inhalation routes (Sax,
Dangerous Properties of Industrial Materials).
2» Phosphorodithiolc and Phosphorothieic Acid Esters (Trjesters)
Health Effects - The -s,s-methylene o,o,o,o-tetraethyl
eater is extremely toxic by various routes of administration to animals
[oral rat LD50 - 13 mg/kg].(l9> Toxic effects In the blood of humans have
been observed at minute doses (100 micrograms/kg],(20) ^^ human death
from ingestlon of this chemical has also occurred at low doses £50 ag/kg].(2l)
The phosphorothioic acid -o,o,o-triethylester Is a member of a family of
compounds, which, when given orally to rats is very toxic [LD50 - 80
mg/kg after 8 days].(22) The -o,o,s-trimethyl ester is extremely toxic
to rats [LD50 - 15 mg/kg].<23> Additional information and specific
references on adverse effects of phosphorodithioic and phosphorothioic
-------
AUG-24-2Q06 THU 03:58 PM FAX NO. P- 23
acid esters can be found In Appendix A*
Industrial Recognition of Hagard - Sax (Dangerous Proper-
ties of Industrial Materiala), liata triethyl phosphorothloate (phosphorc
thtolc acid, 0,0,0-trlethyl escer) as being highly toxic via ingesdon
and inhalation.
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AUG-24-2006 THU 03:59 PM FAX NO, P. 24
IV
References
i. Stanford Research Institute. 1977 Directory of chemical producers.
SRI International, Metilo Park, California. 1977.
2. Kelso, G. L«, R. Wilkettson, T. L. Ferguson, and J . R. Kaloney.
Development of in format ion on pesticides manufacturing for source
assessment, Final Report. Midwest Research Institute. EPA Contract
So. 6B-02-U24. OTIS PB No. 283 OS1/1BE. July 30, 1976.
3. Von Rumker, et al. Production, distribution, use and environmental
impact potential of selected pesticides. U.S. EPA, Office of Pesticide
programs. EPA No. 5AO/L-74-001. NTZS PB Ho. 238 795. 1975.
4. U.S. EPA. Lawless, E. W., R. Von Ruoker, T. L. Ferguson. The pollu-
tion potential in pesticide manufacturing. TS-00-72-04. NTIS PB
No. 213 782/3BA. June, 1972.
5. Hoc used in text.
6. Not used in text.
7. Not used in text.
S. Parsons, T., ed. Industrial process profiles for environmental
use; Chapter 8, Pesticide industry* EPA No. 60Q/77-023h. Technology
Series. NTIS PB Ho. 266 225. 1977.
9. Not used la text.
10. Not used in text.
11. Proprietary Information submitted to EPA by Mobay Chemical Corporation
through 1978 response to "308" letter.
12. Not used In text.
13. Not used in text.
14. Not used in text.
IS. U.S. EPA. Toluene ambient water quality criteria. NTIS PB No. 296 805.
1979.
-------
AUG-24-2006 THU 03:59 Ptt
FAX MO. P- 25
IV. Referencea (Continued)
16. NIOSH. Registry of -toxic effects of chemical substances.
Toluene. U.S. Government Printing Office. Washington, D.C. 1978.
17* Not used In text.
18. U.S. EPA. Toluene: Hazard profile. Environmental Criteria and
Assessment Office, O.S. EPA. Cincinnati, Ohio. 1979.
19. Pharmaceutical Journal 185:361. 1960.
20. Toxicol. Appl. Pharaacol. 22:286. 1972.
21. Gleason, M.H., et al. Clinical toxicology of commercial products.
Acute poisoning, 3rd ed* p. 65- 1969.
22. Mallipute, et al. J. Agric. Food Chep. 27:463-466- 1979.
23. Fukuto. et al. EPA Grant No. R804345-04. Quarterly ptogrenB
reports to EPA, August 1973 November, 1979.
24. U.S. EPA- Physical chemical properties of hazardous mate
constituent*. Prepared by Southeast Environmental Research
Laboratory] Jim Falco, Project Officer. 1980.
-------
AUG-24-2006 THU 03:59 PH FAX NO. P- 26
(ORD
LISTING BACKGROUND DOCUMENT
PHORATE PRODUCTION
Hastewater Treatment Sludges from the Production of Phorate (T)
Filter Cake from Che Filtration of DiethylphosphorodiChioic Acid
in the production of Phorate (T)
Wastewater from the Washing and Stripping of Phorate Production (T)
I. Summary of Tiasia for Listing
The hazardous wastes from phorate production are: (1) wastewater
treatment sludges from the production of phorate, (2) filter cake from the
filtration of diethylphosphorodlthioic acid, and (3) vastewater from the
washing and stripping of phorate product.
The Administrator has determined that these solid wastea from phorate
production nay 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 appro-
priate management requirements under Subtitle C of RGRA. This conclusion
Is based on the following considerations;
1) Wastes from the production of phorate nay contain phorate, for-
maldehyde, esters of phosphorodithiolc acid end phosphorothioic
acid.
2) Phorate is extremely toxic and formaldehyde has been evaluated
by the Agency as exhibiting substantial evidence of carclnogen-
icity. The other constituents expected to be present In the
waste are also toxic.
3) Disposal of these wastes In Improperly designed or operated
landfill;: presents a potential hazard due to the risk of
these hazardous compounds leaching into groundwater. 'As
-------
AUG-24-2006 THU 04:00 PM FAX NO. P. 27
these hazardous compounds are likely to persist in ground-
water, drinking water supplies derived from these sources
ar« likely to be contaminated.
5) Mismanagement of Incineration operations could result in the
release of hazardous vapors to the atmosphere and present a
significant opportunity for exposure of humans, wildlife and
vegetation In the vicinity of these operations to potentially
harmful substances.
II. Sources of the Wastes and Typical Disposal Practices
A. Profile of the Industry
The principal use of phorate is as a soil and systemic Insect-
icide used to control a wide range of insects on a variety of crops:
alfalfa, barley, beans, corn, cotton, hops, lettuce, peanuts, potatoes,
rice, sorghum, sugar, beets, sugar cane, tomatoes and wheat'*'.
Phorate is produced In this country by two manufacturers, Amer-
ican Cyanamid at Hannibal, Hodi6) an(j Mobay Chemical in Kansas City, MO.*
B. Manufacturing Process
A generalized production and waste schematic for phorate is
shown in Figure 1. Phorate is made by the reaction of o,o-diethyl hydro-
gen phosphorodlthloate with formaldehyde, followed by the addition of
ethyl raercaptan (ethanethiol). The o,o-diethyl hydrogen phosphorodi-
thloate Is condensed with formaldehyde and ethyl tnercaptan. The reaction
chemistry Is as follows^);
The Agency has been informed, however, that
_
American Cyanamid no longer produces phorate.
All underlined information is from proprietary reports and data.
-------
P2S5
phosphorous
pentasulflde
C2H5OH-
ethanol
2 (C2HS0)2PSH + H2S
o,o-diethyl
hydrogen
phosphorodithioate
(C2H50)2pSH
0,0-diethyl
hydrogen
phosphoro-
dithioate
H2C=0
formaldehyde
(C2H50)2PS-CH2OH
dithiophosphate
(C5H50)2PS-CH2OH
dithiophosphate
C2H.;SH ----
ethyl
mercaptan
(C2H50)2P-SCH2SEt + H20
Phorate
These reactions Indicate the source of the waste constituents of concern.
C. Waste Generation and Management
Based on the generalized flow diagram shown in Figure 1,
three hazardous waste streams from the production of phorate are expected
to be generated. (See figure 1.) These are:
(a) Process wastewater: The wastewater is likely to con-
tain significant concentrations of phorate, and lesser
concentrations of other process waste constituents inclu-
ding formaldehyde, phosphorodithloc and phosphorothloc acid
esters, and other main reaction byproducts.
T2T
-537-
-------
Figure 1 is Confidential
-------
(b) Filter Cake: The filter cake is expected to contain
high concentrations of esters of phosphorodlthioic
acid and esters of phosphorothioic acid. These esters
are formed immediately prior to filtration in the dithio
acid unit, and filtration is intended to remove the esters
from the process stream.
(c) Wastewater Treatment Sludges: Wastewater treatment sludges
result from the treatment of process waters. The sludges
are expected to contain high concentrations of phorate because
of its relative insolubility in water (about 5(1 ppm).(7'
Lesser concentrations of other process constituents are also
expected to be found in the sludge.
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
These waste streams contain phorate, which is extremely toxic, and
formaldehyde, a GAG carcinogen, and o,o,o-triethyl esters of both phosphoro-
thioic acid and phosphorodithioic acid (as well as other trlethyl esters
which may be present), which are toxic. The presence of phorate and formalde-
hyde in particular, even in small concentrations, is of considerable regulatory
concern, and the Administrator would require strong assurance that these waste
constituents are Incapable of migration, mobility, and persistence if Improperly
managed, before determining not to list these wastes as hazardous.
Such assurance is not forthcoming. Of the constituents likely to
be found in the waste stream, phorate, o,o,o-triethyl esters of both phosphoro-
thioic acid, and formaldehyde are able to reach environmental receptors upon
release, and can persist. Phorate is moderately soluble (50 ppm), could be
transported through permeable soil, and, although subject to some hydrol-
-------
yzation and biodegradation, will persist for weeks in both surface waters
and groundwaterOS). o,o,o,-Triethyl esters of phosphorothioic acid
are soluble and persist In both surface water and groundwaters.^S)
Formaldahyde Is quite soluble and has great migratory potential.O8) If
disposed of in areas with inorganic or permeable soils, it could become
highly mobile. Formaldahyde also persists in surface and groundwatersO*).
Based upon estimates of EPA/7) exposure to these compounds is likely via
drinking water supplies derived from groundwater sources within areas adjacent
to mismanaged land disposal sites. The projected widespread movement of
these compounds when discharged to surface waters will also probably result
in exposure of aquatic life forms in rivers, ponds, and lakes. Another
waste constituent, o,o-diethyl ester of phosphorodithioic acid, is less
persistent than the prevously discussed compounds, but sufficiently soluble
and resistant to degradation to result in widespread movement'^). Thus,
if improperly managed, these constituents are fully capable of migration,
nobility, and persistence in substantial concentrations.
As the subject waste streams contain extremely hazardous
constituents which may be mobile and persistent upon release, disposal of
these wastes In landfills can create a potential hazard if landfills are
Improperly designed or operated. Disposal of these wastes in lagoons or
treatment of wastes in holding ponds prior to final disposal, also presents
substantial potential hazards as well. Unless lagoons are properly designed
and operated (e.g., by lining the site with appropriate liners and employing
leachate collection systems), a strong potential exists for contamination of
soil and groundwaters via leachate percolation. Heavy precipitation
-------
may result In flooding of the lagoon, thus, surface waters can become
contaminated.
In light of the hazards associated with these waste constituents,
and their potential for mobility and persistence in substantial concentra-
tions if mismanaged, the wastes are deemed to be hazardous.
B. Health and Ecological Effects
1. Phorate
Health Effects - Phorate is extremely toxic in animals by
all routed of administration [oral rate LD5Q - 1.1 mg/kg].^1 ' Death
in humans has been reported as a result of ingestion of extremely small
doses. C^-2) Inhalation of phorate by mice caused adverse effects on
reproductive performance at very low concentrations (3.0 ppm), (^3) while
the lethal dose by inhalation in rats is also very low [11 mg/kg].(14)
Phorate metablites are at least twice as toxic as phorate.(I*-,1?)
Additional information and specific references on adverse effects of
phorate can be found in Appendix A.
Industrial Recognition of Hazard - Sax (Dangerous Properties
of Industrial Materials) lists the toxic hazard rating of phorate as very
high via oral and dermal routes.
2. Formaldehyde
Health Effects - Formaldehyde is reportedly carcinogenic(18)
-------
nasal cavity tumors detected In two studies. It has also been mutagenlc in
several bacterial and human cell culture assays.09,22) Formaldehyde is very
toxic to animals by all routes of administration (23,27)^ causing death in
humans In small amounts (36 rag/kg).(28) Additional Information and specific
references on adverse effects of formaldehyde can be found in Appendix A.
Ecological Effects - Formalin, an aqueous solution of formaldehyde
Is lethal to Daphnla Hagna.OO)
Regulatory Recognition of Hazard - Formaldehyde Is a chemical
evaluated by GAG as having substantial evidence of carclnogenicity^39)
OSHA has set a standard air TWA limit of 3 ppm for formaldehyde.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, lists formaldehyde as highly toxic to skin,
eyes, and mucous membranes.
3. Phosphorodtthioic and Phosphorothioic Acid Esters
Health Effects - The phosphorodithlolc acid s,s'-methylene-
0,0,0',o'-tetraethyl ester is extremely toxic by various routes of admini-
stration to animals [oral rat LDcg « 13 mg/kg].' *' Toxic effects
in the blood of humans have been observed at minute doses (100 ug/kg)O*),
while human death from ingestion of this chemical has also occurred at
low doses [50 mg/kg).(35)
The phosphorothiolc acid o,o,o-triethyl ester Is similar to the
-------
o,o,s-triethyl ester, which Is very toxic when given orally to rats [LD5Q -
RO rag/kg]/36) The o,o,s-triethyl ester is extremely toxic to rats [LDi;n "
15 mg/kgl.C7) Additional information and specific references on the
adverse effects of phosphorodithioic and phosphorothloic acid esters can
be found in Appendix A.
Industial Recognition of Hazards - Sax, Dangerous Properties of
Industrial Materials, lists triethyl phosphorothloate (phosphorothioic acid,
o,o,o-triethyl ester) as being highly toxic via ingestion, inhalation and
skin absorption.
-------
IV. References
1. SRI. 1977 Directory of chemical producers. Stanford Research Institute,
Menlo Park, California. 1977.
2. Proprietary information submitted to EPA by American Cyanamid through
1978 response to "308" letter.
3. Farm Chemicals Handbook. Meister Publishing Company, Willoughby,
Ohio. 1977.
4. Lawless, E. W., et al. The pollution potential in pesticide manufac-
turing. U.S. EPA, Office of Water Programs, Technical Studies Report TS-
00-72-04. STIS PB No. 213 782/3BA. 1972.
5. Not used in text.
6. Personal Communication. S. R. Hathaway of American Cyanamid, to D. K.
Oestreich. February 11, 1980.
7. U.S. EPA. Aquatic fate and transport estimates for hazardous chemical
exposure assessments. U.S. EPA, Environmental Research Laboratory,
Athens, GA. February, 1980.
8. Not used in text.
9. Not used in text.
10. Not used in text.
11. National Academy of Sciences, National Research Council. Drinking
water and health. PB No. 2619. 1977.
12. Gleason, M. N., et al. Clinical toxicology of commercial products:
Acute poisoning, 3rd ed., p. 142. 1969.
13. U.S. EPA. M. Greenberg. Hazard profile on phorate. U.S. EPA,
Environmental Criteria and Assessment Office, Reserch Triangle
park, NC. 1980.
14. Newell, G.W., and J.V. Dilley. Teratology and acute toxicology
of selected chemical pesticides administered by inhalation.
NTIS PB No. 277 077. 1978.
15. Not used In text.
16. Not used in text.
-------
17. Curry, A.N., et al. Determination of residue of phorate and its
insectIcidally active metabollties by cholinesterase inhibition.
Jour. Agrtc. Food Chem. 9:469-477. 1961.
18. U.S. EPA. The Carcinogen Assessment Group's preliminary risk
assessment on formaldehyde. Type I - Air Programs. U.S. EPA,
Office of Research and Development, 401 M St., S.U. Washington,
D.C. 20460. 1979.
19. Auerbach, C., M. Moutschen-Dahen, and J. Mouytschen. Genetic and
cytogenetic effects of formaldehyde and related compounds. Mutat.
Res. 39:317-361. 1977.
20. U.S. EPA. Investigation of selected potential environmental
contaminants: Formaldehyde. EPA No. 560/2-76-009. NTIS PB
No. 256 839/2BA. 1976.
21. Wilklns, R.J., and H.D. MacLeod. Formaldehyde-induced DNA protein
crosslinks in £. coll. Mutat. Res. 36:110-16. 1976.
22. Obe, G., and B. Beck. Mutagenic activity of aldehydes. Drug Alcohol
Depend. 4:91-4. 1979.
23. Union Carbide. Toxicology studies: formaldehyde. Industrial
Medicine and Toxicology Department, Union Carbide Corporation.
April, 1967.
24. J. Ind. Hyg. Toxlcol. 23:259. 1941.
25. ACTA Pharmaloglca et Toxlcologlca. 6:299. 1950.
26. J. Ind. Hyg. Toxicol. 31:343. 1949.
27. Horton, A.W., R. Tye, and K.L. Stemmer. Experimental carclnogensis
of the lung. Inhalation of gaseous formaldehyde on an aersol tar by
C3H mice. J. Natl. Cancer Inst. 30 (1):30. 1963.
28. Lefaux, R. Practical toxicology of plastics. Chemical Rubber Company,
Cleveland, Ohio. p. 328. 1968.
29. Not used In text.
30. Dowden, B.F., and M.J. Barrett. Toxlclty of selected chemicals to
certain animals. Jour. Water Pollut. Control Fed. 3:1308. 1965.
31. Not used in text.
32. Not used In text.
33. Pharmaceutical Journal. 185:361. 1960.
34. Toxicol. Appl. Pharmacol. 22:286. 1972
-------
35. Gleason, M.N., et al. Clinical toxicology of commercial products:
Acute poisoning. 3rd ed., p. 65. 1969*
36. Mallipute, et al. J. Agrlc. Food Chem. 27:463-466. 1979.
3/. Fukuto, et al. Quarterly progress reports to EPA, August 1978—
Nov., 1979. EPA Grant No. R804345-04.
38. Dawson, English, Petty. Physical chemical properties of
hazardous waste constituents. I960.
39. U.S. EPA. List of Carcinogens. Carcinogen Assessment Group (CAG),
Office of Research and Development, U.S. EPA, 401 M St., S.W.,
Washington, D.C. 20460. April 22, 1980.
-------
LISTING BACKGROUND DOCUMENT
TOXAPKENE PRODUCTION
Hastewater Treatment Sludge from the Production of Toxaphene (T)
Untreated Process Vastewater from the Production of Toxaphene (T)
I. Summary of Basis for Listing
The production of toxaphene, a chlorinated hydrocarbon pesticide,
results in the generation of process wastewater containing heavily diluted
concentrations of toxaphene, and wastewater treatment sludges that contain
approximately one percent of toxaphene by weight.
The Administrator has determined that process wasteuater and waste-
water treatment sludge from toxaphene production may pose a substantial
present or potential hazard to human health or the environment when
improperly transported, treated, stored, disposed of or otherwise managed,
and therefore should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the following
considerations:
1) Toxaphene Is present in each of these waste streams; In the
case of the wastewater treatment sludge, if it Is found in
very high concentrations. Toxaphene has been reported to
cause cancer in laboratory animals and is extremely toxic.
Toxaphene has also been recognized by the Agency as exhibi-
ting substantial evidence of being carcinogenic. It has also
been shown to be mutagenic.
2) Approximately 7 tons of wastewater treatment sludge containing
about 140 Ibs. of toxaphene are generated per production day.
About 19,000 tons of sludge are already disposed of In a land-
fill In Oeorgla. (5)
-------
3) Disposal or treatment of these wastes in improperly designed
or operated landfills or unlined lagoons could result in
substantial hazard if toxaphene migrates via groundwater or
surface water exposure pathways.
4) Toxaphene is highly persistent in the environment and
bioaccumulates greatly in environmental receptors.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Toxaphene is produced in this country by two manufacturers:
Hercules, Inc. at its Brunswick, Georgia plant, and Vertac Chemical
Company at its Vicksburg, Mississippi plant.
.(2,3)
Toxaphene is a complex mixture of polychlorinated camphenes
containing 67 to 69 percent chlorine and has the approximate composition
of CioHioClg. It has been used exclusively as a non-systemic and persistent
contact and ingestion Insecticide. Toxaphene is marketed as a 90 percent
toxaphene-10 percent solvent solution using mixed or modified xylene
as the solvent. This solution is then formulated by various companies
into emulsiftable concentrates, either alone or with other insecticides.
Little or no toxaphene is currently being used in dust, wettable powder,
or granule formulations.
*A11 underlined data are obtained from proprietary reports and data.
-------
B. Manufacturing Process
Toxaphene is produced in essentially the same manner by both domestic
manufacturers. The reaction chemistry Is as follows;
fl-PWEN£ 'CAMPHSNE TOXAPKEMS
C. Waste Generation and Management*
At the Hercules plant, wastewater Is generated from the toxaphene
production process (leaks, spills and washdowns), as well as from the scrubbing
of vent gases in the HC1 absorption and recovery step (see Figure 1).
()
The treated wastewater
is directly discharged to a navigable waterway.
In Hercules* toxaphene wastewater treatment system, an average
of 7 tons/day of wastewater treatment sludge (settled solids) is
generated.C*.5)* fne siudge results from the addition of diatomaceous earths
Variations in wastewater treatment systems or In wastewater sources at
the two plants may result in different concentrations of toxaphene In the
wastewater treatment sludges.
-------
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I
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LE
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8
Figure 1. HERCULES' PRODUCTION AND WASTE SCHEMATIC FOJ1 TOXAPIIliNU
-------
and line to the wastevater as sorption agents for the removal of toxaphene
from the wastewaterX5) The solids are allowed to settle in holding
ponds and may remain there for months at a time. (13) After the basin
is filled with solids it is taken off line and the sludge is allowed to
dry to approximately 50Z solids. (5) Analyses of the sludge performed
by Hercules Indicate that the sludge contains approximately one percent
toxaphene by weight, or 10,000 mg toxaphene/kg of sludge. (5) Some
140 Ib/day of toxaphene are generated and will be contained in this waste
The ultimate destination of the toxaphene wastewater treatment
sludge generated at the Hercules plant is a state-approved landfill. (6)
The landfill is known as the "009" landfill and is a privately owned
site operating under Georgia permit. It is used exclusively for the
disposal of the toxaphene wastewater treatment sludge generated at th*
Hercules Plant. (6) The "009- landfill used for disposal of the
Hercules toxaphene wastewater treatment sludge has a bentonite clay
liner, and has 6 monitoring wells which are monitored 4 times per year.
To date, no toxaphene has been detected in the wells.
(5)
-------
(3,5)
(3)
.* This pond, or lagoon, is unlined.<14> The treated waste-
water is discharged to the Mississippi River.
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
As noted above, In the Hercules toxaphene wastewater treatment
system, an average of 7 tons/day of waste sludge are generated.(*,"
Th« toxaphene content in the waste sludge is approximately at one percent
by we* ?.ht or 10,000 mg/Kg sludge. Klgh concentrations of toxaphene
are undoubtedly present in process wastewater to account for such high
concentrations in the sludge.
Toxaphene is an exceptionally dangerous waste consitutent. It
is extremely toxic, highly bioaccumulative, and has been reported to cause
Career In laboratory animals. It has also been shown to be mutagenic.
Toxaphene is regulated as a toxic pollutant under §3Q7(a) of the Clean
Water Act. After an adjudiciative proceeding, a discharge concentration
'No Aa~ • .urrently available on the amount of uastewater treatment
sludge. .:>-.; tied solids) generated at the Vertac plant. Nor is any data
availsDi>* .-i the concentrations of toxaphene in these sludges.
-------
limitation of 1.5 ppb has been established for toxaphene discharges into
navigable waters, and this discharge limitation was judicially upheld in
Hercules. Inc. v. EPA. 598 F. 2d 91 (D.C. Ur 1978). (The administrative
and judicial records are incorporated by reference into this listing
background document.) The Agency has also established a national Interim
primary drinking water standard of .005 ng/1 for toxaphene. (That admini-
strative record is likewise incorporated by reference.)
The wastes are listed as toxic based on the potential for waste
mismanagement and resulting environmental harm. Toxaphene is both mobile
and persistent, having frequently been found in clarified and treated
municipal drinking water.(IB) Existing waste management methods could
lead to release of waste toxaphene. Wastewacers are presently treated
in holding ponds. Waste treatment sludge, if generated, is now disposed
in landfills and unlined lagoons. Disposal In landfills represents
a potential hazard if the Landfill Is Improperly designed at operated.
This can result in leaching of hazardous compounds and subsequent
contamination of groundwater. Disposal in unlined lagoons also represents
a potential hazard since the wastes may leach directly into the ground,
resulting in possible groundwater contamination. Care must be taken to
ensure that the lagoons and landfills used for storage or disposal of
the toxaphene product wastes are properly designed and operated (e.g.,
lined with an appropriate thickness of impervious materials or provided
with leachate collection/treatment systems) to prevent contamination
of groundwater or surface water.
-G03-
-------
Prior to disposal in the "009" landfill, the Hercules plant
treats these wastes in holding ponds which, if not properly designed and
operated, may result in groundwater or surface water contamination. The
high water table and the sandy composition of the soil at the location
of the Hercules plant in Brunswick, Ga.t make careful managment of these
wastes particularly important. (13)
Wastewater treatment sludge could also create a hazard if improperly
managed. Although the sludges appear to be managed properly at the present
time (suggesting that industry regards these wastes as hazardous), proper
management of an otherwise hazardous waste does not make the waste non-
hazardous.
One final reason for regulatory concern is noteworthy. Since
toxaphene bioaccumulates in environmental receptors by factors of as
much as 300,000(7), if only a small amount leaches into the environment,
a serious health hazard would be created. In the soil, toxaphene may
persist from several months to more than 10 years (soil half-life is 11
years, Appendix B). It has also been shown to persist for up to 9 years
in lakes and ponds.(7) Thus, the potential for human exposure is con-
siderable. The potential for substantial hazard is, therefore, very high.
The need for the most careful management of toxaphene-contalnlng
substances is thus well-establilshed. In light of the documented health
and environmental hazards associated with toxaphene, and the fact that
substantial hazard is caused by ingestion of extremely small (ppb) toxa-
phene concentrations, the Agency believes it is justified in listing
this waste.
*It should be noted that Hercules' past effluent management practices hava
not always been adequate, as Hercules has conceded that its past effluent
discharge "'had an adverse effect upon the ecology* of local waters." (18)
-------
B. Health and Ecological Effects
1. Toxaphene
Health Effects - Toxaphene is extremely toxic [oral rat
= 40 mg/kg].(8) Death in humans from ingestion of this dosage has also
been reported. O Toxaphene is also lethal to animals by inhalation and
skin absorption at dosages of 1 g/kg or less.^"'
Toxaphene is carcinogenic in rats and mice, causing a significant
increase in the incidence of thyroid and liver cancers when administered
in the diet, f12^ A significant Increase in liver cancer has been
reported in mice at dietary levels of 50 pom.v*-^'
Toxaphene and its subtractions have been found mutagenic in the
standard bacterial assay ^S. typhinmriumn, strain TA100). (1*>)
Ecological Effects - Toxaphene is extremely toxic to fish, and
toxic to lower aquatic organisms, birds, and wild animals. The 1059
(96-hour) of toxaphene in static bloassays is 3.5, 5.1 and 14 ng/1 for
bluegills, fathead minnows, and goldfish, respectively.^ Toxaphene
is also capable of producing deleterious effects in fish at levels as
low as 0.39 ng/1, and bioaccumulates by factors of as much as 300,000.^7'
Regulations - Toxaphene has an OSHA standard for air, TWA at
500 mg/m^ (Skin, SCP-F). Toxaphene is listed as a priority pollutant in
accordance with §307(a) of the Clean Water Act of 1977. A 0.005 mg/1 EPA
National Interim Primary Drinking Water Standard has been established
for toxaphene.
-------
Industrial Recognition of Hazard - Toxaphene has been rated by
Sax, Dangerous Properties of Industrial Materials^) to be highly toxic
through ingestion, inhalation, and skin absorption.
Additional information and specific references on adverse
effects of toxaphene can be found in Appendix A.
-------
IV. References
1. SRI. 1977 Directory of chemical producers. Stanford Research Institute.
Menlo Park, California. 1977.
2. Proprietary information submitted by Hercules, Inc. to the U.S.
Environmental Protection Agency In 1978 response to "308" letter.
3. Proprietary information submitted by Vicksburg Chemical Company to
the U.S. Environmental Protection Agency in 1978 response to "308"
letter.
4. Meiners, A. F., C.E. Mumraa, T. L. Ferguson, and G. L. Kelso.
Waste water treatment technology documentation for toxaphene manu-
facture. Report prepared by the Midwest Research Institute for the
U.S. Environmental Protection Agency. EPA No. 400/9-76-013. NTIS
PB No. 253 676. February, 1976.
5. Telephone communication to Ms. Jennifer Kaduck, State of Georgia,
Land Protection Branch, Environmental Protection Division, Department
of Natural Resources, Atlanta, Georgia (404-656-2833). From Edward Monnig
of TRW, Inc., on February 28, 1980.
6. Telephone communication to Ms. Jennifer Kaduck, State of Georgia,
Land Protection Branch, Environmental Protection Division, Depart-
ment of Natural Resources, Atlanta, Georgia, (404-656-2833). From
S. Quinlivan of TRW, Inc., on February 12, 1980.
7. U.S. EPA. Criteria document for toxaphene. EPA No. 440/9-76-Okl4.
NTIS PB 253 677. June, 1976.
8. Special Publication of Entomological Society of America. College
Park, MD. Vol. 74:1. 1974.
9. DREW. Clinical Handbook on Economic Poisons. U.S. Dept. HEW, PHS,
CDC, Atlanta, GA. NTIS PB No. 218 287. 1963.
10. Council on Pharmacy and Chemistry. Pharmacologlc properties of
toxaphene, a chlorinated hydrocarbon insecticide. JAMA 149:1135-
1137. July 19, 1952.
11. Chernaff, N. and B.D. Carber. Fetal toxicity of toxaphene in rats
and mice. Bull. Environ. Contam. Toxicol. 15:660-664. June, 1976.
12. National Cancer Institute. Guidelines for carcinogenesls bio-
assays in small rodents. Tec. Rep. No. 1 Publ. No. 017-042-00118-8.
U.S. Government Printing Office, Washington, D.C. 20402. 1977.
-------
IV. References (Continued)
13. Telephone Communications to Ms. Jennifer Kaduck, et al., State
of Georgia, Land Protection Branch, Environmental Protection Division,
Department of Natural Resources, Atlanta, Georgia, (404-656-2833).
From Robert Karmen of EPA, on April 8, 1980.
14. Telephone Communication to Edward Monnig of TRW, Inc. From John Ring
of EPA on April 8, 1980.
15. Litton Bionetlcs, Inc. Carcinogenic evaluation in mice. Toxaphene
Final Report. LBI Project No. 20602. Kensington, MD. Submitted to
Hercules, Inc., Wilmington, Del. Nov. 1978.
16. Hill, R.N. Mutagenicity testing of toxaphene. Memo dated Dec. 15,
1977, to Fred Hageman, Special Pesticide Review Division, U.S.
Environmental Protection Agency, Washington, D.C. 1977.
17. Sax, N. Irving. Dangerous properties of Industrial materials,
4th ed., Van Nostrand Reinhold Co., New York. 1975.
18. Hercules, Inc. v. EPA. 598 F. 2d 91, 99 (D.C. Cir. 1978).
19. Lawless, E.W. Pesticide Study Series -5- The Pollution Potential in
Pesticide Manufacturing, Technical Studies Report; TS-00-72-04.
U.S. GPO, Washington, D.C. 20402. 1972.
-------
LISTING BACKGROUND DOCUMENT
2,4,5-T PRODUCTION
0 Heavy Ends or Distillation Residues from the Distillation of
TetracJ\loro\>emene In the Production of 2,<*,5-T(T)
I. Summary of Basis for Listing
The hazardous waste from 2,4,5-Trichlorophenoxyacetic acid (2,4t5-T)
production cons is to of the heavy ends or distillation residues from the
distillation of tetrachlorobenzene in the first step of 2,4,5-T
manufacture*
The Administrator has determined that the tetrachlorobenzene dis-
tillation heavy ends in 2,4,5-T production may pose a substantial pres-
ent or potential hazard to human health or the environment when Im-
properly transported, treated, stored, disposed of or otherwise nan-
aged, and therefore should be subject to appropriate management re-
quirements under Subtitle C of RCRA. This conclusion Is based on
the following considerations:
1. The heavy ends from distillation of tetrachlorobenzene con-
tain several chlorinated benzenes including hexachloroben-
zene and ortho-dichlorobenzene.
2. Hexachlorobenzene is a reported carcinogen. Ortho-dichloroben-
zene is chronically toxic.
3. Disposal of these wastes in Improperly designed or operated
landfills could create a substantial hazard due to the
migratory potential and environmental persistence of these
hazardous compounds! Both groundwater and surface water
are exposure pathways of concern.
A, Vola.tillzati.cn of the waste tOTvatVtuents from landfills, as has
been documented, could result In the release of hazardous
vapors to the atmosphere and present a significant opportunity
for exposure of humans, wildlife, and vegetation in the
vicinity of these operations to potentially harmful substances,
-------
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
*
-------
•*- TETnACJILOnOOENZENE
MONOCHLOROBCNZCNE.
CHLORINE
nEACTOn
TETnACI ILOnOnCNZHNC
DISTILLATION
COLUMN
HEAVY ENDS
(DISTILLATION
TO LANOPILL
Klgurol. GENEnATlON OF HEAVY ENDS (DISTILLATION BOTTOMS) FROM
TETRACHLORODENZONE MANUFACTURE IN THE 2, 4, 6-T PROCESS (7)
-------
C. Waste Generation and Management
The heavy ends or distillation residues generated in separating
TCB from other chlorobenzene make up the hazardous waste stream
~f concern. These residues are likely to contain all of the benzene
chlorination by-products including those higher than chlorobenzene,
such as ortho-dichlorobenzene and hexachlorobenzene. Further, since
the waste consists largely of heavy chlorinated organic by-products,
concentrations of these constituents will probably be high.
Rased on current industry practice Involving similar wastes,
the distillation residues are probably managed by landfilling.
Disposal may Involve surface placement, uncontained burial, or burial
in barrels in a landfill.
III. Discussion of Basts for Listing
A. Hazards Posed by the Waste
The heavy ends discussed above contain hazardous compound!
which can be expected to pose a serious threat to the environment If
improperly managed or disposed. Among the compounds expected to be
present are hexachlorobenzene and ortho-dichlorobenzene.
Hexachlorobenzene is believed to be carcinogenic and terato-
genic, while o-dichlorobenzene may pose a chronic toxic!ty hazard via
a water exposure pathway.* To warrant a decision not to list this
waste, therefore, the Administrator would require assurance that the
waste constituents are incapable of migration and mobility even it*
improperly managed, and that these constituents will not persist if
they are released into the environment.
* It is projected that o-dlchlorobenzene could create a chronic tox-
Icity hazard If it migrated at several orders of magnitude less thaw
-------
Tr
-------
Hexachlorobenzene may also pose a substantial hazard via an air
Inhalation pathway If landfills are not adequately convered, as shown
by a number of actual damage Incidents. In Hay, 1976, hexachloroben-
zene-contalnlng wastes from a Vulcan plant In Louisiana volatilized
and resulted In the death of cattle grazing In contaminated areas.(39)
A similar case history of environmental damage in which air, soil,
and vegetation over an area of 1^0 square miles were contaminated by
hexachlorobenzene (HCB) occurred In 1972.(3q) There was volatiliza-
tion of HCB from landfllled wastes and subsequent bioaccumulatlon in
cattle grazing in the eventually contaminated areas. Accumulation in
tissues of cattle occurred, so the potential risk to humans from eat-
ing contaminated meat and other foodstuffs is significant.
The waste constituents of concern also can be expected to persist
should they migrate from the matrix of the waste. Hexachlorobenzeue
is very persistent.* (App. B) 0-dichlorobenzzene is subject to cer-
tain degredatlve processes, but would be likely to persist in ground-
water. (App. B.) Hexachlorobenzene, in addition to being persistent,
Is very bioaccumulative, Increasing its likelihood to cause harm
should it migrate. (App. B)
3. Health and Ecological Effects
1. Hexachlorobenzene
Health Effects - Hexachlorobenzene has been shown to be
carcinogenic in animals(l'»20) an(] has been identified by the Agency
to be carcinogenic. This chemical Is reportedly teratogenlc, known
^Evidence of mobility and resistance to degradation has been shown
by identification of chlorobenzene Isoraers In ground water in Florida.
Chlorinated benzenes are likely to persist in the environment and to
bloaccurnulate.
-------
to pass through placental barriers, producing toxic and lethal effects
In the fetus.(21) Chronic exposure to HCB
-------
benzene to rats in small doses has caused anemia as well as liver
damage and central nervous system depression.(28) Additional infor-
mation and specific references on the adverse effects of ortho-dichloro-
'icnzene can be found in Appendix A.
Regulatory Recognition of Hazard - Ortho-dlchlorobenzene
has been designated as a priority pollutant under Section 307(a) of
the CWA. The OSHA standard for 0-dichlorobenzene is 50 ppm for an
8 hour TWA. It has been selected by NCI for Carcinogenesis Bioassay,
September, 1978.
The Office of Water and Waste Management has completed
pre-regulatory assessment of 0-dlchlorobenzene under the Clean Water
Act and the Safe Drinking Water Act. Under section 311 of the Clean
Water Act, regulation has been proposed. The Office of Research and
Development has begun pre-regulatory assessment of 0-dichlorobenzene
under the Clean Air Act.
Industrial Recognition of Hazard - Sax, Dangerous Proper-
ties of Industrial Materials, lists the toxic hazard ratings for 0-di-
chlorobenzene as moderate via inhalation and oral routes.
-------
IV. References
1. Prop: ietary information submitted to EPA by Thoropson-Hayward Chemi-
cal Co. Kansas City, Kansas in 1978. Response to "308" Letter.
2. Not used in text.
3. NIOSH. Suspected carcinogens: A subfile of the NIOSH toxic
substances list. U.S. HEW, PHS, CDC. Available from U.S.
Government Printing Office, Washington, D.C. 20402. June, 1975*
4. Not used in text.
5. Proprietary information submitted to EPA by Dow Chemical Corporation.
Midland, Michigan in 1978. Response to "308" Letter.
6. Proprietary information submitted to EPA by Transvaal, Inc. (Ver-
tac). Jacksonville, Arkansas in 1978. Response to "308" Letter.
7. Gilbert, E. E., et al. U.S. Patent 2,830,083. April 8, 1958; As-
signed to Allied Chemical Corporation. In M. Slttig, Pesticides
Process Encyclopedia. Noyes Data Corporation. Park Ridge, New
Jersey. 1977.
3. Farm Chemicals Handbook. Meister Publishing Company, Wlllough-
by, Ohio. 1977.
9. Not used in text.
10. Mot used In text.
11. Not used in text.
12. Not used in text.
13. Not used in text.
14. Not used in text.
15. Not used in text.
16. Not used in text.
17. IARC Monographs. Evaluation of carcinogenic risk of chemicals
to man. 2,4,5- and 2,4,6-TrIchlorophenol. Inter-Agency for
Research on Cancer. Lyon, France. World Health Organization.
Vol. 20:349. 1979.
18. U.S. EPA. Technical support document for aquatic fate and
transport estimates for hazardous chemical exposure assessments.
Environmental Research Lab. Athens, Ga. 1980.
-fi.17-
-------
19. Cabral, J. R. P., et al. Carcinogenic activity of hexachlorobenzene
in haiiiCevs.. I ox. Appl. Pharnacol. 41:155. 1977.
20. Cabral, J. R« P., et al . Carclnogenesia study in nice with
hexachlorobenzene* Toxicol. Appl. Pharmacol. 45:323. 1978.
21. Grant, D. L. , et al. Effect of hexachlorobenzene on repro-
duction in the rat. Arch. Environ. Con tarn. Toxicol. 5:207. 1977.
22. Koss, G., et al. Studies on the toxicology of hexachlorobenzene.
III. Observations in a long-term experiment. Arch. Toxicol*
40:285. 1978.
23. Gleason, M.N. , et al. Clinical toxicology of commercial products -
Acute poisoning. 3rd ed., p. 76. 1969.
24. Carlson, G. P. Induction of cytochrome P-450 by halogenated
benzenes. Biochem. Pharmacol. 27:361. 1978.
25. Gleason, M.N. , et al. Clinical toxicology of commercial products.
3rd ed., p. 49. 1969.
26. U.S. EPA. Dichlorobenzenes: Ambient water quality criteria.
OTIS PB No. 292 429. 1979.
27. Varshavsakaya , S. ?. Comparative toxicological characteristics of
chlorobenzene and dichlorobenzene (ortho- and para-isomers) in re-
lation to the sanitary protection of water bodies. Gig. Sanlt.
33:17. 1967.
28. Ben-Dyke, R. , D.M. Sanderson, and D.N. , Noakes. Acute toxicity
for pesticides. World Rev. Pest Control 9:119-127. 1970.
29. Not used in text.
30. Not used in text.
31. Not used in text.
32. Not used in text.
33. Not used in text.
34. Not used in text.
35. Not used in text.
36. Not used In text.
37. Office of Public Health, New York State Department of Health.
Love Canal-Public Health Time Bomb. September, 1978.
-------
38. Dawson, English, and Petty. Physical chemical properties of
hazardous waste constituents. 1980.
39. U.S. EPA.. Open files. Hazardous Sic, "ontro' Branch, WH-548,
U.S. EPA, 401 M St., S.W., Washingcou, Li.C. 2',-^60. Contact
Hugh Kaufman (202) 245-3051.
40. Not used in text.
-------
Response to Comments - Heavy Ends or Distillation Residues from
the Distillation of Tetrachlorobenzene in the Production of 2,A,5-T
Heavy ends or distillation residues from the distillation of
tetrachlorobenzene in the production of 2,4,5-T (K042) is listed as
hazardous because It contains a number of chlorinated benzenes
including hexachlorobenzene and ortho-dichlorobenzene. One conmenter
objected to the inclusion of ortho-dlchlorobenzene as a constituent
of concern in this particular listing. The commenter argued that
compounds with an 1050 of 500 mg/kg, the oral 1050 of ortho-dichloro-
benzene, is considered by "lexicologists" to be only slightly or moderately
toxic. The commenter, therefore, recommends that ortho-dichlorobenzene
be deleted as a basis for listing waste K042.
The Agency disagrees with this unsubstantiated conclusion. A
number .of standard references, In evaluating acute toxicity, consider
compounds with an oral U>5o of 500 mg/kg to be "very toxic." For
example, "Clinical Toxicology of Commercial Products", Gleason, et.
al., 3rd Edition, Baltimore, Williams and Wllklns, 1969, considers
compounds which have an oral LD5Q (as determined using rats) in
the range of 50 mg/kg to 500 mg/kg to be very toxic. Additionally,
in the Registry of Toxic Effects, a widely used reference book which
is published by the National Institute for Occupational Safety and
Health (NIOSH), guidelines for evaluating acute* dosages differentiating
relatively toxic from non-toxic substances have been set; the 1.050
*Applles to those substances for which acute or short term toxlclty
characterizes the response.
-------
level in-Heated is 5000 mg/kg. The Agency, therefore, could continue
to include ortho-dichlorobenzene as a constituent of concern in this
particular listing, on the basis of acute toxlcity effects alone.
Furthermore, o-dichlorobenzene is chronically toxic (aee Background
Document, pp. 603-04), a point ignored by the commenter. Listing of
this compound as a constituent of concern is consequently further
Justified.
-------
LB-24
LISTING BACKGROUND DOCUMENT
2,4-D PRODUCTION
2,6-Dichlorophenol waste from the Production of 2,4-D (T)
Untreated Wastewater from the Production of 2,4-D (T)
I. Summary of Basis for Listing
These wastes from 2,4-D production may contain a number
of toxic constituents, including 2,4-dichlorophenol, 2,6-
dichlorophenol, 2,4,6-trichlorophenol and chlorophenol
polymers.
The Administrator has determined that the subject solid
wastes from 2,4-D production may pose a substantial present or
potential hazard to human health or the environment when
improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appropri-
ate management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations:
1. The wastewater generated from the production of
2,4-D contains 2,4-dichlorophenbl, and 2,4,6-trl-
chlorophenol. 2,6-Dichlorophenol waste contains
substantial concentrations of 2,6-dIchlorophenol,
2,4,6-trichlorophenol and 2,4-dlchlorophenol.
2. 2,4,6-Trichlorophenol has been Identified by EPA's
Carcinogen Assessment Group as a substance which
has exhibited substantial evidence of carcinogeni-
clty. It has also been cited in the literature as
being mutagenlc. 2,4-Dichlorophenol and 2,6-di-
chlorophenol are toxic.
3. Management of these wastes in treatment lagoons or
landfills creates the potential for soil or ground-
vater contamination via leaching if mismanagement
ccur s.
-------
IT. Sources of Wastes atid_ Typical Disposal Practices
A. Profile of the Industry
2,4-D is a selective herbi-tH-.- - gist red for -ISE on
grasses, barley, corn, oats, sorghum, wh°at a.id non-crop areas
for post-emergent control of weeds.(?)
1.
2.
3.
B. Manufacturing Process
In the 2,4-D manufacturing process, benzene is
chlorinated to produce monochlorobenzene, which is hydrated to
produce phenol.f^a) Chlorination of phenol also leads to the
generation of by-product 2,6-dichlorophenol and other chloro-
phenols (principally 2,4,6-trichlorophenol).(2a) Figure 1
illustrates an example of this manufacturing process.
C. Waste Generation
1. Generation of 2,6-dichlorophenol waste.
Chlorlnation of phenol inevitably leads to the genera-
tion of by-product 2,6-dichlorophenol and other chlorophenols.^a
As shown ln
-------
SOLVENT
on
CATALYST
*- }.t-DICtlLOftOPHENO(. >
1.4-oian.onopiiCHoi.
TO PENTACllLOnOP! !CNOL
UANUI'ACruilG (UOW)
TO WASTE I
(fttlOtMA AND WWNSVAAl»
Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR 2,4-D
(MODIFIED FROM REFERENCE 1)
-------
Figure 1, 2, 6-dichlorophenol is taken off overhead from
the chlorophenol unit as a by-product. This 2,6-dichlorophenol
by-product TS used in the production of pentachlorophenols
li. ae plant, and therefore is not a waste; in two other
2,4-D plants, the 2,6-dichlorophenol by-product is disposed
of as a waste,* and is included in this listing. This waste
is composed of 2,6-dichlorophenol, 2,4,6-trichlorophenol,
2,4-d.Lchlorophenol, and chlorophenol polymers (see page 5).(8»10)
Various 2,6-Dichlorophenol generation rates have been
reported.
(10)
(8)
2. Generation of wastewater,
*The Transvaal (Vertac) plant does not reuse 2,6-dichlorophenol
as feekstock material, so it is quite likely that this plant
generates 2,6-dichlorophenol waste.
-(0-3.5-
-------
Process wastewater is removed
for treatment. This wastewater, prior to treatment, Is listed
as hazardous. 2,4-Dlchlorophenol Is the Intermediate used In
the production of 2,4-D; some of this chemical becomes entrained
in the wastewater. It Is expected that some quantities of
2,6-dichlorophenol are also carried forward (see Fig. 1).
D. Waste Management
Wastewater from Dow Chemical's 2,4-D unit is first
chemically treated, then passed through a trickling filter on
the way to a central biological waste treatment plant.<2a)
Biological treatment sludges from the production of 2,4-D at
the Dow plant are limestone-treated and disposed in an on-site
landfill. At the Transvaal, Inc. (Vertac) plant, wastewater
goes to a neutralization ditch. ____
(9)
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
-------
(The waste constituents of concern are 2,4,6 trichlor*.
phenol and 2,4 dichlorophenol•)*
. Disposal in
landfills, even .if plastic lined drums are used, could create
a potential hazard if the landfill is improperly designed or
operated (i.e., drums corrode in the presence of even snail
amounts of water). This can result in leaching of hazardous
compounds with resultant contamination of surface and ground
waters.
A similar potential hazard exists when wastewaters from
2,4-D production are impounded in treatment lagoons. The
*0ther waste constituents are not deemed present in sufficient
concentrations to be of regulatory significance.
-------
same hazardous constituents are present In the solids that
will settle to the bottom of the lagoon. The concentrations
of the hazardous constituents in the settled solids are expected
to be much higher than those found In the wastewater Itself,
which obviously contains a much greater volume of water*.
Hazardous constituents may leach from the lagoon bottom to
contaminate groundwater. In addition, possible Incomplete
treatment in biological treatment lagoons may allow these
hazardous constituents to reach the ultimate disposal site,
where the potential for leachate exposure exists.
An example of the consequences which may result when
these wastes are mismanaged occured at the Transvaal, Inc.
plant, which produces 2,4-D, in Jacksonville, Arkansas.
Sludge from 2,4-D manufacture is sent to a chemical landfill
adjacent to the plant. Soil and groundwater near the chemical
landfill havQ been found to be contaminated with toxic chloro-
phenols from 2,4-D manufacture.**
As this incident Illustrates, waste constituents may well
prove mobile and persistent. As to mobility, the chlorinated
phenols present in the waste may undergo bio-degradation in
*Thls indicates that the dredged sludges from lagoons are
not expressly listed here. These sludges are nevertheless
reached by this listing; Section 261.3 of the Regulations
provides that the solid wastes discharged from a hazardous
waste treatment facility are also considered hazardous
unless the generator demonstrates otherwise.
**OSU Hazardous Waste Division, Hazardous Waste Incidents, un-
published open file 1978.
-------
soil If present in low concentrations• ?5 It seems
likely, hovsver, the rates of degradation of these compounds
in the soil profile would be low becaus'e of repression of
coil micrj^iai activity by these and other waste components.
V *so, mismanagement could occur in areas where soil is low
in organic content, so mobility in soil would not be sub-
stantially effected.) All of these compounds also are quite
soluble in water [for 2,4-dichlorophenols-4,500 mg/1 at 25'C
JTIG -,600 mg/1 at 20'C]28 and do not exhibit a high propensity
to adsorb in soils.(25) Hence, they would be expected to
move readily into groundwater. The potential for movement
of these compounds into and through groundwater is Illustrated
'^y a case history in California, where long-term pollution
of groundwater by phenolic substances occurred because of
release Into the soil of water containing 2,A-dichlorophenol
"rom 2,4-D nanufacture.(26) High waste loads such as
landfill dumping would inhibit degradation and therefore
increase the likelihood of adverse environmental effects.
B. Health and Ecological Effects
1. 2(4-Dichlorophenol/2,6-dichlorophenol
Health Effects - 2,4-Dichlorophenol has high
oral toxicity [oral LD5Q (rats) = 580 mg/kg].^12^ In addition,
this chemical promotes DMBA-initiated skin cancer in mice.
It is also reported to adversely affect carbohydrate meta-
bolism .(!*»!5) 2,6-Dichlorophenol is also toxic in animals;
-------
it inhibits liver nitochondrial respiration, and, at relatively
high concentrations affects the nervous system.(29) Additional
information and specific references on the adverse effects
of 2,4- and 2,6-dichlorophenol can be found in Appendix A.
Ecological Effects - Small doses of 2,4-dichloro-
phenol have been lethal to fresh water fish and Invertebrates.(l7)
Regulatory Recognition of Hazard -
2,4-Dlchlorophenol is designated as .a priority pollutant
under Section 307(a) of the CWA. The Office of Water and
Waste Management has completed a pre-regulatory assessment
and proposed water quality criteria for 2,4-dlchlorophenol
under sections 304(a) and 311 of the Clean Water Act. The
Office of Research and Development is presently conducting
a pre-regulatory assessment of 2,4-dichlorophenol under the
Clean Water Act.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, designates a toxic hazard rating of
moderate toxicity for 2,4-dlchlorophenol. However, chlorinated
phenols are designated as highly toxic local and systemic
compounds.
2. 2,4,6-Trlchlorophenol
Health Effects - 2,4,6-trlchlorophenol induced
cancer in mice during long-term oral feeding studies.(18)
This compound has also been identified by EPA's Carcinogen
Assessment Group as exhibiting substantial evidence of
-------
carcinogenicity .(^7) It is acutely lethal to humans
by ingestion at 60 percent of the oral LD5Q dose In rats
[500 mg/Kg] (19) and is mutagenic to yeast,(2°) and
adversely affects cell metaboli sin. <21» 22> Additional
information and specific references on the adverse effects
of 2,4,6-trichlorophenol can be found in Appendix A.
Ecological Effects - Very small concentrations
of 2,4,6-trichlorophenol are lethal to freshwater fish
[LC50 - 426 ug/1]; it is also lethal to freshwater invertebrates
at very low concentrations.(24)
Regulatory Recognition of Hazard - 2,4,6-Trichloro-
phenol has been designated as a Priority Pollutant under
Section 307(a) of the CUA. Based on carctnogenicity, EPA has
recommended 12 ug/1 as the ambient water quality criterion
for the ingestion of fish and water.(28)
Industrial Recognition of Hazard, Sax, in Dangerous
Properties of Industrial Materials, lists 2,4,6-trichloro-
phenol as moderately toxic via the oral route.
-------
REFERENCES
L. U.S. EPA.. Office of Water Programs. The pollution
potential In pesticide manufacturing. NT IS PB No.
213 782. June, 1972.
2a. U.S. EPA. Office c£ Pesticide Programs. Production
distribution, use and environmental impact potential of
selected pesticides. EPA No. 540/1-74-001. NTIS PB Ho. 238
395/9BA. 1975.
2b. Aly, O.M., and S.D. Faust. Studies on the fate of 2,4-D
and ester derivatives in natural surface waters. J_.
Agr. Food Chem. 12(6):541-546. 1964.
3. U.S. EPA. Industrial process profiles for environmental
use, Chapter 3: Pesticides. EPA No. 600/77-023h.
Research Triangle Park, North Carolina. NTIS PB No. 266
255/2BE. January, 1977.
4. Not used in text.
5- Not used in text.
6. Not used in text.
7. Farm Chemicals Handbook. Meister Publishing Company,
Willoughby, Ohio. 1977.
8. Proprietary information submitted to EPA by Rhodia, Inc.,
Agri. Division. Portland, Oregon in 1978 response to
"308" letter.
9. Proprietary information submitted to EPA by Transvaal, Inc.
Jacksonville, Arkansas in 1978 in response to "308" letter.
10. Proprietary information submitted to EPA by Rhodia, Inc.,
on March 7, 1977.
11. Proprietary information from Draft Contractor Technical
report for BAT Technology in the Pesticide Chemicals
industry by Environmental Science and Engineering,
Inc., for U.S. EPA, 1979.
12. Deichmann, W. The toxicity of chlorophenols for rats.
Fed. Proc. (Fed. Am. Soc. Exp. Biol.) 2:76. 1943.
13. Boutwell, R. K. and Bosch. The tumor-promoting action
of phenol and related compounds for mouse skin. Can. Res.
19:413-424. 1959.
-------
14. Farqu'u-raon, M.E. , et al. The biological action of
chlorophenols. Br. Jour. Pharmacol. 13:20. 1958.
15. Mitsuda, W., et al. Effect of chlorophenol analogues on
the oxidative phosphorylatlon In rat liver mitochondria.
Agrlc. Blol. Chem. 27:366. 1963.
16. Not used In text.
17. U.S. EPA. In-depth studies on health and environ-
mental impacts of selected water pollutants. Contract
No. 68-01-4646. 1978.
18. NCI. Carcinogenesis bioassay, 2,4,6-trichlorophenol.
NTIS PB No. 223 159. Sept. 1978.
19. Gleason, M.N., et al. Clinical toxicology of commercial
products, 3rd ed. Williams and Wilkins, Co. Baltimore.
1969.
20. Fahrig, R. et al. Genetic activitiy of chlorophenols and
chlorophenol impurities. Pg. 325-338. In; Pentachlorophenol:
chemistry, pharmacology and environmental technology.
K. Rango Rao. Plenum Press, New York. 1978.
21. Weinback, E. C., and J. Garbus. The interaction of uncoup-
ling phenols with mitochondria and with mitochondrial
protein. Jour. Biol. Chem. 210:1811. 1965.
22. Mitsuda, H., et al. Effect of chlorophenol analogues on
the oxidative phosphorylation in rat liver mitochondria.
Agric. Biol. Chem. 27:366. 1963.
23. Not used in text.
24. Not used in text.
25. Kozak, V.P., G.V. Simmons, G. Chesters, D. Stevsby,
and J. Harkins. Reviews of the environmental effects
of pollutants: XI Chlorophenols. EPA No. 600/1-79-012.
U.S. EPA. Washington, D.C. pp. 492. 1979.
26. Slnenson, H. A. The Montebello incident. Proe. Assoc.
Water Treatment and Exam. 11:84-88. 1972.
27. U.S. EPA. Carcinogen Assessment Group, Offfrf'^f Research
and Development. List of Carcinogens. April 22,-1980.
-------
M.S. EPA. Ambient water quality criteria for trichloro-
phenols. EPA 440/5-80-032. 1980.
29. Chung, Y. Studies on cytochemical toxicities of chloro-
phenols to rats. Yakhak Hoe Chi. 22:175. 1978.
-------
Response to Comments - 2 ,6-Dichlorophenol Wast* from
the Production of 2,4-P
One commenter raised several questions viLh resract to waste
K043 (2,6-Dichlorophenol waste from the production of 2,4-D).
1. 2,6-Dichlorophenol waste from the production of 2,4-D
(K043) is listed as hazardous because it contains
substantial concentrations of 2,6-dichlorophenol,
2,4,6-trichlorophenol and 2,4-dichlorophenol. The
commenter objected to the inclusion of 2,4-dichloro-
phenol as a constituent of concern in this particular
listing. The commenter argued that compounds with an
LDjQ of 580 mg/kg, the oral LD50 of 2,4-dichlorophenol,
is considered by toxicologists to be only slightly or
moderately toxic. The commenter, therefore, recommends
that 2,4-diehlorophenol be deleted as a basis for listing
waste K043.
The Agency disagrees with this unsubstantiated conclu-
sion. A number of standard references, in evaluating
acute toxicity, consider compounds with an oral LI>50
of 580 mg/kg to be "toxic". For example, "Clinical
Toxicology of Commercial Products", Gleason
et. al., 3rd Edition, Baltimore, Williams and Wilkins,
1969, considers compounds which have an oral LD5Q (as
determined using by rats) in the range of 500 mg/kg to
5,000 mg/kg to be toxic to moderately toxic; however,
-------
it should be noted that 2,4-dichlorophenol is at the
higher end of the range and would tend to be considered
toxic rather than moderately toxic. Additionally,
in the Registry of Toxic Effects, a widely used
reference book which is published by the National
Institute for Occupational Safety and Health (NIOSH),
guidelines for evaluating acute* dosages differentiating
relatively toxic from nontoxlc substances have been set;
the LDso level indicated is 5,000 mg/kg. The Agency,
therefore, could continue to include 2,4-dichlorophenol
as a constituent of concern in this particular listing,
on the basis of acute toxlcity effects alone.
Furthermore, 2,4-dichlorophenol is chronically
toxic (see Background Document pp. 8-9), a point ig-
nored by the commenter. Listing of this compound as
a constituent of concern is consequently further Justified.
The commenter pointed out that EPA's Health and Environ-
mental Effects Profile on "Chlorinated Phenols" contains
only a general discussion of chlorinated phenols, and that
data on the specific dichlorophenols is lacking. While the
Health and Environmental Effects Profile on "Chlorinated
Phenols" does not contain a great deal of toxicity data
^Applies to those substances for which acute or short term
toxicity characterizes the response.
-------
on the dichlorophenols, the health and ecological effects
of the dichlorophenols are discussed more fully In the
specltic listing background document on 2,4-D production.
As tuere Indicated, both 2,4-dichlorophenol and 2,6-dl-
chlorophenol are toxic and 2,4-dlchlorophenol Is carcinogenic
(based on studies in which the skin of mice is exposed
to the chemical in small doses). The Agency, however,
c,ill modify the Health and Environmental Effects Profile
on Chlorinated Phenols to include more of a discussion
on the dichlorophenols.
3. The commenter argues that no direct mention Is made of
the degradability or adsorptive properties of 2j4-
and 2,6-dichlorophenol in the listing background document
on 2,4-D production despite the conclusion for both
compounds that "the potential for degradation or
elimination is high and movement is projected to be
limited." (BD-13 at 209, 215 respectively.)
The Agency strongly disagrees with the commenter. In
a number of places in the listing background document,
the degradabi11ty/persIstence , adsorptive properties
and nobility of these compounds are discussed. For
example, on pp. 7 and 8, several damage incidents were
discussed which illustrate groundwater contamination and,
thus, confirms empirically the mobility and persistence of
-------
these compounds. A discussion on the low degradability
of these compounds in soils is also included on pg. 8.
Finally, in determining the solubilities of the dichloro-
phenols, the Agency found that their water solubilities
are significant [e.g., 4,500 mg/1 at 25'C and 4,600 mg/1
at 20°C for 2,4-dlchlorophenols1 and that in groundwater
(where photodecompositlon is absent) these compounds
would be expected to migrate and persist. With respect
to the commenter's quote cited from BD-13, the Agency
finds that the quote does not even relate to chlorinated
phenols.
4. The commenter took objection to EPA'a assertion that
"very snail concentrations" of 2,4,6-trIchlorophenol
have been lethal to freshwater fish (LC5f)-426 mg/1).
The commenter maintains that at this level, the chemical
is virtually non-toxic.
Upon scrutiny of this comment, the Agency reaffirms
its position on the aquatic toxicity of 2,4,6-
trichlorophenol. EPA1a Draft Ambient Water Quality
Criteria Document for Chlorinated Phenols (1979)
reports that the LC^n value for 2,4,6-trichlorophenol
is 426 ug/1. This value is three orders of magnitude
less than that stated by the commenter and is con-
sidered quite toxic. Relative to this, the Agency
notes that an error was made in the listing background
-------
document in reporting the LC5Q value of 2,4,6-trichloro-
phenol as 426 ng/1 (pg. 10). The Agency will correct
this typographical error.
Based on the forgoing discussion, the Agency will continue
to list waste K043 (2,6-dichlorophenol waste from the production
of 2,4-D) as hazardous and include 2,4-dichlorophenol, 2,6-
dichlorophenol and 2,4,6-trichlorophenol as a basis for
listing.
-------
Explos ives
-------
SJ-35-01
LISTING BACKGROUND DOCUMENT
EXPLOSIVE INDUSTRY
Wastewater Treatment Sludges from the Manufacture and Processing
of Explosives (R)
Spent Carbon from the Treatment of Wastewater Containing
Explosives (R)
Wastevater Treatment Sludges from the Manufacture, Formulation
and Loading of Lead-Based Initiating Compounds (T)
Fink/Red Water from TNT Operations (R)
I. SUMMARY OF BASIS FOR LISTING
Explosives manufacturing produces wastewatere which are
often sent to treatment facilities; the resulting wastewater,
spent carbon, and/or wastewater treatment sludges resulting
from the production of explosives have been found to contain
explosive components which can pose an explosive hazard; one
of the listed wastes contains the toxic heavy metal lead,
and therefore, poses a toxicity hazard. The Administrator
has determined that the explosives industry generates 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 therefore should be subject to appropriate management
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1. Wastewater treatment sludges from the manufacturing and
processing of explosives con fa In significant concentrs• 'ons
of explosive compounds which could pose an explosion hazard.
-------
If improperly managed, this waste could thus present a
substantial hazard to human heal;1' ?ni '.'ne environmft.it.
Therefore, this waste meets the reactivity characteris-
tic (§261.23).
Spent carbon columns from the treatment or wastewater
containing explosives are saturated with explosive com-
pounds (i.e., RDX, TNT, etc.). This waste, if improperly
managed, could pose a substantial health and environmental
hazard due to the explosive potential of the constituents
in this waste. Therefore, this waste meets the reactivity
characteristic (§261.23).
Wastewater treatment sludges from the manufacture, formu-
lation, and loading of lead based initiating compounds
contain substantial concentrations of the toxic heavy metal
lead. The lead is in a relatively soluble form, and could
migrate from the disposal site into groundwater. Therefore,
if this waste is improperly managed and disposed, it could
pose a substantial hazard to human health and the environ-
ment .
Pink/red water from TNT operations contains high concen-
trations of the explosive compound TNT. If improperly
managed, this waste could thus present an explosive
hazard, resulting in a substantial hazard to human health
and the environment. Therefore, this waste meets the
reactivity characteristic (§261.23).
II. OVERALL DESCRIPTION OF INDUSTRY
The explosives industry is comprised of those facilities
engaged in the manufacture and load, assemble, and pack (LAP)
of high explosives, blasting agents, propellents, and initiating
compounds. High explosives and blasting agents are substances
which undergo violent, rapid decomposition upon detonation by
heat, friction, impact or shock. Initiating compounds, on the
other hand, are used to initiate or detonate large quantities
of less sensitive propellants or explosives.
Explosives are manufactured in both the commercial and
-------
military sectors. Those companies (approximately 40) chat
commercially manufacture explosives are situated geographically
in 104 facilities* located in 30 states throughout the country.
-.e states with the greatest number of facilities are
California, Utah, Missouri, and Pennsylvania. The military
sector of the explosives Industry is segregated into two
groups: Government Owned and Contractor Operated (GOCO) plants
and Government Owned and Government Operated plants (GOGO).
The number of military plants in these two segments is
estimated to be between 23 and 35. The states with major
GOCO installations are Tennessee, Wisconsin, Virginia, and
Illinois.
Approximate production ranges of individual explosive
products are grouped below:
Production (average daily production
Production Range while operating in Ib/day)
Manufacture of Explosives 1,000 to over 40,000
Manufacture of Propellents 200 to over 30,000
Manufacture of Initiating under 1 to over 300
Compounds
According to the U.S. Bureau of Mines', total consumption
of explosives and blasting agents in 1978 was approximately
1.8 million metric tons. This figure only represents domestic
sales by commercial producers. Production of explosives by
*The Bureau of Alcohol, Tobacco and Firearms lists 621 explo-
sj.ve manufacturers, including licensees and permittees for
manufacture of explosives, distributors, users and mix and
blend operators (LAP).
-y-
-------
the military sector is not currently available.
In terms of growth, total commercial consumption of
explosives and blasting agents has increased each year over
_.ie 1973-1978 period. Consumption has risen from approximately
1.3 million metric tons in 1973 to 1.8 million metric tone in
1978, representing an increase of 38 percent.
Out of the total 1978 consumption figure, consumption of
"pernlssibles11* and "other high explosives" were approximately
19,000 metric tons and 81,000 metric tons respectively. Over
the 1973-1978 period, consumption of permissibles has fluctuated
from year to year; in 1978 consumption was approximately 7
percent less than in 1973. However, consumption of permissibles
is expected to increase in the future due to increased coal
mining activity to satisfy energy demands. Over the sane
five year period, consumption of "other high explosives" has
declined each year; in 1978 consumption was approximately 32
percent below 1973 levels. This downward trend is largely
attributable to the increase use of water gels (permissiblee
in a slurry form).
A. Manufacturing Process**
For the purpose of discussing specific manufacturing
processes, explosives can be subcategorized into the following
three groups: explosives manufacturing (for example, TNT and
*High explosives approved by the U.S. Bureau of Mines for the
Safety and Health Administration for use in underground coal
mines.
**This document describes only a few processes in the explosives
Industry. For a more detailed description, see Reference 22.
-------
RDX), explosives processing (for example, dynamite and
nitrocellulose-base propellents) and initiating compounds
(for example, lead azide).
Explosives Manufacturing
Most explosive compounds are manufactured in a nitration
reaction. The raw material varies, but always Includes a.
nitrating acid, usually nitrfc acid or a mixture of nitric
and sulfuric acids or nitric and acetic acids with various
organic compounds (i.e., toluene, cellulose, glycerin, etc.).
The major explosives produced are nitroglycerine (NG), nitro-
glycerine ethylene glycol dinltrate (NG/EGDN), pentaerythritol
tetranitrate (PETH), nitrocellulose (NC), trinitrotoluene (TNT),
cyclotrimethylene trinitramine (RDX), and cyclotetramethylene
tetranitramine (HNX) (see Table 1). Figures 1 and 2 represent
typical production diagrams for NG and RDX, respectively.
Explosives Processing (Dynamite and Propellents)
Two types of explosive processes will be discussed below
as examples; dynamite and nitrocellulose-base propellents.
Dynamite - Dynamite formulations are usually composed of
several dry ingredients in varying proportions and nitro-
glycerin (see Tables 2 and 3). In the formulation of
dynamite, all ingredients except for nitroglycerIn and/or
ethylene glycol are premixed in batch dry blenders in
buildings called "dope houses". The dope and the nitro-
glycerine and ethylene glycol are then batch blended in
the mix house. The mix is transported to packaging
-------
houses whers they are loaded into waxed c?rdboard box*s
or plastic tubes.^
Nitrocellulose-Based Propellants
Nitrocellulose-based propellants can be divided Into single,
double, and multi-based propellants. These propellents are
made by colloiding and molding processes not unlike those
used in the plastics industry. Single base propellants are
compositions consisting mostly of nitrocellulose with minor
amounts of plastlcizers, stabilizers, burning rate catalysts,
etc. Double base implies nitrocellulose plus a liquid nitrate
ester, usually nitroglycerin, with stabilizers, catalysts,
etc.; and multi-base implies a combination of several nlticatc
materials such as nitrocellulose, nltroglycerin, nitroguanidine,
triethyleneglycol dinitrate, with stabilizers and the like.26
Initatlng Compounds
Initiating compounds are manufactured by nitrating the
starting materials (see Table 4) and precipitating the
explosive. The three general steps are: (1) reacting the
starting ingredients and precipitating the product in a
kettle; (2) filtration; and (3) washing the product to
remove Impurities. Typical initiating compounds include
tetracene, trinltroresorcinol (TNR), lead azlde, lead
styphnate, lead monomltroresorclnate (LMR), tetry and nitro-
mannite. Figures 4 and 5 are typical flow diagrams for the
production of initiating compounds, illustrating typical
lead azide and lead raononitrorescorcinate production schema-
tics respectively.
-------
B. Waste Generation and General Description
Four solid wastes generated in the explosives industry have
been identified and are described below. The production and waste
treatment methods which generate these wastes are not usually found
in any single facility.
Wastewater Treatment Sludges from the Manufacturing
and Processing of Explosives*
Sludges are generated when wash waters pass through settling
or catch basins or screens to remove particulate explosive residues
Some, but not all of the concentrated sludges are returned to the
process. For clarity, explosive manufacturing and explosive pro-
cessing will be discussed separately.
Explosive Manufacturing
As illustrated in Figures 1 and 2, during the manufacturing
of explosive compounds, wastewaters are generated during the
filtration/washing and the cleaning of the production equip-
ment and facilities. Such wastewaters consist of particles
of the explosive compound suspended in the wastewater along
with solvents and cleaning agents. The particles of explo-
sives are removed by gravity separation in catch basins or
settling tanks. The resulting sludges contain significant
concentrations of the explosive compound (i.e., nitro-
glycerine, TNT, RDX/HMX, etc.). While some of these sludges
may be recycled back to the process, they are generally too
*Catch basin materials in RDX/HMX production was proposed as
a hazardous waste on December 18, 1978 (43 FR 58959). This
waste stream will not be listed in the final regulations since
it is already incorporated in this listed waste stream.
-------
lriaced with extraneous material to be reused. These .
sludge 5 constitute the first listed waste stream and are
marked T in Figures 1 and 2.*
Explosive Processing (e.g., blasting agents and ordinance)
During the processing of explosive compounds into commercial
and military explosive agents and propellents, wastewaters
containing explosive compounds are produced during several
operations. Among these operations are the following:
0 Cleaning of blending, packaging and handling equip-
ment and storage facilities;
0 Wet milling of propellant castings;
0 Operation of air pollution control devices which
employ wet scrubbers to control emissions and
dust inside production buildings;
0 Loading, assembling and packaging of ordinance.
Treatment of these wastewaters also produces a wastewater
treatment sludge.(14)
Spent Carbon from the Treatment of Explosives Containing
Wastewaters
Because of the potential hazard that might result from
the discharge of wastewater contaminated with explosives,
a number of military installations employ carbon treatment
*The other waste which is generated (as shown in Figures 1 and 2}
consists of spent acid solutions resulting from the nitration
step. Acidic wastes are usually recovered for reuse following
acid reconcentrat ion or reprocessing. Presently, the Agency does
not have any data to justify listing this waste. However, if these
spent acids are hazardous as defined in Subpart C of Part 261, the
generator would be responsible for managing these wastes under the
Subtitle C regulatory control system.
-------
of these wastewaters, which result from the loading, assembling,
and packaging operations. This treatment is designed to
remove organic contaminants (including those that are explosive)
from the wastewater after the initial settling (see Wastewater
Treatment Sludges from the Manufacturing and Processing of
Explosives).
During carbon treatment, the aqueous waste is passed
through chambers or columns containing activated carbon. The
explosives and other organic contaminants are then abosrbed
into the carbon. After the carbon becomes saturated, it is
removed from the chamber or column; fresh carbon is then
added and the spent absorbent discarded. At this point,
the carbon contains high concentrations of explosive com-
pounds .
Wastewater Treatment Sludges from the Manufacture, Formulation
and Loading of Lead-Based Initiating Compounds
During the various stages in the manufacture and
formulation of lead-based initiating compounds and their
fabrication into finished products, wastewater contaminated
with the Initiating compounds and their feedstock is produced.
These wastewaters are treated in a catch basin and the re-
sulting sludges treated with either sodium hydroxide or heat
to remove any residual explosive material. However, while
this process removes any possible reactivity hazard, the
sludge still contains substantial quantities of leachable
lead.
-------
Pin«.,'aeu ..'..t.t.. L^.® ib£ Operations
During the production and formulation of TNT and TNT-
containing formulations and producti, % ••• *l.»line, red-colored
aqueous waste is generated. This w?? . icre-a is compose! of
TNT purification filtrates, air pollution control scrubber
effluents, washwater from cleaning of equipment and facilities,
and washwater from product washdown operations (e.g., cleaning
of loaded shells prior to packaging). The pink or red
coloration of the waste stream results from contaminacion of
the water with traces of TNT (solubility of TNT in water is
1 mg/liter). Red water is more concentrated, and thus more
contaminated than the pink water.
C. Quantities of Waste Generation
It is estimated that the total amount of hazardous waste
generated by all commercial and GOCO facilities is approximately
21,500 tons (19,350 metric tons dry basis) per day.5 Approxi-
mately eight percent of the waste is from commercial sources
and 92 percent is from military and GOCO sources (Table 5).
IV. CURRENT DISPOSAL PRACTICES
Current disposal practices for the four listed wastes may
be summarized as follows:
* Wastewater treatment sludges from the manufacturing
and processing of explosives.
In explosives manufacturing, the wastewater treat-
ment sludges removed from the manufacturing of explosives
are typically disposed of by open burning. Some plants,
however, make use of percolation/evaporation ponds for
-------
final disposal of compounds like NG, where the liquid
leaches into the ground. Another technique employed by
some plants is the discharge of wastewater to earthen
sumps where, twice a year, the sumps are allowed to dry
up and the sediments decontaminated for residual NG and
DNG (dinitroglycerin); decontamination usually Involves
placing the explosives on the bottom of the sump and
detonating the explosives.
0 Spent carbon from the treatment of wastewater con-
taining explosives
At present, the spent carbon are typically disposed
of through open burning or incineration.
0 Wastewater treatment sludges from the manufacture,
formulation and loading of lead-based Initiating
compounds •
The wastewater treatment sludges are treated by
boiling and/or the addition of a caustic solution,
usually sodium hydroxide and aluminum, to decompose any
residual explosive compounds. After treatment, the
sludges are sent to a lagoon. The sludges from the
lagoons are removed every few years and disposed of in
a landfill.(*) In some cases, however, the sludges
from the sumps and storage tanks will be sent directly
to a landfill after treatment.
0 Pink/red water from TNT operations *
*The Agency Is aware that under full production, AAP's have
used the rotary kiln to incinerate pink and red water.
However, presently the Agency does not have adequate information
on the residual ash to warrant a listing.
-------
Disposal practices that have been used Include
the placing of pink/red water in evaporation ponds.*
v. DISCUSSIOM OF BASIS FOR LISTING
A. Hazardous Properties of the Wastes
Solid waste materials generated by the explosives
industry contain a number of explosive components which, if
improperly managed, could pose a substantial hazard to human
health or the environment. Data presented in Tables 7-10
support the listing of these waste streams.
1. Wastewaters generated from the manufacturing and
processing of explosives have been found to contain
significant concentrations of explosive compounds
such as nitroglycerine, nitrocellulose, TNT, RDX, HKX,
and other nitrated compounds (Table 7). These explo-
sives are highly sensitive to impact, heat, and friction.
Most of these compounds are relatively insoluble in
water (see Table 6); thus they are expected to settle-
out of the wastewater and be present In the waste-
water treatment sludges. The presence of these ex-
*The disposal of pink/red water in evaporation ponds generates
a bottom sludge which is typically removed and open burned.(22)
These sludges are Included in the first listed waste stream
(i.e., "Wastewater Treatment Sludges from the Manufacture and
Processing of Explosives." The industry practice of open burn-
Ing these wastes is employed because it is by far the safest
method of handling these highly reactive wastes. This cautious
disposal practice- by the industry substantiates further the
hazards posed by these wastes if they are not properly disposed
of and managed.
-------
plosives in the sludges pose a substantial explosive
hazard to human health and the envrionment; therefore,
this waste meets the reactivity characteristic (§261.23).
2. The spent carbon, when wasted, are saturated with
high concentrations of explosive compounds (i.e., TNT
and RDX) (Table 8). These compounds are highly reactive/
explosive, and thus, the presence of these explosives
in the spent carbon would thus pose a substantial hazard
to both human health and the environment; therefore, this
waste would meet the reactivity characteristic (261.23).
3. Wastewater treatment sludges from the manufacture,
formulation, and loading of lead based initiating com-
pounds have been shown to contain significant concentra-
tions of lead (Table 9). This waste, if improperly
managed, could pose a substantial hazard to human health
and the environment. Typical Industry disposal of this
waste is in a landfill, which, if subjected to an acidic
environment, will certainly enhance the solubility of lead
and other heavy metals, since their solubility is pH de-
pendent (i.e., solubility increases as the pH decreases).
The hazard associated with the leaching of lead from
Improperly designed and operated landfills is the migra-
tion of this contaminant into ground and surface waters.
Thus, if solids are allowed to be disposed of In areas
with permeable soils, the solubllized lead could migrate
from the site to an aquifer. Surface waters may also
become contaminated if run-off from the landfill is not
-------
controlled by appropriate diversion 5,:siems.
Compounding this problem, arc* ^.n important considera-
tion for the future, Is the fact that should the lead
escape from the disposal site, it will not degrade with
the passage of time, but will provide a potential source
of long-term contamination.
4. Finally, red and pink water from TNT operations have
been shown to contain significant concentrations of TNT,
which Is an explosive (Table 10). These compounds are
also highly reactive/explosive , and thus, the presence
of TNT In the pink/red water would also pose & substantial
hazard to both human health and the environment; therefore,
this waste would meet the reactivity characteristic ($261.23).
B. Health and Environmental Effects
Lead is a toxic compound that could threaten the health
of bath humans and other organisms. The hazards associated
with lead include neurological damage, renal damage and
adverse reproductive effects. In addition, lead is carcino-
genic to laboratory animals, and relatively toxic to fresh-
water organisms. It also bloaccumulates in many species.
Additional information on lead can be found in Appendix A.
Hazards associated with exposure to lead has been
recognized by other regulatory programs. For example, Congress
designated lead as a priority pollutant under $307(a) of the
Clean Water Act and an interim drinking water standard of
0.05 ppm has also been promulgated by EPA. Under *»6 of the
-C.55-
-------
Occupational Safety and Health Act of 1970, a final standard
for occupational exposure to lead has been established.(23,24)
Also, a national ambient air quality standard for lead has
been announced by EPA pursuant to the Clean Air Act.'*4)
In addition, final or proposed regulation of the states of
California, Maine, Maryland, Massachusetts, Minnesota,
Missouri, Hew Mexico, Oklahoma and Oregon define lead con-
taining compounds as hazardous wastes or components thereof.'25)
-------
GUCIHIII
ISfllYLGME
GLYOOL
I I
T1
T
TJHAVI1Y
SLPAIIAIOH
IIG SPLHT
ACID
in;
ACID
(TO ULCD.YIJ11I
IIAIIK
i
\iAr.u
1AIIK
•ncumiiiii in;
CAHROIIAK
1
IICUIRALUF.lt
1AHK
rn(s)
t
i
1AIIR
I. HASrt SLUDGE
(10 TBlAlHEHI/DlSroSAL)
\
run
Figure 1. Schematic Flow Diogrom for NG Production
Souroat (5); Figure 5-31» pg. 520.
-------
AlillYdnOUS AltlQKIA
mime AC iw
ACUICACIO
ACIIIC AMHTOIUOl
. NlIAIItlll
HAun YAi'on
1
CYAPOnAMOII
IlKlj/liu^in,
- --
HU1HG AllU-
ACt TIC AltliTDRtllC
do ncusc)
"cwvctiiir,"
ACIIIC
AlllltUHIDC
iiuTAi)ijif / *" —
AUMC AC 10
1
(U
(to must I
,_
-. L -
'!')'* ACt MC
ACID
i
(ttumtr (in PAiift noil}
HllRAflOfl
cnuuc mix
(siuimrj
rilfRAtlOII
MAMIIHG
NUMART riUHAIC
(601 ACUIC AC III:
Z-Jl IHlOj)
I -MASUWAUft
1 RIUUlCHAIlAIIOri
ill ».Ar.oou)
Ati.ottioric
lllMIUAflliri
(IX IIIIQ AIIIITIHIIIIK AlIkllUA LI
i * IH) IIUISU
lltUtnALIIAUQlt
CAUSIIC Ml
_, AitniiiA
HUOYUIT
1(1%
tn ACL
601 ACIIIC
ACIU
IIC ATttl
SI CVUIIARY
IICUiaALItAllON
riutvuu
tYAPOHAI (Oil
_ _ i nri/A re n ini* *
CRTSIAUUntlOll)
runirico
irofi uu
cxnosiv
-^-lUOII FOWULAI
nox
IN
c
I0f()
"SLUHct" (coiHAiiuiiG nnx)
nox
ctciont
StfAltAl IQIt
nox
CftYSTALUZATIOfl "
*^
(SOIL
rnn rcnniiiin)
llftUII
• nccovcnco nnx
(IU fILinAtlOfl/UAJIIIHO)
Figure 2 Schematic Flow Diagram for ROX Production.
Source (5)i Figure 5-32, pg. 5-123.
-------
SINGLE-BASS
[SOLVENTS
-------
WATER
LEAD
NITRIC ACJD
PRECIPITATOR
KILL TANK
DISCHARGE
WATER
ft
-P- .PPT IEAD CARBONATE
Figure 4. Ivpical Lead Azice ?rccuctico Scheretic.
Source: (2); Figure IV-3, pg. 53.
-------
NaOH
f,',MR LEA
Jj I
LEAD NITRATE
REACTOR TUB
REACTOR TUB
EXCESS WATER
1 WATER WASH
2 ACETONE WASH
3 AMYLACETATE WASH
WASK.F1LTER
•*- AMYLACETATE WASH
CAUGHT AND BURNED
L
V.'ATER WASH WASTE
ACETONE WASH WASTE
Figure .5. IV'pical Lead Jtons^trcreseorcis&ie Production Sciienatic
Source: (2> ; Figure IV-10, po. 57.
-------
VII. TABLES
-------
Material (s)
Nirratirg ^rLd
.-^ditives
glvcszriise
nitric acid a.«vi
sulfurlc aric
glycsrins
ethvlene clycol
rdtric pr?t3 and
salfuric acid
ethvl acetate
PEIS
pentaerythritol nitric acid
ecetons
KC
cellulose
nitric f^'* diiutyl phthalita
salfuric acid phenylanine
nitric add and
acetic j-7>'
acetic anhycride
ccrrcoiim nitrste
cydchexanceie
acetcne
TNT
toluene
nitric P~\& sodiun sulfite
and sulfuric acid
-------
TftSIS 2. CCMKCN INGSEDIZNIS CF D2C2E— i
Nitrcglycedn
Earitra sulf ate
tenccira nitrate
fcrmiua chlcrioe
Sociira nitrate
Scdiua chlcrixie
Caldua stearate
•Su2fur
Kitrceellulose
Phenolic resin or glass besds
Bagasse
Sawdust and vncd flour
Coal
Com Tpo"? and corn stares
Xncrcanib salts
Grain* end seed hnT's and flours
Soerce: (4J page H-2.
TR3LS 3. Ti?ICRL CCMPCSmCN CF
ecmoniua nitrate 50-55
nitroglycerine ^*&
sodixa nitrate 0-17
cf Uf tsace ij^redients 10-35
Source: (11) Table 1, pg.30.
-------
MS23IAIS sea
Tetracene
styphnatfi
Nirranannits
IKS.
Tetryl
icins "zicarbanate, sulfcric acid,
scdiua n
Jtesorcinol, suifuric acid, r-itzic acid
Socira arics, leaf, nitrate or lead acetate,
nitric acid, scdi:=a nitrate
TNR, irecriesi\=i cxide, lead nitrate
Mannitol, salf-jric acid, nitric acid
irfl hydroxide^
lead nitrate
Nitric acid, sulfurlc acid, dineti
-------
TJVDLB 5; - EXPICSIVKS*
Industrial Hafirdous Mute Quantities by Disposal Htlhod
Industry Scqncnl
•
Private Exploslvei Industry:
j
1 Government Owned, Contractor
Operated (COCO)
(iploslves Industry:
1
1
tiplosUei IniKiilry
t Grand Totals
Vatic lype
Fined high explosive wtjle
ftUtllng igcnlt
SubtoltU
Explosive H«ile»
t»plo\1ifc conlamlntUd
tntrl wnlei
Olher hanrdoui wastes
SubloUli
Total Iliiaritaut Waste
lonnes/Tear. 19/7 (Dry BasU)
J ~*6<>
-t.ZOO
-1.700
f-'S.SOQ-Mel Basts)
4.900
H.roo
?4JQ
>t.ioo
>1.SOO
4.000
13,700
no
IB, 600
20.100
UnrfnUt*
Ke^llglble
Kein^lble
negligible
1.000
HO
t.MO
1,110
Sold 1 Othcrc
j
<5
ill
-------
T~rrr- a
^J~ : ' f, O
<% FACTORS FOR ZXPICSB7Z C2CCO2S
KG
Soluticn
water
water
0.14 g/lOOg
0.24
TerperEt^re
25*C
S06C
water
acerone
ethyl ether
water
0.68 g/lOOg
very( soluble
very soluble
insoh±ile
20eC
2SeC
wat
insoluble
azice
Kitzunannite
Lead
water
water
water
cthaasl
ether
0.02 s/100g
0.09 s/100g
insolnble
2.9 s/lOOg
4 g/lOOg
18CC
70°C
13"C
9°C
water
O.D4 s/100g
-------
1.
TABLE 7.
Wastewater treatment sludges from the manufacture
and processing of explosives (R)
Process
Nitration of cellulose
(Note: nitrocellulose
is used in a number of
industries)*'
Nitrocellulose
(NC) Production5
Nitroglycerin (NG) production5
Nitroglycerln production^
TNT production^
Nitrocellulose production'
Batch Nitroglycerin Production7
Combined wastewater of Radford
AAP continuous NG Nitration and
Spent Acid7
Waste (Concentration^
Sludge (25Z water and
75Z nitrocellulose) at
60 ton/yr at one plant
NC fines lost in overflow
will be picked up In settle
basin or other waste water
sludge and is estimated at
1 metric ton (2200 Ibs) per
day per line or about 0.072Z
of NC output.
NG lost to waetewater at
0*006 kg per Kg NG produced
NG discharges In wastewater:
as high as 1000 mg/1
100 mg/1 of TNT to vastewater
NC fines can produce level* of
solids from 1000 to 10,000 og/1
Wastewater (315 to 12,700 ppm)
Nitroglycerln In wastewatet
(800 to 1,800 ppm)
RDX/HMX production7
Catch basins remove 33
percent of RDX and 62
percent of HHX from
-------
TABLE 8.
Spent carbon from the treatment of wastewater containing
explosives (R)
jcess
LAP Melt loading of
.105mm Cartridge*
LAP 40mm Cartridge^
Waste (Concentration)
Composition B* washings
to Carbon Columns at a
rate of 3.64 kg per 10,000
loaded rounds
Composition B to Carbon
Columns at a rate of 0.45
kg per 10,000 loaded rounds
*Composition B--60% RDX. 39X TNT, 1% Wax
-yt-
-------
TABLE 9.
4. Wastewater treatment sludges from manufacture, formu-
lation and loading of lead based Initiating compounds (T)
Process
Initiating Compounds1'
1 Q
Initiating compounds '
Initiating Compounds19
Production of lead azide
and lead styphnate^
Waste (Concentration)
Aqueous waste containing
0.3% Pb @ at one plant
that produced 300 M gal
per year
Precipitate 100%. Pb C03,
one plant produced 1 ton
per year.
Aqueous Waste (Pb 1.2 ppm)
one plant producing 12.5 M
gal/yr
200 mg/1 in wastewater which
contributes approximately
2 Ibs a day of Pb
-V-
-------
TABLE 10.
5. Pink/red water from TNT operation?
Process
TNT Production5
(batch process)
TNT Production5
(continuous process)
LAP2
TNT Production6
Evaporator Condensate7
(A source of pink water)
Jaste (Concentration)
Red water solids are
produced at a rate of
(0.2398 kg per Kg TNT
pr oduced)
Red water produced at
a rate of )0.50 kg per
kg TNT) produced which
contains 6% TNT Isomers
and alpha- TNT
Pink water with about
4.5% TNT (2,4,6-TNT)
and by products (isomers)
Red water (0.34 kg per %--g
produced TNT)
Pink water (as high as 150
mg/1 of TNT)
Note: Despite the relatively low TNT concentration of
evaporator condensate, the mass discharged may be substantial.
For example, at full TNT production the condensate discharged
for Joliet AAP Is projected at 325 gals per minute. A TNT
concentration of 4 mg/1, this represents a daily-discharged
of 15.6 pounds of TNT.7
-------
VI. References
1. Van Noordwyk, H., L. Schalit, W. Wyss, and H. Atkins.
Quantification for municipal disposal methods for
industrially generated hazardous wastes. EPA No.
600/2-79-135. Municipal Environmental Research
Laboratory. Cincinnati, Ohio. NTIS PB No. 140 528.
August, 1979.
2. U.S. EPA. Development document for interim final efflu-
ent limitations, guidelines and proposed new source
performance standards. Effluent Guidelines Division,
Office of Water and Hazardous Materials. Washington,
D.C. EPA No. 440/176-060. March 1976.
3. Bureau of Mines, U.S. Department of the Interior.
Mineral industry surveys. Explosives Annual 1978.
4. Patterson, J., N. I. Shapira, J. Brown, W. Duckert, and
J. Poison. State-of-the art: Military explosives and
propellents production industry. V.II. Waste characteri-
zation. EPA No. 600/2-76-213b. NTIS PB No. 260 918.
August, 1976.
5. TRW Systems Group. Assessment of industrial hazardous
waste practices: Organic chemicals, pesticides, and
explosives industries. NTIS PB No. 251 307. April, 1975.
6. Hudak, C. E., and T. B. Parsons. Industrial process
profiles for environmental use. Chapter 12, The explo-
sives industry. NTIS PB No. 291 641. February, 1977.
7. Patterson, J., J. Brown, W. Duckert, J. Poison, and
N.I. Shapira. State-of-the-art: Military explosives
and propellants production Industry. V.III, Waste-
water treatment. EPA No. 600/2-76-213c. NTIS PB No.
265 042. October, 1976.
8. Not used in text.
9. Not used in text.
10. Not used in text.
11. Patterson, J.W., and R.A. Minear. State-of-the-art
for the inorganic chemicals industry commercial
explosives. EPA No. 600/2-74-009b. NTIS PB No.
265 042. March, 1975.
12. Not used in text.
-------
13. Not used in text.
14. Hydroscience, Inc. Draft development document for proposed
effluent limitations guidelines, new source performance
standards and pretreatraent standards for the explosives
manufacturing point source category. April, 1979.
15. Not used in text.
16. U.S. EPA. The health and environmental impacts of lead
and an assessment of the need for limitations.. Office
of Toxic Substances. EPA No. 560/2-79-001. NTIS PB No.
296 603. 1979.
17. Not used in text.
18. Not used in text.
19. State of New Jersey. Unpublished Data. Waste characteri-
zation data from the State file of "Industrial Waste
Surveys". To Claire Welty of OSW. 8/31/79 and 9/4/79.
20. Not used in text.
21. Not used in text.
22. JRB Associates, Inc. Evaluation of treatment, storage
and disposal techniques for ignitable, volatile and
reactive wastes. U.S. EPA, OSW. Contract Number 68-
01-5160 (Draft). January 17, 1980.
23. U.S. Department of Interior, Bureau of Mines. Mineral
commodity summaries. 1979.
24. NIOSH. Registry of toxic effects of chemical substances.
U.S. Department of Health, Education and Welfare,
National Institute for Occupational Safety and Health.
1977.
25. U.S. EPA. States Regulations Files. Hazardous Waste
State Programs, WH-565, U.S. EPA, 401 M St., S.W.,
Washington, D.C. 20460. Contact Sam Morekas. (202) 755-9145.
26. Not used in text.
27. .'ourbaix, M. Atlas of electrochemical equilibria
'. n aqueous solutions. Pergaraon Press, London. 1966.
28. i'CRA 3001 Docket. Memo of telephone conversation between
1iomas Hess of JCAP and Chester Oszman of EPA, dated
A»gust 25, I960.1
-------
f.y • RCRA 3001 Docket. Memo of telephone conversation between
Major Bankowski of the U.S. Army and Chester Oszman of
EPA, dated August 25, 1980.
-------
Response r .\ Co;raents_ - Explosives Industry
Wastewater treatment sludges from the manufacturing and
processing of explosives (K044), spent carbon from the trea tme:s'.
of wastewater containing explosives (K045) and pink/red water
from TNT operations (KQ47) are listed as hazardous because
these wastes have been found to contain significant concentrations
of explosive components which can pose an explosive hazard;
thus, meets the reactivity characteristic (§261.23). One
commenter disagrees with the Agency since these wastes are
not reactive as determined by DOD test methods and, thus,
recommends that these wastes be removed from Section 261.32.
Specifically, In reference to hazardous waste listing
No. K045, the commenter stated that filtration of pink water
through carbon absorption columns results In the accumulation
of spent carbon (i.e., granulated carbon contaminated with
TNT/RDX/HMX). Further, regular disposition of wet spent
carbon is by open burning. In testing spent carbon, the
results indicate that this material is insensitive to initiation
when wet (25-30 percent l^O).
In reference to hazardous waste listing No. K047, the
commenter has tested the waste using detonation propagation
tests and reported results which have shown that aqueous
slurries will not support a propagating detonation at concen-
trations of 30 percent or lower (i.e., less than 312 TNT in
water) in either a gelled or settled condition. Similarly,
-------
aqueous gelled slurries of RDX and HMX at concentrations of
20 percent and HMX at 5 percent or less concentration ire
non-propagating. Further, data on 35 percent TNT liqu-r
indicated that the waste stream was insensitive to friition
pendulum, drop weight, rifle bullet, sliding rod, and confined
steel pipe tests.
Finally, for hazardous waste listing No. K044, no direct
comment was put forth except that the background documentation
is insufficient to support the listing and that the determination
of whether it be listed should wait further documentation.
Two other points were made in the comments on the explosive
listing. First, red water has been previously sold as a raw
material to the paper Industry and therefore is not a manufac-
turing by-product which has been typically discarded. Secondly,
rather than a blanket Inclusion of these wastes (K044, K045, and
K047) in the hazardous waste list, the commenter suggests that
the determination of whether and when the above listed wastes
are subject to the hazardous waste rules is best made (on a
case by case basis) by each generator, in light of whether
his waste exhibits at any time any of the hazardous waste
characteristics set forth in Subtitle C.
The Agency agrees with the commenter that those explosive
industry wastewaters, wastewater sludges, and spent carbon
which contain a significant amount of water will not be
-------
sensitive to detonation. For example, spent carbon
• •'•taining 25-30 percent or more of water and TNT sludges
r. m tain in g 65 percent or more or water would be difficult to
detonate .
The Agency Is aware,(as is the commenter) however, that
3 problem does arise when the spent carbon and wastewater
sludges are allowed to dry; the drier the material, the more
reactive the substance. This point was confirmed during
a telephone discussion with the Department of Army.28,29
An additional consideration is that this particular comment
was restricted to TNT, HMX, and RDX, which leaves a large
segment of the explosive industry without comment. For example,
nitroglycerine shavings from the production of rocket motors
being practically insoluble In water presents a different
Handling problem than the TNT liquor (red water). The milled
shaving are easily separated from the water stream and may,
over time, self-ignite.
Therefore, the Agency believes, in light of plausible
mismanagement practices (for example, the deposition of red
water in sanitary landfills or surface impoundments), that
sludges, generated from the manufacturing and processing of
explosives, red/pink water from TNT operations, and spent
carbon from the treatment of wastewater containing explosives
will dewater over time and accumulate solids thus resulting
in an increased reactivity hazard. Surface impoundments
-------
have been used In the past for the deposition of red/pink water,
and a bottom sludge has accumulated over the years which tends
to dry over the depth of the sludge. Further, the TNT sludge
is not readily degraded, becomes reactive when dry, and is
somewhat toxic. Dry TNT, is also classified as a Department
of Transportation-Explosive A.2*
In view of the above discussion, the Agency will maintain
the current listings of the explosive industry (K044, K045, and
K047). The Agency recommends that individual explosive plants
who believe their waste stream(s) has properties which are
fundamentally different from those which the Agency has cited
in the background document as the basis for listing should
file a petition for dellsting in accordance with Sections
260.20 and 260.22 (petitions to amend Part 261 to exclude a
waste produced at a particular facility).
-------
LISTING BACKGROUND DOCUMENT
PETROLEUM REFINING
API Separator Sludge From the Petroleum Refining Industry (T)
Dissolved Air Flotation (DAF) Float From the Petroleum
Refining Industry (T)
Primary Oil/Solids/Water Separation Sludge From The
Petroleum Refining Industry (T)*
Secondary (Emulsified) Oil/Solids/Water Separator Sludge
From The Petroleum Refining Industry (T)*
Slop Oil Emulsion Solids From The Petroleum Refining
Industry (T)
Heat Exchanger Bundle Cleaning Sludge From The Petroleum
Refining Industry (T)
Tank Bottoms (Leaded) From The Petroleum Refining Industry
(T)
*Note: The Agency, on May 19, 1980, promulgated as interim
final hazardous waste listings the waste streams "Dissolved
air flotation (DAF) float from the petroleum refining industry"
(K048) and "API separator sludge from the petroleum refining
industry" (K051). The Agency is now promulgating these listings
as "final-final" regulations. In addition, in response to a
petition for rulemaking, the Agency is proposing to expand
these listings to include additional waste streams which are
said to be identical in composition because they derive from
the same st'eps and serve the same functions in the treatment of
wastewater in the petroleum refining industry. These addi-
tional listings are the other sludges from the primary and
secondary treatment of wastewater in the petroleum refining
industry.
Throughout this background document, the Agency now
refers to all primary and secondary wastewater treatment
sludges in the aggregate, thus including the API and DAF
sludges. We think this approach proper, since we believe
the same rationale encompasses the listing of all primary
and secondary sludges. We repeat, however, that we are
accepting comments on the proposed listing of the other
primary and secondary wastewater treatment sludges, and we
will revise this proposal to the extent it is demonstrated
that other primary and secondary wastewater treatment sludges
differ significantly from those generated by API separators
and the DAF.
**These wastes also contain concentrations of certain other heavy
metals listed in Appendix VIII of Part 261. However, in the
Administrator's view, the concentrations of these waste con-
stituents are insufficient to warrant regulatory concern.
-------
Summary of B_a_s_is f oj: Listing
The listed wastes discussed in this document are sludges
which arise either from the treatment of wastewater generated
during petroleum refining operations (i.e., primary oil/solids/
water separation sludge, secondary (emulsified) oil/solids/water
separator sludge and slop oil emulsion solids) or from the
clean-up of equipment/storage tanks used in the refinery
(i.e., heat exchanger bundle cleaning sludge and tank bottoms
(leaded)). The Administrator has determined that these
sludges are solid wastes which may pose a substantial present
or potential hazard to hunan health or the environment when
improperly transported, treated, stored, disposed of, or
otherwise managed, and therefore should be subject to manage-
ment under Subtitle C of RCRA. This conclusion is based on
the following considerations:
1. These wastes contain significant concentrations of
the toxic metals, lead and chromium. In some waste
streams, the concentrations of lead and chromium exceed
1,000 rag/kg (dry weight). In addition to being toxic,
lead has been shown to be potentially carcinogenic and
bloaccumulative; hexavalent chromium compounds are
carcinogenic.
2. Large quantities (a combined total of approximately 66,610
metric tons (dry weight)) of these wastes are generated
annually.
3. Chromium and lead have been shown to leach from the
waste API separator sludge and DAF float in significant
concentrations when subjected to a waterwashing step
which simulates leaching activity. The Agency would
also expect the other sludges from the primary and
secondary treatment of wastewater to leach chromium and
lead in significant concentrations since these sludges
are likely to be identical in composition and form.
Furthermore, if the last three listed wastes are disposed
of in an acidic environment, the solubility of the lead
will certainly be enhanced, since the solubility of
this toxic metal Is pH dependent (i.e., solubility
-------
increases as tne pH decreases). Most hexavalent chromljm
compounds are extremely water soluble at all pH value-?.
Therefore, these metals could potentially migrate from
the waste Into the environment. £• .'I t ion.11 ly , if
these wastes are incinerated without proper air pollution
control equipment, the possibility :..
-------
distribution. A survey of operating refineries in the United
States between 1962 and 1972 is presented in Table 1 and the
geographic distribution of these plants are shown in Figure 1,
Based on the Bureau of l.'ines figures for 1974, total
U.S. refining capacity for 1974 was 14,486,000 BPD. As
presented in Figure 2, District III* has by far the greatest
capacity (6,086,000 BPD). The four other districts, arranged
in decreasing order of capacity, are District II (3,950,000
BPD), District V (2,289,000 BPD), District I (1,643,000 BPD)
and Distric IV (518,000 BPD). (Figure 2 indicates which
states are included in each region.) In the period between
1960 and 1974, Districts II, III, and V experienced the
greatest growth.
A typical breakdown of refinery capacity is shown in
Table 2 and indicates that a majority (55%) of the
individual plants are in the size range of 10 - 100,000 BPD
while a majority of total capacity (57%) lies in those
facilities which are greater than 100,000 BPD.
Future Trends
The number of refineries in the United States has
decreased in the last few decades (see Table 1), while the
average size of a refinery has increased. Few new refineries
have been built in the past five years; however, changes
* For purposes of collecting statistics on the refining
industry, the U.S. have been divided into several refining
regions called Petroleum Administration for Defense (PAD)
districts.
-------
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-------
CKOCHAl'll 1C
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-------
FIGUW; 2
PKTKOI.KUN AONINlSTKATfON FOR DKFKNSK (I'AD) DISTRICTS
W
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/
SOUKCB: Rcfurcncc 5
-------
TABLE 2
SURVEY OF U.S. REFINING INDUSTRY
BY CAPACITY AND NUMBER OF PLANTS
PLANT SIZE, BPD;
Under
10.000
10.000-100,000
Over
100,000
No. of plants
Total Refining Capacity,
74
141
1,000 BPD
% of Plants
% of Capacity
348
28
2.3
6,032
55
40.7
8,465
17
57.0
Source: The Oil and Gas Journal, Annual Refining Survey (1J75).
-x-
-------
have been made in existing refineries to reflect changing
technology and product demand, largely through expansion and
revamping of units of existing refineries. Although there
a several new facilities in the planning stages, many such
projects have been either cancelled or greatly delayed primarily
because of the uncertainty caused by unresolved energy and
environmental issues.
Growth in petroleum demand within the next 10 years is
expected to be lower than historical growth rates, thus
reducing projected waste generation rates for the industry.*
Processing Operations
A petroleum refinery is a complex combination of
interdependent operations engaged in the separation of crude
oil by molecular cracking, molecular rebuilding and solvent
<:ef inishing, to produce a varied list of intermediate and
finished products, including light hydrocarbons, gasoline,
cMesel and jet fuels, light distillate fuel as well as heavy
residual fuel oil. During the processing of the crude oil, a
number of waste streams are generated either from the clean-
up of equipment/storage tanks used in the refining process or
from the treatment of wastewater generated during petroleum
refining operations. The remainder of this document will
discuss these particular waste streams and provide reasons
*Projected decrease in growth is due to a number of factors:
(1) improved fuel economy for automotive engines (2) the
trend among consumers to purchase smaller cars (3) slow down
in jet fuel (4) rapid increase in the construction costs of
petroleum refineries and (5) scarcity of capital (Reference 5)
-------
for identifying these wastes as hazardous. (\ detailed
description of the petroleum refining process is not Included
in this document. However, to assist the reader in understand-
ing some of the basic processing operations cairied out in a
petroleum refinery, a brief description of some of the individual
operations is included as Attachment I.)
Waste Generation and Management'1'
1. Waste Streams
The five waste streams listed as hazardous are:
o Primary oil/solids/water separation sludge
o Secondary (emulsified) oil/solids/water separator
sludge
o Slop Oil Emulsion Solids
o Heat Exchanger Bundle Cleaning Sludge
o Tank Bottoms (Leaded)
Lead and hexavalent chromium are the constituents of
concern in these waste streams. Lead in the waste streams
comes predominantly from the use of tetraethyl lead in the
blending of leaded products. Chromium in the waste stream
comes predominantly from blowdown of cooling towers that
use hexavalent chromium compounds as a corrosion inhibitor.*
Concentration ranges for lead and total chromium in represen-
tative samples of each waste are presented in Table 3.
*The Agency recognizes that refineries not implementing these
systems will have lower concentrations levels of these toxic
metals. The delisting provisions of §260.20 and 260.22 are
available to generators with fundamentally different waste
streams to justify delisting of their wastes.
-------
Primary un/suj.iui./waier separation sludge - The primary
oil/solids/water separator provides fir p-lnsry refinery
wastewater treatment. The separators a LJ t>. usu..ily connected
to the oily water plant sewer. As a result, the resultant
sludges contain a mixture of all sewered waste, including
tank bottoms, boiler blow-down, desalter wastes, and also
traces of all chemical elements which enter the refinery
process.
Oil that is present in the sludge will most likely be
present in the form of heavy tars since the surface oil is
skimmed periodically from the prlnary oil/solids/water
separator. Oil content of the sludge is approximately 23%
by weight while water and solids constitute approximately
53% and 24%, respectively. Most of the solids content is
silt and sand, but a significant amount of heavy metals are
also present in the sludge.
This waste stream is listed because it contains significant
concentrations of the two metals, chromium (presumably in
part hexavalent, since it derives from cooling tower blowdown)
and lead. (Table 3 lists the concentration ranges of the
constituents of concern in each waste stream.)
Secondary (emulsified) oil/solids/water separator sludge -
Some refineries utilize secondary treatment of their wastewater
(i.e., dissolved air flotation (DAF), induced air flotation
(IAF), parallel plate flotation separators, etc.) following
separation in the primary oil/solids/water separator to
-------
TABLE 3
RANGE* IN CONCENTRATION** FOR CONSTITUENTS OF CONCERN
-SOURCE-
Contaminant
No. of Samples
Chromium
Lead
API***
separator
12
. 10-6,790
.25-1,290
DAF****
5
28-260
2.3-1,250
Slop Oil
4
1-1,7SO
.25-580
Bundle Sludge
2
310-311
Tank Bottoms
15R-1.420
*Range values represent high and low concentrations for samples of each waste stream
**Concentratlon in ng/kg dry weight, including inert solids but excluding oil
***API separator Is only one of many processes which function as a primary oil/
solids/water separator
****DAF is only one of many processes which function as a secondary (emulsified)
li p/water sei'trj.:"
SOURCE: Reference 1
-------
remove aa-. .r.ional oil and solids. The process brings finely
'-.Lvided oil and solid particles to the surface where they
•2 skimired for disposal.
Water typically constitutes 82% by weight of this waste
stream, while oil and solids constitute approximately 12.5%
-jnrf 5.5% respectively. The solids are generally fine silts
which did not have sufficient residence time in primary
separators to settle; the waste stream contains the toxic
raer.als chromium (presumably in part hexavalent, again derived
mostly from cooling tower blowdown) and lead, for which it
is listed.
Slop Oil Emulsion Solids - The skimmings from the primary
oil/solids/water separator generally consist of a three-phase
mixture of oil, water and a third emulsified layer. The oil
is returned to crude storage, the water discharged to the
wastewater treatment system, while the emulsion (oil, water
and solids) becomes a process waste stream. A typical combi-
nation of the waste stream by weight is 40% water, 43% oil
and 12% solids. Among the solids are compounds of the metals
chromium (presumably in part hexavalent) and lead, for which
the waste is listed.
Heat Exchanger Bundle Cleaning Sludge - Heat exchanger bundles
are cleaned during plant shutdown to remove deposits of scale
and sludge. Depending upon the characteristics of the
deposits, the outside of the tube bundles may be washed,
-------
brushed, or
-------
2« Waste Generation Ratio and Composition
Many factors can affect the quantity and quality of
individual waste streams. Factors thac affect quality include
crude oil characteristics, composition uf process wastewater,
occurence of spills and leaks, composition of cooling water
blowdown, use of corrosion inhibitors and the use of tetraethyl
lead for specific products and modifications. In particular,
it is expected that the concentration of sulfite in these
wastes (and therefore the proportion of hexavalent chromium
in their chromium loadings) will vary with the feedstocks
used. ?actors that affect both the quantity and quality of
the Individual waste stream include the refinery size and
age, the segregation of refinery oil drains, and the actual
quantity of process wastewater (Reference 2).
The constituents of concern in the individual waste
streams are shown in Table 3. As this data illustrates,
although each waste stream varies with regard to lead and
chromium concentrations, these metals are found generally in
high concentrations with some levels exceeding 1000 mg/kg
dry weight.* The reference for the data in Table 3 reports
analyses for total chromium, but infers the presence of more
of this element in the trivalent form. This reference was
based on knowledge of the process, possible reductive reactions
(e.g. by algae, as a consequence of corrosion inhibition, or the
*The Agency is aware that these wastes generally contain very
high concentrations of zinc. Zinc is one of the secondary
drinking water standard parameters, with an MCL of 5 mg/1.
At this time, however, the Agency does not believe that ex-
posure to concentrations of zinc which may leach from the
waste will result in a human health hazard, and therefore
is not presently designating zinc as a constituent of concern
In these waste-;.
-G1I-
-J/f-
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presence p- - • if Id -s) . <12> Since the chromium in these wpsies
derives solely froa (hexavalent) chromates, and the assum.i.< •
reductive reactions are only incidental, we strongly bili«."e
that significant concentrations of hexavalent chromium will
be present in the waste.
The estimated quantities of individual waste streams
range from 600 - 33,000 kkg per year (dry weight) (Including
inert solids but excluding oil). The combined total estimated
quantity is 66,610 kkg per year (dry weight)(including inert
solids but excluding oil) based upon capacity of 14,200,000
BPCD*.
The relative quantities of waste for the individual
waste components for each waste stream, shown^in Table 4,
indicate that the primary oil/solids/water separator, slop
oil and the secondary (emulsified) oil/solids/water separator
are the major waste generating streams in terms of quantity.
Additionally, the data indicates that chromium (presumablj
largely in the hexavalent form) and lead are present in
substantial quantities in these wastes.
A second source of data, the American Petroleum Institute
(API), performed an extensive survey of the quantities of
each waste component present in two of the waste streams
from Petroleum Refining Processes.
*BPCD - Barrels per Calendar Day
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As saovw-n in Table 5, the API data on the API separator
sludge* and the dissolved air flotation (DAF) float* generally
supports the data found in Table 3. (It is important to
•Cognize that the API data reflects a much larger sampling
effort relative to that encompassed in the EPA survey.)
C.irrent Disposal Practice - There are currently four principal
methods for disposing of petroleum refinery solid wastes.
These processes Include land treatment, landfilling, lagooning
and incineration, and may be conducted either on-site or off-
site, depending upon the particulars of a given operation.
The results from both the EPA and API studies are
presented in Table 6 to provide comparisons regarding the
disposal methods currently employed for refinery wastes.
Land treatment and landfilling appear to be the most widely
employed disposal processes.
Hazards Posed by Waste
As indicated earlier (Table 3), the five waste streams for
the petroleum refining industry contain significant concentrations
of the toxic metals lead and chromium, (presumably partly In
hexavalent form), with some levels exceeding 1,000 mg/kg
(dry weight). Additionally, information submitted by the
API for two of the waste streams (API separator sludge and
the DAF float) in which a water-washing step was conducted
to simulate leaching (see Table 7), indicates that lead and
*As already indicated, API separators and DAF are only one
of many processes which derive from the same step and serve
the same function in the treatment of wastewater as other
primary oil/solids/water separators and secondary (emulsified)
oil/solid/water separators, respectively.
-------
TABLE 4
Primary oil/solids
water separation
sludge
TOTAL QUANTITIES OF EACH WASTE COMPONENT
Metric Tons/Yr (Dry Weight)*,**
Secondary
(emulsified)
oil/solids/
water separator
sludge
SLOP OIL
HEAT EXCHANGER SOLIDS
TANK BOTTOMS
TOTAT.
hromlum
ead
17.6
1.2
8.4
.5
17.7
.06
1.1
OURCE: Reference 1
F.xcludes inert solids and oil
Even though the quantity of heavy metals from any one waste generated at any particular petroleum refinery
may be small, these wastes are normally disposed of together; therefore, the total contribution and impact of
these heavy metals at any individual refinery would be substantial.
-------
RESULTS OF API SURVEY
TOTAL WEIGHT CONCENTRATION
METRIC TONS/YR rag/kg
API separator sludf-e*** DAP**** APT*.*** DAF**»****
separator sludge
Chromium
Lead
R.6
2.4
5.3
.23
0-10,800
0-6200
0-300.1
0-540
*Sample size ranges from 61-6R
**Sample size ranges from 13-15
***API separator Is only one of many processes which function as a
a primary oil/solids/water separator
****DAF Is only one of many processes which function as a secondary
(emulsified) oil/solids water separator
SOURCE: Reference 3
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TABLE 6
DISPOSAL METHODS FOR REFINERY WASTES8
Disposal Method
Landfill
Lagoon
Incineration
Land Treatment**
On-Site
5
3
1
10
Off-Site
14
2
0
n
EPA Survey** API Surveyc
On-Site Off-Site
47 36
15 4
3 0
27 3
aReported In terms of number of refineries.
^Nineteen refineries reported.
cSeventy-fIve refineries reported.
^ercent refineries using land treatment on-site plus
off-site, Jacobs 10 of 19 equal 53 percent, API 30 of
75 equals 40 percent.
SOURCE: Reference 3.
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TABLE 7
MEAN WASTE EXTRACT CONCENTRATIONS (WATER EXTRACTNANT)
(mg/1)
„ . AI.T* *** n*i?** ****
Contaminant API « DAF >
Chromium (total) 1.9 3.3
Lead '..3 2.1
'Sample size: 60-63
**Sample size: 12-15
***API separator is only one of many processes which function
as a primary oil/solids/water separator
****DAF is only one of many processes which function as a
secondary (erasulfied) oil/solids/water separator
SOURCE: Reference 3.
-4,97-
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chromium will leach from the waste in significant concentrations
(between 10 and 100 times the National Interim Primary Drinking
Water Standard) even when these metals are subjected to mild
environmental conditions. In view of the relative insolubility
of trivalent chromium compounds (see Attachment II), the water-
extractable chromium in these wastes points to the presence
of hexavalent chromium. In many cases, off-site waste disposal
is implemented and these sites may be characterized by acidic
environments (for instance, if they contain domestic refuse
or other acidic wastes) in which case the hazardous constituents
would be released for environmental migration.
Although leaching data for the other waste streams (including
other sludges from the primary and secondary treatment of
wastewater) is not presently available, the Agency believes
that the contaminants found in these wastes would also tend
to migrate from the waste based on the solubility of the
contaminants. An additional factor supporting this belief
is the fact that chromium and lead have been shown to migrate
in significant concentrations from the API separator sludge
and DAF float, and since the other waste streams are of
roughly similar composition and are generated as part of the
same production process, migration patterns of these similar
waste streams can be readily anticipated. Solubilization of
lead is pH dependent, and increases as the pH of the solubilizing
medium decreases.(8) If the sludges are exposed to acidic
conditions (which could occur due to co-disposal with waste
-------
acids, or in municipal landfills or in areas where acid rain
is prevalent) this toxic metal could he- rr'l e;.sed form the
waste matrix. Furthermore, lead hydrcx1.-a, present in these
wastes^2), is sufficiently soluble to exceed the National
Interim Primary Drinking Water Standard (NIPDWS) of 0.05 mg/l^11
Hexavalent chromium compounds are highly soluble and mobile
(Attachment II).
Once released from the matrix of the waste, lead and
chromium can migrate from the disposal site to ground
and surface waters utilized as drinking water sources.
Present practices associated with landfilling, land treatment
or impounding the waste may be inadequate to prevent such an
occurrence. While the Agency is presently unaware of all
management practices employed for these wastes, since there
are a great number of generating and management sites and
because wastes that are disposed of off-site out of the
generator's personal supervision are particularly susceptible
to mismanagement, there is a strong likelihood that some of
these wastes are not properly managed in actual practice.
One example of inadequate management would be improper selection
of disposal sites in areas with permeable soils, permitting
contaminant-bearing leachate from the waste to migrate to
groundwater. This is especially significant with respect to
lagoon-disposed wastes because a large quantity of liquid is
available to percolate through the solids and soil beneath the
fill.
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An ovp'^low problem might also be encountered if the
liquid portion of the waste has been allowed to reach too
high a level in a lagoon. Under these circumstances, a
heavy rainfall could cause flooding which might reach surf^e
wafers in the vicinity.
In addition to difficulties caused by improper site
selection, unsecure landfills are likely to have insufficient
leachate control practices. There may be no leachate collection
and treatment system to diminish leachate percolation through
the wastes and soil underneath the site to groundwater, and
there may be no surface run-off diversion system to prevent
contaminants from being carried from the disposal site to
nearby ground and surface waters, thereby increasing the
likelihood of drinking water contamination. Further, once
lead and chromium have escaped from the disposal site, they
will persist in the environment (in some form) for virtually
indefinite periods, since they are elements and not subject
to degradation.
Additionally, if these wastes are incinerated without
proper air pollution control equipment, the possibility exists
that lead (a volatile heavy metal*) will be released into the
environment and create an air pollution problem. Also,
incineration of chromium-bearing wastes results in the oxidation
of chromium to the carcinogenic hexavalent form.
A further possibility of substantial hazard arises during
-70O-
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transporcacion of these wastes to off-site disposal facilities.
T'lis increases the likelihood of their being mismanaged, and
••lay result either in their not being properly handled during
ransport or in their not reaching their destination at all,
thus making them available to do harm elsewhere. A transport
manifest system combined with designated standards for the
management of these wastes will thus greatly reduce their
availability to do harm to human beings and the environment.
The Agency has determined to list these wastes as
hazardous wastes on the basis of lead and hexavalent chromium
constituents, even though these constituents are also measurable
by the characteristic of extraction procedure toxicity.**
Although the concentrations of these constituents in an EPA
extract of wastes from Individual sites might be less than
100 times the National Interim Primary Drinking Water Standards,
che Agency, nevertheless, believes that there are factors in
addition to metal concentrations in leachate which justify
che T listing. Some of these factors already have been
identified, namely the significant concentrations of chromium
(presumably in part in hexavalent form) and of lead in the
*An incinerator operating to destroy organic materials operates
in the range of 1000° C - 1200° C. This would cause lead to
evaporate out of the equipment as fast as water would' evaporate
at 11° C. The temperature at which vapor pressure equals 10 mm
Hg for water is 11° C and for lead is 1162° C (11).
**Hexavalent chromium, although not currently measurable by
the characteristic of EP toxicity, the Agency has proposed
to amend to characteristic of EP toxicity to apply to hexa-
valent chromium rather than total chromium (45 FR 72029,
October 30, 1980).
-Vf-
-701-
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five waste slrea.»., the non-degradabil 11 y of fhese subs taru:as ,
and the possibility cf improper management of the wastes in
actual practice.
The quantity of these wastes generated (a combined total
of approximately 66,610 metric tons dry weight) is an additional
supporting factor. As previously indicated, the wastes from
petroleum refining industry contain significant concentrat-
ions and quantities of chromium and lead. Large amounts of
these metals from the five waste streams are thus available
for potential environmental release. The large quantities
of these contaminants pose the danger of polluting large
areas of ground or surface waters. Contamination could also
occur for long periods of time, since large amounts of pollutants
are available for environmental loading. Attenuative capacity
of the environment surrounding the disposal facility could
also be reduced or used up due to the large quantities of
pollutant available. All of these considerations increase
the possiblility of exposure to the harmful constituents in
the wastes, and in the Agency's view, support a T listing.
Health Effects of Waste Constituents of Concern
Toxic properties of chromium and lead have been well
documented. Hexavalent chromium is toxic to man and lower
forms of aquatic life. Lead is also poisonous in all forms.
It is one of the most hazardous of the toxic metals because
it accumulates in many organisms, and its deleterous effects
-------
are nu.iei-ui ai..J. sivere. Lead may enter t'-.e human system
through inhalation, Ingestlon or skin ccncac-.. Improper
management of these sludges may lead to inges:ion of
contaminated drinking water. Additiona. information on
adverse health effects of chromium and lead can be found in
Appendix A.
The hazards associated with exposure to lead and chromium
have been recognized by other regulatory programs. Lead and
chromium are listed as priority pollutants in accordance with
5307 of the Clean Water Act of 1977. Under Section 6 of the
Occupational Safety and Health Act of 1970, final standards
for Occupational Exposure have been established and promulgated
in 29 CFR 1910.1000 for lead and chromium. Also, a national
anbient air quality standard for lead has been announced by
EPA pursuant to the Clean Air Act (9). In addition, final
or proposed regulations of the States of California, Maine,
Massachusettes, Minnesota, Missouri, New Mexico, Oklahoma
and Oregon define chromium and lead containing compounds as
hazardous wastes or components thereof (10).
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-70S-
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References
1. Jacobs Engineering Company. Assessment of hazardous
waste practices in the petroleum refining industry.
NTIS PB. No. 259 097. June, 1976.
2. Jacobs Engineering Company. Alternatives for hazardous
waste management in the petroleum refining industry.
OSW Contract Number 68-01-4167. Unpublished data.
July, 1977.
3. Engineering-Science Inc. The 1976 API refinery solid
waste survey, prepared for the American Petroleum
Institute. April, 1978 - 4 parts.
4. Radian Corporation. Environmental problem definition
for petroleum refineries, synthetic natural gas plants
and liquified natural gas plants. EPA No. 68-02-1319.
NTIS PB No. 252 245. November, 1975.
5. A.D. Little, Inc. Environmental considerations of
selected energy conserving manufacturing process
options. Vol. IV. Petroleum refining industry.
EPA No. 600/7-76/034-d. NTIS PB No. 264 270. December,
1976.
6. U.S. EPA. Effluent Guidelines Division. Development
document for effluent limitations guidelines and standards
for the petroleum industry. EPA No. 440/1-79/014-b.
December, 1979.
7. The Merck Index, 8th ed. Merck & Co., Inc. 1968.
8. Pourbaix, M. Atlas of electrochemical equilibria in
aqueous solutions. Pergamon Press, London. 1966.
9. U.S. Department of Interior, Bureau of Mines. Mineral
commodity summaries. 1979.
10. U.S. EPA State Regulations Files. Hazardous Waste State
Programs, WH-565, U.S. EPA, 401 M St., S.W., Washington,
D.C. 20460. Contact Sam Morekas (202) 755-9145.
11. CRC Handbook of Chemistry and Physics, 56th ed. CRC Press,
Cleveland, Ohio. 1975.
12. Memorandum from J. Bellin (OSW), to Docket, dated October 8,
1980.
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sf-. -. from Petroleum Refining Process - Response
to Comments from Proposed Regulations
(December 18, 1980)
i.- A number of comraenters stated that the proposed listing
"SLC 2911 API separator sludge (T,0)" should not apply to
all wastes from API separators but only to waste generated
from petroleum refineries*. The comnenters argued that API
separators are used in numerous industries and processes
(I.e, the food industry, soap and detergent industry, etc.)
which generate sludges of widely differing characteristics.
These separators, however, do not necessarily generate a
hazardous waste (i.e., the term does not automatically suggest
chat the sludge from any use of such a piece of equipment
would be a hazardous waste). Therefore, the comraenters want
the listing to be either clarified to indicate that the API
separator sludge is meant to be specific to separators used
in the petroleum refining industry; or otherwise, want the
process deleted from the hazardous waste list in Section
250.14.
o The Agency agrees with the commenters. The listing
has therefore been clarified to indicate that the
API separator sludge is meant to be specific to
separators used in the petroleum refining industry.
*A note appeared before the listed waste in §250.14 which
specified that the SIC code used in the listing was for
ease of reference only. Thus, the SIC classification of
the industry generating the waste would have no effect on
the listing of that process waste as hazardous.
-705--
-------
2. One commenter suggested that additional wastes from the
petroleum refining industry be added to the hazardous waste
list. These wastes included: (1) petroleum refining sulfur
removal, (2) petroleum refining wastewater treatment sludges,
(3) petroleum refining boiler cleaning, (4) petroleum refining
alkylation* and (5) petroleum refining-coke from asphalt
cracking. Data was submitted along with the suggested
listings.
o After evaluating all the available data on the
additional listed wastes, the Agency has decided
not to add these wastes at the present time due
to the lack of supporting data. However, the
Agency will reconsider these listings at some later
time once sufficient data becomes available.
3. One coaraenter objected to the proposed listing "SIC 2911
Petroleum refining lube oil filtration clays" due to the lack
of supporting data.
o The Agency, in re-evaluating the available data, has
decided to defer the listing "SIC 2911 Petroleum
refining lube oil filtration clays" until additional
data is collected by the Agency on which to make a
decision.
*This waste was listed in the December proposal (43 FR 5R959).
-------
Attachment I
The refinery process can be categorized l.ico the following
individual operations vhich are display: schematically in
Figure A-l.
o Separation
o Treating
o Conversion
o cracking
o combination
o rearrangement
o Blending
o Auxiliary Process
o Storage
Separation
The individual process steps and operation in this area
Include:
o Topping Unit - This unit separates the crude in an
atmospheric stage. The process streams from this unit normally
include fuel gas, naphtha, middle distillates, and discillated
fuel oil. The naphtha may be split into light and heavy
fractions and the fuel oil into light, middle, and heavy
distillate components.
o Vacuum Towers - Vacuum towers are utilized for
separation of the heavier fractions from the entire crude
stream. For a comparable crude input, these units are capable
-yf-
-707-
-------
F. Al
m AIIIJAN n
KKKI NKKY
MA IIIU AI
GAS
I ••--•»
_. ll,t
•IMIMOV-L j
. .
1 iJi AM
CRUDE
OH
OHIIUAflOM
~| STRAIGHT
I RUN RESIDUE
PI i If II *f
lull li^'i
IUORICATING
. OH
MANUfACIUKE
:i 1.-.05 — i T,rM;,,^i i *
TRAIGIIT RUN
ASOUNE
. CATAIYTIC
JWC*OG€NI H REFORMING
p* TREATING] 1
TRAIGHT ]
UN NAPHTHA
IOHI STRAIGHT RUN GAS OH •-
ItAVY STRAlGHI RUN GAS OH
IE
I I
CAI CtlAC
LJUM -ACIIMII ^ CATAUTIC "AI-IIIMA
AIION wiiiUAii' CKAt.WNO CAI ouc
•-J-RCK.ISSINC; i "' 1 AL/VI.\TE
1i 1 srPAiont nuN
_ J'«?' ! CASOUNt
I J CATAIirllC v
xro
[TREAT ^i^.VAo
TREAT
A.. '
II 1
,..., """
— ^ fi^i _^____ *
rBAf-VIMr i~* 10 CA30l-IMl W.I10IMO
V.KAUMniJ TOCAtAUtflC IHfOKMINO
KID 1 1 JlREAll J
UOIIIttAJM. j 1. 'J.U
1 VACUUM CAT. CRACKTO
MTTOMS IIIAWOAJOH.
1 IP
— V OR > ..... > TO HArNTHA HTOnOOCN THE
'. 1MERMAI i • 1UI"""
f > cc*t an uninv'AL ruti -fi
— — i
f
c
D1
I
G
i
0
I
E
N
D
1
M
G
-;>
->
-»
%
AT CH
CH:H
ppf MH:
KEROSENE
JEF lUit
DUSEl III
RCSIPUAl
vSi
I'B" .1
SOURCE: Reference 6
(1)
(7) AO UO O« MfOROCEN
ruii
ornc
-------
of producing a broader spectrum of process streams than a
topping unit. For example, these units may either recover
(Ulitional gas oil from the reduced crude while producing a
vy vacuum residual or may separate the reduced crude into
special lube oil cuts with an accompanying residual stream.
One of two stages may be utilized, depending upon the individual
end-product requirement.
o Light Ends Recovery - This operation is sometimes
referred to as vapor recovery and involves the separation of
refinery gases from the crude distillation unit and other
units into individual component streams. The separation
phase is accomplished by absorption and/or distillation,
depending upon the desired purity of the product stream.
Treating
o Gas Treating - The major component of the various
species separated in the crude distillation unit or produced
In the various processing units Is hydrogen sulfide. Acid
gases, such as l^S, normally are removed from the light ends
fraction by absorption with an aqueous regenerative solvent.
There is a variety of treating processes available with the
most common refinery operations based upon amine-based
solvent s.
o Hydrotreating - Hydrotreatlng involves the catalytic
conversion of organic nitrogen, sulfur, and oxygen compounds
into hydrocarbons and the more readily removable sulfldes,
ammonia, and water. Various process streams normally are
-yf-
-7O°t-
-------
treated separately because of various fuel specifications and
the wide range of catalysts and reactor conditions required
to hydrotreat the various petroleum fractions.
Conversion
Conversion processes typically involve cracking,
combination, and rearrangement.
o Cracking
Thermal Cracking - This is a relatively simplistic
process which Involves the heating of hydrocarbon fractions
in the absence of catalysts. A modification to this traditional
process, known as vis-breaking, is used to minimize coke
formation. The moderate heating to 880°F is employed to
reduce the feed viscosity and, therefore, reduce the quantity
of blending stock required to upgrade the feed to fuel oil
specifications. Delayed coking uses severe heating conditions
(1800°F-2000°F) to crack feedstock to coke gas, distillates,
and coke. Fluid coking is a recent innovation which converts
the feed stream to higher valued products and produces less
coke.
Hydrocracking - This process involves the cracking
of feedstocks in the presence of a high hydrogen partial
pressure. This process normally Is employed on a high sulfur,
straight-run gas or on a gas-oil effluent from another cracking
process.
Catalytic Cracking - Catalytic cracking involves the
application of catalytic reactions to reduce heavy oils raaxi-
-7/O-
-------
raizing product Lor. of I ight €4 hydrocarbons an<< €5 and C$
gasoline compounds. This process is primarily employed to
naxiraum gasoline production.
o Combination - These processes involve the combination
of two light hydrocarbons through polymerization or alklation
to produce a gasoline-range hydrocarbon. The polymerization
process combines two or more gaseous olefins into a liquid
product, while the alkylation process joins an isoparaffin
and olefin. The feedstock origin is either a catalytic or
hydrocracker and the catalysts include phosphoric, sulfuric,
or hydrofluoric acid.
o Rearrangement - This process involves the application
of catalytic reforming and isomerization to rearrange the
molecular structure of a feedstock to produce a high quality
stream for gasoline blending.
Catalytic reformers create high octane naphthas (rich In
benzene, toluene, and xylene) from a desulfurized, straight-
run, or cracked naphtha. Hydrogen also may be produced as
part of the reforming operation and other end-products,
including non-aromatlcs.
Isomerization units are used to increase the octane
ratings of pentane and hexane fractions to produce a gasoline-
blending stock having an octane nunber of 80-85. The reaction
is conducted at elevated temperatures (> 300°F) and pressure
(400 psig) over a chlorinated-platinun-alumlnum-oxide catalyst
-in-
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Blending
The typical in-line blending operations most commonly
involve the final processing of gasoline prior to storage.
variety of gasoline components, such as cracked gasoline,
reformate, isomerate, alkylate, and butane, are combined with
selective additives in the necessary proportions to meet
marketing specifications.
Auxiliary Operations
o Crude Desalting - This process involves the separation
of inorganic salts and brines from an incoming crude to
prevent process fouling, corrosion, and catalyst poisoning.
The desalting process can be conducted either electrically or
chemically with the former being the more prevalent. In the
electric process, the raw crude is heated, emulsified with
water, and routed through a high-voltage vessel where the
electric field demulsifies the oil and water, In the chemical
version of this process, coalescing agents are applied to
deraulsify the two-phase aqueous-organic system.
o Hydrogen Generation - Large quantities of hydrogen
are consumed in numerous refinery operations, Including
hydrotreating, hydrocracking„ and isomerization. The proper
maintenance of a hydrogen balance within the typical refinery
requires that the hydrogen available from the catalytic
reformers be supplemented by either stream-hydrocarbon
reforming or partial oxidation. The selection of either
-7/2-
-------
process dep-^.ds upon the characteristics of the raw feedstock
material.
o Sulfur Recovery - This process involves the application
o' specific processes, such as the Glaus process, to convert
the hydrogen sulfide content of acid gas to elemental sulfur.
In this process, the hydrogen sulfide is combusted in an
oxygen-deficient atmosphere to produce sulfur, sulfur dioxide,
and water. Additional sulfur recovery is obtained in a series
of catalytic reactors through reaction of hydrogen sulfide
and sulfur dioxide. The tall gas from the Glaus unit may be
treated further through a variety of processes.
o Power Generation - The major factor affecting power
generation in refining operations is the requirement for
steam and the overall facility steam balance. Facility
requirements can range from a simple back-up boiler for
operations where there are significant anounts of by-product
steam to other situations where continuous steam generation
is necessry.
Storage Technologies
o No Storage - Raw material is not stored, but is pumped
directly from an adjacent process area or petroleum refining
facility where it is produced. This procedure is employed
when the production in two process areas in Integrated to the
degree that simultaneous operations occur and no intermediate
storage is necessary. Material transfer would occur by
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-7/3-
-------
pumping through steel or other piping from o:.e process area
directly to the other.
o Tank Storage
Fixed Roof - These cylindrical steel ranks have
permanently attached conical steel roofs. The rigid construction
of these tanks necessitates that the roof be installed with
pressure-vacuum valves set at a few inches of water to contain
minor vapor volume expansion. Greater losses of vapor
resulting from tank filling should be controlled with an
attached vapor recovery unit.
Floating Roof - Unlike fixed roof tanks, these tanks
are equipped with a sliding roof that floats on the surface
of the product and eliminates the vapor space between product
and roof. A sliding seal attached to the roof seals the
annular space between the roof and vessel wall from evaporation.
Internal Floating Cover - To remedy the problems of
snow and rain accumulation encountered with floating roofs,
this design utilizes both a fixed outer roof and an internal
floating cover. Again, the floating cover is equipped with
sliding seals to prevent annular space evaporation.
Variable Vapor Space - These tanks may appear in two
basic designs: lifter roof and diaphragm. The lifter roof
type utilizes a telescopic roof, free to travel up or down as
the vapor space expands or contracts. The diaphragm design
has an internal flexible diaphragm to accomodate vapor volume
changes.
-V-
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Pressure - These tanks are especially useful for
storing highly volatile materials. These tanks come in a
wide variety of shapes and are designed * a eliminate vapor
emissions by storing the product under pressure. These tanks
nay be designed for pressures up to 200 psi.
It has been noted that fixed roof, floating roof, and
internal floating cover tanks are the most common varieties
in use for storage of organic materials. These tanks may
range in size from 20,000 to 500,000 bbl. and* average 70,000
bbl.
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Attachment II
SOLUBILITY AND ENVIRONMENTAL MOBILITY
CHARACTERISTICS OF CHROMIUM COMPOUNDS
The triposltive state Is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of ligands such as water,
ammonia, urea, halides, sulfates, amines and organic
acids.(a»b) Thousands of such compounds exist. This
complex formation underlies the tanning reactions of chromium,
and is responsible for the strong binding of trivalent chromium
by soil elements, particularly clays.(c»d)
At pH values greater than about 6, trivalent chromium
forms high molecular weight, Insoluble, "polynuclear" complexes
of Cr(OH)3 which ultimately precipitate as 0^03.nl^O. This
process is favored by heat, increased chromium concentration,
salinity and time.(a) These chromium hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form, Cr
is therefore resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubillzation of
chromium hydroxide:
A/1
-------
Reaction
2. Cr(OH),
3. Cr(OH)
CrOH""" +2H20
Cr+3+30H~
HrCrOo~+H,0
in1
6.7x10
-31
9x10
,-17
Cr(III) Concentration
Calculated from keg (mg/1)
pH5
520
35
i
pH6
5.2
0.035
1
pH7
0.052
i*
1
*i= <0.001 mg/1
It is apparent from these figures that, in theory, trivalent
chromium could leach from sludges to sorae extent. Such
solubilized chromium, however, is unlikely to contaminate
aquifers. It is complexed with soil materials, and tenasiously
held.
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soils.(c»d) Hexavalent chromium remains as such in a
soluble form in soil for a shore time, and is eventually
reduced by reducing agents if present.(e»i) As compared
with the trivalent form, hexavalent chromium is less strongly
adsorbed and more readily leached from soils(d) and thus, is
expected to have mobility in soil materials.
v*
-7/8"-
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References
U.S. EPA, Relvews of the Enviroraenta1 Effects of Pollutants;
III Chromium. 01NL/EIS-80; EPA-600/ :-,'8-023; May 1980.
Transistion Metal Chemistry, R.L. Carlin, ed. Marcel
Dekker, New York. 1965; Volume 1.
Bartlett, R.J. and J.M. Kimble. Behavior of Chromium in
Soils: I Trivalent Forms. J. Environ. Qual. 5: 379-383:
1976.
Griffin, R.A., A.K. Au, and R.R. Trost. Effects of
pH on adsorption of chromium from landfill leachate by
clay minerals. J. Environ. Sci. Health A12(8):
430-449:1977.
U.S. EPA. Application of Sewage Sludge to Cropland;
Appraisal of Potential Hazards of the Heavy Metals to
Plants and Animals. EPA 430/9-76-013. NTIS PB No.
264-015. November, 1976.
Bartlett, R.J. and J.M. Kirable. Behavior of Chromium in
Soils: II Hexavalent Forms. Ibid. 5:383-386. 1976.
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Iron and Steel Industry
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COKING
Ammonia Still Lime Sludge (T)
I. Summary of Basis for Listing
Ammonia still lime sludge is generated when by-products
are recovered from coke oven gases. The Administrator has
determined that ammonia still lime sludge may pose a 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 appropri-
ate management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations:
1. These sludges contain the hazardous constituents cyanide,
naphthalene, phenolic compounds, and arsenic which adhere
to the lime floes and solids in significant concentrations
2. Cyanide and phenol leached in significant concentrations
from an ammonia still lime sludge waste sample which was
tested by a distilled water extraction procedure.
Although no leachate data is currently available for
naphthalene and arsenic, the Agency strongly believes
that based on constituent solubilities, the high concen-
tration of these constituents in the wastes, and the
physical nature of the waste, these two constituents
are likely to leach from the wastes in harmful concentra-
tions when the wastes are improperly managed.
3. It is estimated that a very large quantity, 963,000
tons (1), of ammonia still lime sludge "(5% solids by
weight) is currently generated annually, and that this
quantity will gradually increase to 1.45 million tons (5%
solids by weight) per year as the remaining coke plants
add fixed ammonia removal capability to comply with BPT
limitations (1). There is thus the likelihood of large-
scale contamination of the environment if these wastes
are not managed properly.
4. Coke plant operators generally dispose of these sludges
on-site in unlined sludge lagoons or In unsecured land-
fill operations. These management methods may be in-
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adequate to impede leachate migration .
II. Industry Profile and Process Description
The stripping of ammonia during the hy-product cokemaking
process is currently practiced at 39 facilities, distributed
across 17 different states, with about half of the operating
plants located in Pennslyvania, Ohio and Alabama (1). These
plants are currently producing AS,000,000 tons of coke per
year (1). (Coke, the residue from the destructive distillation
of coal, serves both as a fuel and as a reducing agent in the
making of iron and steel.) Of the 39 plants which practice
ammonia recovery, 31 use lime, generating, in the process, an
ammonia still lime sludge.**
During the recovery of chemical by-products from the
cokemaking process, excess ammonia liquor is passed through
stills to strip the NH3 from solution for recovery as ammonium
sulfate, phosphate or hydroxide* About half of the ammonia
originally present (5,000 mg/1) strips readily, but the
remaining fraction can only be recovered by elevating the pH
*Although no data on the corrosivity of ammonia still line
sludge are currently available, the Agency believes that
these sludges may have a pH greater than 12.5 and may, there-
fore, be corrosive. Under 3262.11, generators of this waste
stream are responsible for evaluating their waste in order
to determine whether their waste is corrosive.
**Eight plants currently use sodium hydroxide as their alkali
and produce about 1/5 of the sludge volumes common to lime
systems (1). These eight plants tend to be smaller In capacity,
with lesser volumes of process wastewater to treat. The Agency
believes that this sludge will be similar in composition to the
ammonia still lime sludge, and plans on collecting additional
data to determine whether this waste should also be listed.
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of the WciUte liquor to 10-12 through the addition of lime,
and passing additional steam through the solution. This
stripping transfers some of the contaminants to the gas stream,
but enough remains behind for the lime sludges to contain high
levels of hazardous constituents (i.e., cyanide, naphthalene,
phenol and arsenic; see page 6, following).
II . Waste Generation and Management
Ammonia still lime sludge is generated in the recovery
of ammonia, by the addition of lime, from coke manufacturing
operations. Currently it is estimated that 963,000 tons of
ammonia still lime sludges (5X solids by weight) are generated
annually, and this amount will gradually increase to about
1.45 million tons per year as the remaining coke plants add
fixed ammonia removal capabilities to comply with BPT
limitations (1). Baaed on process wastewatec analytical
data at 9 coke-making plants, an estimated industry total
of 1,468 tons (dry weight) of cyanide, naphthalene, phenolic
compounds, and arsenic result each year from ammonia still
lime sludges ( 1) .
Cyanide, naphthalene, phenol and other organic constituents
are formed as a result of the destructive distillation of
coal and are present in the ammonia liquor. Arsenic, on the
other hand, is present along with other naturally occuring
metallic contaminants in the coal and is also present in the
ammonia liquor. (Although other metals are present in the
waste, only arsenic is deemed present in sufficient concen-
-722-
-------
trations LJ present a problem (1).)
Review of the chemical mechanisms, pH and operating tem-
peratures at which the ammonia stripping process is conducted
Indicates that cyanide, naphthalene, phenol and arsenic tend
to remain relatively chemically unreactive in the ammonia
still stripping process. As a result, the presence of these
four pollutants in the ammonia still lime sludge is predictable.
Sludges are typically settled out in sedimentation basins,
from which settled material is periodically removed for
disposal (1). Figure 1 presents a process schematic of the
ammonia still recovery process.
Current Disposal Practices
Of the 39 ammonia recovery operations, approximately 30
plants presently dispose of the ammonia still lime sludges ID
on-slte unllned sludge ponds. t1) Lined lagoons or carefully
controlled landfills have not been routinely used by the
Industry to dispose of these sludges (1).
Hazardous Properties of the Waste
Using data collected by EPA at coking operations from the
process wastewater samples taken before and after the addition
of lime(l), an accounting of the differences in pollutant mass
before and after the lime addition reveals that 13,640 ppm of
cyanide, 4,770 ppm naphthalene, 680 ppm of phenols*, and 1,086
*The mass of phenolic compounds present in the sludge is
estimated and has been adjusted for partial volatilization
of the phenol in the stripper.
-723-
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To Ammonia Abtorbtr
Cooling
Jack.I
•Cooling Wolir
-^Cooling WaUr Rtlurn
Ammonlo Liquor
Irom Slorogi
IS«« Fig. I)
Sltom
Fluid L»g
Sltom
DEPIILEGMATOn
SECTION
AMMONIA STILL
WASTE LIQUOR SETTLING BASIN
W»ok Ammonlo Llquo; I
Further Ti»olm«nl.
•LImi SUM Sludgtt
P«flodleolly
lor DUpoiol.
Maiordout Wosio Sourct
Rtqulrlng Conlrolltd Diipoiai
ENVIRONMENTAL PRQTCCTION ACf.NJ
STEEL INDUSTRY STUDY
OY-PRODUCT COKEMAKINQ OPERATE
HAZARDOUS WASTE SOURCE
AMMONIA STILL LIME SLUOCE9
I
FIGURE
-X-
-------
ppm of arse-lie aic present In the ammonia still lime sludge.*
A separate study of ammonia still lime sludge indicated
phenol and cyanide concentrations ranging from *70 ppm to
IQin ppm for phenol and 343 ppm to 1940 ppm for cyanide (?).
Leaching tests (distilled water) were also performed on
this waste sample. Results of these test revealed- leachate
concentrations of 19ft ppm for cyanide and 20 ppm for phenol
(2).
The concentration of cyanide in the leachate is far in
excess of concentrations in water considered harmful to
human health and the environment. For example, the U.S.
Public Health Service's recommended standard for cyanide in
drinking water is 0.2 mg/1. The proposed EPA Water Quality
Criteria limits the level of cyanide at 0.2 mg/1 and phenol
at 1 ppm for domestic water supply.**
Although no leachate data is currently available for naph-
thalene and arsenic, the Agency strongly believes that these
constituents will leach in harmful concentrations from these
wastes if not properly managed. Some compounds of arsenic are
quite soluble. Arsenic trloxlde has a solubility of 12,00(1
mg/1 at 0°C, and arsenic pentoxlde has a solubility of 2,300 g/1
at 20*C (Appendix A). The solubility, the high concentrations
*These concentration figures are not contained in reference
I but are calculated using data contained In that reference.
**The Agency is not using these standards as quantitative
benchmarks, but is citing them to give some Indication that very
low concentrations of -these contaminants may give rise to a
substantial hazard.
-------
of arsenic in the ammonia still lime sludge and arsenic's ex-
treme toxicity make it likely that it will leach from the wastes
in harmful concentrations (i.e., a small quantity of arsenic
is .afficient to present a problem to human health and the
environment) if the wastes are not properly managed. Naphthalene
is water soluble, with solubility ranging from 30,000 g/1
to 40,100 g/1. The solubility of naphthalene in water and
its presence in such high concentrations in the waste make
it likely that it will also leach from the waste in harmful
concentrations if the wastes are not properly managed.
In addition, cyanide, phenol, naphthalene and arsenic
tend to remain chemically unreactive in the ammonia still
lime sludge. Since lime is a relatively porous substance,
constituents in the lime sludge will themselves therefore
tend to be released when the waste sludge is exposed to
a leaching medium.
As previously discussed, a very large quantity of ammonia
still lime sludge is produced annually, and is thus available
for large scale contamination of the environment. Such large
quantities of waste likewise present the danger of continued
migration of and exposure to waste constituents. These wastes
consequently present a serious hazard to human beings if not
properly managed.
Current practices of disposing of these wastes in fact
appear inadequate. Disposal of ammonia still lime sludge in
unlined sludge lagoons or unsecured landfills (see p. 4 above)
-726,-
-------
makes It likely that the hazardous constituents In the wastes
will leach out and migrate into the environment, possibly
contaminating drinking water sources.
An overflow problem might also be encountered if the
xiquid portion of the waste has been allowed to reach too
high a level in the lagoon; a heavy rainfall could cause
flooding which might result in the contamination of surface
waters In the vicinity. Given the large quantities of this
waste produced, other types of mismanagement are likely to
result and to cause damage to the environment.
As demonstrated above, the waste constituents appear
capable of migrating from the waste in harmful concentrations.
The waste constituents are also persistent, and thus have an
increased likelihood of reaching an environmental receptor.
Arsenic, as an element will persist Indefinitely In some
form. Cyanides also tend to persist after migration (see
background document "Spent or Waste Cyanide Solutions and
Sludges" for further Information supporting this conclusion).
Cyanide and phenols have been implicated in actual damage
incidents as well, again confirming the ability of these
waste constituents to be mobile, persist, and cause substantial
harm. For example,
A firm in Houston, Texas, as early as 1968, was made
aware that its practices of discharging such hazardous wastes
as cyanide, phenols, sulfides, and ammonia into the Houston
Ship Channel was creating a severe environmental hazard. The
toxic wastes in question were derived from the cleaning of
blast furnaces from coke plants. According to expert testimony,
levels as low as 0.05 mg/1 of cyanide effluent are lethal to
shrimp and small fish. The court ordered the firm to cease
discharging these wastes Into the ship channel. (EPA open files)
-73.7-
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In 197j. a newl> drilled industrial wtll In an artesian
aquifer in Garfield, New Jersey, contained water with an
unacceptably high concentration of phenolic materials. The
pollutants originated from nearby industrial waste lagoons.
(Draft Environmental Impact Statement, ..snuary, 1979).
Fifteen thousand drums of toxic and corrosive metal
Industrial wastes were dumped on farmland in Illinois in
1972. As a result, large numbers of cattle died from cyanide
poisoning and nearby surface water was contaminated by runoff.
(House Report Number 94-1491, 94th Congress, 2nd Session, page 19).
Health and Ecological Effects
Cyanide
*.. Congress listed cyanide as a priority pollutant under
§307(a) of the Clean Water Act.
The toxicity of cyanide has been well documented.
Cyanide in its most toxic form can be fatal to humans in a
few minutes at a concentration of 300 ppm. Cyanide is also
lethal to freshwater fish at concentrations as low as about
50 mg/1 and has been shown to adversely affect invertebrates
and fish at concentrations of about 10 mg/1.
The hazards associated with exposure to cyanide have
also been recognized by other regulatory programs. The U.S.
Public Health Service established a drinking water standard
of 0.2 mg/1 as an acceptable level for water supplies. The
Occupational Safety and Health Administration (OSHA) has
established a permissible exposure limit for KCN and NaCN at
5 mg/m^ as an eight-hour time-weighted average.
Finally, final or proposed regulations of the states of
California, Maine, Maryland, Massacuse t ts , Minnesota, Missouri,
-72*-
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New Mexico, Oklahoma, and Oregon define cyanide containing
compounds as hazardous wastes or components thereof. Additional
information and specific references on the adverse health
effects of cyanide can be found in Appendix A.
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 concentrations have resulted in chronic liver
damage in humans.(3) Chronic poisoning, following prolonged
exposures to low concentrations of the vapor or mist, results
in digestive disturbances (vomiting, difficulty in svollowlng,
excessive sallvtion, diarrehea), nervous disorders (headache,
fainting, dizziness, mental disturbances), and skin eruptions.(^)
Chronic poisoning may terminate fatally in some cases where there
has been extensive damage to the kidneys or liver.
Phenol biodegrades at a moderate rate in surface water and
soil, but moves readily. Even with persistence of only a few
days, the rapid spreading of phenol could cause widespread
damage of the ecosystem and contamination of potable water
supplies.
OSHA has set a TLV for phenol at 5 ppm.
Phenol Is listed In Sax's Dangerous Properties of
Industrial Materials as a dangerous disaster hazard because
-------
when heated it emits toxic fumes. Additional information and
specific references on the adverse effects of phenol can be
found in Appendix A.
Arsenic
Congress has designated arsenic as a priority pollutant
under Section 307(a) of the Clean Hater Act.
Arsenic is extremely toxic in humans and animals.
Death in humans has occurred following ingestion of very
small amounts (Smg/kg) of this chemical. Several epidemiolog-
ic^l studies have associated cancers with occupational expoure
to arsenic, including those of the lung, lymphatics and
blood. Certain cases Involving a high prevalence of skin
cancer have been associated with arsenic in drinking water,
while liver cancer has developed in several cases following
ingestion of arsenic. Results from the administration of
arsenic in drinking water or by injection in animals supports
the carcinogenic potential of arsenic.
Occupational exposure to arsenic has resulted in
chromosomal damage, while several different arsenic compounds
have demonstrated positive mutagenlc effects in laboratory
studies.
The teratogenicity of arsenic and arsenic compounds is
well established and includes defects of the skull, brain,
gonads, eyes, ribs and genito-urinary system.
The effects of chronic arsenic exposure include skin
diseases progressing to gangrene, liver damage, neurological
-vt-
-730-
-------
disturbances, red blood cell production, and cardiovascular
disease •
OSHA has set a standard air TWA of 500 ng/m3 for arsenic.
DOT requires a "poision" warning label.
The Office of Toxic Substances under YIFRA has issued a
pre-RPAR for arsenic. The Carcinogen Assessment Group has
evaluated arsenic and has determined that It exhibits sub-
stantial evidence of carcinogenicity • The Office of Drinking
Water has regulated arsenic under the Safe Drinking Water
Act due to Its toxicity and the Office of Air Quality Planning
and Standards has begun a pr e-regula tory 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 on oncogeniclty and environmental
effects. Finally, the Office of Toxic Substances has completed
Phase I assessment of arsenic under TSCA. Additional informa-
tion and specific references on the adverse effects of arsenic
can be found in Appendix A.
Naphthalene
Naphthalene is designated a priority pollutant under
Section 307(a) of the CWA.
Systemic reaction to acute exposure to naphthalene
includes nausea, headache, diaphoresis, hematurla, fever,
anemia, liver damage, convulsions and coma. Industrial
exposure to naphthalene appears to cause increased Incidence
of cataracts. Also, hemolytic anemia with associated
-73J-
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jaundice and occassionally renal disease from precipitated
hemoglobin has been described in newborn Infants, children,
and adults after exposure to naphthalene by ingestlon,
inhalation, or possibly by skin contact-
OSHA's standard for exposure to vapor for a time-weighted
industrial exposure is 50 mg/ra^.
Sax(ln) warns that naphthalene is an experimental neo-
plastic substance via the subcutaneous route; that is, it
causes formation of non-raetastasizing abnormal or new growth(s).
Additional information and specific references on the adverse
effects of naphthalene can be found in Appendix A.
-732-
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References
1. U.S EPA. Draft development document for proposed effluent
limitations guidelines and standar-J? for the iron
and steel manufacturing point sourf.- category; by-
product cokemaking subcategory, V.il, October, 1979.
EPA No. 440/l-79-024a. 1979.
2. Calspan Corporation. Assessment of industrial hazardous
waste practices in the metal smelting and refining industry.
Appendices 12,37. Contract Number 68-01-2604, Volume III,
pages 97-144. NTIS PB No. 276 171. April, 1977.
3. Merllss, R.R. Phenol Moras. Mus. Jour. Occup. Med.
14:55. 1972.
4. Sax, N. Irving. Dangerous properties of industrial materials,
5th ed. Van Nostrand Reinhold Co., New York. 1979.
-733-
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LISTING BACKGROUND DOCUMENT
ELECTRIC FURNACE PRODUCTION OF STEEL
Emission control dusts/sludges from the primary
production of steel in electric furnaces (T)*
Summary of Basis for Listing
Emission control dusts/sludges from the primary production
of steel in electric furnaces are generated when particulate
matter in the gases given off by electric furnaces during the
production process is removed by air pollution control equip-
ment. Dry collection methods generate a dust; wet collection
methods generate a sludge. The Administrator has determined
that these dusts/sludges are solid wastes which may pose a
present or potential hazard to human health and 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 conclusion is based on the following considerations:
(1) The emission control dusts/sludges contain signifi-
cant concentrations of the toxic metals chromium,
lead, and cadmium.
(2) Lead, chromium and cadmium have been shown to leach
in harmful concentrations from waste samples subjected
to both a distilled water extraction procedure and
the extraction procedure described in 5250.13(d)
of the proposed Subtitle C regulations.
*This listing~was originally proposed on December IB, 1978
(43 FR S8959) under SIC Code 331? and states as "Iron
Making: Electric furnace dust and sludge." In response to
a comment submitted by the American Iron and Steel Institute
that the electric furnace process is used for steelmaklng
only, not Iron and steelmaking as was previously listed, the
Agency modified the listing on May 19, 19RO (45 FR 33124) as
"Emission control dusts/sludges from the electric furnace
production of steel." In further response to a comment submitted
by the American Foundryraan's Society, the Agency is again modi-
fying the listing to make it clear that this listing is meant
to apply to primarly steel producers only(see Response to
Comments In back of this document for more detailed discussion).
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(3) A large quantity of these wastes (a combined total
of approximately 337,000 metric tons) is generated
annually and is available for disposal. There is
thus a likelihood of large scale contamination
of the environment if these wastes are mismanaged.
(4) The wastes typically are disposed of by being dumped
in the open, either on-site or off-site, thus
posing a realistic possibility of migration of
lead, cadmium, and chromium to underground drinking
water sources. These metals persist virtually
indefinitely, presenting the serious threat of
long-term contamination.
(5) Off-site disposal of these wastes will increase
the risk of mismanagement during transport.
I. Profile of the Industry
The electric furnace (arc) process is one of the three
principal methods of producing steel in the United States.
In 1974, the iron and steel industry had the capacity to
produce approximately 27,000,000 metric tons/year of steel
via the electric furnace process (1).
Plants are located in 31 different states, with 70% of
the estimated capacity located in Ohio, Pennsylvania, Illinois,
Texas, Michigan and Indiana (1). A typical integrated electric
furnace steel plant has an electric furnace capacity of
about 500,000 metric tons/yr (1). Capacities at different
plants range from about 50,000 to 2,000,000 metric tons/yr (2).
II. Manufacturing Process
The raw materials for the electric arc steelmaking
process Include cold iron and steel scrap, and fluxes such
as limestone and/or fluorspar. The raw materials are charged
into a refractory-lined cylindrical furnace and melted by
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passing an electric current (arcing) through the scrap steel
by means of three triangularly spaced carbon electrodes
inserted through the furnace roof. The process proceeds at
high temperatures and an oxidizing atmosphere (air or p^re
oxygen are used).(2) The electrodes are consumed at a
rate of about 5 to 8 kg/kkg of steel, with the emission of
CO and C02 gases. The hot gases entrain finely divided
particulate, 70% of which (by weight) are less than 5 microns
in size, the majority of this less than 0.5 microns. The
particulate fume or dust consists primarily of iron oxides,
silica and lime, with significant concentrations of the
toxic metals lead, chromium and cadmium (!)•
III. Waste Generation
The waste products from the electric carbon furnace
process is a mixture of gases consisting of smoke, slag,
carbon, nitrogen, ozone and oxides of iron as well as other
metals. (2) The particulates produced during the electric
furnace steelmaking process are removed from the furnace
off-gases by means of baghouse filters, electrostatic preci-
pitators, or high-energy Venturi scrubbers. The baghouse
filters and electrostatic precipitators, which are used by
93% of electric arc steelmaking furnaces, produce an emission
control (dry) dust for disposal at a rate of 12.8 kg of dust
per metric ton of steel produced. Scrubbers, used by the
remaining 7% of the steelmaking industry, produce slurries
or sludges for disposal at a rate of about 8.7 kg (dry solids
-7-iC.-
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basis) pti metric Con of steel produced.
Based on an electric furnace steelmaking capacity of
27,000,000 kkg/yr (see p. 2 above), and assuming that the
electric furnaces that use dry air pollution control
equipment represent 93% of that capacity, the industry-wide
estimated quantities of emission control dusts and sludges
produced at full operating caoacity are 321,000 kkg/yr,
and 16,000 kkg/yr (dry solids basis), respectively.
The Agency has information indicating that these wastes
are typically dumped in the open at on-site or off-site
disposal facilities (1,2). The emission control sludges,
however, are also amenable to other forms of disposal, such
as disposal in lagoons or surface impoundments. The large
quantities of these wastes generated annually, combined with
the fact that other emission control dusts/sludges generators
handle their wastes in this manner, nake this type of management
situation plausible. (See, for example, Secondary Lead
Hazardous Waste Listing Background Document).
IV. Hazardous Properties of the Wastes
1. Migrating Potential of Waste Constituents
An analysis of the electric furnace dust supplied by
U.S. Steel Corporation is given in Table 1 (3). As the data
indicate, two of the toxic metals of concern, lead and chromium,
are present in significant concentrations. Lead, for example,
which has a usual range of lead-in-soil concentrations of 2
-737-
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to 200 ppm (4), is present in this waste sample at a con-
centration of 1,400 ppm.*
Another analysis of waste samples from both electric
furnace dusts and sludges also shows lead and chromium to be
present in the wastes in significant amounts. The analysis
of the emission control dust waste sample revealed chromium
to be present at 13RO ppm and lead to be present at 24,220
ppm. The analysis of the emission control sludge sample
revealed total cttromium to be present in the waste at 2,690
ppm and lead at 7,900 ppm (1).
The metal oxide partlculates in these dusts are formed
at high temperatures in an oxidizing atmosphere. Such
conditions are known to result in the oxidation of chromium
to its hexavalent form.(16) The dusts and sludges, therefore,
are presumed to contain hexavalent chromium compounds.
The presence of such high concentrations of lead and
(presumably hexavalent) chromium in this waste stream, in and of
itself, raises regulatory concerns. Furthermore, the Agency has
data see table 2, p. 8) from the proposed EPA Extraction Proce-
dures (Samples 1-4) and an industry-conducted water extraction
(Sample 5) which show that lead, chromium and cadmium may
*The absence of cadmium from the waste sample described in
Table 1 may be attributable to the fact that 29% of the
constituents (by weight) of the waste sample are not accounted
for, or the fact that the composition of electric furnace
dust can vary considerably depending on the type and quantity
of cold scrap used to charge the furnace. Cadmium is a demon-
strated waste constituent as evidenced by its presence in
significant concentrations in the leachate tests on electric
furnace dusts shown in Table 2 below.
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Table 1
Composition of an Electric Furnace Dust*
Parameter
Fe (total)
MnO
Si02
A1203
CaO
CuO
Ni
Pb
Zn
F
Weight % (not intended to
total 100Z)
Total
70.89
Source: Reference 3
^Although the data in Table 1 is presented for the
electric furnace dusts collected by baghouse filters or
electric precipitators and not for the sludges produced
by Venturi scrubbers, the solids composition of the sludges
produced by scrubbers can be assumed to be virtually the same
as that of the electric furnace dusts since both wet and dry
air pollution systems entrain the same heavy metal particulate
-7VJ-
-------
leach from electric furnace dusts in significant concentrations.
In view of the relative insolubility of trivalent chromium
(see Attachment I), the demonstrated leaching of chromium in
these tests points to the probable presence in these wastes
of hexavalent chromium. All of the waste extracts--either
by the EPA EP procedure which uses acetic acid as its leaching
solution, or by the industry test which uses distilled water--
contain contaminants in concentrations which are either
equal to or, for the most part, exceed EPA's National Interim
Primary Drinking Water Standards, in some instances by several
orders of magnitude. The distilled water extraction shown
in Sample 5 of Table ? indicates that these wastes may leach
harmful concentrations of lead, cadmium, and (presumably
hexavalent) chromium even under relatively mild conditions.
This conclusion is further supported by different
solubility tests done on electric furnace emission control
dust waste samples, also using water as the leaching medium
(1). In this test, lead was again found to leach at dangerous
concentrations, e.g. ISO ppn. Another water solubility test
done on an electric furnace sludge waste sample likewise
showed chromium and lead to leach from the sludge in signifi-
cant concentrations of 94 ppra and 2.0 ppra, respectively (1).
If these wastes are exposed to more acidic environments
(landfills or disposal environments subject to acid rainfall)
these metals' concentrations in leachate would likely be
higher, since most compounds of lead, cadmium, and chromium
are more soluble in acid than in distilled water (S, 6,7) .
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Table 2.
Leach Test Results (mg/1) on Electric Furnace Emission Dusts
National Interim
Pr imary
Drinking Water Sample Sample Sample Sample Sample Sample
ontaminant Standard 1* 2* 3* 4* 5** 6***
Cd 0.01 0.05 2.84 3.85 4.8-13.4 3.5
Cr 0.05 <0.1 0.48 - 0.05 1,248.0 120.0
Pb 0.05 0.5 0.06 36.7 <0.2 0.3 .16
*EP extraction data submitted by an American Iron and Steel Institute
letter to John P. Lehman from Earle F. Young, Jr., dated May 15, 1979
**Waste Characterization Data for the State of Pennsylvania,
Department of Environmental Resources. The data for Sample 5
was supplied by Allegheny Ludlum Steel Corporation from a
water extraction procedure. The apparent discrepancy between
the result obtained for chromium in Sample 5 and those obtained
for chromium in Samples 1-4 may be attributable to the particu-
lar type and quantity of scrap metal used in the steelmaklng
processes which produced these waste samples.
***Source: Reference 3 water extraction.
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Many of the states in which the majority of these wastes
are generated, including Ohio, Pennsylvania, Illinois and
Indiana, are known to experience acid rainfall (8).
A further indication of the migratory potential of the
waste constituents is the physical form of the waste itself.
These waste dusts/sludges are of a fine partlculate composition,
thereby exposing a large surface area to any percolating
medium, and increasing the probability for leaching of hazardous
constituents from the waste to groundwater.
2. Substantial Hazard from Waste Mismanagement
In light of the demonstrated migratory potential of
harmful concentrations of the waste constituents, im-
proper management of these wastes could easily result in the
release of contaminants. For instance, selection of disposal
sites in areas with permeable soils can permit contaminant-
bearing leachate from the waste to migrate to surface water
and/or groundwater. The possibility of groundwater contami-
nation is especially significant with respect to disposal of
these wastes in surface impoundments, since a large quantity
of liquid is available to percolate through the solids and
soil beneath the fill.
An overflow problem might also be encountered if these
wastes are ponded and the liquid portion of the waste has
been allowed to reach too high a level in the lagoon; a
heavy rainfall could cause flooding which might result in
the contamination of soils and surface waters in the vicinity.
-------
In addition to difficulties caused by improper site
selection, unsecure landfills in which dusts and dredged
solids could be disposed of are likely to have insufficient
leachate control practices. There may be no leachate collection.
ar. treatment system to diminish leachate percolation through
the wastes and soil underneath the site to groundwater and
there may not be a surface run-off diversion system to prevent
contaminants from being carried from the disposal site to
nearby surface waters.
In addition to ground and surface water contamination,
airborne exposure to lead, chromium, or cadmium particulate
escaping from mismanaged emission control dusts is another
pathway of concern. These minute particles could be dispersed
by wind if waste dusts are piled in the open, placed in
unsecure landfills or improperly handled during transportation.
As a result, the health of persons who inhale the airborne
participates would be jeopardized. This is especially true for
hexavalent chromium compounds, whose carcinogenicity via
inhalation is especially well substantiated.
Transportation of these wastes to off-site disposal
facilities increases the likelihood of their causing harm to
human beings and the environment. The mismanagement of these
wastes during transportation may thus result In an additional
hazard. Furthermore, absent proper management safeguards,
the wastes might not reach the designated destination at
all, thus making them available to do harm elsewhere.
-------
The ?ead ^brcmJi'n anH. cadmium that may migrate from
Lhe waste to tha environment as a result of such improper
disposal practices ar» elemental metals that persist inde-
finitely in the environment in some form. Therefore,
contaminants migrating from these wastes may pollute the
environment for long periods of time.
3. Justification for T Listing
The Agency has determined to list emission control dusts/
sludges from the primary production of steel in electric furnaces
as a T hazardous waste on the basis of lead, chromium and
cadmium constituents, although these constituents are also
measurable by the E toxicity characteristic. Although concen-
trations of these constituents in an EP extract from waste
streams from particular sites may not always be greater than
100 times the National Interim Primary Drinking Water Standards,
the Agency believes that there are factors in addition to
metal concentrations in leachate which justify the T listing.
Some of these factors have already been identified, namely
the high concentrations of cadmium, chromium and lead in the
actual waste and in leachate samples, the non-degradabillty
of these substances, and the strong possibility of the lack
of proper management of the wastes in actual practice.
The quantity of these wastes generated is an additional
supporting factor. As indicated above, electric furnace
emission control dusts/sludges are generated in very substan-
tial quantities, and contain high concentrations of the
-------
toxic metals Ir-^d, chrotaiura and cadmium. Large amounts
of each of these metals are available for environmental
release. The large quantities of these <. <~ ntam' nant s pose
the danger of polluting large areas of g :ound or surface
waters. Contamination could also occur for long periods of
time, since large amounts of pollutants are available for
environmental loading. Attenuative capacity of the
environment surrounding the disposal facility could also be
reduced or used up due to the large quantities of pollutant
available. All of these considerations increase the possibility
of exposure to the harmful constituents in the wastes, and
In the Agency's view, support a T listing.
V. Hazards Associated with Lead, Chromium, and Cadmium
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.
Lead may enter the human system through inhalation, ingestion
or skin contact. Hexavalent chromium is toxic to man and
lower forms of aquatic life. Cadmium is also a cumulative
poison, essentially irreversible in effect. Excessive
intake leads to kidney damage, and inhalation of dusts also
damages the lungs. Additional information on the adverse
health effects of lead, chromium, and cadmium can be found
in Appendix A.
The hazards associated with exposure to lead, chromium,
and cadmium have been recognized by other regulatory programs.
-------
Lead, chromium &nd cadmium are listed as priority pollutants
in accordance with §307(a) of the Clean Water Act of 1977.
Under §6 of the Occupational Safety and Health Act of 1970, a
final standard for occupational exposure to lead has heen
established and a draft technical standard for chromium has
heen developed (9, 10). Also, a national ambient air quality
standard for lead has been announced by EPA pursuant to the
Clean Air Act (9). In addition, final or proposed regulations
of the State of California, Maine, Massachusetts, Minnesota,
Missouri, New Mexico, Oklahoma and Oregon define chromium and
lead containing compounds as hazardous wastes or components
thereof (11).
SPA has proposed regulations that will limit the amount
of cadmium in municipal sludge which can be landspread on
cropland (12). The Occupational Safety and Health Administration
(OSHA) has issued an advance notice of proposed rulemaklng
for cadmium air exposure based on a recommendation by the
National Institute for Occupational Safety (13). EPA has also
prohibited the ocean dumping of cadmium and cadmium compounds
except when present as trace contaminants (14). EPA has
also promulgated pretreatment standards for electroplaters
which specifically limit discharges of cadmium to Public
Owned Treatment Works (15).
-yf-
-------
References
1. U.S. EPA. Office of Solid Waste. Assessment of hazardous
waste practices in the metal smelting and refining industry.
v.3. EPA No. 8w-145c3. NTIS PB No. 276 179. April, 1977.
2. U.S. EPA. Development document for proposed effluent
limitations guidelines and standards for the iron and
steel manufacturing point source category, v.5. EPA No.
440/l-79/024a. October, 1979.
3. Waste Characterization Data from the State of Pennsylvania
Department of Environmental Resources; letter from
P.Y. Masciantonio to T. Orlando, dated September 8, 1975.
4. U.S. EPA. Quality criteria for water. Washington, D.C.
1976.
5. CRC Handbook of Chemistry and Physics, 52nd ed. The Chemical
Rubber Company, Cleveland, Ohio. 1971-72.
6. The Merck Index, 8th ed. Merck & Co., Inc., Rahway, N.J.
1968.
7. Pourbaix, M. Atlas of electrochemical equllbria in aqueous
solutions. Pergamon Press, London. 1966.
8. Not used in text.
9. U.S. Department of Interior, Bureau of Mines. Mineral
commodity summaries, 1979.
10. NIOSH. Registry of toxic effects of chemical substances.
U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health. 1977.
11. U.S. EPA State Regulations Files. Hazardous Waste State
Programs, Wh-565, U.S. EPA, 401 M St., S.W., Washington,
D.C. 20460. Contact Sam Morekas. (202) 755-9145.
12. 44 FR 53449.
13. 42 F_R 5434.
14. 38 F_R 28610.
15. Federal Register. Vol. 44. No. 175. Friday, September 7, 1979,
(40 CFR Part 413).
-7^7-
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Attachment I
ITY AND ENVIRONMENTAL MOBILITY
CHARACTER1STICS OF CHROMIUM_COMPOUNDS
The trlposltive state is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of ligands such as water,
ammonia, urea, halldes, sulfates, amines and organic
acids.(ai*0 Thousands of such compounds exist. This
complex formation underlies the tanning reactions of chromium,
and is responsible for the strong binding of trivalent chromium
by soil elements, particularly clays.(c»ri)
At pH values greater than about 6, trivalent chromium
forms high molecular weight, insoluble, "polynuclear" complexes
of Cr(OH)3 which ultimately precipitate as Cr203.nH20. This
process is favored by heat, increased chromium concentration,
salinity and time.C3) These chromium hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form, Cr
is therefore resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubilization of
chromium hydroxide:
A/1
-------
Reaction
1. Cr(OH)3+2H+
2. Cr(OH)3
3. Cr(OH)
+2H20
Cr+3+30H~
Keg
.(18)
10°
6.7xlO~31
9x10'
,-17
Cr(III) Concentration
Calculated from keg (mg/1
pH5
520
35
i
pH6 pH7
5.2 0.052
0.035 1*
i i
*i= <0.001 mg/1
It is apparent from these figures that, in theory, trivalent
chromium could leach from sludges to some extent. Such
solubilized chromium, however, is unlikely to contaminate
aquifers. It is complexed with soil materials, and tenasiously
held.(a»d) Little soluble chromium is found in soils.(«»e)
If soluble trivalent chromium Is added to soils it rapidly
disapperas from solution and is transformed into a form that
is not extracted by ammonium acetate or complexing agents.(cifi)
However, it is extractable by very strong acids, indicating
the formation of insoluble hydroxides.(d»e) Thus: above pH5,
chromlum(III) is immobile because of precipitation; below
pH4, chrooiura(III) is Immobile because it is strongly absorbed
by soil elements; between pH 4 and 5 the combination of
absorption and precipitation should render trivalent chromium
quite immobile.(c»d)
In contrast, hexavalent chromium compounds are quite
soluble, and hexavalent chromium is not as strongly bound to
-------
soils.(c»d) Hexavalent chromium remains as such in a
soluble form in soil for a short time, and is eventually
reduced by reducing agents if present.'e»*' As compared
with the trivalent form, hexavalent chromium is less strongly
adsorbed and more readily leached from soils(d) and thus, is
expected to have nobility in soil materials.
-------
Response to Comments-Emission Control Dust/Sludge from the
Electric Furnace Production of Steel
One coramenter requested a clarification on the scope of
waste K061 (Emission control dust/sludge from the electric
furnace production of steel). The commenter indicated that
It was not clear whether the listing description applied
only to primary steel production or to both primary steel
producers and to foundries using steel scrap In their electric
furnace production.
In listing waste K061 (Emission control dust/sludge from
the electric furnace production of steel), the Agency Intended
only to include wastes from primary steel production. This
Intent is reflected in the listing hackground document, which
refers throughout to primary steel production. The Agency
is uncertain whether foundry electric furnace emission control
dusts and sludges are sufficiently similar in composition to
warrant inclusion in the same listing, and so we are evaluating
the potential hazardousness of foundry Industry wastes in
separate actions. (See 44 F_R at 49404 (August 22, 1979), and
4-i FR at 47836 (July 16, 19RO).)
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References
a. U.S. EPA, Reivews of the Enviromental Effects of Pollutants;
III Chromium. ORNL/EIS-80; EPA-600/1-78-023; May 1980.
b. Translstion Metal Chemistry, R.L. Carlin, ed. Marcel
Dekker, New York. 1965; Volume 1.
c. Bartlett, R.J. and J.M. Kirable. Behavior of Chromium in
Soils: I Trivalent Forms. J. Environ. Qual. 5: 379-383:
1976.
d. Griffin, R.A., A.K. Au, and R.R. Frost. Effects of
pH on adsorption of chromium from landfill leachate by
clay minerals. J. Environ. Sci. Health A12(B);
430-449:1977.
e. U.S. EPA. Application of Sewage Sludge to Cropland;
Appraisal of Potential Hazards of the Heavy Metals to
Plants and Animals. EPA 430/9-76-013. NTIS PB No.
264-015. November, 1976.
f. Bartlett, R.J. and J.M. Kimble. Behavior of Chromium in
Soils: II Hexavalent Forms. Ibid. 5:383-386. 1976.
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JB-03(a)-l
LISTING BACKGROUND DOCUMENT
Steel Finishing
Spent Pickle Liquor (C) (T)*
I. Summary of Basis for Listing;
Spent pickle liquor is generated in the pickling of
iron and steel to remove surface scale. The Administrator
has determined that spent pickle liquor is a solid waste
which may pose a present or potential hazard to human health
and the environment when improperly trans po-rted , treated,
stored, disposed of, or otherwise managed, and, therefore,
should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the
following considerations:
1. Spent pickle liquor is corrosive (has been shown to
have pH less than 2), and contains significant
concentrations of the toxic metals lead and
chromium.
2. The toxic metals in spent pickle liquor are present
in highly mobile form, since it is an acidic solution.
Therefore, these hazardous constituents are readily
available to migrate from the waste in harmful
concentrations, causing harm to the environment.
*In response to comments received by the Agency on the
interim final list of hazardous waste (45 FR 33124, May 19,
1980), sludge from lime treatment of spent pickle liquor
has been removed from the hazardous waste list (see Response
to Comments at the back of this listing background document
for more details).
-------
3. Current waste management practices of untreated spent
pickle liquor consist primarily of land disposal
either in unlined landfills or unlined lagoons
which may.be Inadequate to prevent the migration of
lead and chromium to underground drinking water
sources. Treatment of the spent pickle liquor by
neutralization is also comraonly practiced by the
industry in which case, a lime treatment sludge is
generated.
4. A very large quantity (approximately 1.4 billion
gallons of spent pickle liquor) is generated
annually. There is a great likelihood of
large-scale contamination of the environment
if these wastes are not managed properly.
5. Damage incidents have been reported that are
attributable to the improper disposal of poorly
treated spent pickle liquor.
II. Industry Profile and Process Description
Pickling operations are very widespread across the
United States. Spent pickle liquor is generated at 240 plants
located in 34 states. Approximately 70% of these plants are
situated in Pennsylvania, Ohio, Illinois, Indiana and Michigan.
Pickling capacity within the Iron and steel Industry, according
to the type of acid used, is shown in Table 1 below.t1'
The pickling operation involves the immersion of oxidized
steel in a heated solution of concentrated acid or acids (the
pickling agent) to remove surface oxidation or to impart specific
surface characteristics. At integrated steel plants, acid pickle
liquors are used in cold rolling mills and galvanizing mills.
Depending on the type of steel being processed, or the type
of surface quality desired, different types of acids may be
used. For example, most carbon steels are pickled in sutfuric
-------
or hydrochloric acids, while most stainless and alloy steels
are pickled in a mixture of nitric and hydrofluoric acids. C1)
After a certain concentration of metallic ions build up in
the pickling bath, the solution is considered spent or exhausted
and roust be replaced.
Table 1
Number of Annual Capacity,
Pickling Agent Plants* tons of steel/yr_
HC1 43 30,000,000
149 28,000,000
Mixed acid
(e.g. HF-HN03) 152 6,000,000
III . Waste Generation and Management
Approximately 1.4 billion gallons of spent pickle liquor
are generated annually: 500 million gallons of spent sulfuric
acid, 800 million gallons of spent hydrochloric acid, and 74
million gallons of a combination (mixed) of pickling acids.**
When treated with lime, spent pickle liquors form a spent pickle
liquor lime treatment sludge.
The spent pickle liquor is a strongly acid solution (pH <1)
containing very high concentrations of dissolved iron, and
*If the same plant uses two or three pickling agents, it Is
listed once for each agent used.
**Estimates based on waste generation data contained in
Reference 1.
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significant amounts of many other metals, including chromium
(26-4250 ppra).(*-) Hexavalent chromium concentrations are
rarely reported, but since steel is manufactured in an oxidiz-
ing environment, and at high temperatures, and since it is the
purpose of the pickling operation to remove residual metal
oxides from the steel surface, it is expected that the pickling
liquor will, in fact, contain significant amounts of hexavalent
chrome.
Approximately 40% of the mills utilizing the sulfuric
acid pickling process discharge these and other pickling
wastes after treatment to a receiving body of water. Another
452 of these mills have the spent pickle liquor hauled off-
site by private contractors. Outside contract disposal
services generally neutralize spent pickle liquors in unlined
lagoons.'2) The remaining 15% of the sulfuric acid
pickling mills either utilize deep well disposal, engage in
acid recovery, or discharge the treated waste to Publicly
Owned Treatment Works (POTWs) along with other pickling
wastes which have undergone varying degrees of treatment.
Disposal practices of combination acid pickling mills and
hydrochloric acid pickling mills are known to be similar to
those used by sulfuric acid pickling mills.(1)
IV. Hazardous Properties of the Waste
The pickling process requires highly acidic solutions;
hence, spent pickle liquors are highly corrosive, with a
-------
pH of less than 2 (see Table 2). Therefore, this waste
meets the corroslvity characteristic (§261.22) and is thus
defined as hazardous. In addition, Agency data indicate that
significant levels of the toxic metals lead and chromium are
found in the spent pickle liquor (see Table 2 below).
Table 2
Typical Concentratons of Lead and Chromium in
Spent Pickle Liquors (mg/1 )
Parameter HpSO^Bath
pH 1.0-2.0
Cr 26-269
Pb ND*-2
*ND=Nondetectable
Source: Reference 1
HCL Bath Mixed Acid Bath
1.0-4.5 1.3-1.5
2-37 3300-4250
2-1550 1-4
Based on the higher concentration levels listed in
Table 2 for chromium and lead (4250 and 1550, respectively),
if only .12% of the chromium (if hexavalent) and .33% of the
lead leach from the spent pickle liquor, this amount would
exceed the permissible concentrations of chromium and lead
in the EP extract.* Since the spent pickle liquor is a
highly acidic solution, these toxic metals are readily
available to migrate into the environment, as they are more
*The concentrations of lead and chromium in these wastes can vary,
depending upon the composition of the raw materials used to nanu-
facture the steel and the particular type of steel pickled.
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soluble in acidic environments.^) In particular, since
trivalent chromium has only slight solubility in acids and
the hexavalent form is extremely soluble, the chromium in
the acid leachate will be overwhelmingly hexavalent. Thus,
disposal of this waste in landfills or lagoons, if improperly
managed, is likely to lead to the migration of harmful consti-
tuents into the environment and pose a substantial hazard
via a groundwater exposure pathway.
Possible Types of Improper Management and Available
Pathways of Exposure
As shown above, disposal of spent pickling liquors
creates the potential for leaching of the toxic metals
(presumably hexavalent) chromium and lead to groundwater, a
common source of drinking water. In addition, improper
storage and/or disposal of spent pickling liquor poses poten-
tial hazards stemming from the high acidity of the wastes.
In particular, if not segregated in a landfill, spent pickle
liquors can extract and solubilize toxic contaminants (especially
metals) from other wastes disposed in the landfill. In view
of the low solubility of most trivalent chromium compounds,
and the high solubility of most hexavalent forms (see Attachment I),
the leachate is expected to contain predominately the hexavalent
form. If not stored in special containers, pickle liquors
can, over time, corrode the containers, resulting in leakage
and potential acid burns to individuals who may come in
contact with the waste.
Transportation of about 45% of the spent pickle
-------
neutralization (see p. 4, above) increases the likelihood of
their causing harm to people and the environment. Improper
containment of these wastes may result in their doing harm to
individuals or to the environment during transportation to their
designated destination. Moreover, mismanagement of these wastes
during transportation may result in their not reaching their
designated destination at all, thus making them available to do
harm elsewhere.
Once released from the matrix of the waste, lead and (presumably
hexavalent) chromium can migrate from the disposal site to ground
and surface waters used as or constituting potential drinking
water sources. Present practices associated with landfilling
or impounding the waste may be inadequate to prevent such an
occurence. For instance, selection of disposal sites in areas
with permeable soils can permit contaminant-bearing leachate
from the waste to migrate to groundwater.
An overflow problem might also be encountered if the liquid
portion of the waste has been allowed to reach too high a level
in the lagoon. Thus, a heavy rainfall could cause flooding
which might reach surface waters in the vicinity.
In addition to difficulties caused by improper site selection,
unsecure landfills in which wastes may be disposed of are likely
to have insufficient leachate control practices. Available
information, in fact, indicates that liners are not presently
used in the landfilling or lagooning of these wastes.'*'
There may be no leachate collection and treatment system to
diminish leachate percolation through the wastes and soil
-------
underneath the site to groundwater and there may be be no
surface run-off diversion system to prevent contaminants
from being carried from the disposal site to nearby surface
wa t e r s .
An additional regulatory concern is the huge quanti-
ties of these wastes generated annually. Spent pickle liquor
is generated in very large quantities. The large quantities
of this waste and the contaminants it contains pose a serious
danger of polluting large areas of ground or surface waters.
Contanination could also occur for long periods of time
since large amounts of pollutants are available for environmental
loading. Attenuative capacity of the environment surrounding
the disposal facility could also be reduced or used up due
to the large quantities of pollutants available.
V. Hazards Associated with Lead and Chromium
The lead and chromium that may migrate from the wastes
to the environment as a result of such improper disposal
practices are metals that persist in the environment In some
form and, therefore, may contaminate drinking water sources
for long periods of time. Hexavalent chromium Is toxic to nan
and lower forms of aquatic life. 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 deleterous
effects are numerous and severe. Lead may enter the human
system through inhalation, ingestion or skin contact.
-------
Improper management of these wastes may lead to ingestion of
contaminated drinking water. Aquatic toxicity has been observed
at sub-ppb levels. Additional information on the adverse health
effects of chromium and lead can be found in Appendix A.
The hazards associated with lead and chromium have been
recognized by other regulatory programs. Lead and chromium
are listed as priority pollutants in accordance with §307(a) of
the Clean Water Act of 1977. National Interim Primary Drinking
Water Standards have been established for both parameters.
Under §6 of the Occupational Safety and Health Act of 1970, a
final standard for occupational exposure to lead and chromium
has been established and promulgated in 19 CFR 1910.1000.(8>9)
Also, a national ambient air quality standard for lead has been
announced by EPA pursuant to the Clean Air Act. ^8) In addition,
final or proposed regulations of the States of California, Maine,
Massachusetts, Minnesota, Missouri, New Mexico, Oklahoma and
Oregon define chromium and lead-containing compounds as hazardous
wastes or components thereof.(10)
V I. Damage Incidents*
These damage incidents are attributable to the improper
disposal of spent pickle liquor. They are just a few
examples of the damage which may result if these wastes are
mi smanaged.
*Draft Environmental Impact Statement for Subtitle C, Resource
Conservation and Recovery Act of 1976, Appendices-Reference 7.
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c In Washington County, Pennsylvania, leachate from a
landfill has entered the groundwater and has contaminated
a farmer's well and spring a half mile away. The
landfill accepts sludges containing heavy metals and
poorly neutralized pickle liquor from steel mills.
0 In April, 1975. An employee in York County, Pennsylvania,
siphoned wastes from a company's settling pond into a
storm drain emptying into a fishing creek. The acidity
of the drained wastes caused a fish kill in the creek.
The waste and sludge in the ponds were spent pickle
liquors which had allegedly been neutralized. The
sludge is to be hauled to a landfill and the lagoons
ar e to be 1ined .
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References
U.S. EPA. Draft development document for the proposed
effluent
Iron and
sulfuric
pickling
November,
limitations guidelines and standards for the
steel manufacturing point source category;
acid pickling subcategory, hydrochloric acid
subcategory. v.8. EPA No. 440/l-79-024a.
1979.
2. U.S. EPA. Office of Solid Waste. Assessment of industrial
hazardous waste practices in the metal smelting and
refining industry, v.3. EPA No. SW-145c3. NTIS
PB No. 276 171. April, 1977.
3. Waste characterization data from the State of Illinois
EPA, as selected from State files by U.S. EPA/OSW on
3/14/79 and 3/15/79.
4. Waste characterization data from the State of Pennsylvania
Department of Environmental Resources, Division of
Solid Waste Management, March 20, 1978, as selected
from State files by U.S. EPA/OSW, on 1/4/79 and
1/5/79.
5. Not used in text.
6. Pourbaix, M. Atlas of electrochemical equilibria in aqueous
solutions. Pergaraon Press, London. 1966.
7. Appendix J—Hazardous waste incidents, Draft Environmental
Impact Statement for Subtitle C, RCRA. January 1979,
as synopsized from Office of Solid Waste, Hazardous
Waste Management Division; Hazardous Waste Incidents,
unpublished open file data. 1978.
8. U.S. Department of the Interior, Bureau of Mines.
Mineral commodity summaries. 1979.
9. MIOSH. Registry of toxic effects of chemical substances.
U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health. 1977.
10. U.S. EPA States Regulations Files. January, 1980.
11. Not used in text.
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Attachment I
SOLUBILITY AND ENVIRONMENTAL MOBILITY
CHARACTERISTICS OF CHROMIUM COMPOUNDS
The tripositive state Is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of llgands such as water,
ammonia, urea, halides, sulfates, amines and organic
acids. (a»b) Thousands of such compounds exist. This
complex formation underlies the tanning reactions of chromium,
and is responsible for the strong binding of trivalent chromium
by soil elements, particularly clays.(c,d)
At pH values greater than about 6, trivalent chromium
forms high molecular weight, insoluble, "polynuclear" complexes
of Cr(OH)3 which ultimately precipitate as Cr203.nH20. This
process is favored by heat, increased chromium concentration,
salinity and time.^a^ These chroniura hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form, Cr
is therefore resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubilization of
chromium hydroxide:
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Reaction
1. Cr(OH)3+2H+
2. Cr(OH)3
3. Cr(OH)
Cr+3+30H~
H+Cr02~+H20
Keq
.(18)
103
6.7xlO~31
9xlO~17
Concentration
Calculated from keg (mg/1)
pH5
520
..U £ Mil 7
>>rtD pfl /
5.2 0.052
0.035 i*
i i
*i= <0.001 rag/1
It is apparent from these figures that, in theory, trivalent
chromium could leach from sludges to some extent. Such
solubilized chromium, however, is unlikely to contaminate
aquifers. It is complexed with soil materials, and tenasiously
held. Little soluble chromium is found in soils.<*•«>
If soluble trivalent chromium is added to soils it rapidly
disapperas from solution and is transformed into a form that
is not extracted by ammonium acetate or complexing agents.(c»e/
However, it is extractable by very strong acids, indicating
the formation of insoluble hydroxides. (d ,,e) Thus: above pH5,
chroralumC III) Is immobile because of precipitation; below
pHA, chromium(111) is immobile because it is strongly absorbed
by soil elements; between pH 4 and 5 the combination of
absorption and precipitation should render trivalent chromium
quite immobile.(c>d)
In contrast, hexavalent chromium compounds are quite
soluble, and hexavalent chromium is not as strongly bound to
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soils.(°>- ' Hexavalent chromium remains as such in a
soluble form in soil for a short time, and is eventually
reduced by reducing agents if present.(e»*) As compared
with the trivalent form, hexavalent chromium is less strongly
adsorbed and more readily leached from soils(d) and thus, is
expected to have mobility in soil materials.
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References
U.S. EPA, Reivews of the Enviroraental Effects of Pollutants;
III Chromium. ORNL/EIS-80; EPA-600/1-78-023; May 1980.
Transistion Metal Chemistry, R.L. Carlln, ed. Marcel
Dekker, New York. 1965; Volume 1.
Bartlett, R.J. and J.M. KImble. Behavior of Chronium in
Soils: I Trivalent Forms. J. Environ. Qual. 5: 379-383:
1976.
Griffin, R.A., A.K. Au, and R.R. Frost. Effects of
pH on adsorption of chromium frots landfill leachate by
clay minerals. J. Environ. Scl. Health A12(8);
430-449:1977.
U.S. EPA. Application of Sewage Sludge to Cropland;
Appraisal of Potential Hazards of the Heavy Metals to
Plants and Animals. EPA 430/9-76-013. NTIS PB No.
264-015. November, 1976.
Bartlett, R.J. and J.M. KImble. Behavior of Chromium in
Soils: II Hexavalent Forms. Ibid. 5:383-386. 1976.
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Response L.» •>... .....it. Spent Pickle Liquor and Sludge
1 >om Lime Tr&ataent of Spent Pickle Liquor ',.n Steel
Finishing Operations
Spent Pickle Liquor from Steel Finishing Operations (K062)
One comraenter requested that this particular listing be
deleted, in its entirety, from the hazardous waste regula-
tions. In the comment, it is pointed out that spent pickle
liquor is widely used to precipitate phosphorous from wastewater
in publicly owned treatment plants (POTW's). The commenter
also states that pickle liquor is used for sludge conditioning.
These practices have been the subject of numerous demonstration
grants, research reports, major technology transfer promotions,
etc., and the commenter argues that if pickle liquor is desig-
nated as hazardous, then many POTW's may be considered unrealis-
cically to be storers and treaters of hazardous waste.
Finally, the commenter indicates that in several literature
reviews, including several EPA reports, it is stated that
inorganic coagulants, preclpltants and sludge conditioners,
such as pickle liquor, contribute to the removal and precipita-
tion of various components from wastewaters that were originally
present from other natural sources and are not in themselves
a significant source of toxic heavy metals such as Cr and Pb.
The short answer to this comment is that POTW's using
spent pickle liquor in treatment operations are deemed to have
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a permit by rule, subject to the conditions specified in
§122.26(c) (45 FR 33435). Thus, Che coraraenter's principal
concerns have already been dealt with.
Moreover, the comment is misplaced in that it faily
to challenge the Agency's determination that spent pickle
liquor is hazardous* The Agency continues to stand on
its finding that this waste streao is indeed hazardous. We
note in this regard, that the American Iron and Steel
Institute, whose members are among the principal* generators
of this waste, does not challenge the listing.
It may be that the commenter is arguing that the
reuse of spent pickle liquor should not be deemed hazardous
waste management.
As discussed in the preamble to the Part 261 regulations
promulgated on May 19, 1980 (45 FR 33091-33095), the Agency
has concluded that it does have jurisdiction under Subtitle C
of RCRA to regulate waste materials that are used, reused,
recycled or reclaimed. Furthermore, we reasoned that
such materials do not become less hazardous to human health
or the environment because they are intended to be used,
reused, recycled or reclaimed in lieu of being discarded.
Although the materials after being recycled and reclaimed
may not pose a hazard, the accumulation, storage and transport
of a hazardous waste prior to use, reuse, recycle or reclamation
will present the same hazard as they would prior to being
discarded. In addition, the act of use, reuse, recycling or
-------
rec" imation1, in many cases, poses a hazard equivalent to
tha enountered if the waste were discarded. Thus, the
Agency believes it has a strong environmental rationale for
r. lating hazardous wastes that are used, reused, recycled
it reclaimed.
For the particular wastes at issue, the Agency found
that this waste for most ?/ all of its existence prior to
being recycled is sto:.:d in tanks or drums. If not stored
in special contair«-.rs, pickle liquors can corrode the containers,
resulting in ^C-akage and potential acid burns to individuals
who may co.ie in contact with the waste. Consequently, the
waste must be considered a hazardous waste in this environment.
Sludge from Lime Treatment of Spent Pickle Liquor from
Steel Finishing Operations
A number of comments were received which objected to the
listing of sludge from lime treatment of spent pickle liquor
from steel finishing operations as a hazardous waste. The
coramenters argue that the Agency's rationale for listing
this particular waste is objectionable both on procedural
grounds and on technical grounds. With respect to the pro-
cedural arguments, the commenters point out that the Agency
has failed to articulate the bases for its conclusion, effec-
tively precluding meaningful comment. In addition, they
argue that in analyzing the listing background document, the
Agency has Ignored its own standards and procedures for de-
termining hazardousness; and thus, they claim that the Agency
-------
has violated fundamental principles of administrative law,
and that Its decision to list sludge from lime treatment of
•"pnt pickle liquor is unlawful.
On the technical side, the commenters argue that the Agency
has relied on inadequate or inappropriate data to reach its con-
clusions, and that to the extent that the conclusion is discussed,
none of the assertions are adequately substantiated in the
listing background document or references cited therein.
For example, the commenter points out that the listing
background document does not show the specific data or go
through the calculations from which EPA derived the "average"
chromium and lead concentrations in the sludge. The most
important objection, however, relates to the use of a single
leaching teet, using the Illinois EPA extraction procedure,
to make the statement that leaching of chromium and lead has
been shown to occur. The coramenters took special exception
to the use of the Illinois EPA extraction procedure, a test
which calls for the addition of an unlimited amount of acid
to maintain a pH of 4.9 to 5.2, rather than the U.S. EPA
extraction procedure which calls for maintenance of acid
conditions, but allows only limited acid addition. To refute
the leaching argument, one commenter submitted data on leachate
tests carried out by a number of steel companies using the
Agency's extraction procedure (see Table 1).
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Table 1
Leachate Analysis Using EPA's Extraction
Procedure on Sludge from che Lj^e Treatment
of Spent Pickle Liq-ioi
Sludge
Sample
6
12
28
1
2
Cr(mg/l)
0.002
0.002
0.002
0.05
0.03
Pb(mg/l)
0.006
0.004
0.002
0.15
0.19
The commenter felt that these data indicate that the
sludge from lime treatment of spent pickle liquor is not
hazardous because all concentrations are well below EPA's
promulgated limit for classification as a hazardous waste.
Therefore, the commenters recommended the sludge from lime
treatment of spent pickle liquor be deleted from the list of
hazardous waste.
The Agency strongly disagrees with the commenter that
the Agency has ignored its own standards and procedures for
determining the hazardousness of the waste. This particular
waste (K063) was assigned a "T" hazard code, indicating a
toxic waste. The listing criteria for toxic wastes provide
that a waste will be listed as hazardous where it contains
any of a number of designated toxic constituents, unless
after consideration of certain specified factors (261.11(a)(3)),
the Agency concludes that the waste does not meet part [B] of
the statutory definition of hazardous waste.
-------
In waste K063, rhe Agency Identified two toxic constituents
(chromium and lead) ir. the waste. The Agency then evaluated
the toxicity of this waste based on a nujioer of the factors
cited in §261.11(a)(3) (i.e., concentration of the constituent
in the waste, potential of the constituents to migrate from
the waste, the persistence of the toxic constituents, plausible
types of improper management, etc.). Based on the available
data, the Agency felt that sludge from lime treatment of spent
pickle liquor may present a substantial hazard to human health
or the environment, if improperly managed. With respect to
the commenters objection to consideration of data derived from
use of the Illinois EPA extraction procedure, the Agency strongly
believes that any extraction testing, whether used by the States,
industry or Federal government, may be considered by the Agency In
evaluating the migratory potential of the toxic constituents
In the waste. § 26 1.11 (a) ( 3) ( Hi ) does not require the
Agency to use the EP but rather to assess "...the potential
of the constituent or any toxic degradation product of the
constituent to migrate from the waste into the environment
under the types of improper management considered In paragraph
(a)(3)(vll) of this section." For this particular waste, the
Illinois EPA extraction procedure may be most appropriate for
determining the potential mobility of the heavy metals in the
waste because of the potential for this waste to be mixed with
other acid wastes or the potential for the spent pickle liquor
to be poorly neutralized (see section VI of the background document).
-------
However, in recognition of the comnenter's data, the
Agency has decided to delete this waste from the interim
final hazardous waste list, and to rely on the provisions of
§2m.3 to bring these wastes within the hazardous waste
management system. Since these line treatment sludges are
generated from the treatment of a listed hazardous waste
(K062), they are considered to be hazardous wastes (§ 261.3(c)(2))
and will remain as hazardous unless and until they no longer
meet any of the characteristics of hazardous waste and are
delisted ($261. 3
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Non-Ferrous Smelting and Refining Industry
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SJ-22-02
PRIMARY COPPER SMELTING AND REFINING
Acid plant blowdown slurry/sludge resulting from
the thickening of blowdown slurry (T)
Summary of Basis for Listing
Acid plant blowdown slurry/sludge, resulting from
the thickening of the blowdown slurry, is a waste stream
from the treatment of the acid plant blowdown slurry at
facilities where primary copper is smelted in a reverberatory
furnace. The Administrator has determined that these
sludges 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 requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations
1) Acid plant blowdown slurry contains high concentrations
of the toxic heavy metals lead and cadmium.*
2) A large quantity of these wastes is generated annually
(approximately 286,000 MT (dry weight) was produced in
1977) and this quantity is expected to increase to
360,360 MT by 1983.
3) A solubility study has shown that lead and cadmium can
he ledched from these sludges by even a mild (distilled
water) leaching media. Therefore, even under the mild
conditions, the possibility of groundwater contami-
*For concenrrations of other listed toxic heavy metals that
Ho not warrant waste listing, see Attachment 1.
-------
nation via leaching will exist if these waste materials
are improperly disposed.
4) Current waste management practices consist of storage or
disposal in unlined lagoons. These waste management
practices may not be adequate to prevent a hazard
to human health and the environment.
Discussion
A. Profile for the Industry
A 1977 review (1) indicated that there were 15 primary
copper smelters in the United States operated by eight
companies. A more recent source (2) identifies seventeen
primary smelters operated by nine companies. Table 1 lists
the seventeen plants and their production capacities. Almost
all of the smelting capacity is concentrated in the south-
western United States, primarily Arizona and New Mexico. An
average smelter can be assumed to have a capacity of 100,000
metric tons per year (1). Total national production of
copper is increasing, based on a comparison of total capacities
cited by References 1 and 2.
B. Manufacturing Process
Processing of copper includes mining, concentrating of
ores, smelting and refining. The smelting process involves
two basic steps (3). First, the copper concentrate is melted
in a reverberatory furnace to yield matte, which is essentially
a mixture of copper and iron sulfides. The matte is then
fed to converters in which air oxidation converts the copper
sulfate to impure copper and the iron sulfide to an iron
-if-
-------
oxide/silicate slag that can be separated from the copper.
The product resulting from the reverberatocy furnace converter
smelting is blister copper. Depending on the intended final
use, the blister copper is purified by fire refining and
electrolytic refining. A flow diagram for the primary copper
smelting process is shown in Figure 1.
The source of the listed waste stream is also indicated
in Figure 1. (Note that the reverberatory furnace slag is
not included in the listing since data submitted during the
comment period indicated that the contaminants in the slag
tend not to migrate out of the waste.) Lead and cadmium,
the metals that constitute the basis for listing, are always
in the waste since they are always present in the basic raw
material, namely copper ore.
C. Waste Generation and Management
As indicated in Figure 1, the listed waste addressed in
this document arises from the acid plant which constitutes
the principal controller for removal of sulfur dioxide from
furnace and converter off-gases (3). The converter off-gases
typically contain 5% or more of sulfur dioxide (3). According
to the Calspan report (1), the acid plant for an average
100,000 metric ton/year smelter generates a blowdown slurry
at a rate of about 2,270 cubic meters/day. After thickening,
the bulk of the solid content of slurry is recycled to the
-777-
-------
IXST TO
JlUCA AtV[*n
/ IAI \ ^ rW
"i ^ ' ' -u* \ v_
Figure 1 PRIMARY COPPER SMELTING AND FIHt REFINING'
Source: reference
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reverberatory furnace.* The overflow from the thickener -
about 2,200 cubic meters per day, conLainlng 0.77 metric tons
of suspended solids and 40 metric tons of dissolved solids -
is sent to a lagoon for settling. The suspended solid content
is eventually recovered and recycled to the smelter.* The 40
metric tons/day of dissolved solids remain in the aqueous la-
goon effluent which is discharged to the main tailings pond.
Available documentation (1) indicates that this sludge
is allowed to accumulate, along with the tailings waste, in
the tailings pond. There is no evidence that this sludge/
tailings mixture is dredged out for further treatment or
disposal. Available documentation also indicates that
these tailings ponds are unlined. These unlined tailings
ponds are, therefore, the point of disposal for the 40 MT/day
of material from the acid plant blowdown slurry that is
not recycled. In comparison, 46 MT/day of thickener
underflow solids and 0.8 MT/day of the overflow suspended
*At this time, applicable requirements of Parts 262 through
265 apply insofar as the accumulation, storage and transpor-
tation of hazardous wastes that are used, reused, recycled,
or reclaimed. The Agency believes that this regulatory
coverage is appropriate for the subject wastes. The slurry/
sludge is hazardous insofar as they are being accumulated
and stored in surface impoundments and insofar as they may
be stored in piles prior to recycling. This waste may not
pose a substantial hazard during the recycling and, even
though listed as a hazardous waste, this aspect of their
management is not now being regulated.
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Table 1
GEOGRAPHICAL DISTRIBUTION AND CAPACITIES OF
PRIMARY COPPER SMELTERS
Company
Location
Smelting
Capacity (MT*/yr)
Anaconda
ASARCO
Cities Service
Copper Range
Hecla Mining
Inspiration
Kennecott
Magma
Phelps Dodge
Anaconda, MT
Hayden, AZ
El Paso, TX
Tacoraa, WA
Copper Hill, TN
White Pine, MI
Casa Grande, AZ
Miami, AZ
Garfield, Utah
Hurley, NM
Hayden, AZ
Me Gill, NV
San Manuel, AZ
Morenci, AZ
Hidalgo, NM
Douglas, AZ
Ajo, AZ
198,000
180,000
115,000
100,000
22,000
90,000
31,000**
150,000
280,000
80,000
80,000
50,000
200,000
177,000
140,000
127,000
70,000
* MT - metric tons
** Smelting is done by a leach process, but the plant has an
acid plant associated with the roaster.
-------
solids are eventually recycled during treatment of the acid
plant blowdown slurry.
Table 2 summarizes the total quantities of acid plant
blowdown slurries (and miscellaneous other small volume
slurries) that are generated. A total of 286,000 metric
tons (dry weight) of waste sludge from primary copper
smelters was generated in 1977. It is estimated (1) that
this quantity will increase by about 267, to 360,360 metric
tons by 1983. The total quantity of waste sludge disposed
of (not recycled) by primary copper smelters in 1977 was
128,400 metric tons (dry weight).
D. Hazards Posed by the Waste
1. Concentrations of Lead and Cadmium in the Waste Stream
The listed waste has been analyzed (1) and found
to contain toxic metals. The concentrations found are
summarized in Table 1.
Sludges also have been subjected to leaching tests
and have been shown (1) to leach lead and cadmium in
significant concentrations. The leaching tests in the
Calspan Study (1) was performed on one sample by
agitating one part waste with two parts distilled water
(initial pH 5.5) for 72 hours. The mixture was then
filtered and analyzed. Table 4 presents the concentrations
found in the leachate from the sludge sample.
As shown by the test results in Table 4, cadmium
appears in concentrations 17,000 times the EPA
National Interim Primary Water Standard, and lead
-79'-
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TABLE 2
ESTIMATED TOTAL WASTE SLUDGES FROM PRIMARY COPPER SMELTERS
IN 1977*
State
Tennessee
Michigan
Texas
New Mexico
Montana
Utah
Ar i zona
Nevada
Washington
(METRIC TONS - DRY
Total Slowdown
Slurry
2,300
17,500
14,800
24,800
28,500
34,300
143,600
6,100
14,100
WEIGHT)
Total Disposed
1,000
7,900
6,700
11,200
13,000
15,000
64,600
2,700
6,300
Total 286,000 128,400
*A number of copper smelters which were in existence in 1974
are no longer in operation, thus, the wastes produced by
these smelters are not Included in this table.
Source: Reference 1, Table 7d
-r-
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TABLE 3
CONCENTRATIONS OF HEAVY METALS IH WASTE
SLUDGES FROM PRIMARY COPPER SMELTERS (PPH)
Metal Sludges
Cadmium 520
Lead £000
Source: Reference 1
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appears in concentrations ISO times the National
Interim Primary Standard.
The distilled water leaching procedure used in
the Calspan tests (1) thus indicates that lead and
cadmium will leach from the waste even when subjected to
mild environmental conditions. A more aggressive leaching
agent may lead to more substantial release of the toxic
metals. Disposal/storage in a surface Impoundment or
landfill with an acidic environment will certainly
enhance the solubility of lead and other metals, since
their solubility is pH dependent (i.e., solubility
Increases as the pH decreases (4)).
The information on the solubility of the compounds
coupled with the fact that solubilization can occur more
readily due to the fine particulate composition of the
sludges suggests that the metals present in the listed
waste may be released from the acid plant blowdown
under improper storage/disposal conditions.
Once released from the matrix of the waste, the
toxic metals can migrate from the disposal/storage site
to ground and surface waters utilized as drinking water
sources. Present practices associated with impounding
the waste may he inadequate to prevent such an occurence.
For instance, selection of disposal sites in areas with
permeable soils can permit contaminant-bearing leachate
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Table 4
CONCENTRATIONS OF HEAVY METALS IN FILTERED DISTILLED
WATER LEACHATE. PPM
Sludges
Cadmium 8.4
Lead 7.8
Source: Reference 1
-------
from the waste to migrate to groundwater. This is
especially significant with respect co ponded wastes
because a large quantity of liquid is available
to percolate through the solids arH soil beneach
the fill.
In addition to difficulties caused by improper
site selection, the lagoon/tailing ponds are likely to
have insufficient leachate and surface run-off control
practices. Therefore, there nay be no leachate collection
and treatment system to diminish leachate percolation
through the wastes and soil underneath the site to
groundwater. Further, there may be no surface run-off
diversion system to prevent contaminants from being
carried from the disposal site to nearby surface waters.
An overflow problem would thus be encountered if
the liquid portion of the waste has been allowed to
reach too high a level in the lagoon/tailings pond; a
heavy rainfall could cause flooding which might reach
surface waters in the vicinity.
Should lead and cadmium migrate from this waste,
they would persist in the environment (in some form)
virtually indefinitely and, therefore, may contaminate
drinking water sources for long periods of time.
Furthermore, cadmium is bioaccumulated at all tropic
levels. Lead can be bioaccumulated and passed along
-------
the food chain, but not biomagnifled. Ihe liklihood
of human exposure is thus increased.
The large quantities of this waste stream generated
(a total of approximately 286,000 MT (dry weight) in 1977)
is an 'additional factor supporting the listing of this
solid waste as hazardous. As previously indicated, the
waste from primary copper smelting is generated in
substantial quantities and contains significant concen-
trations (See Table 3) of cadmium and lead. Large
amounts of these metals from the waste sludge are thus
available for potential environmental release. The large
quantities of these contaminants pose the danger of
polluting large areas of ground or surface waters.
Contamination could also occur for long periods of time,
since large amounts of pollutants are available for
environmental loading. 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
considerations Increase the possiblity or exposure
to harmful constituents and, in the Agency's view,
support a T listing.
2. Hazards Associated with Lead and Cadmium
As presented below, The actual toxicity of these
harmful constituents is well documented.
-l/-
-787-
-------
A 1977 review (6) summarizes much of the available data
on the toxicity of lead and cadmium. Capsule descriptions
of adverse health and environmental effects based on Reference
are summarized below; more detail on the adverse effects
of lead, and cadmium can be found in Appendix A.
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 deleterous effects are numerous and severe.
Lead may enter the human system through inhalation, ingestion
or skin contact. Lead is a cumulative poison in humans,
leading to damage in kidneys, liver, gonads, the nervous
system and blood vessels. Lead compounds also have been
reported to cause oncogenic and teratogenic effects in animals.
Toxicity to aquatic organisms occurs at ppb concentrations.
Cadmium shows both acute and chronic toxic effects in
humans. The LDjg (oral, rat) is 72 mg/kg of CdO. Cadmium
and its compounds have been reported to produce oncogenic
and teratogenic effects. Aquatic toxicity has been observed
at sub-ppb levels.
The hazards associated with exposure to lead, and cadmium
have been recognized by other regulatory programs. Lead and
cadmium are listed as priority pollutants in accordance with
S307(a) of the Clean Water Act of 1977. Under Kfi of the
Occupational Safety and Health Act of 1970, a final standard
for occupational exposure to lead has been established (7,8).
Also, a national ambient air quality standard for lead has
-l/-
-------
been announced by EPA pursuant to the Clean Air Act (R). In
addition, final or proposed regulations of the States of
California, Maine, Maryland, Massachusetts, Minnesota, Missouri,
Mexico, Oklahoma and Oregon define cadmium or lead containing
compounds as hazardous wastes or components thereof (9).
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Attachment 1
These wastes contain measurable concentrations of certain
other constituents listed in Appendix VIII of Part 261, in-
cluding arsenic, chromium, mercury and selenium. The concen-
trations of these constituents in both the waste and distilled
water leachate samples are, however, deemed insufficient to
warrant listing the wastes on basis of these additional
constituents, as demonstrated by the following tables:
CONCENTRATIONS OF HEAVY METALS IN WASTE SLUDGES
FROM PRIMARY COPPER SMELTERS (PPM)
Metals Sludges
Chromium 50
Mercury n«8
Selenium 31
Source: Reference 1.
-I/-
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REFERENCES
U.S. EPA, Office of Solid Waste. Assessment of hazardous
waste practices i.- -he metal smelting .MTU, refining industry,
v.2. EPA No. SW-145c2. NTIS PB Ho. 276 1/0. April, 1977.
U.S. Department of the Interior, Bureau of Mines,. Copper -
mineral commodity profiles. September, 1979.
P. D. Dougall. Copper. In; M. Grayson and D. Eckoth, eds.
Kirk-Othraer encyclopedia of chemical technology, 3rd. ed.
v.6. John Wiley and Sons, New York. 1979.
Pourbaix, M. Atlas of electrochemical equilibria in
aqueous solutions. Pergamon Press, London. 1966.
The Merck Index, 8th ed. Merck and Company, Inc,
Rahway, NJ. 1968.
Cleland and Kingsbury. Multimedia environmental goals.
v.2. EPA No. 600/7-77-136B. November, 1977.
U.S. Department of Interior, Bureau of Mines. Mineral
commodity summaries. 1979.
NIOSH. Registry of toxic effects of chemical substances.
U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health. 1977.
U.S. EPA States Regulations Files, Hazardous Waste State
Programs, WH-565. U.S. EPA, 401 M St., S.W., Washington, D.C.
20460. Contact Sam Morekas (202) 755-9145. January, 1980.
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JB:01-13 -
LISTING BACKGROUND DOCUMENT
PRIMARY LEAD SMELTING
Surface impoundment solids contained in and dredged from surface
irapoundmencs at primary lead smelting facilities.(T)
Summary of Basis for Listing
The smelting of primary lead produces a number of
wastewaters and slurries, including acid plant blowdown,
slag granulation water, and plant washwater. These waste-
waters and slurries are sent to treatment and storage
impoundments to settle out the solids. The solids may be left
in the lagoons, or they may be periodically dredged and
disposed of elsewhere.
The Administrator has determined that the solids con-
tained in and dredged from surface impoundments used to
treat or store wastewaters and slurries from primary lead
smelting may pose a present or potential hazard to human
health or the environment when improperly managed and
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 concentr-'-
tions of the toxic metals, lead and cadi I >
-------
Significant concentrations of lead and
cadmium have been shown to leach from samples
of the waste which were subjected to an extrac-
tion procedure designed to predict the release
of contaminants into the environment. If the
wastes are not properly managed, leachate
could migrate from the waste disposal site
and contaminate underlying drinking water
sources. Further, lead and cadmium do not
degrade, so that contamination, and the oppor-
tunity for contaminant contact with living
receptors, will be long-term.
Estimates indicate that large quantities
of the waste are generated each year
(raore than 49,100 tons in 1978) and that the
typical waste management practices may be
inadequate to prevent substantial environ-
nental harm caused by lead and cadmium
migration.
Manufacturing Process and Sources of Hazardous Wastes (1)
The primary lead facilities that generate the
hazardous wastes that concern EPA. are four Integrated
lead smelter/refineries. These facilities are located in
Missouri and Idaho. Production capacity ranges from 110,000
to 225,000 tons per year. Total primary lead production
(from the four integrated smelter/refineries, two smelters
and one refinery) was 611,650 tons in 1977. Forecasts indicate
that domestic demand will increase to 1,030,000 - 2,"140,000
tons in the year 2000.
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All jc-inest j.c smelters and refineries produce lead
by pyrometal]urgical smelting and refining processes. The
major process steps are the same at all the smelters, with
the exception that those that treat non-Missouri ore
concentrates use auxiliary operations to recover valuable
metals or remove undesirable impurities. The following is
a step-by-step description of the manufacturing process
as presented in Figure 1. This description includes the major
process steps for all primary lead smelting and refining plants.
During the smelting process, concentrates produced by
the beneficiation of various lead bearing ores are converted to
an impure lead bullion suitable for refining. The ore concen-
trate is the major feedstock material. Other raw materials
that may be added during the process include iron, silica,
limestone flux, coke, soda, ash, pyrlte, zinc, caustic, and
particulates and sludges collected in pollution control devices.
The ore concentrate and the pollution control dusts and sludges
are the primary sources of lead and cadmium found in the
settled solids from the surface Impoundments.
The first of the processes in smelting is sintering, an
operation which agglomerates the fine particles, converts metallic
sulfides to oxides, drives off volatile metals, and eliminates
most of the sulphur as sulphur dioxide. Off-gases from
sintering may contain sulphur dioxides in concentrations that
-y-
-------
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^»l»»l
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Figure i. Flow chart depicts primary lead sroel<:i.ng
and refining.( umbera correspond Uo_process numbers _in_text
and alsd~cx>rrespond txj'step process" in~lJu.s clocusnent. Tiv^ jrirat LJxcce
steps produce the hazcxrdous miscellaneous slurries of concern.)
-------
are practical for recovery. Of particular concern, though, are
the lead and cadmium entrained in those off-gases. Four
plants have sinter machines designed to produce an off-gas
'^ntaining enough sulphur dioxide to permit recovery of
sulphur as sulphuric acid. The sulphur recovery operation
generates a stream of weak acid called acid plant "blowdown".
The acid plant blowdown stream contains lead and cadmium.
Neutralization of the blowdown with lime usually generates
a slurry destined for an on-site surface impoundment.
This waste stream, resulting 'from the sulphur recovery
operation, requires proper management.
In the second step in primary lead smelting and refining,
sinter is charged to the blast furnace and smelted to crude
lead bullion that can be further refined. During this
reduction process, the components of the sinter are separated
Into four distinct layers, bullion, speiss, matte and slag.
The two layers of concern are the bullion layer and the slag
layer which result from the interaction of fluxes and
metal impurities. The crude lead bullion is charged to
drosslng (the fourth step in this process.) The blast furnace
slag may be disposed of or sent to a zinc fuming furnace (an
interim step) for recovery of lead and zinc, rather than
opting for direct disposal. The zinc fuming process, in turn,
also generates a slag. Blast furnace slag and zinc fuming
slag disposal practices are similar. The waste is either
-X-
-------
sent directly to a slag pile or granulated in a water jet
before being transported to the slag pile. The granulation
process cools newly generated, hot slag with a water spray.
'ag granulation water is often transported to surface impound-
ments for settling.
The blast furnace bullion undergoes "drossing" (Step 4)
to remove common metallic impurities. Dross separated from
the lead bullion must be further treated in a reverberatory
drossing furnace (Step 5) to recover metal values. Rough-
drossed lead bullion, still containing copper, is decopperized
(Step 6) before further refining. One of three usual processes
is then used to remove metals that cause lead to harden. This
process is called softening (Step 7). Softened lead bullion
contains precious metals, gold, and silver, which are
recovered for their economic value through the Parkes
desilverizing process (Step 8). To remove the excess zinc
added during desilverization, a dezincing process (Step 10)
which removes the bismuth, which is in excess of the 0.15
percent specification for desilvered and dezinced lead bullion.
Lead bullion from dezincing or debismuthlng is combined with
flux to remove remaining impurities before casting (Step 11)
and, finally, the refined lead bullion is cast into ingots
for sale (Step 12).
The listed hazardous wastes generated by primary lead
-t-
-797-
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smelting plant1-: TS settled solids fro«n surface impoundments.
The impoundments jire used to collect P '•' -' d s from miscellaneous
slurries, such as acid plant blowdown, ;lag granulation
water and plant washings. Plant washing is a housekeeping
process; plant washdown normally contains a substantial
amount of lead and other process material.
Data indicate that in 1978 four integrated smelter/refineries
that process lead ore concentrates combined to produce more
than 49,100 tons of impoundment solids considered hazardous.
The data also indicate that the bulk of this waste is generated
and managed at three plant locations.
The waste contains high concentrations of lead and cadmium.
The presence of such high concentrations of toxic metals.
in a waste stream in and of itself raises regulatory concerns.
Furthermore, distilled water extraction test data indicate
that these dangerous constituents may leach from the waste
in harmful concentrations unless the wastes are properly
managed.
Waste Generation and Management (1)
As previously mentioned, the miscellaneous slurries
generated by primary lead smeltering plants are settled in
-------
surface Impoundments. Typically a minimal effort is expended
for impoundment site selection. Site selection is based
primarily on convenience. Site preparation usually consists
of simply scooping out earth to form impoundments. EPA is
unaware of any sealants or liners being employed beneath
disposal areas. Leachate or groundwater monitoring is not
adequately utilized, or not utilized at all.
Four facilities have surface impoundments. Currently,
some of the impoundments are dredged of their accumulated
solids on an "as needed" basis. Dredging is done with
common equipment at frequencies from once per year to once
every 3 years or longer. The dredged material is either
dumped beside the impoundment or trucked to an on-site dump.
Some of this material may be recycled to sintering if it
contains enough metals.*
Hazardous Properties of the Waste (3)
EPA has sampled process wastewater before and after
treatment in an effort to quantify the amounts of lead and
cadmium likely to be in the waste. The settled solids are
assumed to contain the pollutants removed from the process
wastewater. The data are summarized as follows:
*See "Response to Comments" at the end of this document for a
discussion on the coverage of those materials recycled back
co the process.
-y-
-------
Plant A
Flow = 1,300,000 gpd (gallons per day)
1
iMetal
1
1 Cd
1
1 Pb
1
1
Influent
Concentration
0.89 ppm
17 ppra
Effluent
Concentration
1
| 0.044 ppm
1
I 0.925 ppm
|
1
]
Difference s
1
I 0.846 ppm
1
I 16.075 ppm
1
1
.bs/day in
.olids
9.172
174.3
«lant B
Flow = 280,000 gpd
Metal
Cd
Pb
Influent
Concentrat ion
15 ppm
50 ppm
Effluent
Concentration
0.43 ppm
0.39 ppm
1
Difference
14.57 ppm
49.61 ppra
bs/day in
solids
34
115.85
Based on continuous year round plant operation, these
data show that approximately 3300 Ibs/yr of cadmium accumu-
late in an impoundment in Plant A and approximately 12,400
Ibs/yr accumulate in Plant B. Lead in the impoundment
solids from Plant A accunulates at a rate of almost 64,000
Ibs/yr., and at a rate of almost 42,300 Ibs/yr at Plant B.
Should only one percent of each metal leach from the settled
solids from Plant B, the result would be 124 Ibs/yr of cadmium
-t-
-------
and 423 Ibs/yr of lead potentially available to the environment
from that one plant.
The above evidence indicating that significant amounts
of lead and cadmium are present in the settled solids is
supported by actual waste analyses which reveal that the
waste does in fact contain high concentrations of these
toxic metals. The Calspan Corporation tested samples of the
impoundment dredgings at two plants and found the following
concentrations of lead and cadmium: (2)
Hazardous Constituents of Impoundment Dredgings (ppm)
Cd
700
640
1 Pb
1
1 115
1
1
I 140
1
,000
,000
Plant I
Plant II
Calspan Corporation also subjected a sample of the waste
believed to be representative of the lagoon dredgings to a
water extraction to determine whether the toxic metals could
leach from the waste. Approximately 50 grams of a sample
was placed in a 200 milliliter jar and two parts by weight
of water were added. The bottle was gently agitated on a
rotary tumbler for 72 hours. The extract was then filtered
through a 0.45 micron micropore filter and the filtrate was
analyzed for toxic metals. This waste leached 11 ppm of
-901-
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cadmium (1,100 times the amount permitted by the National
Interim Primary Drinking Standard) and 4.5 ppm of lead (90
times the amount permitted by the National Interim Primary
Drinking Standard). Therefore, cadmium and lead are likely
to be leached from the waste in harmful concentrations even
when they are placed in a raonodisposal site subject to mild
environmental conditions. If these wastes are placed in
acidic environments such as disposal sites subject to acid
rainfall or co-disposal with acids, the concentrations will
probably be higher, since lead and cadmium compounds are
generally more soluble in acid than in distilled water.
The hazard associated with leaching of hazardous
constituents from the impoundments during the interim storage
period is the migration of those constituents to ground and
surface waters. The miscellaneous slurries are probably
composed of particulates of various sizes, ranging from dust
particles to fine slag from slag granulation water. The
potential of the hazardous constituents being released from
the matrix is influenced by the physical form of the waste.
For instance, wastes composed of fine particles provide
greater surface area on which a solubilizlng medium can act
and therefore the probability is increased that hazardous
constituents will leach from the waste. Contaminant-bearing
leachate can then migrate to ground and surface water.
-•300.-
-------
Thus, Improper disposal of surface impoundment solids
may result in contamination of ground and surface waters by
lead and cadniun. Aquatic species might be affected,
and, where ground and surface waters are sources of drinking
water, ingestion of the contaminants by humans could
occur. For this reason, proper waste management is essential
and of major concern to EPA.(2)
Present management practices appear to be inadequate
to prevent contamination of ground and surface waters used
as drinking water sources. Presently, if solids are allowed
to settle in unlined and unsealed impoundments in areas
with permeable soils, the solubllized lead and cadmium in
the liquid phase could migrate from the site to an aquifer.
Groundwater contamination might also occur if the dredged
solids are dumped on permeable soils since no provision
presently appears to be made to prevent percolation of
rainfall through the waste or to collect resulting leachate.
Surface waters may become contaminated if run-off from
dumping sites and overflow from surface impoundments are not
controlled by appropriate diversion systems.(2)
Compounding this problem, and an important consideration
for the future, is the fact that should lead or cadmium
escape from the disposal site, they will not degrade with
-vt-
-•803-
-------
the passage of time, but will provide a potential source of
longterra contamination.
Further, as indicated previously, the cadmium and
particularly the lead found in the impoundments are generated
in very substantial quantities. Large amounts of each of
these metals are thus available for potential environmental
release. The large quantities of these contaminants pose
the danger of polluting large areas of ground and surface
waters. Contamination could also occur for long periods
of time, since large amounts of pollutants are available
for environmental loading. The attenuation capacity of
the environment surrounding the disposal facility could
also be reduced or exhausted by such large quantities of
of pollutants. All of these considerations increase the
possibility of exposure to harmful constituents in the
wastes, and in the Agency's view, demand recognition.
Adverse Health Effects Associated with Lead and Cadmium
Lead and cadmium are toxic metals that threaten both
human health and that of other organisms. The hazards of
human exposure to lead Include neurological damage, renal
damage and adverse reproductive effects. In addition, lead
Ls carcinogenic to laboratory animals, and relatively toxic
-•ao1-/-
-------
to freshwater organisms. It also bioaccumulates in many
species. Additional information on lead can be found in
Appendix A. Cadmium (see Appendix A for more information)
also can cause toxic effects in many species. It is bio-
accumulated at all trophic levels and has been shown to be
mutagenic and teratogenic in laboratory animals.
Hazards associated with exposure to lead and cadmium
have been recognized by other regulatory programs. For
example, Congress designated lead and cadmium as priority
pollutants under §307(a) of the Clean Water Act. The
Occupational Health and Safety Administration has a final
exposure standard for lead and a draft standard has been
developed for cadmium under §6 of the Occupational Safety
and Health Act of 1970. The states of Maine, Vermont, New
Mexico, Missouri, Massachusetts, Minnesota, Oklahoma, Oregon,
and California either regulate or are considering regulation
of lead and cadmium as hazardous waste. The implications of
these regulations or considerations thereof are obvious:
unregulated lead and cadmium management is a real and recog-
nized hazard.
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1. U.S. EPA. IERL/ORD and Office of Solid Waste. Assessment
of solid waste management problems and practices in
nonferrous smelters. Prepared by PEDCO Environmental
Inc., Contract No. 68-03-2577. November, 1979.
2. U.S. EPA. Office of Solid Waste. Assessment of hazardous
waste practices in the metal smelting and refining
Industry. V's 1-4. NTIS PB Nos. 276 169, 276 170, 276 171,
276 172. April, 1977.
3. U.S. EPA. Office of Water Planning and Standards, Effluent
Guidelines Division. Draft development document for
effluent limitations guidelines and standards for the
nonferrous metals manufacturing point source category.
EPA No. 440/l-79/019c. September, 1979.
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Response to Comments (Proposed Listings; December 18, 1980)
1. One comraenter indicated that the listed waste (surface
impoundment solids contained in and dredged from surface
impoundments at primary lead smelting facilities) was
recycled at his facility and, therefore, should not be
listed as a hazardous waste.
The Agency has concluded that it does have juris-
diction under Subtitle C of RCRA to regulate wastewater
treatment sludges and other waste materials that are
used, reused, recycled or reclaimed. Furthermore, it
has reasoned that such materials do not become less
hazardous to human health or the environment because they
are intended to be used, reused, recycled or reclaimed
in lieu of being discarded. Although the materials
recycled and reclaimed may not pose a hazard, the accumu-
lation, storage and transport of a hazardous waste prior
to use, reuse, recycle or reclamation will present the
same hazard as they would prior to being discarded. In
addition, the act of use, reuse, recycling or reclamation,
in many cases, poses a hazard equivalent to that encountered
if the waste were discarded. Thus, the Agency believes
it has a strong environmental rationale for regulating
hazardous wastes that are used, reused, recycled or
recla imed .
-------
For the particular waste at Issue, the Agency recog-
nizes that it is a wastewater treatment sludge and for
most or all of its existence prior to being recycled, it
is deposited in a surface impoundment where the potential
for leaching of the hazardous constituents is real and
significant. Consequently, the waste must be considered
a hazardous waste in this environment; to avoid listing
it as a hazardous waste would be unjustified. Likewise,
if the waste is piled and stored on the land, prior to
recycling, the potential of leaching of its hazardous
constituents into the environment would still prevail and
avoiding Its regulations would be unjustified.
The key question, therefore, is not whether or not
it is a hazardous waste and should be listed as a hazardous
waste, but whether or not or to what degree it should be reg-
ulated during recycling; that is, should the recycling
process and facility be considered a hazardous waste
management operation and facility required to obtain
interim status and eventually a permit and required to
meet the standards set forth in Farts 264 and 265 of the
regulations. At this time, the Agency has deferred
regulation of such facilities because it recognizes that
the full set of Subtitle C management requirements may
not be necessary. As and when it concludes that regulation
of these facilities is necessary, it will terminate this
-------
deferral and impose either the requirement of Farts 264 and 265
(as well as 122) or special tailored requirements under
Part 266.
At this time, applicable requirement of Farts 262
through 265 and 122 will apply insofar as the accumulation,
storage and transportation of hazardous wastes that are
used, reused, recycled or reclaimed. The Agency believes
this regulatory coverage and the above described deferral
of regulated coverage is appropriate to the subject
wastes. These sludges are hazardous insofar as they are
being accumulated and stored in surface impoundments and
insofar as they may be stored in piles prior to recycling.
Therefore, these sludges should be listed as hazardous
waste. These sludges may not pose a substantial hazard
during their recycling and,- even though listed as
hazardous waste, this aspect of their management is not
now being regulated.
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LISTING BACKGROUND DOCUMENT
PRIMARY ZINC SMELTING AND REFINING
Sludge from treatment of process wastewater and/or
acid plant blowdown (T)
Electrolytic anode slimes/sludges (T)
Cadnium plant leach residue (iron oxide) (T)
Summary of Basis for Listing
The primary zinc industry is comprised of 7 plants that
enploy one of two major zinc manufacturing processes—electro-
lytic or pyrometallurgical processing. The five electrolytic
and two pyroraetallurgical plants recover zinc metal from ore
concentrates. Cadmlura and lead contaminants found in the raw
materials are carried through numerous processes and are sub-
sequently found in high concentrations in the wastewater treat-
ment sludge generated by the treatment of process wastewater
and/or acid plant blowdown, in the electrolytic anode slimes/
sludges and in cadmium plant leach residue (iron oxide).
The Administrator has determined that these wastes 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 therefore should be subiect to appropriate management
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
L) The wastes contain significant concentrations of the
toxic metals cadniun and lead.
2) Cadmium and lead have been shown to leach from
samples of these wastes in significant concentrations
-------
the neutralization and precipitation reactions in the WWTP,
is continuously removed and hauled to an off-site landfill
operated by a private contractor. At the plant that uses
preleaching, the WWTP sludge also contains solids from acid
plant blowdown, anode slimes (electrolytic cell cleanings),
and miscellaneous slurries. The available information indicates
that 9,400 tons of WWTP sludge is generated annually by this
plant (3>.
All zinc concentrates received at zinc plants are roasted
to drive off sulfur and convert the zinc sulfide in the con-
centrate to an impure zinc oxide called calcine (3).' The
conversion to calcine in the roaster produces a roaster off-
gas stream containing enough sulfur dioxide to permit sulfur
recovery as sulfuric acid. All electrolytic plants treat the
roaster offgas in sulfuric acid plants to produce a saleable
sulfuric acid. The acid production results in a weak acid
waste stream from the scrubbing columns that clean the off-gas.
This waste is referred to as a bleed stream or acid plant
blowdown. The acid plant blowdown is neutralized and thickened,
and the solids are allowed to settle in ponds (3). Whether or
not the solids are being stored for recycling, the solids do
constitute a solid waste as defined by §261.2*. Treatment of
*The Agency has concluded that it does have jurisdiction under
Subtitle C of RCRA to regulate waste water treatment sludges and
other waste materials that are used, reused, recycled or reclaimed.
Furthernore, it has reasoned that such materials do not become
less hazardous to human health or the environment because they
are intended to be used, reused, recycled or reclaimed in lieu
of being discarded. Therefore, at this time, applicable require-
ments of Parts 262 through 265 and 122 will apply insofar as the
aceunulatlon, storage and transportation of hazardous wastes
c '-1.11 are used, reused, recycled or reclaimed.
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-he acid plant blowdown generates an estimated 1,400 tons of
sludge per year, (3) which has been designated as hazardous.
All electrolytic plants also generate a waste of anode
slimes or sludges from cleaning of the electrolytic cells.
Anode slimes/sludges consist of gangue material that is
rassed through earlier process steps but is not plated
rut, or electrolyzed, in the electrolysis step. It is
estimated that anode slimes/sludges make up 2,600 tons of
-he annual solid waste produced (3). This waste is also
designated as hazardous.*
Pyrometallurgical Process
There are two pyrometallurigical zinc plants with a combined
annual production rate of about 261,000 tons of zinc netal (3).
These plants account for approximately 51 percent of the total
production of zinc metal by the primary zinc industry, but 91
rercent of the total solid waste produced by the industry.
Although the two plants use the same basic processes (see Fig-
ure 2), they differ greatly in the quantities of solid waste
venerated and in the ultimate disposal or control of the waste (3)
Pyrometallurgical processing entails the following steps:
wintering, retorting, refining and casting. Sintering develops
the desired characteristics for pyrometallurgical smelting of the
lalcine by processing the calcine in a sinter machine where the
*A11 electrolytic plants also generate a leach residue
from filtration of the leach slurrv, which is not currently
listed as hazardous and will not be further discussed in this
:ackground document.
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ZINC CONCENTRATES
SLUBSE-
WATER
COLLECTION
WASTEWATER
TO TREATMENT
CO
SA
1
KE •*•
r
C5NCENTR1TS
DRTINC
^
p
ROASTER
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:INE
r
SINTERING
ZINC-RICM "~
RESIDUE
i
TREATMENT
w« A »
' T
! FERftOSIUCOS
T
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'ESIDUS70
A.O REFINERY
i
FURNACE
^
HATER CAS
_ DUST ACID 1 h wg".
1 *" coascncN PLAMT J
t
PLANT ..C_C - le.
DUST »-CJLS
t^LLeCTK3N
y
CADMIUM PLANT 1 K^ _
. ,( H- -v-oroGuct
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'
CASTING
1
\
BLO
^COOLING TOWER
^" SLOWDOWN
1
CKS
f
OTHER
Sl-.APES
FI 6 D R E 2. PY7.0MIIALL7SC-ICA1
ZiKC PRODUCTION PROCESS
-x-
1 -? -
-------
calcine burns autother-a 11 y and is fused into hard, permeable
sinter. Retorting consists of reducing the calcine in the
sinter with carbon in a rstort to produce zinc metal. Pre-
heated feed of sinter and coal or coke is then fed into the
top of the retort; the temperature reaches 1300°C-1400eC
inside. Because of the zinc's low boiling point (906°C), it
is volatilized as soon as it is formed. In this way the
zinc is purified by separating it from the gangue material
in the calcine. Zinc fron the retort smelting may need
further purification for some commercial uses. The zinc is
purified by dis ti Hat io-. in a graphic retort. Molten zinc
from the graphic retort is either cast pure into bars or
blocks or is alloyed with other metals and cast.
The sources of solid vaste generated by the pyroraetallurgical
process which are hazardous are: (1) collection and treatment
of acid plant blowdown, and (2) leaching of high-cadmium dusts
in the cadmium plant (3).*
Both pyronetallurgical plants treat roaster off-gas in
their sulfuric acid plants to control sulfur dioxide emissions.
The process is the same as the one described above for electrolytic
plants. The acid plants produce a saleable sulfuric acid and
a bleed stream (acid plant blowdown) that must be neutralized.
One plant neutralizes t'~e Slowdown with lime, which leads to
tl-e generation of an estimated 10,000 tons per year of settled
*Two other wastes eeierated by this process (i.e., resid
from the production of z i r. c oxide in Waelz Xins (one plant
onlv) and furnace resi.J._e from the operation of retort and
o xId1zing furnaces) are -on currently listed as hazardous and
will not he further di=iissed in this background document.
ue
-------
sludge, half of which is recycled to the process. The sludge
contains significant concentrations of cadmium and lead and
Is designated as hazardous.
The other pyrometallurgical plant uses the acid plant
blowdown to cool and humidify the roaster off-gas In a humi-
difying scrubber. Acid plant blowdown from the scrubber Is
thickened and then cooled before being recycled to the
scrubber. A bleed stream from the thickener bottoms is sent
to the cadmium plant for cadmium recovery. This acid plant
process generates no wastes.
Both of the pyrometallurglcal plants operate cadmium
plants to process dusts with high cadmium content that are
collected from the sinter machine off-gas. Processing in
the cadmium precipitation to produce a cadmium sponge. The
leaching steps produce two residues. One contains relatively
large quantities of lead, silver, and gold, and is sold as a
by-product. The other residue constitutes a solid waste
that contains cadmium and lead and is generated at a rate of
200 tons per year.(3) The latter residue has been classified
as hazardous.
Waste Generation and Management (3)
At both the electrolytic and pyrometallurglcal facilities
off-gases from the roaster are treated in sulfuric acid
plants to control sulfur dioxide emissions. This process
generates acid plant blowdown which may be mixed with the
process wastewater prior to treatment by lime precipitation.
-------
The resulting sludge contains significant levels of lead and
cadmium and is designated as hazardous.
Electrolytic refining generates a waste of anode slimes/
sludges from cleaning the electrolytic cells. These slimes/
sludges consist of gangue material that has passed through
the earlier process steps but was not plated out in the
electrolysis step. This waste also contains significant
amounts of lead and cadmium and is designated as hazardous.
Pyrometallurgical plants process high cadmium dusts
collected from the sinter baghouse to recover cadmium.
Processing involves acid leaching which produces two residues.
One contains significant amounts of lead, silver and gold;
this residue is sold as a by-product. The other residue is a
solid waste designated as hazardous because of its lead and
cadmium content.
Current solid waste control practices are fairly uniform
throughout the zinc Industry. Of the total solid waste gen-
erated, about 90 percent is controlled through on-site stockpiling,
7 percent is removed by private and municipal organizations
and individuals for various uses (such as winter road sand),
and the remaining 3 percent is hauled and landfilled by private
contractors.
Control Practices at Electrolytic Plants (3)
Electrolytic zinc plants produce solid waste consisting
of anode "slimes/sludges", neutralized acid plant blowdown,
surface impoundment dredgings, wastewater treatment sludge,
and goethite residue.
-------
Two of the electrolytic plants use wastewater treatment
plants (WWTP) to treat plant wastewater and various process
sludges. At both of these plants, the WWTP sludge is
removed and hauled to off-site landfills. One of the two
plants removes this sludge continuously as It is filtered
(dewatered). There is no on-site storage or disposal at this
plant. This particular sludge contains solids from anode
sludge, neutralization of acid plant blowdown, impoundment
dredgings, and sludge generated from the treatment of a
preleach slurry. The other plant using a WWTP piles WWTP
sludge on-site temporarily for drying prior to removal and
transportation to an off-site landfill. This particular
sludge contains solids from the neutralization of acid plant
blowdown and solids precipitated from plant runoff and washdown
At this plant, anode sludge is not treated in the WWTP but
is stockpiled on site. The WWTP sludge from these two plants
amounts to about 31 percent of the solid waste generated at
electrolytic plants. All of this sludge is hauled to off-site
landfills, either immediately or after temporary on-site
storage. Because the WWTP at each of these plants treats
acid plant blowdown, the WWTP sludges generated containing
cadmium and lead, are considered hazardous.
Two of the remaining three electrolytic plants stockpile
dredgings from surface impoundments on-site. One of these
plants generates two additional solid wastes that none of
the other plants generate. These two wastes, goethite and a
sulfur residue, are also stockpiled on-site.
-------
Three of the four electrolytic zinc plants operating
through 1978 used lined surface Impoundments. Two of these
plants use synthetic liners; the other uses a clay liner.
The fourth plant has an unlined surface impoundment. Moni-
toring wells are used by at least one plant.(')*
It Is assumed(3) that the fifth plant, one which has
recently come on-line and will have a WWTP, will generate a
sludge which will be removed to an off-site landfill. It is
also assumed(3) that this plant will use a lined surface
inpoundiaent which treats the anode sludge, acid plant blowdown,
impoundment dredgings, and plant wastewater in the WWTP.
These assumptions, based on plant similarities indicated in
the available literature(3), were necessary to estimate
quantities of solid waste generation at this new facility.
In order to avoid underestimation, the new plant ie also
assumed to generate a solid waste (such as goethite residue)
that is stockpiled on-slte.
Control Practices at Pyrometallurgical Plantg
The two pyrometallurgical zinc plants produce acid plant
blowdown, furnace (retort, oxide, and Waelz kiln) residue,
scrap furnace brick, and a cadmium plant residue. One of
these plants has a relatively small solid waste stockpile.
The other pyrometallurgical plant has an extremely large
stockpile of solid waste. This plant alone generates about
89 percent of the solid waste produced by all primary zinc
*The groundwater monitoring system at this one plant may
not be sufficient to adequately monitor leaching from the
surface Impoundment.
V*
-------
plants(3). Solid waste stockpile sites are selected primarily
for convenience. No site preparation is conducted other
than clearing and grubbing.
Both plants have surface impoundments. The impoundment
at one plant is lined with synthetic material; the impoundment
at the other is not lined. At one plant, the impoundment
collects acid plant blowdown and plant water. At the other
plant, acid plant blowdown is not slurried to the impoundment,
but is instead sent to the cadmium plant for further processing.
Dredgings from both impoundments are controlled on-site. One
plant recycles all dredgings to the process; the other recycles
about half of the dredgings and stockpiles the remainder. One
of the plants also stockpiles cadmium plant residues on-site.
These plants do not use surface water control by collection
and diversion ditching to its fullest potential.<3> Neither do
the plants currently use barriers to prevent seepage from
solid waste stockpiles, or wells to monitor or collect any
seepage or leachate(3).
Hazardous Properties of the Wastes
The Administrator has classified the process wastewater
and/or acid plant blowdown treatment sludge, electrolytic
anode slines/sludges, and the cadmiun plant leach residue
(iron oxide) as hazardous because of the high levels of
toxic cadmium and lead found in Che wastes. In EPA's "Assessment
of Hazardous Waste Practices in the Metal Smelting and Refining
Industry," Calspan Corporation tested samples of the wastes
-------
and performed extraction zests on the wastes using distilled
water as the extraction nsdium (1). The results are as
follows:
Waste Analysis (ppraj Extract Analysis (ppm)
Cd^ Pb Cd_ Pb
Sludge from acid <10 98 2.1
plant blowdown <10 1750 1.0
(Electrolytic 550 IS,100
Plant)
Sludge from acid 2000 4350 <0.01 1.3
plant blowdown 6^^ 4280
(Pyronetallur-
gical Plant)
Anode slimes/ 12 170,000 1? 2.0
sludges 1400 89,000
Cadmium Plant 280 215,000 <0.01 9.0
Residue
Calculations of sl-dge contents from llme-and-settle
wastewater treatment also indicate that significant amounts
and concentrations of lead and cadraiura are present in these
wastes (2).
Plant Conta-.inants Percent in Sludge
#1 Cad mi-a 4-0*
Lead 2.5*
#2 Cadni-m 2.6%
Lead I-7*
Cadmium and lead ire alwavs expected to be In the
sludges after treatment because 1} the treatment processes are
designed to remove such elements from the wastewater to meet
-------
effluent standards, and 2) cadmium and lead will not be lost
(e.g., volatilized) in the treatment process.
Based on the data presented above, the waste is classified
as hazardous because it contains significant concentrations
of cadmium and lead which are toxic and because the extraction
tests performed on these wastes indicate that the cadmium
and lead may be in a soluble form and could be released to
the environment in harmful concentrations. The fact that
water extractions of the wastes have shown that the wastes
could leach potentially hazardous concentrations of toxic
metals indicates that under the mildest environmental condi-
tions (e.g., neutral pH rainfall) at a mono-disposal site,
the wastes may leach contaminants to the groundwater in con-
centrations which would be harmful to human health and the
environment. Where conditions tend to be acidic, the release
of these toxic metals over the lifetime of a landfill is
expected to be even higher than indicated by the water extrac-
tion data, since cadmium and lead solubilities increase with
a decrease in pH (4)._'
On-site stockpiling is most likely not an environmen-
tally acceptable means of disposing of a waste which contains
_/The Agency has determined to list wastes from primary
zinc smelting and refining as a "T" hazardous waste, on the
basis of lead and cadmium constituents, although these con-
stituents are also measureable by the EP toxicity character-
istic. The Agency believes that there are factors in addition
to metal concentrations in leachate which -justify the "T"
listing. Some of these factors are the high concentrations
of lead and cadmium in actual wastes streams, the non-degrada-
bility of these substances and indications of lack of proper
management of the wastes in actual practice.
I/
-------
significant concentrations of toxic metals that have been
shown to migrate from the waste. Surface water can becone
contaminated with contaminants from these wastes via runoff
from rainfall. Similar hazards exist if these wastes are
disposed of in improperly managed landfills or surface
impoundments; leaching, run-off, or overflow may result in
contamination of surface and ground waters.
The cadmium and lead that may migrate from the waste to
the environment as a result of improper disposal practices
are toxic metals that persist in the environment and therefore
may contaminate drinking water sources for extremely long
periods of time. Cadmium is toxic to practically all systems
and functions of the human and animal organism(5). Acute
poisoning may result from the inhalation of cadmium dusts
and fumes (usually cadmium oxide) and from ingestion of
cadmium salts(6). Lead is poisonous in all forms; it is one
of the most hazardous of the toxic raetals because it accumu-
lates in many organisms and the deleterious effects are
numerous and severe. Lead nay enter the human system through
inhalation, ingestion or skin contact. Ingestion of contami-
nated drinking water is a possible neans of exposure to
humans as a result of improper management of these wastes.
Additional information on the adverse health effects of
cadmium and lead can be found in Appendix A.
The hazards associated with exposure to cadmium and lead
have been recognized by other regulatory programs. Lead and
-------
cadmium are listed as Priority Pollutants in accordance with
§307(a) of the Clean Water Act of 1977. Under §6 of the
Occupational Safety and Health Act of 1970, a final standard
for occupational exposure to lead has been established (7).
Also, a national ambient air quality standard for lead has
been announced by EPA pursuant to the Clean Air Act (7).
In addition, final or proposed regulations of the State of
California, Maine, Massachusetts, Minnesota, Missouri, New
Mexico, Oklahoma and Oregon define cadmium and lead-containing
compounds as hazardous wastes or components thereof (8). EPA
has proposed regulations that will limit the amount of cadmium
In municipal sludge which can be landspread on crop land (9).
The Occupational Safety and Health Administration (OSHA) has
issued an advance notice of proposed rulemaking for cadmium
air exposure based on a recommendation by the National
Institute for Occupational Safety and Health (NIOSH) (10).
EPA has prohibited ocean dumping of cadmium and cadmium
compounds except as trace contaminants (11). EPA has also
promulgated pretreatment standards for electroplaters which
specifically Holt discharges of cadmium to Public Owned
Treatment Works (12).
-S2.7-
-------
References
1. U.S. EPA, Office of Solid Waste. Assessment of hazardous
waste practices In the metal smelting and refining
Industry. Vols. II and IV. EPA Nos. SW-145c2 and SW-145c4.
NTIS PB Nos. 276 170 and 276 172. April, 1977.
2. U.S. EPA, Effluent Guidelines Division. Draft development
document for effluent limitation guidelines and new
source performance standards for the major nonferrous
metals segment of the nonferrous manufacturing point
source category. EPA No. 440/1-79/019. September, 1979.
3. U.S. EPA, Office of Solid Waste. Assessment of solid waste
management problems and practices In nonferrous smelters.
1979.
4. Pourbalx, M. Atlas of electrochemical equilibria in
aqueous solutions. Pergamon Press, London. 1966.
5. Waldbott, G.L. Health effects of environmental pollutants.
C.V. Mosby Company, St. Louis. 1973.
6. Gleason, M.N., R.5. Gosselln, H.C. Hodge, B.P. Smith. Clinical
toxicology of commercial products, 3rd ed. The Williams
and Wilklns Co., Baltimore. 1969.
7. U.S. Department of Interior, Bureau of Mines. Mineral
commodity summaries, 1980. December, 1979.
8. U.S. EPA State Regulations File, Hazardous Waste State
Programs, WH-565. U.S. EPA, 401 M St., S.W., Washington,
D.C. 20460. Contact Sam Morekas. (202) 755-9145.
9. 44 FR 53449.
10. 44 FR 5434.
11. 38 FR 28610.
12. 40 CFR, Part 413. Federal Register, Vol. 44, No. 175,
Friday, September 7, 1979.
-------
Response to Comments to Proposed Regulations (December 18, 1978)
Comments were received from three companies pertaining
to the listing of wastes from the primary zinc industry.
The comments address the following general points:
1. Listed wastes are recycled and not discarded.
2. Listed wastes are being stored on-site but will
eventually be recycled.
The Agency has concluded that it does have jurisdiction
under Subtitle C of RCRA to regulate wastewater treatment
sludges and other waste materials that are used, reused,
recycled or reclaimed. Furthermore, it has reasoned that
such naterials do not become less hazardous to human health
or the environnent because they are intended to be used,
reused, recycled or reclaimed in lieu of being discarded.
Although the naterials recycled and reclaimed may not pose a
hazard, the accumulation, storage and transport of a hazardous
waste prior to use, reuse, recycle or reclamation will present
the same hazard as they would prior to being discarded. In
addition, the act of use, reuse, recycling or reclamation,
in many cases, poses a hazard equivalent to that encountered
if the waste were discarded. Thus, the Agency believes it
has a strong environmental rationale for regulating hazardous
wastes that are used, reused, recycled or reclaimed.
For the particular wastes at issue, the Agency recognizes
that these wastes for most or all of its existance prior to
being recycled is deposited in a surface impoundment when the
-------
potential for leaching of the hazardous constituents is real
and significant. Consequently, the waste must be considered
a hazardous waste in this environment; to avoid listing it as
a hazardous waste would be unjustified. Likewise, if the
waste is piled and stored on the land, prior to recycling,
the potential of leaching of its hazardous constituents into
the environment would still prevail and avoiding its regu-
lation would be unjustified.
The key question, therefore, is not whether or not it
is a hazardous waste and should be listed as a hazardous
waste, but whether or not to what degree it should be regu-
lated during recycling; that is should the recycling process
and facility be considered a hazardous waste management opera-
tion and facility required to obtain interim status and event-
ually a permit and required to meet the standards set forth
in Parts 264 and 265 of the regulations. At this time, the
Agency has deferred regulation of such facilities because it
recognizes that the full set of Subtitle C management require-
ments may not be necessary. As and when it concludes that
regulation of these facilities Is necessary, it will terminate
this deferral and impose either the requirements of Parts 264
and 265 (as well as 122) or special tailored requirements
under Part 266.
At this time, applicable requirements of Parts 262
through 265 and 122 will apply insofar as the accumulation,
storage and transportation of hazardous wastes that are used,
-------
reused, recycled or reclaimed. The Agency believes this
regulatory coverage and the above described deferral of
regulated coverage is appropriate to the subject wastes.
These sludges are hazardous insofar as they are being ac-
cumulated and stored in surface inpoundments and insofar
as they may be stored in piles prior to recycling. There-
fore, these sludges should be listed as hazardous waste.
These sludges may not pose a substantial hazard during their
recycling and, even though listed as hazardous waste, this
aspect of their management is not now being regulated.
-------
LISTING BACKGROUND DOCUMENT
SECONDARY LEAD SMELTING
Emission control dust/sludge from secondary lead smelting (T)
Waste leaching solution from acid leaching of emission
control dust from secondary lead smelting (T)
I. Summary of Basis for Listing
The emission control dust/sludge from reverberatory furnace
smelting of secondary lead products is generated when lead,
cadmium, and chromium contaminants found in the source materials
are entrained in the furnace fumes during the smelting process
and subsequently collected by air pollution control equipment.
Dry collection methods generate a dust as a solid residue;
wet collection methods generate a sludge as a solid residue.
The sludge is usually land disposed as a waste. The dust is
usually recycled for further lead smelting; before recycling,
however, the dust may be leached with acid for zinc recovery,
and the resulting waste acid leaching solution containing
cadmium, chromium and lead is land disposed. The Administrator
has determined that these dusts/sludges and the waste acid
leaching solutions from acid leaching of these dusts/sludges
are solid wastes which may pose a substantial present or poten-
tial hazard to human health or the environment when improperly
transported, treated, stored, disposed of or otherwise managed,
and therefore should be subject to appropriate management
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1) The emission control dusts/sludges contain significant
-------
concentrations of the toxic metals lead, cadmium
and hexavalent chromium.
2) Waste leaching solutions from acid leaching of the
emission control dusts/sludges likewise contain
significant concentrations of lead, cadmium, and
hexavalent chromium, since the acid leaching medium
solubilizes these heavy metals.
3) The hazardous constituents of these waste streams
may migrate from the waste in harmful concentrations,
since distilled water extraction procedures performed
on samples of the emission control dust and sludge
leached significant concentrations of cadmium and
lead from the sludge and significant concentrations
of lead, cadmium, and chromium from the dust.
4) The emission control sludge and the waste leaching
solutions are typically disposed of in unlined
lagoons, thus posing a realistic possibility of
migration of lead, cadmium and hexavalent chromium
to underground drinking water sources. Further,
these elemental metals persist in the environment,
thereby posing a real danger of long-term contamination,
5} Very large quantities of these emission control dust/
sludges are generated annually (7,151,500 metric
tons of sludge and 127,158,700 metric tons of dust
in 1977) and are available for disposal as solid
waste. There is thus greater likelihood of large
scale contamination of the environment if these
wastes are not managed properly.
I . Industry Profile and Manufacturing Process i. ^, a
Eighty-two plants located in 27 states manufacture
secondary lead products. The major production centers are
located in the Great Lake States, in Texas and in Louisiana
(1,5). Plant locations by state are shown In Table 1.
Plant capacities range from 25,000 to 40,000 metric tons
of lead per year (1, "5) . The total quantity of lead produced
by the secondary lead industry was 769,000 metric tons in
1078 and the estimate for 1979 is 760,000 metric tons (4).
-y-
-------
Table 1 (1)
Distribution of Secondary Lead Smelters by State
State
Alabama
California
Colorado
Delaware
Florida
Georgia
Illinois
Indiana
Kentucky
Louis iana
Maryland
Massachuset tes
Michigan
Minneso ta
Mississippi
Mi ssouri
Nebraska
New Jersey
New York
North Carolina
Ohio
Pennsylvania
Texas
Tennessee
Virginia
Washington
Wisconsin
No. of Plants
2
1
3
3
7
4
1
2
1
2
4
1
1
2
2
3
4
2
6
7
9
2
1
1
1
-y-
-------
Four products are manufacturer3 in the secondary lead
industry: refined lead, lead oxide, antiraonal lead and lead
alloy. Individual plants may produce any or all of the
products. As shown In Figure 1, the source materials will
vary for each. Discarded batteries comprise the major source
material. Other source materials are lead residues, lead
slags and scrap iron.
II. Generation and Management of Listed Waste Streams
1. Emission Control Dust/Sludge
Emission control dust/sludge is generated from the
manufacture of refined lead, lead oxide, and lead alloy in
reverberatory furnaces. In the production process, "soft
lead" (low antimony lead) is smelted in a reverberatory
furnace from lead residues, scrap lead, and, In the case of
lead alloy, recycled secondary lead emission control dust is
a source material. The soft lead is then further processed
to either refined lead or lead oxide. In the scrubbing of
reverberatory furnace emissions, cadmium, chromium and lead
entrained in the fumes are collected by either wet scrubbing
or by baghouse, resulting in a sludge or dust that may be
discarded. The Agency attributes the presence of lead,
cadmium and chromium in the waste stream to their presence in
the source materials. (See p. 11 below confirming the presence
of these toxic metals in the waste stream in significant
concentrations.) The smelt!nR processes takes place at high
-------
LEAD RESIDUES
WASTE
SOLIDS
BAQHOUSE
EMISSIONS
WASTE BATTERIES
i
BATTERY
CRACKING
HiO
1
SCRUBBER
LIQUOR TO RECYCLE
^Sludge
to
Lagoon
RDVEftucriATonr
PlinilACB
RE MELT
KETTLE
I
REFINED LEAD
SLAO
M,O « ELECTROLYTE
TO TREATMENT.
•CASINOS TO DISPOSAL
SCRAP IRON
u.
BLAST
FUI1NACE
SOFT LEAD
EMISSIONS
ANTIMONIAL
LEAD
BAOHOUSE
UQUOH TO RECYCLE
1
SCHUBBER
BARTON
OXIDATION
HtO
EMISi
At.CD
REMBLT
KCTTUI
LEAD OXIDE
ANTIMONIAL LEAD
LEAD ALLOT
FIGURE i. SECONDARY UAD/ANTIHONT SKCITING flOCESS
-------
temperatures, and in oxidizing atmospheres. Such conditions are
known to cause oxidation of chronium to the hexavalent form.(12)
Three plants in the industry use wet scrubbing which
generates a sludge. The sludge is typically disposed in
unlined lagoons (1,5).
Dry collection methods (i.e., baghouses) are used by all
other plants, generating a dust as a solid residue. This dust
is available for disposal or for recycling.
1. Waste Leaching Solution
Emission control dusts are often recycled for use as input
material for lead alloy ("white metal") production. The recy-
cling process, however, generates a separate waste stream which
is listed along with emission control dust/sludge. Before
the dust is recycled to the remelt kettle for lead alloy produc-
tion, it is leached with dilute sulfuric acid to remove zinc.
The waste leaching solution contains chromium, cadmium, and lead
leached from the emission control dust. Since trivalent chromium
has only slight solubility in dilute sulfuric acid, and the
hexavalent form is extremely soluble, the chromium in the acid
leachate will be overwhelmingly hexavalent.
Uith regard to the management of the waste leaching
solution, EPA is presently aware that a plant in New Jersey
receives secondary lead emission dusts for recycling. The
dusts are leached, and the waste acid solution is Disposed of
on-site in unlined laROons (3). EPA presently lacks Information
-------
On OCner WaSCt: ledCH J.ll>i SUJ.ULIUU geiiel a LJ. u* j.u<.a <- J.UUB ouvi
management practices.
The Agency wishes to make clear that it is not regulating
those wastes which are recycled directly to the process as a
hazardous waste. However, if the dusts are stored prior to
recycling, they are defined as solid wastes and are subject
to Subtitle C jurisdiction.*
3. Secondary Lead Smelting Industry Waste Generation Levels
and Trends
Generation of emission control dust/sludges from
reverberatory furnaces is already very substantial, and is
expected to increase in the future. Table 2 shows the historic
sludge/dust generation from wet and dry scrubbing of
reverberatory furnaces (5). Historic quantities are given
for 1957 and 1977 as well as minimum and maximum generation
projections predictions for 19RO, 19R4, and 1987. The total
dust/sludge generation for 1977 (dry weight basis) was
1?7,158,700 metric tons. While not all of these materials
are disposed (due to dust recycling), it is nevertheless clear
that substantial quantities of wastes are generated annually.**
*At this time, requirements of Parts 262 through ?65 and
122 will apply to the accumulation, storage, and transportation
of hazardous wastes that are used, reused, recycled or reclaimed.
The Agency believes this regulatory coverage is appropriate to
the subject waste. These dusts/sludges are defined as hazardous
only if they are being accumulated and stored in piles prior to
recycling. These dusts may not pose a substantial hazard during
their recycling and, even though listed as a hazardous waste, this
aspect of their management is not now being regulated.
**The Agency presently lacks data to estimate the percentage
of secondary lead smelting emission control dust which is
recycled, although a maior percentage of dusts generated
mav he recycled. In light of the large quantities of dust
generated, the Agency believes large amounts of these
dusts are managed as wastps, and not recycled.
-------
TARLF. 2. ATR POLLUTION CONTROL SUIDCE/DUST GENERATION — RI-VERBRRATORY FURNACES —
SECONDARY LEAD INDUSTRY - (dry weight b.isis) (5)
I
60
^
-D
I
Total Sludge/Dust Generation
Stare
Illinois
Kansns
Pennsy 1 van la
A l.ihnma
Historic
SCC Code
3-04-00/.-02
3_n4-004-02
3-04-004-02
3-04-004-02
Arizona 3-04-004-02
California (3-04-004-02
Tnrllann 13—04-004—02
Lonslslana (3-04-004-02
Minnesota J3-04-004-02
Mississippi 13-04-004-03
Missouri J3-04-004-03
Nebraska 3-04-004-02
N. Jersey 3-04-004-02
Ohio | 3-04-004-02
Tennessee 1 3-04-004-02
Texas 13-04-004-02
1 1
1 1
I
1
1
1 1
1
Process
Wet Controls
Reverberatory furnace
IReverberatory furnace
Reverberatory furnace
Total sludf>e from]
I wet controls
l»ry Controls
iReverberatory furnace
1967
4^05.
77.
431.
4064.
660.
Reverberatory furnacel 8-
Reverberatory furnacel 360-
Reverberatory furnacel 1R49-
Reverberatory furnace 1 7/iRl.
Reverberatory furnace 1.377 •
Reverberatory furnacel 541.
Reverberatory furnace 2L73.
Reverberatory furnace 73RO.
Reverberatory furnace 1RS6.
Reverberatory furnacel 550.
Reverberatory furnacel 5403.
Reverberatory furnace f 62043 .
IReverberatory furnace 11R7.
IReverberatory furnace 340.
Total dust from
dry controls
8*163.
1
s
S
7
2
1977
6490. R
39.fi
621.2
71Sl.fi
0| 950. R
(in3
r^
I Win
r
| 19RO
r
i
1 697.4.
1 «.
1 667.
]
1 7629.
1
I 1014.
3| 11.91 12.
S] 519.3| 554.
•? 3574.5! 3813.
31 1912. ll 2039.
f> 7RD.2I 832.
5| 3131.7.1 3340.
B| 10633. ll 11343.
•>! 2674. 1| 2R57.
0| 792.31 R45.
0| 77R.4| 830.
2 R93R2.4J 95352.
9 1711.4J 1875.
7 490. R| 523.
„
Total sludge/dust I9317R-
I from wet/Hry
controls
170007.1
12715R.7
1
1128077..
1
1
i
1
I1356S1.
1
metric tons/year)
tmiiin Scenario
1
1
1
1
31
7- 1
7 |
1
7.1
1
\
3!
7|
o|
?\
81
31
31
31
7|
41
41
71
1
Si
1
I
7|
1
19R4
7 7 1R . 4
47.0
73R.7
8504.1
1130.6)
14.21
617.51
316B.6I
4250.51
2273.71
927. R|
3723.4
12644.2
3179.9
942. ll
925.6|
2035. ll
1
142705. 1
1
151209. ll
1
19R7
R314.0I
_ rt *. 1
50.61
795.7
9160.3
1717. R
15.3
665-1
3413.1
457R.5
2449.2
999.4
4010.7
13619.9
342S.3
1014. Rl
997.0|
1144R9.9|
2192.1
628.7
53716. R
145319.81
1
Maximum Scenar:
1QRO 1984 1
— • 1 T
77*5.7
l\l , 3
742 .2
8544.7
1136.0
14.?
620.5
3133.7
4770. R
27*4.6
932.2
3741.1
12704.5
319S.O
946.6
930.0
L06794.7
2044.8
586. 4
1433«5.1
151929.8
i
1
|
8644.61
S2.6
9524.51
1
1
i
\
1
1766.31
, r n I
I1! .4 |
691.6)
3548. fl|
4760.51
2546.51
1039. ll
4170-?!
14]61.5i
3f>(il.S|
1036.71
119042.71
2279.31
653.71
i r
1
159R79.5
1
1
169354. 1
I
-------
These quantities can be expected to increase — particularly
dust generation. First, New Source Performance Standards
will limit participate emissions from new reverberatory furnaces,
resulting in increased collection of particvilate wastes. Since
baghouses are the most cost-effective means of meeting NSPS,
it is expected that dry collection of emissions will continue
to be used in the industry and lead to increased generation
of emission control dusts (5).
Production of secondary lead is also increasing, again
with the likely result of increasing emission control
dust/sludge generation. Secondary lead production in fact
increased by 200% between 1969 and 1979 (•>). Projected
dust/sludge generation levels (estimated on a minimum/maximum
basis) are 145,319,fiOO - 274,475,700 metric tons (dry weight)
by 19R7 (Table 2).*
Ill. Hazardous Properties of the Wastes
1. Concentrations of Lead, Cadmlura and Chromium in the Waste
Streams.
Agency data Indicates that significant levels of the toxic
metals lead, cadmium and chromium are found in the emission
control dust/sludge. As indicated in Table 3, lead may comprise
as much as 5 - 12% of the entire waste stream. Chromium and
cadmium concentrations are also high (although nowhere near
so elevated ) :
*The Agency does not presently have data showing
quantities of waste leaching solution generated. Increased
rate of emission control dust recycling nay, however, lead
to increased generation of waste leaching solution.
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Table 3
Waste Analysis (ppm)
Cd Pb Cr
Emission Control Sludge 140 53,000 30
From Soft Lead Smelting
Emission Control Dust 900 120,000 150
From Lead Alloy Smelting
The Agency does not have metal concentration data for
the waste leaching solution. Concentrations of these toxic
metals in the waste leaching solution, however, can be expected
to be significant since the acid leaching medium will solubiHze
cadmium, lead and hexavalent chromium fairly aggressively —
indeed, it is intended to perform this function. Some concrete
idea of concentrations in the waste leaching solution can be
gained from comparision of a distilled water extract of
emission control dust presented in Table 4 below. Since
lead and cadmium are more soluble in acid than in distilled
water (7,8), and since most hexavalent chromium compounds are
extremely soluble in all aqueous media (see Attachment I),
the concentrations of these constituents in the dilute sulfuric
acid leaching solution can be expected to be at least as
great as, and more likely higher than concentrations in the
distilled water extract.
?. . "ropensity of Lead, Cadmium, and Hexavalent Chromium to
Migrate from the Wastes in Dangerous Concentrations and
Possible Pathways of Exposure of Improperly Managed
Wastes.
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The presence of such high concentrations o'f toxic metals
in a waste stream may pose a serious threat to human health
and the environment should these toxic metals he released.
Furthermore, distilled water extraction test data indicate
that these toxic constituents may leach from the waste in
harmful concentrations unless the wastes are properly managed.
Thus, a distilled water extract from samples of the secondary
lead emission control dust and emission control sludge presented
in Table 3 indicates that lead, cadmium, and (in the case of
the emission dust) chromium may solubillze from the waste in
concentrations several orders of magnitude greater than
Interim "rimary Drinking Water Standards. See Table 4.
Tahle
Emission Control Sludge
From Soft Lead Smelting
Emission Control Dust
From Lead Alloy Smelting
Interim Primary Drinking
Water Standard
Distilled Water
Extract Analysis (ppm)
Cd_ JPb Cr_ (total)
5 2.5 .05
230 24.0 12.0
.01 .05 .05
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I.'hlle Che Agency has not performed any analyses of the
waste acid leaching solution, as noted above, the Agency
believes lead, hexavalent chromium and cadnium concentrations
in waste acid leaching solution will probably be higher than
in the distilled water extract of the emission control dust.
Furthermore, since the waste leaching solution may be disposed
of in liquid form, i.e., with harmful constituents already
solubilized and available for migration into the environment,
there is a corresponding danger of exposure to harmful concen-
trations of these metals if the waste is improperly managed.
Thus, these wastes may leach harmful concentrations of
lead, cadmium, and hexavalent chromium even under relatively
n:ild environmental conditions. If these wastes are exposed
to more acidic disposal environments, for example disposal
environments subject to acid rainfall, these raetals would
aost likely be solubilized to a considerable extent, since
lead, and cadmium (including their oxides), as well as
nost chromium compounds, are more soluble in acid than in
distilled water (6,7,8, and Attachment I). (See Table 1
indicating that a number of secondary lead plants are located
in states known to experience acid rainfall including New Jersey,
Ohio, Illinois, and Indiana.)
A further indication of the migratory potential of the
waste constituents is the physical form of the waste itself.
These waste dust/sludges are of a fine particulate composition,
thereby exposing a large surface area to any percolating medium,
-IX-
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and increasing the probability for leaching of hazardous
constituents from the waste to groundwater. Waste acid
leaching solution, as noted above, is disposed of in liquid
form with harmful constituents directly available for migration.
The Agency thus believes that emission control dust/sludge,
and waste acid leaching solution may pose a threat of serious
contamination to groundwater unless proper waste management
is assured. These wastes do not appear to be properly managed
at the present time. Thus, present Industry practices of
disposing of these wastes In unlined lagoons (see p. 7 above)
may well not be environmentally sound. For example, location
of disposal sites in areas with permeable soils could permit
contaminant-bearing leachate from the waste to migrate to
the groundwater in harmful concentrations* This is a parti-
cular concern for lagoon-disposed wastes because a large
quantity of liquid is available to percolate through the
solids and soil beneath the fill, increasing heavy metal
solubilization and migration.
The Agency is also concerned that the lagooned wastes
could contaminate surface waters if not managed to prevent
flooding or total washout. While the Agency is not aware
whether disposal lagoons presently have diking or other con-
trol mechanisms to prevent washout, it is certainly possible,
given the number of sites, that in some cases, present flood-
control measures are inadequate. Nor can proper flood manage-
ment (or leachate control, for that matter) be assured without
regulation.
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Another pathway of concern Is through airborne exposure
to lead, chromium, or cadmium particulates escaping from
emission control dust. These particulates could escape if
waste dusts are piled in the open, or placed in uncontrolled
landfills. For cadmium and hexavalent chromium compounds this
pathway is known to be particularly dangerous (see Appendix A,
Health Effects BD). Although the Agency is not aware whether
waste dusts are managed in this manner, this type of improper
management situation appears plausible in light of the large
quantities of emission control dust generated annually.
Should lead, cadmium, or hexavalent chromium escape from
the disposal site, they will persist in the environment and
therefore may contaminate drinking water sources for extremely
long periods of time. Cadmium is bioaccumulated at all trophic
levels (9, 10). Lead can be hioaccumulated and passed along
the food chain but not biomagnifled.
3. The Large Quantities of Waste Dust/Sludge Generated Are
A Further Factor Supporting a "T" Listing of These Wastes
The Agency has determined to list secondary lead emission
control sludge/dust as a "T" hazardous waste, on the basis of
lead, hexavalent chromium, and cadmium constituents, although
these constituents are also measurable by the EP toxicity
characteristic. Moreover, concentrations of these constituents
in an EP extract from waste streams from individual sites
might be less than 100 times interim primary drinking water
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standards (although the Agency's own extraction data suggests
that extract concentrations may exceed the 100 x benchmark for
some generators). Nevertheless, the Agency believes that there
are factors in addition to metal concentrations in leachate
which justify the "T" listing. Some of these factors already
have been identified, namely the high concentrations of cadmium
and chromium (presumably largely in hexavalent form), and
especially lead in actual waste streams, the non-degradabillty
of these substances, and indications of lack of proper manage-
ment of the wastes in actual practice.
The quantity of these wastes generated is an additional
supporting factor.
As indicated above, secondary lead emission control
dust/sludge is generated in very substantial quantities, and
contains very high lead concentrations, as well as elevated
concentrations of cadmium and (presumably hexavalent) chromium.
(See p. 11 above.) Large amounts of each of these metals are
thus available for potential environmental release. The
large quantities of these contaminants pose the danger of
polluting large areas of ground or surface waters. Contami-
nation could also occur for long periods of time, since
large amounts of pollutants are available for environmental
loading. All of these considerations increase the possibility
of exposure to the harmful constituents in the wastes, and
in the Agency's view, support a "T" listing.
IV . Hazards Associated With Lead, Chromium and Cadmium
Lead is poisonous in all forms, and is one of the most
hazardous o F the toxic metals because it accumulates in many
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organisms. Its deleterious effects are numerous and severe.
Lead may enter the human system through inhalation, ingestion
or skin contact.
The carcinogencitv of cadmium and its compounds, and of
various hexavalent chromium compounds in humans is well
documented;(13) EPA's CAG has determined that there is
substantial evidence that cadmium and its compounds, as well
as hexavalent chromium compounds are carcinogenic to roan.
The degree of absorption of hexavalent chromium compounds is
higher than that for trivalent chromium, except when the
latter is in some specific chemically-complexed form. Chronic
toxicity problems associated with hexavalent chromium Include
damage to liver, kidney, skin, respiratory passages and lungs.
Allergic dermatitis can result from exposure to both tri- and
hexavalent chromium. Cadmium is toxic to practically all
systems and functions of human and animal organ!sras(9).
Acute poisoning may result from the inhalation of cadmium
dusts and fumes (usually cadmium oxide) and from ingestion
of cadmium salts (10). Additional information on the adverse
health effects of cadmium, chromium, and lead can be found
In Appendix A.
Lead, cadmium, and chromium historically have been regarded
as toxic. Thus, EPA has established maximum concentration
limits for lead, cadmium and chromium In effluent limitations
guidelines adopted pursuant to Section 104 of the Clean Water
Act, and under National Interim Primary Drinking Mater
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Standards adopted pursuant to the Safe Drinking Water Act.
Lead also is regulated under the New Source Performance
Standards of the Clean Air Act.
The Occupational Safety and Health Administration (OSHA)
has set a work place standard for exposure to lead, cadmium
and hexavalent chromium compounds.
In addition, several states that are currently operating
hazardous waste management programs specifically regulate
cadmium, chromium, and lead containing compounds as hazardous
wastes or components thereof. These states include Maryland,
Minnesota, New Mexico, Oklahoma and California (final regula-
tions), and Maine, Massachusetts, Vermont, and Louisiana
(proposed regulation).
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References
1. U.S. EPA. Office of Solid Waste. Assessment of hazardous
waste practices in the metal smelting and refining
industry, v.2 and v.4, EPA No. SW-145c2 and SW-145c4.
NTIS PB Nos. 276 170 and 276 172. April, 1977.
2. U.S. EPA. Effluent Guidelines Division. Draft development
document for effluent limitation guidelines and new
source performance standards for the major nonferrous
metals segment of the nonferrous manufacturing point
source category. Washington, D.C. September, 1979.
3. U.S. EPA. Office of Solid Waste. Assessment of solid
waste management problems and practices in nonferrous
smelters. EPA No. 68-03-2577. November 1979.
4. U.S. Deparment of Interior, Bureau of Mines. Mineral
commodity summaries. 1980. December, 1979.
5. U.S. EPA. Office of Solid Waste. Background document
for comprehensive sludge study relevant to section
3002(9) of the Resource Conservation and Recovery Act
of 1976 (P.L. 94-580). SCS Engineers. EPA Contract No.
68-01-39A5. Volume 2, App. E. December, 1978.
6. CRC Handbook of Chemistry and Physics, 52nd ed.
The Chemical Rubber Company, Cleveland, Ohio. 1971-72.
7. The Merck Index, 8th ed. Merck & Co., Inc., Rahway, NJ. 1968,
8. Pourbaix, M. Atlas of electrochemical equilibria in
aqueous solutions. Pergamon Press, London. 1966*
9. Waldbott, G.L. Health effects of environmental pollutants.
C.V. Mosby Company, St. Louis. 1973.
10. Gleason, M.N., R.E. Gosselin, H.C. Hodge, and B.P. Smith.
Clinical toxicology of commercial products, 3rd ed.
The Williams and Wilkins Co., Baltimore. 1969.
11. Not used in text.
12. Latimer, W.J. Hand, H. Hildebrand. Reference book of
inorganic chemistry. MacMillan Company, N.Y., 1940.
13. Casaret, J. and J. Doull. Toxicology, the basic chemistry
of poisions. MacMillan Company, New York. 1979.
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Attachment I
SOLUBILITY AND ENVIRONMENTAL MOBILITY
CHARACTERISTICS OF CHROMIUM COMPOUNDS
The trlpositive state Is the most stable form of chromium.
In this state chromium forms strong complexes (coordination
compounds) with a great variety of ligands such as water,
ammonia, urea, halides, sulfates, amines and organic
acids.(a»b) Thousands of such compounds exist. This
complex formation underlies the tanning reactions of chromium,
and is responsible for the strong binding of trlvalent chromium
by soil elements, particularly clays.(c»d)
At .pH values greater than about 6, trivalent chromium
forms high molecular weight, insoluble, "polynuclear" complexes
of Cr(OH)3 which ultimately precipitate as C^Os-n^O. This
process is favored by heat, increased chromium concentration,
salinity and time.'8' These chromium hydroxy complexes,
formed during alkaline precipitation treatment of Cr-bearing
wastes, are very stable, and relatively unreactive, because
the water molecules are very tightly bound. In this form, Cr
is therefore resistant to oxidation. Three acid or base
catalyzed reactions are responsible for the solubilization of
chromium hydroxide:
A/1
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Cr(III) Concentration
Reaction Keq.(18> Calculated from keg (mg/
pH5 pH6 pH7
1. Cr(OH)3+2H+ CrOH^ +2H20 108 520 5.2 0.05!
2. Cr(OH)3 Cr+3+30H" 6.7xlO~31 35 0.035
3. Cr(OH) HH"Cr02~+H20 9xltf17 i i
*i= <0.001 mg/1
It is apparent from these figures that, in theory, trivalent
chromium could Leach fron sludges to some extent. Such
solubilized chroniura, however, is unlikely to contaminate
aquifers. It is complexed with soil materials, and tenasiously
held.
If soluble trivalent chromium is added to soils it rapidly
dlsapperas from solution and is transformed into a form that
is not extracted by ammonium acetate or complexing agents.(cie)
However, it is extractable by very strong acids, indicating
the formation of insoluble hydroxides. Thus: above pH5,
chromiura(III) is immobile because of precipitation; below
pH4, chromlum(III) is immobile because it is strongly absorbed
by soil elements; between pH 4 and 5 Che combination of
absorption and precipitation should render trivalent chromium
quite immobile.
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Is.Cc.d) Hexavalent chromium remains as such in a
-oluble form In soil for a short time, and Is eventually
reduced by reducing agents if present.'e»*) As compared
with the crivalent form, hexavalent chromium is less strongly
adsorbed and more readily leached from soilsC^/ and thus, is
expected to have nobility in soil materials.^'
V*
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References
a. U.S. EPA, Reivews of the Enviromental Effects of Pollutants;
III Chromlura. ORNL/EIS-80; EPA-600/ 1-78-023 ; May 1980.
b. Transistion Metal Chemistry, R.L. Carlin, ed. Marcel
Dekker, New York. 1965; Volume 1.
c. Bartlett, R.J. and J.M. Kimble. Behavior of Chromium In
Soils: I Trivalent Forms. J. Environ. Qual. 5: 379-383:
1976.
d. Griffin, R.A. , A.K. Au, and R.R. Frost. Effects of
pH on adsorption of chromium from landfill leachate by
clay minerals. J. Environ. Sci. Healtn A12(8):
430-449:1977.
e. U.S. EPA. Applies .ion of Sewage Sludge to Cropland;
Appraisal of Potential Hazards of the Heavy Metals to
Plants and Animals. EPA 430/9-76-013. NTIS PB No.
264-015. November, 1976.
^tb, R.J. and J.M. Kimble. Behavior of Chromium in
Soii.s: II Hexavalent Forns. Ibid. 5:383-386. 1976.
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Petroleum Refining
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Re/fereaces
1. U.S. EPA, Office of SoJltd Waste. Assessment of Hazardous
Waste Practices in the Metal Smelting and Refining
Industry. Calspan Corporation. EPA Contract Number
68-01-2604, April 197**, Volumes II aad IV.
2. U.S. EPA, Effluent Guidelines Division, Draft Development
Document for Effluent Limitation Guidelines and Hew
Source Performance Standards for the Major Sonferrous
Metals Segment of the Honferrous Manufacturing Point
Source Category. Washington, D.C. September, 1979.
3. U.S. EPA, Office of Solid Waste. Assessment of Solid
Waste Management Problems and Practices in Nonferrous
Smelters. PEDCo Environmental, Inc. EPA Contract
Number 66-03-2577. November, 1979.
4. U.S. Deparment of Interior, Bureau of Mines. Mineral
Commodity Summaries, 1980. December, 1979.
5. U.S. EPA, Office of Solid Waste. Background Document
for Comprehensive Sludge Study Relevant to Section
8002 (9) of the Resource Conservation and Recovery Act
of 1976 (P.L. 94-580). SCS Engineers.. .EPA Contract
Number 68-01-3945. December, 1978.' Volume 2, App. E.
6. Handbook of Chemistry and Physics, 52nd Edition.
Cleveland, The Chemical Rubber Company, 1971-72.
7. The Merck Index. 8th Edition, 1968.
8- Pourbaix, Marcel. Atlas of Electrochemical Equilibria
in Aqueous Solutions, London, Pergamon Press, 1966.
9. Waldbott, G.L. Health Effects of Environmental Pollutants.
St. Louis, C.V. Mosby Company,1973.
'1CK Gleason, M., R.E. Gosselin, B.C. Hodge, B.P. Smith.
Clinical Toxicology of Commercial Products. Baltimore,
.The Williams and Wilkins Co., 1969. 3rd Edition.
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