BACKGROUND DOCUMENT
RESOURCE CONSERVATION AND RECOVERY ACT
SUBTITLE C - IDENTIFICATION AND LISTING OF HAZARDOUS WASTE
§§261,31 and 261.32 - Listing of Hazardous Wastes
May 2, 1980
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF SOLID WASTE
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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 to
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 i,d,ent i f ied 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 mav
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 §§260.20 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)(1) 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)(2) (i.e., may pose a substantial
present or potential hazard to human health or the
environment w-h-en it is improperly treated, stored,
transported, disposed of or otherwise managed) of
the regulations (see Criteria for Charazcteristics/
Listing/De 1 isting background document for a discussion
of the various factors).
The Agency considered several approaches for formulating
the list. The approaches can be broken down into three main
types:
Hazardous Waste from Non-Specific Sources - these
are wastes which are generated from a number of
different sources (i.e., electroplating, etc.)
Hazardous Waste from Specific Sources - these are
wastes which would be generated from a very specific
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source (i.e., distillation bottoms from the produc-
tion of acetaldehyde from ethylene, etc.)
Commercial Chemical Products - these are a list of
commercial chemicals or manufacturing chemical
intermediates which if discarded either as the
commercial chemical or manufacturing chemical
intermediate itself; off-specification commercial
chemicals or manufacturing chemical intermediates;
any container or inner liner removed from a container
that has been used to hold these commercial chemical
products or manufacturing chemical intermediates
unless decontaminated; or any residue or contaminated
soil, water.0x^.0ther debris resulting from the
clean-up of a spill into or on any land or water,
of these commercial chemical products or manufacturing
chemical intermediates are hazardous wastes.
(This listing background document will cover the first two
categories; the third category of hazard waste is discussed in
the background document entitled, "Hazardous Waste from Dis-
carding of Commercial Chemical Products and the Containers
and Spill Residues Thereof".)
HAZARDOUS WASTE FROM NON-SPECIFIC AND SPECIFIC SOURCES
Testing of pure substances is the traditional approach
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used by regulatory agencies to control toxic/hazardous chemicals*
The purpose of RCRA, however, is to control waste materials;
these are not normally pure substances (except as in the case
not ed above) .
In order for a regulation to be effective, it should be
structured so that it reflects the organization of the
regulated community. Since waste process streams are often
the units of the solid waste regulated by the Act, these same
waste process streams can be used to provide a ready means
of identification; such that, for our purposes, it is more
useful (for identification purposes) to list "still bottoms
from the XYZ process - ignitable". Likewise, there are
certain waste c las s es , —soich as halog.enated solvents which,
if classified as wastes, would be unambiguously identified
by such a designation.
In this document, the Agency is providing the technical
support for the 85 waste streams promulgated (interim final)
today. This document also includes the technical support for
the eleven new wastes proposed today. This listing (both
interim final and proposed) includes 16 waste streams from
non-specific sources and 80 wastes from specific sources.
*Pure substance listings work well for many agencies, since
their responsibilities lie with some aspect of the pure
substance. The Department of Transportation, for example,
uses this approach. Benzene is listed by DOT as a flammable
liquid. A transporter knows, after consulting the DOT listing,
that benzene must be handled according to the DOT flammable
liquid regulations.
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The background data used to support these listings comes pri-
marily from two sources. The majority of this data or infor-
mation comes from studies undertaken bv 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.)*. The second source of
data came from information collected from State Agencies
(i.e., manifest data, etc.).
In addition, this Document discusses the comments received
on the proposed listings (43 FR 58957-58959 and 44 FR 49402-49404)
which are promulgated today, and the changes subsequently made.
*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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Table of Contents
Background Document Page
1. Wastes From Usage of Halogenated Hydrocarbon 2
Solvents in Degreasing Operations
The spent halogenated solvents used in
degreasing, tetrachloroethylene, methylene
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, trichloroethy-
lene, 1,1,1-trichloroethane, chlorobenzene,
1,1,2-trichloro-1,2,2-trifluoroe-thane, 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, eyelohexanone,
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 disulfide, isobutanol, pyridine,
and the still bottoms from the recovery of
these solvents (I,T)
3. Electroplating and Metal Finishing Operations 82
Wastewater 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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P_ag e
Plating bath sludges from the bottom of
plating baths from electroplating
operations (R,T)
Spent stripping and cleaning bath solutions
from electroplating operations (R,T)
Plating bath and rinse water treatment
sludges from electroplating operations (T)*
Quenching bath sludge from oil baths from
metal heat treating operations (R,T)
Spent solutions from salt bath pot cleaning
from metal treating operations (R,T)
Quenching wastewater treatment sludges from
metal heat treating operations (T)
Flotation tailings from selective flotation
from mineral metals recovery operations (T)
- Cyanidation wastewater treatment tailing pond
sediment from mineral metals recovery opera-
tions (T) -"-"
- Spent cyanide bath solutions from mineral
metals recovery operations (R,T)
- Dewatered air pollution control scrubber
sludges from coke ovens and blast furnaces (T)
5. Wood Preserving 141
- Bottom sediment sludge from treatment of
wastewaters from wood preserving processes
that use creosote or pentachloropheno1 (T)
- Wastewater from wood preserving processes
that use creosote or pentachloropheno1 (pro-
posed) (T)
6 . Chromium Pigments and Iron Blues 171
Wastewater -treatment sludge from the pro-
duction of chrome yellow and orange pigments (T)
-Same as "Wastewater treatment sludges from electroplating
opera tions .
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Page
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)
7. Acetaldehyde Production 204
- Distillation bottoms from the production of
acetaldehyde from ethylene (T)
- Distillation side-cuts from the production
of acetaldehycfe from ethyl'ene (T)
8. Acrylonitrile Production 224
Bottom stream from the Wastewater stripper
in the productionof acrylonitrile (R,T)
Still bottoms from final purification of
acrylonitrile in the production of
acrylonitrile (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)
9. Benzyl Chloride Production 245
Still bottoms from the distillation of benzyl
chloride (T)
10. Carbon Tetrachloride Production 260
Heavy ends or distillation residues from the
production of carbon tetrachlor ide (T)
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") Q £
11. Epichlorohydrin Production •
Heavy ends (still bottoms) from the puri-
fication column in the production of
epichlorohydrin (T)
12. Ethyl Chloride Production 312
Heavy ends fromt he fractionation column
in ethyl chloride production (T)
13. Ethylene Bichloride and Vinyl Chloride Monomer Pro- ... 326
due tion
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)
14. Fluorocarbon Production 357
- Aqueous spent antimony catalyst waste from
fluoromethane's" production '(1)
15. Phenol/Acetone Production 373
- Distillation bottom tars from the production
of phenol/acetone from cumene (T)
16. Phthalic Anhydride Production 386
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
(propos ed) (T)
Distillation bottoms from the production
of phthalic anhydride from ortho-xylene
(proposed) (T)
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Page
17. Nitrobenzene Production . 403
Distillation bottoms from the production of
nitrobenzene by the nitration of benzene (T)
18. Methyl Ethyl Pyridine Production 416
Stripping still tails from the production
of methyl ethyl pyridine (T)
19,. Toluene Diisocyanate Production 431
- Centrifuge residues from toluene diisocya-
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_y_ia the vinyl chloride
proces s (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 trichloroethylene and
perchloroethylene (T)
22. MSMA and Cacodylic Acid Production 500
By-product salts generated in the production
of MSMA and cacodylic 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
Wastewater treatment sludges from the pro-
duction of chlordane (T)
Filter solids from the filtration of hexa-
chlorocyclopentadiene in the production
of chlordane (T)
- Vacuum stripper discharges from chlordene
chlorinator in the production of chlordane
(propsed) (T)
24. Creosote Production 544
Wastewater treatment sludges generated in
the production of creosote (T)
- Process wastewater from creosote production
(proposed) (T)
25. Disulfoton Production 560
Wastewater treatment sludges from the pro-
duction of disulfoton (T)
Still bottoms from toluene reclamation
distillation in the production of disulfo-
ton (T)
26. Phorate Production 573
- 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 from the washing and stripping
of phorate production (T)
27. Toxaphene Production 585
- Wastewater treatment sludge from the pro-
duction of toxaphene (T)
Untreated process wastewater from the pro-
duction of toxaphene (proposed) (T)
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28. 2,4,5-T Production
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597
Heavy ends or distillation residues from
the distillation of tetrachlorobenzene in
the productionof 2,4,5-T (T)
29. 2,4-D Production 610
- 2,6-Dichloropheno1 waste from the produc-
tion of 2,4-D (T)
Untreated wastewater 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""~pr ocessing 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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33. Leather Tanning and Finishing Industry
Page
709
Chrome (blue) trimmings generated by the
following subcategories of the leather
tanning and finishing industry: hair
pulp/chrome tan/re tan/wet finish; hair
save/chrome tan/retan/wet finish; retan/
wet finish; no beamhouse; through-the-
blue; and shearlings (T)
Chrome (blue) shavings generated by the
following subcategories of the leather
tanning and finishing industry: hair
pulp/chrome tan/retan/wet finish; hair
save/chrome tan/re tan/wet finish; retan/
wet finish; no beamhouse; through-the-
blue and shearlings (T)
Buffing dust generated by the following
subcategories of the leather tanning
and finishing industry; hair pulp/
chrome tan/retan/wet finish; hair save/
chrome tan/refan/wet finish; retan/wet
finish; no beamhouse; and through-the-
blue (T)
Sewer screenings generated by the following
subcategories of the leather tanning and
finishing industry: hair pulp/chrome tan/
retan/wet finish; hair save/chrome tan/
retan/wet finish; retan/wet finish; no
beamhouse; through-the-blue; and shearlings (T)
Wastewater treatment sludges generated by
the following subcategories of the leather
tanning and finishing industry: hair pulp/
chrome tan/retan/wet finish; hair save/chrome
tan/retan/wet finish; retan/wet finish; no
beamhouse; through-the-blue; and shearlings (T)
Wastewater treatment sludges generated by
the following subcategories of the leather
tanning and finishing industry: hair pulp/
chrome tan/r e tan/we t finish; hair save/chronie
tan/re tan/wet finish; and through-the-blue (R,T)
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Page
Wastewater 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 Sm'eTting 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 siimes/sludges from primary
zinc production (T)
Cadmium plant leach residue (iron oxide) from
primary zinc production (T)
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.Page
40. Secondary Lead Smelting
841
Emission control dust/sludge from
secondary lead smelting (T)
Waste leaching solution from acid
leaching of emission control dust
from secondary lead smelting (pro-
posed) (T)
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Generic Listings
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LISTING BACKGROUND DOCUMENT
Wastes from Usage of Halogenated Hydrocarbon
Solvents in Degreasing Operations
The spent halogenated solvents used in degreasing, tetra-
chloroethylene, methylene chloride, trichloroethylene,
1,1,1-trichloroethane, carbon tetrachloride and the chlorinated
fluorocarbons; and sludges resulting from the recovery of
these solvents in degreasing operations. (T)*,**,***
I. SUMMARY OF BASIS FOR LISTING
Solvent degreasing operations remove grease, wax, dirt,
oil, and other undesirable substances from various materials.
All degreasing facilities which use the halogenated hydro-
carbon solvents listed above generate spent solvent solutions
which are either discarded or processed to recover the
solvent from the spent solution. 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 trade names; the
listing obviously includes all trade name solvents
which containt he enumerated constituents of concern.
Another point of consideration is that different names
may be used to refer to the same solvent:
tetrachloroethylene = perchloethylene
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 heavy metals (i.e., lead
and chromium) in the degreasing operations; therefore, the
generator will be responsible for determining whether the
waste would also meet the EP toxicity characteristic.
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The Administrator has determined that spent halogenated
solvents from degreasing and the sludges that result from
associated solvent reclamation operations are solid wastes
which may pose a substantial present or potential hazard to
human health or the environment when improperly transported,
treated, stored, disposed of, or otherwise managed; therefore,
these wastes should be subject to appropriate management
requirements under Subtitle C of RCRA.
For all of the listed waste solvents, this conclusion
is based on the following considerations:
1. The chlorinated waste hydrocarbons are toxic and, in
some cases, genetically harmful, while chlorofluoro-
carbons may remove the ozone layer following environ-
mental release.
2. Approximately 99,000 metric tons of waste halogenated
solvents from degreasing operations are generated
each year(l). There are approximately 460,000
facilities dispersed throughout the country that
use halogenated solvents and generate these wastes(l).
It is estimated that about 30,000 metric tons per year
of halogenated hydrocarbons from these facilities are
either disposed of annually in landfills or by open-
ground dumping, either as crude spent solvents
or as sludges. The remainder of these wastes are
usually incinerated. The large quantity of wastes
generated and the large number of disposal sites
utilized, increases the possibility of waste mis-
management and environmental release of harmful
cons ti tuents .
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 uniformly high, increasing their migratory
po tential.
4. The spent solvent solution from degreasing operations
contains up to 90 percent of the original solvent.
Depending on the recovery technique, sludges that result
from reclamation processes can contain up ,t o 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
wastes.
For the five chlorinated solvents (not including chlorofluoro-
carbons) found in the waste streams, this conclusion is
based on the following considerations:
6. Incomplete combustion of the spent chlorinated
hydrocarbon solvents during incineration can
cause emissions of the solvent and generate
toxic degradation products (e.g. phosgene).
7. These spent halogenated solvents can leach from
the waste to effect adversely 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
mutagenic, or are suspected carcinogens or mutagens,
and are lethally toxic to humans 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 chorine atoms. These
atoms catalytically remove ozone, leading to adverse
effects, including skin cancer and climate changes.
II. OVERALL DESCRIPTION OF INDUSTRY USAGE
Degreasing operations are not industry specific. Degreasing
operations are prevalent in twelve major SIC (Standard Industrial
Classification) categories, numerous subcategories , and auto-
motive maintenance shops. The pertinent industries where
halogenated hydrocarbons are used primarily are presented in
Table 1. A summary of the number and types of plants that
conduct degreasing operations is presented in Table 2.
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Table 1
Industries Using Halogenated Hydrocarbons
in Degreasing Operations
Source SIC Code
Metal Furniture 25
Primary Metals 33
Fabricated Products 34
Non-electric Machinery 35
Electric Equipment 36
Transportation Equipment 37
Instruments and Clocks 38
«
Miscellaneous Industry 39
Automotive Repair Shops 75
Automotive Dealers 55
Automotive Maintenance Shops
Texitile Plants (Fabric Scouring) 22
Gasoline Stations
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c B L JL la u L u u 11 u in u t:
;j o u r c e
Material Degreasing
Metal Furniture
Pr ima ry Me tale
Fabricated Products
Non-electric Machinery
Electric Equipment
Transportation Equipment
Instruments and Clocks
Mis eellaneous
Automo t ive
Auto Repair Shops
Automotive Dealers
Gasoline-Stations
Maintenance Shops
Textiles
Textile Plants (Fabric Scouring) 22
Total
SIC
25
33 ,
34
35
36
37
38
39
.75
55
55
Number of of V'a p o r D e g r e a 8 i u g
Plants , Operations
9,
6,
29,
.40.
12,
8,
5,
15.
127,
121,
226,
320,
233 492
792 1,547
525 5,140
792 5,302
270 6,302
802 1,917
t
983 \ 2,559
187 886
i
1
203
369
445
701
of Cold Cleaning
Operat tons
22,
17,
76,
105,
31,
22,
15.
39,
141,
135,
869
5.58
329
456
720
756
467
262
977
463
277,440
252,735
7,201
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 DECREASING 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 trichloro-
ethylene and trichlor ethane. 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
maintained well below its boiling point. The item
to be cleaned is either immersed in agitated solvent
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Table 3 - Estimated Number of Plants using Halogenated
Solvents by Type of Degreasing (1974) (1)
Solvent
bon tetrachloride
or ocar bons*
hylene Chloride
rachloroethylene
chloroethylene
c h 1 ofoethane
Total
Vapor
(open top )
2,130
298
3,121
11,440
4, Oil
21, 000
Cold Cleaning
10,568
66,932
21,136
45,795
149,715
137, 386
431, 532
Vapor Fabric
Conveyorized Scouring
319
45
467
1, 713
601
3,145
2,522
693
3,215
Note: Blanks indicate no use of specified solvent in that type
of degreasing operation.
*This refers to all fluorocarbons, some of which are chlorinated.
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or suspended above the solvent where it 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 conveyorized vapor degreaser operates in much
the same manner, except that the objects to be cleaned
•
are continuously conveyed through the vapor zone.
Auxiliary solvent sprays are also used to improve the
cleaning efficiency of the operations.
Fabric scouring operations are slightly more complex.
Generally, the fabric is conveyed through the degreasing
machine, where it is sprayed with solvents. The solvents
are then removed with an aqueous solution of alcohol.
3. Waste Generation Levels and Projected Levels
The annual growth rate for the use of the listed
halogenated solvents in degreasing applications is expected to
-V
-------
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-triehloroethane
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, New York, Ohio, Pennsylvania and
Texas). Figure 1 and the associated Table 4 present the
geographic distribution of these plants.
There are about 431,532 operations that perform
cold cleaning using about 35 percent of the total
halogenated solvent consumption, while approximately
3,125 fabric scouring operations consume about 13 percent
of the total halogenated solvent(l). Assuming an equal
distribution of halogenated solvent use among cold
cleaning and fabric scouring operations, over 59 percent
-V
-10-
-------
^ '::?|||ferj-;i: 'i'::r-i.^;:T :;,.:;•'\;; !'••' ^O^
..i-.'~';:' ;"::•!""•'.:.-';:'=:. t:;iif
Figure 1
> 1.000
3HIC DISTRIBUTION OF
VAK5R DECREASING OPERATIONS (1)
Table 4
• t ^ i_,W^ . W^A H~\~
CONVEYORIZ
State
*
. , . ,
Alaska ' ^ -
Arizona
California
Colorado
Ccr.;-.*cticut
Delavare
District of Colu.-iia
Florida
Georgia
Hawaii
Idaho
Illinois
* ~<- Ic..--
Tcva
Kar.sas
Kc-r.tucky
louisiaria
.
'.-'.& me
t>. ^, . • - — /j
•'•- - .v A -'"-
,'•'.; oh i can
'•'. i r.r. £ s o t a
:•'•' isii's irci
«.. .- ^ . . • • • »• i
ED)' DSGRSAS
Nuroer
of slants
247
0
1S9
147
3,313
212-
€43
29
11
730
315
29
39
1,737
6S3
225
217
193
174
6 5
227
S23
1,539
^ t 0
IIS
455
••^ in 1 ^^ ^ r t * •• *^ * >•
«*• iN *• i? y^j £f ^— , i\i^™% JK • ^»
St =te
Xcr.tar.a
N'ebraska
'tavada
New Hi-t shire
N"«w Jersey
N'ow :-:-=xloo
**ew York
North Carolina
North D'kcta
Ohio
Creccn
•• G "* * **^ ^** ^ " -^ r*i i 2.
".hoc a 1 3] and
* •« ^» T *
South Circlir.a
South Dakota
Texas
\j ^ ."; [^
» * «. ,» ^
'« C^ « ..••w' • * ^
; . .• ^ „ : . ; -
• »-';-•••
'-•-"£ shine ton
Wiscor.sin
Wycrir.g
^* *• 4. - *
» -* V — ^
NS (1).
N'u.-.cer
of clints
25
102
30
36
1,200
54
i , :14
20
1 C T ^
1,5-5
^ C. ~
25^
246
i * ' i
I , - in
221
* - 1
25
356
1,119
Ci G
-? J
"> Q
**" ^
213
^ •» *
33
—
'
24,145
-------
of the total halogenated solvent used for degreasing
occurs in ten states (California, Illinois, Massachusetts,
Michigan, New Jersey, New York, Ohio, Pennsylvania, Texas
and North 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)
increases to about 30°C above that of the pure solvent, the solvent
is discarded. 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 are either disposed of, reclaimed
and recycled by the waste generator, or processed by a contract
solvent reclamining 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
-13. ~
-------
USE PATEERN OF HALOGENATED SOLVENTS IN DEGREASING AND
FABRIC SCOURING OPERATIONS IN 1974
Chemical
Halogenated hydrocarbons:
Carbon t e trachlor Ide
Fluoro carbons*
Methylene Chloride
Perchloroethylene
Trlchloroethylene
Trichloroethane
Total U.S.
Consump tion
(103 kkg)
U.S. Consumption
for Degreasing
(103 kkg)
Cold
Vapor
534.
428.
235.
330.
173.
236
8
6
4
2
7
.3
0
6
46
11
43
7
.72
.2
1
.4 ;
.8 '
i
8
1
1
5
1.
0
1
43
11
2.
90
7
U.S. Consumption
for Fabric Scouring
(103 kkg)
54.6
15
Total U.S.
Consumption
for Degreasing
and Scouring
(103 kkg)
5.72
17.1-
56.2
109
171.5
168
TOTAL
1939.0
186.12
271.8
69.6
527.52
*Thls refers~to all fluorocarbone , a percentage of which are chlorinated.
-12--
-------
solution contains up to 90 percent of the original solvent(A)*
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 WASTE AND TYPICAL DISPOSAL PRACTICES
Disposal practices include overt open ground dumping,
containerized landfilling, and incineration (3). Approximately
99,000 metric tons of waste halogenated solvents from degreasing
operations are generated annually(l). It is estimated that
about 30,000 metric tons of these are either landfilled or
open ground dumped. The remaining quantity of waste halogenated
solvents from degreasing operations are incinerated. The
rationale and derivation of this estimated quantity is presented
in Ap pend ix 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
•jih-a original solvent. The landfilling or open ground dumping
of these wastes in an unsecure land disposal facility may
-------
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
majority of these wastes are in liquid form — including all
of the spent solvents -- these wastes' physical form makes
them amenable to migration from a the land disposal facility.
Additionally, the solubility in water of these halogenated
solvents is quite high (13): 1 ,1 ,1-trichloroethane - 950
mg/1, tetrachloroethylene 45,000 mg/1, methylene chloride -
20,000 mg/1, carbontetrachloride 800 mg/1, and trichloroethy-
lene - 1,000 mg/l(36). Again, these high solubilities demon-
strate a strong propensity to migrate from inadequate 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, thus
demonstrating the propensity of these solvents to migrate from the
-------
waste disposal environment and to persist in drinking water follow-
ing migration* (14 a, 14b, 14c, 14d, 14e). In addition, a number
of actual documented damage incidents show the potential for a
very common halogenated solvent, trichloroethylene, to leach
from disposal sites into groundwater. (See Damage Incidents
Resulting from the Mismanagement of Halogenated Hydrocarbons,
p. 17.)
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 landfilling
of these wastes is the potential for the contaminants to volatilize
into the surrounding atmosphere. All of the listed chlorinated
solvents are volatile and thus could present an air pollution
problem if they are improperly managed (for example, disposed of
in the open, or without adequate cover), since they are uniformly
toxic via inhalation.
A special problem is posed by chlorofluorocarbon solvents.
These solvents are also highly volatile, but instead of posing a
direct toxicity hazard, they may be released at the 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 tri-
chloroethylene and trichlorofluoromethane .
-------
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 o-f 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).
-------
vhere they are decomposed by ultra violet radiation to r e-
laase 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 (33,34).
In March, 1978, EPA banned the use of chlorofluoro-
carbons in aerosol propellants. The primary concern in the
enactment of this ban was the ozone depletion effects resulting
from chlorof1uorocarbons entering the stratosphere and
reacting with the ozone. The Agency's concern, however, is
with chlorofluorocarbon use in general, due to the present
or future health and environmental hazards resulting from
their use. Therefore, the Agency has proposed the regulation
of non-aerosol uses of chlorofluorocarbons(8) .
Additionally, the U.S. EPA is expecting to propose regu-
lations 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 percursors of the 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-triehloroethane and
-X-
-------
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 carcinogenicity is a candidate for regulation
under Section 111 as a pollutant "reasonably anticipated to
endanger public health and welfare". Finally, trichlorofluoro-
methane, as indicated in the earlier discussion of chlorofluoro-
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
h urn ans.(^^»^'
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 organics, partially combusted organics
and newly formed organic compounds. Phosgene is an example
of a partially combusted chlorinated organic which is produced
by the decomposition or combustion of chlorinated organics
by 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.
-------
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 am-ounts 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 t e tr achloro e thylene , methylene chloride,
1 , 1 , 1-trichlor ethane , t ric hlo roe thylene , carbon t e trachlor ide
and chlo ro f luo rocarbons 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.
Te trachloroethyl ene has been included on EPA ' s list of
chemicals which have demonstrated substantial evidence of
car cinogenic i ty . ( 21) jn addition, repeated exposure in
rats and mice to t e trachl oro ethyl ene in air or in the diet
has resulted in central fatty degeneration in the liver,
increased kidney weights and toxic nephr opa thy . ( 18 , 19 , 20 ) .
Additionally, t e tr ac hlo r oe t hyl ene has demonstrated toxicity
to freshwater f ish( 14 b , 22 , 23 ) .
-30-
-------
Methylene chloride has been shown to be mutagenic(24).
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 carboxy-
hemoglobin(25 ) •
1,1,1-trichloroethane has been shown in an NCI bioassay
for carcinogenicity to induce a variety of neoplasms(26). A
high incidence of deaths in test animals has led to retesting
of this compound by NCI(26). Human toxic effects seen after
exposure to 1,1,1-trichloroethane include several central
nervous system functions, including reaction time, perceptual
speed, manual dexterity and equilibrium(27). In addition,
animal studies have prod-uced 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 tetrachloride has been included on EPA's list of
chemicals which have demonstrated substantial evidence of
carcinogenicity.(21) In addition, toxicological data for
non-human mammals are extensive and show carbon tetrachlor ide
to cause liver and kidney damage, biochemical changes in
-K-
-------
liver function and neurological damage(32).
The hazards associated with exposure to the above
halogenated solvents have been recognized by other regulatory
programs. Tetrachloroethylene, methylene chloride, 1,1,1-
trichloroethane, trichloroethylene, carbon tetrachloride and
the two fluorocarbons, trichlorofluoromethane and dichloro-
difluoromethane, are listed as priority pollutants in accordance
with §307 of the Clean Water Act of 1977. Under §6 of the
Occupational Safety and Health act of 1970, final standards
for occupational exposure have been established and promulgated
in 29 CFR 1910.1000 for carbon tetrachloride, methylene
chloride and 1,1,1-trichloroethane. On March 17, 1979,
fully halogenated fluorocarbons were banned by the Consumer
Products Safety Commission as propellants in the United
State, except for essential uses because of their threat to
the ozone. In addition, final or proposed regulations in
the States of California, Louisiana, Maryland, Massachusetts,
Minnesota, Missouri, New Mexico, Oklahoma and Vermont define
compounds containing one or more of the solvents tetrachloro-
ethylene, methylene chloride, 1,1,1-trichloroethane, trichloro-
ethylene, carbon tetrachloride and trichlorofluoromethane
as hazardous wastes or components thereof.^5
-------
ATTACHMENT I
DERIVATION OF THE ESTIMATED QUANTITIES OF THE WASTE
I. ANNUAL QUANTITIES OF WASTES
Total amount of spent solvents (Halogenated and non-
halogenated)C1) « 425,560 kkg
Total amount of spent solvents from vapor degreasing^
= 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)
0 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 landfills(3).
(amount of waste) (1-percent recovery)(percent of
plants with on site recovery) x (percent of plants
that landfill) = Amount of waste landfilled.
-------
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 landfilled 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.
0 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
-------
that are used for degreasing. The implication is
that, on the average, the solvent throughput
rate is much lower in this segment of the
degreasing industry than that of the vapor
degreasing segment.
Although some cold cleaning and fabric scouring
operations probably operate on a scale that would
make a recovery strategy economically attractive,
it is not possible to estimate the extent of recovery-
operations in this segment of the industry. The
economics seem to indicate that the incidence of
recovery from these operations is probably very low.
C. THE GROSS ESTIMATE
In estimating the disposition of all the wastes,
the best and worst cases pertaining to the portion
of the waste which cannot be documented in the
literature are considered. The ideal case is where
all of the wastes from cold cleaning and fabric
scouring operations are processed by contract re-
claimer using maximum efficiency recovery techniques
(i.e., 99 percent recovery). The worst case would
be where all of this waste is simply disposed of.
The following is the basis for the estimate.
From Section A
249 kkg 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
-------
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. United States Environmental Protection Agency. 1979.
Source Assessment: Solvent Evaporation - Degreasing
Operations.
2. Mansville Chemical Products. 1976. Chemical Products
Synopsi s-Trichloroethylene.
3. United States Environmental Protection Agency. 1976.
Assessment of Industrial Hazardous Waste Practices
Electroplating and Metal Finishing Industries - Job
Shops Pb-264-349.
4. United States Environmental Protection Agency. 1979.
Organic Solvent Cleaners-Background Information for
Proposed Standards. EPA-45/12-78-045a .
5. United States Environmental Protection Agency. 1978.
Source Assessment: Reclaiming of Waste Solvents. State
of the Art. Pb-289-934.
6. United States Environmental Protection Agency. 1977.
Assessment of Industrial Hazardous Waste Practice Special
Machinery Manufacturing Industries. PB-265-981.
7. Scheflan, L. , Jacobs^ M.B., 1953. The Handbook of Solvents,
D. Van Nostrand Company, Inc., New York.
8. March 17, 1978, 43 FR 11301.
9. United States Environmental Protection Agency. 1977.
Control of Volatile Organic Emissionf From Solvent Metal
Cleaning. EPA-450/2-77-022.
10. Michigan Department of Natural Resources - Geological Survey
Division. Case History #48.
11. Shellenbarger, P. 1979. "New Charge Hits Air Force." The
Detroit News, May 17, 1979.
12. Mitre Corporation. 1979. Draft Report in Support of Sub-
Section C. Prepared for U.S. Environmental Protection Agency.
13. Technical Support Document for Aquatic Fate and Transport
Estimates for Hazardous Chemical Exposure Assessments. 1980,
USEPa, Environmental Research Laboratory, Athens, Georgia
14a. U.S. EPA. 1979. Trichloroethylene: Ambient Water Quality
Criteria. U.S. Environmental Protection Agency.
14b. U.S. EPA. 1978. In-depth Studies on Health and Environ-
mental Impacts of Selected Water Pollutants. Contract
No. 68-01-4646. U.S. Environmental Protection Agency.
-------
14c. U.S. EPA. 1975. Preliminary Assessment of Suspected
Carcinogens in Drinking Water, and Appendices. A
Report to Congress, Washington, D.C.
14d. U.S. EPA. 1977a. Determination of Sources of Selected
Chemicals in Waters and Amounts from These Sources.
Draft Final Report. Contract No. 68-01-3852. U.S.
Environmental Protection Agency.
14e. U.S. EPA. 1978b. The. National Organic Monitoring Survey.
Rep. (unpublished), Tech. Support Div., Off. Water
Supply, Washington, D.C.
15. "Combustion Formation and Emission of Trace Species",
John B. Edwards, Ann Arbor Science, 1977.
16. NIOSH Criteria for Recommended Standard: Occupational
Exposure to Phosgene, HEW, PHS, CDC, HIOSH, 1976.
17. Chemical and Process Technology Encyclopedia, McGraw
Hill, 1974.
18. National Cancer Institute. 1977. Bioassay of Tetrachloro-
ethylene for Possible Carcinogenicity. CAS No. 127-18-4
NCI-CG-TR-13 DHEW Publication No. (N1H) 77-813.
19. Rowe, V.K., et al. 1952. Vapor Toxicity of Tetrachloro-
ethylene for Laboratory Animals and Human Subjects. AMA
Arch. Ind. Hyg. Occup. Med. 5:566.
20. Klaassen, C.D., and G.L. Plaa. 1967. Relative Effects
of Chlorinated Hydrocarbons on Liver and Kidney Function
in Dogs. Toxicol. Appl. Pharmacol. 10:119.
21. The U.S. EPA. Carcinogen Assessment Groups. List of Car-
cinogens. April 22, 1980.
22. Alexander, H., et al. 1978. Toxicity of Perchloroethylene,
Trichloroethylene, 1,1,1-Trichloroethane, and Methylene
Chloride to Fathead Minnows. Bull Environ. Contam. Toxicol.
20:344.
23. U.S. EPA. 1979. Tetrachloroethylene: Ambient Water
Quality Criteria (Draft).
24. Simmon, V.F. et al. 1977. Mutagenic Activity of Chemicals
Identified in Drinking Water. S. Scott, et al . , eds . J_n_
Progress in Genetic Toxicology.
25. National Academy of Sciences. 1978. Nonfluorinated
Halomethanes in the Environment. Washington, D.C.
-------
26. National Cancer Institute. 1977. Bioassay of 1,1,1-
Trichloroethane for Possible Carcinogenic!ty. Carcinog.
Tech. Rep. Ser. NCI-CG-TR-3 .
27. U.S. EPA. 1979. Chlorinated Ethanes: Ambient Water
Quality Criteria. (Draft)
28. Nomiyama, K., and H. Nomiyama. 1971. Metabolism of
Trichloroethylene in Human Sex Differences in Urinary ,
Excretion of Trichloroacetic Acid and Trichloroethanol.
Int. Arch. Arbeitsmed. 28:37.
29. Bardodej, A., and J. Vyskocil. 1956. The Problem of
Trichloroethylene in Occupational Medicine. AMA Arch.
Ind. Health 13:581.
30. McBirney, B.S., 1954. Trichloroethylene and Dichloro-
ethylene Poisoning. AMA Arch. Ind. Hyg. 10:130.
31. U.S. EPA. 1979a. Carbon Tetrachloride: Ambient Water
Quality Criteria Document. (Draft)
32. Von Oettingen, W.F. 1964. The Halogenated Hydrocarbon
of Industrial and Toxicological Importance. In E.
Browning, ed. Elsevier Monographs on Toxic Agents.
Elsevier Publishing Company, New York.
33. National Academy of Sciences, National Research Council.
1976. Halocarbons: Environmental Effects of Chloromethane
Release.
34. National Academy of Sciences, National Research Council.
1979. Stratospheric Ozone Depletion by Halocarbons:
Chemistry and Transport.
35. U.S. EPA States Regulations Files; January 1980.
36. U.S. EPA. 1979. Trichloroehylene Ambient Waste Quality
Criteria Draft.
37. Dawson, English, Petty, 1980, "Physical Chemical Properties
of Hazardous Waste Constituents".
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WASTES FROM USAGE OF ORGANIC SOLVENTS
I. LISTING
The listed wastes are those major streams which result
from usage of organic solvents and which contain a significant
concentration of one or more organic solvents. The solvents
referred to include both halogenated and non-halogenated
organic compounds. The specific wastes listed are presented
b elow.
The spent halogenated solvents tetrachloroethylene , methyl
chloride, trichloroethylene, 1,1,1-trichloroethane , chlorobenzene,
1,1,2-trichloro-1,2,2-trifluoroethane, o-dichlorobenzene, tri-
chlorofluoromethane, 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, cyclo-
hexanone and the still bottoms from the recovery of these
solvent s (I);
The spent non-halogeanted solvents, cresols and cresylic acid,
nitrobenzene and the still bottoms from the recovery of these
solvents (T); and
The spent non-halogenated solvents, methanol, toluene, methyl
ethyl ketone, methyl isobutyl 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 on Table 1-1, and codes for
widely-used non-h'alogenat ed organic solvents are on 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 recovery and spent solvents from dry cleaning
operations and maintenance and repair shops.
The Administrator has determined that waste from usage
of the 24 organic solvents listed in Tables 1-1 and 1-2 may
be a solid waste, and as a solid waste, may pose a substantial
present or potential hazard to human health or the environment
when improperly transported, treated, stored, disposed of or
otherwise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations*:
1. Of the list of 24 solvent types presented in Tables
1-1 and 1-2, each solvent exhibits one or more
properties (i.e., ignitability and/or toxicity)
*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.
-X-
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TABLE 1-1
LISTING CODES FOR HALOGENATED ORGANIC SOLVENTS*
(in. order of usage as solvent)
S olvents
Listing
Codes
Flash
Point (°F)
Perchloroethylene
Methylene chloride
Trichloroethylene
1,1,1,-Triehioroethane
Chlorobenzene
1,1,2-Triehloro-l,2,2-
Trifluoroethane
o-Dichlorobenzene
Trichlorofluoromethane
T
T
T
T
T
T
T
T
*A11 data in this table are based on information contained in
Reference (!)• Dashes in place of data mean either the values
were not available or (in the case of flash points) not
applicable.
-v
-------
TABLE 1-2
LISTING CODES FOR NON-HALOGENATED ORGANIC SOLVENTS*
(in order of usage as solvent)
Toluene
Acetone
Ethyl acetate
Ethyl benzene
Ethyl ether
Isobutanol
Cyclohexanone
Nitrobenzene
Pyridine
yl ketone
butyl ketone
ulf ide
ate
ene
r
cohol
d cresylic acid
one
ne
Listing
Codes
x**
I,T**
I,T**
I,T**
I**
I>T**
I,T**
x**
x**
x* *
x**
I,T**
T
x* *
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 on 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 would contain a large percentage of
these solvents, the listed wastes would fail the ignitability
characteristic for liquids--a flash point less than 60 °C
(140°F).
-------
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, seven are listed for meeting only the
ignitability characterisitc. These seven spent
solvents all have a- flash point below 60°C (140°F)
and are thus considered hazardous.
The seventeen solvents listed as either toxic
or toxic and ignitable pose a further hazard to
human health and the environment. If improperly
managed, these solvents could migrate from the
disposal site into ground and surface waters,
persist in the environment for extended periods
of time, and cause substantial hazard to environ-
mental receptors.
The two fluorocarbons, 1, 1,2-1richloro-1,2 , 2-
trifluoroethane and trichlorof1uoromethanes 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 so Ivent s;
(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 therefrom.
-53-
-------
Table II-l
RANKING AND AMOUNTS OF THE LISTED SOLVENTS^1)
Chemical Name
Amount Used As
Solvent (kkg/yr)
Xylenes
Methanol
Toluene
Perchloroethylene
Methylene chloride
Methyl ethyl ketone
Trichloroethylene
1,1,1-Trichloroethane
Acetone
Methyl isobutyl ketone
Chlorobenzene
Carbon disulfide
Ethyl acetate
Ethyl benzene
Ethyl ether
n-Butyl alcohol
l,l,2-Trichloro-l,2,2-tri-fluoroethane
Isobutanol
o-Dichlorobenzene
Cresols & cresylic a
Cyclohexanone
Nitrobenzene
Trichlorofluoromethane
Pyridine
489,900
317,500
317,500
255,800
213,200
202,300
188,200
181,400
86,200
78,000
77,100
77,100
69,900
54,430
54,430
45,360
24,040
18,600
11,800
11,800
9, 072
9,072
9,072
907
Consumption amounts for cresol and cresylic acid were
combined.
-V
-------
Ill. 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 follows:' '
Paint & Allied Products and Industrial 1,153,500 kkg/yr
Operations
Surface Cleaning 610,600 kkg/yr
^
Pesticide Production 266,700 kkg/yr
Laundry and Dry Cleaning Operations 214,550 kkg/yr
Pharmaceuticals Manufacture 34,740 kkg/yr
Solvent Recovery 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 pharmaceuticals). The ten
specific solvents included in this table are believed to
account for about 80 percent of all organic solvent usage. (-*-)
*Large amounts of chemicals listed on 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 III-l
USE DISTRIBUTION OF THE 10 MOST WIDELY USED ORGANIC SOLVENTS
(All data in units ©f 103 kkg/yr)
05
Paint & Allied Products
Surface Cleaning
Pesticides
Pharmaceuticals
Laundry & Dry Clean.
TOTAL
Listed Use Level
in Reference (1)
-------
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,
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
0 Roll Coatings
0 Paper Coatings
0 Dye Manufacture
0 Ink Manufacture
0 Adhesive Manufacture
0 Printing Operations
*United States Environmental Protection Agency. 1976.
Assessment of Industrial Hazardous Waste Practices
Electroplating and Metal Finishing Industries - Job
Shops PB-264-349.
** United States Environmental Protection Agency. 1979.
Organic Solvent Cleaners-Background Information for
Proposed Standards. EPA-45/12 - 78-045 a.
***United States Environmental Protection Agency. 1978.
Source Assessment: Reclaiming of Waste Solvents. State
of the Art. PB-289-934.
-------
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
than 1500 plants. Solvents are important ingredients in
formulations for soIvent-thinned paints, lacquers, and factory-
applied coatings.
Solvent containing wastes arise from the use of solvents
to clean equipment, and still bottoms from the recovery of the
solvents used in production*. It is estimated^' 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
* 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.
-------
equipment cleaning.(1) 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.
Spent solvents used for equipment cleaning, if not re-
claimed, are drummed and land filled(^). Most paint companies
contract for waste disposal services. Solvent recovery still
bottoms are incinerated, landfilled, or injected into deep
walls. (5)
C. Surface Cleaning
The Surface Cleaning category consists of two
important subcategories:
0 Industrial Degreasing
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.(^) According to Reference
(5), the total number of degreasing operations in the United
States for 1976 was over 1,300,000, of which nearly half
-X-
-------
were associated with manufacturing operations of various
types. The major solvents used are trichloroethylene, 1,1,1-
trichloroethane, 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.
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
same pattern as the population itself. (->t)
The major types of wastes from solvent usage in the
industrial degreasing subcategory are used (spent) solvent
and solvent recovery still bottoms. Wastes from the repair
work subcategory would include both halogenated and non-
halogenated solvents, and would take the form of relatively
-------
small amounts of used solvent (typically up to a few gallons),
plus contaminated rags and other materials.
D. Production of Pesticides, Pharmaceuticals and
Other Organic Chemicals
Solvent 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 pharma-
ceuticals manufacture, methanol is used as the reaction
solvent in Nylon 66 production, and acetone is used as the
solvent in the production of cellulose acetate. ^-^ '
Wastes 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 riot known, but a large percentage is
reclaimed either in-house or by contract recovery operations.^'
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/yr^7) and 208,000 kkg/yr^1^ of perchloroethy lene. 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.(7) The
solvents are used 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-
bottom 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 remaining 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.
*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 sys tem .
**A "cooker" is a type of still in which solvent-contaminated
diatomaceous filter powder is heated to drive off the solvent
fraction of the total liquid residue contained in the filter
powder .
-------
With regard to contract solvent recovery operations,
there are between 80 and 100 contract solvent recovery
operations in the U.S.(4) The surface cleaning category,
and particularly industrial degreasing operations is one of the
largest sources of spent solvents sent to contract reclaimers.
Other important sources of spent solvents are the paint, ink,
and coatings manufacturers and manufacturing processes where
very pure solvents are used in organic synthesis (e.g., the
organic chemical and pharmaceuticals industries).'°' Some
contract reclaiming of solvents is also carried out on sol-
vents from commercial and industrial dry cleaning operations.
The geographic distribution, by state, of contract solvent
recovery operations is presented in Table III-2.
The volume of feedstock sent to the contract solvent
recovery industry is approximately 287,000 kkg/yr; of this
volume, about 27 percent are halogenated.(^)
Although there are approximately 100 contract solvent
recovery companies, the total number of solvent recovery
operations is much larger due to on-site recovery. Of the
total number of plants involved in "cleaning operations",
97.89 percent perform on-premises solvent recovery. (8)
Excluding the dry cleaning plants, which are distributed
geographically in the same pattern as population, the geographic
distribution of all solvent recovery operations is as shown
in Table III-3*
-1§L-
-vv-
-------
Table III-2
GEOGRAPHIC DISTRIBUTION OF CONTRACT SOLVENT
RECOVERY OPERATIONS^)
New Jersey
California
Ohio
Illinois
Michigan
New York
Indiana
Massachus e 1 1 s
Rhode Island
Maryland
South Carolina
Georg ia
Kent ucky
Tennessee
Mis sour i
Texas
Connecticut
North Carolina
Florida
Kansas
Arizona
9
9
8
8
7
5
4
3
2
2
2
2
2
2
2
2
1
1
1
1
1
74
-------
Table III-3
STATE DISTRIBUTION CF SOLVENT RECLAIMING OPERATIONS
State
Alabama
Arizona
Arkansas
California
Colorado
Connect icut
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Mich igan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
Soudi Carolina
Tennessee
Number
of Plants
72
37
39
424
44
60
12
141
98
14
224
113
59
49
70
83
19
83
85
178
76
45
98
15
30
10
13
153
21
372
105
13
213
56
40
245
21
55
83
Percent
of Total
1.8
0.94
0.99
10.
0.16
1.5
0.35
3.5
2.4
0.4
5.5
2.8
1.4
1.2
1.7
2.0
0.5
2.0
2.0
4.3
1.8
1.1
2.3
0.41
0.77
0.29
0.38
3.7
0.57
8.9
2.5
0.37
5.1
1.3
1.1
5.9
0.57
1.3
2.0
-X-
-------
Table III-3 (cont'ci)
Number Percent
State of Plants of Total
Texas 242 5.8
Utah 21 0.56
Vemont 8 0.24
Virginia 97 2.3
Washington 72 1.7
West Virginia 41 0.99
Wisconsin 90 2.2
Wyoming 6_ 0.14
Total 4,158 100
-X-
-Y7-
-------
Solvent recovery still bottoms (sludges) from contract
reclaiming 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.'4' Thus,
the total still bottom waste from contract reclaiming consists
of the following components:
18,250 kkg/yr solvent, including 13,320 kkg/yr non-
halogenated and 4,930 kkg/yr halogenated;
54,750 kkg/yr nonsolvent contaminant, including oils, waxes,
metals and chlorinated and nonehlorinated organics.
The estimate of 25 percent average solvent content, as
presented above, can probably be applied to solvent recovery
still bottoms for all of the industries discussed herein,
since the technology used to reclaim solvents is roughly
similar throughout U.S. industry. (8)
Waste Management Practices*
The most widely used management practices for spent
*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
from the recovery of these solvents are hazardous in so far
as they are being accumulated or stored in drums or tanks
prior to recycling. Therefore, these wastes will be con-
sidered as hazardous whether recycled or disposed. However,
at the present time, the management of these wastes during
recycling operations will not be regulated.
-------
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 bottoms, about 8()(8) to 86^)
percent of these bottoms from contract solvent reclaimers
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.(8>5) Land disposal
of st'ill 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). (^)
-------
IV. References to Section III
1. Lee, B. B., G. E. Wilkins and E. M. Nichols, "Organic
Solvent Use Study", Final Report, Contract 68-03-2776,
Work Effort 1. Prepared for EPA by Radian Corporation,
Austin, Texas (October, 1979).
2, Wildholz, M. (ed.), The Merck Index, 9th Edition. Merck
and Company, Rahway, New Jersey (1976).
3. Sax, N. I., Dangerous Properties of Industrial Materials,
Reinhold Publishing Company, New York, 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." Pre-
pared for EPA by WAPORA, Inc., Washington, D.C., as
Final Report, Contract 68-01-2656.
5. WAPORA, Inc., "Assessment of Industrial Hazardous Waste
Practices - Special Machinery Manufacturing Industries"
NTIS PB-262-981 (March, 1977).
6. Goodwin, D. R., and D. G. Hawkins, "Organic Solvent
Cleaners - Background Information for Proposed Standards".
EPA-450/2-78-045a. (October, 1979).
7. International Fabricare Institute, Silver Spring, Maryland.
Personal communication with B. Fisher (December, 1979).
8. Monsanto Research Corp., "Source Assessment Reclaiming
of Waste Solvents." NTIS PB-282-934 (April, 1978).
-------
IV. HAZARDS POSED BY THE WASTES
A. Hazardous Properties of the Solvents
The major halogenated solvents exhibit organic toxic
properties which make them potentially hazardous to human
health and the environment. In particular, the two halo-
genated solvents, perchloroethy 1ene and trichloroethy 1ene
are on CAG's List of Carcinogens. 1,1,1-trichloroethane was
determined to be an animal carcinogen. All of the listed
halogenated organic solvents, except 1,1,2-trich loro- 1, 2 , 2-
crifluoroethane , are priority pollutants under Section 307(a)
of the C.W.A.
A number of the non-halogenated organic solvents also
exhibit toxicity properties. Nitrobenzene has been identi-
fied as a suspected carcinogen. These compounds are toxic
via one or more of the exposure routes inhalation, inges-
tion and/or through the skin. Short term 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. 38-46). In addition, almost all
of these non-halogenated solvents also present an ignitability
hazard .
In light of the health hazards associated with the waste
-------
solvents--particularly those which are genetically active--
and the high concentrations of hazardous solvents contained
in the waste, the Agency believes a decision not to list
these waste solvents as hazardous would be warranted only if
the Administrator were convinced that waste solvents could not
migrate and persist, reaching human or environmental receptors
(if improperly managed). Such assurance does not appear
possible. Not only do all of the waste solvents have
significant potential for migration, mobility, and persistence,
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 eleven most-used non-halogenated organic solvents exhibit
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 dumps), into storm sewers, and into
deep wells. Mismanagement and improper disposal of these
-X-
-------
wastes by any of these methods could result in a substantial
health and environmental hazard.
Actual damage incidents (see pp. 33-35) involving certain
of these listed wastes confirm the dangers of ignitability,
and of leaching of waste constituents from landfills to
groundwater. Improper waste incineration could also lead to
substantial hazard. Thus, inadequate incineration conditions
(temperature and residence time) can result in emission of
solvents or toxic degradation products. Where a chlorinat.ed
solvent is involved, emissions could be more dangerous than
the waste itself. For example, phosgene is a partially
combusted chlorinated organic (halogenated solvent) which is
produced by the decomposition or combustion of chlorinated
organics by heat . ^ •*• a > ^ " » ^c ' Phosgene has been
used as a chemical warfare agent and is recognized as extremely
toxic .
B. Migratory Potential and Persistence of Halogenated And
Non-Halogenated Solvents
The following section of the document 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 management occur.
Environmental fate data showing the potential for release
°f the individual halogenated and non-halogenated solvents is
-------
U-34-01
described below and summarized in Table IV-1 and Table IV-2.
Perchloroethylene
Perchloroethylene, if not properly disposed of, may
migrate from the waste into the environment via both air and
groundwater exposure pathways.
Having been detected in several sites away from the
disposal area (i.e., found in varying amounts in school
basement air, in basement sumps, and on solid surface samples
at the Love Canal site), 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 extremely water-
soluble (20,000 mg/1), thus could leach into groundwater
and persist there due to its stability.10 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 mm Hg at 40°C8), so it may be released from
the waste into the air; it has been detected in school and
basement air at the Love Canal site.9
-------
TABLE IV-1
Halogenated Solvents*
Compound
P erchloroethy lene
Methylene chloride
Trichloroethylene
1,1, 1-Trichloroethane
Chlorobenzene
1,1,2-Trichloro-
1,2 ,2-Trif luoroethane
1,2-Dichlorobenzene
Tr ichlor of luorome thane
Vapor Pressure
(mm Hg)
19 at 25 °C5
350 at 20 °C
77 at 25°C5
100 at 20 °C
10 at 22 °C
270 at 20°C
1.56 at 25°C5
687 at 20 °C11
Solubility in
Water (mg/1)
150 at 25 °5
20,000 at 25°5
1,000 at 20°5
950 at 25 °C
488 at 25 °C
10 at 25°C
145 at 25 °C
1,100 at 25 o11
Octanol/Water
Partition
Coefficient
3392
20 |
1952
158
690
100
24002
3392
* Table compiled from data given in "Physical Chemical Properties of Hazardous Waste
Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
-5-T-
-------
Table IV-2
Non-Halogenated Solvents'
Compound
Methanol
Toluene
Methyl ethyl ketone I
I
Methyl isobutyl ketone |
Carbon disulfide
Isobutanol
Cresols and cresylic
acid ortho (1,2)
meta
para (1,4)
Nitrobenzene
Pyridine
Vapor Pressure
(mm Hg)
100 at 21.2°C
28.4 at 25°C
100 at 25°C
16 at 20°C
260 at 20°C
10 at 25 °C
0.24 at 25°C1:L
0.04 at 200C1:L
0.11 at 250C1;L
1 at 44.4°C
20 at 25°C
Solubility
in Water
Miscible I
470 at 25°C
[1000,000 at 25°C
I 19,000 at 25°C
2,200 at 25°C
| 95,000 at 18°C
Octanol/Water
Partition Coefficient
131,000 at 40°C1:L 1
I !
| 23,500 at 20°C1:L I
I
| 24,000 at 40°C1:L
I
| 1,900 at 25°C i
I
I Miscible
117
1
1
100
8
HO2
102'
982
62
5
Waste
piled from data given in "Physical Chemical Properties of Hazardous
Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
com
-------
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 number of wells and
residue ponds near groundwater contaminated by a chemical
company dump, as well as in basement sumps at the Love Canal
site, confirming its miblity and persistence in groundwater.^
1,1,1-Trichloroethane
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;
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 may
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 quite water-soluble and
mobile, particularly where soils are low inorganic content
It is also relatively persistent in groundwater where it
reacts slowly, releasing hydrochloric acid.^
Chlorobenzene
Chlorobenzene may migrate from the disposal site into
the environment if disposed of inadequately. It is soluble
in water (488 nig/1) such that it may leach into groundwater
where it would persist since it is unamenable to hydrolyza-
-------
tion.10 Chlorobenzene is also volatile so it could be
released from wastes into the air.1-0 It has been detected
in school and basement air, basement sumps, and solid surface
samples at the Love Canal site.^ Because it does not biodegrade
well, chlorobenzene is very persistent in the environment.
1,1,2-Trichloro-l, 2,2-trifluoroethane/Trichlorofluoromethane
These two solvents, if improperly managed, can migrate from
the disposal site into the environment. The are extremely
volatile ( 1 , 1 ,2-Trichloro-1,2,2-trifluoroethane, 270 mm Hg at
20°C, to over 500 mm Hg at 40°C;i0 trich1 orfluoromethane,
687 mm Hg at 20°C') and very persistent in the environment
due to resistance to biodegradation, photodecomposition, and
chemical degradation.^ Because of their high volatility, 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 including an increase in the amount
of ultraviolet radiation reaching the earth, as well as
possible changes in the earth's climate induced by the "green-
house effect" . 3 > 4
o - Dich lorobenzene
o - Dich lorobenzene, 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
-------
the Love Canal site), o-dichlorobenzene have been demonstrated
to be mobile and persistent.9
o-Dichlorobenzenes has a very high octano1/water par-
tition coefficient of 2,400, indicating a high bioaccurau1 ation
potential. Thus, migration, even in small concentrations,
could lead to a chronic toxicity hazard (Appendix A).
Methano1
Methanol, if improperly managed, can migrate from the
disposal site into the environment. It is miscible
(1,000,000 mg/1) and mobile in soils, so that it may
leach into groundwater^0. While biodegradable, it would
persist in the abiotic environment of most aqui f er s . ^
Methanol is also highly volatile (100 mm Hg at 21.2°C)
so it may migrate via an air exposure pathway. Since, it is
eliminated slowly from the body, methanol could bioaccumu1 ate
causing numerous adverse health effects from prolonged and/or
repeated exposure.°
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 is photochemically degraded, but
it can re-enter the hydrosphere in rain.12 Toluene is also
capable of migration via a groundwater pathway since it
is relatively soluble, 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.9
Methyl Ethyl Ketone
Methyl ethyl ketone, if disposed of inadequately may
migrate from the disposal site into the environment. It is
very soluble in water (100,000 mg/1), such that it could
leach into groundwaters. It is also very volatile (185.4 mm
Hg at 40°c8), and could present an air pollution problem
if improperly contained.
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."
Methyl Isobutyl Ketone
Methyl isobutyl ketone, if improperly managed, may
migrate from the disposal site into the environment through
water and air pathways. It is very soluble in water (19,000
mg/1), and mobile in most soils, so that it could leach into
the ground water and persist due to its nonreactivity with
water.10
It is also volatile (vapor pressure of 16 mm Hg at 20°C and
known toxicity), so it could pose an air pollution problem if im-
properly contained. Methyl isobutyl ketone biodegrades slowly, °
and is demonstrated to be mobile as well as persistent, having
-------
been detected at the Love Canal site.°
Carbon Bisulfide
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 soluble in water (2200 mg/1),
and is not known to attenuate in soils; therefore it could
leach into the groundwater, where, being unamenable to hydro-
lysis, it is likely to persist for an extended time period. -^
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.^-0 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 mg/1) and are not known to attenuate
significantly in soils; thus, they could leach into groundwater
if disposal is inadequate. Once in water, cresols rapidly
form chlorinated compounds, which are more environmentally
objectionable .-^ Cresols are not known to hydrolyze and so
would be likely to persist in groundwater.^^
-------
Ni trobenzene
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 an£i 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 hydro-
lization and does not biodegrade well. ^
Pyridine
Pyridine, if disposed of inadequately, may migrate from
the disposal site. Because pyridine is miscible with water,
it has high migratory potential. It would be mobile as well,
unless soil has high clay content.^-® Pyridene also would be
likely to persist in the abiotic environment of most ground-
wat e r s .
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:
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-methanol solvent
mixture. When the load was compacted by a bulldozer,
the waste ignited, engulfing the bulldozer in flames
and dispersed pesticide wastes, v
-------
(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
possible dispersed hazardous beryllium oxide. (^3)
(3) Two serious fires at the Merl-Milam Landfill, St. Clare
County, Illinois (August, 1973 and April, 1974) were
attributed to the presence of solvent wastes from plastics
manufacture.(13)
Contamination of Groundwaters
(1) In two separate instances in Michigan, trichloroethyl ene
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.^1^)
In the other case, the Air Force at a base near
Oscoda, Michigan, had problems with contaminated
groundwater because of a leaking tank used to hold
trichloroethylene. The problem was compounded when
a waste hauler apparently mismanaged the trichloro-
ethylene that was hauled from the leaking tank, and
groundwater contamination up to four miles away was
-------
considered one of the results, v 11 '
(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 s ite . (13 ^
(3) Open dumping of wastes, including solvent wastes, from
a chemical packing plant by U.S. Aviex Company resulted
in entry of organic solvents into the water table and
contamination of several nearby water wells in 1973.
One family reported illness resulting from use of the
contaminated well water. '^3 )
The damage incidents presented above illustrate the
following potential hazards associated with wastes from usage
of organic solvents:
(1) Ignitability hazard during mismanagement;
(2) Potential toxicity hazard to humans via groundwater
exposure pathways.
-------
IV• References to Section IV (A, B and C)
1. Jacobs, S. 1957. The handbook of solvents. D. Van
Nostrand Company, Inc., New York.
la. Combustion Formulation and Emission of Traces Species",
John B. Edwards, Ann Arbor Science, 1977.
lb« NIOSH Criteria for a Recommended Standard; Occupational
Exposure to Phosgene, HEW, PHS, CDC, NIOSH, 1976.
lc. Chemical and Process Technology Encyclopedia, McGraw
Hill, 1974.
2. Leo, A., C. Hansch, and D. Elkins. 1971 (Updated 1977).
Partition coefficients and their uses. Chem. Rev. 71:
525-616.
3. National Academy of Sciences, National Research Council.
1976. Halocarbons: Environmental Effects of Chloro-
methane Release.
4. National Academy of Sciences, National Research Council.
1979. Stratospheric Ozone Depletion by Halocarbons:
Chemistry and Transport.
5. Patty, F. A., Editor. 1963. Industrial hygiene and
toxicology. Interscience Publishers, New York.
6. Sax, N. I. Dangerous Properties of Industrial Material,
Fifth Edition. Van Nostrand Reinhold Company, New York,
1979.
7. U.S. EPA. 1975. Environmental Hazard Assessment of
One- and Two-Carbon Fluorocarbons. EPA-560/2-75-003.
8. U.S. EPA. 1980. Evaluation of treatment, storage, and
disposal techniques for ignitable, volatile, and reactive
wastes. Contract Number 68-01-5160. (Draft final report)
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. 1980 Physical Chemical Properties of Hazardous
Waste Constituents. (Prepared by Southeast Environmental
Research Laboratory; Jim Falco, Project Officer).
11. Verschueren, K. 1977. Handbook of Environmental Data on
Organic Chemicals. Van Nostrand Reinhold Company, New
York.
-------
12. Walker, P. 1976, Air pollution assessment of toluene.
MTR-7215. Mitre Corp. McLean, Virginia.
13. U.S. EPA Office of Solid Waste Division, Hazardous Waste
Incidents, Open File, 1978.
-------
D. Health and Environmental Effects*
Perchloroethylene (Tetrachloroethylene)
Perchloroethylene (PCE) was reported carcinogenic to
mice. (•'•6) 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 d amage ; (^ > ^ > 2 1) ancj to humans, causing impaired
liver function.(^' Subjective central nervous system complaints
were noted in workers occupationa1 ly exposed to PCE.(^' PCE
exposure is reported to cause alcohol intolerance to humans.
PCE is also reported to be acutely toxic in varying degrees
to several fresh- and salt-water organisms, and chronically
toxic to some saltwater organisms. (28 , 32 ) (Appendix A)
PCE is a priority pollutant under Section 307(a) of the
Clean Water Act .
Methylene Chloride ( Dichloromethane )
Methylene chloride was reported as being mutagenic to a
bacterial strain, S. typhimurium.(^) It was also reported to
be feto- or embryo-toxic to rats and mice.(23) Female workers
had gynecological problems after prolonged exposure to methylene
chloride.(36; Methylene chloride is acutely toxic, causing
central nervous system depression and elevation of carboxy-
hemoglobin levels. (18) Severe contamination of food or water
can cause irreversible renal and hepatic injury.(30; Acute
toxicity values range from 147,000 to 310,000 mg/1 for aquatic
*Ethyl benzene, which is only being listed for its ignitability
hazard, is also considered a priority pollutant under Section
307(a) of the Clean Water Act.
-------
organisms (Appendix A)
Trichloroethylene
Trichloroethylene (TCE) has been reported to be carcino-
genic to mice.(15) It has 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). ( ^> -^ ) Rare cases of hepatic damage have been reported
following repeated abuse of TCE.(6)
TCE was also found to be acutely toxic in varying degrees
to several freshwater o rgani sms; (*• °' there was a 50% decrease
noted in -^ C uptake by a salt-water algae at a concentration
of 8,000 mg/1.(2°)(Appendix A)
1,1, 1-Trichloroethane (Methyl Chloroform)
1,1 , 1-Trichloroethane has been determined to be carcino-
genic to all tested animals.'^-') It was found to cause several
central nervous system disorders (changes in rection time,
perceptual speed, manual dexterity, and equilibrium) in
humans, and, in animal studies,(34) was found to produce
toxic effects in the central nervous system, cardiovascular
system, pulmonary system, and to induce liver and kidney
damage in tested animals. 1,1 , 1-Trichloroethane was reported
acutely toxic in varying degrees to some freshwater fish and
some marine organisms.(28,34)(Appendix A)
-------
1,1,1-Trichloroethane is a priority pollutant under
Section 307(a) of the Clean Water Act.
Chlorobenzene (Monochlorobenzene, MCB)
Ch lorobenzene has been found to produce histopatho logica 1
changes in lungs, liver, and kidneys following its inhalation
by rats, rabbits and guinea pigs.'?' Oral administration of
raonoch lor obenzene to rats was reported to cause growth retar'-
dation in males.(11) >*CB also appears to increase the activity
of some microsomal enzyme systems, which enhances the metabolism
of many drugs, pesticides, and other xenobiotics.^9;(Appendix A)
MCB was reported to be toxic to varying degrees to
several fresh- and salt-water organisms, including algae.'28;
MCB is a priority -pollutant under Section 307(a) of the
Clean Water Act.
1,1,2 Trichloro-l,2,2 trif1uoroethane (Trif 1 uorotri-ch 1 oroethane)
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. ( 39 , 40 )
JD2-Dichlorobenzene (ortho isomer)
Ortho 1,2-Dichlorobenzene exhibits moderate toxicity via
inhalation and oral routes. The major toxico logica 1 effect
is injury to the liver and kidneys; it can also act as a
central nervous system depressant after short periods of
exposure.(19,22)(Appendix A)
-------
1,2-dichlorobenzene is designated a priority pollutant
under section 307(a) of the Clean Water Act.
Trichlorofluorom ethane
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.(39»^' However, additional
adverse health effects have been found and are presented
b elow.
Exposure of rabbits to trichlorofluoromethane was reported
to cause cardiac arrhythmias in all rabbits exposed. (26) jt
induced cardiac arrhythmias, sensitized the heart to epine-
phrine-induced arrhythmias, and caused tachycardia (increased
heart rate) myocardial 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.
Methanol (Methyl Alcohol)
The main toxic effects resulting from methanol exposure
to humans are exerted upon the nervous system, particularly
the optic nerves and the retinae. Upon ingestion and/or
inhalation followed by absorption from the gastrointestinal
and respiratory tracts, methanol is slowly elimated. Because
of this, methanol should be regarded as a cumulative poison.
Though single exposures to fumes may cause no harmful effect,
daily exposure may result in accumulation of methanol to
-------
cause illness including intoxication, headache, weakness,
apathy and convulsions. Severe exposures may cause dizziness,
unconsciousness, cardiac depression, permanent blindness and
eventual death.^>^2'(Appendix A)
Toluene
Toluene is a toxic chemical absorbed into the body by
inhalation, ingestine, and through the skin. The acute toxic
effect in humans is excessive depression of the central
nervous system,(45) and this occurs at low concentrations
[200 ppm].^"' Chronic occupational exposure to toluene
has led to the development of neuro-muscu1ar disorders.
Occupational exposure to female workers to toluene reported
to cause several reproductive problems, both to the woman
and the offspring. ' 25;
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 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.
-------
Methyl Ethyl Ketone
Methyl ethyl ketone is a highly volatile liquid whose
chief effect is narcosis; it is also a strong irritant of the
aiucous membranes of the eyes and nose. Additionally, lethal
doses in animals (LC50 - 700 ppm) has caused marked congestion
of the internal organs and slight congestion of the brains.
Lungs also showed emphysema (Appendix A).
Methyl Isobutyl Ketone
In a study(^l) reported on 19 employees who worked with
methyl isobutyl ketone for 20-30 minutes daily during an 8-
hour shift, Linari et. al . concluded that methyl isobuty
ketone irritates the conjuctive and respiratory tract and
produces disturbances of the gastrointestinal tract and
central nervous system. Other reported effects due to exposure
include weakness, loss of appetite, headache, eye irritation,
stomach ache, nausea, vomitting, and sore throat.
Further, Linari et. al.^^-) found skin lesions in 3 of
the 19 workers exposed to methyl isobutyl ketone at 80-500 ppm
for 20-30 minutes daily. Evidence also suggests that ketones
in liquid form may cause dermatitis (Appendix A).
All of the ketones except methyl isomyl ketone have been
reported to produce irritation of the eye, nose, or throat. (42)
Carbon Bisulfide
Short term human exposure to low atmospheric concentrations
of carbon disulfide may result in central nervous system
depression, headaches, breathing difficulty and ga s t r o in t e s t i-
/"S -1 _
/«*
-------
nal disturbances. Exposure to short term but high atmospheric
concentrations can lead to narcosis and death. The symptoms
of humans subjected to repeated exposure to high concentrations
or prolonged exposure to low concentrations include insomnia,
fatigue, loss of memory, headache, melancholia, vertigo and
loss of appetite. Visual impairment, loss of reflexes, and
lung irritation has been reported . ^ •*•'»^^ ' Rats and mice exposed
8 hours per day for 20 weeks to an average concentration of 37
ppra carbon disulfide showed evidence of toxic effeets.^"^(Appendix A)
Isobut ano 1
Rats receiving isobutyl alcohol, either orally or subcu-
taneously, one to two times a week for 495 to 643 days showed
liver carcinomas and sarcomas, spleen sarcomas and myeloid
leukemi a . ^^ )
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.(43)
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)
-------
Pyridine
Pyridines exhibit moderate toxicity when introduced into
(22)
the human body through oral, dermal, and inhalation routes.
Liver and kidney damage has been produced in animals and man
after oral administration.^) In small doses, conjunctivitis,
dizziness, vomiting, diarrhia 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.^^'
Adverse taste in fish (carp, rudd) has been reported at
5 ppm. Pyridine causes inhibition of cell multiplication in
algae and bacteria at 28 and 340 ppm r e s pe c t ive ly . ^ -* ' (Appendix A)
Nitrobenzene
Nitrobenzene is a suspected carcinogen.' ^'
When administered to pregnant rats, it caused abnor-
malities 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 actually toxic in varying degrees to
several salt- and fresh-water organisms . ( 3 1 )(Appendix A)
Nitrobenzene is a priority pollutant under Section
307(a) of the Clean Water Act.
-------
Cresols (Cresylic Acid)
Cresol exhibits moderate toxicity via oral and inhala-
tion routes. Acute exposure can lead to absorption causing
kidney and liver damage as well as central nervous system
disturbances. Other symptoms include gastroenteric problems,
severe depression, collapse and even death. In addition,
exposure to cresol can cause severe skin burns and derma-
titis . (^ > 22 ) (Ap pendix A)
-7.T-
-------
VII. References to Section IV, D
1. Bardodej, Z., and J. Vyskoch. 1956. The Problem of
Trichloroethylene in Occcupational Medicine. AMA
Arch. Ind. Health 13:581.
2. Coler, H.R., and H. R. Rossmiller. 1953. Tetrachloro-
ethylene Exposure in a Small Industry. Ind. Hyg . Occup.
Med . 8:227 .
3. Deichmann, W.R. Toxicology of Drugs and Chemicals.
Academic Press Inc. New York, 1969.
4. Dorigan, J. and J. Hushon. 1976. Air Pollution Assessment
of Nitrobenzene. U.S. Environmental Protection Agency.
5. Gosselin, Robert E. et. al., Clinical Toxicology of
Commercial Products, Fourth Edition, The Williams and
Wilkin Company, Baltimore, 1976.
6. Huff, J.E., 1971. New Evidence on the Old Problems of
Trichloroethylene . Ind. Med. 40:25.
7. Irish, D.D. 1963. Halogenated Hydrocarbons: II. Cyclic.
In Industrial Hygi en.e and Toxicology, Volume II, Second
E~dition (F. A. Patty, Editor), In t er sc i ene e , New York
p. 1333.
8. Kazanina, S.S. 1968. Morphology and Histochemistry of
Hemochorial Placentas of White Rats During Poisoning of
the Maternal Organisms by Nitrobenzene. Bull. Exp. Biol.
Med. (USSR) 65:93.
9. Kirk-01hmer . , Encyclopedia of Chemical Technology, Third
Edition, Volume 9. John Wiley and Sons, New York. 1980.
10. Klaassen, C.D., and G.L. Plaa 1967. Relative Effects
of Chlorinated Hydrocarbons on Liver and Kidney Function
in Dogs. Toxicol. Appl. Pharmacol.
11. Knapp, W. K., Jr., et al . 1971. Subacute Oral Toxici'ty
of Monochlorobenzene in Dogs and Rats. Toxicol. Appl.
Pharmacol. 19:393.
12. Matsushita, T., et al. Hemato logical and Neuro-muscular
Response of Workers Exposed to Low Concentrations of
Toluene Vapor. Ind. Health 13:115.
13, McBirney, B.S. 1954. Trichloroethylene and Dichloroethylene
Poisoning. AMA Arch. Ind. Hyg. 10:130.
-------
14. Medek, V. and J. Kavarik. 1973. The Effects of Per-
chloroethylene on the Health of Workers. Pracovni
Lekarstvi. 25:339.
15. National Cancer Institute. 1976. Carcinogenesis
Bioassay of Trichloroethylene. CAS No. 79-01-6,
NCI-CG-TR-2.
16. National Cancer Institute. 1977. Bioassay of Tetra-
chloroethylene for Possible Carcinogenicity. CAS No.
127-18-4, NCI-CG-TR-13, DHEW Publication No. (NIH)
77-813.
17. National Cancer Institute, 1977. Bioassay of 1,1,1-
Trichloroethane for Possible Carcinogenicity. Carcinog.
Tech. Rep. Ser. NCI-CG-TR-3.
18. National Institute for Occupational Safety and Health.
1976a. Criteria for a Recommended Standard: Occupational
Exposure to Methylene Chloride. HEW Pub. No. 76-138.
U.S. DHEW., Cincinnati, Ohio.
19. Patty, Frank A., Editor. Industrial Hygiene and Toxicology,
Volume II, Interscience Publishers, New York. 1963.
20. Pearson, C., and G_._Mc Connell . 1975. Chlorinated GI and
G£ Hydrocarbons in the Marine Environment. Proc. R. Soc.,
London B. 189 : 302 .
21. Rowe, V. K., et al., 1952. Vapor Toxicity of Tetrachloro-
ethylene for Laboratory Animal and Human Subjects. AMA.
Arch. Ind. Hyg. Occup. Med. 5:566.
22. Sax, N. Irving. Dangerous Properties of Industrial Materials.
Fifth Edition, Van Nostrand Reinhold Company, New York. 1979.
23. Schwetz, B. A., et al. 1975. The Effects of Maternally
Inhaled Trichloroethyl ene, Perchloroethylene, Methyl
Chloroform, and Methylene Chloride on Embryonal and Fetal
Development in Mice and Rats. Toxicol. Appl. Pharmacol.
32:84.
24. Simmon, V. F., et al., 1977. Mutagenic Activity of
Chemicals Identified in Drinking Water. S. Scott, et al.,
Editors: In Progress in Genetic Toxicology.
25. Syrovadko, 0. N. 1977. Working Conditions and Health
Status of Women Handling Organosiliceous Varnishes Con-
taining Toluene. Gig. Tr. Prof. Zabol. 12:15.
-7'7-
-------
26. Taylor, O.C., 1974. Univ. of California, Riverside.
Unpublished Data, (as cited in U.S. EPA, 1976a.)
27. U.S. EPA. 1976a. Environmental Hazard Assessment
Report: Major One- and Two-Carbon Saturated Fluoro-
carbons, Review of Data. EPA-560/8-76-003.
28. U.S. EPA. 1978. In-depth Studies on Health and
Environmental Impacts of Selected Water Pollutants.
Contract No. 68-01-4646.
29. U.S. EPA. 1979. Chlorinated Benzenes: Ambient Water
Quality Criteria (Draft).
30. U.S. EPA. 1979. Halomethanes: Ambient Water Quality
Criteria (Draft).
31. U.S. EPA. 1979. Nitrobenzenes: Ambient Water Quality
Criteria (Draft).
32. U.S. EPA. 1979. Tetrachloroethylene: Ambient Water
Quality Criteria (Draft).
33. U.S. EPA. 1979. Toluene: Ambient Water Quality Criteria
(Draft) .
34. U.S. EPA. 1979. Chlorinated Ethanes: Ambient Water
Quality Criteria (Draft).
35. Verchuerer K., Handbook of Environmental Data on Organic
Chemicals. Van Nostrand Reinhold Company. 1977.
36. Vozovaya. 1974.
37. Wolf, M. A., et al. 1956. Toxicological Studies of Certain
Alkylated Benzenes and Benzene, Arch. Ind. Health 14:387.
38. EPA Carcinogen Assessment Group's List of Carcinogens,
April 22, 1980.
39. National Academy of Sciences, National Research Council.
1976. Halocarbons: Environmental Effects of Chlorome fhane
Release .
40. National Academy of Sciences, National Research Council.
1979. Stratospheric Ozone Depletion by Halocarbons:
Chemistry and Transport.
41. Linari, F., Perrelu, G., Varese, D.: [Chemical Observa-
tions and Blood Chemistry Tests Among Workers Exposed
to the Effect of a Complex Ketone--Methyl-Isobutyl Ketone,]
Arch. Sci. Med., 1964, pp. 226-237 (Ita).
-------
42. Specht, H., Miller, J. W., Valaer, P. J., Sayers R. R.:
Acute Response of Guinea Pigs to the Inhalation of Ketone
Vapors, NIH Bulletin No. 76. Federal Security Agency.
Public Health Service, National Institute of Health,
pp. 66 •
43. Gibel, et al . , Exp. Chir. Forsch. JL:235, 1974.
44. Smith et al. , Arch. Ind. Hyg. Occup. Med . 1Q_:61, 1954.
45. U.S. EPA. 1979. Toluene Ambient Water Quality Criteria.
46. NIOSH (1978) Registry of Toxic Effects of Chemical Sub-
stances. Toluene.
-------
Response to Comments
One commenter objected to the listing "Waste non-
halogenated solvent (such as methanol, acetone, iso-
propyl alcohol, polyvinyl alcohol, stoddard solvent
and methyl ethyl ketone) and solvent sludges from
cleaning, compounding milling and other processes."*
The commenter argued that without indicating the con-
centration or quantity of the solvent in the waste,
the Agency would be listing wastes as hazardous even
if the solvent were present in small concentrations and
quanti ties .
In the listing promulgated today for waste solvents,
the Agency is only listing those spent solvents or
still bottoms fro m.__t..h e 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.
A 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, it will be covered under the generic
listing "The Spent non-halogenated solvents...."
-------
The Agency agrees with the commenters and therefore,
has removed PVA from the listing.
A number of commenters 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 commenters1 objection.
-------
Electroplating and Metal Finishing Operations
Wastewater Treatment Sludge from Electroplating Operations (T)
Summary of Basis for Listing
Wastewater treatment sludge from electroplating operations
are generated by a number of industry categories located nation-
wide. This waste contains a variety of heavy metals such as
chromium, cadmium/ nickel as well as cyanide. The Administrator
has determined that waste from these processes may be solid
wastes which 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:
1. Wastewater treatment sludge from electroplating
operations contain significant concentrations of
the toxic heavy metals chromium/ cadmium/ and nickel/
and highly toxic cyanide.
2. Leaching tests using the extraction procedure (used
in the extraction procedure toxicity characteristic)
have shown that these metals leach out in significant
concentrations, with some samples failing the extraction
procedure toxicity characteristic. Therefore, the
possibility of groundwater contamination via leaching
will exist if these waste materials are improperly
disposed.
3. A large quantity of this waste is generated annually
(specific quantities have not been calculated at this
time) and amounts are expected to increase substantially
when the pretreatment standards for these sources become
effective. Damage incidents (i.e., contaminated wells,
destruction of animal life, etc,) that are attributable
to the improper disposal of wastewater treatment sludge
from electroplating operations have been reported, thus
-------
indicating that the wastes may be mismanaged in actual
practice, and are capable of causing substantial harm
if mismanagement occurs.
Sources of the Waste and Typical Disposal Practices
Industry Profile
The electroplating industry consists of both job shops
and captive platers. Job shops are small, 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
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.(D
Electroplating 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, phosphating and
immersion plating), electroless plating, chemical etching and
milling and printed circuit board manufacturing (5).* The
"Among the industries included in this listing are segments of
the printing and publishing category associated with rotogravure
and metalic plate manufacture, continuous electroplating proces-
ses of the iron and steel industry and chromic acid waste treat-
ment from magnesium carbon battery production.
-------
primary 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 1 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 (5).)
The metals used in ...electroplating operation (both common
and precious metal plating) include cadmium, lead, chromium,
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 nickel acetate
seal. Chemical conversion coating most commonly involves the
use of chromate or phosphate-containing baths. A number of
-------
rai
my
j
L
TVlkallne
G*lorination
Chcml cal
Precipitation
wast'ewater
Wastewater
Treatment
Sludge
Rinse Water
to
Sanitary Sewer*
FIGURE 1 TYPICAL ELFCTROPLATING PROCESS
-------
acids can also be used (as in passivating), but are not as
common as the phosphate/chromate baths. Typical process baths
used in the industry are shown in Table 1.'^0 '
Waste Stream Description
As indicated in Figure 1, the spent plating/coating
solution and rinse water is chemically treated to precipitate
out the toxic heavy metals and to destroy the cyanide. The
extent to which plating solution carry-over or drag-out 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 would generate one type of
sludge. A different processing sequence, on the other hand,
would generate a sludge with a differing composition. However,
is expected that since most platers conduct a number of differer
electroplating operations, all sludges will contain significant
concentrations of toxic heavy metals, and may also contain
complexed cyanides in high concentrations if cyanides are not
properly isolated in the treatment process. Table 2 illustrates
the varying composition of these sludges for two of the heavy
metals in twelve different plating processes.
The predominant type of wastewater treatment sludge
generated from this industry is metal hydroxide sludge (which
_
"~ Q Lo
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Table 1
(10)
Typical Electroplating Baths and Their Chemical Composition
plating Compound
Cadmium Cyanide
Cadmium Fluoborate
Chromium Electroplate
Copper Cyanide
Electroless Copper
Gold Cyanide
Acid Nickel
Silver Cyanide
Sine 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
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
Silver cyanide
Potassium cyanide
Potassium carbonate
Metallic silver
Free cyanide
Zinc sulfate
•Sodium sulfate
Magnesium sulfate
8
30
30
30
330
45
37
35.9
59.9
(min.) 15.0
23.8
41.2
374.5
71.5
59.9
- si
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Table 2
Heavy Metal Content for Chromium, and Cadmium_
in Electroplating Sludges-Dry Weight (mg/1) * '
Primary Plating Process Cr Cd
Segregated Zinc 200 <100
Segregated Cadmium 62,000 22,000
Zinc Plating and Chromating 65,000 1,100
Copper-Nickel-Chromium
on Zinc 500 ND
Aluminum Anodizing 1,700 ND
Nickel-Chromium on Steel 14,000
Multi-Process Job Shop 25,000 1,500
Electroless Copper on Plastic,
Acid Copper, Nickel Chromium 137,000 ND
Multi-Process with Barrel or
Vibratory Finishing 570 -
Printed Circuits 3,500 <100
Nickel-Chromium on Steel 79,200 <100
Cadmium-Nickel-Copper on
Brass and Steel 48,900 500
-------
results from alkaline precipation). Metallic sulfide sludges,
although not widely used, are also generated when wastewater is
treated by sulfide precipation. Among those facilities which
discharge to publicly owned treatment works (POTW's)/ approxi-
mately 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 electroplaters will generate a
sludge and drastically increase the quantity of wastewater
treatment sludge produced.
Typical Disposal Practices
A recent study '2) using a 48 plant survey indicated
that approximately 20 percent of the electroplating facilities
dispose of their waste on-site while the remaining 80 percent
haul their waste off-site to commercial or municipal disposal
facilities. The actual disposal practices utilized by the
industry varies 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 their waste
sludges in a dry river
-89 -
-------
Hazards Posed by the Waste
As indicated earlier in Table 2 and as shown in Table 3,
wastewater treatment sludges from electroplating facilities
contain significant concentrations of the toxic heavy metals
cadmium, chromium and nickel with some levels exceeding 1,000
mg/kg (dry weight) and cyanide. Additionally, 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 character-
istic (Table 4). The leaching tests used in the AES study
were performed on twelve separate samples using the proposed
extraction procedure (43 FR 58956-58957). A leaching test was
also performed on two samples using the ASTM distilled water
leaching test; the results of this test as indicated in
Table 4 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 an acid environment
(i.e., sanitary landfill), the acid leach test would closer
replicate what would be expected to happen under field condi-
tions, and thus is more predictive of potential hazards from
improper management. Cyanides have also been shown to leach
from these wastes at a concentration range from 0.5 to
170 mg/l.(6) <£he public Health Service's recommended concen-
tration limit for cyanide in drinking water in .02 mg/1
-------
Table 3
Projected Sludge Concentrations For Various Heavy
Metals and Cyanides (mg/1) (5)*
.utant
'n. urn
eel
?mium, Total
lide, Total
Raw Waste Cone
(mean)
0.08
5.0
3.8
0.4
Projected Sludge Cone.
(mean)
2% Solids 20% Solids
3.2
486.2
369.7
42.9
32.5
4862.0
3697.0
429.2
DJections of sludge concentrations are based on mean raw waste
pled during an effluent guidelines study. This study utilized an
plant data base and the data are derived from analyses of actual
waste concentration, assumptions of clarifier removal efficiencies
-98%) and non-dewatered and dewatered sludge solids content (2% and
t
respectively). To estimate pollutant concentrations in sludge, the
uraption 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%.
refore,
Mass removed = influent flow x influent waste concentration -
(1-.01) x influent flow x effluent concentration
mass removed
Sludge pollutant concnetration = .01 x influent flow
-------
Table 4
Extract Concentrations From Electroplating Wastewater
Treatment Sludge 0
Primary Plating Process Cr* Cd*
1A Segregated Zinc 1.22 0.2J
2A Segregated Cadmium 1.89 126
3A Zinc Plating and Chromating 85.0 6,0
4A Copper-Nickel-Chromium on "•"
Zinc 21.8
5A Aluminum Anodizing <0.01
6A Nickel-Chromium on Steel 25.4
7A Multi-Process Job Shop** 0 .24 2,1{
8A Electroless Copper on Plastic,
Acid Copper, Nickel, Chromium 400
9A Multi-Pocess with Barrel or
Vibratory Finishing** 0.32 O.OJ
10A Printed Circuits 0.12
11A Nickel-Chromium on Steel 4.22 <0.01
12A Cadmium-Nickel-Copper on
Brass and Steel 4.85 268^
Note: Those concentrations underlined would fail the Extraction
Procedure Toxicity Characteristic
* These values were determined using the proposed extraction procedl
contained in the toxicity characteristic.
** The ASTM distilled water extraction procedure was run on these
samples with the following results obtained:
Plant Cr (mg/1) Cd (i
7A 0.63 0.03
9A 0.04
-------
indicating that cyanide leaching may also lead to a substantial
hazard.
Once released from the matrix of the waste, cadmium/
chromium, nickel, and cyanide could migrate from the disposal
site to ground and surface waters utilized as drinking water
sources. Present practices associated with the landfilling,
dumping or impounding of the waste may be inadequate to prevent
such occurences. Actual damage incidents involving electro-
plating wastes are presented.-In Attachment I, again showing
that actual mismanagement of electroplating wastes has
occurred. 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.
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 unmanifested 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 heavy rainfall could
cause flooding which might reach surface waters in the vicinity
unless the facility has proper diking and other flood control
measures.
-X-
-------
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 may 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 metal 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 (12), and have been
shown to move from soils to groundwater.(13) Thus cyanide
is also available for potential release and transport to
environmental receptors.
The Agency has determined to list wastewater treatment
sludge from electroplating operations as a T hazardous waste,
on the basis of chromium, cadmium, nickel and cyanide, although
chromium and cadmium are also measurable by the (E) character-
istic. Moreover, concentrations for chromium and cadmium in
the EP extract from this waste from individual sites might be
less than 100 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 these are factors in addition to metal concen-
trations in leachates which justify the T listing. Some of
these factors already have been indentified, 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 pretreatment standards are implemented in
October 1982 and these sludges will contain extremely high
cadmium, chromium and nickel concentrations (see p. 7 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 and surface waters. Contamination could also occur
for long periods of time, since large amounts of pollutants
are available for environmental loading. Attentative 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 Constitutents
The toxicity 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.
Chromium is toxic to man and lower forms of aquatic life.
Contact with chromium compounds can cause dermal ulceration in
humans. Data also indicates that there may be a correlation
between worker exposure to chromium and development of hepatic
lesions.
Cadmium shows both acute and chronic toxic effects in
humans. The LD5Q (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 sub-ppb levels.
Nickel has been found to bring about a carcinogenic
response upon injection in a number 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 (5 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. Addition-
ally, in the aquatic environment, nickel has been found to be
toxic to fish at concentrations of 2,480 mg/1 and chronically
toxic at levels as low as 433 mg/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. 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-
trations as low as about 50 mg/1 and has been shown to adversely
affect invertebrates and fishes to concentrations of about
10 mg/1. The hazards associated with exposure to chromium/
cadmium/ nickel and cyanide have been recognized by other
regulatory programs. Chromium/ cadmium, nickel and cyanide
are listed 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; permissable exposure limits
have also been established for KCN and NaCN. The U.S. Public
Health Service established a drinking water standard of
0.02 mg CN/1 as an acceptable level for water supplies. In
addition/ final or proposed regulations for the State of
Maine, Massachusetts/ Vermont, Maryland, Minnesota -, New Mexico,
Oklahoma, and California define chtromium, cadmium, nickel, and
cyanide containing compounds as hazardous wastes or components
thereof.(14)
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Attachment I
Damage Incidents Resulting From the Mismanagement
of Electroplating Wastes'17/
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, alkylbenzenesulfonate
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 poisoning
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. Contaimination of this water resulted in
the death of fish and cattle below Bronson 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 near the city dump.
-------
Significant concentrations of hexavalent chromium and traces
of cyanide were measured in an adjacent stream by several local
residents as a drinking water supply.
South Farmingdale, New York - An aircraft plant, operating in
South Farmingdale on Long Island during World War II, generated
large quantities of electroplating wastes containing chromium,
cadmium and other metals. It has been estimated that between
200,000 to 300,000 gallons per day of these wastes were
discharged into unlined disposal basins throughout the 1940's.
A treatement unit for chromium was constructed in 1949, but
discharge of cadmium and the other metals continued. The
local groundwater flows in three unconsolidated aquifers
resting on crystalline bedrock. The uppermost aquifer consists
of beds and lenses of fine-to-coarse sand and gravel and
extends to within 15 feet of the land surface. Groundwater
contamination by chromium was first noted in 1942 by the
Nassau County Department of Health. Extensive studies in
1962 indicated that a huge plume of contaminated groundwater
had been formed, measuring up to 4,300 feet long, 1,000 feet
wide and extending from the surface of the water table to
depths of 50 to 70 feet below the land surface. Maximum
concentrations of both chromium and cadmium were about 10
mg/1 in 1962, (Chromium had been measured as high as 40
mg/1 in 1949.) This huge contaminated plume cannot be removed
or detoxified without massive efforts and will take many
more years of natural attenuation and dilution before it
-------
becomes useable again. Meanwhile, the plume is still slowly
moving, threatenting 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 mg/1 and 18 others contained trace amounts.
The National Interim Primary Drinking Water Standard for
total chromium is 0.05 mg/1.
-------
References
1. Economic Analysis of Pretreatment Standards for Existing
Sources of the Electroplating Point Source Category,
U.S. EPA, EPA-440/2-79-031, August 1979.
2. Assessment of Industrial Hazardous Waste Practices,
Electroplating and Metal Finishing Industries -
Job Shops, U.S. EPA, EPA 68-01-2664, September 1976.
3. Electroplating Category RCRA Review. Technical Contractors
Final Report, October 1979, Contract 68-01-5827.
4. Electroplating Wastewater Sludge Characterization Study.
AES-EPA Cooperative Agreement No. R880026-01, September
1979.
5. Development Document for Existing Source Pretreatment
Standards for the Electroplating Point Source Category,
U.S. EPA, EPA/440-1-79/085, August 1979.
6. Composite of State Files of "Special Wastes Disposal
Applications." 1976-1979. Result of Leachate Tests
on Cyanide Containing Wastes from Illinois, Iowa,
Kansas and Pennsylvania.
8. Development Document for Pretreatment Limitations Guide-
lines and Standards for the Electroplating Point Source
Category; August 1979. EPA 440/1-79/085.
10. Metal Finishing Guidebook and Directory, Volume 77, No, 13
Metals and Plastics Publications, Inc., Hackensack, New
Jersey, January 1979.
11. U.S. EPA, Effluent Guidelines On-going BAT Study.
12. Aiesii, B.A. and W.A. Fuller. 1976. The Mobility of Three
Cyanide Forms in Soil. pp. 213-223. In Residual Management
Land Disposal. W.H. Fuller (ed.), Environmental Protection
Agency, Cincinnati, Ohio. PB 256768 268.
13, The Prevalence of Subsurface Migration of Hazardous Chemical
Substances at Selected Industrial Waste Land Disposal Sites.
1977. EPA/530/SW-634. U.S. EPA, Washington, D.C.
14. U.S. EPA State Regulations Files, January 1980.
15. U.S. EPA 1979. Cyanides: Ambient Water Quality Criteria.
(Draft) EPA ?3 296792. National Technical Information
Service, Springfield, Virginia.
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Listing Background Document
SPENT WASTE CYANIDE SOLUTIONS AND SLUDGES
1. LISTING
The listed wastes are those major waste streams, from
several industry segments, which specifically contain either
cyanide salts or complexed cyanide compounds. The specific
wastes listed are as follows:
Cyanide Salts
Electroplating
Plating bath solutions (R,T)*
Spent stripping and cleaning bath solutions (R,T)
Plating bath sludge from the bottom of plating baths (R,T
Metal Heat Treating
Quenching bath sludge from oil baths (R,T)
Spent solutions from salt bath pot cleaning (R,T)
Mineral Metals Recovery
Spent cyanide bath solution (R,T)
Complexed Cyanides
Electroplating
Plating bath and rinse water treatment sludges (T)*
Metal Heat Treating
Quenching wastewater treatment sludges (T)
Mineral Metals Recovery
Cyanidation wastewater treatment tailing pond sediment (?'
Flotation tailings from selective flotation (T)
Coke Ovens and Blast Furnaces
Dewatered air pollution control scrubber sludges (T)
* S p e n t plating bath solutions and plating bath sludge from the
bottom of placing baths also contain complexed cyanides, but
are more significant as sources of cyanide salts.
-------
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,
mineral metals recovery, and coke ovens and blast furnace
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 waste from these
processes may be a solid waste, and as a solid waste may pose
a substantial present or potential hazard to human health and
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 generated exhibits either
reactive or toxic properties or both due to their
cyanide content.
2. The land disposal of cyanide wastes is widespread
throughout the United States with 1,940 kkg of
cyanide (CN~) contained in these wastes annually.
These wastes generally contain high concentrations
of cyanide. This large annual generation rate,
and high cyanide concentration level increases the
likelihood of exposure and possibility of 'substantial
haz ard.
3. Cyanides can migrate from the wastes to adversely
affect human 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 was t es;
(b) contamination of soil and surface waters in the
vicinity of inadequate waste disposal resulting
in destruction of livestock, wildlife, stream-
dwelling organisms, and local vegetation; and
(c) contamination of private wells and community
drinking water supplies in the vicinity of
inadequate waste disposal.
Ill. SOURCES OF CYANIDE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Overall Description of Industry Sources
Waste cyanide solutions and sludges containing both
cyanide salts and complexed cyanides are generated by a number
of different industries including electroplating, metal heat
treating and mineral metals recovery operations. Approximately
20,000 facilities in the United States use one or more electro-
plating or heat treating processes in manufacture of primary
metals, fabricated metals, machinery, and electronics equipment.'"^
An additional 73 facilities use cyanide in the proces of
recovering various metals, particularly gold and silver.
Complexed cyanide waste solutions or sludges containing only
complexed cyanide are generated by a number of other industrial
processes, principally iron blue manufacturing*, coke ovens,
and blast furnace operations.
*!ron blue manufacturing is discussed in the chromium pigments
background document and thus is not presented here.
-------
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 with cyanide plating
baths or cyanide stripping or cleaning baths, (2) metal heat
treating using cyanide quenching baths, and (3)^ mineral metals
recovery with cyanide plating baths. Complexed cyanide
wastes (primarily ferro and ferricyanides) are generated from
(1) treatment of electroplating wastewater, (2) treatment of
quenching process wastewater from the metal heat treating
industry, (3) selective flotation and cyanidation for mineral
and metals recovery and the air oxidation and chemical
treatment of their wastewaters, and (4) coke oven and blast
furnace air scrubbers.
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,
-------
Table 1
Annual Consunption of Cyanide for Cyanide
Generating Processes (kkg of Of equivalents)
Electro- Heat
plating Treating
Cvanide Salts
NaCN 10,292 1,428
KCN 72 65
CaCN2
Complexed Cyanides
Heavy Metal 2,346
Ferrocyanides - 65
Ferri cyanides - -
TOTAL 12,710 1,558
Mineral
and
Metals
Recovery
1,592
30
90
451
30
2,193
Coke
Cvens
and
Blast
Furnace
0
-------
Table 2
CYANIDE WASTE SOURCES
Source
Number of Facilities
Types of Wastes(s)
Electroplating
Minerals and Metals
Recovery
Metal Heat Treatment
Coke Ovens and
Blast Furnac e s
13,
73
(b)
7,000
287 coke ovens,
200 blast furnaces,
48 with both^8)
Cyanide salts and
complexed cyanides
(Solution and sludge)
Cyanide salts and
complexed ferro
and ferricyanide
(s olut i ons and
sludges in tailing
pond s)
Sodium and potassium
cyanide (solution
and sludge)
Iron cyanide com-
plexes (slud ge)
'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.).
^'Estimate of facilities using cyanidation or selective flotation
with cy anide .
-107-
-------
coating (i.e., coloring, chromating, phosphating and immersion
plating), chemical etching and milling, electroless plating,
and printed board manufacturing. The primary 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,
to restore worn parts to their original dimensions, or for
decor at ion. (7' The operation itself involves immersing
the article to be coated/p1 ated 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 electro-
plating 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 are used to make-up the various
pi at ing/coat ing solutions and as stripping and cleaning bath
solutions . ^'' For example, the electrolytic baths used
in both chromium and precious metal electroplating typically
consist of cyanide salts or sodium, potassium, cadmium,
zinc, copper, silver, and gold.^' Seventy-five percent
of those facilities that conduct both common and precious
metals electroplating utilize cyanide.^' After extended
use, plating baths become deficient in the specific ion
-log-
-------
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 dumped.''' These 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) .
b . Management of Spent Plating, Stripping and Cleaning
bath Solutions, and Generation of Treatment Sludges
Spent plating, stripping and cleaning bath solutions
and rinse waters are chemically treated primarily with hypo-
chlorite or chlorine to convert cyanide compounds to carbon
dioxide, metal salts, nitrogen, and water. (?)
Complexed 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
^Another major source of cyanide salt waste is the rinse water
contaminated 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 RCRA jurisdiction
under § 26 1 .4(a)(1) . The Agency is in the process of developing
pre-treatment standards for the electroplating industry.
-------
( 1 8 ^
not destroyed and thus may be present in the sludges.^ > '
These sludges are typically disposed of in a sanitary
landfill .( 1>8)
c . Plating bath sludge from the bottom of cleaning
baths
Additionally, 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 and typically are placed in drums for
chemical landfill disposal. (1)
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 system or landfill spent solutions.^)*
2 . Metal Heat Treatment
a . Generation of 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
*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.(9)
-no -
-------
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 carbonitrid ing processes.
Cyanide salt containing-wastes from this process arise
generally 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
settles to the bottom of the quenching tank as a sludge. Another
source of cyanide waste (although 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 are chemically
treated, sludges from these operations are typically disposed
of in landf ills . ( ^-° ) During waste treatment some of the
untreated cyanide may complex with heavy metals and precipitate
in the sludge.(? )
3. Mineral and Metals Recovery
Cyanides are used extensively in the extraction and
beneficiation of gold and silver from ore and as a depressant
in selective flotation processes.
-------
a. Generation and Management of Cyanidation Wastewater
Tailings Pond Sediment
Use of cyanide (cyanidat ion) 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 so lutions. ^^' The gold or
silver-laden caustic cyanide solution is then e 1 e c t r o ly z ed.,
and the 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 hypochlorite 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 1 andfi 11 s. (^'
b . Generation of Spent Cyani d e B ath So lu tions^'
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. Generation of Froth Flotation Tailings
Froth flotation tailings are also cyanide-containing
wastes discharged to tailings ponds without prior chemical
treatment. Inorganic cyanide salts, and calcium cyanides
and sodium ferro- and ferricyanides , are extensively used as
chemical additives in froth flotation as a depr es s ant . ( !•)
Froth flotation is a process by which desired mineral (copper,
lead, zinc, silver) attach to air bubbles, float to the
surface as a foam or froth, and overflows the flotation
cell.'^-' Undesirable ore ("gangue") is removed from the
bottom of the cell and discharged to a tailings pond as
shown in Figure 1-5 in Apendix I. Cyanides are often added
to depress the flotation of undesirable components of the
pulverized ore. Cyanide-containing wastes are discharged to
the tailings ponds along with the gangue. Tailings pond
sediment containing complexed cyanide is disposed of in
landfills similar to cyanidation wastes.^1'
^ * Coke Oven and Blast Furnace
a. Coke Oven Cyanide Waste Generation
Thermally generated cyanides result from the high
temperature reaction of carbon and nitrogen compounds in a
%
reducing atmosphere.^) Conditions favorable to cyanide
generation exist in coking operations, blast furnace
production or iron and ferroallys, and production of ferro-
alloys by means other than blast furances.
-------
During coke production, carbon compounds and ammonia,
both produced by coal breakdown, combine to produce hydrogen
cyanide, some of which is collected as condensate in de-
su1ferizat ion scrubber sludges. (8) Desu1furization scrubbers
installed on many of the coke oven stacks collect an estimated
36,300 kkg of solids in a scrubber solution per year of which
3,555 kkg are cyanide equiva 1 ents. ( 8) The scrubber solution* is
dewatered, and the resulting scrubber supernatant is filtered
and discharged.** Solids from the dewatering operation are
then combined with the solids filtered from the scrubber liquor,*'
forming the listed waste, the dewatered scrubber sludge.
Most of the cyanide (3,553 kkg) goes to the scrubber liquor,
and approximately 2 kkg of cyanide remains in the scrubber sludge,
Estimated concentrations of complexed cyanide in the dewatered
scrubber sludge are 55 ppm (2 kkg of cyanide in 36,300 total
solids) .
b . B1 as t Fu_rnace Cyanide Waste Generation
Hydrogen cyanides are also produced in blast furnace
operations when nitrogen, water, and carbon react at high
*The "scrubber solution referred to in the text is properly
referred to as scrubber sludge. The term "scrubber solution'
is used to aviod confusing this stream with the listed waste,
which is dewatered scubber sludge.
**Discharge of scrubber supernatant is usually regulated under
the NPDES permit program.
' * * F i11 e r e d solids (filter cake) may be recycled back into the
orocess for sintering.
-------
temperatures. Although no data are available on amounts of
hydrogen cyanide generated in blast furnace operations, it
is estimated that scrubber systems remove in solution 915 kkg
of cyanide equivalents (CN~).'°' The scrubber solution is
then dewatered (much as in coking operations). The resulting
sludge is the listed waste stream.
Based on limited surveys, blast furnace scrubber liquor
appears to contain most of the cyanide. Analysis of the
scrubber sludge indicates that 2,720 kkg of solid waste produced
annually contain approximately 1 kkg of CN~~ or cyanide con-
centrations of about 400
G. 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. ^^ 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 cyandie processes include
some form of chemical treatment which destroys most of the
cyanide prior to precipitaion of solids and heavy metals. Of
the total 16,400 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. ' •*• ' 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 3,750 kkg (from the
total of 16,460 kkg) equivalent cyanide (CN~) consumed
annually, about 48 percent (1,940 kkg - 127 kkg = 1,813
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 1,813 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. 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
s^lc and complexed cyanide concentration data from listed
electroplating and metal heat treating wastes. Concentrations
-------
Source
Electroplat ing
Mineral and
Metals
Recovery
Metal Heat
Treating
Coke oven and
Blast Furnac e
Annual Waste
Quanity/Facility
kkg
Cyanide (CN~)
Quant i ty/
Facility
(kkg)
Total Annual
Waste Quantity
(kkg)
Type of Waste
Spent plating,
Stripping and
Cleaning bath
solutions; plating
bath sludge; plating
bath and rinse
water treatment
sludge
Tailing pond sedi-
ment and cyanida-
tion wastewater
treatment sludge
Quenching bath
sludge and spent
bath solution and
quenching waste-
water treatment
sludge
Air polluti on
control sludge
20-300
(d)
H-51(f)
Cyanide Salts
(Cn-)
Disposed
Annually
(kkg)
42,000
0
6,125<10>
0.2-l.l
-------
Table 3 (Continued)
"Total based on mining capacity and NaCN and depressant consuption data'-*-'.
C50% of NaCN equivalent consuption^'
^Hange of total annual waste for facilities included in a composite of state wste disposal applications
assuming waste density ^ke/gallon^). Based on total waste disposal estimates average quantity per
facility is 3.5 kkg/yr^10'.
BTotal based on estimated 25 employees per facility; 7,000 facilities of which 25% use cyanide^!);
0.14 kkg/yr-employee(1^) ($ee figure 1)
nRunge of content of waste per facility for facilities iincluded in a composite of state
wnate disposal applications assuming waste density and kg/gallon(2)
*Total based on estimate that 13% of waste are cyanide wastes and 25% of all cyanide waste is
destroyed.
-------
Indua L ry
Sou rc e*
Metal Heat Treating
Metal Heat Treating
Cyanide Salts
Quenching Bath sludge
and Spent Solution
Quenching Bath sludges
Elec t roplat ing
Elect roplating
Electroplating
Electroplat ing
Electroplating
Elect roplat ing
Electroplating
Electroplating
Metal Heat Treating
Speht 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
So lut ion
Plating Bath Treatment
Sludge
Quenching Wastewater
Treating Sludge
Waste/
Potassium and
Sodium Cyanide/
Solid**
Potassium and
Sodium Cyanide/
Sludge
Sodium Cyanide/
Solut ion
Cyanide Salts/
Solution
.Sodium Cyanide
{Solution
Metal Salts/Sludge
Complex Metal
Cyanide/Solution
Complex Metal
Cyanide/Solution
Complex Metal
Cyanide/Solution
Complex Metal
Cyanide/Sludge
Coraplea Metal
Cyanide Solids***
3,000
13 ,200
92 ,300
8,530
22
14
6
1
15
6
36
12
6
,500
,000
,600
,000
,600
,•600
,000
,000
,600
350,000
38
14,547
64
80
14,329
2,000
1,681
26,803
-------
Industry
Source*
Table 3A
Cyanide, Wastes^)
Concentrations
Continued
Type of
Was t e/Form**
Annual Disposal
in Gallons
Cyanide
Concent ra tions
Metal Heat Treating
Quenching Wastewater
Treatment Sludge
Complex Metal
Cyanides/Sludge
5,500
8,400
*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 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 wste quantities are expressed in
gallons related to the size of the drum used to containerize waste for disposal.
-X-
-------
range 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.27-29 below), these concentrations are deemed
to be of regulatory concern.
The Agency presently lacks concentration data on 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 Ta-ble 3)
Cyanide concentrations in coke ovens and blast furnace
scrubber sludges are somewhat less, probably not exceeding
400 ppm (see pp. 14-15 above). These concentrations could still
prove significant in light of cyanide's migratory potential and
extreme toxicity.
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.'1'
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 chlorination
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 landfills.'!'
Mineral and metals recovery wastes from extraction of
gold and silver (cyanidation) and selective flotation of
copper, lead, zinc, and silver are diposed of in tailing
ponds which may be lined with clay and are sometimes constructed
to control run-off and dam seepage.^' The size, construction,
and location of tailing ponds and retention of waste solutions
in ponds varies from site to site depending on whether mineral
and metals recovery wastes include cyanide containing solutions
or sludges. When wastes are not alkaline chlorinated to
destroy cyanide prior to disposal, tailing ponds are used as
holding ponds whera natural air oxidization and sunlight
destroy the cyanide or where the cyanides are complexed with
metals in solution and by attachment to gangue materials. O-'
Scrubber sludges from coke ovens and blast furnaces are
generally dewatered and the filter cake reused in the sintering
process feed. The remaining solid wastes, which contain
small quantities of complexed cyanides, are disposed of in
company owned or off-site landfills.
This data suggests that cyanide-containing wastes are
sometimes managed properly. Many damage incidents involving
-------
cyanide-containing wastes (set forth at pp. 25-26 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 POSED BY THE WASTES
A. Nature of Hazards
Cyanide salt-containing wastes exhibit both reactive
and toxic properties which make them potentially hazardous to
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.
*Additional damage incidents are described in the electroplating
vaste background document.
-------
Indus try
Source *
Type of
Waste/Form**
Annual
Disposal
In Gallons
Cyanide
Concent rat Ions
Leachable
Cyanide/
Metals
(pH 5.5
Conditions)
Within Theae
Wastes (ppm)
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
Cyanide/Solution
•
Complex Metal
Cyanide/Solution
Complex Metal •
Cyanide/Solids*** (
Complex Metal
Cyanide/Sludge
36,000
12,000
6,600
5,500
2,000
1,681
i
26,803
8,400
80
170
915
9.3
*Source descriptions Included in special waste disposal applications were not always the same aa
those presented In the Us ting'^'. An attempt was made to classify the waste Inits appropriate
category.
**These descriptions were taken directly from the special waste disposal applicatIonsv*).
***Solld 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.
-------
utilized in the Subtitle C EP.* This data indicates that the
complexed 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.(l^)
Even clay liner systems may not adequately impede migration;
as in the presence of water, montmorillonite clays (• which
have high surface areas) sorbed cyanide only weakly.(15)
Cyanide has also been shown to move through soils into
groundwater.(1"' 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.
*In light of the prevalent landfilling of these wastes, and
the great number of different disposal sites utilized in
managing different listed waste streams, it is certainly
a plausible assumption that these wastes may be disposed
of in acidic environments.
-------
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
cows 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. ( ^2)
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 al Iky Ibenzenesul f onat e , and pho s ph at e . ' ^2 '
A landfill in Monroe County, Pennsylvania, that accepts
plating process wastes such as hydrocyanic acid, has created
-------
a groundwater pollution problem in the area.'^J
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 quantitie
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
/ -I O 'J
discharged directly into a nearby wat e rway . ^ 1J '
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 §261.23
(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 a 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 amounts of
toxic hydrogen cyanide gas. A potential disaster
was averted when a local chlorine dealer was
s
-------
quickly called to oxidize the cyanide with
i
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 mg.
(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
the 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 C0£ and organic acids produced
in the decomposition of refuse. (12)
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 mg/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.(^,lo;
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 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 rag/m^ as^an eight-hour time-weighted average.
Additionally, the OSHA permissible limit for exposure to HCN
is 10 ppm (11 mg/m^) 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.(17)
A more detailed discussion of the health effects of
cyanide is contained in Appendix A.
-130 -
-------
V. REFERENCES
1. Midwest Research Institute. April 1976. The Manufacture
and Use of Selected Cyanides. Kansas City, Mo. Prepared
for U.S. Environmental Protection Agency. EPA 560/6-76-
012. Pp. 6-11, 24-99.
2. Composite of State Files of "Special Waste Disposal
Applications." 1976-1979. Results of Leachate Tests
on Cyanide Containing Wastes from Illinois, Iowa,
Kansas and Pennsylvania.
3. Cotton, F. A. and G. Wilkinson. 1979. Advanced Inorganic
Chemistry. John Wiley & Sons, Inc., New York. pp. 300-301.
4. Production and Use of Cyanide, Draft Report, Contract
68-01-3852, Task Order 22. Prepared for EPA-MDSD by
Versar, Inc., Springfield, Virginia (1978).
5. U.S. Environmental Protection Agency. July 1976. Quality
Criteria for Water. Office of Water and Hazardous Materials.
Washington, D.C. p. 67.
6. Webster, W. 1979. U.S. Environmental Protection Agency.
Personal communication.
7. U.S. Environmental Protection Agency. February, 1978.
Development Document for Proposed Existing Source Pre-
treatment Standards for the Electroplating Point Source
Category. EPA 440/1-78/085.
8. Radian Corporation. February 1977. Industrial Process
Profiles for Environmental Use: Chapter 24 The Iron and
Steel Industry. Austin, Texas. Prepared for U.S. Environ-
mental Protection Agency, IERL, Research Triangle Park,
N.C. EPA 600/2-77-023X.
9. Lancy, L.E. 1979. Dart Industries, Inc. Lancy Labora-
tory Division, Elienople, Pa.
10. Wapora, Incorporated. March, 1977. Assessment of Indus-
trial Hazardous Waste Practice Special Machinery Manu-
facturing Industries. Washington, D.C. Prepared for
the U.S. Environmental Protection Agency, Office of
Solid Waste, Washington, D.C. SW-l41c.
11. U.S. Environmental Protection Agency. July 1975. Develop-
ment Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Iron and Steel
Foundry Industry.
-------
12. U.S. Environmental Protection Agency. 1978. Hazardous
Waste Incidents. Office of Solid Waste, Hazardous
Waste Management Division. Unpulished, open file data.
13. Philadelphia Inquirer. October 15-26, 1979. Series of
Articles Related to Pittston Cyanide Disposal.
14. Alesi, B.A. and W.A. Fuller. 1976. The Mobility of
Three Cyanide Forms in Soil. Pp. 213-223. In Residual
Management by Land Disposal, W. H. Fuller (ed.),
Environmental Protection Agency, Cincinnati, OH
PB 256768 268.
15. Cruz, M., Et al. 1974. Absorption and Trans Formation
of HCN on the Surface of Copper and Calcium Montmorillanite
Clay Minerals 22: 417-425.
16. The Prevalence of Subsurface Migration of Hazardous Chemical
Substances at Selected Industrial Waste Land Disposal
Sites. 1977. EPA/520/SW-634. U.S. EPA, Washington, D.C.
17. Chemical Engineering News, Editors Newsletter, November,
1979.
-------
APPENDIX I
FLOW DIAGRAMS
-------
Metal
Parts
' Surface
Preparation
and Cleanim
* E1
, "'
V V
ectro- ^
a ting
_
Alkaline
Chlorination
4
Chemical
Precipitation
wa
ntncfnn t Single-Coated
Rinsing Electroplated
Parts
i i
1
1 l
i i
i i
i i
i
stewater J
Sludge and Solvent
to
Sanitary Landfill
2.5 kkg/yr-Dept. employee (wet)
1.0 kkg/yr-Dept. employee (dry)
Rinse Water
to
Sanitary Sewer*
*Due to pending EPA effluent guidelines, rinse water discharge to sewers may
be prohibited in the future, lliis wastewater generation rate presently
amounts to 1.0 kkg/yr-Dept. enployee.
FIGURE 1-1 SIMPLIFIED TYPICAL EUDCTROPLATING OPERATION
(10)
-------
strong
acid
itfong
olkali
hold
hold
gpm
gpm
dilute acid CB6 „
and alkali
gpm
Neutral*
izatlon
700
gpm
chromium
Reduction
225
gpm
MCI
strong
cyanide
WtlH
Hold
gpm
340
360
cyanide
ypm
Dtitruo-
tion
3KO
lump
25 gpm
1300
1275 1300
gp™
Final
Neutral-
ization &
Precipitation
1300 ^
gpm
gpm
Clarilier
gpm
gpm
" 7 gpm
Filter
1.8 gpm
iludqc
FIGURE 1-2 DIAGRAM OF A TYPICAL CONTINUOUS TREATMENT PLANT
-/JET-
-------
Metal
Ports
Heating 1n
Furnace
Heating 1n
, Molten Salt
Dath
i
i
Cooling In
flitrtft^r^itinrt
*s ijuCiicii i ny
" Uath
t
i
t
i
i
i
i
: r"""":::::::::;:
Metal
f^k f* 1 rk ^t rt • n ri
Ix L 1 Gall 1 liy
1
1
1
1
I
1
1
1
1
Meat
Trea tod
Parts
Waste Disposal to Landfills
Total 2.00 kkg/yr-Dcpt. employee (wet)- 0.07 (dry)
Quench oils 0.06 kkg/yr-Dept. emp. (wet)~0.65 (dry)
Cyanide waste 0.14 kkg/yr-Dept. emp. (wet)
Acids/alkalies 1.00 kkg/yr-Dept. emp. (wet)
FIGURE 1-3 SIMPLIFIED TYPICAL HEAT TREATING AND CARBURIZING OPERATION
(10)
-------
Ore
Crushing
Rod Milling
Bali Milling
Launder Traps
CJossi flection
Cycloning
Lime
NoCN
1
Sands (60%)
Sand Leach Vats
I
Residue
to Fill
Mine
Stopes
Barren Solution
Zinc
Dust
Precipitation
Filtration
I
Bullion
to Refinery
Adapted from Gold and Silver
Cyonidotion Plant Practice.
Barrel
Amaloamotion
•To Refinery
r
Carbon m Puio Plant
Slimes (40%) '
Thickeners
NoCN 1
ir
NaCN
NoOH
Lime
& Air
Conditioning
Adsorption Agitators
To Toiling Pond
Desorption
Carbon Reactivation
Electrolysis
Sponge to
Refinery
T
Undersize
to Refinery
FIGURE 1-4 GOID AND SILVER RECOVERY PROCESS SCHH^ffiTIC
(1)
-------
O
ie
Crushing
Rod Milts
r
Doll Mill*
Classification
Conditioning
Copper Ore
-H
<
fe»
<
Flotation
^-Copper Concentrates
Copper - Molybdenum Ore
Bulk 0
Flotation
Copper
Moly •
.Cone.
Copper - Lead - Zinc Ore /Tv
Selective ^-/
Flotation
Selective •
Flotation «
Flotation •
^2\ — «*~ Molybdenum Concentrates
». Selective
Flotation — *- Copper Concentrates
»-Lead Concentrates
•*• Copper Concentrates
»- Zinc Concentrates
Copper - Zinc - Iron - Sulfide Ore
Selective \5)
Flotation
Leod - Zinc Oie
Selective ffr\
Flotation
— *•
—
Leod - Zinc - Silver Oi
Selective /y\
Flotation
Zinc Ore
Selective /g\
Flotation
:luorspar Ore
Selective fi\
Flotation
•»-
-*-
— »-
Copper Concenl
Selective ,
Flotation
Lead Conccnlra
Flotation I
rales
•*. Zinc Concentrates
cs
^•Zlnc Concentrates
e
Lead Concentrates With Silver
Flotation
^" Zinc Concentrates
Lead Concentrates
Flotation
•"- Zinc Concentrates
Fluorspar Concentrates
Flotation I
•""Zinc Concentrates
Cyanides
Used
NaCN
Ca(CN)2
^ NoCN
{*) Ca(CN)2
NoCN
f) Ferrocyanide
Ferrlcyonide
^y co(CN)2
^ NaCN
^ Ca(CN)2
/Tk NoCN
W Ca(CN)2
©NoCN
Co(CN)2
xrs NoCN
v:/ Ca(CN)2
^~, NaCN
Mojoi Sj>rcies
Dcpresse<<
lion Sulfidcs
,1 J Iron Sulfiilrs
[2) Copper Sulfidn
(3) Zint SuHides
[4) Copper Sulfides
©Zinc Sulfides
Iron Sulfides
(^T\ Zinc Sulfidcs
^^ Iron Sulfidcs
0Zinc Sulfides
Iron Sulfidcs
(O) Zinc Sulfides
© Zinc Sulfidcs
FIGLIRE 1-5 GENERALIZED SELECI'IVE FIOl'ATION PROCESS SCHEMATIC
(1)
-------
flaw WoUr
02OI IA«c —
II3.OOO
MOISTURE
SEPAKAIOR
scnuoeEn
Slnlir Plant
020.1 I/MC
(13.000 gpm)
ALKALINE
CIILOnUUTION
336 I/MC
gpm|
onir
CHAMBER
To
PLANT5O2T
PRODUCTIONS 3494 M«Ulc Too* SU«l/Oay
(6O37 Tone SU«l/Oay)
Outfall
079 f»«c
13.932 gpm
PI.ml
Hot Mttol Dftiulfurliallon
12.« l/»»c
(200 gpm)
FIGURE 1-6 aiLORINATION OF BLAST FURNACE CYANIDE WASTE
(8)
-------
Response To Comments
One commenter suggested that the listings of "Spent or
waste cyanide solutions or sludges" should be modified
so as ot to include solutions or sludges containing
small amounts of cyanide formed during one or more
proces operatins. The following language was
recommended:
"Spent or waste cyanide solutions or sludges
resulting from cyanide-based processes (R,T)"
°The Agency agrees with the commenter 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 problme,
if improperly managed. For example, during blast
furnace operations nitrogen, water and carbon combine
to produce hydrogen cyanide. Desulfurization 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 ).
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 gnerate hydrogen cyanide
under mild, acidic, or basic conditions.
"The Agency agrees that only cyanide salt-
containing wastes pose a reacivity hazard,
and the listing descriptions reflect this
distinction, since no complex cyanide wastes
are listed for reactivity.
-------
Wood Preserving
-------
LISTING BACKGROUND DOCUMENT
WOOD PRESERVING
Wastewater from wood preserving processes that use
creosote or pentachloropheno1 (T)
Bottom sediment sludge from 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 tetrachloropheno1, volatile organic solvents such as
benzene and toluene, and polynuclear aromatic (PNA) components
of creosote. Treatment of this wastewater results in the
generation of a bottom-sediment sludge that must be removed
for ultimate disposal. The Administrator has determined
that wastewater from these wood preserving processes and the
resulting bottom sediment sludge 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, 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, although limited data is currently available on the
sludges generated from these wood preserving processes (i.e.,
from work tanks, cylinders or storage tanks), the Agency
plans to study these wastes in the future to determine whether
they should also be listed.
-------
This conclusion is based on the following considerations:
1) The wastewater generated from wood preserving
processes using pentachloropheno1 as a preservative
and the sludge generated from the treatment of this
wastewater will contain significant concentrations
of toxic phenolic compounds and volatile organic
solvents such as benzene.
2) The wastewater from wood preserving processes that
use creosote and the sludges generated from the
treatment of this wastewater will contain significant
concentrations of toxic polynuclear aromatics components
of creosote and volatile organic solvents such as
toluene. Wastewater and 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.
3) Polynuclear aromatics, as a group, are known to be
toxic, rautagenic, teratogenic and carcinogenic.
Phenolics are toxic and, in some cases, bioaccumu-
lative and carcinogenic substances. Benzene and
toluene are relatively toxic, and benzene is a
carcinogen.
4) Approximately 200,000,000 gallons of wastewater are
generated annually. About 90 percent of this waste-
water is treated by treatment methods which generate
a bottom sediment sludge.
5) 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, if mis-
managed, could lead to the release of hazardous
constituents into the atmosphere and result in
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.
7) The Agency has 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.
II. Sources of the Wastes and Typical Disposal Practices
A. Industry Profile and Manufacturing Process
There are approximately 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 Northern Pacific coast.
These areas correspond to the natural ranges of the southern
pine and Douglas fir-western red cedar, respectively (2).
Approximately 240 million cubic feet of wood are
treated each year (1), principally for railroad ties, utility
poles, and lumber for construction materials. Of the 250
million cubic feet of wood treated annually, it is estimated
that approximately 85 percent is treated with creosote or
pentachlorophenol 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 by chemical processes
to increase their resistance to natural decay, attack by
-------
TABLE 1
VOLUME OF WOOD TREATED IN 1975 BY PRESERVATIVE (4)
Preservative Type
I Quantity of
(Wood Treated
I(million cubic feet)
I Oil Borne 85%
Waterborne 15%
Creosote and creosote-coal tar
Creosote-petroleum
Creosote-pentachlorophenol
Petroleum—pentachlorophenol
Chromated copper arsenate (A,B,C)|
Fluor-chrome-arsenate-phenol
Chromated zinc chloride
Acid copper chrornate
All other preservatives
110.5
32.1
0.9
60.8
29.9
1.8
0.5
1.4
1.8
TABLE 2
QUANTITY OF PRESERVATIVES USED IN 1975.
LIQUIDS:
Creosote
Coal Tar
*Petroleum (with PCP)
*Petroleum (with creosote)
96.3 million gallons (0.84 gal/cu ft)
23.6 million gallons (added to above)
48.7 million gallons (0.80 gal/cu ft)
16.7 million gallons (0.52 gal/cu ft
plus creosote)
SOLIDS:
Pentachlorophenol
Chromated Copper Arsenate
Other Solids (zinc, fluor,
chromate, etc.)
35.5 million pounds (0.58 Ib/cu ft
plus petroleum)
15.9 million pounds (0.55 Ib/cu ft)
4.5 million pounds (0.82 Ib/cu ft)
*The petroleum listed in Table 2 acts as a dissolving
and/or carrying medium for the preservatives with which they
are used.
-------
insects, micro-organisms, or fire. Briefly, the treatment consists
of debarking, forming, drying, impregnation of preservative,
and s torage (3).
The two major wood preserving processes, producing large
quantities of wastewater and sediment sludge, are called steaming
and boultonizing.* Both 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
1 ' i
flow diagrams for the major wood preserving processes (Source:
Re ference 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 already 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 boultonizing processes are
*Vapor drying is another wood preserving process, also
generating a wastewater and sludge of concern.
-------
WOOD' IN
WOOD OUT
PRESERVATIVES
TO WORK TANK
WORK TANK
TREATING CYLINDER
STEAM
PRESERVATIVES
TO CYLINDER
COOUHO
WATER
-C COrlO£N5fci\ Jr
CYLINDER WATErt
CYLINDER DRIPPINGS
AND RAIN WATER
RECOVERED OILS
OIL - WATER
SEPARATOR
VACUUM
PUMP
ACCUMULATOR
CONDENBATE
WASTE WATER
AIR AND
VAPORS
COOLINd
WATER
FigUr.e la> ,
OPEN STEAMING PROCESS WOOD TREATING PLANT
»s~
-------
wodo IN
WOOD OUT
PRESERVATIVES
TO WORK TANK
WORK TANK
I
TREATING CYLINDER
VAPORS
J
CONOCNSATE
•TEAM
PRESERVATIVES
TO CYLINDER
RECOVERED O!U
CYLINDER
WATER
STORAGE
CYLINDER DRIPPINGS
AND RAIN WATER
Oil-WATER
SEPARATOR
COOLINQ
WATER
CONDENSER >
VACUUM
PUMP
ACCUMULATOR
CONDEN8ATE
WASTE WATER
AIR AND
VAPORS
COOLINQ
WATER
lb CLOSED STEAMING PROCESS WOOD TREATING PLANT
-------
WOOD IK
WOOD OUT
PRESERVATIVES
TO WORK TANK
WORK TANK
TREATING CYLINDER
COMPENSATE
STEAM
PRESERVATIVES
TO CYLINDER
CYLINDER WATER
CYLINDER DRIPPINGS
AND RAIN WATER
RECOVERED OILS
OIL - WATER
SEPARATOR
WASTE WATER
COOLINO
WATER
CONDENSER >
AIR AND
VAPORS
VACUUM
PUMP
COOLING
WATER
ACCUMULATOR
COMPENSATE
Figure Ic
MODIFIED STEAMING PROCESS WOOD TREATING PLANT
-------
wooo
WOOD OUT
:
PRESERVATIVES
TO WORK TANK
WORK TANK
VAPORS
TREATING CYLINDER
PRESERVATIVES
TO CYLINDER
RECOVERED OILS
CYLINDER DRIPPINGS
AND RAIN WATER
OIL - WATER
SEPARATOR
WASTE WATER
COOLINQ
WATER
COOLINQ
( CONDENSER )
VACUUM
PUMP
ACCUMULATOR
CONDEN3ATE
AIR AND
VAPORS
Figure id BOULTON WOOD TREATING PLANT
-------
WUUU IN
WOOD OUT
PRESERVATIVES
TO WORK TANK
WORK TANK
TREATINQ
PRESERVATIVES
TO CYLINDER
I
CONDEN8ED VAPORS
STEAM SOLVENT
VAPORIZER
STEAM
CYLINDER DRIPPINGS
AND RAIN WATER
RECOVERED OILS
OIL -f WATER
SEPARATOR
WASTE WATER
AIR AND
VAPORS
SOLVEN1
•«—+^+~*~-
WATER
VACUUM
PUMP
ACCUMULATOR
CONDENSATE
Figure le
VAPOR CONDITIONING PROCESS WOOD TREATING PLANT
-------
condensed and transported to an oil/water separator to reclaim
any free oils and preserving chemicals before treatment and/or
disposal of the wastewater, usually an oil/water emulsion.'*' »1° '
II. Generation, Composition, and Management of Listed Waste
Streams (17,1ST" ~"~~
•. A. Generation
Based on the quantity of wood treated with
creosote or pentachloropheno1 preservatives in 1975, and
assuming that about one gallon of wastewater is generated
per cubic foot of wood treated, approximately 200 million
gallons of wastewater will be generated annually.
About 90% of this wastewater is treated by treatment
methods that generted a bottom sediment sludge. The remaining
wastewater is typically discharged directly, to POTW's. The
listing covers both of these instances.*
Table 3 shows estimates of the amounts of sludges
generated by creosote and pentach loropheno1 preserving
processes, and the amount of 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 pub lielyowned treatment works (POTW) for treatment.
"Domestic Sewage" means untreated sanitary wastes that passes
through a sewer system.
-------
TABLE 3. POTENTIALLY HAZARDOUS SOLID WASTES FROM THE
WOOD PRESERVING INDUSTRY (8)*
(Source: American Wood Preserver's Association (1979)
Total Process
Solid Waste
metric tons/yr
Total Potentially
Hazardous Constituents
met ri c tons/yr
Creosote-oil emulsion
230-930
Penta-oil emulsion
600*
Creosote
1.1-4.6
Pentachlorophenol
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.
*Estimated maximum amount.
-------
B. Compos i t ion
Table 5 presents a list of some of the typical organic
compounds found in wood treating plant wastewaters.* Bottom
sediment sludge from wood preserving plants contains primarily
creosote, polynuclear aromatics (creosote compounds), chlorinated
phenols and volatile organic solvents such as toluene and benzene,
as listed in Table 6.
According to data taken from California State hazardous
waste manifests, (7) this waste may contain 5-20% pentachlofo-
pheno1.
EPA has tested samples of bottom sediment sludge and
found that it contains polynuclear aromatic hydrocarbons and
phenolic compounds. Many wood processing plants, such as the
two listed below, may use both creosote and pentachloropheno1
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. The pertinent information from two plant's sludge
samples (Plants 10 and 11) is summarized below:**
*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.
**For details of sampling program and further information,
see Reference 6.
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TABLE 5. HAZARDOUS ORGANIC COMPOUNDS FOUND IN WOOD PRESERVING
PLANT WASTEWATER.(17)
Using Pentachlorophenol
Using Creosote
Phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Nitrophenol
4,6-Dinitro o-cresol
Te.tr achlorophenol
Pentachlorophe.no 1
Benzene*
Toluene*
Fluoranthene
Naphthalene
1,2-Benz anthracene
Chrysene
TABLE 6 .
HAZARDOUS ORGANIC COMPOUNDS FOUND IN WOOD PRESERVING
PLANT BOTTOM SEDIMENT SLUDGE (17)
Creosote Polynuclear Aromatics
Benz(a)anthracene
Benzo(a)pyrene
Chrysene
Phenolies**
Phenol
2-chlorophenol
Pentachlorophenol
2,4-dime thyIpheno1
2,4,5-trichlorophenol
*Certain volatile compounds in the wastewater, such as
toluene and benzene,may volatilize completely during the evaporation
process and thus may not appear in the sludge.
**A test conducted on a cooling tower sludge at a plant
treating with pentachloropheno1 revealed the presence of octa-
chlorodibenzo-p-dioxin as well as phenolics. The .presence
of this dioxin and the possibility of the presence of other
more hazardous dioxins (such as TCDD) is of great concern to
the Agency since various chlorinated dibenzo-dioxins are
known carcinogens, mutagens and teratogens (IARC Monographs
on the Evaluation of Carcinogens Risk of Chemicals to Man,
Vol. 15).
However, the Agency is not listing these waste streams
for the presence of these constituents until further information
of the presence and fate of dioxins in the waste is made
available.
-------
Plant 10
Bottom Sediment Dry Weight (mg/kg)(6)
Polynuclear Aromatics
Benz(a)anthracene
Chrysene
Phenolies
Pheno1
2,4-dimethylphenol
2-chlorophenol
2,4,6-trichlorophenol
Pentachlorophenol
Aerated Lagoon
3,700
4,500
9,030
4,398
396,000
No data
302,000
Final
149
2,060
16,000
3,418
1,200
25,000
58,000
One sediment waste sample was taken from an aerated lagoon;
the analytical data for this plant are summarized below:
Plant 11
Polynuclear Aromatics
Benzo(a)anthracene
Benzo(a)pyrene
Chrysene
Bottom Sediment Dry Weight
Aerat ed Lagoon
1,250
5 ,980
9,280
Phenolics
Pheno1
2-chlorophenol
Pentachlorophenol
4,500
300
4,800
Additionally, a contractor/hauler that disposes of
bottom sediment sludge for a wood treatment plant has provided
an analysis of the waste for EPA (3). The analysis is as
fol lows:
-------
Component Concentration, mg/l(6)
Total phenols 5,043
Pentachlorophenol 34
Dinitrophenol 24
Creosote . 10,000
C. Typical Disposal Practices
I
These plants typically dispose of their wastewater
- j
streams by .one of two treatment methods, namely evaporation
or combined biological and irrigation process.
In the evaporation treatment process, water is evaporated
off, leaving the bottom sediment sludge. Currently there
are four prinicipal evaporative methods: still ponds, pan
evaporators, stripper/cooling towers and spray ponds. All
four methods produce bottom sediment sludge.
A still pond depends on the natural evaporation of water
from the pond surface. A pan evaporator adds heat to the
wastewater in order to accelerate evaporation. (In both cases,
a sludge remains in the evaporation vessels.)
In a stripper/cooling tower, wastewater is pumped to the
top of the tower and flows down slatted surfaces in contact
with the air. Sludge accumulates in the base of the tower and
is removed when its build-up hinders tower performance.
A spray pond uses a high-pressure pump and nozzle assembly
to spray wastewater droplets into the air. The resulting
large droplet surface area contacts the air, promoting
evaporation. Again, the accumulated sludge remains in the
pond .
-------
When sufficient sludge residue has been accumulated, it
is removed from the bottom of the evaporation device and
transported to a dry bed. The sludge is typically disposed
of in an off-site landfill (6).
The second (although less typical) method used by wood
preserving plants is a combined biological and irrigation
process. This process consists of (1) settling, (2) storage,
(3) aerated treatment, (4) spray irrigation, and (5) runoff
storage. Rainfall runoff water is collected in a storage
pond, recycled through spray nozzles, and then bled into a
settling basin for treatment. The wastewater flow at a
particular plant equipped with this type of treatment system
averaged approximately 50,000 gallons a day.^"' Wastewater
flows from the settling basin to a storage pond, and then
into an aerated lagoon. The wastewater remains in both the
storage pond and the aerated lagoon for 40 to 60 days. From
the aerated lagoon, the wastewater is intermittently pumped
and sprayed through spray nozzles onto a planted field.
Runoff from this field is collected in a runoff storage
pond. Sludge is generated in this treatment system on the
bottom of the aerated lagoon (6); typically the sludge is
disposed in an off-site landfill.
The Agency, believes that incineration is another,
chough less frequently used, disposal practice for these
s ludges .
-------
Ill. Discussion of Basis for Listing
A. Hazardous Properties of the Waste
As discussed earlier, the most commonly used wood
preservatives are pentachloropheno 1 and creosote. The
- ^
principal toxic pollutants in wastewater from plants that
treat with these preservatives are phenolic compounds, vola-
tile, organic solvents such as benzene and toluene, and poly-
nuclear aromatic hydrocarbon components of creosote.
Phenolics are toxic and, in some cases, bioaccumu-
lative and carcinogenic. Polynuclear aromatics, as a group,
are known to be toxic, mutagenic, teratogenic and carcinogenic.
Benzene and toluene are relatively toxic, and benzene is a
carcinogen.
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 benzene have
been detected in rivers, demonstrating ability to persist.
Naphthalene and benzene have been identified in finished
-------
drinking water and wells, demonstrating ability to
migrate to drinking water sources and to persist. (20)
The migratory potential and persistence of phenol,
benzene, toluene, trichlorophenol and dichlorophenol is con-
firmed by the fact that these constituents have been identified
in samples taken at the Love Canal site in Niagra, New York.
Toluene and benzene have migrated from the Love Canal site
into surrounding residential basements and solid surfaces,
demonstrating ability to migrate through soils. Toluene,
benzene and dichlorophenol have also been found in 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).)
Studies on biodegradability* indicate that under specific
idealized conditions, pentachlorophenol is biodegradable
(9,10,11). Pentachlorophenol has been shown to be degradable
*Comments were received from industry that the Agency
failed to take into consideration the biodegradability of
waste constituents in listing wastewater sludges. This
document now discusses biodegradability of constituents of
wastewater and wastewater treatment sludge.
In addition, some comments were received stating that
a hazardous waste designation would discourage biological
treatment of wastewater. Where biological treatment, in fact,
proves successful in degrading hazardous constituents, the
delisting mechanism provides generators a means of avoiding
hazardous waste status for their treatment sludges.
Furthermore, the Agency's legal obligation is to list
wastes based on their potential to cause substantial harm if
mismanaged, and the comment does not even challenge that
such hazard may result. Finally, a hazardous waste designation
may encourage biological treatment, since it may prove easier
to obtain a permit for this type of waste management.
-------
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 pent ach lorophenol and the p'ent ach loro-
phenol concentration is carefully controlled (13). As mentioned
before, typical concentrations of pentachlorophenol in the
s.ludge range.from 5 to, 20 percent or 5000 to 200,000 ppm,
although concentrations as high as 302,000 have been reported
(see p. 10). The sludge, therefore, would need J:_o be combined
with noncontaminated permeable soil in a ratio of 1:20 in
order to ensure that the reported level of degradation
at the disposal site is possible.
Furthermore, presence of harmful constituents in such
high concentrations in sludge samples taken at two plants
which treated wastewater with nutrient addition (see pp. 10-11)--
with high concentrations being present at one plant in both
the aerated lagoon and final retention pond — shows that the
constituent may persist in these sludges even after biological
treatment (i.e., won't fully biodegrade).
Studies on pentachlorophenol leaching have shown that
water contamination from soil leaching is low (10,12). Also,
this contaminant tend to be bound by the soil, limiting the
possibility for migration (10,12). In one laboratory study
on soils containing between 100 and 300 ppm pentachlorophenol,
the leachate, due to an equivalent of 1/2 to 1 inch of rainwater,
-------
contained less than 0.01 percent of the original pent ach lorophenol
in the soil (4). Again, however, these studies were conducted
on soils with PGP concentrations well below the levels reported
in the California State hazardous waste manifests, and, as
noted above, phenolic compounds have demonstrated ability for
mobility and persistence.
Creosote compounds have also demonstrated ability for
mobility and persistence. An actual damage incident of
surface and grounwater contamination due to improper manage-
ment of creosote-containing wastes confirms the migratory
potential, mobility and persistence of the waste constituents
in these wastes. In the 1950's, waste chemicals including
creosote and other types of wood preserving oils 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
f migration via both ground and surface waters, and were
able to persist and cause damage for a long time.
Since large quantities of bottom sediment sludge contain-
ing such large concentrations of harmful constituents are
o
-flfS -
-------
disposed of in landfills or sometimes allowed to accumulate
at the bottom of ponds and lagoons for long periods of time,
attenuative capacity of the environmental surrounding these
facilities could be reduced or used up.
Finally, many of the constituents of concern are
i
highly bioaccumulat i'v.e in environmental, rec.eptors.
Benz (a)anthracene and pentachloropheno1 are extremely bioaccumu-
lative with octano1/water partition coefficients of 426,579
and 102,000, respectively. Tetrachloropheno1, trich loropheno1
and dichloropheno1 are also highly bioaccumulative with octanol/
water partition 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 and of the extreme dangers to
human health and the environment posed by these constituents,
there is insufficient indication of environmental degradation
and inability to migrate to justify a failure to list this
waste as hazardous.
*An octano I/water coefficient of 100 means, thjat after an
aqueous solution of the test 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 bioaccumu1 at ion
potential.
-------
C• Exposure Pathways
Mismanagement of these wastes, therefore, could lead
to environmental contamination since constituents are available
for release and persist following release. Thus, as previously
noted, the wastewaters generated by wood preserving operations
are typically treated by evaporation or by a combined biological
and irrigation process. Bottom sediment sludge, generated
by the treatment of the wastewater, is typically disposed of
in an off-site landfill, although incineration is another
possible disposal method.
The treatment of wastewater in ponds and/or lagoons,
if mismanaged, could also lead to the release of hazardous
constituents, 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 consti-
tuents and contaminate groundwater. As previously noted,
these sludges may be allowed to sit at the bottom of ponds
for up to five years (8), thus increasing the potential for
release of harmful constituents and for eventual groundwater
cont aminat ion.
-------
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 an-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 liklihood of mismanagment 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 of proper managment 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 pentachloropheno1 and creosote process wastewater
samples using a bench scale pan evaporator indicated that a
large fraction of the organic constituents were entrained in
the vapors given off during the treatment(18). Benzene and
toluene have vapor pressures of 75.1 mm Hg @20°C and
-------
28.4 mm Hg @25°C and are therefore likely to volatilize
(App. B). Thus, evaporation of wastwaters in ponds, lagoons,
stripper/cooling towers and evaporation pans could lead to
the release of hazardous and volatile constituents into the
air .
i
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.
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.
D. Hazards Associated with Constituents of the
Waste
Phenolics are toxic and in some cases bioaccumulative
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 mutagenic,
and pentachlorophenol has shown mutagenic and teratogenic
effects .
-------
Polynuclear aromatics, as a group, are known to be
toxic, mutagenic, teratogenic and carcinogenic.
Benzo(a)anthracene and chrysene have been identified by the
Agency as compounds exhibiting substantial evidence of being
carcinogenic. Benzene and toluene organic solvents, are
relatively toxic, and benzene is a carcinogen. Additional
information and specific references on the adverse effects
of the following substances can be found in Appendix A:
*Benzene
*Benzo(a)anthracene
*Benzo(a)pyrene
*Chrysene
*Phenol
*2,4,6-Trichlorophenol
*Pentachlorophenol
*2-Chlorophenol
*4-Nitrophenol
*Toluene
*Naphthalene
4,6-Dinitro-o-cresol
Tetrachlorophenol
2,4-Dimethylephenol
*Starred compounds are designated as priority pollutants under
Section 307(a) of the CWA.
-------
References
1. Federal Register, Vol. 44, No. 212. Wednesday,
October 31, 1979.
2. Development Document for Effluent Limitation. EPA:
440/l-74-023a.
'i
3. Federal Register No. 202. Wednesday, October 18, 1978.
4. Ernst and Ernst. Wood Preservation Stat is tics. 1976.
American Wood Preservers Association.
5. Nicholas. Wood Deterioration and its Prevention by
Preservation Treatments. Syracuse University Press,
Volume II, 1973.
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.
10. Young, A.L. et al, Fate of 2 , 3,7,8-tetrachlorodibenzo-
p-dioxin (TCDD) in the Environment: Summary and
Decontamination Recommendations, United States Air
Force Academy, Colorado, USAFA-TR-76-18, October, 1976.
11. Kirsch, E.J., and J.E. Etzel. Microbial Decomposition
of Pentachlorophenol, Journal of Water Pollution Control
Federation, Vol. 45, No. 2, February, 1983.
2. Arsenault, R.D., "Pentachlorophenol and Contained
Chlorinated Dibenzodioxins in the Environment—A
Study of Envrionmental Fate, Stability, and Significance
when Used in Wood Preservation." American Wod Preservers
Association, 1976.
-------
13. Proceedings: Technology Transfer Seminal on the
Timber Processing Industry—March 10,11, 1977.
Toronto, Ontario. EPS: 3-WP-78-1, January, 1978,
14. Crosby, D.G., et al. "Environmental Generation and
Degradation of Dibenxodioxins and Dibenzofurans."
Environmental Health Perspectives. September, 1973.
15. "Army Handling of Wood Preservative is Questioned",
Louisville Courier Journal, October 8, 1979.
16* "Rep. Carter calls for Faster Research on Properties
of Wood Preservative", Louisville Courier Journal,
October 4, *1979.
17. Acurex Corporation, "Solid Waste from Wood Treating
Processes - a Hazardous Waste Background Document",
December 20, 1979.
18. Acurex Corporation, "Fate of Toxic Pollutants in the
Wood Treating Industry".
19. Development Document for Effluent Limitations, EPA
440/l-79/Q23b.
20. Shakleford and Keith, "Frequency of Organic Compounds
Identified in Water," EPA-600/4-76-062, Environmental
Research Laboratory, Athens, Ga., Dec. 1976.
21. Damage Incident, U.S. Environmental Protection Agency,
open file, unpublished data.
-------
inorganic Chemicals
-------
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
-------
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 heavy metals lead or chromium (and
often both) and also contain ferric ferrocyanide when
iron blue pigments are produced. The oven residue contains
a substantial amount of 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 cyanide 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 60% of that
total is manufactured by two plants in the northeastern
United States. All other plants are located in the midwest
and south.
-------
Manufacturing Processes
1. Manufacture of Chrome Yellow and Orange Pigments
Chrome yellow and orange pigments are produced by reacting
sodium dichromate, caustic soda and lead nitrate as follows (1):
(a) 2HNC-3 + PbO ---- > Pb(N03>2 + H20
(b) Na2Cr207 + 2NaOH + 2Pb(N03)2 ----- > 2PbCr04 + 4NaN03 + H20
Lead chromate is formed as a precipitate and is recovered by
filtration, then treated, dried, milled and packaged. The
filtrate, containing lead and 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 (PbCr04) 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 proceed as follows (1):
a. Mo03 + 2NaOH ---- > Na2Mo04 + H20
b. PbO + 2HN03 ---- > Pb(N03)2+ H20
c. Na2Mo04 + Pb(N03)2 ---- > PbMo04 + 2NaN03
d. Na2Cr04 + Pb(N03)2 ---- > PbCr04 + 2NaN03
The precipitate is filtered, washed, dried, milled and
packaged. The filtrate, containing lead and chromium compounds,
is sent to the wastewater treatment facility. A flow diagram
is given in Figure 2 (3).
-------
714
LEAD OXIDE
WATER
403 NITRIC AGIO—
(OH ACETIC ACID)
DISSOLVING
263 60% NoOII—**
490 SODIUM
DICHROMATE
DISSOLVING
MIXING
AND
DEVELOPMENT
FILTRATION
AND
WASHING
9.911^0,,
9.7 SO,,-
2. Ca(OH)e-
DRYING,
MILLING
AND
PACKAGING
,1000
'PRODUCT
WASTE
TREATMENT
VALUES WILL DIFFER DU£ TO DIFFERENT
REACTANTS USED TO MAKE DIFFERENT
SHADES OF CHROME YELLOW
SOLIDS
30 PbCKX,
10.4 Cr{OM)3
26.1 Co SO,
2.6 Pb(OH)2
EFFLUENT
544
14.3
1.7
OR Ca(Ac)z)
WATER
FIGURE 1
CHROME YELLOW MANUFACTURE
-------
212
MOLYODIC
WATER
CAUSTIC
SODA
LEAD
OXIDE
NITRIC
ACID
255 SODIUM
CIIROMATIi
WATER
I WAIt
L I
K;
% *-
•»
—
MIX
TANK
17.5 NaCI
\
MIXER
9.9 H2f
9.7 S02
HOLDING
TANK
FILTRATION
WASHING
CHEMICAL TREATMENT
VENT
t
DRYING,
MILLING
• AND
PACKAGING
IOOO
PbCr
PRODUCT
CONTAINED IN MOLYOD/C
OXIDE «AW MATERIAL
SLUDGE SEPARATION
SOLIDS TO LANDFILL
i.eo uioz*
£0 PbCrQ,'PbMoOi4
10 Cr(OII)5
2.5 Pb{OH)2
J
17.0 NaCI :
502 NaN05
14 NajSO^
1.7 Ca{N03
WATER
FIGURE
MOLYBDATE ORANGE MANUFACTURE
-------
3. Manufacture of Zinc Yellow Pigments
Zinc yellow pigment is a complex compound of zinc,
potassium and chromium. It is produced by the reaction of
zinc oxide, hydrochloric acid, sodium dichromate and potassium
chloride (1):
a. 2KCL + 2HC1 + 2Na2Cr207 . H20 > K2Cr40i3 + 4NaCl + 3H20
b. 4ZnO + K2Cr4013 + 3H20 > 4Z,nO . K20 . 4Cr03 . 3H20
The product forms as a precipitate and is filtered, washed,
dried., milled and packaged. The filtrate, containing chromium,
is 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 iron 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 is
given by the following reaction (1):
(1) PbCr04 + Fe(NH4) [Fe(CN6)J > PbCr04Fe(NH4) [Fe(CN)6]
The co-precipitate is filtered, dried, ground, blended and
packed. The filtrate, containing lead and 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).
5. Manufacture of Anhydrous and Hydrated Chrome Oxide Green
P igment s.
Anhydrous chrome oxide is produced by the calcination
-------
404 ZnO
105 HCI -
218 KCI —
-H»
7G5 NaftCr£0|-I^O
REACTION
TANK
23 HtSOv
71 S0r
166 NaOH
WATER
VAPOR
VENT
DEWATER,
CENTRIFUGE
AND
WASH
-*,
t
DRYING,
MILLING
AND
PACKAGING
TREATMENT
PRODUCT
SOLID RESIDUE
20 ZINC YELLOW
24 ZnO
40 Cr(OH)B
LIQUID EFFLUENT
44 KCI
131 NatS04
433 NaCl
WATER
FIGURE 3
ZINC YELLOW MANUFACTURE
-------
WATER
776 LEAD
NITRATE
190 SODIUM.
CIIROMATE
167 SODIUM
SUUFATE
WATER
I
263 IRON BLUE-
WATER
I
RESLURRY
REACTION
TANK
i
WASH
SHADE
TANK
, .... , ta «.
FILTER
DRY
••M.ttari
GRIND,
BLEND
AND
PACK
IOOO
CHROME
GREEN
PRODUCT
NOTE:
INPUT VALVES WILL
VAHY DEPENDING ON
SHADE OF GflEEN
DEStnED.
LIQUID EFFLUENT
WATER I
400 NaNOj
5 CMROf^E GREEN PIGMENT
(AS SUSPENDED SOLIDS IN WATER)
RGURE 4
CHROME GREEN MANUFACTURE
-------
of sodium dichromate with sulfur or carbon according to
either of the following reactions (1):
a. Na2Cr2Oy + S > Cr203 + Na2804
b. Na2Cr207 + 2C > Cr203 + Na2CC>3 + CO
The recovered oxide is slurried with water, filtered,
washed, dried, and packaged. The washwaters, containing a
chromium compound, are sent to wastewater treatment. A
process flow diagram is given in Figure 5 (3).
.Hyd.rat.ed chrome oxide is made by reacting sodium dichromate
with boric acid as follows (1):
2Na2Cr207 + 8H3B03 > 2Cr203 . 2H20 + 2Na2B40y + 8H20 -I- 302
The raw materials are blended in a mixer, then heated in an
oven at 550° C. Oven residues, which contain chromium, remain
to be disposed of as wastes. The reacted material is slurried
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 chromium compound, are
sent to wastewater treatment. A process flow diagram is
given in Figure 6 (3).
G. Manufacture of Iron Blue Pigments
Iron blue pigments are produced by the reaction of
sodium ferrocyanide with an aqueous solution of iron sulfate
and ammonium sulfate. The precipitate formed is separated
and oxidized with sodium chlorate or sodium chromate to form
-------
O
i
1994 SODIUM
DICIIROMATE
WATER
198 SULFUR
22 WHEAT'
FLOUR
BLENDER
63 C02,CO,S02
i
KILN
WATER
SLURRY
TANK
33
666
WATER
1
FILTER
TREATMENT
VENT
1
DRYER
SOLID RESIDUE LIQUID EFFLUENT
Z?. Cr(OM)
993
GRIND,
SCREEN
AND
PACKAGE
JOOO C
VROOU
FIGURE S
ANHYDROUS CHROMIC OXIDE PIGMENT MANUFACTURE
-------
1695 SODIUM
DtCHROMATE
1630 BORIC ACID
exi
BLENDER
258 Ot
_1_
OVEN
SLURRY
TANK
SOUD WASTE TO LANDFILL
10 CfjOj- 2H20
646SULFURICACiD
DORIC ACID
RECYCLE
BORIC ACID
RECOVERY
UNIT
300
l
61
76 NoOU fr*
TREATMENT
WATER
WATER
WASH
1
VENT
FILTER
DRYER
GRIND,
SCREEN
AND
PACKAGE
1000
•Cr,0s-2l
PRODUCT
RESIDUE
66Cr(OH)3 IH7
300ttaOu3 p|GURE ^
HYDRATED CHROMIC OXIDE MANUFACTURE
-------
iron blues (Fe (Nfy)[Fe(CN)e])• The product is filtered,
dried and packaged as shown in Figure 7. The filtrate, con-
taining ferric ferrocyanide (and 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. Wastewater treat-
ment generally involves precipitation of heavy metals with lime
or caustic soda. This process generates a sludge containing
heavy metal hydroxides and pigment particles. The sludge also
contains ferric ferrocyanide if iron blues are produced, due to
the reaction of feedstock materials. The remaining listed hazar-
dous 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 is found in the oven residue as a result
of chromium in the feed material.
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-
tment. 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.
-------
^v
Reaction
Tank
L" ^
...s
T
Digestion ^ Oxidalion
Tank Tank
/ /
O •• ,OT
\T- *•
O /•C"
•* O
/
, o
-cm |:«llcr
& Wasli
;.,
1 rr»/"ifii
-------
TABLE 1
Composition of Wastewater Treatment
Sludge and Oven Residue from Chromium
Pigments Production
Source of Sludge
Mass Units of
Contaminants in sludge per
1000 Mass Units of Product
Production of Chrome
Yellow and Orange Pigments
30 PbCr04 (Lead chromate)
10.4 Cr(OH)3 (Chromium hydroxide)
2.5 Pb(OH)2 (Lead hydroxide)
Produc tion of
Molybdate Orange Pigments
20 PbCr04 . PbMo04 (Molybdate Orange
10 Cr(OH>3 (Chromium hydroxide)
2.5 Pb(OH)2(Lead hydroxide)
Production of
Zinc Yellow Pigments
20 4ZnO.K20.4Cr03.3H20 (Zinc Yellow)
48 Cr (OH)-3 (Chromium hydroxide)
Production of
Chrome Green Pigments
5 PbCr04Fe(NH4)[Fe(CN)6] (Chrome Gree
Production of
Anhydrous Chromic Oxide
P igments ^^^
22 Cr(OH>3 (Chromium hydroxide)
Production of Hydrated
Chromic Oxide Pigments
66 Cr(OH)3 (Chromium hydroxide)
Production of
Iron Blue Pigments
25
(Fe(CN)5)3 (Ferric Ferrocyanide
Oven Residue from
Production of Chromic
Oxide Pigments
10 Cr203.2H20 (Chromium Oxide)
* Note: Iron blue wastewater treatment sludge will contain
chromium compounds when sodium chromate is used as an oxidizing
agent. Generators, should they seek to delist their iron
blue waste streams should thus address chromium concentrations
as well as cyanide concentrations in their wastes.
-------
The Agency lacks data on the precise concentrations of
*
hazardous constituents in the sludges. These concentrations,
however, are believed to be substantial. Data indicates
that wastewaters from all chromium pigments 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 sludge, the
sludge is expected to contain much higher concentrations of
those contaminants. Moreover, as shown by the material
balances indicated on Figures 1-7 above, chromium and lead-
containing compounds are significant constituents of the
sludge, and thus obviously are present in substantial
concentrations .
Furthermore, the amount of sludge generated is quite
substantial. The Agency estimates that approximately 2100 to
2600 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 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 the wastewaters. Using current produc-
tion 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).
-------
EPA solicits information on the composition of wastewater
treatment sludges and concentrations of hazardous constituents
in extracts of those samples. The Agency emphasizes, however,
that hazardous constituent amounts in these sludges appear to
be sufficiently high to be of regulatory significance.
Current Waste Management Practices
A report done 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 by 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. Lead and chromium
occur in pigment particles and as hydroxides in the sludge
and may be solubilized if the wastewater treatment sludges
are improperly managed. Solubilization of the lead and
chromium hydroxides is pH-dependent and will increase as the
pH of the solubilizing medium deereases.(3)jf t^e 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), the toxic heavy
?
metals could be released from the waste matrix. Furthermore,
o
lead hydroxide, if present in sufficient quantities, is
soluble enough in water alone to exceed the National Interim
Primary Drinking Water Standard of 0-05 mg/1 (5). Although
chromium hydroxide is relatively insoluble in water, its
solubility is enhanced in the presence of chloride ions.(3)
Chloride ions .are common in the environment and would almost
certainly be found in many landfills, increasing the likelihood
that chromium could be leached by water from chromium hydroxide
containing wastes.
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 chromium by ground-
water. Clearly, wastes that require ponding are already in
contact with a substantial amount of liquid, which could
•
encourage leaching or form a head, facilitating leachate
migration to groundwater. If control practices are nonexistent
or inadequate, contaminant-bearing leachate, run-off or
impoundment overflow may reach ground and surface waters,
polluting valuable water supplies for a considerable period
of time.
Wastewater treatment sludges from iron blues production
-------
may 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 from the
matrix 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, montmorillonite
clays sorbed cyanide weakly (6). Cyanide thus is capable of
migrating from the waste disposal site to ground and surface
wa ters .
Should lead and chromium escape from the disposal site,
they will not degrade with the passage of time, but will
continue to provide a potential source of long-term
contamination. Lead can be bioaccumulated and passed along
the food chain but not biomagnified.
The Agency has determined to list chromium pigments and
iron blues as T hazardous wastes on the basis of lead, chromium,
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
t
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 amount generated will increase. Each
waste contains substantial amounts of lead, chromium, or
f errocyanides, and several wastes contain more than one of
these contaminants. (see Table 1, p. 8 above). Large amounts
of each of these contaminants are thus available for potential
environmental release. These large quantities 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
•
exhausted by large quantities of pollutants released from the
wa s t e .
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.
(\9o-
-------
Adverse Health Effects of Constituents of Concern
Ingestion of drinking water from ground and surface
j
waters contaminated by lead and chromium threatens human
health. Aquatic species exposed to the heavy metals may
also be adversely effected.
The hazards of human exposure to lead include neurological
damage, renal damage and adverse reproductive effects. In
addition, lead is relatively toxic to freshwater organisms
and bioaccumulates in many species. Contact with chromium
compounds can cause dermal ulceration in humans. Data also
indicates that there may be a correlation between worker
exposure to chromium and development of hepatic lesions.
Additional information on the adverse health effects of
these elements can be found in Appendices A.
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 meta-
bolism. Adverse health and environmental effects of cyanide
are discussed in Appendix A.
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 have
-X-
-------
been established pursuant to the Safe Drinking Water Act.
)
The Occupational Health and Safety Administration has a
final standard for occupational exposure to lead and a draft
technical standard for occupational exposure to chromium.
In addition, a national ambient air quality standard for
lead has been announced under the Clean Air Act. Final or
proposed regulations of the States of California, Maine,
Massachusetts, Minnesota, Missouri, New Mexico, Oklahoma and
Oregon define lead and chromium compounds as hazardous wastes
or components of hazardous wastes (7).
Cyanide is also listed as a priority pollutant under
§307 (a) of the Clean Water Act. Cyanide compounds are
defined as hazardous waste or components of hazardous waste
in proposed or final regulations of California, Louisiana,
Missouri, New Mexico, Oklahoma and Oregon (7).
-------
References
(1) US EPA, Effluent Guidelines Division. Draft Development
Document for Inorganic Chemicals Manufacturing Point
Source Category. US EPA Contract No. 68-01-4492.
April 1979.
(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.
(4) Personal Communication to Virginia Steiner from US EPA
Effluent Guidelines Division. December 1979.
(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 Montmorillonite.
Clay Minerals 22:417-425.
(7) US EPA Office of Sql^id Waste. State Hazardous Waste
Program Files. January 1980
-------
Organic Chemical.s
-------
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 (CH3CHO) 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.
Apetaldehyde is produced in three plants,in the U.S., which ;utilize
ethylene for starting material. (*) •
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
Capacity Raw
Company Facility (Gg/Yr) Material
(metric tons/yr x 10-5)
Celanese Corp.
Celanese Chem. Bay City, Tx. 136 Ethylene
Co. Div. Clear Lake, Tx. 277 Ethylene
Eastman Kodak Co.
Eastman Chemical
Products, Inc.,
subsid. Texas
Eastman Co. Longview, Tx. 277 Ethylene
(90%); ethyl
alcohol (10%)
Total 690
-------
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.(3,4,5;
The process involves the oxidation of ethylene by palladium chlo-
ride to form product acetaldehyde, palladium metal and hydrogen chloride:
C2H4 + PdCl'2 + H20 > 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, reoxidized 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
WASTE
REGENERATED CATALYST
>
REACTOR
FLASH
TOWER
CRUDE
DISTILLATION
COLUMN
PRODUCT
SCRUBBER
LIGHT ENDS
DISTILLATION
COLUMNS
ACETALDEHYDE
PRODUCT
CATALYST
REGENERATION
'SPENT CATALYST
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)
Formula
Distillation
Bottoms
(Discharge Distillation
Wastewater) Side-Cut Combined *>
Ethylene C2H4
Acetaldehyde C 2*140 - ,
Acetic Acid ,C2H4°2 13.9
Chloroacetaldehyde C2H30C1
Acetyl chloride C2H30C1 4.2
Chloral C2HOC13 2.1
Paraldehyde (02^0)3 1.6
Other organics (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
49.8
—
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)
-------
Table 3
Estimated Still Bottom Generation from Acetaldehyde Production - 1978a
Company
Celanese Chemical
Texas Eastman
TOTAL:
Location
Celanese Chemical Bay City, TX
Clear Lake City,
TX
Longvlew, TX
1978
Production
Capacity
(1000 MT/yr)
136
277
277
690
Estimated Estimated
Still-Bottom Side-Cut
Estimated Wastewater Waste
Production*3 Generated Generated0
(1000 Mt/yr) (1000 Mt/yr) (1000 Mt/yr)
97
197
197
491
Total
(1000 Mt)
111
227
227
565
10
10
• ••••• ••
25
116
237
237
590
aBased on data from reference 4.
bfiased 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.^ Waste water from the distillation bottoms has been disposed of both
by deep well injection and in anaerobic lagoons.W 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, and 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 include 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 Chlotoacetaldehyde
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. 6 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 chloroacet aldehyde 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 hydrolises 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. (17)
Chloroform has been detected in groundwater supplies in Miami, Florida. (18)
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.
-j/J-
-------
Chloroform is projected to be released to the atmosphere from
surface water systems (App. B.). Although chloroform decomposes slowly in
air when it is exposed to sunlight, the photochemical degradation products
are carbon tetrachloride, a carcinogen, (47) 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 miscible.
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 miscible. (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. (46)
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 that 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 oncogenic 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 11)50= 800 mg/Kg].
-3.il*-
-------
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. (1^' Manifestation of the toxic
nature'of chloroform is, in part, attributable to the observation that
metabolism results in toxication rather than detoxication. (15., 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 highly mutagenic.(22,23) Methylene chloride is very toxic [oral rat
LD50 a 1,67 mg/Kg].
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 carboxyhemoglobin,
-------
levels that reduce the blood's ability to carry oxygen and thus cause
asphyxiation. Similar toxicological 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. (*-v) 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, (3^,31) mutagenic(32) an
-------
Ecological Effects - Formalin, an aqueous solution of for-
maldehyde, can cause toxic effects to exposed aquatic life.(35) jt is
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.
4. Chloroacetaldehyde
Health Effects - Chloroacetaldehyde is a toxic chemical which
is mutagenic and a proposed carcinogen.(37,38,39) jt ^s 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
dessignated as a highly toxic irritant in Sax, Dangerous Properties of
Industrial Materials.
-X-
-J/1-
-------
5. Paraldehyde
Health Effects - Paraldehyde is a toxic chemical [oral
rat LD5Q = 1530 rag/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.^1'
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 LD50 =
1,210 mg/Kg] and ingestion of even small amounts for short periods may
cause permanent injury or severe damage to .skin, 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. Klrk-Othmer Encyclopedia of Chemical
Technology. 2nd Ed. Volume 1. Interscience Publishers, New York,
1963. pp.77-95.
2. Stanford research Institute. 1978 Directory of Chemical Producers -
U.S.A. SRI International, Menlo Park, California, 1978. 1127 pp.
3. Kirk-Othmer Encyclopedia of Chemical Technology. 2nd Ed. Vol. 1
John Wiley and Sons, New York, 1970. pp. 86, 87.
4. Lovell, R.J. Acetaldehyde Pro luct 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. Environmental Protection Agency. Industrial Process Profiles
for Environmental Use: Chapter 6. The Industrial Organic Chemicals
Industry. EPA-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. American Conference of Governmental Industrial Hygienists.
TLV's for Chemical Substances and Physical Agents in the Workroom
Environment. Cincinnati, Ohio. 1977.
9. Sittig, M. Pollution Control In the Organic Chemical Industry.
Noyes Data Corporation, Park Ridge, New Jersey, 1974.
10. United States Environmental Protection Agency. Carcinogen Assessment
Group Type II Risk Assessment, 1979.
11. National Cancer Institute. Report on Carcinogenesis Bioassay of Chloro-
form, NTIS PB264018, 1976.
12. Schwetz et al. Toxicology and Applied Pharmacology 28: 442, 1974.
13. Thompson et al. Toxicology and Applied Pharmacology 29: 348, 1974.
14- National Institute of Occupational Safety and Health. Recommended Cri-
teria for . . . Occupational Exposure to Chloroform, No. 75-114, 1974.
15. Uett et al. Exper. Mol. Pathology, jg: 215, 1973.
-------
References (cont.)
16. McLean. British Journal of Experimental Pathology 51: 317, 1970.
17. Roberts, P. Removal of Trace Contaminants from reclarified water during
aquifer passage. NATO-CCMS Conference, Sept. 11-13, 1978, West Germany.
18. USEPA. Preliminary Assessment of Selected Carcinogens in Drinking
Water EPA-560/4-75-0()3a, 1975.
19. United States Environmental Protection Agency. Carbon tetrachloride:
Ambient tfater Quality Criteria Document, 1979.
20. National Academy of Sciences, Stratospheric Ozone Depletion by Halocarbqn
Chemistry and Transport, 1979.
21. United States Environmental Protection Agency. Unpublished Results of
the Health Effects Research Laboratory, 1979.
22. Andrews et al, 1976.
23. Simmon et al, 1977.
24. Pattie, Industrial Handbook of Toxicology, 1965.
25. United States Environmental Protection Agency. Methyl Chloride: Ambient
Water Quality Criteria. PB 296797, 1979.
26. MacDonald, 1964.
27. Dawson, et al. The Acute Toxicity of 47 Industrial Chemicals to Fresh
and Saltwater Fishes. J. Hazard. Materials, Jj303, 1977.
28. USEPA. 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 Methylene Chloride to Fathead Minnows. Bull.
Environ. Contam. Toxicol. 20:344, 1978.
30. Nelson, N. 1979. Letter to Federal agencies: A status report on
formaldehyde and HC1 inhalation study in rats. October 19, 1979.
31.
Katanabe, F., et al. 1954. Study on the carcinogenicity of aldehydes;
1st Report. Experimentally produced rat sarcomes by repeated infections
of aqueous solutions of formaldehyde. Genn. 45: 451.
32. Auerbach, C., et al. 1977. Genetic and cytogenetical effects of
formaldehyde and relative compounds. Mut. Res. 39:317.
-------
References (cont.)
33. Humi, H. and H. Olnder. 1973. Reproduction study with formaldehyde
and hexamethylenetetramine in beagle dogs. Food Cosmet. Toxicol.
11: 459.
34. Coon, R.S., et al. 1970. Animal inhalation studies on ammonia, ethyl-
ene glycol, formaldehyde, dimethylamine and ethanol. Tox. Appl.
Pharmacol. 16: 464.
35. U.S. EPA. 1976. Investigation of selected potential environmental
contaminants: Formaldehyde. EPA 560/2-76-009.
. \
36. Dowden, B.F. and M.J. Barrett. •1965. Toxicity of selected chemicals
to.certain animals. Jour. Water Pollut. Control Fed. 37: 1308.
37. Rannug et al« The Mutagenicity of Chloroethylene Oxide, Chloroacetaldehyde,
2-Chloroethanol and Chloroacetic Acid, Conceivable Metabolites of Vinyl
Chlloride. Chem. Biol. Inter. 12(3-4): 251-263, 1976.
38. Hussain and Osterman-Golkar. Comment on the Mutagenic Effectiveness of
Vinyl Chloride Metabolites. Chem. Biol. Interact. 12(3-4):265-267, 1976.
39. Guengerich et al. Biochem. L8:5177-5182, 1979.
40. Waskell, L., A Study-o-f the Mutagenicity of Anesthetics and their Meta-
bolites. Mut. Res. 57(2): 141-154, 1978.
41. Browning, 1965.
42. Dawson, English and Petty, 1980. Physical Chemical Properties of
Hazardous Waste Constituents.
43. Barth, E.F., Cohen, J.M., "Evaluation of Treatability of Industrial
Landfill Leachate", Unpublished report, U.S. EPA, Cincinatti.
Nov. 30, 1978.
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, N.Y., April, 1979.
46. Sturino, E., Analytical Results: Samples From Story Chemicals,
Data Set Others 336", Unpublished data U.S. EPA Region 5, Central
Regional Laboratories, Chicago, Illinois, May, 1978.
47. Cancer Assessment Group List of Carcinogenic Substances, April 22, 1980.
-------
LISTING BACKGROUND DOCUMENT
ACRYLONITRILE PRODUCTION
Bottom stream from the wastewater stripper in the production of
acrylonitrile (R, T)
Still bottoms from final purification of acrylonitrile in the
production of acrylonitrile (T)
Bottom stream from the acetonitrile column in the production of
acrylonitrile (R>t)*
Bottoms from the acetonitrile purification column in tne production
of acrylonitrile (T)*
* * Summary of Basis for Listing
The hazardous wastes generated in the production of acrylonitrile
contain the toxic constituents acrylonitrile, acrylamide, acrolein,
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 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 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. Acrolein is extremely
toxic and a suspected mutagen. Hydrocyanic acid is
extremely toxic, as is HCN gas. Acetonitrile is also
toxic.
*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
acetonitrile column, and the bottoms from the acetoni-
trile purification column are typically 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) Still bottoms from the final purification of acrylonitrile
are typically incinerated. Improper incineration could lead
to dispersion of waste contaminants.
4) The bottom streams from the wastewater stripper and :he
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.
5) 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 acrylonitrile may be represented by the following
equation:
2CH2 - CH - CH3 -1- 2NH3 + 302 > 2CH2 - CH - CN + 6H20
The reaction of propylene and ammonia results in acrylonitrile (70-80
percent), acetonitrile (3 percent), and hydrogen cyanide (HCN)
(8-13 percent).O)W(5) (Acetonitrile and hydrogen cyanide would
-------
TABLE 1
U.S. Producers of Acrylonitrile
Producer
Location
Capacity
American Cyanamid Co.
E.I. duPont de Nemours
& Company, Inc.
E.I, duPont de Nemours
& Company, Inc.
Monsanto Company
Monsanto Company
Vistron Company
New Orleans, LA
Memphis, TN
Beaumont, TX
Chocolate Bayou, 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
400 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
form acetonitrile and water.)
By-product hydrogen cyanide is currently recovered by American
Cyanamid, duPont, Monsanto, and Vistron. Acetonitrile by-product is recovered
by duPont and Vistron.(3)(4)(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 organics 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^7\ 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 155 gallons per minute.
-------
WASTE HEAT BOILER
/
STEAM
PROPYLENE
STORAGE
AMMONIA , 0
STORAGE X2
CRUDE
ACRYLONITRILE
STORAGE
PROCESS AIR
ACRYLONITRILE
LOADING
D
COMPRESSOR
ACETONITRIIE
runiriCATiofi
COLUMN
ACETONITRILE
COLUMN
WASTE
WATER
COLUMN
HCN
LOADING
TO DEEP-WELL STORAGE
<
FUGmVE EMISSIONS
OVERALL PLANT
DEEP-WELL POND
ACETONITRILE
STORAGE
ACETONITRILE
LOADING
Figure 1. FLOWSHEET FOR ACRYLONUBILE PRODUCTION
BY THE SOHIO PROCESSES (6)
-------
Table 2 summarizes the 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
mg/1
Acrylonitrile | 500 or less :
I
Acetonitrile I 3,000
I
HCN I 7,000
I
Sulfates I 32,000
!
Ammonia I 15,000
1 , '
I Additional non-toxrc solids I • 40,000 approximately
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.(8)
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. Still bottoms from final purification of acrylonitrile.
(Stream 22, Figure 1)
Crude acrylonitrile is purified by successive distillation of
the absorber bottoms.
The absorber bottoms go to a recovery column where crude
-------
acylonitrile is separated from crude acetonitrile and sent to crude
acrylonitrile storage. The crude acrylonitrile then is sent to the
light ends column which separates the hydrogen cyanide and other light ends.
The bottoms from this column go to the product column where the heavy
impurities are removed and disposed of in an incinerator. W(7) -j^g
still bottoms from this process (Stream 22) are typically incinerated. (6)(8)
' i
A typical rate of production for this stream is 8.1 g/Kg. of product^).
Applying this factor to the 1977 production results in an estimate of 13
MM Ib. of this stream produced per year. The column bottoms contain
acetonitrile (25 percent) and toxic materials such as acrolein and acrylamide
(75 percent)^''. Acrylonitrile is also probably present, since it is
unlikely purification will be complete.'®-'
3. 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. acrylonitrile
product.'"J Applying this factor to the total nameplate capacity of
the acrylonitrile producers who are recovering acetonitrile results in an
upper limit estimate of 675 MM Ib. of the waste stream produced per. year.
At the Vistron plant, approximately 180 gallons per minute of column
bottoms are produced.
-X-
-J30-
-------
A typical composition of this waste stream is shown in Table 3
TABLE 3
Typical Composition of Bottom Stream from
Acetonitrile Column (8)
(waste constituents of concern only)
mg/1
HCN I 22.5
Acrylonitrile ' . | <10
Acetonitrile 35
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).
4. 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 acryloni-
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 acrylonitrile,
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
these highly diluted waste streams*, acrylonitrile is present in concentra-
tions up to 500 ppm (Table 2, p. 6).** Hydrocyanic acid may be present in
*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 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.
-------
concentrations of 7000 ppm. Concentrations of these constituents in pond
sediments are likely to be significantly 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. '
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 be prolonged, since large amounts of
pollutants are available for loading. Site attenuative 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, acrylamide, and acetonitrile are all highly soluble
(App. B). (Acetonitrile, in fact, is miscible.(46)) in addition,
acrylamide and acrylonitrile tend to volatilize (46) f and so 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.(46) Acrylamide has in fact been documented
to have moved from a sewer grouting operation through the soil to a
private water will.d®)- These waste constituents also may persist
-------
after migrating from the waste site. The major degradation
mechanism for acrylamide and acetonitrile is biodegradation^4"', which
would not affect these constituents in the abiotic conditions of an
aquifer. Acetonitrile also degrades (although slowly) to highly toxic
cyanide W-6)^ increasing the opportunity for hazard if it is released.
The major degradation mechanism for acrylonitrile is photodetoxification'13,14)
which again would not affect this compound's persistence in groundwater.
Hydrocyanic acid, the other major waste constituent, is
also highly mobile 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. dU Also,
cyanide has been shown to move through soils into groundwater.d^; £n
surface waters, cyanide often volatizes. The hydrogen cyanide vapors
pose a hazard to workers or nearby populations because of their
extreme toxicity.
An actual damage incident involving wastes containing
hydrocyanic acid confirm that cyanide can migrate, persist and con-
taminate groundwater, public drinking water, and soil. A landfill in
Monroe County, Pennsylvania, that accepts plating process such as hydro-
cyanic acid, has created a groundwater pollution problem in the area. ^^^
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.
C. Toxicity Hazard of Still Bottoms from Final Purification of
Acrylonitrile
The acrylonitrile final product purification column emits a
concentrated bottom waste containing large concentrations of acrolein,
acrylamide and acetonitrile. These bottoms are typically disposed of by
incineration. Mismanagement of this stream by improper incineration
(inadequate temperature or residence time) creates a high probability of
health risks resulting from exposure to uncontrolled contamination of
ambient air with these waste constituents. Also, incineration is not an
assured waste management method, so that the wastes could be improperly
land disposed as well. The waste is therefore deemed hazardous.
B. 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) it has also been identified
by the Agency as a compound exhibiting substantial evidence of being a
carcinogen. Evidence has also developed from positive laboratory tests in
several organisms that acrylonitrile is a mutagen. (25,27; jt ^as
also been reported to be teratogenic and toxic to mothers.(28,29;
Acrylonitrile is an extremely toxic chemical by inhalation, ingestion, 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/1, which demonstrates the toxicity of this substance
to aquatic biota(-^. 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 - Acrylonitrile 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
-to-
-------
extremely toxic via ingestion, inhalation, and percutaneous routes. Addi-
tional information on the adverse effects of acrylonitrile can be found in
Appendix A.
2. Acrylamide
Health Effects - Acrylamide is regulated by OSHA as a carcinogen
under OSHA Standard 1910.1000(g). Acrylamide is a highly toxic chemical by
inhalation, ingestion or dermal routes (oral rat LD5Q=170 mg/Kg). Acrylamide
exposure produces a progressive neuropathy in humans, involving both the
central nervous system. Reversal of symptoms is seen following removal
from exposure.(36; 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. (36)
Ecological Effects - Acrylamide has been found to be toxic
to freshwater fish after acute exposures at concentrations ranging from
89,000 to 1,000,000 micro-g/1.(36>
Regulations - Acrylaraide 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 micro-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. Acrolein
Health Effects - Acrolein is suspected to be mutagenic and is
an extremely toxic chemical by ingestion (oral rat LD5Q=46 mg/Kg). Mutagen-
icity was evidenced in several test systems involving various species. (38,39)
Toxicity was demonstrated in animals chronically exposed to low levels of
acrolein in.air.
Priority Pollutant - Acrolein is a priority pollutant
under Section 307(a) of the CWA.
Industrial Recognition of Hazard - Sax (Dangerous Properties
of Industrial Materials) lists the toxic hazard rating of acrolein as high
via oral routes and moderate via dermal routes. It is considered a
priority pollutant by EPA.
Regulations - OSHA has set a TWA of 0.1 ppm and has regulated
it under OSHA Standard 1910.1000. Acrolein is regulated by the Office of
Water and Waste Management under the Clean Water Act Sections 311 and 304(a)
and under the Safe Drinking Water Act. The Office of Air, Radiation and
Noise has regulated acrolein under the Clean Air Act. The Office of Toxic
Substances has requested additional testing under Section 4 of TSCA and
has regulated acrolein under FIFRA. Additional information in the adverse
effects of acrolein can be found in Appendix A.
4. Hydrocyanic Acid/Hydrogen Cyanide (HCN)
Health Effects - Hydrocyanic acid in acrylonitrile produc-
-------
tion wastes is extremely toxic to humans and animals via ingest ion, 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 (LC5Q = 544 ppm.) 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/nH) 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 ingestion, inhal-
ation and skin absorption. Additional information on the adverse effects
of cyanide can be found in Appendix A.
5. Acetonitrile
Exposure to acetonitrile occurs primarily through vapor
inhalation and skin absorphion. Exposure may cause liver and kidney
damage, disorders of the central nervous system, cardiovascular system and
gastrointestginal 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
-------
Acetonitrile is a component of cigarette smoke and is absorbed by the oral
tissues. (4-7,50) Nitriles and their metabolic products have been
detected in the urine., blood, and tissues. ^0) jn a two year study
with rats, carcinogenesis was not shown for the chemical.(49; Mutagenic
effects have not been demonstrated. Teratogenic effects in rats include
fetal abnormalities in pregnant rats^9) an(j skeletal abnormalities. (53)
From chronic exposure, rat developed liver and kidney lesions, and
monkeys showed poor coordination.^^ Until recently, acetpnitrile
has been investigated by toxicologist chiefly because of its relationship
to thyroid metabolism.
-X-
-------
IV. References
1. Synthetic Organic Chemicals. United States 1977 Production and Sales.
United States International Trade Commission. Washington, B.C.
2. 1979 Directory of Chemical Producers, SRI International, Menlo Park,
California.
3. Blackford, Judith L. Chemical Conversion Factors and Yields. Chemical
Information Services, Stanford Research Institute. Menlo Park,
California, 1.977.
4. Lowenheim & Mbran. Faith, Keyes & Clark's Industrial Chemicals, 4th ed.
.1975.
5. EPA-IMPQCE Series 02/78-03 February 1978.
6. Hobbs, F. D. and J. A. Key. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry. Acrylonitrile Draft Product
Report. EPA Contract 68-02-2577. Hydroscience. August, 1978.
7. Hughes, T. W. and D. A. Horn. Source Assessment: Acrylonitrile Manu-
facture (Air Emissions). EPA 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. Bernstein and Avital. HCN poisoning in a tobacco warehouse,
Harefuah £2:165-167, 1962 (Hebrew).
10. 1978 Registry of Toxic Effects of Chemical Subs lances. U.S. Depart-
ment of Health, Education, and Welfare. National Institute of Occupa-
tional Safety and Health. Cincinnati, Ohio. January, 1979.
11. Alesii, B.A. and W.A* Fuller. 1976. The Mobility of Three Cyanide
Forms in Soil. pp. 213-223. In Residual Management by Land Disposal.
W.H. Fuller (ed.), EnvironmentaT Protection Agency, Cincinnati, OH.
PB 256768 268.
12. Cruz, M., et al. 1974. Absorption and Transformation of HCN on
the Surface of Copper and Calcium Montmorillonite. Clay Minerals
22:417-425.
-------
13. Water-Related Environmental Fate of 129 Priority Pollutants. 1979.
EPA-440/4-79-029a. U.S. EPA, Washington, D.C.
14. The Prevalence of Subsurface Migration of Hazardous Chemical
Substances at Selected Industrial Waste Land Disposal Sites. 1977.
EPA/530/SW-634. U.S. EPA, Washington, D.C.
15. Oil and Hazardous Materials Technical Assistance Data System. EPA/
NIH (124) Water Chemistry.
16. Preliminary Assessment of Suspected Carcinogens in Drinking Water.
EPA-560/4-75-003a. U.S. EPA, Washington, D.C., June 1975.
17. Sheldon, S. Lande,,Stephen J. Bbsch, and Philip H. Howard. 1979.
Degradation and Leaching of Acrylamide in Soil. J. Environ. Qual.
8:133-137.
18. Igisu, Hideki, et al. 1975. Acrylamide Encephaloneuropathy Due to
Well Water pollution. J. of Neurology, Neurosurgery and Psychiatry.
38:581-584.
19. Midwest Research Institute, 1977. Sampling and Analysis of Selected
Toxic Substances. Section V Sampling and Analysis Protocol for
Acrylonitrile. Progress Report 10. 13. Oct. 1-31, 1977.
20. O'Berg, M. Epidemiologic Studies of Workers exposed to acrylonitrile:
Preliminary Results. E.I. DuPont de Nemours, 1977.
21. Monson, R.R. Mortality and Cancer Mortality Among BF Goodrich White
Male Union Members who Ever Worked in Departments 5570 through 5579.
Report to BF Goodrich Company and to the United Rubber Workers. FR
43FR 45762, 1977.
22. Norris, J.M. Status report on 2-year study incorporating Acrylonitril
in the drinking water of rats. Health Environ. Res. Dow Chemical
Company, 1977.
23. Quast et al. Toxicity of Drinking Water Containing Acrylonitrile
in Rats: Results after 12 Months. Toxicol. Res, Lab Health Environ
Res., Dow Chemical, 1977.
24. Maltoni et al. Carcunogenicity Bioassays on Rats of Acrylonitrile
administered by inhalation and by ingestion. La Medlcina del Lavoro
68:401, 1977.
25. Benes and Sram. Mutagenic Activity of Some Pesticides in Drosophila
melanogaster. Ind. Med Surg 38:442, 1969. "
-------
26. Milvy and Wolff. Mutagenic Studies with acrylonitrile. Mut. Res.
48:271, 1977.
27. Venitt et al. Mutagenicity of Acrylonitrile (cyanrethylene) in
Escherichia cole. Mut. Res. 45:283, 1977.
28. Murray et al. Teratologic evaluation of acrylonitrile monomer given
to rats by garbage. Dow Chemical, 1976.
29. Murray et al. Teratologic evaluation of inhaled acrylonitrile
monomer in rats. Dow Chemical, 1978.
30. NIOSH. A Recommended Standard for Occupational Exposure to
Acrylonitrile. NIOSH #78-166, 1928.
31. Plunkett. Handbook of Environmental Toxicology,. 19? .
32. Babanov et al. Adaptation of an Organism to Acrylonitrile at a
low concentration factor in an industrial environment. Toksikol.
Gig. Prod. Neftekhim 45:58, 1972.
33. Sakarai and Kusimoto. Epidemiologic Study of Health Impairment
Among AN Workers. Rod. Kagaku 48:273, 1972.
34. Henderson et al. The effect of some organic cyanides (nitriles)
in fish. Eng. Bull. Ext. Ser. Purdue Univ. No. 106, 130, 1961.
35. U.S. EPA, 1979. In-Depth Studies on Health and Environmental
Impacts of Selected Water Pollutants. U.S. EPA, Contract 68-01-4646.
36. U.S. EPA. 1979. Environmental Criteria and Assessment Office.
Acrylamide: Hazard Profile. (Draft)
37. U.S. EPA. 1976. Investigation of selected environmental contami-
nants: Acrylamides.
38. NIOSH. 1978. Registry of Toxic Effects of Chemical Substances.
OHEW Pub. No. 79-100, p. 51.
39. U.S.E.P.A. Environmental Criteria and Assessment Office. Hazard
Profile of Acrolein, December 1979.
40. NIOSH. Criteria for recommended standard occupational exposure to
HCN and cyanide salts, #77-108, 1976.
41. Henderson, et al. 1961. The Effect of Some Organic Cyanides on
Fish. Eng. Bull. Ext. Ser. Purdue University No. 106:130.
42. Deguidt et al. Mortality from poisoning by acetonitrite. Europ J
Toxicol Environ Health 7:41-97, 1974.
-------
43. Chemical Engineering News, Editors Newsletter, November 1979.
44. U.S. Environmental Protection Agency. 1978. Hazardous Waste Incidents,
Office of Solid Waste, Hazardous Waste Management Division. Unpublished,
open file data.
45. Kirk-Othmer Encyclopedia of Chemical Technology. 2nd Edition. John
Wiley Interscience Publishers, New York, 1963.
46. Dawson, Petty, and English, 1980. Physical Chemical Properties of
Hazardous Waste Constituents.
47. Dalhamn, T., et al. 1968. Mouth absorption of various compounds in
cigarette smoke. Arch. Environ* Health 16: 831.
48. Dequidt, J., et al. 1974. Intoxication with acetonitrile with a
report on a fatal case. Eur. J. Toxicbl. 7: 91.
49. Dorigan, et al. 1976. Preliminary scoring of selected organic
air pollutants. Environ. Prot. Agency, Contract No. 68-02-1495.
50. McKee, H.C., et al. 1962. Acetonitrile in body fluids related
to smoking. Public Health Rep. 77: 553.
51. Patty, Frank A., Editor, Industrial Hygiene and Toxicology, Vol. II,
Interscience Publishers, New York, 1963.
52. Pozzani, V.C., et al. 1959. An investigation of the mammalian
toxicity of acetonitrile. J. Occup. Med. 1: 634.
53. Schmidt, W., et al. 1976. Formation of skeletal abnormalities
after treatment with aminoacetonitrile and cycylophosphamide
during rat fetogenesis. (Verh. Anat. 71:635-638 Ger.)
Chem. Abst. 1515w.
-p
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LISTING BACKGROUND DOCUMENT
BENZYL CHLORIDE
Still Bottoms from the Distillation of Benzyl Chloride (T)
!• 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 manag.ed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. 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 bioaccumulate in environmental
receptors.
-------
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Benzyl chloride (Cg^CI^Cl) is used as a raw material for Pharmaceuticals
and as an intermediate in the preparation of p-benzylphenol and benzyl alco-
hol. (1) 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
-------
To Hydrochloric Acid P^ant
CHLORINE
TOLUENE
REACTOR
1
VENT
VENT
^S
COLUMN
X
Be
i *
*
*
Crude
nzyl Chlor
v
.de
^
PRODUCT FRACTIONATION
COLUMN
X_^
f/
BENZYL CHLORIDE
i ll
Bottom WASTE
figure 1. BENZYL CHLORIDE BY THE CHLORINATION OF TOLUENE
-Modified from (1,?.)
-------
from the reactor may be passed to a hydrochloric acid plant or recovered as
compressed gas.
The following equation shows the main reactions:
C6H5CH3
Toluene
C12
Chlorine
C6H5CH2C1
Benzyl Chloride
HC1
Hydrogen
Chloride
One side reaction is as follows:
C6H5CHCl2
Benzyl
Bichloride
C12
Chlorine
C6H5CC13
Benzotrichloride
HC1
Hydrogen
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-fractionation 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
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)
X-
-------
If the liquid phase 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
benzo trichloride 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 catalytic process would be
generated in quantities of approximately 3.3 million kg annually (assuming
benzal chloride is not recovered), with hazardous waste loadings of approx-
imately 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 la'ndfills 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 inadequately 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, di, tri, tetra, and penta) and toluene
have 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 File, 1978.)
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 bioaccumula-
tive (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, mixing, 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.*
B. Health and Ecological Effects
1. Benzyl Chloride
Health Effects - Benzyl chloride has been identified as a
carcinogen^), and is also mutagenicW. 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 la.bej.ing as a corrosive. The Office of Water and Waste
Management, EPA, has regulated benzyl chloride under Section 311 of the Clean
Water Act- Preregulatory assessment has been completed by the Office of Air,
Radiation and Noise under the Clean Air Act. The Office of Toxic Substances
has requested additional testing under Section 4 of the Toxic Substances 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 moderate 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
*Furthermore, 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.
-------
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 toxicity of chlorobenzene is indicated from studies
with saltwater shrimp species. Chlorobenzene has been shown to bioaccumulate
in fishC1*).
Regulations - The OSHA TWA in air is 75 ppm. Chlorobenzene is
designated as a priority pollutant under Section 307(a) of the CWA. (10, H,
12, 13, 14)
Industrial Recognition of Hazard - Chlorobenzene is listed in
Sax1s 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(17). In animal studies, pre-
liminary evidence of bone marrow chromosomal abnormalities was report-
edttS, 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-
-------
cals into the body. Thus, synergistic effects of toluene on the toxici-
ties 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. Additional 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 toxicity is also reported
for marine fish(20) . The USEPA recommended criterion levels to protect
aquatic life are: freshwater, 2.3 mg/1, and marine, 100 mg/l^O).
Regulations - Toluene has an OSEA 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).
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^1'. In-
halation of 125 ppm for 4 hours was lethal to rats(22). 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. Kirk-Othmer. Encyclopedia of Chemical Technology. _5. John Wiley and
Sons, Inc., New York, 1964.
2. Lowenheim, F. A. and Moran, M. K. Faith, Keyes and Clark's Industrial
Chemistry. Fourth Ed. John Wiley and Sons, New York, 1975.
3. Preliminary Assessment of Suspected Carcinogens in Drinking Water.
EPA-560/4-75-003. USEPA, Washington, D.C., pp. 70-71.
4. Lu, P. and R. Metcalf, 1975. Environmental Fate and Biodegradability
of Benzene Derivatives as Studied in a Model Aquatic Ecosystem. En-
viron. Health Perspect. 10:269-284.
5. Individual Plants1 Responses to EPA's 308 questionnaire.
6. Altshuller, A. P., Lifetimes of Organic Chemicals in the Atmosphere,
Environmental Scientific Technology, 1980, in press.
7. U.S. EPA, 1979. Chlorinated Benzenes: Ambient Water Quality Criteria
(Draft).
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. Krbsforsch
74:241-70, 1970 (Ger).
9. McCann, J., E. Choi, E. Yamasaki, B. N. Ames: Detection of carcinogens
as Mutagens in the Salmon el la/micro some Test — Assay of 300 chemicals.
Proc. National Academy of Sciences VSA 72:5135-39, 1975.
10. U.S. EPA, 1977. Investigation of selected potential environmental
contaminants: Halogenated benzenes. EPA-560/1-77-004.
-------
11. Lr, A. Y. H., et al, 1974. Liver microsomal electron transport systems.
III. Involvement of cytochrome 85 in the HADE-supported cytochrome
p5-450 dependent hydroxylation of chlorobenzene. Biochem. Biphys,
Res. Comm. 61:1348.
12. Brodie, B. B. et al, 1971. Possible mechanism of liver necrosis caused
by aromatic organic compounds. Proc. Natl. Acad. Sci. 68:160.
13. Knapp, W. R., Jr., et al, 1971. Subacute oral toxicity of monochloro-
benzene in dogs and rats. Toxicol. Appl. Pharmacol. 19:393-
14. Irish, D- D., 1963. Halogenated hydrocarbons: II. Cyclic. In Indus-
trial Hygiene and Toxicology, Vol. II, 2nd Ed., (ed. F. A. Patty),
Interscience, New York. P. 1333.
15. Lu, P. and Metcalf, 1975. Environmental Fate and Biodegradability of
Benzene Derivatives as Studied in a Model Aquatic Ecosystem. Environ.
Health Perspect. 10:269-285.
16. U.S. EPA, 1979. Toluene ambient water quality criteria (Draft).
17. Matsushita, T., et al, 1975. Hematological and neuro-muscular re-
sponse of workers exposed to low concentration of toluene vapor.
Ind. Health 13:115.
18. Dobrokhotov, V. B., and M. I. Enikeev, 1977. Mutagenic effect of ben-
zene, toluene, and a mixture of these hydrocarbons in a chronic experi-
ment. Gig. Sanit. 1:32.
19. Lyapkalo, A. A., 1973. Genetic activity of benzene and toluene. Gig.
Tr. prof. Zabol.
20. U.S. EPA, 1979. Toluene: Hazard Profile. Environmental Criteria
and Assessment Office, U.S. EPA, Cincinnati, Ohio.
-------
21. Merck Index.
22. Sax, I. Dangerous Properties of Industrial Materials.
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,
B.C., 1978.
-------
LISTING BACKGROUND DOCUMENT
CARBON TETRACHLORIDE PRODUCTION
Heavy ends or distillation residues from the production of
carbon 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 8.6 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.
-------
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.(2)
B. Manufacturing Process
Carbon tetrachloride is produced principally via four processes:
direct chlorination of methane, pyrolysis or chlorinolysis 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.*(4,2,31)
* 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^3)
I
Company
Location
Annual Capacity
(Millions of Pounds)
Allied Chemical Corp.|
Specialty ChemicalsI
Division
Moundsville, WV
8
Dow Chemical, U.S.A.
Freeport, TX
Pittsburg, CA
Plaquemine, LA
135
80
125
E.I. duPont de
Nemours & Co., Inc.
Petrochems Dept.
Freon® Prod. Div.
Corpus Christi, TX
500
Stauffer Chemical Co.
Ind. Chems. Div.
Le Mogne, AL
Louisville, KY
200
70
Vulcan Material Co.
Chemical Div.
Geismar, LA
Wichita, KA
90
60
FMC Corporation
S. Charleston, WV
300
Total
1,568
-------
1. Direct Chlorination of Methane (31)
The sequence of reactions for production of carbon
tetrachloride from the direct chlorination of methane is:
CH4+C12 > CH3CH-HC1
CH3C1+C12 > CH2C12+HC1
CH2C124C12 > CHC13+HC1
CHC13+C12 > CC14+HC1
The reaction is conducted adiabatically at temperatures ranging from
350° - 370°C and at approximately atmospheric pressure. In this process,
methyl chloride, methylene 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 chloromethanes, usually a refrigerated
-------
MtlHANt
METHYL CHLORIDE
MOHYLENE CHLORIDE
CARBON TETRACHLORIDE
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CHLORINE-
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METHYL CHLORIDE
Figure 1.
METHYLENE CHLORIDE
CHLOROFORM
CARBON
TETRACHLORIDE
COLUMN
->-HEAVY ENDS
CARBON TETRACHLORIDE
Methyl chloride, methylene 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
photochemically, 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, perchloroethylene (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 G£ 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).
*Chlorinolysis reactions refer to those chlorination reactions which
result in extensive rupture of carbon-carbon bonds.
-------
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
28
trace
0.3
39
16
0.6
17
16
33
Source: Wasselle, "Chlorinated Hydrocarbons", Process Economics Program Report No. 126, Stanford Research Institute,
Menlo Park, CA, August, 1978.
^Based on hydrogen chloride product. To convert from hydrogen chloride product to a specific chlolorinated
hydrocarbon product, the following factors are used: 0.72 Ibs HCl/lb ClvjCl
0.86 Ibs HCl/lb CH3C12
0.92 Ibs HCl/lb CH2C13
0.95 Ibs HCl/lb CC14
-------
carbon bonds (at severe reaction conditions), followed by rechlorination
of the fractured portions. Waste residues result from incomplete chlorina-
tion of the cracked hydrocarbons. Hydrocarbon chlorinolysis reactions
thus tend to produce similarly-composed residual wastes. Waste con-
stituents predicted to be generally present are hexachlorobenzene,
hexachioroethane, perchloroethylene, hexachlorobutadiene, and carbon
tetrachloride. Two principal chlorinolysis processes for the
production of carbon tetrachloride are described more fully below.
a. Chlorinolysis of Propane (31)
The basic chemical equation representing the direct chlorination of
propane to produce carbon tetrachloride and perchloroethylene is:
C3H8 +8C12 > C2C14+C12
C2C14+C14 > C2C16
2C2C14 > C4Cl6-K:i2
Figure 2 is a simple block flow diagram for the production of carbon tetra-
chloride and perchloroethylene by the direct chlorination of propane.
Feedstock chorine, 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 25% excess. The mixed gases react adiabati-
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 (mainly carbon tetrachloride, perchlorethylne,
hydrogen chloride, chlorine, and unreacted hydrocarbon) is quenched with
perchloroethylene to minimize formation of by-products.
Carbon tetrachloride, separated by fractionation, is condensed and
-------
CC1
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C£
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ac
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*Mocliflcd from 31
CARBON TETRACHLORIDE AND PERCHlOROETHYLENE MANUFACTURE VIA* Chlorlnolysis of Propane
r
!!IOi!IMIifliliIllH
-------
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 column. Light ends from this
column are recycled to the reactor. In the heavy ends column, the
perchloroethylne-rich 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 contgrolled 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 chlorination of product perchloroethylene.
Free radical reactions will result in the formation of hexachlorobutadiene
(see p. 8 where the reaction chemistry is described). Hexachlorobutadiene
could also be formed by chlorination of ethylene radicals under chlorinolysis
conditions. Hexachlorobenzene would result from the cyclization and
chlorination of G£ 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 3, 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.
-------
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 (4,2)
Expected waste constituents of concern from this process (Figure 4)
are hexachlorobenzene, hexachlorobutadiene, 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. Hexachloroethane is a feedstock and thus is
also expected to be found in the waste. Hexachlorobenzene will result
from the cyclization and chlorination of C2 molecules under high tempera-
ture pyrolysis conditions.
The final production process considered is the production of carbon
tetrachloride by chloronation 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:
2CS2+6C12 > 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
13
-------
CHLORINE
t
PURGE ON RECYCLED CHLORINE (GAS)
CARBON
TETRACHLORIDE
1 ........
r\
PERCHLOROETHYLENE
PERCHLOROETHYLENE
RECYCLE
• HEAVIE!
J
1 ,
I
rioN
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ER
(iEAWENDs
Figure^. CARBON TETRACHLORIDE BY THE PYROLYSIS OF
" HEXACHLOROETHANE & PERCHLOROETHYLENE
(Modified from A, 2)
-------
The sulfur monochloride formed reacts with a fresh feed of carbon disulfide
to form additional carbon tetrachloride:
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 disulf ide/carbon tetra-
chloride/sulfide monochloride from dechlorination, and chlorine (approx.
1% wt over the stoichiometric requirement) . react in the ehlorinator 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 monochloride, 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 monochloride 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 chlorination 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
*•«. ,
-S "7V-
-------
monochloride and dichloride. 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
from 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^^) and 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.
-------
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 demonstrably 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
TT
-------
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. (31)
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.
-------
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.(^/ It has been lethal in humans when ingested at one-twentieth
(12}
the known oral LD^Q ^ose f°r 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.^ 3) 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 bioaccumulate
in fish and other aquatic organisms.(6)
Regulations - Hexachlorobenzene is a chemical evaluated by
GAG as having substantial evidence of carcinogenicity. 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 animalsC1^). It has also been identified by the
-------
Agency as a compound which exhibits substantial evidence of being
carcinogenic. It is an extremely toxic chemical [LD5Q (rat)" 90 mS/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 HCBD^**15*16). Effluents from industrial
plants have been found to have HCBD concentrations as high as 240 g/l,(19)
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(^8).
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 (19) an(j 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)
X
-------
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.(22) Adverse effects of carbon
tetrachloride on liver and kidney functions(23) an£j on respiratory
and gastrointestinal tracts(23>24) have also been reported. Death has
been caused in humans through small doses.(25) 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*(^6) it aiso causes harmful effects in
undernourished humans, those suffering from pulmonary diseases, gastric
ulcers, liver or kidney diseases, diabetes, or glandular disturbances.(27)
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
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.(28)
Regulations - OSHA has set a TWA for carbon tetrachloride
at 10 ppm. 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.
-------
4. Hexachloroethane
Health Effects - Hexachloroethane has been reported to be
carcinogenic to animals, meaning that humans may be similarly affected\25)t
Humans exposed to vapors at low concentrations for long periods have had
liver, kidney and heart degeneration and central nervous system damage(26)t
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 for 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 - Perchloroethylene (PCE) was reported
carcinogenic to mice (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 PCE (40). PCE is also reported acutely toxic in
varyin degrees to several fresh and salt water organisms, and chronically
toxic to salt water organisms (41,42).
-------
IV. References
2. Kirk Othmer, Encyclopedia of Chemical Technology, Second Edition, 1968
3. 1979 Directory of Chemical Products of the US., SRI.
4. Source Assessment: Chlorinated Hydrocarbons., Z.S. Kahn and T.W.
Hughes. EPA-600/2-79-019g. August 1979.
5. Report No. 48 Chlorinated Solvents by Lloyd M. Elkin. February 1961.
Process Economics Program SRI.
6. Technical Support Document for Aquatic Fate and Transport Estimates
for Hazardous Chemical Exposure Assessments. 1980. , U.S. EPA,
Environmental Research Lab., Athens, GAi
7. U.S. EPA. Hazardous Waste Disposal Reports, No. 3, EPA/530/SW 151.3,
1976.
8. Cabral, J. R. P., et al. Carcinogenic activity of Hexachlorobenzene
in hamsters. Tox. Appl. Pharmacol. bl_:l55 (1977).
9. Cabral, J. R. P., et al. 1978. Carcinogenesis study in mice with
hexachlorobenzene. Toxicol. Appl. Pharmacol. 45:323.
10. Grant, D. L. et al• 1977. Effect of hexachlorobenzene on reproduc-
tion in the rat. Arch. Environ. Contam. Toxicol. Jx207.
11. Koss, G., et al. 1978. Studies on the toxicology of hexachloroben-
zene. III. Observations in a long-term experiment. Arch. Toxicol.
40:285.
12. Clinical Toxicol. of Commercial Products - Acute Poisoning. Gleason,
M. N. et al (1969) 3rd Ed., p. 76.
13. Carlson, G. P., 1978. Induction of cytochrome P-450 by halogenated
benzenes. Biochem. Pharmacol. 27:361.
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 Toxicity Study with
Hexachlorobutadiene in Rats. Amer. Ind. Hyg. Assoc. 38: 589, 1977.
16. SchwetZj et. al., Results of a Reproduction Study in Rats Fed Diets
Containing Hexachlorobutadiene. Toxicol. Appl. Pharmacol. 42:387,
1977.
-------
17. Li, et. al., Sampling and Analysis of Selected Toxic Substances.
Task IB - Hexachlorobutadiene.EPA-56076-76-015^USEPA, 1976.
18. U.S. EPA, 1979. Water-Related Environmental Fate of 129 Priority
Pollutants. EPA-440/4-79-029b.
19. National Cancer Institute. Carcinogens Bioassay of Carbon Tetra-
chloride, 1976.
20. Schwetz, B. A., B. K. J. Leong and P. H. Gehring, "Embryo- and
Fetotoxicity of Inhaled Gabon Tetrachloride, 1,1-Dichloroethane
and Methyl Ethyl Ketone in Rats," Toxicolgy and Applied Pharma-
cology, Vol. 28, No. 3, June 1974, p. 452-464.
21. Elkins, Hervey B. The Chemistry of Industrial Toxicology. 1959.
2nd Ed. John Wiley & Sons: , New York, p. 136.
22. Association of American Pesticide Control Officials, Inc. 1966 Ed.
Pesticide Chemical Official Compendium, p. 198.
23. Texas Medical Association, Texas Medicine, Vol. 69, p. 86, 1973.
24. Davis, Paul A. "Carbon Tetrachloride as an Industrial Hazard," The
Journal of the American Medical Association. Vol. 103, July-Dec.
1934, p. 962-966.
25. Dreisbach, Robert H. 1974. Handbook of Poisoning: Diagnosis and
Treatment, 8th Ed. Lange Medical Publications, Los Altos, CA,
p. 128.
26. U.S. EPA. Carbon Tetrachloride: Ambient Water Quality Criteria
Document, 1979.
27. Von Oettingen, W.F., The Halogenated Hydrocarbons of Industrial and
Toxicological Importance. In: Elsevier monographs on Toxic Agents,
E. Browning, Ed., 1964.
28. U.S. EPA. Determination of Sources of Selected Chemicals in Waters
and Amounts from these Sources, 1977.
29- National Cancer Institute. Bioassay of Hexachloroethane for
Possible Carcinogenicity. No. 78-1318, 1978.
30. U.S. EPA. Chlorinated Ethanes: Ambient Water Quality Criteria,
1979.
31. Acurex Corp., 1980, "Chlorinated Hydrocarbon Manufacture: An
Overview", pp. 44-59.
-------
32. "Combustion Formation and Emission of Trace Species", John B.
Edwards, Ann Arbor Science, 1977.
33. NIOSH Criteria for Recommended Standard: Occupational Exposure
to Phosgene, HEW, PHS, COC, HIOSH, 1976.
34. Chemical and Process Technology Encyclopedia, McGraw Hill, 1974.
35. U.S. International Trade Commission, Synthetic Organic Chemical,
1979.
36. National Cancer Institute 1977. Bio Assay of Tetrachloroethylene
For Possible Carcinogenicity. CAS No. 177-18-4, Nc I-C6-TR-13,
DHEW Publication No. (NIH) 77-813.
37. Rowe, v.k; et al 1952. Vapor Toxicity Of Tetrachloroethylene For
Laboratory Animal and Human Subjects. AMA Arch. Ind. Hyq. occup.
med. 5: 566.
38. Klaasen, c.d., and g.c. place 1967. Relative Effects Of Chlorinated
Hydrocarbons On Liver and Kidney Function In Dogs. Toxicol.
Appl. Pharmocol.
39. Coler, H. R., ano H. R. Rossmiller* 1953
Tetrachloroethylene Exposure In a Small Industry. Ind. hyg, med.
8:227
40. Medek, V. and J. Kavarik. 1973. The Effects of Perchloroethylene on
the Health of Workers. Pracovni Lekarstvi. 25:339
41. U. S. EPA 1978. In-depth Studies on Health and Environmental Impacts
of Selected Water Pollutants. Contract No. 68-01-4646.
42. U. S. EPA 1979- Tetrachloroethylene Ambient Water Quality criteria
(Draft).
X
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LISTING BACKGROUND DOCUMENT
EPICHLOROHYDRIN PRODUCTION
Heavy ends (still bottoms) from the purification column in the production of
epichlorohydrin. (T)
I. Summary of Basis for Listing
Heavy ends from the fractionator column for 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. Approximately 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
-------
»is incomplete, airborne dispersion of hazardous vapors presents a
potential of human risk.
4. Incidents of epichlorohydrin contamination of water supplies
have occurred.
XI. 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. (25)
Growth is expected at 6 to 7% per year. (25)
B. Manufacturing Process
Epichlorohydrin is produced by the following reaction sequence:
Step 1:
+ H20 ---------- > HOC1 + HC1
(Chlorine) (Water) (Hypochlorous (Hydrochloric
Acid) Acid)
Step 2:
CH2 - CH-CH2C1 + HOC1 ---- > CH2OHCHC1CH2C1 (65-70%) + CH2C1CHOHCH2C1( 30-55%
(allyl chloride) HC1 1,2-dichloropropanol-l) (1,3-dichloropropanol-:
hypochlorous acid
and hydrochloric
acid
-------
Step 3:
CH2OHCHC1CH2C1 + CH2C1CHOHCH2C1 +NaOH • >
(1,2-dichloropropanol-l) (l,3-dichloropropanol-2) (Epichlorohydrinj
By-products produced in small quantities are 1,2,3-trichloro-
propane (CH2C1 CHC1CH2C1) and chloro-ethers such as:
(CH2C1-CHC1~CH2)2 - 0 • [(CH2C1)2 - CH]2 - 0
bis-2,3-dichloropropyl ether bis-1,3-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 dehydochlorinated
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.
-V
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o
f
v»
2.
WATER
HYPGCHLOROUS ACID RECYCLE
AQUEOUS PHASE
CHLORINE
ADSORBER
HYPOCIILOROUS ACID FEED
REACTOR
CHLORINE
ALIYI
CHLORIDE
I
01ILORINATION
REACTOR
I
CRUDE CHLOROHYDRIN
1
SEPARATOR
Y 1 AQUEOUS PHASE
UL
SEPARATOR
STEA
STRIPPER
I
ORGANIC PHASE
AQUEOUS
PHASE
STRIPPER
STEAM
STEAM
WASTEWATER
CRUDE
EPICHLOROHYDRIN
h CALCIUM CHLORIDE
ORGANIC PHASE I 2
^ WATER STRIPPER
(TO AQUEOUS
PHASE _^
STRIPPER)? **
| ORGANIC PHASE
SODIUM
HYDROXIDE'
•e
PURIFICATION
COLUMN
'--.»
DEHYDROCHLORINATION
REACTOR
It
WASTEWATER
EPICHLOROHYDRIN
(09% PRODUCT)
HAZARDOUS
WASTE STREAM
(TRICHLOROPROPANE)
Figure 1: EPICHLOROHYDRIN FROM ALLYL CHLORIDE VIA DEHYDROCHLORINATION
OF DICHLOROHYDRINS
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The waste water from the bottom of the steam stripper'1' is stripped
in the aqueous phase stripper where small amounts of epichlorohydrin
are recovered overhead and recycled to the steam-stripper condenser;
the 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 epichlorohydrin is fed to the purification column
where it is purified by fractionationC3) 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). ^e 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.
Ill. 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)
*This water stream is not presently listed as hazardous
-3OO-
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Percent
Epichlorohydrin 2
Chioroethers 14
Trichloropropane 70
Dichloropropanol 10
Chlorinated aliphatics 4_
100
The waste constituents of concern are epichlorohydrin, the chloroethers,
trichlorpropanel and dichloropropanol. Epichlorhydrin has been identified
as a substance exhibiting substantial evidence of carcinogenicity by
EPA's Carcinogen Assessment 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 toxicity
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 mismanagment may certainly occur. As noted above, 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
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.(^2,33,34) 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, epichlorohydrin is stable enough
to be transported to surface waters. (Appendix B) This eventually
could result in drinking water contamination. Actual contamination of
-302."
-------
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.(6)**
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
ppm), 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.
-305-
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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 with 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, ehanol and isopropyl alcohol some 30 years after disposal.
(29,30,31)
Data show that chemical analogs, dichloroethane( ' and
dibromochloropropane,'°' have permeated the soil mantle to contaminate
ground water, again suggesting a similar behavior for propanols. In
addition the chioropropanels tend to bioaccunulate in aquatic
organisms,^' thus increasing potential exposure to higher levels of
the food chain, including man.
Epichlorohydrin could also pose a threat via an inhalation exposure
pathway due to its relatively high volatility. (28) Thus, lack of adequate
cover could result in air pollution to surrounding areas.
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B. Health and Ecological Effects
1. Epichlorohydrin
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. (^5) Epichlorohydrin
is very toxic [oral rat LD5Q=90mg/Kg]. Both respiratory cancers and
leukemia are in excess among some exposed worker populations.(l®>11)
Epichlorohydrin vapor also has been demonstrated to induce aberrations in
humans and animal chromosomes'^, 13) ancj 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'^'. Altered reproductive
function has been reported for workers occupationally exposed to epichloro-
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.^°>*'' 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'ppm. DOT
requires a label warning that this chemical is a poison and a flammable
liquid.
-------
Industrial Recognition of Hazards - Epichlorohydrin 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'*°»*"'
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 LD5Q=210 mg/Kg; inhalation
rat LD5Q=7ppm/7h]. Bis (2chloroethyl) ether is also very toxic (oral
rat LD5Q=75mg/Kg]. Epidemiological studies of workers in the United
States, Germany and Japan who were occupationally exposed to both ethers
indicate that they are human carcinogens. (™) They have also been
shown to be mutagens in bacterial screening systems.(20) 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 OSHA ceiling of 15 ppm. Bis (chloromethyl) ether
is designated by OSHA as a carcinogen. Chlormethyl 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 ingest ion, 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.^1, 22)
Trichloropropane is very toxic [oral rat LD^Q=320 mg/Kg]. Tsulaya et al^ '
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 ppm.
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 LD5o=90 mg/Kg] and l,2-dichloropropanol-3 [oral rat
490 mg/Kg] are very toxic to laboratory animals, causing systemic as well
as local toxic effects. The toxic symptoms caused by the 1,3 isomer have
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been compared to that of the liver toxin carbon tetrachloride which causes
acute and often irreversible hepatic failure. Both compounds are potent
skin and lung irritants, absorbed by all routes of exposure and tend to accum-
ulate in the organism.'^4) 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*0.
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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 epichlorohydrin. 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, EPA, OAQPS, 1979.
4. Zoeteman, B. C. J., K. Harmsen, J. B. H. J. Linders, C. F. H.
Morra and W. Sloof. Persistent Organic Pollutants in River Water
and Ground Water of the Netherlands. L979. Paper presented at
3rd Int'l Symposium on Aquatic Pollutants. Jekyll Island, GA,.
5. Subsurface Transport and Fate of WS-12 Epichlorohydrin, Ada Oklahoma
Lab, 1980.
6. U.S.E.P.A. Preliminary Assessment of Suspected Carcinogens in Drinking
Water. Report to Congress. USEPA, 1975.
7. De Walle, F. P., and E.S. K. Chian. 1979. Detection of Trace
organics in well Water Near a Solid Waste Landfill. Environ. Sci.
Technol. (In Press).
8. Weisser, P. Aug. 23, 1979. News Release, Department of Health
Services, Sacramento, CA.
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
31 July 1978. Distributed to Document Control Office, Office of Toxic
Substances (WH-557), USEPA.
12. Syracuse Research Corporation. Review and evaluation of recent scien-
tific literature relevant to an occupational standard for epichloro-
hydrin. Report prepared by Syracuse Research Corporation for NIOSH,
1979.
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IV. References (Continued)
13. Santodonato et al. "Investigation of selected potential environmental
contaminants: Epichlorohydrin and epibromohydrin." Syracuse Research
Corporation. Prepared for the Office of Toxic Substances, USEPA, 1979.
14. Halen, J. D. "Post-testicular and anti-fertility effects of epichloro-
hydrin and 2,3-epoxypropanol." Nature 226:87, 1970.
15. Cooper et al. "Effects of alpha-chlorohydrin and related compounds on
the reproduction and fertility of the male rat." J. Reprod. Fert.
38:329, 1974.
16. Quast, J. F. et al. "Epichlorohydrin - subchronic studies I. A 90-day
inhalation study in laboratory rodents." January 12, 1979. Unpublished
report from Dow Chemical Company, Freeport, Texas.
17. Quast, J. F. et al. "Epichlorohydrin - subchronic studies II. A 12-day
study in laboartory rodents." January 12, 1979. Unpublished report
from Dow Chemical Company, Freeport, Texas.
18. Innes et al. "Bioassay of pesticides and industrial chemicals for
tumorigenicity in mice, A preliminary note." J. Nat'l. 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_:739 1975.
20. U. S.E.P. A. Chloroaklyl Ethers: Ambient Water Quality Criteria, 1979.
21. Hawley, G. G., 1977. Condensed Chemical Dictionary, 9th Edition.
Van Nostrand Reinhold Co.
22. NIOSH 1978. Registry of Toxic Effects of Chemical Substances.
23. Tsulaya, V. R. et al, 1977. Toxicology Features of Certain Chlorine
Derivatives of Hydrocarbons. Gig. Sanit. _8:50-53.
24. Sax, I. , Dangerous Properties of industrial Materials.
25. Kirk-Othmer Encyclopdia of Chemical Technology. 2nd Ed. Vol. 1.
John Wiley and Sons, New York, 1970.
26. Peterson, C. A., "Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry: Glycerin and It's Intermediates."
Hydroscience, Inc. (Draft report prepared for EPA/OAQPS, March 1979.
-•310-
-------
27. Gruber, G. I., "Assessment of Industrial Hazardous Waste Practices,
Organic Chemicals, Pesticides and Explosives Industries." TRW, Inc.
USEPA, SW Il8c, January, 1976, p. 5-20.
28. Dawson, English and Petty, 1980. Physical Chemical Properties
of hazardous Waste Constituents.
29. Earth, E. F., and Cohen, J.M., "Evaluation of Treatability of Industrial
Landfill Leachate, unpublished report, U.S. EPA, Cincinatti.
(Nov., 1978).
30. O'Brien, R.P., City of Niagra Falls, N.Y., Love Canal Project,
Unpublished Report, Calgon Corp., Calgon Environmental Systems
Division, Pittsburgh, Pa.
31. Rcera Research, Inc., P:riority Pollutant Analyses prepared for Nuco
Chemical Waste Systems, Inc., unpublished report, Tonawanda, N.Y.,
1979.
32. "Combustion Formation and Emission of Trace Spcies", John B. Edwards,
Ann Arbor Science, 1977.
33. NIOSH Criteria for Recommended Standard: Occupational Exposure
to Phosgene, HEW, PHS, COC, HIOSH, 1976.
34. Chemical and process Technology Encyclopedia, McGraw Hill, 1974.
35. Carcinogen Assessment Group's List of Carcinogens, April 22, 1980.
-------
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 fractionation column used in
the production of ethyl chloride contains 1,2-dichloroethanene 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 fractionation column bottom or heavy end sludges contain
3% ethyl chloride*, 22% dichloroethanes, 32% trichloroethylene,
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 toxicity 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 is 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. ^' 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
hydrochlorination of ethylene.^D 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, 32Z trichloroethylene, and 43% heavy chlorinated organics.^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
-------
t I
BASIS: 1 KG ETHYL CHLORIDE
ETHYLENE 0.488
HYDROGEN 0.625
CHLORIDt
MIXER
ALUMINUM CHLORIDE (
-------
of about .093 tons per ton of ethyl chloride produced/2) 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. ^2' More recent information indicates that
some wastes are being incinerated in thermal destruction facilities
(see p. 1, above).
VI. DISCUSSION OF BASIS FOR LISTING
A. HAZARDOUS POSED BY THE WASTE
As indicated earlier, the heavy ends from fractionation in
ethyl chloride production contain 22% dichloroethanes, 32% trichloro-
ethylene, and 43% heavy chlorinated organics (such as hexachlorobutadiene,
and hexachlorobenzene'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 toxicity, generally showing increasing
toxicity 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 ppm^), trichloroethylene - 1000 ppm^) f and hexachlorobenzene -
500 ppm^). The 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. 7-8) 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 environment 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)^ 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 constituents (22% dichloroethanes, 32% trichloroethylene,
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, hexachlorobenzene^):
(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 plasmal 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.
-^/^7-
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(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 landfil management and inhalation.
There have also been three damage incidents resulting from the
mismanagement of trichloroethylene, 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, trichloroethylene 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
-JIS-
-------
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, 1975, two more wells were reported to be contaminated with tri-
chloroethylene at concentrations of 20 mg/1 and 3 mg/1, respectively ^8^.
This further illustrates the migratory potential and persistence of this
compound.
C. Health and Ecological Effects Associated With The Constituents
1. 1,2-Dichloroethane
Health Effects - 1,2-Dichloroethane is a carcinogen.'^) in
addition, this compound and several of its metabolites are highly mutagenic
(10, 11). 1,2-Dichloroethane crosses the placental barrier and is embryo-
toxic and teratogenic ^^ ~ ^ > and has been shown to concentrate in the
milk of nursing mothers. d?) Exposure to this compound can cause a variety
of adverse health effects including damage of the liver, kidneys and other
organs, internal hemorrhaging and blood clots d°'. 1,2-Dichloroethane
is a designated priority pollutant under Section 307(a) of the CWA.
Additional information and specific references on adverse health effects
of 1,2-dichloroethane can be found in Appendix A.
Ecological Effects - Values for a 96-hour static LC5Q for
bluegills ranged from 236 to 300 mg/1 making it moderately toxic. (19)
Regulations - 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, 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 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 Substances
Control Act.
Industrial Recognition of Hazard - Sax, in Dangerous Properties
of Industrial Materials, rates 1,2-dichloroethane as highly toxic upon
ingestion and inhalation.
2. Trichloroethylene
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) Trichloroethylene has been shown, both through acute
and chronic exposure, to produce disturbances of the central nervous
system and other neurological effects(22,23,24)t Trichloroethylene
has been found to cause heptacellcer cancinoma in mice.
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(25,26) an
-------
foreign organic compounds present in the body through its metabolism.
The recommended ambient criterion^) level for RGB 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. (2D
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; jjpon 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.(30)
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 - Hexchlorobutadiene is considered
to have a high toxic hazard rating via both oral and inhalation routes (Sax,
Dangerous Properities of Industrial Material).
Additional information on the adverse effects of hexachlorabutadiene
can be found in Appendix A.
-------
IENCES
1. 1979 Directory of Chemical Producers, Stanford Research Insititute.
2. Assessment of Industrial Hazardous Waste Practices: Organic Chemicals
Pesticides and Explosive Industries," TWR report to U.S. Environmental
Protection Agency.
3. OSW - Hazardous Waste Management Division, "Hazardous Waste Incidents":
Incidents": Unpublished Cpen File Data, 1978
4. Dawson, Siglish, Petty, 1980, "Physical Chemical Properties of Hazardous
Waste Constitutents11.
5. Patty, Franle A., Editor, Industrial Hyginene and Toxicology. Volume II,
Interscience Publishers, New York, 1963.
6. Michigan Department of National Resources - Geological Survey Divison.
Case History #48.
7. Schellenbarger, P. 1979, "new Charge Hits Air Force." Ihe Detroit
News, May 17, 1979.
8. Mitre Corporation, 1979. Draft Report in Support of Subsection C.
Prepared for U.S. Environmental Protection Agency.
9. 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, Carcinogenesis Testing Program, DEEW Publication No. (NIH)
78-1305, January 10, 1978.
10. McCann, J., E. Choi, E. Yamasaki, and B. Anes. Detection of Carcino-
gens a Mutagenic in the Salmonella/Microsome Test: Assay of 300
Chemicals. Proc. Nat. 2cad. Sci. USA 72^(2):5135-5139, 1975a.
11. McCann, J., V. Simmon, D. Streitwieser, and B. Ames. Mutagenicity
of Chlorocetaldehyde, a Possible Metabolic Product of 1,2-Dichloro-
ethane (ethylene dichloride), Chloroethanol (ethylene cholorhydrin),
Vinyl chloride, and cyclcphosphamide. Proc. Nat. Acad. Sci. 72
(8)"3190-3193.
12. tozovaya, 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.
13. Vozovaya, M., Developnent of Offspring of two Generations Obtained
fron Females Sujected to the Action of Dichloroethane. Gig. Sanit.
7:25-28, 1974
-------
14. Vozovaya, M., The Effect of Lew 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. ^zoakya, M., Effect of Low Cbncentrations of Gasoline, Dichloro-
ethane and Their Gscribination on the Reproduction Function of
Animals. Gig. Sanit. 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 vjomen vhen contacted under industrial
conditions.)
18. Parker, J.C., et al. 1979. Chloroethanes: A Review of Toxicity.
Amer. Indus. Hyg. Assoc. J., 40; A 46-60, March 1979.
19. U.S. EPA, 1979. Chlorinated Ethanes: Atrnbient Water Quality
Criteria (Draft).
20. U.S. EPA States Regulation Files? January 1980.
21. Mansville Chemical Products. 1976. Chemical Products Synopsis -
Tr ichloroethylene.
22. tfcmiyama, K. and H. Nomiyama. 1971. Metabolism of Trichloroethylene
in Human Sex Differences in Urinary Excretion of Trichloroacetic
Acid and Trichloroethanol. Int, Arch. Arbeitsmed. 28:37.
23. Bardodej, A., and J. Vyskocil. 1956. The Problem of Trichloroethylene
in Occupational Medicine. AMA Arch. Ind. Health. 13:581.
24. MsBirn'ey, B.S., 1954. Trichloroethylene and Dichloroethylene
Poisoning. AMA. Ind. Hyg. 10:130.
25. Cabral, J. R. P- et al. Carcinogenic Activity of Hexachlorobenzene
in Hamster. Tox. Appl. Pharmacol. 41:155 (1977).
26. Cabral, J. R. P., et al. 1978. Carcinogensis Study in Mice with
Hexachlorobenzene. Tox. Appl. Paramacol. 45:323.
27. Grant, D. L. et al. 1977. Effect of Hexachlorobenzene on Reproduction
in the Rat. Arch, Environ. Contam. Toxic. 5_:207.
28. Koss, G. et al. 1978. Studies on the Toxicology of Hexachlorobenzene.
III. Observation in a long-term experiment Arch. Tbxicol. 40:285.
-32.V-
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29. Carlson, G. P., 1978. Induction of Cytochrone P-450 fcy Haulcgenated
Benzenes. Brochem. Eharmacol. 27:361.
30. Technical Support Document for Aquatic Fate and Transport Estimates
for Hazardous Chemical Exposure Assessments. Estimates for Hazardous
Chemical Exposure Assessments. 1980. USEPA, Environmental Research
lab., Athens, Georgia.
31. U.S. EPA. Chlorinated Benzenes: Ambient Water Quality Criteria, 1979.
32. U.S. EPA. 1979. Water-Related Environmental Fate of 129 Priority
Pollutants. EPA-^40/4-79-029b.
33. Itociba, R. J., Results of a Two-year Chronic Ibxicity Study vdth
Hexachlorobutadiene in Rats. Amer. Ind. Hyg. Assoc. 38:589, 1977.
34. Kbciba 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. "Emission Control Optional for the Synthesis Organic Chemicals
tfenufacturing Industry: Carbon Tetrachloride and Perchloroethylene,"
EPA, Office of Air Quality Planning and Standards. Contract Number
68-02-2257.
38. U.S. EPA. 1975. "Preliminary Assessment of Suspected Carcinogens
in Drinking Water", Report to Congress. EPA 560/4-75-003,
Environmental Protection Agency, Washington, D.C.
39. CAG List of Carcinogens, April 22, 1980
-------
LISTING BACKGROUND DOCUMENT
ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER PRODUCTION
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)
I. Summary of Basis for Listing
The heavy ends from the distillation of ethylene dichloride in
ethylene dichloride (EDC) production, and the distillation of vinyl chloride
in production of vinyl chloride monomer (VCM) contain toxic chemicals
and chemicals that are carcinogenic, mutagenic, or teratogenic. The
waste constituents of concern are ethylene dichloride, trichloroethanes
(1,1,1/1,1,2), tetrachloroethanes (1,1,2,2/1,1,1,2), vinyl chloride,
vinylidene chloride, chloroform, and carbon tetrachloride.
The Administrator has determined that the heavy ends generated
during the purification (distillation) of crude EDC and VCM is a solid
waste stream 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:
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1. Of the compounds present in the ethylene dichloride
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 1 presents a summary of the chemical reactions
involved in producing EDC and VCM.
Production in 1978 was 6.346 million metric tons for EDC
and 3.776 million metric tons for VCM (Table 1).
-------
TABLE 1. PRODUCERS AND 1978 PRODUCTION CAPACITIES OF
ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER
(metric tons/yr) (1, 2)
Company
Allied
Borden
Conoco
Diamond Shamrock
Dow
Ethyl
Goodrich
PPG
Monochem
Shell
Stauffer
Union Carbide
Vulcan
Plant location
Baton Rouge, Louisiana
Geismer, Louisiana
Lake Charles, Louisiana
Deer Park, Texas
LaPorte, Texas
Freeport, Texas
Oyster Creek, Texas
Plaquemine, Louisiana
Baton Rouge, Louisiana
Pasadena, Texas
Calvert City, Kentucky
Lake Charles, Louisiana
Guayanilla, Puerto Rico
Geismar, Louisiana
Deer Park, Texas
Norco, Louisiana
Long Beach, California
Taft, Louisiana
Texas City, Texas
Geismar, Louisiana
Ethylene
dichloride
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
Vinyl chloride
monomer
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 BICHLORIDE VIA DIRECT CHLORINATION OF ETHYLENE
CH2=CH2 + C12 -> CH2C1CH2C1
ETHYLENE BICHLORIDE VIA OXYCHLORINATION OF ETHYLENE
CH2=CH2 + 1/202 + 2HC1 -> CH2C1CH2C1 + H20 (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)
-> 4CH2-CHC1 + 4HC1 (5)
t ....__ I
2CH2«CH2 + 02 + 4HC1 -> 2CH2C1CH2C1 •«• 2H20
Figure 1. Alternative methods of producing ethylene
dichloride and vinyl chloride monomer.
(6)
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B. Manufacturing Process, Waste Composition and Waste Management (1, 65, 66)
As noted above, ethylene dichloride (EDO) is produced by two
processes: the 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
HCL by-product produced by the thermal cracking of EDC to form VCM 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 hydrochlorination 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 dibromide 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
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VENE
CHLORINE ETHYLENE
DILUTE
NaOH
1
CHLORINATION
REACTOR
VENT SCRUBBER
i
>
. /
* (
6 TO 8%
NaOH
AQUEOUS
WASTE
I
AIR
OXYCHLORINATION
REACTOR
CAUSTIC WASH
EDC DISTILLATION
HEAVY
ENDS
TO
SHIPPING
VCM DISTILLATION
HEAVY
ENDS
HEAVY
WASTES
AQUEOUS
ALKALINE WASTE
LIGHT ENDS AND
WATER COL
I
LIGHT ENDS TO
RECYCLE
WASTE
WATER
2ND. DISTILLATION
COLUMN
PURIFIED EDC
VCM
CRACKING
FURNACE
HCI REMOVAL
VCM
DISTILLATION
VCM
RECYCLE HCI
Figure 2. PRODUCTION OF EDC & VCM
Modified from 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 82 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; 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
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2. EDO 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 fluidized-
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 180°C and 280*C, and pressure ranges
from 340 to 680 kPa gauge (50 to 100 psig). Yields are over 902 based
on ethylene, depending on the presence of excess ethylene or hydrogen
chloride. Excess hydrogen chloride favors the reaction.
Stoichiometric amounts of ethylene, anhydrous hydrogen chloride,
and air are fed to a catalytic reactor. The air is compressed and preheated
prior to entering the reactor as a means of initiating the reaction. Con-
version of ethylene 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 the product from direct chlorination and is contacted with aqueous
-333"
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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 landfilling,
based on common practice in the chlorinated hydrocarbon industry.
3. VCM Production
Vinyl chloride is produced from purified EDC. The purified
EDC is thermally cracked to yield crude VCM and hydrochloric acid (HCl).
The HCl is recovered and used as feed to the oxychlorination reactor.
jV This waste stream is not presently listed as hazardous.
-------
Crude VCM is distilled to yield pure VCM. Heavy ends from VCM distillation
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 EDC
heavy ends and VCM heavy ends. In an integrated plant some heavy ends
from the VCM plant are cycled to the ethylene dichloride still. In a
non-integrated plant, they are stripped of the ethylene dichloride,
which is to be recycled to the VCM unit. In either case, the ultimate
residue is expected to be disposed of by incineration or landfill,
based on common practice in this industry (i.e., the chlorinated hydro-
carbon industry).
The bottoms from the ethylene dichloride plant are partially
cycled to a downstream chlorination unit where the residual heavy ends
are partially retained and partially sent to disposal. 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 dichloride 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 Dichloride 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
-•he
-33S--
-------
This estimate assumes that the major constituents of EDC 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
-33G -
-------
constituent of EDC heavy ends). Trichloroethylene 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 Basis 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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-------
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 organics, 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. ( 61 > 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
-33?-
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and surface waters is a particular danger. All of the 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 minotoring
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 dichloride, 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
-------
dichloride and/or 1,1-dichloroethane) has been found migrating from the
landfill through nearby ground water.(5) In New Jersey, seepage from
landfilled 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
-X-
-------
wastes clearly should be listed as hazardous.
B. Health and Ecological Effects
1. Sthylene Dichloride
Health Effects - Ethylene dichloride (1,2-dichloroethane)
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 embryotoxic 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-dichloroethane) 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 LC5Q
for bluegills range from 256 to 300 mg/1 making it moderately toxic.(20)
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 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. Ethylene dichloride is currently
being studied by the Consumer Product Safety Commission under the Consumer
Product Safety Act.
-------
Industrial Recognition of Hazard - Sax in Dangerous Properties
of Industrial Materials rates 1,2-dichloroethane as highly toxic upon
ingestion and inhalation.
2. 1,1, l~Tridiloroethane (Methylchlorof orm )
Health Effects - 1,1,1-Trichloroethane is a suspected
carcinogen and when tested for carcinogencity by NCI was found to induce
a variety of malignant tuners in two species of rodents. (21) Experiments
involving rat embryo cell cultures indicated that 1,1,1-txichloroethane
transforms cells in vitro. Transplantation of these premalignant trans-
formed cells into an intact animal produced cancers in all of the animals
injected. (22)
1,1,1-Trichloroethane was found to be mutagenic in the Ames Sal-
monella essay (23) and was shown to cause fetal development abnormalities. (24)
Acute and chronic intoxication of humans have caused severe
central nervous systsn impairment, such as lengthened reaction and per-
ception time, decreased manual dexterity, equilibrium disturbance (3).
Animal studies have shown that methylchloroform causes organ damage to
heart, lungs, liver and kidneys. (25) 1,1,1-Trichloroethane is designated
as a priority pollutant under section 307(a) of CWA. Additional informa-
tion and specific references on the adverse effects of 1,1,-trichloroethane
can be found in j^ppendix A.
Ecological Effects - 1,1,1-Trichloroethane is very toxic
to aquatic life. Lethal concentrations (96 hour) of 37-38 mg/1 were
registered for bluegills, 52 mg/1 for fathead minnows and 26 mg/1 for
shrimp. (26) lfae gcp factor is set by USEPA at 21. (2°)
Regulations - OSHA has set the TWA at 350 ppn.
-J43-
-------
Industrial Recognition of Hazard - Sax Dangerous Property
^^^^*^^»
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 also been
shovvn to cause cancer in mice. '^7) 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 sribryo toxic or cause teratogenic effects.'13-17,28-30)
1,1,2-Trichloroethane is considered toxic [oral rat 11)50 = 1140 rag/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 Q&.
Additional information and specific references on the adverse effects of
1,1,2-trichloroethane can be found in Appendix A.
Ecological Effects - Aquatic toxicity data are Limited
with only three acute studies in freshwater fish and invertebrates with
doses ranging frcm 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 ty inhalation, ingestion and skin absorption.
4. Tetrachloroethanes
-------
Health Effects - 1,1,2,2-TetracMoroethane has been
shewn to produce liver cancer in laboratory mice. (31) It has also been
identified by the Agency as a compound etfiibiting substantial evidence of
being carcinogenic. (67) It is also shown to be very toxic [oral rat
1X50 = 20° rag/Kg]. In addition, passage of 1,1,1, 2-tetrachloroethane
across the placenta! barrier has been reported. (29) In Ames Salmonella
bicassay 1,1, 2, 2-tetrachloroethane was shown to be mutagenic.(32)
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 tetrachloroethanes can be found in Aperdix 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 1WA at 5 ppn (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) It has also been identified by the
Agency as a ccmpound exhbiting substantial evidence of carcinogenic ity.(67)
-2V
-------
This compound nay be absorbed into the bocty by inhalation, by ingestion,
or ty 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 nutations in mice. (36)
Numerous fatalities resulting from anesthesia with tri-
chloroethylene and fron industrial intoxications have been reported. (34)
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
sepcific 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 ppn.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists trichloroethylene as a high
systemic toxicant via inhalation and moderate via ingestion.
-------
6. Tetradhloipethylene
Health Effects - Tetrachloroethylene is a carcinogen
in laboratory mice. (38) It has also been identified by the Agency as a
compound exhibiting substantial evidence of carcinogenicity.(67) The
conpound can be absorbed into the body via inhalation, by ingest ion,
and through the skin to increase its toxic effects. (39)
It has also been reported to be inutagenic and to cause
trans formation of mamnalian eel Is. (39) ^ excess of lung, cervical and
skin cancers and a slight excess of leukemias and liver cancers ware observed
in a study of 330 deceased laundry and dry-cleaning vorkers Who had been ex-
posed to carbon tetrachloride, trichloroethylene, and tetrachloroethylene.
There is sone 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.(39)
A case of "obstructive jaundice" in a six veek old
infant has been attributed to tetrachloroethylene in breast milk.(40)
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 carcinogen in laboratory studies. (41,42) it has also been identified
ty the Agency as a compound exhibiting substantial evidence of carcino-
genicity.(67) ihis finding has subsequently been supported ty epidemological
-x-
-------
findings.^43'44^ Vinyl chloride is very toxic [oral rat
= 500 mg/Kg]. Acute exposure to vinyl chloride results in anaesthetic
effects as veil as uncoordinated muscular activities of the extremeties,
cardiac arrythmas^4^ and sensitization of the myocardium. '46) in severe
poisoning, the lungs are congested and liver and kidney damage occur. (47)
A decrease in \foite blood cells and an increase in red blood cells vas
also observed and a decrease in blood clotting ability. (48) Vinyl chloride
is designated as a priority pollutant under Section 307(a) of the CWk,
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) it has also been identified
by the Agency as a compound exhibiting substantial evidence of (sarcinogencity.
'67^ It is very toxic [oral rat LDgQ = 200 mg/Kg]^49^. Chronic exposure
to vinylidene chloride can cause damage to the liver and other vital
organs as well as causing central nervous system effects. Mditional
information and specific references on the adverse effects of vinylidene
chloride can be found in Appendix A.
Regulations - OSHV has set the 1WA at 10 ppn.
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 hunan carcinogen. (51) it has also
been identified ty the Agency as a compound eriiibiting substantial evidence
of carcincgenicity(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 anbryos.(54,55) chronic exposure causes liver and kidney danage and
neurological disorders. (52) Additional information and specific references
on the adverse effects of chloroform can be found in ^pperrlix 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 ppn. FDA pro-
hibits use of chloroform in drugs, cosmetics, and food contact materials.
The Office of Water and Waste ffenagement has proposed regulation of
chloroform under Clean Water Act 311 and is in the process of developing
regulations under dean 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 conducting preregulatory assess-
nent 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. ^"' It has been identified by the Agency as a compound
exhibiting substantial evidence of carcinogenicity. (67) -j^e toxic effects
[oral rat LD5Q = 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.'58) xt 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) jn 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. (6°)
Carbon tetrachloride is a priority pollutant under Section 307(a) of the
C¥A. Additional information and specific references on the adverse
effects of carbon tetrachloride can be found in Appendix A.
Ecological Effects - Movement of carbon tetrachloride
within surface water systems is projected to be widespread, (see App. B)
- 3.T6 -
-------
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.
-k-
-3S1-
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IV. References
1. Industrial Process Profiles for Environmental Use: Chapter 6,
The Industrial Organic Chemicals Industry. Reimond Liepins, Forest
Mixon, Charles Hudak, and Terry Parsons, February 1977, EPA-600/
2-77-023f.
2. Engineering and Cost Study of Air Pollution Control for Petrochemical
Industry-Vol. 3. Ethylene dichloride manufacture by oxychlorination,
November 1974, EPA-450/3-73-006-C.
3. Source Assessment: Chlorinated Hydrocarbons Manufacture, EPA-600/
2-79-019g, August 1979.
4. Water Quality Issues in Massachusetts, Chemical Contamination,
Special legislative Commission on Water Supply. September 1979.
5. DeWalle, Foppe B. and Edward S. Chian. Detection of Trace Organics
in Well Water Near a Solid Waste Landfill. Environ. Sci. Technol.
(In Press).
6. Memo from Roy Albert to E.G. Beck, Administrator EPA Region II,
Drinking Water Contamination of New Jersey Well Water, March 31, 1978.
7. Buller, R.D. 1979. Trichloroethylene Contamination of Ground Water
Case History and Mitigative Technology. Presented at American
Geophysical Union Fall Meeting, December 3-7, San Francisco, CA.
8. Wilson, J.T. and C.G. Enfield, 1979. Transport of Organic Pollutants
Through Unsaturated Soil. Presented American Geophysical Union Fall
Meeting, December 3-7, San Francisco, CA.
9. Zoetman, G.C.J., K. Harmsen, J.B.H.J. Linders, C.F.H. Morra, W. Sloop,
1979, Persistent Oranic Pollutants in River Water and Ground Water
of the Netherlands. Presented at the 3rd International Symposium
on Aquatic Pollutants, October 15-17, Jekyll Island, GA.
10. Roberts, P.V., P.L. McCarty, Mr. Reinhard, and J. Schriener, 1978.
Organic Contaminant Behavism During Ground Water Recharge. Presented
at the 51st Annual Conference of the Water Pollution Control Feder-
ation. October 1-6, Anaheim, CA.
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.
-------
IV. References (Continued)
I2a. McCann, J., E. Choi, E. Yamasaki, and B. Ames. Detection of Carcin-
ogens as Mutagenic in the Salmonella/Micro some Test: Assay of 300
Chemicals. Proc. Nat. Acad. Sci. USA _72(2): 5135-5139, 1975a.
12b. McCann, J., V. Simmon, D. 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. Sci. 72(8):
3190-3193, 1975.
13. Vozovaya, M. Changes in the Esterous Cycle of White Rats Chronically
Exposed to the Combined Action of Gasoline and Dichloroethane Vapors.
Akush. Geneko. (Kiev) £7_(12): 65-66, 1971.
14. Vozovaya, M. Development of Offspring of Two Generations Obtained
from Females Subjected to the Action of Dichloroethane. Gig. Sanit.
£ 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. Ginekol.
(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. 1979. Chloroethanes: A review of Toxicity.
Amer. Ind. Hyg. Assoc. J., 40; 46-60, March 1979.
20. U.S. EPA 1979. Chlorinated Ethanes: Ambient Water Quality Criteria
(Draft)
21. NCI 1977. Bioassay of 1,1,1-trichloroethane for possible carcinogen-
icity. Carcinog. Tech. Rep. Ser. NCI-CG-TR-3.
22. Price, P.J. et al. 1978. Transforming activities of trichloroethane
and proposed industrial alternatives.
23. U.S. EPA Report 1980 in Vitro 14:290. In Vitro microbiological muta-
genicity of 81 compounds.
-------
IV. References (Continued)
24. Schwetz, B.A. et al. 1974. Embryo and fetal toxicity of inhaled
carbon tetrachloride, 1,1-dichloroethane and methylchloroform in
rats. Toxicol. Appl. Pharmacol. 28: 452.
25. Walter, P. Chlorinated hydrocarbon toxicity a monograph PB-257185
Natl. Tech. Inf. Serv. Springfield, Virginia.
26. U.S. EPA, 1979. In-depth studies on health and environmental impact
of selected water pollutants. Contract No. 68-01-4646.
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, 1978.
28. Elovaara, E., et al. Effects of CH2C12, CH3C13, TCE, Perc and
Toluene in the development of Chick Embryos, Toxicology 12; 111-119,
1979.
29. Truhaut, R., Lich, N.P., Dutertre-Catella, H. , Molas, G., Huyen,
V.N.: Toxicological 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., I.W.F. Davidson, and M.M. Greenberg. EPA Health
Assessment Report of 1,2-Dichloroethane (Ethylene Diehloride (Ethylene
Dichloride) In Preparation.
31. National Cancer Institute. Bioassay of 1,1,2,2-Tetrachloroethane
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.
32. Brem H., et al. 1974. The Mutagenicity and DNA-modifying effect
of Haloalkanes. Cancer. Res. 34: 2576.
33. National Institute for Occupational Safety and Health. Criteria
for a Recommended Standard ... Occupational Exposure to 1,1,2,2-
Tetrachloroethane. U.S. Department Public Health Service, Center
for Disease Control, National Institute for Occupational Safety and
Health, DHEW (NIOSH) Publication No. 77-121, December 1976.
34. Page, Norbert P., and Jack L. Arthur Trichloroethylene. Special
Occupational Hazard Review with Control Recommendations DHEW
Publication No. (NIOSH) 78-130. January, 1978.
35. Blair, et al. 1979. Causes of death among laundry and dry cleaning
workers. Am. J. Publ. Health 69: 508-511.
- 3S4 '
-------
IV. References (Continued)
36. IARC Monographs, Volume 20: 545-572.
37. U.S. EPA, 1979. Trichloroethylene. Ambient Water Quality Criteria.
38. National Cancer Institute (1977) Bioassay of Tetrachloroethylene
for Possible Carcinogenicity, DHEW Publication No. (NIH) 77-813.
39. C. Parker, EPA, ECHO/ICTP.
40. Bignell, P.C. & Ellenberger, H.A. (1977). Obstructive jaundice
due to a chlorinated hydrocarbon in breast milk. Con. Med. Assoc.
£., 117, 1047-1048.
41. Viola, P.L., et al. Oncogenic 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 & 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 3: 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.
49. Environmental Health Perspectives, 1977. Vol. 21, 333 pp.
50. USEPA, 1979 Vinylidene Chloride Hazard Profile, USEPA/ECAO
Cincinnati, Ohio 45268 1979.
51. National Cancer Institute, 1976. Report on Carcinogenesis Bioassay
of Chloroform. National Technical Inf. Serv. PB-264018. Spring-
field, VA.
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IV. References (Continued)
52. USEPA, 1979. Trichloromethane (chloroform) Hazard Profile, USEPA/
ECAO Cincinnati, Ohio 45268. 1979.
53. McCabe, L.J., 1975. Association between Trihalomethanes in Drinking
Water (NORS data) and Mortality. Draft report. U.S. Environmental
Protection Agency.
54. Thompson, D.J., et al. 1974. Teratology Studies on Orally Admin-
istered Chloroform in the Rat and Rabbit. Toxicol. Appl. Pharmacol.
29: 348.
55. Schwetz, B.A., et al. 1974. Embryo and Fetotoxicity of Inhaled
Chloroform in Rats. Toxicol. Appl. Pharmacol. 28: 442.
56. National Cancer Institute. Carcinogens Bioassay of Carbon Tetra-
choride, 1976.
57. U.S. EPA. Carbon Tetrachloride: Ambient Water Quality Criteria
Document, 1979.
58. U.S. EPA, 1979. Water-Related Environmental Fate of 129 Priority
Pollutants. EPA-440/4-79-029b.
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. Determination of Sources of Selected Chemicals in
Waters and Amounts from these Sources, 1977.
61. "Combustion Formation and Emission of Trace Species",
John B. Edwards, Ann Arbor Science, 1977. .
62. NIOSH Criteria for Recommended Standard: Occupational Exposure
to Phosgene, HEW, PHS, COL, HIOSH, 1976.
63. Chemical and Process Technology Encyclopedia, McGraw Hill, 1974.
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. Cancer Assessment's Group List of Carcinogens, April 22, 1980.
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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 wastewater from
the production of chlorofluoromethanes via the liquid phase
fluorination process is a solid waste which may 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.
(3) Chloroform and carbon tetrachloride 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 fluorination and will be in the aqueous waste
stream. The substantial quantity of waste generated increases
the possibility of exposure should mismanagement occur.
(5) Damage incidents involving the contamination of groundwater
by antimony compounds, chloroform and carbon tetrachloride
confirm the ability of these waste constituents to be mobile,
persist, and cause substantial harm.*
II. Industry Profile and Process Description (29,30)
Chlorofluoromethanes are manufactured by the fluorination 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 corrosivity 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.
-------
chlorofluoromethanes that are produced via liquid phase
fluorination.* The commercial products produced by this
segment of the fluorocarbon industry include chlorotrifluoro-
methane (CC1F3), dichlorodifluoromethane (CCl2F2), trichloro-
fluoromethane (CC13F) , and chlorodifluoromethane (CHC1F2). Of
the five (5) 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:
(1)
(2)
(3)
(4)
(5)
Plant Size - Million
Company
DuPont
Allied Chemical
Kaiser Aluminum
& Chemical
Pennwalt
Racon, Inc.
Location Pounds Per Year
Antioch, CA
Deepwater, NJ
East Chicago, IN
** Louisville, KY
Matague, MI 500
Baton Rouge, LA
Danville, IL
Elizabeth, NJ
El Segundo, CA 190
Gramercey, LA 80
Calvert City, KY
Throughfare, NJ 60
** Wichita, KS 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.
-359-
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The chlorofluoromethanes in the product family of concern are
manufactured by fluorinating either carbon tetrachloride (CCl^) or
chloroform (CHC13) using hydrogen fluoride (HF) and antimony penta-
chloride (SbC^) as a catalyst (see Figure 1) . Carbon tetrachlorid*
is used as a starting material when trichlorofluoromethane (CC13F),
dichlorodifluoromethane (CC12F2), and chlorotrifluoromethane (CClF3)
are the desired products. (Tetrafluoromethane (CF4> is also formed
as a co-product waste.) Chloroform is used as feedstock when
chlorodifluoromethane (CHC1F2) and dichlorofluoromethane (CHC^F)
are the desired products. (A small amount of trichlorotrifluoroethi
(C2C13F3) and trifluoromethane (CHF3> are formed as co-product wasti
In both processes, the chlorine (Cl) in the starting materials is
successively replaced with fluorine (F) . For example, starting witl;
carbon tetrachloride (CC14), and hydrogen fluoride, the reactionist
carried out continuously to produce the product mix desired, usually
a 50/50 blend of trichlorof luoromethane (CC^F) and dichlorodifluori
methane (CCl^F^) 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
(SbCl5) is reduced to antimony trichloride (SbCl^). A slip
K
-------
I
IAJ
HEAT
LIQUID PHASE
FLUORINATION,
CF4.CHF3. CCiFa
VENT
*~ (TO OTHER PLANT USES)
HF SOL'N.
HEAT
HEAT
~l
COOLING
CRUDE
PRODUCT
+ HCI
,RECYCLEV
CHLORO AND
Cl ILORO-
FLUORO
ARBONS; ,
CHLORO-
CARDONS
STILLATION FROM
LIQUID PHASE
FLUORINATION 2]
CO
10- U-
1O /
^klt•?/
SEP.. NEUT.,
OF PRODS. FROM
LIQ.PH. FLUORIN.3
DECANT
SPENT
CATALYST
DISTILLATE
CRUDE
PRODUCT
CALCIUM
FLUORIDE
SILICA
GEL
WORN-OUT
MOLECULAF
1 SIEVE
*- TO LANDFILL
TO HF PLANT
Figure 1. FLOWSHEET FOR PRODUCTION OF FLUOROCARBONS
BY LIQUID PHASE FLUORINATION (Baged on lnformatlon ln Refere'nce§ 29 and
-------
s
cream is taken from (F) (see Figure 1.) to remove an aliquot
portion of the spent catalyst. After washing, the aqueous
spent 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
antimony pentachloride, which is recycled to the fluorinator.)
Ill. 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
a
-362-
-------
that 30-60 thousand Ibs. of spent catalyst are generated annually
and will be contained in the spent catalyst wastewater.* The
wastewater will also contain dissolved chloroform and carbon
tetrachloride in maximum concentrations of about 0.8 gms/100 gms
of wastewater (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 typically 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
improperly designed or managed disposal or storage sites and
contaminate ground and surface waters. Antimony trichloride
is extremely soluble (601.6 gm/100 gm H20 @ 0°C), chloroform
is highly soluble (2200 mg/1 @ 25°C), and carbon tetrachloride
is quite soluble (800 mg/1 @ 20°C). Chloroform and carbon
tetrachloride are also highly volatile: 160 mm Hg @ 20°C and
91 mm Hg @ 20°C, respectively (water has a volatility of about
17.5 mm Hg
-------
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, persist and cause substantial hazard
if improperly managed. The migratory potential of antimony
compounds is confirmed by the fact that groundwater contamina-
tion 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
-------
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 te trachloride 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 . ( ^ > ^8 ) The incidents of the migration of these harm-
ful constituents previously mentioned (see p, 9) demonstrate
-364-
-------
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 LD5o=800 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 mice 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 ppm.
Industrial Recognition of Hazard - Chlorofrom has
been given a toxic hazard rating via oral routes by Sax in
Dangerous Properties of Industrial Materials.
-------
2. Carbon Tetrachlorlde
Health Effects - Carbon tetrachloride is a very
potent carcinogen (11) and has also been shown t,o be teratogenic
in rats when inhaled at low concentrations (12). It has also
been evaluated by GAG 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 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 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 (19).
-------
Regulations - OSHA has set a TWA for carbon
tetrachloride as 10 ppm. Carbon tetrachloride has been banned
under the Hazardous Substances Act by the Consumer Product
Safety Commission.
Industrial Recognition of Hazard - According to Sax,
Dangerous Properties of Industrial Materials, carbon
tetrachloride is considered a high systemic poison through
ingestion and inhalation.
3. Antimony Compounds
Health Effects - Chronic antimony exposure has been
most commonly associated with pulmonary, cardiovascular, (20)
dermal, and certain effects on reproduction, (21) development,
(22) and longevity (23,24). Antimony trichloride [oral rat
LD5Q=525 mg/kg] and antimony pentachloride [oral rat 1050=!,115
mg/kg] are considered toxic. Adverse effects can be expected
from the tri- and pentachlorides based on acute toxicities of
the compounds to rats. Additional information on the adverse
health effects of antimony compounds can be found in Appendix A,
Regulations - OSHA has set the TWA at 0.5 mg/rn3.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists antimony as highly
toxic via oral and inhalation routes.
-------
IV. References
1. Jennings, A.F. and M.C. Schroeder, 1968. Laboratory
Evaluation of Selected Radioisotopes as Groundwater
Tracers. Water Resources Res. 4:829-838.
2. Iowa Department of Environmental Quality, South Charles
City, IA, 1977.
3. Zoetlman, B.C.J., et al. 1979. Persistent Organic
Pollutants in River Water and Ground Water of the
Netherlands. Presented at 3rd International Symposium
on Aquatic Pollutants, Oct. 15-17, Jekyll Island, Ga.
4. Water Quality Issues in Massachusetts, Chemical
Contamination, Special Legislative Commission on Water
Supply, Sept. 1979.
5. Naitonal Cancer Institute, 1976. Report on Carcinogenesis
Bioassay of Chloroform. National Technical Inf. Serv. PB-
264018. Springfield, Virginia.
6. McCabe, L.J. 1975. Association between trihalomethanes
in drinking water (NORS data) and mortality. Draft
report. U.S. Environmental Protection Agency.
7. U.S. EPA, 1979. Trichloromethane (Chloroform), Hazard
Profile, USEPA/ECAO, Cincinnati, Ohio, 1979.
8. Schwetz, B.A., et al. 1974. Embroy and Tetotoxicity of
Inhaled Chloroform in Rats. Toxicol. Appl. Pharmacol.
28:442.
9. Thompson, D.J., et al. 1974. Teratology Studies on
Orally Administered Chloroform in the Rat and Rabbit.
Toxicol. Appl. Pharmacol. 29:348
10. National Academy of Sciences. 1978a. Non-fluorinated
Halomethanes in the Environment, Environmental Studies
Board, National Res. Council, Washington, D.C.
11. National Cancer Institute, 1976. Carcinogen Bioassay of
Carbon Tetrachloride.
12. Schwetz, B.A., B.K.K. Leong and P.J. Gehring, "Embroy-
and Fetotoxicity of Inhaled Carbon Tetrachloride, 1,1-
Dichloroethane and Methyl Ethyl Ketone in Rats,"
Toxicology and Applied Pharamacology, Vol. 28, No. 3,
June 1974, p. 452-464.
IX
-------
13. Association of American* Pesticide Control Officials,
Inc. 1966 ed., Pesticide Chemical Official Compendium
p. 198.
14. Texas Medical Association, Texas Medicine, Vol. 69,
p. 86, 1973.
15. Davis, Paul A. "Carbon Tetrachloride as an Industrial
Hazard," The Journal of the American Medical Association.
Vol. 103, July-Dec. 1934, p. 962-966.
16. U.S. EPA. Carbon Tetrachloride: Ambient Water Quality
Criteria Document, 1979.
17. U.S. EPA. Water-related Environmental Fate of 129 Priority
Pollutants. EPA-440/4-79-0296, 1979.
18. Von Oettingen, W.F., the Halogenated Hydrocarbons of
Industrial and Toxicological Importance. In: Elsevier
Monographs on Toxic Agents, E. Browning, Ed., 1964.
19. U.S. EPA. Determination of Sources of Selected Chemicals
in Waters and Amounts from These Sources, 1977.
20. Brieger, H. , et al. 1954. Industrial Antimony Poisoning.
Ind. Med. Surg. 23:521.
21. Belyaeva, A.P. 1967. The Effect of Antimony on
Reproduction. Gig. Truda. Prof. Zabel 11:32.
22. Gross, Hal, 1955. Toxicological Study of Calcium
Halophosphate Phosphors and Antimony Trioxide in Acute
and Chronic Toxicity and Some Pharmacological Aspects.
Arch. Indust. Health 11:473.
23. Schroeder, H.A., 1970, A Sensible Look at Air Pollution
by Metals. Arch. Environ. Health, 21:798.
24. Schroeder, H.A., and L.A. Kraemer. 1974. Cardiovascular
Mortality, Municipal Water, and Corrosion. Arch. Environ.
Health. 28:303.
25. Casarett and Doull, Toxicology, p. 627, MacMillan, New York.
26. Personal Communication, Richard Deutsch, E.I. Dupont de
Nemours and Company, Louisville, KY, December 1979.
27. Sax, N. Irving, Dangerous Properties of Industrial Materials.
^th Edition, Litton Education Publishing, Inc., 1975.
-------
28. Dawson, English, and Petty, 1980. Physical Chemical
Properties of Hazardous Waste Constituents.
29. Kirk-Othemer. Encyclopedia of Chemical Technology. j[.
John Wiley and Sons,Inc.,New York,1964.
30. Lowenheim, F.A. and Moran, M.K. Faith, Keyes and Clark's
Industrial Chemistry. Fourth EdTJohn Wiley and Sons,~
New York, 1975.
31. SRI International, Directory of Chemical Producers -
United States, Menlo Park, California, 1979.
32. CAG List of Carcinogens, April 22, 1980.
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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 Basis for Listing
Distillation bottom tars from the production of phenol/acetone from
cumene contain 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 a suspect carcinogen and 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 incinerator combustion.
*T&e 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.
-373-
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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 acetone^.
B. Manufacturing Process(13,14)
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 hydrpper-
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
-------
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
then 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.
-375"-
-------
CUMENE
RECYCLE
RECYCLE
Na2CO3
SODIUM STEARATE
CUMENE
HYDROPEROXIDATION
REACTOR
AIR
J
ACE1GNE
(TO PURIFICATION)
DILUTE
SODIUM HYDROXIDE
Zh:
ofe
o
80%
I
U)
N/
e^
i
CUMENE HYDRO-
PEROXIDE
20%
CUMENE
O
SEPARATOR
RECYCLE
cc
DC
UJ
z
ACID
SEPARATOR
ujO
OH
<2
O
WATER
cc
I
mO
r
oc
UJ
N
O
UJ
O
CC
O
RECOVERED
CUMENE
(TO a -METHYL
STYRENE REMOVAL
& RECYCLE)
PHENOL
UjQ
CRUDE
/PHENOL
SURGE
to
cc
ui
H
I
LIGHT ENDS
(TO ACETONE
PURIFICATION
OR INCINERATION)
ACETOPHENONE
D.CC
D
CL
PURIFIED
PHENOL
BOTTOMS
PHENOL. ACETOPHENONE. TARS
Figure 1. FLOW DIAGRAM— PHENOL/ACETONE FROM CUMENE
(MODIFIED FROM REFERENCE 13)
TARS
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-X-
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
lb 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 polyaromatic 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 a suspect
carcinogen and is toxic. The tars are also suspect carcinogens due
to the presence of polycyclic aromatic hydrocarbons (PAH). These
waste constituents are capable of migration from the waste to ground-
water. Phenol is extremely soluble (67,000 ppm 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 predictions 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, lowa.d^) Levels some
eight times above the proposed water quality criteria were found in
runoff 1.5 miles from a disposal site near Byron, Illinois.(13)*
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 Kin-Buc Landfill (Middlesex, NJ)(13>.
The primary means of disposal of residue are landfilling or in-
cineration,^' 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 leach-
ate migration to groundwater, and resulting 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
biodegrades at a moderate rate in surface water and soil, but moves
readily (App. B.). Even with persistence of only a few days, the
rapid 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
humans 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 Sess., 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 toxicity 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.(15) 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 one 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-
carbons (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 LD5Q in animals (dog,
rabbit) is 600 mg/kgW. 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(7). 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
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 it migrates from the waste in small concentrations.
-------
industrial waste disposal. Polycyclic aromatic hydrocarbons are desig-
nated as priority pollutants (acenaphthylene, anthracene, benzo(a)
anthrocene, 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.(^)
Regulations - The NIOSH 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/m^ 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 - NIOSH lists phenol as a suspected carcin-
ogen. Prolonged exposure to phenol vapors has resulted in human diges-
tive disturbances and skin eruptions(10). Damage to liver and kidneys
from this exposure can lead to death.(10) Exposure to phenol can re-
sult 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]/11' Additional information and spe-
-------
-X-
cific references on the adverse effects of phenol can be found in Ap-
pendix A.
Ecological Effects - Concentrations of phenol as low as 79
mg/l have been reported to be toxic to freshwater minnows(12),
Regulatory Recognition of Hazard - OSHA has set a TLV for
phenol at 5 ppm.
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. Synthetic Organic Chemicals, United States Production and Sales,
1978. U.S. Trade Commission, Washington, DC
2. U.S. EPA, Survey Reports on Atmospheric Emissions from the Petro-
chemical Industry, Volume III. EPA 450/337/005C. Research Tri-
angle Park, NC April 1974.
3. Stuewe, C. Emission Control Options for the Synthetic Organic Chem-
icals Manufacturing Industry, Trip Report - Allied Chemical Cor-
poration, Frankford, PA, EPA Contract No. 68-02-2577, March 1977.
4. U.S. EPA, 1979 Phenol: Ambient Water Quality Criteria (Draft)
5. Baker, E.L. et al. 1978. Phenol Poisoning Due to Contaminated
Drinking Water. Archives Env. Health, Mar/Apr pp. 89-94.
6. NIOSH Registry of Toxic Effects of Chemical Substances. U.S.
Dept. of health, Educatin, and Welfare. January 1979 p. 370.
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, Cancer Assessment Group, Derivation of the Water Quality
Criterion for Polycyclic Aromatic Hydrocarbone, July 1979.
9. Carlton, W. W. Experimental Coal Tar Poisoning in the White Peking
Duck. Avian Dis 10:484-502, 1966.
10. Sax, N. Dangerous Properties of Industrial Materials, 1975. 4th
Ed. Van Nostrand Reinhold Co., New York, p. 1008.
11. EPA Multimedia Environmental Goals for Environmental Assessment.
Volume II. Nov. 1977. EPA-600/7-77-1366.
-------
-X-
12. National Academy of Sciences, National Academy of Engineering,
Water Quality Criteria 1972. A Report, National Academy of Sci-
ences, Washington, DC EPA-R3-73-033 (1973).
13. Lowenheim and Koran, Faith, Reyes, and Clarks's Industrial
Chemicals, 4th ed., John Wiley and Sons, Inc., 1975
14. Industrial Process Profiles for Environmental Use: Chapter 6,
The Industrial Organic Chemicals Industry. Ralmond Liepins, Forest
Mixon, Charles Hudak, and Terry Parsons, Beb. 1977, EPA - 600/2-
77-023f.
15. Section 304(a)(l) Draft Water Quality Criteria Document, Poly-
nuclear Aromatic Hydrocarbons.
16. Dawson, English and Patty. 1980. Physical Chemical Properties
of Hazardous Waste Constituents.
-3*5--
-------
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 napthalene (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 napthalene or ortho-xylene results in the
generation of distillation residues which contain carcinogens,
suspected 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, napthoquinones, quinones,
and miscellaneous organic compounds composed primarily of
polynuclear tarlike materials.
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 and miscellaneous
organic compounds composed principally of polynuclear tar-
like materials. The heavy bottoms from the napthalene-based
process will contain napthoquinones and the heavy bottoms
from the ortho-xylene-based process will contain quinones.
(2) Phthalic anhydride, maleic anhydride, napthoquinone,
quinones and the tars containing miscellaneous organic com-
pounds are organic toxicants. Napthoquinone and maleic
anhydride are animal carcinogens and quinones are suspected
carcinogens. The tar-like waste constituents may also
contain fused ring components that are potential carcinogens.
(3) More than 16 million pounds of the constituents of
concern will be generated annually and require disposal as
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 pollu-
tion through release of hazardous vapors, due to incomplete
combustion. Transportation of wastes off-site by contract
haulers increases the possibility of mismanagement.*
II. Sources of Waste and Typical Disposal Practices
A. Industry Profile
The major use of phthalic anhydride is in the
manufacture of plastics, plasticizers, paints and synthetic
resins (3). Producers of phthalic anhydride from ortho-xylene
or napthalene and the production capacities of these plants
are listed in Table 1. About 70% of industry capacity is
ortho-xylene-based.
*Although no data on the corrosivity of these waste
streams are currently available, the Agency believes that
phthalic anhydride, maleic anhydride and napthoquinone are
highly corrosive materials, and that these waste streams may
therefore be corrosive. Under §§261.22 and 262.11, generators
of these waste streams are responsible for testing their
wastes in order to determine whether they are corrosive.
-SS7-
-------
Table 1. Producers of phthalic anhydride
Producer
Allied Chem. Corp.
Specialty Chems. Div.
BASF Wyandotta Corp.
Colors and Intermediate Group
Intermediates Div.
Exxon Corp.
Exxon Chem. Co., div.
Exxon Chem. Co. U.S.A.
Koppers Co., Inc.
Organic Materials Group
Monsanto Co.
Monsanto Chem. Intermediates Co.
Location
El Segundo, Calif.
Kearny, N.J
Baton Rouge, La
Bridgeville, Pa
Cicero, 111.
Annual Capacity
(Millions of Pounds)
36
150
130
90
235
Raw Material
Bridgeport, N.J,
Texas City, Tex.
85
150
o-xylene
o-xylene
o-xylene
Desulfurized coal-tar
naphthalene
o-xylene or
naphthalene
Petroleum naphthalene
o-xylene
Occidental Petroleum Corp.
Hooker Chem. Corp., subsid.
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.
Arecibo, P.R.
Richmond, Calif.
Millsdale, 111.
Neville Island, Pa
TOTAL
87
50
100
205
1318
o-xylene
o-xylene
o-xylene
Desulfurized coal tar
naphthalene
Source: Reference 1
-------
Manufacturing Process
phthalic anhydride is manufactured by the vapor phase
oxidation of ortho-xylene or napthalene (see Figures 1 and
2 for flow diagrams). The primary napthalene-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
^--_TIL i
VzOs
/\
i
0 -r 2HrO + 2CO2
NAPHTHALENE
Ortho-xylene based
PHTHALIC ANHYDRIDE
V2°5
+ 3 0.
0-xylene Oxygen
3 H20
Phthalic
Anhydride (PAN) Watei
In the napthalene-based process, napthalene 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 tubes). Both processes typically use a vanadium
pentoxide catalyst (3).
-3<3tt-
-------
i
V
NAPTHALENE.
AIR
DISTILLATION
COLUMN
FILTER
CATALYST
RECYCLE
MULTIPLE
SWITCH
CONDENSERS
1
CRUDE
STORAGE
FLUIDIZED
BED REACTOR
-ALIGHT ENDS
PURIFIED
PHTHALIC
ANHYDRIDE
BOTTOMS
STORAGE
PRETREATMENT
TANK
Figure 1. PHTHALIC ANHYDRIDE PRODUCTION FROM NAPHTHALENE
Source: Reference 3
-------
H gure 2. pntna i ic nnnyari
i~lV*fl I I wilt v* • **i »w
AltZ.
S.TE-AU
(Source: reference 3)
MULTIPLE-
MOT A.VJO COOU
O«U
&4.1.T COOLfcrR
11II
TO
•*• nj c i vj tr a. /kT ox.
VfrUT
Cg.UOEr
pe.ooucT
(OOLTErU)
HEM EXCHANGER
-o
I
~2
J)
2
4
0)
tJ
^-
JJ
cJ
a
BLfjlOUEr
i. UUMtfetfeO btet^M^ A.OLC:
fHEr
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3
3
J
0
0
3
&
-
l-
lA
^-^ •<— **^
^
•3
3
0
.»
4
5
a
a.
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J^>.
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^ t
-T~a
A
-------
The reactor effluent from both processes will contain
phthalic anhydride, maleic anhydride*, and miscellaneous organ-
ics (including fused-ring compounds). The ortho-xylene-based
process will generate quinones as part of its waste stream. The
napthalene-based process will generate napthoquinones.(3)
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 napthalene-based plant, with a
published production capacity of 125 million pounds/year
phthalic anhydride, reported to dispose of 58,000 pounds/month
light ends and 400,000 pounds/month bottoms. This plant had
these wastes hauled off-site by a contractor O), probably for
disposal by landfill.
A second napthalene-based plant, with nominal capacity
of 90 million pounds/year, reported a combined total waste
*Process chemistry indicates that maleic anhydride will
be present in lower concentrations in the effluent generated
from ortho-xylene-based phthalic anhydride production.
-------
load of 45,000 pounds/month. This plant utilized an on-site
landfill f°r 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(3).
Based on typical material balance data(3)*, it can fce
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
Amount from xylene-based production
(million Ibs./yr.)
light ends heavy bottoms
>4.9 X).9
**
Amount from Napthalene-based
(million Ibs./yr.)
light ends heavy bottoms
>0.2 >2.5
>1.9
quinones ***
napthoquinone
misc. Org. (as tars) >1.1
*Estimates based on typical material balance data for average plants
producing 130 million Ibs./yr of phthalic anhydride from ortho-xylene
and from napthalene. 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 napthalene, due to
the nature of the basic chemical reactions.
***Although no data are currently available on the concentrations of
quinones in the bottoms from ortho-xylene-based production of phthalic
anhydride, process chemistry indicates that quinones will be present
in this waste stream, due to the oxidation of para-hydrogens on the
xylene molecules.
-------
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 contractorO) , probably to a landfill disposal site.
Distillation bottoms may also be incinerated, but are typically
disposed of in landfills either on or off-site.(3)
III. Discussion of Basis for Listing
A» Hazards Posed by the Waste
As noted above, distillation residues (light ends
and heavy bottoms) from phthalic anhydride production contain
the following components as they are discharged from the
plant distillation units:
Phthalic anhydride
Maleic anhydride *>
Quinones
Napthoquinones
Miscellaneous polynuclear organic compounds in
distillation tars
All of the above waste constituents are toxic. Napthoquinone
and maleic anhydride are demonstrated carcinogens, and quinones
are suspected carcinogens. The miscellaneous organic component
of this waste has not been chemically characterized but is composed
principally of tar-like materials probably including fused-ring
compounds that are potential carcinogens.
*Maleic 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.
-y-
-VH-
-------
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 landfilling
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. Various quinones have been identified in rivers, wells,
groundwater, effluent from landfill leachate, and in finished
drinking water. Phthalic anhydride has been identified in
finished drinking water.(14)
Napthaquinones and quinones are 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
-ViS-
-------
polyneuritis in workers exposed primarily to dibutyl^phthalate
(see Appendix A). Further information on incinerator emission
content is solicited by the Agency.
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 wildlife through direct exposure to 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 a'ffected. 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.(5) 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=0.25 ppm for an 8-hour day.
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.
-yt-
-------
2. Phthalic Anhydride
Health Effects - There is evidence that phthalic
anhydride may act as a teratogen in chick embryos'6'. 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'°>9).
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. Napthoquinone
Health Effects - Napthoquinone 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 naphthoquinone exposure
which may develop into hemolytic anemia. Naphtoquinone is also
suspected of causing adverse reproductive effects. Additional
-------
information and specific references on the adverse effects
of napthoquinone can be found in Appendix A.
Ecological Effects - Napthoquinone, 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 - Naphthoquinone
is designated in Saxfs Dangerous Properties of Industrial Materials
as a moderately toxic irritant to skin, eyes, and the upper
respiratory tract.
4. Quinone - (p-Bezoquinone; 1,4-Benzoquinone)
Health Effects - Quinones are highly toxic [Oral rat
LD50=120 mg/Kg]. Quinone has been reported to produce neo-
plasms but upon review by the International Agency for Research
on Cancer it was determined that there was insufficient data to
conclude that it was a carcinogen.(H/ Upon exposure local
changes in humans may include discoloration, severe irritation,
erythemia, swelling, and the formation of papules and vesicles.
Prolonged contact may lead to necrosis. (12) Vapors condensing
upon the eyes are capable of inducing serious disturbances of
vision. Ulceration of the cornea has resulted from one brief
exposure to a high concentration of the vapor of quinone, as
well as from repeated exposures to moderately high concentra-
tions . (12)
Regulations - Threshold limit values have been
established in air for quinone in the United States at a
concentration of 0.1 ppm, and the U.S.S.R. at a concentration
of 0.01 ppm.(13)
-------
Industrial Recognition of Hazard - Quinone is
designated in Sax's Dangerous Properties of Industrial
Materials as highly toxic via oral and inhalation routes.
5. Tars
Health Effects - Tar-like material containing quinones
and asphalt materials must be considered suspect carcinogens
based on the data available on chemical tars. (NIOSH Criteria
for Recommended Standard for Occupational Exposure to Coal Tar
Products.) Considering the highly reactive nature of maleic
anhydride, various toxic effects such as skin and respiratory
tract irritation and sensitization would also be expected from
tars containing this material.
Industrial Recognition of Hazard - Sax's Dangerous
Properties of Industrial Materials designates dehydrated and
liquid tars as highly toxic skin and respiratory irritants
when exposure is of long duration. Tar dusts are designated
as moderate skin and eye irritants upon acute exposure.
-yS-
-WOO-
-------
IV. References
1. SRI International, Directory of Chemical Producers -
United States, Menlo Park, California, 1979.
2. U.S. Environmental Protection Agency, Source Assessment:
Phthalic Anhydride (Air Emissions), EPA-600/2076-032d ,
Washington, B.C., December, 1976.
3. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Engineering and Cost
Study of Air Pollution Control for the Petrochemical
Industry, Volume 7; Phthalic Anhydride Manufacture from
Ortho-Xylene, EPA-450/3-73-006g, Research Triangle Park,
North Carolina, July, 1975. PB 245 277
4. Protsenko, E.I., 1970. Gonadotropic Action of Phthalic
'Anhydride. Gig. Sanit. 35;105.
5. NIOSH, Registry of Toxic Effects of Chemical Substances,
1979. GPO.
6. Preliminary Environmental Hazard Assessment of Chlorinated
Naphthalenes, Silicones, Flourocarbons, Benzenephlycarboxylates
and Chloraphearls, Syracuse University Research Corporation,
EPA Report PB-238-074, 1973.
7. American Conference of Governmental Industrial Hygienists,
1971. Documentation of Threshold Limit Values for
Substances in Workroom Air. 3rd Edition, pg. 263.
8. Markman and Savinkina, 1964. The Condition of the Lungs
of Workers in Phthalic Anhydride Production (an X-ray study).
Kemerovo 35.
9. Plunkett, E.R., Handbook of Industrial Toxicology, pg. 338.
10. Applegate, V.C., J.H. Howell, and A.E. Hall, Jr. 1957.
Toxicity of 4,346 chemicals to larval lampreys and
fishes. Department of Interior, Special Scientific
Report Number 207.
11. IARC Monographs on the Evaluation of Carcinogenic Risk
of Chemicals to Man, Vol. 15. World Health Organization.
(1977).
12. Patty, F.A. (editor). Industrial Hygien and Toxicology.
Second Revised Edition. Interscience Publishers. New York
1967.
-------
13. Verschueren, Karel. Handbook of Environmental Data on
Organic Chemicals. Van Nostrond Reinhild Co., New York.
1977.
14. Shackelford and Keith, Frequency of Organic Compounds
Identified in Water, EPA-600/4-76-062, Environmental
Research Laboratory, Athens, Ga., Dec. '76.
-yf-
-------
LISTING BACKGROUND DOCUMENT
NITROBENZENE PRODUCTION
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 human 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 (^1^02) (about 97%)
is as an intermediate in the manufacture of aniline dyes.^
The balance is purified for use chiefly as a solvent or in the manufac-
-------
ture 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^)
Company
American Cyanamid Co.
Organic Chems 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 Chems., Inc.
Facility
Bound Brook, NJ
Willow Island, WV
Beaumont, TX
Gibbstown, NJ
Pascagoula, MS
New Martinsville, WV
Geismar, LA
1978
Production
Capacity
(Gg)*
48
33
140
90
151
61
34
TOTAL
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
was 260 (103) mt.<2'
-------
The production of nitrobenzene has been fairly stable 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 3% of production, or 7.8 Gg/yr (8580 tons).^22)
B. Manufacturing Process (2D
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% sulfuric acid; 32-39% nitric acid; 8% water;
a stochiometric 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 SULFURIC
NITRIC ACID
BENZENE
s~
C
~x
D
V
:
TO'ANILINE'
MANUFACTURE
.. •* HFC A MTFR < . '
i
SPENT MIXED
ACIDS TO
NazCOs
H2O NITROBENZENE
< -
WASHING
*" DECANTER
WASTE
WATER
C
1
ISTILLATIO
1
ORGANIC
WASTES
M
I
o
-------
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 (0.1%) and
paraffinic hydrocarbons of the C$ to CQ range (0.1%). (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.
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III. Discussion of Basis for Listing
A. Hazards Posed by Waste
As stated above, the constituents of concern in this waste are
meta-dinitrobenzene, an acutely toxic compound, and 2-4-dinitroben-
zene, a carcinogen and mutagen. Both of these constituents are esti-
mated 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 come 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, meta-dinitrobenzene has been demonstrated to be only
slowly biodegradable in a synthetically prepared sewage effluent. ^>5) '
-WO*-
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If the wastes are landfilled, 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 groundwater 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 nitrotoluenes 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-dinitrobenzene
Health Effects - Meta-dinitrobenzene is extremely toxic
[LD5Q rat 30mg/Kg.] acting as a potent methemoglobin-forming agent,
i.e., an agent that reduces the oxygen-carrying capacity of the blood,
a condition that can rapidly lead to death.(?) Meta-dinitrobenzene
can also cause liver damage, serious visual disturbances, and severe
anemia, as well as a variety of central nervous system and gastrointes-
tinal symptoms.(?)(8) Meta-dinitrobenzene can be stored in body fat.
Exposure to sunlight or ingestion of alcohol may potentiate or in-
crease the adverse effects of poisoning.(?) Meta-dinitrobenzene
is designated as a priority pollutant under Section 307(a) of the
CWA. Additional information on the adverse effects of meta-dinitro-
benzene 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.^9'^-10' Meta-dinitrobenzene has been shown to inhibt photosyn-
thesis in algae. (ID
ft
-------
Regulatory Recognition of Hazard - OSHA has set the TWA
for dinitrobenzene at 0.15 ppm. Dinitrobenzene is regulated by the
Office of Water and Waste Management of EPA under the Clean Water Act,
Section 311. Technical assistance has been requested to obtain data
on environmental effects, high-volume production, and spill reports.
Industrial Recognition of Hazard - According to handbooks
used by industry such as, Sax, Dangerous Properties of Industrial
Chemicals, (12) the oral toxic hazard rating is high for dinitro-
benzene. When heated, it is dangerous, decomposing to emit toxic
fumes; it is also an explosion hazard. According to Plunkett,
Handbook of Industrial Toxicology, (8) M-dinitrobenzene is extremely
toxic by oral, inhalation, and percutaneous routes. According to
Patty, Industrial Toxicology, '^) m-dinitrobenzene is highly toxic.
2. 2,4-Dinitrotoluene
Health Effects This compound has been shown to be a
carcinogen^) (15) an
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Ecological Effects - An aquatic toxicity for 2,4-dinitrotoluene
of 10-100 ppm has been established^20).
Regulatory Recognition of Hazard OSHA has set the TWA for
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 teterials(12)
the oral toxic hazard rating for 2,4-dinitrotoluene is very high.
-------
IV. References
1. Gruber, G.I. Assessment of Industrial Hazardous Waste Practices,
Organic Chemicals, Pesticides, and Explosive Industries. EPA/530/
SW-118C TRW Systems Group, Redondo Beach, California, January, 1976.
2. Directory of Chemical Producers, 1979. Stanford Research Institute.
3. Recommended tethods of Reduction, Neutralization, Recovery, or Dis-
posal of Hazardous Wastes, Volume XI: Industrial and Mmicipal Dis-
posal Candidate Waste Stream Constituent Profile Reports, Organic
Compounds (continued) EPA 670/2-73-053-k, TRW Systems Group, August
1973.
4. Bernhard, E.L. and G.R. Campbell, "The Effects of Chlorination on
Selected Organic Chemicals," U.S. Environmental Protection Agency,
PB-211-160, NTIS, Springfield, Virginia, 1972.
5. G. Bringmann and R. Kuehn, "Biological Decomposition of Nitroto-
luenes and Nitrobenzenes by Azotobacter agilis," Gesundh. Ing.
92(9):273-276 1971.
6. L.A. Allen, "the Effect of Nitro-Compounds and Some Other Sub-
stances on Production of Hydrogen Sulphide by Sulphate-Reducing
Bacteria in Sewage," Proc. Soc. Appl. Bact. (2):26-38, 1949.
7. U.S. EPA, 1976, Investigation of Selected Potential Environmental
Contaminants: Nitroaromatics.
8. Plunkett, E.R., Handbook of Industrial Toxicology.
9. JfcKee and Wolf.. 1963. Water Quality Criteria. The Resource Agen-
cy of California State Water Quality Control Board Publication
No. 3-4.
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10. teinck, et al. 1956. Industrial Waste Water, 2nd Edition, Gustay
fisher Verlag Stugart, p. 536.
11. Howard, et al • 1976. Investigation of Selected Potential Environ-
mental Contaminants; Nitroaromatics, Syracuse Research Corporation,
TR 76-573.
12. Sax, N. Irving, Dangerous Properties of Industrial teterials, Fourth
Edition, New York, Van Nostrant Reinhold Company, 1975.
13. Patty, Frank A. Industrial Hygiene and Toxicology. G.D. Clayton and
F.E. Clayton, (Eds.) Third Revision. NY, Wiley Publications, 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. Bioassay of 2,4-dinitrotoluene for
Possible Carcinogenicity. U.S. Department of Health, Education
and Welfare, Public Health Service, National Institute of Health,
1978.
16. Won, W.D., et al. Mitagenicity Studies on 2,4-dinitrotoluene.
Mitation Research 3jh387 (1976).
17. Hodgson, J.R., et al. Mitagenicity Studies on 2,4-dinitrotoluene.
Mitation Research ^:387 (1976).
18. Friedlander, A. 1900. On the clinical picture of poisoning with
benzene and toluene derivatives with special reference to the so-
called anilinism. Neurol. Centrlbl. 19; 155.
19. teGee, L.C., et al. 1942. tetabolic disturbances'in workers ex-
posed to dinitrotoluene. Am. Jour. Dig. Pis. 9; 329.
20. NIOSH, Registry of Toxic Effects of Chemical Substances, 1976 Edition.
-------
21. Lowenheim and fcbran, Faith, Keyes and Clark*s Industrial
Chemicals, 4th ed., New York, 1975.
22. Synthetic Organic Chemicals U.S. Production and Sale, U.S
International Tariff Commission, 1978.
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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 picoline(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 picolines. Paraldehyde is included on the
NIOSH list of suspected carcinogens. The constit-
uents also exhibit human and aquatic toxicity.
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 75% of the total generated is paraldehyde.
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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 study^1) 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^) does not include
methyl ethyl pyridine among the cyclic intermediates
for which production and sales data are available.
The TRW study
identified Union Carbide
as a major producer of 2-me thyl-5-e t hyl pyridine
(Diagram I, p. 3). This appears to be the isomer of
major commercial impo r tanc e . ( -*- » •* ) Koppers Company,
Inc., Nepara Chemical Company, Inc., and Reilly Tar and
Chemical were cited as other producers. Chem Sources-USA,
1980 edition(^) lists RIT-Chem Company, Inc. as a
producer of 4-methyl-3 - ethyl pryridine.
' (II )j
No important commercial end uses of MEP have been
identified.(3,5) 2-Methyl-5-ethyl pyridine is a raw
material used for the industrial production of
nicotinic acid (3-pyridien-3-carboxylic acid) by
-X-
-MH-
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nitric acid oxidation and decarboxylation.^' 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 MEP 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.
-HIS--
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BASIS: 1 KG METHYL-ETHYL PYRIDINE
1.94
I.ULIII UC.
«»-•
1C ACIO~*~
REACTOR
t
1
Ajft0.rjJA
BKD'itRTf
»
AMMONIA
.«»j ,
REFRIGERATION
• >
RECYCLt 1.94
AWOJ11A
SlBimNG
STILL
,
BATCH STILL
REFINED PARALHIHYOE
[ - i. pM
»
;—*- ^ STILL TAILS -*-
\ f
CRUDE PARALDEHY\T_
-01
\
REAfTnn
'
s
V
.. J
\ \
•* '' PREHEATER
} AMMONIA 0.3]
ACETIC AC 10
Aqueous
WASTE HATER
TREATMENT
SLUDGE
BATCH STILL
REFINED *
HEP 1.0
METRES I PUSS TO
Sl O.O1
IITEH).«J
/
WATER LAYER
STRIPPING
sim
v
LIGHTS
PROCE!
WATER
FOR Fur,; HER .
RECOVERED BENZENE
.STILL TAILS 0.4^
BENZENE
BATCH STILL5
PICOLINES 0.044
—~-LIGHTS TO
STORAGE 0.3-1
AMMONIA
PYRIOINI.5
. PICOLINIS
PHENOL 0.0000003
SULFUR1C ACID 0.003
CHLORIDES 0.00015
SOLUBLE ABIDES 0.000004
ACETATES 0.0025
PARALDEHYOE 0.03
PICOLINES 0,0025
VATER
LWIO DISPOSAL'
Source: Reference 1.
WASTE WATER TREATMENT
SLUCC-t | | AQUT013
I l
. U/IO
DISPOSAL
WATER
Figure 1: Pyridines (2-Methy1» 5-Ethyl Pyridine and ot-Picoline) Manufacture,
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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 ozide, ammonium fluoride
or cobalt chloride cayalyst.(3) This process which takes
place in the reactor is shown by equation (!)•'
Odz CV\j
CO.)
As shown in the equation, an identified by-product
in the reaction is 2-methyl pyridine ( <=C -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.C1) 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
s tr earn .
-sf-
- <-\2O-
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to 720 metric tons of waste in 1973.
The TRW StudyC1) identifies the following as the major
contaminants in the listed waste stream:
paraldehyde 0.03 Kg/Kg MSP
sulfuric acid 0.003 Kg/Kg MEP
pryidines and picolines 0.0025 Kg/Kg MEP
soluble acetates 0.0025 Kg/Kg MEP
phenol 0.0000003 Kg/Kg MEP*
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 to
wastewater treatment. As part of the wastewater treatment
system, the waste is most likely stored/treated in lagoons.
«
IV. HAZARDOUS PROPERTIES OF 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.
-Mai-
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effects). The waste constituents are present in the wastes
in high concentrations (see p. 5), 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-picoline are
infinitely water-soluble). (See Table 1.)
As a result of this high constituent solubility, this
waste are likely to leach harmful constituents even under
relatively mild environmental conditions, and to be highly
mobile in ground and surface waters* (App. B). 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 waste water
treatment in lagoons. The potential for environmental
^Mobility 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.
-y-
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Table 1
Physical/Chemical Properties of Organics Identified
in Stripping Still Tailsa
Compound:
Structure :
paraldehyde
CH3
pyridine
2-picoli,neb
II c
rf,j
xk N ,
Formula :
NW:
3 • P • j « •
Vp> mm, 25°C :
Sat'd. vapor<*
conc'n, 25°C, g/m3
Water solubility6:
Octanol/wa ter*
partition co-
efficient :
Acid dissociation
cons tant &:
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-picoline. 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 Weast(6) pD-123.
yp MW
Calculated from vapor pressure data: g/m3 760 x RT
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Table 1 (Continued)
e v = very soluble (probably > 1 % )
inf = infinitely soluble
s = soluble (probably > 0.1%)
f Source, Reference 7.
& For pyridine and picoline, value indicated is pka of the
conjugate acid. Source, References 8,9.
-x-
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contamination exists from improper lagooning, or through
subsequent improper disposal of wastewater treatment sludges.
Thus, improperly designed or managed lagoons - for example,
those 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/ ch emical 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.
-I-12.M-
-------
Once released from the matrix of the waste these constituents
can persist and reach environmental receptors. Available dat-a
(21) indicates that 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
Subs tances.C11) Paraldehyde is included in the NIOSH List
of Suspected Carcinogens.'-^)
1. Parald ehyde
Paraldehyde exhibits moderate toxicity when injested
and low toxicity when applied to the skin.(13) Signs and
symptoms of paraldehyde poisoning are uncoordination and
drowsiness, followed by sleep. With larger doses, the
pupils will dilate and reflexes will be lost; comotosis
will follow. The systems 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)
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Table 2
Summary of Data on Toxlcity of Organics
Identified in Stripping -Still Tails
Compound
Paraldehyde Pyridine 2-Picoline
14 500
1530 — " 891 790
100-1000
-u'-
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2. Pyr ines
Pyrines exhibit moderate toxicity when introduced
to the human through oral, dermal and inhalation routes. (13)
Liver and kidney damage have been produced in animals and
in man, after oral administration.^^' In smaller doses,
conjunctivitis, dizziness, vomiting, diarrhea and jaundice
may appear ;(-*-->) also tremors and atoxia (deffective 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.(^5) 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 ppra = 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 ppni.^ '
Adverse taste in fish (carp, rudd) is reported at 5 ppm.' '
Pyridine causes inhibition of cell multiplication algae
Federal Republic of Germany
-yf-
-------
(Michrocystis aeruginosa) and bacteria (Pseudomas
putida) at 28 and 340 ppm, respectively. SaxC1^)
reports a number of other hazards assoiated with pyridines:
(1) fire hazard, that is dangerous when it is exposed
to heat, flame or oxidizer; (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 pyridine 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 5000 mg/L.
3 . Picolines
Picolines as a class exhibit high toxicity via
dermal route and moderate toxicity via oral and inhalation
routes.(13) ^ -picolines, °L -picolines andQ -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/m3 for
mixed i s oiner s . ( 1" '
An EPA report(2°) suggests that, based on a health
criteria, the ambient levels of picolines in water should
not exceed 316 mg/1.
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REFERENCES
lt G. I. Gruber, et_ aj_. , (TRW) "Assessment of Industrial
Hazardous Waste Practices: Organic Chemical, Pesticides
and Explosives Industries," U.S. EPA, SW-118C, January
1976, pp. 5-26 to 5-28.
2. United States International Trade Commission, Synthetic
organic Chemicals: United States Production and Sales,
1978. USITC Publication 1001, 1979. pp. 33-80.
3. R. A. Abramovitch, "Pyridine and Pyridine Derivatives,"
in E.. P. Dukes, C. Coleman, P. Hirsch, G. Joyce,
P. Van Reyen and G. C. Wronker, eds., Kirk-Othmer
Encyclopedia of Chemical Technology, 2nd Edition, Vol. 16,
John Wiley and Sons, N.Y., 1968. pp. 780-803.
4. M. J. Baker, B. D. Bradley, C. L. Gandenberger, E. M.
Giordano, J. B. Mertz, L. E. Nash and M. S. Nash, eds.,
Chem-Sources-USA, 1980 edition, Directories Publishing
Co., Ormond Beach, FLorida, 1980. pp. 296.
5. M. J. Astle, Industrial Organic Nitrogen Compounds, ACS
Monograph Series, ReAnhold Publishing Corporations N.Y.,
1961. pp. 134-145.
6. R. C. West, Ed. in Chief, Handbook of Chemistry and
Physics, 47th Editon, Chemical Rubber Company, Cleveland,
Ohio, 1966.
7. C. Hansch and A, J, Leo, Substituent Constants or Correlation
Analysis in Chemistry and Biology, John Wiley and Sons,
N.Y., 1979. Paraldehyde value is for oil/water rather than
octanol/water.
8. D. D. Perrin, Dissociation Constants of Organic Bases in
Aqueous Solution, Butterworts, London, 1965.
9. G. Kortum, W. Vogel and K. Andrussow, Dissociation of
Organic Acids in Aqueous Solution, Butterworths, London,
1961 .
10. Federal Register, Vol 4_3, No. 243, 59025-27, "B i oaccumul at i on
Potential Test."
H- R. J. Lewis, Sr;, and R. L. Tatked, eds., NIOSH, Registry
of Toxic Effects of Chemical Substances, U.S. Department
of Health, Education and Welfare, 1978.
-------
12.
13.
14.
15.
16.
18.
19.
20.
21 .
U.S. EPA, An Ordering of the NIOSH Suspected Carcinogens
List, NITS Report No. PB 251 851 (EPA No. 660/1-76-003);
March, 1976.
Sax, N. Irving, Dangerous Properties of Industrial Material,
fifth edition, VAn Nostrand Reinhold Company, 1979.
Deichmann, W. R., Toxicology of Drugs and Chemicals.
Academic Press, Inc. Ill Fifth Avenue, New York, New York
10003. 1969
Toxic and Hazardous Industial Chemical Safety Manual
for Handling and Disposal with Toxicity and Hazard Data.
The International Technical Information Institute.
Toranomon-Tachikawa Bldg., 6-5, 1 Chome, Nishi-Shimbashi ,
Minato-ku, Tokyo, Japan. 1976.
Verchuerer, Karek, Handbook of Environmental Data on
Organic Chemicals. VanNostrandReinhold Company.
1977.
Merli ss , R. R
14:55. 1972.
Phenol moras. Mus. Jour. Occup. Med.
Gosselin, R. E., H. C. Hodge, R. P. Smith and M. N.
Gleason, Clinical Toxicology of Commercial Products,
Acute Poisoning.Fourth edition.The Wi11iams and
Wi1ki ns Co., Baltimore , Md. 1976.
J. G. Cleveland and G. L. Kingsbury, "Multimedia
Environmental Goals for Environmental Assessment,"
Vol. 2. EPA Report No. 600/7-77-1365, November, 1977.
Dawson, English and Petty, 1980. Physical Cheminal
Properties of Hazardous Waste Constituents.
-------
LISTING BACKCS.ODND DOCUMENT
TOLUENE DIISOCYANATE PRODUCTION
Centrifuge residues from toluene diisocyanate production (R,T)
I. Summary of Basis for Listing
The centrifuge residues from the production of toluene diisocyanate
(TDI)* contain toxic organic substances, mutagenic substances, and
substances that are probably carcinogenic. The wastes are also highly
reactive upon contact with water. These wastes result from the produc-
tion 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:
I) The TDI centrifuge and vacuum distillation wastes consist of
toluene diisocyanates, toluene diamines, and polymeric tars,
all of which are suspected carcinogens.
2) More than 6000 metric tons of TDI production wastes are
produced per year.
3) Storage in drums in a landfill, a known 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
*This compound is also referred to as tolylene diisocyanate or tolyl
diisocyanate.
-------
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 1973^ ) was 330,000 metric tons (661 million pounds). The major
producers of mixed toluene diisocyanate isomers^' 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, Olin Corporation, Pvubicon
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-dianiine, 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
-------
TOLUENEDIAMINE-
PHOSGENE—i
TWO
REACTORS
(SERIES)
RECYCLE
PHOSGENE
1
WASTE GAS
SCRUBBER
TO
WASTE WATER
©
STEAM EJECTOR
DEGASSER
VENT KETTLE
NnOH ,
rQ
rv
1
TO
i
ST
A^
EVAPO
TO WASTE WATER
t
PHOSGENE &
HCI
RECOVERY
WASTE
WATER
.SOLVENT RECOVERY .
VENT COMPRESSOR
RECYCLE
VENT GAS
REFINED TOLUENE
DHSOCYANATE 1.0
EVAPORATOR
RESIDUE
PROCESSING
CENTRIFUGE
OR
VAC. DISTILL.
1
VENT
TOAiR
•WATER
TO
WASTE
WATER
BYPRODUCT 37.5%
HYDROCHLORIC ACID
CENTRIFUGE OR DISTILLATION
RESIDUE
STEAM EJECTOR
WASTE GAS SCRUBBER (WATER)
HCI
I
WASTEWATER
CENTRIFUGE/DISTILLATION RESIDUE (LIQUID & SOLID)
POLYMERS AND TARRY MATTER
FERRIC CHLORIDE
WASTE ISOCYANATES
LAND
Figure 1. TOLUENE DIISOCYANATE MANUFACTURE
(MODIFIED FROM REFERENCE 9)
-------
following reactions shown in Figure 2 and 3 take place. An excess of
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__jLn water, is neutralized and then sent to the
plant industrial outfall.
The dehydrochlorination 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 dehydrochlorinated by blowing an
inert gas such as natural gas through the solution to remove HC1. The
degasser gas is sent to the phosgene and HC1 recovery system, where the HC1
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 toluenediamine
-M3M-.
-------
CH-
NH2
CH3
+ COCI,
25-3CPC
HC!
2,4 TOLUENE DIAMiNE
NH2
PHOSGENE
NHCCC!
(REACTOR 1)
'CH3
CH3
- HCI
+ COC!2
NHCOC!
2,6 TOLUENE DIAMINE
180-190°C
NHCOCi
O
II
CI —C
COCI2
CH3
H
NH2-HCI
COCI2
2HC1
(REACTOR 2)
CH3
NHz-HCI
C-CI
Figure 2. REACTIONS OF 2,4 AND 2,6-TOLUENEDiA.ViINE ( 9 )
CH3
NHCOCI
95-11Cr-C
NHCOC!
CH3
INERT GAS fl
NCO
-2HCl|
NCO
iqure 3, 'DEHYDROCHLORINATICN REACTION TO FORM TDl(9 )
- <-/ S if-
-------
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, C11) 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 tarlike matter, 6 percent
ferric chloride (largely from process impurities) and 3 percent waste
isocyanates.C11)
The wastes are 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. 5-6 following.)
Ill. Discussion of Basis for Listing
A. jiazards 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 - 6%
o Waste isocyanates (including TDI) - 3%
-------
The waste isocyanates and polymer and tar-like material are
toxic and the free 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 similiar
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 I landfill where it exploded, requiring the hospitalization of
several people.* In Detroit in May of 1978, a tank 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 §26'1.23(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 to their toxicity and potential for genetic harm. The
principal component of...concern for this route of exposures 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.) TDI tars are
also suspect carcinogens, and are toxic as well (Id.)
These materials are capable of migrating from improperly designed
and managed waste disposal sites. Toluene-2,4-diamine, produced by the react
of the diisocyantes with water (12) j_s 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 diisocyanate, while toxic and a suspect carcinogen, 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.
-43S-
-------
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 making them 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 (although polymeric tars
are generally persistent due to their physical character). It is assumed
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. Further information as
to the waste's and waste constituents' persistence is, however, solicited.
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 groundwater 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 a suspect carcinogen under bioassay
study by National Cancer Institute. TDI is toxic [inhalation rat LD5Q
=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 sensitization so that sen-
sitized individuals are subject to asthmatic attacks upon re-exposure to
extremely low concentrations 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 diisocyanate 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-2,4-diamine
-vs-
-MWO-
-------
Health Effects - Toluene-2,4-diamine is a suspect carcino-
gen^). 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 tuniors(^) in rats,(6) morphological
aberrations in mammalian cells('), and causes bacterial mutation in the
Ames test.W Additional information and specific references on the ad-
verse effects of toluene 2,4-diamine 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.
3. Tar from TDI Manufacturing
Health Effects - Tarllke material from TDI manufacturing con-
tains benzidimidazapone and must be considered suspect carcinogen based on
the data available on coal tar and other chemical tars. (NIOSH Criteria
for recommended standard for occupational exposure to Coal Tar Products.)
Considering the highly reactive nature of isocyanates and their polymers,
various toxic effects such as skin and respiratory tract irritation and
sensitization also would be expected. Sensitized individuals are subject
to asthmatic attacks upon re-exposure to extremely low concentrations
of this material. Additional information on the adverse effects of
tarlike materials can be found in Appendix A.
Industrial Recognition of Hazard - Sax's Dangerous Properties
of Industrial Materials(2> designates dehydrated and liquid tars as highly
-MMS-
-------
toxic skin and respiratory irritants when exposure is of long duration.
Tar dusts are designated as moderate skin and eye irritants upon acute
exposure.
-------
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 # 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-Toluenediamine 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(1):251-252, 1976.
6. Shah, M.J., et al. Comparative Studies of Bacterial Mutation
and Hamster Cell Transformation Induced by 2,4-Toluenediamine
(Meeting Abstract). Proc. Am. Assoc. Cancer Res., 18:22, 1977.
7. Cancer Research_,_29:1137, 1969.
8. Pienta, R.J., et al. Correlation of Bacterial Mutagenicity and
Hamster Cell Transformations with Tumorigenicity 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., New York, 1979.
11. Industrial Process Profiles for Environmental Use: Chapter 6, The
Industrial Organic Chemicals Industry. Reimond Liepins, 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).
-------
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
- HHM-
-------
contain 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1 2-tri-
chloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane-
vinylidene 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-trichloroethane 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.
2) 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-trichloroethane has shown a steady in-
crease in production as shown in Table 2. It is mainly used (92%) for
metal degreasing and for electrical, electronic and instrument cleaning.
Growth in the use of 1,1,1-trichloroethane is being accelerated because
of the potentially greater health hazard exhibited by trichloroethylene.
- 4HS-
-------
TABLE 1
1,1,1-Trichloroethane Producers, Sites, Capacities and Processes (1»2)
Company
Location
Annual Capacity
(Millions of Pounds)
Process
Dow Chemical
U.S.A.
Freemport, TX
Plaquemine, LA
450
300
Via Vinyl
Chloride
PPG Indus-
tries
Lake Charles, I
LA !
350
Via Vinyl
Chloride
Vulcan
Materials
Geismar, LA
65
Via Chloro-
nation of
ethane
TOTAL
I 1,165
-HHC.-
-------
TABLE 2
U.S. International Trade Commission
1,1,1-Trichloroethane Production (3)
Year !
i
1968
1969
1970
1971
1972
1973""
1974
1975
(Millions of Pounds)
299.4
324.3
366.3
374.6
440,7
548.4
i
590.8
|
i
i
i
1976 1 631.2
!
1977
634.8
-MM1-
-X-
-------
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-trichloroethane 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 1,1-dichloroethane,
which is then thermally chlorinated to produce 1,1,1-trichloroethane.
The yields based on vinyl chloride are approximately 95%.
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-trichloroethane is the only desired product, vinyl chloride and
vinylidene chloride are hydrochlorinated to 1,1-dichloroethane and
1,1,1-trichloroethane 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 hydrochlorination of vinyl chloride is:
Fed 3
H2C-CHCl-i-HCl > CH3HC12
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,
SPA 68-02-2577, July 1979
-------
Chlorination of 1,1-dichloroethane is represented as:
CH3-CHCl2-K:i2 > CH3CC13+HC1
Figure 1 represents a simplified process for production of 1,1,1-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 35-40°C in the presence of ferric chloride. The re-
actor effluent is neutralized with ammonia. The resulting solid com-
plex (residual ammonium chloride and 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 chlorination 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 HC1 is
used, it can contain as much as 3.5% of 1,2-trichloroethane which
will carry forward to the product stream stripper waste streams.
**The Agency requests further information on the existence and compo-
sition of this Identified waste stream. It is anticipated that
most heavy waste constituents will be found in the residue of the
final distillation column.
-------
o
I
HCI
(
__-^
TC2A(=-
T
'•
d
1
>
LO
, X.
AD,
)
M i *^-C £
WJCq
Figure 1. Flow Diagram for 1,1,1-Trichloroethane from Vinvl 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-
tric hi oro ethane, 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, vinylidene 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 G, 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:
+ ci2 > CH3CH2C1 + CH3CHC12 + CH3CC13 + HC1
+ C12 > CH2HC1 + CH2CC12 + HC1
t
-------
TABLE 3
ESTIMATED EMISSIONS FRCM 1,1,1-TRICHLORDETHANE MANUFACTURE: Vinyl Chloride Process
Species
Mr
EMISSIONS kg/Mg
Aqueous
Solid
Hydrogen chloride
Ethane
Ethene
NH4-FeCl3~3 Complex
1,1-Dichloroetihane
1,1-Dichloroethene
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-TGr ichloroethane
1,1,1,2-Tetxachloroethane
1,1,2,2-Tetrachloroethane
Pent-achloroethane
Sodium hydroxide
Sodium chloride
1.6
1.6
2.2
9.9
3.5
2.6
33.7
449.
2.2
0.8
0.8
3.9
51.2
35.3
40.8
1.8
Sources EUcin, L.M. "Chlorinated Solvents," Process Economic Program Report No. 48,
Stanford ReseaarcVi Institute, Menlo Park:, Califiornia, February, 1969.
-------
Small amounts of 1,2-dichloroethane and 1,1,2-trichloroethane are also
formed in minor amounts. The product mix, however, can be varied some-
what by operating conditions. Furthermore, to maximize 1,1,1-trichloro
ethane production, ethyl chloride and 1 ,1-dichloroethane are recycled
to the chlorination reactor; vinyl chloride and vinylidene chloride
are catalytically hydrochlorinated to 1 ,1-dichloroethane and 1,1,1-
trichloroethane respectively:
FeCl3
H2C=CHCr «• HC1 _ .
FeCl3
CH2=CCl2 + HC1 _ CH3CC13
Figure 3 represents a simplified process for production of 1 ,1 , 1-trichloro-
ethane 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 hexachloroe thane, 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 hydrochlorination reactions; excess hydrogen
chloride is purified for reuse or resale. The bottom stream from
-W53-
-------
HYDROGEN
CHLORIDE •
VINYL
CHLORIDE
HYDROGEN CHLORIDE +
TRICHLOROETHANE + DICHLOROETHANE
r
TO ATMOSPHERE
•NaOH +H2O
B
SCRUBBER
WASTEWATER
A
-(CONDENSER) 'DICHLOROETHANE
-(DECANTER)
HYDROCHLORINATOR
REACTOR
PURIFICATION
COLUMN
REACTOR SPENT
CATALYST
WASTE
STEAM STRIPPER
GAS EFFLUENTS
CHLORINE
J
STEAM
STRIPPER
STEAM-
CHLORINATOR
REACTOR
DECANTER
1,1,1-TRICHLOROETHANE
DISTILLATION
COLUMN
HEAVY ENDS
STEAM STRIPPER WASTE
Figure 2. 1,1,1-TRICHLOROETHANE BY THE HYDROCHLORINATION AND DIRECT
CHLORINATION OF VINYL CHLORIDE. (53)
-------
TO MCI
PV.AMT
FR.CM
COUUMM
FCCM
HCI
COL.UMKJ
CCK.UMM
HEAVY
OCCUMIJ
^>
J
l,l,l-TRt-
CHLOEOETHMJC
COuUMM
TO
C»^»-^
Figure 3. Flow Diagram fpr 1,1,1-Trichloroethane from Ethane
-------
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 all the heavy waste materials (tetrachlorinated ethanes
and higher). The bottoms may be disposed of as waste or used as
feedstock for as a bottom stream and are suitable as feedstock for
other chlorinated hydrocarbon processes. These bottoms are the
waste stream of concern from the ethane chlorination process. (The
remaining process description is provided for informational purposes.)]
The overhead product (principally 1,1,1-tricholroethane, vinyl
chloride, vinylidene chloride, ethyl chloride, and 1,1-dichloroethane)
is fractionated and 1,1,1-trichloroethane removed as a bottom product.
The overhead stream from the 1,1,1-trichloroethane column is fed to
the 1,1-dichloroethane column, where 1,1-dichloroethane is separated
as the bottoms stream and is recycled as a feedstock to the chlorination
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
-------
listed as hazardous when arising in the ethane chlorination process
since it consists 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) is
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 1,2-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
ment practices for these wastes, but based on typical waste management
practices in the chlorinated organic manufacturing industry it is
likely that distillation bottoms and heavy ends are landfilled
(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. Hazards 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
-------
TABLE A
ESTIMATED EMISSIONS FROM 1,1,1-TRICHLOROETHANE MANUFACTURE: Chlorlnation of Ethane
Species
Air
EMISSIONS kg/Mg
Aqueous
Solid
Ethene
2.4
1,1-Dlchloroethane
1,2-Dlchloroethane
1,1,1-Trichloroethane
1,1,2-Trlchloroethane
Tetrachloroethanes
Hexachloroethanes
trace
30.7
39.0
49.7
Oo
\n
T
I
51.4
Iron (III) chloride
Hydrogen Chloride
2.8
173.6
Source: Elkln, 1969
-------
TABLE 5
Via Vinyl Chloride Process
Stream
:illation bottoms and
rj 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
> from product - stream
)per*
1,2-dichloroethane
1,1,1-trichloroethane *
0.8
3.9*
catalyst
**
NH4Cl-FeCl3-NH3 complex
2.2
**
Via Chlorination of Ethane
:e Stream
rj 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
* spent steam stripper waste is also expected to contain small concentrations
rtnyl chloride, vinylidene chloride and chloroform. Vinyl chloride is expected
>e present since it is a feedstock constituent. Vinylidene chloride is a"
Jroduct from the dehydrochlorination of 1,1,2-trichloroethane. Chloroform
mother predicted reaction by-product, and is expected to be formed from
splitting off of vinyl chloride monomer and ethane into single carbons,
* are subsequently chlorinated.
1 spent catalyst waste is also expected to contain small concentrations of
^chloride feedstock, 1,1,1-trichloroethane product and some polymeric
trials. The Agency solicits information as to the presence of these or
ler compounds in this waste, and notes that hazardous constituent concen-
lt*ons in this waste stream may be too minute to be of regulatory significance.
-------
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 GAG 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 solubilize 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 Hg.)**; 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.).
VI
-VfcO-
-------
problem via inhalation as well.
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.(4) £n jqew 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.(48) Trichloroethane has also migraged and contaminated
private drinking wells in Canton, Connecticut.(48)
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
residue is expected to be incinerated. Improper landfilling —
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 mimimized. 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 s Love Canal, the Kin-Buc
Landfill, and Story Chemical in Michigan County, Michigan.™^»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 volati-
lization^.
In addition to landfilling, the 1,1,1-trichloroethane steam strip-
per bottoms waste stream that is recycled or incinerated is often
stored temporarily at the production site. Should leaks occur, simi-
lar 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-
V*
-------
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 ttiese waste constituents are expected,
on the basis of literature degradation values, to persist in groundwater
(1,1,2-Trichloroethane is subject to hydrolysis, but has a hydrolysis
half-life of 6 months. 1,1,2-Trichloroethane may also persist in 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) in any
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; (7)
it has also been identified by the Agency as demonstrating substantial
evidence of carcinogenicity.C^A) in addition, this compound and
several of its metabolites are highly mutagenic (8>9). 1,2-Dichloro-
ethane crosses the placental barrier and is embryotoxic and terato-
genic(10~14) , and has been shown to concentrate in the milk of
-------
nursing mothers. Exposure to this compound can cause a
variety of adverse health effects including damage to the liver,
kidneys and other organs, internal hemorrhaging and blood clots
1,2-Dichloroethane is designated a priority pollutant under Section
307(a) of the CWA. Additional information and specific references
on adverse health effects of 1,2-dichloroethane can be found in
Appendix A.
•Ecological Effects - Values for a 96-hour static
-------
genie in the Ames Salmonella assay(2°) and was shown to cause fetal de-
velopment abnormalities.(21)
Acute and chronic intoxication of humans have caused severe
central nervous system impairment.(22^ Animal studies have shown that
1,1,1-trichloroethane causes organ damage to heart, lungs, liver and
kidneys, t23-' Additional information and specific references on the
adverse effects of 1,1,1-trichloroethane can be found in Appendix A.
Ecological Effects -.1.1.1-Trichloroe'thane is very toxic
to aquatic life. Lethal concentrations (96 hour) of- 37-58 mg/1 were
registered for bluegills, 52 mg/1 for fathead minnows and 26 mg/1 for
shrimp.(2^'
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"'re commended an ambient water quality criterion
at 15.7 mg/1.
Industrial Recognition of Hazard - Sax (Dangerous Properties
of Industrial Materials) listsvl,1,1-trichloroethane as moderately toxic
via inhalation.
3. 1,1,2-Trichloroethane
Health Effects - 1,1,2-Trichloroethane has been shown to
cause cancer in mice;(2^) it has also been identified by the Agency
as demonstrating substantial evidence of carcinogenicity. ^' There
is evidence that 1,1,2-trichloroethane is mutagenic 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
-------
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 toxicity data are limited
with only three acute studies in freshwater fish and invertebrates,
with doses ranging from 10,700 to 22,000 ug/.l.^17^
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; ancj to ^e mutagenic. ^8)
It has also been identified by the Agency as demonstrating substan-
tial evidence of carcinogenicity. ' It is very toxic [1^50
(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 vinylidene 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 vinyli-
dene chloride is 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;<31,32,33) it hag algo been identi_
fied by the Agency as demonstrating substantial evidence of carcino-
genicity.(54) This finding has subsequently been supported by
epidemiological findings.(33-37)
Vinyl chloride is very toxic [LD50 (rat) = 500 rag/kg] and
acute exposure results in anaesthetic effects as well as uncoordinated
muscular activities of the extremities, cardiac arrythmias(38) atl(j
sensitization of the myocardium. (39) in severe poisoning, the lungs
are congested and liver and kidney damage also occur.(40) 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.(41)
Vinyl chloride is designated as a priority pollutant under Section
307(A) of the CWA. Additional information and specific references
on the adverse effects-o-f vinyl chloride can be found in Appendix A.
Regulations - OSHA has set the TWA at 1 ppm with a 5 ppm
ceiling over 15 minutes. DOT requires this to be labeled "flammable
gas."
Industrial Recognition of Hazard - A 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 (42,54) and tangential evidence links human cancer epidemiology
with chloroform contamination of drinking water.(43,44) Chloroform
has also been shown to induce fetal toxicity and skeletal malforma-
tion in rat embryos.(45»4°) 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 fish.^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).^3Q'
7. Tetrachloroethanes
Health Effects - 1,1,2,2-Tetrachloroethane has been
shown to produce liver cancer in laboratory mice; (31.) £t ^as aiso
been identified by the Agency as demonstrating substantial evidence
of carcinogenicity.(54) xt is also shown to be very toxic [oral rat
-------
LD5Q s 20° mg/Kg-K In addition, passage of 1,1,1,2-tetrachloroethane
across the placental barrier has been reported.^29) In Ames Salmonella
bioassay 1,1,2,2-tetrachloroethane was shown to be mutagenic.
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.^3) Both 1,1,1,2-tetrachloroethane
and l,l,2,2^tetrachloroethane are designated as priority pollutants
i
under Section 307(a) of the CWA. Additional information and specific
references on the adverse effects of tetrachlorbethanes can be found
in Appendix 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 ppm (skin) for
1,1,2,2-tetrachloroethane.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, lists 1,1,2,2-tetrachloro-
ethane as being highly toxic via ingestion, inhalation and skin
absorption.
-------
IV. References
1. 1979 Directory of Chemical Producers United States.
2. Chemical Economics Handbook, Menlo Park, California. December
1978. (May be purchased from SRI.)
3. Synthetic Organic Chemicals, U.S. Production and Sales, U.S. Inter-
national Trade Commission.
4. Water Quality Issues in Massachusetts, Chemical Contamination,
Special Legislative Commission on Water Supply, Sept. 1979
5. Memo from Roy Albert to E.G. Beck, Administrator, EPA Region II,
Drinking Water Contamination of New Jersey Well Water, March 31, 1978.
6. Wilson, J.T., and C.G. Enfield, 1979, Transport of Organic Pollu-
tants Through Unsaturated Soil. Presented American Geophysical
Union. December 3-7, San Francisco, CA.
7. National Cancer Insti-tute. 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, Carcinogenesis Testing Program, DHEW
Publication No. (NIH) 78-1305, January 10, 1978.
8. McCann, J., E. Choi, E. Yamasaki, and B. Ames. Detection of Carcino-
gens as Mutagenic in the Salmonella/Microsome Test: Assay of 300
Chemicals. Proc. Nat. Acad. Sci. USA 72(2):5135-5139, 1975a.
9. McCann, J., V. Simmon, D. Streitwieser, and B. Ames. Mutagenicity
of Chloracetaldehyde, a Possible Metabolic Product of 1,2-Dichloro-
ethane (ethylene dichloride), Chloroethanol (ethylene chlorohydrin),
Vinyl chloride, and Cyclophosphamide. Proc. Nat. Acad. Sci. T2.
(8):3190-3193.
-------
10. Vozovaya, M., Changes in the Esterous Cycle of White Rats Chronically
Exposed to the Combined Action of Gasoline and Dichloroethane Va-
pors. Akush. Genecol. (Kiev) 47 (12): 65-66, 1971.
11. Vozovaya, M., Development of Offspring of Two Generations Obtained
from Females Subjected to the Action of 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.
13. 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-
cow) _2:57-59, 1977.
15. Urusova, T.P. (About a possibility of dichloroethane absorption into
milk of nursing women when contacted under industrial conditions.)
16. Parker, J.C., et al. 1979. Chloroethanes: A Reveiw 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
Carcinogenicity. Carcing. Tech. Rep. Ser. NCI-CG-TR-3.
19. Price, P.J., et al. 1978. Transforming Activities of Trichloro-
ethane and Proposed Industrial Alternatives.
20. U.S. EPA Report, 1980, In Vitro, 14:290. In Vitro Microbiological
Mutagenicity of 81 Compounds.
-Mil-
-------
21. Schwetz, B.A., et al. 1974. Embryo and Fetal Toxicity of In-
haled Carbon Tetrachloride, 1,1-Dichloroethane and Methyl Chloro-
form in Rats. Toxicol. Appl. Pharmacol. 28:452.
22. Stahl, C.J., et al. 1969. Trichloroethane Poisoning. Observa-
tions on the Pathology and 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 CH2C12, CH3C13, 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 Assess-
ment Report of 1,2-Dichloroethane (Ethylene Dichloride). In prepara-
tion.
28. Environmental Health Perspectives, 1977, Vol. 21, 333 pp.
29. Van Duuren, B.L., et al. 1979. Carcinogenicity of Halogenated
Olefinic and Aliphatic Hydrocarbons in Mice. 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. Maltoni, C., and G. Lefemine, Carcinogenicity Bioassays of Vinyl
Chloride. Am. NY Acad. Sci. 246:195 (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, Angiosarcoma 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. Assoc. 230:59
(1974).
36. Makk, L., et al. Liver Damage and Liver Angiosarcoma 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. Anesthesis, XXVII, Narcosis with Vinyl
Chloride Anesthesiology 8: 359, 1947.
39. Carr, J., et al. Anesthesis XXIV. Chemical Constitution of
Hydrocarbons and Cardiac Automaticity. J. Pharmacol. 97:1 (1949).
40. Torkerson, T.R., et al. The Toxicity of Vinyl Chloride by Re-
peated Exposure of Laboratory Animals - Amer. Ind. Hyg. Assoc.
Jour. ^:354 1961.
41. Lester, D., et al. Effects of Single and Repeated Exposures of
Humans and Rats to Vinyl Chloride. Amer. Ind. Hyg. Assoc. Jour.
2.4^:265, 1963.
A2. National Cancer Institute, 1976. Report on Carcinogenesis Bio-
assay of Chloroform. National Technical Information Service,
PB-264018. Springfield, Virginia.
A3. U.S. EPA, 1979. Trichloromethane (Chloroform) Hazard Profile,
USEPA/ECAO, Cincinatti, Ohio 45268. 1979.
-------
44. McCabe, L.J., 1975. Association Between Trihalomethanes in
Drinking Water (NORS Data) and Mortality. Draft Report. U.S.
EPA.
45. Schwetz, B.A., et al. 1974. Embryo and Fetotoxicity of Inhaled
Chloroform in Rats. Toxicol. Appl. Pharmacol. 28:442.
46. Thompson, D.J., et al.1974. Teratology Studies on Orally Admin-
istered 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, "Annual Study of Personal Injury, Economic Damage or
Fatalities from Hazardous Waste", 1978.
49. Barth, E. F., Cohen, J. M., "Evaluation of Treatability of Industrial
Landfill Leachate", unpublished report, U.S. EPA, Cincinnati, November
30, 1978.
50. O'Brien, R. P., City of Niagra 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 Regional
Laboratories, Chicago, Illinois, May, 1978.
53. Source Assessment Chlorinated Hydrocarbons Manufacture. EPA-600/2-
78-004.
-SIS-
-------
LISTING BACKGROUND DOCUMENT
TRICHLOROETHYLENE AND PERCHLOROETHY.LENE PRODUCTION
Column bottoms or heavy ends from the combined
production of trichloroethylene and perchloroethylene (T)
Summary of **
The column bottoms or heavy ends from the combined pro-
duction of trichloroethylene 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 , hexachlorobutadiene , 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 lif.e
and bioaccumulate 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
mutagenic properties.
(2) A large quantity (a combined estimated total of at
least 15,000 metric tons) of these wastes is generated
annually.
-M7S"-
-------
(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 ^>2» 3> *)
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 es t imated~'±'979 production are shown in Table 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
-------
ESTIMATED CAPACITY AND PRODUCTION
PERCHLOROETHYLENE AND TRICHLOROETHYLENE
COMPANY
LOCATION
1979 CAPACITY (MT/YR)B 1979 PRODUCTION (MT/YR)
PERCHLOROETHYLENE TRICHLOROETHYLENE PERCHLOROETHYLENE TRICHLOROETHYLENE
Diamond Shamrock
Dow
Deer Park, TX
Freeport, TX
Pittsburg, CA
Plaquemine, LA
75,000 A
68,000 68,000
18,000
54,000
52,500
47,600
12,600
37,800
47,600
Dupont
Corpus Christ!, TX 73,000
51,100
Ethyl
Baton Rouge, LA
23,000
20,000
16, 100
14,000
PPG
Lake Charles, LA
91,000
91,000
63,700
63,700
Stauffer
Louisville, KY
32,000
22,400
Vulcan
Geismar, LA
Wichita, KS
68,000
23,000
TOTAL 525,000
179,000
47,600
16,100
367,500
125,300
A23,000-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
\ V.-.
> \ !•
.
.-' \
,./.. \
—"' \
6)
7)
8)
9)
1) Diamond Shamrock Corp., Deer Park,
2) Dow Chemical Co., Freeport, IX
3) Dow Chemical Co., Pittsburg, CA
4) Dow Chemical Co., Plaquemine, LA
5} DuPont, Corpus Christi, IX
Ethyl Corp., Baton Rouge, LA
PPG Industries, Inc., Lake Charles, LA
Stauffer Chemical Co., Louisville, KY
Vulcan Materials Co., Geismar, LA
10) Vulcan Materials Co., Wichita, KS
A = perchloroethylene, B = trichloroethylene
SOURCE: Reference 9
Chemicals Produced
A
A,B
A
A
A
A,B
A,B
A
A
A
-*-
-------
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 (3)
•••••>—>—>im m' ** *""" *" '*" ^*••• •
Perchloroethylene and trichloroethylene are produced
either separately or as co-products by either the .chlorination
or oxychlorination of ethylene dichloride or other €£-
chlorinated hydrocarbons. The ratio of raw material feed
determines the relative yields of perchloroethylene and
trichloroethylene. Perchloroethylene is also produced by the
chlorlnolysis of light hydrocarbons with by-product production
of carbon tetrachloride.
This listing document covers wastes generated by the
co-production process.
° Direct Chiorinationo^ Ethylene Pichloride (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 and at
about 425°C. Feed adjustments may be employed to vary product
-------
NI
FIGURE 2
DIRECT CIILORINATION OF ET1IYLENE BICHLORIDE
Ethylene
dichloride-H
Chlorine
Oxygen
Steam
Reactor
l
0)
x>
,0
3
M
O
4-J
d
fd
(U
r
•
J
c
<
1
(
r-
J
(
*r
>
t
H
H
_i
n
D
M
H
3
J
H
-i
H
V
^
J
> f
K
a
ts
*r"
i —
tt
«_
4-
t-
CL
^
Z
>
i
)
1
1
1
t
»
»-
Q
*r
^
c
*
4
)
H
-l
5
*T*v 4 »-.
i ric
V
§
M
PI
^C
W
«J
iH
PH
0
„ v
Perchlor Still
Flash
Drum
Trichloroethylene
a;
J3
Q)
•H
M
Perchloroethylene
Waste
Reaction
2CJ1,C1.
7HC1
1.750
1.5C12'+ 1.7502
5HC1
- C2HC15
2HC1 + (
3.5H20 + 3.5C12 (Deacon)
+ CCl + 3.5H0
85 to 90% yield
SOURCE: Reference 3.
-------
ratios, depending upon producer requirements.
The condensed crude and weak acid are then phase-separated
with 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 the bottom, neutralized with ammonia, washed,
and dried.
This process description is an example of one of several
processes for the manufacture of perchloroethylene and tri-
chloroethylene 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.
-M9I-
-------
Waste Generation and Management
1. Waste Generation
The column bottoms or heavy ends from the combined pro-
duction of perchloroethylene and trichloroethylene 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»9) This information indicates
that the primary constituents of the waste.stream are 1,1,2,2-
tetrachloroethane, hexachlorobutadiene, and hexachlorobenzene.
(Table 2 also includes solubilities of the waste stream
constituents.)(2,9,20)
The information presented in Table 2 was employed to cal-
culate the expected quairtities of each hazardous component which
is generated on an annual basis. Personal communications(5,6, 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 3% 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
—
rlene Bichloride
rTrichloroethane
ihloroethylene
1 2-Tetrachloroethane
,2 2-Tetrachloroethane
tachloroethane
achlorobutadiene
achlorobenzene
ichloroethane
TOTAL
ICE: References 2,9
Dnverted to PPM, Value -
SOLUBILITY OF P
IN
plene Bichloride
a-Trichloroethane
COMPOSITION OF HEX-WASTES
MOLE % 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
2.9.1 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 x 104
ARTICULAR HEX WASTE CONSTITUENTS
PPM (DISTILLED WATER)
8,690
4,500
in
PPM*
8,000
5,000
100
100
2,900
<500
0.005
<500
Very low
:hloroethylene 150 - 200
,2,2-Tetrachloroethane 2,900
achlorobutadiene
.achlorobenzene
achloroethane
: Reference 20
0.006 - 0.020
50
-------
Table 3
PROJECTED QUANTITIES OF INDIVIDUAL HEX-WASTE COMPONENTS
MOLE %
Hexachlor
1,
He
1,
He
Et
Pe
be
Pe
1,2,2-T
xachlor
1,1, 2-T
xachlor
hylene
rchloro
ta-Tric
ntachlo
ob
et
ob
u
r
e
etr
oe
Di
et
hi
ro
t
c
t
a
n
a
adiene
chloroe thane
zene
chloroethane
hane
hlor ide
hylene
0
e
r
t
oe thane
hane
TOTAL
27
29
14
7
3
1
5
7
2
100
.5
.1
.9
.9
.6
.4
.7
.2
.7
.0
WEIGHT % ANNUAL PRODUCTION
33
23
20
6
4
0
4
4
3
100
.8
.0
.0
.3
.0
.6
.5
.5
.3
.0
4,9
96
3,400
2,956
931
5
91
88
665
6
65
448
14,7
80
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.)
-vf-
-S34-
-------
individual basis. The available information indicates that
these wastes are either being incinerated or disposed of
through landfill or deep well injection into limestone for-
mations. Table 4 identifies the estimated quantities of
waste being generated at each production facility and the
current procedures for disposing of these wastes. As shown
in Table 4, approximately 70% of the wastes are incinerated,
with 22% going to landfill and 7% to deep well injection.
D. Hazards -Posed by Waste
•m mf *m • • »• •• m\\ mi'umi •§•§!• \m n> in m MI HI • m
As noted above, most of these hex wastes are incinerated.
Inadequate incineration conditions -- i.e., temperature and
residence times—can result in the airborne disposal of uncom-
busted chlorinated organics, partially combusted organics
and newly formed organic compounds. Phosgene is an example
of a partially combusted chlorinated organic which is produced
by the decomposition or combustion of chlorinated organics
by heat.(1Q»11i12) Phosgene has been used as a chemical
warfare agent and is recognized as extremely toxic.
The landfilling of column bottoms or heavy ends in an
unsecure land disposal facility may result in groundwater
contamination caused by migration of the toxic chlorinated
organics from the waste into the surrounding environment.
The most carcinogenic wastestream pollutant, 1,1,2,2-tetra-
chloroethane, is highly soluble in water, as shown in Table 2.
Ethylene dichloride, another carcinogen found in the waste-
stream, is even more soluble and thus would also tend to migrate
-------
TABLE 4
WASTE GENERATION RATES AND MANAGEMENT PROCEDURES
Company
Diamond Shamrock Corporation
Location
Deer Park, TX
Waste Production
MT
1,570
Current Disposal
Practice
LF
Dow Chemical U.S.A.
Freeport, TX
Pittsburg, CA
Plaquemine, LA
2,850
370
1,130
I
I
I
I
£
oO
^
I
E.I. DuPpnt de Nemours
Company, Inc.
Ethyl Corporation
PPG Industries
Corpus Christi, TX
Baton Rouge, LA
Lake Charles, LA
1,530
940
3,820
DWI
Stauffer Chemical Company
Louisville, KY
670
LF
Vulcan Material Company
I - Incineration
DWI - Deep Well Injection
- L,andfill
SOURCE: References 5, 6, 7
Geismar, LA
Wichita, KS
1,420
480
TOTAL 14,780
-------
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.(1?) (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 wi'fh" the landfilling 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 1970Ts, 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'.
Jn 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
°«5 ppb with a high of 1.8 ppb (Farmer et. al., 1976).
-------
Additionally, cattle in the surrounding area absorbed HCB 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 i"s~"~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.
-------
and EcologicalEf f ects
1. Hexachlorobenzene (HCB)
Priority_Pollutant - HCB is currently listed as a pri-
ority pollutant under Section 307(a) of the Clean Water Act.
££? ~ Hexachlorobenzene (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.(15) 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.'*7)
Virtually all hexachlorobenzene emitted from an uncontrolled
landfill is expected to persist in groundwater or reach
surface waters via groundwater movement.(*°/ Such behavior
is likely to result in exposure to humans using potable
water supplies within the exposed adjacent areas.
The recommended ambient criterion(*^^ 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
nobility and persistence of the material (See Appendix A.)
-------
Ecological Effects - Hexachlorobenzene is very persistent.
It has been reported to move through the soil into the ground-
water.^^ Movement of hexachlorobenzene within surface
water systems is projected to be widespread.(1°) 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.(18)
Regulatory Recognition of Hazard - As indicated in Appendix
A, hexachlorobenzene is a chemical evaluated by GAG as having
substantial evidence of carcinogenicity. 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 FWPCA.
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.(22,23,24,25)
The recommended human health -criterion level for this compound
-------
in water, 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 groundwater movement.C18)
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. (18)
HCBD is likely to contaminate accumulated bottom sediments
within surface water systems and is likely to bioaccumulate in
fish and other aquatic organi sms . ( ^ )
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.^^)
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-
*°SW Hazardous Waste Division, Hazardous Waste Incidents,
Published, Open File, 1978.
Un-
-vf-
-------
chlor obutadiene can be found In Appendix A.
3 . Hexachloroethane
Priority Pollutant - Hexachloroethane is a priority
pollutant under Section 307(a) of the FWPCA.
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
/ O Q A
and centra:! nervous system damage, \*-'° '
Virtually all hexachloroethane emitted from a 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 such groundwater sources as
drinking water supplies -within adjacent areas,
Ecological Effects - Movement of hexachloroethane within
surface water systems is projected to be widespread . (1 8)
Movement to this degree will likely result in exposure to
aquatic life forms in rivers, ponds, and reservoirs.
Hexachloroethane is likely to be released to the atmosphere
from surface water systems. (18)
Reognition 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. Tetrachloro ethanes
«•«••'• ^*^r^r-^r*^^mr*^**r*r*mr***^**r
Priority Pollutant - Both 1 , 1 , 1 , 2-tetrachloroethane and
1,1,2,2-tetraehloroethane are designated as priority pollutants
under Section 307(a) of the FWPCA.
, Hgaitj^Ej^g^s ~ 1,1, 2, 2-Tetrachloroetharie has been shown
to produce liver cancer in laboratory mice. (29) in addition,
passage of 1 , 1 , 1 , 2-tetrachloroethane across the placental
barrier has been reported. (30) jn an Ames Salmonella bioassay,
1,1,2,2-tetrachloroethane was shown to be mutagenic. ( 31)
Occupational exposure o.f_. 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 invertabrat es are sensitive
to 1,1,2,2-tetrachloroethane with a lethal concentration of 7-
8 mg/1 being reported. ( 33) USEPA estimates the BCF to be 18. (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'
Priority Pollutants - Ethylene dichloride (1 , 2-dichloroethane)
is designated as a priority pollutant under Section 307(a) of
-------
the FWPCA.
Health Effects - Ethylene dichloride has been shown to
cause cancer in laboratory animals.(34) jn addition, this
compound and several of its metabolites are highly mutagenic.(35)
Ethylene dichloride crosses the placental barrier and is
embryotoxic and teratogenic.(36»37»38>39»40^ It has also
been shown to concentrate in milk.(4D 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. (42)
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.
Indus trial 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.
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References
1. Chemical Profiles, Schnell Publishing Company, Inc.,
New York,New York.
2. "Emission Control Options for the Synthetic Organic
Chemicals Manufacturing Industy: Carbon Tetrachloride
and Perchloroethylene," EPA, Office of Air Quality
Planning and Standards. Contract Number 68-02-2257.
3. Lowenhein, F. A., and Moran, M. K., Faith, Keyes, and
Clark's Industrial Chemicals, 4th Ed., Wile.y Inter-
science, 1975.
4. TRW, "Assessment of Industrial Hazardous Waste Practice:
Organic Chemicals, Pesticides, and Explosives," USEPA,
SW-118c, 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. OSW - Hazardous Waste Management Division - "Hazardous Waste
Incidents": Unpublished Open File Data, 1978.
9. Emmission Control Options for the Synthetic Organic Chemical
Manufacturing Industry: 1,1,1-trichloroethane Product Re-
port," EPA, Office of Air Quality Planning and Standards,
July 1979, Contract Number 68-02-2577.
10. Combustion Formation and Emission of Traces Species", John
B. Edwards, Ann Arbor Science, 1977.
11. NIOSH Criteria for a Recommended Standard: Occupational
Exposure to Phosgene, HEW, PHS, CDC, HIOSH, 1976.
12. Cabral, J. R. P., et al. Carcinogenic activity of Hexa-
chlorobenzene in hamsters. Tox. Appl. Pharmacol. 41:155
(1977).
13. Cabral, J. R. P., et al. 1978. Carcinogenesis study in
mice with hexachlorobenzene. Toxicol. Appl. Pharmacol.
45:323.
14- Grant, D. L. et al. 1977. Effect of hexachlorobenzene on
reproduction in the rat. Arch. Environ. Contam. Toxicol.
5:207.
-------
15. Grant, et. al., 1977.
16. Koss, G., et al., 1978. Studies on the toxicology of
hexachlorobenzene . III. Observations in a long-term
experiment. Arch. Toxicol. 40:285.
17. Carlson, G. P., 1978. Induction of cytochrome P-450 by
halogenated benzenes. Biochem. Pharmacol. 27:361.
18. Technical Support Document for Aquatic Fate and Transport
Estimates for Hazardous Chemical Exposure Assessments.
1980. USEPA, Environmental Research Lab., Athens, Georgia.
19. U.S. EPA. Chlorinated Benzenes: Ambient Water Quality
Criteria, 1979.
20. U.S. EPA. 1979. Water-Related Environmental Fate of
129 Priority Pollutants. EPA-440 /4-7 9-02 9b .
21. Zoeteman, B., et. al., 1979. Persistent Organic Pollutants
in River Water and Ground Water of the Netherlands.
Presented at 3rd International Symposium on Aquatic
Pollutants, October 15-17, 1979. Jekyll Island, Georgia.
22. Kociba, R. J., Results of a Two-year Chronic Toxicity Study
vith Hexachlorobutadiene in Rats. Amer . Ind . Hyg . Assoc.
38: 589, 1977.
23. Kociba 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. 4_2_:387, 1977.
25. Schroit, et. al., Kidney Lesions Under Experimental Eexa-
chlorobutadiene Poisoning. Aktual, Vpo. Gig. Epidemiol.
73. CA:81:73128F (translation), 1972.
26. Li, et. al., Sampling and Analysis of Selected Toxic
Substances . Task IB- Hexachlorobutadiene. EPA-560/
6-76-015. USEPA, 1976.
27. National Cancer Institute. Bioassay of Hexachloroethane for
Possible Carcinogenicity . No. 78-1318, 1978.
28. U.S. EPA. Chlorinated Ethanes: Ambient Water Quality Criteria,
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,
-HU-
-------
National Institutes of Health, National Cancer Institute
DREW Publication No. (NIH) 78-827, 1978.
30. Truhaut, R. , Lich, N.P., Dutertre-Catella, H. T. Molas, G.
Huyen, V.N.: lexicological Study of 1,1,1,2-tetrachloro- '
ethane. Archives des Maladies Professionnelles, de Medecine
du Travail et de Securite 3_5_( 6): 593608, 1974.
31. Brem, H., et al. 1974. The Mutagenicity and NDA-Modifying
Effect of Haloalkanes. Cancer Res. 34:2576.
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, December, 1976.
33. U.S. EPA, 1979. Chlorinated Ethanes: Ambient Water Quality
Criteria (Draft).
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, Carcino-
genesis Testing Program, DHEW Publication No. (NIH) 78-1305,
January 10, 1978.
35a. McCann, J., E. Choi, E. Yamasaki, and B. Ames. Detection
of Carcinogens as Mutagenic in the Salmonella/Micro some
Test: Assay of 300 Chemicals. Proc. Nat. Acad. Sci.
USA ^2_(2): 5135-5139, 1975a.
35b. McCann, J., V. Simmon, D. Streitwieser, And B. Ames.
Mutagenicity of chloroacetaldehyde, a possible metabolic
product of 1,2-dichloroethane (ethylene dichloride),
chloroethano1 (ethylene chlorohydrin), vinyl chloride,
and cyclophosphamide. Proc. Nat. Acad. Sci. 72(8):
3190-3193, 1975.
36. Vozovaya, M. Changes in the Esterous Cycle of White Rats
Chronically Exposed to the Combined Action of Gasoline
and Dichloroethane Vapors. Akush. Genekol. (Kiev)
47(12): 65-66, 1971.
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.
38. 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.
-------
39. Vozovaya, M- The Effect of Low Concentrations of
Gasoline, Dichloroethane and Their Combination on the
Reproductive Function of Animals. Gig. Sanit. 6:
100-102, 1976.
40. Vozovaya, M. A. The Effect of Dichloroethane on the
Sexual Cycle and Embryogenesis of Experimental Animals.
Akusk. Ginekol. (Moscow) 2_: 57-59, 1977.
41. 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).
;,'
42. Parker, J.C., et al. 1979. Chloroethanes: A Review of
Toxicity. Amer. Ind. Hyg. Assoc. J., 40: A46-60, March, 1979.
43. U.S. EPA 1979. Chlorinated Ethanes: Ambient Water Quality
Criteria (Draft).
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Pesticides
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LISTING BACKGROUND DOCUMENT:
MSMA AND CACODYLIC ACID PRODUCTION
By-product 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 MSMA (monosodium
oiethanear senate) and cacodylic acid is an arsenic-contaminated salt byproduct
The Administrator has determined that the solid waste from MSMA and cacodylic
acid 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. 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
teratogenic. The waste generated at one plant was con-
taminated with arsenic at a concentration of 6300 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 arsenite, to be relatively mobile, and to persist
virtually indefinitely.
4. Several incidents of environmental contamination have occurred
due to the leaching of MSMA/cacodylic acid wastes disposed of
in landfills, resulting in adverse human health effects.
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II• Sources of the Waste
A. Profile of the Industry - MSMA is used primarily as a
herbicide, and is also an intermediate in the production of cacodylic acid
MSMA is produced in the U.S. by Diamond Shamrock (Green Bayou, Texas);
Crystal Chemical (Houston, Texas); and Vineland Chemical (Vineland, New
Jersey). Estimated production of MSMA in 1974 was 35 million pounds. C1)
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 methylarsenate (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 methylarsenate (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 MSMA product is formulated to various strengths and is shipped in
either bulk form or containers. Arsenic is persent in the salt byproduct
^Crystal Chemical evidently combines its two waste streams, since its
state disposal permit provides' for disposal of the combined waste
streams.
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in substantial concentrations, since it is a prevalent feedstock con-
stituent. The production scheme for MSMA 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 MSMA salt cake waste generated by Crystal
Chemical and provided to the Texas Department of Water Resources. This
analysis indicates that the waste contains arsenic concentrations of 6,300
mg/1 (6). The National Inferim 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 or arsenic in the waste stream.*
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
combined 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
Water Standards, which assume environmental release, although not all
the arsenic contained in the waste is likely to be released from the
waste into the environment, arsenic in these wastes may well be released
in concentrations well above .05 mg/1. (see p. 2 following).
-£"02-
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o
u)
i
CH3CI.
H2SO4,
SODIUM
ARSENITE
UNIT
25%
Na3AsO3
STORAGE
1
METHYLARSONIC
ACID UNIT
T
CRUDE
DSMA
Y
MSMA
REACTOR
PURIFICATION
-*>-
EVAPORATOR
STRIPPER
I
^AQUEOUS
CH3OH
CHjOH
I
RECOVERED
DSMA SALES
CENTRIFUGE
50% MSMA
BY-PRODUCT SALTS
WASHER
Na2SO4
NaCI
LIQUID
TO
APPROVED
LANDFILL
Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR MSMA.
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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
i
in environmental harm. Descriptions of damage incidents resulting from
mismanagement of these wastes are set forth at p. 6-7 following.
Vineland 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_._c.ompounds.
* (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
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as hazardous. First, these 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
the 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
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was left open to the weather with no containment of runoff. The State
of Wisconsin Department of Natural Resources has ordered Ansul to cover
the pile as an interim measure and to truck the waste to a landfill in
Illinois.(28)
A report from the files of the Texas Department of Water
i
Resources (Attachment I) indicates that a landfill containing these waste
streams was subject to overflow conditions during high rainfall periods,
causing waste washout, so.il 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 ground water 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. 8-10 following).
Two likely exposure pathways for the leaching of arsenic are
into groundwater and surface water. The potential for this to occur from
a waste/soil matrix depends on the concentration of arsenic in the soil,
soil type (clay, sand, loam, etc.), the soil pH, as well as the concen-
trations of cadmium, magnesium, iron, and aluminum in the soil. Arsenic
is not easily leached in fine-textured soils (clay materials) but may
be leached downward in sandy or loam soils.(30)
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Once arsenic 'escapes from these wastes and migrates to groundwater,
it can be expected to bi> both mobile and persistent. Thus, in mildly reducing
environments present in most shallow groundwaters, arsenic is most likely to
be present in the form of arsenite, a mobile and highly toxic compound/7)
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
1 t
Minnesota in 1972. (8) 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 ground water at a land treatment
site for municipal wastewater.v^-0)
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
MSMA and cacodylic acid by-product salts are generated in large
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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 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(H). 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(13-15) j
including those of the lung, lymphatics and blood(16,17). Certain
cases involving a high prevalence of skin cancer have been associated
with arsenic in drinking water(18), while liver cancer has developed in
several cases following ingestion of arsenic(19). 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(™), while several different arsenic compounds have demonstrated
positive mutagenic effects in laboratory studies(21~23).
The teratogenicity of arsenic and arsenic compounds is
well established (24-26) and inciudes defects of the skull, brain, kidneys,
-X-
-50S-
-------
gonads, eyes, ribs and genito-urinary system.
The effects of chronic a-senic exposure include skin diseases
progressing to gangrene, liver damage, neurological disturbances^7)
and cardiovascular disease(13).
Arsenic is designated as a priority pollutant under Section
307(a) of the CWA. Additional information and specific references on
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/1. Based on one chronic life cycle test using Daphnia magna, a chronic
value for arsenic was estimated at 853 ng/1.(28)
Bioaccumulation factors can reach 13,000 in oysters, 8,600
in lobsters, and 23,000 in mussels.(28)
Regulations - OSHA has set a standard air TWA of 500 mg/M3
for arsenic. DOT requires a "poison" warning label.
The Office of Toxic Substances under FIFRA has issued a
t
pre-RPAR. The Carcinogen Assessment Group has identified arsenic as a com-
pound which exhibits substantial 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
preregulatory assessment of arsenic based on its suspected carcinogenic
effects. The Office of Water Planning and Standards under Section 304(a)
of the Clean Water Act has begun development of a regulation based on
-SCft-
-------
health effects other than on carcinogenicity 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.
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-SJO-
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V. References
!. Kelso, G,, R. Wilkinson, J. Malon, Jr., and T. Ferguson. Develop-
ment of Information on Pesticides Manufacturing for Source Assessment
EPA-600/2-78-100. Environmental Protection Agency, Research
Triangle Park, NC, 1978.
2. Proprietary information submitted to EPA by Diamond Shamrock in
response to a "308" letter.
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, 1978. Registry of Toxic Effects of Chemical Substances.
8. Thornhill, J., 198.0,... USEPA-ORD, Ground Water Research Branch,
Ada, OK Personal Communication.
9. Koerner, E. L. and D. A. Haus, 1979. Long-Term Effects of Land
Application of Domestic Wastewater. EPA-600/2-79-072. USEPA,
Washington, D.C.
10. Hounslow, A. W. 1980 Ground Water Geochemistry: Arsenic in Land-
fills. Ground Water Journal (in press).
11. Gleason, M. N., et al. Clinical Toxicology of Commercial Products.
Acute Poisoning. (1969) 3rd ed., p. 76.
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 Bennett, B. M. Effect of arsenic trioxide exposure
on mortality. Arch. Environmen. Health 7:5883 (1963).
14. Kwratune, M., et al. Occupational lung cancer among copper swelters.
Int. Jor. Cancer 13:552 (1974).
15- OH, M. G., et al. Respiratory cancer and occupational exposure to
arsenicals. Arch. Environ. Health 29:250 (1974).
-SM-
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16. Baetjer, A. M., et al. Cancer and occupational exposure to inorganic
arsenic. 18th Int. Cong. Occup. Health. Brighton, England, p. 393
jLn Abstracts, September 14-19 (1975)
17. Tseng, W. P., et al. Prevalence of skin cancer in an endmeic area
of chronic arsenicism in Taiwan. Jour. Natl. Cancer Inst. 40:453
(1968).
18. ECAO Hazard Profile; Arsenic. (1980) SRC, Syracuse, NY
19. Nordenson, I., et al. Occupational and environmental risks in and
around a swelter 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 Allison, A. C. Chromosome damage in human cell
cultures induced by metal salts. Mutat. Res. 16:332 (1972).
i
22. Moutsheen, J. and Degraeve, N. Influence of thiol-inhibiting
substances on the effects of ethyl methyl sulphonate on chromosomes.
Experientia 21:200 (1965)
23. Hood, R. D. and Bi,shpp, S. L. 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 hamster. Arch. Environ. Health 22:557 (1971).
26. U.S. EPA. 1979. Arsenic: Ambient Water Quality Criteria. Environ.
Protection Agency, Washington, D.C.
27. WHO. 1979. Environmental Health Criteria: Arsenic. World Health
Organization. Geneva.
28. Sperling, L. Wisconsin's Hazardous Waste Line, Wisconsin Natural
Resources. Vol 4 (1): 14-16, 1980.
29. Sax, N. Irving, 1975. Dangerous Properties of Industrial Materials.
Fourth Edition, Van Nostrand Reinhold, New York.
30. National Research Council, Arsenic, National Academy of Sciences,
Washington, D. C. 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
t
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
Rogerdale Road facility.
-SJ3-
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MSMA - Arsenic trioxide and liquid caustic soda are reacted to
form sodium arsenite. This solution of sodium arsenite is then reacted
with methyl chloride to form a DSMA (disodiun 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 uethylarsenate. 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 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 enulsifiers are added. The product is then either drummed at the
plant or shipped in bulk form to a packager.
Cacodylic Acid - MSMA is reduced using sulfur dioxide. This
reduced HSMA is neutralized with caustic soda and then reacted with methyl
chloride to form cacodylic acid. The cacodylic acid is concentrated,
cooled and centri'fuged with the cacodylic acid in the liquid phase going
to a formulating tank and the salt cake collected for disposal.
Chemical Analysis - Samples from the Company's existing waste
water holding ponds have yielded the following analysis.
pH
Total Residue (105°C)
Alkalinity, as CaC03
Hydroxyl
Bicarbonate
Carbonate
Chloride
Nitrate N
Sulfate
Total Organic Carbon
Metals
Arsenic
Barium
Boron
Cadmium
Calcium
Chromium
MSMA
Salt Cake
Wastewater
(Pond)
Wastewater
(Sump)
-_7. 9
30%
0 mg/1
1,800
3,920
78,000
0.60
103,000
2,400
6,300
<0.5
<0.02
4.6
116
26
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
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
-SV6--
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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.
-------
*• Biological treatment - The nature of this waste does not enable
it to support sustained biological growth. Any sludge produced by this method
would be highly contaminated and would pose additional disposal problems.
5. Neutralization - Neutralization is not a viable method of dis-
posal in this instance because highly toxic precipitates would be produced.
6. Incineration - Since the principal contaminant in this waste
stream is arsenic, incineration is not an acceptable method of-disposal.
Arsenic trioxide sublimes at a temperature of 192 degrees C. and results
in highly toxic conditions with the potential for serious air pollution.
Compatibility - Compatibility studies will be conducted after cores are
taken from the injection interval and a sample of formation water is obtained.
Pretreatment Facilities - Existing settling ponds will be closed at the
company's plant site. Crystal proposes to transfer waste from the process
area to two welded steel storage/settling tanks comprising a total capacity
of 420,000 gallons. A portion of the waste stream will be diverted to
slurry the salt cake by-product of the MSMA process. This slurry will
then be transferred to the settling tanks. From the settling tanks, fil-
tration will be accomplished by two 60 GPM units installed in parallel.
From these filters, the waste stream will enter a 2,000 gallon surge tank,
and pass through a cartridge-type guard filter on the way to the injection
pumps and the wellhead.
Solids accumulating in the settling tanks will be removed periodically
and transported to an approved off-site disposal facility. Crystal currently
-------
operates under Registration No. 30781, Class I, and No. 30722, Class I
and Class II covering off-site disposal of solid waste.
Emergency Storage - In the event of an extended well shut down, normal
waste output plus any contaminated runoff will be stored in steel tanks
and will be transported off-site to a commercial deep well facility.
DRILLING AND COMPLETION OF THE DISPOSAL WELLS
A 14-3/4" hole will be drilled to 2,200 feet. Surface casing
(10-3/4") will be set to this depth and cemented in place. From 2,200
feet, a 9-7/8" hold will be advanced to the total depth of 4,500 feet,
whereupon longstring casing (7") will be set to TD and cemented in place.
Only the primary injection zone from a subsurface interval of 4,350 + to
4,500 + will be initially^completed. Injection into this zone will be
accomplished through 3-1/2" steel tubing. A 4" wire-wrapped stainless
steel screen will be utilized throughout the injection zone. Isolation
of the injection zone from the tubing longstring casing annulus will be
maintained by a packer. Gravel packing will be employed to control sand
influx to the wellbore in the injection zone.
-svs-
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ATTACHMENT II
PHONE LOG
-sn-
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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, 717-787-7381
Re: Vineland Chemical Solid Waste Telephone JXX| Conference
(MSMA & Cacodylic 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% NaCl, 40%~Na9S04 and less than 1%
arsenic (according to VineJand). Vineiand 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 Cacodylie Acid production.
-520-
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MEMORANDUM OF ORAL ADVICE
Date: December 18, 1979
Name: David Barker, TDWR 512-475-5633
Re; HSMA Waste - Diamond Shamrock Telephone |xx| Conference |"~
Facts and Query: Quantity, Composition and Disposal practices ,of MSMA
solid waste — Diamond Shamrock.
Answer; Waste contains NaCl-Na?SO,4 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; E.G. Monnig
Comments:
-------
MEMORANDUM OF ORAL ADVICE
Date; December 31, 1979
Name: David Jeffrey TDWQ
Re; Cacodylic Acid and MSMA Waste Telephone |XX| Conference
Facts and Query: 1) Is the Crystal Chemical Solid waste report a matter
of public .record? Yes* •
j
2) Does MSMA salt also contain Cacodylic Acid by-
products? Probably*
Answer:
By: E.G. Monnig
Comments:
-------
LISTING BACKGROUND DOCUMENT
CHLORDANE PRODUCTION
Wastewater and Scrub Water from the Ch lor inat ion of
Cyclopentadiene in the Production of Chlordane (T)
Wastewater Treatment Sludges from the Production of Chlordane (T)
Filter Solids from the Filtration of Hexachlorocyc lopent adiene
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 hexachlorocyc lopent a-
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 chlorination of
Cyclopentadiene, wastewater treatment sludge and
filter solids from hexach lorocyc lopent adiene
filtration contain hexach lorocyc lopent adiene .
Hexachlorocyclopent adiene 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 mutagenic.
-5-23-
-------
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
proiected 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 Producers^)
and two other sources'^ , 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.'^)
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, nonagricu1tural 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 eyelopentadiene to
* All underlined information is from properietary reports
and data files.
-------
3RUBE
I
iA
JO
r-
t
CYCrOPeNTAD16Rl~ VENT
•f CHLORINE p '
I Wj _
1 il i
5ER WATER WASTE WATER
r
_r
SOLIDS
/ENT
DECA
WASTE
MTCD
IM 1 tn
WATER"
f
POND
>
FILTER"
t
"DEEP
WELL
m—m—m^ ^11 TfTH M.
i T s
( III
1 FILtER CAKE
TO CLAY PIT
OR LANDFILL
< II
WASTE WATER
•TREATMENT
SLUDGE
I
fO OFF-SITE
LANDFILL
CYCLOPENTADIENE
1_
._ lfci oriMnr
I
KBfDIELS"
"" * ALDER
I
CHLORDENE
02C12 f
,(C) VI
I
.CHLORDANE
. „,_„„,,_ \/i^MT \iAr*t 11 iim
'NSCri VCNTr VACUUM
.nouii — *- STRIPPtH
J...
STRIPPER
^"WATER TO
' HOLDING PON!
..- ^ __ ^n __ „
ENT ^ / VACUUM
1
~~~i\r
'STRIPPER
, WATER
! TO
HOLDING
POND
PROCESS AND WASTE SCHEMA1TC~(MO^
-------
to obtain hexachlorocyclopentadiene. The hexachlorocyclopen-
tadiene is 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)
+ Cl,
CYCLOPENTADIENE
(B)
KEXACHLOROCYCLOPEN lADIENE
(C)
+ C\z or
S02CL2
C!
C!
CHLORDENE
HEXACHLOROCYCLOPENTADIENE
Cl
DIELS
ALDER
CONDENSATION
Cl
CHLORDENE
Cl
Cl
CHLORDANE
Cl
Cl
HEPTACHLOR
+ OTHER ISOMERS
-X-
-------
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:
Wastewater and scrub water from the chloric-nation
of eyelopentadiene
Wastewater treatment sludges
Filter solids from the filtration of hexachlorocvclo-
pent ad iene
Vacuum stripper discharges from chlordene chlorinator
in the production of chlordane
Hexachlorocyclopentadiene is the constituent of concern
in the first three listed wastes; chlordane, heptachlor, and
other chlorinated organics are the constituents in the last
listed waste.
Each 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 eyelopentadiene and subsequent separation
steps.
-x-
-------
(4). The eyelopentadiene contai
ns
numerous cyclic compounds, which when chlorinated result in
a multiplicity of toxic chlorinated cyclic compounds, among
which hexach lorocyc lopent adiene predominates, since it is the
principal reaction product. Wastewater from reactor cleanup,
decanting and vent scrubbing thus contain significant amounts
of these components. As shown in Figure 1, this waste is
sent to a settling pond.
The second listed waste (II) is a result of the treatment
of the wastewater which contains hexach lor ocyc lopent adiene and
other toxic chlorinated organics. Since, hexach lor ocyc lopent-
adiene is relatively insoluable (25mg/l) (29) and is amenable
to b iode gr adat ion due to its physical chemical form, the Agency
expects this toxic organic to be present in the sludge.
Furthermore, concentrations of hexach lor ocyc lopent ad i ene in
the sludge would be expected to be significantly higher than
in wastewaters due to the undiluted composition of this waste.
'4") Wastewater treatment sludge is
sent to an off-site landfill for disposal. '^)
The third waste, namely filter solids from the filtration
of hexachlorocyc lopent adiene (III) results when the crude
hexach lorocyc lopent adiene is filtered before it is reacted to
form chlordene (before reaction B). The filtration process is
intended to remove organic impurities, including hexachloro-
cyc lo pen t ad iene . It is thus expected that this constituent
-------
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. (3)
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 toxicity and capacity for genetic harm, as well as the
history of waste mismanagement associated with the sole
producer of chlorodane (see pp. 12-13 below). In any case,
concentrations 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 product (chlordane).
III. DISCUSSION OF BASIS FOR LISTING
A* Hazards Posed by the Wastes
As previously mentioned, the listed 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,
hexachloropentadiene has been documented to alter kidney
-------
functions, and cause eye and throat irritation and headache
in humans. (For further information, see Health and Ecological
Effect of Constituents pp. 14-17.)
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.(3) sludges from this holding pond
and filter solids from hexachlorocyclopentadiene filtration
are taken off-site for disposal*(3) 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 of even small
amounts of water) . ThJLs 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 Damage Incidents,
pp. 10-14) 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
-S3O-
-------
either in their not being properly handled during transport
or in their not reaching their destination at all (thus
making them 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
/
tp this particular consideration, there was a damage incident
in'Memphis/.Tennessee, .(discussed in detail on p. 12), due to
similar, unmanifested waste being illegally transported and
disposed.
2. Fate of Constituents in Waste Stream
The 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 chlordane
are relatively insoluble, their ability to migrate has been
demonstrated by documented damage incidents (see pp. 10-14).
Based upon estimates by EPA,(6) 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 sites 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
-X-
-5-31-
-------
heptachlor respectively, have been observed in surface waters,
confirming these compounds' mobility and persistence.'(?,8)
Chlordane 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 hexachlorbcyclopentadiene 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 hexa-
chlorocyclopentadiene reaction product. The link between
disposal and management of heptachlorocyclopentadiene 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 chlorinator
are of particular concern to the Agency because there also
have been documented damage incidents which show the mis-
-vf-
-------
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 mar;/ 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 or 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, many cause a potential health or environmental
hazard via air exposure or contamination of drinking water
sources.
-5-33-
-------
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 waste 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 hexachlorocyclopentadiene containing wastes
and Velisicol. 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.
-------
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 u,p 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
-535--
-------
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.(9) 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.d^)
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 toxicity of
this compound is even more severe across all freshwater and
-------
marine animal life.in particular, fish embroyos appear
to suffer devastating damage from as little as a tenth of a
microgram of chlordane.(14) The acquatic 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
' K
moderately tpxic to some soil bacteria and to earthworms.
Regulations - The OSHA standard for amounts of chloraane
in air is a TWA of 600 n/m3 (skin), based on the "one hit"
model of chemical carc.inogenesis. The USEPA has estimated
levels of chlordane in ambient water which will result in a
risk of 10""" cancer incidence of 0.12 nanograms/liter.
Presently, a limit of S^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 0.36
micrograms/liter. For saltwater species, the draft criterion
is 0.0091 micrograms/liter for a 24-hour average, not to exceed
0.18 micrograms/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 LD5Q = 40 mg/Kg], also causing deaths in
humans following ingestion of very small amounts..(16)
Heptachlor is carcinogenic, causing liver cancer in, mice.(l^)
^
Heptachlor has also been evaluated by GAG as having substantial
evidence of carcinogenic!ty,
This chemical is mutagenic and teratogenic in animals,
causing resorbtion of fetuses^"), chromosomal abnormalities
in bone marrow cells in*-adults, and' cataracts in of f spring. (^)
Heptachlor has caused a marked decrease in litter size and
lifespan in newborn rats.(^O) 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.
-------
3. 1,2,3,4,5,5-Hexachloro-l,3-cyclopentadiene (HCCP)
Health Effects - 1,2,3,4,5,5-Hexachloro-l,3-cyclo-
pentadiene (HCCP) is very toxic to animals [oral rat LD50 *
113 mg/kg]. Adverse effects have been reported when plant
workers were exposed to this chemical as a volatile component
of municipal sewage.(2^) These included alterations in kidney
functions, elevation of liver enzyme, eye and throat irritation
•• i
and headache*
While the hexachlorocyclopentadiene is not metabolicly
activated to a mutagenic form in vitro, it may form a number
of halogenated hydrocarbon residues [which have been demonstrated
to be mutagenic (^->) ] when exposed in the ecosystem. Hexachloro-
cyclopentadiene has been designated as a priority pollutant
under Section 307(a) of^the CWA. Additional information
and specific references on adverse effects of hexachlorocyclo-
pentadiene can be found in Appendix A.
Ecological Effects - HCCP is extremely toxic to minnows
with an LC$Q of 7 micrograms/liter following 96 hours of ex-
posure. (27) Bioaccumulation of HCCP in these fish is evident
from the recovery of 89% of this contaminant (on a wet-weight
basis) and, moreover, the extremely low chronic lethal concen-
tration of 6.7 micrograms/liter over a 30-day period.
Regulations - Hexachlorocylopentadiene is regulated by
the Office of Water and Waste Management of EPA under the
Clean Water Act, Section 311. Technical assistance data has
been requested to obtain data on environmental effects, high-
-yf-
-------
^olume production and spill reports. Under Judicial Order of
December 15, 1978 pursuant to the case of NRDC VS. Costle,
preregulatory assessment of suspect carcinogenicity/mutagenicity
and establishment of Safe Drinking Water Act and Clean Water
Act, Section 304(a), criteria was initiated in February 1979.
In addition, in April 1979, under the Clean Air Act, hexa-
chlorocyclopentadiene was proposed, Section 112, as a hazardous
pollutant and as a potential airborne, carcinoger*. Under the;
Toxic Substances Control Act, preregulatory assessment is
underway pursuant to possible Section 6 control actions.
-------
References
lt 1977 Directory of Chemical Producers, Stanford Research
Institute, Menlo Park, California.
2. Farms Chemical Handbook, 1977, Master Publishing Company,
Willoughby, Ohio.
3. von Rumker et al. Production, Distribution, Use and
Environmental Impact"Potential of Selected Pesticides,
USEPA Office of Pesticide Programs, EPA 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. 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. Clinical Memoranda on Economic Poisons, (1956). U.S.
Department of HEW, PHS, CDC, Atlanta, GA.
10, National Cancer Institute, (1977). Bioassay of chlordane
for possible carcinogenicity. NCI-CG-TR-8.
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 Sapena, S. C. Chronic chlordane toxi'city:
effect on blood biochemistry of meriones hurrianae.
13. Chlordane Hazard Profile, USEPA, 1979 (draft).
14. Kats, M., 1961. Acute toxicity of some organic insecticide
to three species of salmonids and to the threespine
stickleback. Trans. Am. Fish. Soc. 90:264.
-------
15. U.S.E.P.A., 1979. Chlordane: Ambient Water Quality
Criteria (draft).
16. Clinical Toxicology of Commercial Products. Acute
Poisoning. Gleason, et. al.., 3rd Ed., Baltimore,
Williams and Wilkins (1969).
17. U.S. EPA 1977. Risk Assessment of chlordane and hepta-
chlor. Carcinogen assessment group. U.S. Environmental
Protection Agency, Washington, D.C.
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. frxperientia 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 glutamine in con-
vulsions in the rat., and cockeral. Jour. Neuroceue.
18:365 (1971).
22. Kacew, S. and Singhal, R. L. The Influence of p.p^-DDT,
and Chlordane, Heptachlor and Endrin on Hepatic and
Renal Carbohydrate Metabolism and Cyclic AMP-adenyl
Cyclase system. Life Sci. 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-
pentadiene Due to Metabolic Activation. Biochem. Pha'rmacol^
27:2927-2930. ~~
26. Winteringham, P. Chemical Residues and Pollution Program
of the Joint Division of the International Atomotic
Energy Agency and the Food and Agriculture Organization
of the United Nations. Ecotoxicol. Environ. Safety.
1:407-25. (1977)
-ssa-
-------
27. Spechar, R. L. et al, Toxicity and Bio-accumulation of
Hexachlorocyclopentadiene, Hexachloronorbornadiene,
and Heptachlorobornene in Larval and Early Juveniles
Fathead Minnows. Hull. Environ. Contam. Toxicol.
21:576-83.
28. Control of Hazardous Material Spills; Proceedings of
the 1978 National Conference on Control of Hazardous
Material Spills, Miami Beach, Florida, April 11-13, 1978.
29. Dawson, English, Petty, 1980. "Physical Chemical
Properties of Hazardous Waste Constituents"
M
•
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LISTING BACKGROUND DOCUMENT
CREOSOTE PRODUCTION
Wastewater Treatment Sludges Generated in the
Production of Creosote (T)
Process Wastewater from Creosote Production (T)
I. Summary of Basis for Listing
The process Wastewater and was t ewa t er . tr,ea tment sludges
generated in the production of creosote have been found to
contain the toxic substance, creosote and the constituents of
creosote, benz(a)anthracene, benzo(b)fluoroanthene and
benzo(a)pyrene. Creosote is contained in the GAG list of
chemicals having substantial evidence of carcinogenicity, as
are its three constituents, benz(a)anthracene, benzo(b)
fluoranthene.
The Administrator has determined that solid wastes from
creosote 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 managment
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1. The hazardous substances likely to be present in
the wastes include creosote and its constituents,
-5MH-
-------
benz(a)anthracene, benzo(b)fluoroanthene, and
benzo(a)pyrene , all of which are carcinogens.
Several reported cases of cancer in humans have
been attributed to creosote exposure.
2. If the lagooning/landfilling of these wastes is
improperly conducted, the contamination of soil,
land, ground, and surface water is likely to result.
Since creosote is highly mobile and persistent,
there is increased likelihood of hazardous waste
constituents reaching environmental receptors.
There is a reported incident of surface and ground-
water contamination due to improper disposal of
creosote contaminated wastes, demonstrating that
creosote is capable of migration, mobility and
persistence and of causing substantial hazard if
improperly managed.
3. It is estimated that 60-115 million Ib/yr of creosote
is contained in the listed wastewater treatment
sludge. Thus, substantial amounts of waste con-
stituents are potentially available for environmental
release.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
In 1972, creosote was produced by six companies at
25 locations; the estimated 1972 production was 521,000 metric
tons (575,000 tons).(^) A complete list of producers, pro-
duction plants and the estimated 1972 production at each site
is presented in Table 1. Creosote is a wood preservative,
characterized by a high toxicity to wood-destroying organisms
and a very low evaporation rate. (2) Nearly all creosote
produced is used for wood preservation. However, creosote
has other uses, including as a preservative, insecticide,
herbicide, fungicide, disinfectant and tree dressing.
B. Manufacturing Process
Creosote is produced by the distillation of coal
-x-
-SHS-
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Table 1. CREOSOTE PRODUCTION PIANTS IN THE
Estimated
Plant Capacity
(million Ib/year)
ALLIED CHEMICALS CORPORATION
Detroit, Michigan
Ensely, Alabama
Ironton, Ohio
KOPPERS COMPANY, INC.
Cicero (Chicago), Illinois
Follansbee, West Virginia
Fontana, California
Houston, Texas
Portland, Oregon
Kearney (Seaboard), New Jersey
St. Paul, Minnesota
Swedeland, Pennsylvania
Woodward, Alabama
Youngstown, Ohio
REILLY TAR AND CHEMICAL CORPORATION
Cleveland, Ohio
Granite City, Illinois
Ironton (Provo), Utah
Lone Star, Texas
Chattanooga, Tennessee
USS CHEMICALS
Clairton, Pennsylvania
Fairfield, Alabama
Gary, Indiana
THE WESTERN TAR PRODUCTS' CORPORATION
Memphis, Tennessee
Terre Haute, Indiana
WITCO CHEMICAL CORPORATION
Point Comfort, Texas
100-200
100-200
100-200
100-200
100-200
200-300
10-20
10-20
10-20
10-20
10-20
100-200
100-200
10-20
10-20
10-20
10-20
10-20
100-300
100-200
100-200
10-20
10-20
Estimated
Annual Production
(million Ib)
250-350
350-450
50-100
250-350
20-40
10-20
10-20
TOTAL ANNUAL PRODUCTION (1972)
930-1,310
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tar which is produced by the high temperature carbonization
Of bituminous coal. A generalized production and waste
schematic for creosote is presented in Figure 1.
C. Waste Generation and Management
The two waste streams generated in the production
of creosote are (1) the process wastewater and (2) the sludge
resulting from the wastewater treatment plant.
During the distillation process, an appreciable
quantity of the water contained in the coal tar (1-2 percent
of the total volume) (1) is boiled off and disposed of along
with other process waters. This aqueous waste from the
distillation step in the process is the source of hazardous
constituents of both listed waste streams.
Creosote wastewater is either discharged to publicly owned
treatment works (at smaller facilities)* or treated on-site in
holding ponds (at larger plants). Where on-site treatment is
utilized, ponds are dredged periodically, giving rise to the
second listed waste stream. Based on the prevalent waste
disposal practice in the chemical industry, these wastewater
treatment sludges are transferred to a landfill for final
disposal .(!)
Discussion of Basis for Listing
A. Hazards Posed by the Wastes
1. Creosote Wastewater
listing does not include any wastewater which is dis-
charged to a POTW and which is mixed with domestic sewage
and that passes through a sewer system before it reaches a
POTW.
-X-
-5H7-
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COAL LIGHT
GAS AMMONIA OIL
CARBOLIC OIL
BIOLOGICAL TREATMENT IN HOLDING PONDS
COAL
COKE OVEN
1650-2150°F
I
NAPHTHALENE OIL
(OTHER PRODUCTS)
COAL TAR
t
T
1
WATER
DISTILLATION
(B.P. 106-395°C)
CREOSOTE
COKE
PITCH
Rgure 1. PRODUCTION AND WASTE SCHEMATIC FOR CREOSOTE'"
00
i
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The raw wastewater from the production of creosote
is expected to contain varying amounts of creosote, the
creosote constituents benz(a)anthracene, benz(b)fluoranthrene
and benzo(a)pyrene, all of which are polycylic aromatic hydro-
carbons, and other distillation intermediates. The actual
composition of the constituents in the wastewater from creosote
production depends on the source of the coal used to produce
the tar, the design and attendant operating conditions (temper-
ature, coking time, gas collection systems) of the coke
ovens, and the design and operating parameters of the still
(e.g., the feed rate, temperature, and the blending of various
tar distillation fractions). As a result of these factors
the fractional distillation is ordinarily incomplete so that
a certain amount of creosote residue is present in the raw
wastewa ter .
Based on the estimated annual production of 1,150 million
Ib/yr of creosote,* and a generation of 1 Ib creosote per 12
Ibs coal tar(6), and a 1-2% volume water content in coal tar
which is boiled off in the distillation process and disposed
of as wastewater, it is estimated that 60-115 million Ibs of
creosote per year are present in the raw process wastewater
sent to treatment. Obviously, such large quantities of this
waste have the propensity for large-scale environmental harm.
There is a greater chance that exposure (since larger expanses
*Hls figure was calculated by rounding off the mean total
annual production estimated' for 1972 shown in Table 1.
-------
of groundwater may be contaminated) and environmental loading
will occur for longer period in light of contaminant availa-
bility.
The components of this waste stream are also of con-
siderable concern as potential health hazards. As previously
mentioned, these wastes contain benz(a)anthracene, benzo(b)
fluoranthene, and benzo(a)pyrene and creosote which are
known carcinogens.
As will be demonstrated below, these waste components
could be released from holding ponds into the environment,
unless proper waste management is assured. Creosote and
the other waste constituents may be both mobile and highly
persistent, increasing the likelihood of its reaching receptors
in concentrations sufficient to cause a substantial hazard
should migration occur, the migratory potential via ground
and surface water, as well as the persistence of creosote has
been demonstrated by the damage incident described below (see
damage incident, p. 10). Further, the sheer quantity of
creosote and its constituents in the waste could overload the
sorptive capacity of the sediments. Accordingly, those con-
stitutents of creosote not adsorbed to sediments are mobile.
The following section elaborates on these points.
(a) Wastewater's Constituents' Potential to Migrate and
Cause Substantial Hazard
The two most likely exposure pathways for this waste
-x-
-S"S"O-
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are groundwater and surface water via migration from holding
ponds «
As to the migratory potential of creosote that is present
in the waste, creosote has proven, in spite of its relatively
low solubility (3°) in water (5 ppm) , to have sufficient
migratory potential and persistence to cause long-term con-
tamination following improper waste disposal. Creosote can
be expected to be highly persistent in groundwater, since
the chief degradation mechanism is oiod egr ada t ion , (30 )
which would not be expected to be a factor in the abiotic
conditions of an aquifer. Exposure also may occur via a
surface water exposure pathway should precipitation result
in flooding of holding ponds.
The waste constituents of creosote: benz ( a) anthracene ,
benzo(b) f luoranthene and benzo( a) pyr ene , are also capable
of migrating and persisting if these wastes are managed
improperly. While these constituents tend to adsorb to
organic matter, (30) management could occur on sites with
soils low in organic content or with highly permeable soil
so that mobility would not be deterred.
The polycyclic aromatic hydrocarbons are persistent in
nature, especially soils^10) with half lives, for benzo(a)-
anthracene and benzo( a) pyr ene, reported to be 7,000 and 21,000
hours, respectively^11) The Agency possesses no evidence
that benzo(a)anthracene, b enzo( a) pyr ene or benzo( b) f luorathene
do not persist. Furthermore, benzo(a)pyrene is bioaccumula-
-55)-
-------
tive,(30) ancj benz( a) anthracene is extremely bio accumula-
tive (octanol/water partition coefficient of 426,579 (30)),
so that these constituents could accumulate in harmful concen-
trations if they reach a receptor.
If this waste is improperly managed, these constituents
of creosote may be released and reach environmental receptors
and cause substantial hazard. Improper management iss certainly
reasonably plausible or possible; holding ponds may be sited
in areas with highly permeable soils, or they may lack adequate
leaching control features. Further, there may be inadequate
cover to impede migration of the waste constituents or
inadequate flood control measures to impede waste washout in
the event of heavy rainfall. Thus, mismanagement could
realistically occur, resulting in substantial hazard.
For both the creosote and its related constituents, the
Agency presently does not possess information indicating that
these compounds would no t migrate and persist in the environmen
and cause a substantial health hazard. Therefore, the Agency
would be unjustified in not listing this waste (the treatment
sludges) on the basis of these contaminants until such
contradictory information is readily available.
Additionally, there has been a documented incident of
surface and groundwater contamination due to improper disposal
of creosote containing wastes. In the 1950's, waste chemicals
including creosote and other types of wood-preserving oils
-------
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
odor and biological damage. Although injection of the wastes
into the wells ceased in the 1950's, contamination was first
observed in 1961.'*) 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.
2. Creosote Wastewater Treatment Sludge
The wastewater treatment sludges that remain after
biological treatment are also hazardous. The carcinogenic
constituents of creosote, namely benz( a) anthracene , benzo(b)-
fluoranthene and benzo ( a) pyr ene , are especially likely to be
present in the treatment sludge since these constituents
adsorb to sediments at very high levels (App. B) . Where
treatment is incomplete, creosote (which is, however, somewhat
amenable to biodegradation (App. B)), is projected to be
present in the sludge as well. If these sludges are placed
in a leaking landfill, an unlined holding pond or an improperly
sited facility (i.e., as in an area with permeable soil) the
waste constituents may be released.
As demonstrated above, the waste constituents of concern
are capable of migrating and persisting and reaching environ-
mental receptors if managed improperly. Since the waste
constituents include benz( a) anthracene , benzo( b) f luoranthene ,
-55S-
-------
benzo(a)pyrene and, creosote, which are known carcinogens
should substantial environmental harm can result from exposure
even to minute concentrations* if mismanagement should occur.
B. Health and Ecological Effects
1. Creosote
Health Effects - Creosote is carcinogenic in animals(25)
and has been associated with several occupational cases of
skin cancer over a fifty year period.(26) Creosote has also
been identified by the Agency as a compound which exhibits
substantial (31) evidence of carcinogenicity. This chemical
is mutagenic in a variety of bioassay test systems,(25)
and reportedly affects fetal development.^/)
Creosote is toxic in rats (oral LD5Q = 275 mg/Kg],
while death in humans has resulted from ingestion of much
smaller doses.(24)
Additional information and specific references on adverse
effects of creosote can be found in Appendix A.
Ecological Effects - Creosote is a mixture of chemical
compounds, and while there was an abundance of data on its
various components, data were somewhat limited on creosote
itself. Ellis'^' found fish kills occurring at concentrations
*See 44 Fed. Reg. 15926, 15930 (March 15, 1979) (no zero
exposure level for carcinogens).
-------
as low as 6.0 mg/1 in less than 10 hours. Applegate, et al.,(13)
in a large battery of tests with a limited number of animals,
including rainbow trout Salmo gainneri and lamprey larvae
marinus, found that concentrations of 5.0 mg/1
induces mortality.
It has been reported that PAH's from a contaminated
lagoon were accumulated to a greater degree of biota species
near the top of the food chain . C12 ), One PAH, benzo( a) pyr ene ,
1 ' ' i
•( ' ' ' i • • > 'i
has been reported to accumulate in mussels taken from PAH-
treated pilings. (3)
Regulatory Recognition of Hazards - The Office of Toxic
Substances has issued an RPAR on creosote and is continuing
preregulatory assessment under Section 6 of the Federal
Insecticide, Fungicide and Rodenticide Act.
Industrial Recognition of Hazard - Sax, Dangerous
Properties of Industrial Materials, designates creosote as
moderately toxic via oral, inhalation, and dermal routes.
2 . Benz(a) anthracene , B enzo ( b) f luoranthene and
Benzo(a)pyrene.
Health Effects - Benz ( a) anthracene and Benzo ( b) f luoran-
thene are carcinogenic in animals .( 28 > 29) Benzo( a)pyrene
has been tested extensively for carcinogenic! ty and found to
exert positive results by all routes tested. (22) The Agency
has also identified these compounds as carcinogenic'3 '.
Additional information and specific references on the ad-
verse effects of benz( a) anthracene , benzo( a) pyr ene and benzo(b)-
-sss-
-------
f luor an thene can be found in Appendix A.
Ecological Effects - Eighty-seven percent of freshwater
fish exposed to 1,000 ug/1 benz ( a) ant hr acene for six months
Regulations - Benz( a) anthracene and benzo ( b) f luoranthene
are undergoing pr e-r egula to ry assessment by the Office of
Water and Waste Management under the Safe Drinking Water Act
for health effects other than oncogenici ty . The Office of
Water and Waste Management under the Safe Drinking Water Act
is also conducting a pr e-r egula tory assessment of benzo(a)-
pyrene based on its car cinogenici ty and other health effects.
-sst,-
-------
References
lt von Rumker et al, Production, Distribution, Use and
Environmental Impact Potential of Selected Pesticides
EPA 540/1-74-001, 1975.
2, Farm Chemicals Handbook, 1977, Meister Publishing Company
Willoughby, Ohio. '
3. American Wood Preservers' Association (1976). A.V.P.A.
Book of Standards, Washington, D.C.
4. .NIOSH Registry of Toxic Effects of.Chemical Substances,
U.S. .Department of Health, Education and Welfare.
5. Damage incident, u.b. environmental Frotection Agency,
open file, unpublished data.
6. Telephone communication to: Mr. J. Burroughs, Manager,
Allied Chemical Corporation, Detroit, Michigan, 12
February 1980. (S. Quinbran, TRW.)
7. (1978) Wood Preservative Pesticides - Notice of Rebuttable
Presumption. Fedejcal Register - Vol. 43:48154-48295.
8. I. S. Schipper (1961). The Toxicity of Wood Preserva-
tives for swine. Am. J. Vet. Res. 22:401-405.
9. (1978) NIOSH. Registry of Toxic Effects of Chemical
Substances.
10. National Academy of Science. 1972. Particulate Polycyclic
Organic Matter. Committee on Biological Effects on
Atmospheric Pollutants, Div. of Med. Sci., Natl. Res.
Council, Natl. Acad. Sci., Washington, D.C. 361 pp.
11. Herbes, S. and L. Schwall. 1978. Microbial Transfor-
mation of Polycyclic Aromatic Hydrocarbons in Pristine
and Petroleum Contaminated Sediments. Appl. Environ.
Microbial. 35(2): 306-316.
!2. Naiussat, P. and C. Auger 1970. Distribution of benzo-
(a)pyrene and Perylene in various organisms of the
Cliperton Lagon Ecosystem. C.R. Acad. Siv., Ser. D.
270(22): 2702-2705.
13» Applegate, V.C., J.H. Howall, and A.E. hall, Jr. 1957.
Toxicity of 4346 chemicals to larval lampreys and
fishes, Dept. of Interior, Special Sci. Rept. No.
207.
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-5S-7-
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14. Ellis, M.M. 1943. Stream pollution studies in the State
of Mississippi. U.S. Dept. of Interior, Special Sci.
Kept. No. 3
15. Gleason, et al 1969. Clinical toxicology of commercial
products. Acute poisoning. 3rd ed. Baltimore, Williams
and Wilkins, p.42.
16. NIOSH, 1978. Registry of Toxic Effects of Chemical
Substances. DHEW Publication No. 79-100, p. 370.
(crossed out in notes)
17. Patty, F.A. 1963, Industrial Hygiene and Toxicology,
Vol. 2, 2nd ed. New York, Interscience.
18. U.S. EPA. 1979. Environmental Criteria and Assessment
Office. Benz(a)anthracene: Hazard Profile, (draft)
19. U.S. EPA. 1979. Environmental Criteria and Assessment
Office. Benz(b)fluoranthene: Hazard Profile (draft)
20. U.S. EPA. 1979. Investigation of selected environmental
contaminants: Acrylamides.
21. U.S. EPA. 1979. Environmental Criteria and Assessment
Office. Acrylami^de: Hazard Profile (draft)
22. U.S. EPA. 1979. Environmental Criteria and Assessment
Office. Benzo(a)pyrene: Hazard Profile (draft)
23. Toxicol. Appl. Pharmacol. 6:378 (1964).
24. Gleason, et al., (1969) Clinical Toxicology of Commercial
Products. Acute poisioning, 3rd ed. Baltimore, Wiliams
and Wilkins, p.42.
25. Wood Preservation Pesticides - Notice of Rebuttle Resumptin.
Fed. Reg. 43:48154-48295 (1978).
26. Farm Chemicals Handbook. (1977) Meister Publishing
Company, Willoughby, Ohio.
27. Schipper, I.S. The Toxicity of Wood Preservatives for
Swine. Am. J. Vet. Res. 22:401-405 (1961).
28. U.S. EPA. (1979) Environmental Critera and Assessment
Office. Benz(a) anthracene: Hazard Profile (draft).
29. U.S. EPA. (1979) Environmental Criteria and Assessment
Office. Benz(b) fluoranthene: Hazard Profile (draft).
-------
30. Dawson, English, and Petty, 1980, "Physical Chemical
Properties of Hazardous Waste Constituents.
31. Cancer Assessment Groups List of Carcinogenic Compounds,
April 22, 1980.
-------
LISTING BACKGROUND DOCUMENT
DISULFOTON PRODUCTION
Wastewater Treatment Sludges from the Production of Disulfoton (T)
Still Bottoms from Toluene Reclamation Distillation in the Production
of Disulfoton (T)
I. SUMMARY OF BASIS FOR LISTING
The organic waste streams from disulfoton production contain a
variety of intermediate products which are toxic (i.e., toluene and
o,o,o-triethvl ester of phosphorodithioic acid).
The Administrator has determined that the solid waste from disulfoton
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. It is estimated that disulfoton production is responsible for
generating approximately 300 Ibs/day of wastewater treatment
sludges. The sludge is expected to contain the toxic constituents
toluene and 0,0,0 triethyl ester of phosphorodithioate.
2. It is estimated that 120 metric tons/yr of still bottoms con-
taining o,o,o-triesters of phosphorodithioic acid and toluene
are generated from the production of disulfoton.*
*The Agency is aware that these wastes also contain the toxic organic, disulfo-
ton. However, due to the propensity of disulfoton to rapidly hydrolize, it
will not persist in the waste for extended periods of time. Based on this
fact, the Agency will not presently regulate these wastes on the basis of
disulfoton contamination.
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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. V' Production for 1974 was estimated at 10 mil-
: '
lion pounds.
Disulfoton is a systemic insecticide, primarily used to control
sucking insects, especially aphids 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.
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(B) PCL3 + 3HOC2H4-S-C2H5 > 3C1C2H4-S-C2H5 + H3P03
"Thio-Alcohol" "Chloro Thio Alcohol" (CTA)
(C) (C2H50)2P(S)SNa + C1C2H4-S-C2H5 —> (C2H50)2P(S)-S-C2H4-S-C2H5 + NaCl
DES CTA Disulfoton
A process flow diagram and waste schematic is shown in Figure 1.
The reaction between P2S5 and ethanol in toluene solvent occurs and
produces the diethyl phosphorodithioic acid. The major side product of
the reaction is the o,o,o-triethylester of'the phosphorodithioic acid*.
The dithioic acid is next converted on the diethyl salt (DES) 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,o,o-triethyl
ester of phosphorodithioic acid go to disposal.
PC13 and thio alcohol are then reacted to form the chloroethyl
thioethyl ester ("chloroethyl thioethyl alcohol, CTA") and phosphorous
acid (Reaction B, above, and corresponding (B) in Figure 1).
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 to in this document as o,o,o-triester.
-------
MAKEUP
.TOLUENE
!SOLVENT
ETHANOL
PC13
RECOVERED TOLUENE
DES
UNIT (A)
CRUDE
DES
TOLUENE
RECOVERY
UNIT
DES
WASTE
SOLIDS
(II) 0.0.0 TRIES TER ,
TO BURIAL
WASTE WATER
'THIO-ALCOHOL
CTA
UNIT (B)
CTA
I
DISYSTON
UNIT
(C)
•\ f
DISYSTON
SOLVENT
RECOVERY
UNIT
WASTE
WATER
TREATMENT
(I) WASTE WATER
TREATMENT SLUDGE
DISULFOTON
PRODUCT
WASTE
WATER
Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR DISULFOTON
[ADAPTED FROM CHEMAGRO DRAWING (3)]
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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 diethyl salt from the DES 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 disyston recovery unit
and sent for burial in landfills.^ '
The disyston 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)
*/ The waste stream from the disyston recovery unit is not specificically
listed as hazardous, but the combined waste stream is deemed hazardous
under the 'mixing' provision of §261.3.
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HI. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Wastes
There are two solid waste streams which are 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 Stream II)
\
are expected to contain triesters and unreacted toluene. There is
little information on the toxicity of the triesters; however, the
compound is structurally similar to 0,0,s-triethylester, a member of
a family of compound which is very toxic (LD5Q = 80 rag/kg after 8
days) (22)t Toluene is a toxic chemical with such acute toxic effects
in humans exposed to low concentrations (200 ppm) as excessive depression
of the nervous system. d°)
The wastewater treatment sludges (Waste Stream I) also contain
toluene solvent and o,o,o-triethylester of phosphorodithioic acid,
which is a process intermediary. (For information on the toxic effects
of these compounds, see Section ill B.)
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
-sw-
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plastic lined drums are used, represents a potential hazard if the landfill
is improperly designed or operated (the drums corrode in the presence of
even small amounts of water). This can result in leaching of hazardous
compounds and subsequent contamination of ground water.
As a result, the waste constituents of concern may migrate from
improperly designed and managed landfills and contaminate ground and
surface waters. Toluene is highly soluble (470 ppm)^4) an<£ by
virtue of'its solvent properties, can facilitate mobility and
dispersion of other toxic constitutents assisting their movement toward
ground and surface waters. The migratory potential of toluene is confirmed
by the fact that toluene has been detected migrating from the Love Canal
site into surrounding residential basements and solid surfaces, demon-
strating ability to migrate through soils ("Love Canal Public Helath
Bomb", 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 is likely to persist in soil and groundwater.
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 Hg (24)) and is mobile and persistent
in air, having been found in school and basement air at Love Canal
("Love Canal Public Health Bomb", supra).
Although very little information is available on the characteristics
of o,o,o-triethylesters, the Agency is aware of the hazardous characteristics
of the same family of compounds as this particular triester. The Agency
-------
would require some assurance that the waste components will not migrate
and persist to warrant a decision not to list the vaste. No cuch assurance
appears readily available.
Thus, these waste constituents could leach into groundwater if
landfills are unlined, or have inadequate leachate collection systems.
Waste management facilities located in areas with highly permeable
soils would likewise facilitate leachate 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 Hg (24)) and is mobile and persistent
in air, having been found in school and basement air at Love Canal
("Love Canal Public Health Bomb," 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 skin. The acute toxic
effect in humans is excessive depression of the central nervous system,^15'
and this occurs at low concentrations [200 ppm] . - Chronic occupational
exposure to toluene has led to the development of neuro-musnular 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 matabolic 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 chemicals into the body. Thus, synergistic effects of toluene on the
toxicities 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 shovn to be acutely
toxic to freshwater fish ^and to marine fish. Chronic toxicity is also
reported for marine fish.'•A***'
Regulations - Toluene has an OSHA standard ,for air TWA of
200 ppra. The Department of Transportation requires a "flaamable 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. Phosphorodithioic and Phosphorothioic Acid Esters (Triesters)
Health Effects - The -s,s-methylene o,o,o,o-tetraethyl
ester is extremely toxic by various routes of administration to animals
[oral rat LD^Q = 13 mg/kg]/19' Toxic effects in the blood of humans have
been observed at minute doses [100 micrograns/kg],(20) v^^e human death
from ingestion of this chemical has also occurred at low doses [50 mg/kg].^ '
The phosphorothioic acid -o,o,o-triethylester is a member of a family of
compounds, which, when given orally to rats is very toxic [LD5Q = 80
rag/kg after 8 daysj.^22' The -0,0,s-trimethyl ester is extremely toxic
to rats [LD5Q = 15 mg/kg],'23' Additional information and specific
references on adverse effects of phosphorodithioic and phosphorcihioic
-------
acid esters can be found in Appendix A.
Industrial Recognition of Hazard - Sax (Dangerous Proper-
ties of Industrial Materials), lists triethyl phosphorothioate (phosphoro-
thioic acid, o,o,o-triethyl ester) as being highly toxic via ingestion
and inhalation.
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IV. References
1. 1977 Directory of Chemical Producers, Stanford Research Institute,
Menlo Park, California.
2. Kelso, G. L, R. Wilkenson, T. L. Ferguson, and J. R. Maloney,
Development of Information on Pesticides Manufacturing for Source
Assessment, Final Report, Midwest Research Institute, EPA Contract
No. 68-02-1324, July 30, 1976.
3. von Rumker et al, Production, Distribution, Use and Environmental
Impact Potential of Selected Pesticides, USEPA Office of Pesticide
Programs, EPA 540/1-74-001, 1975.
4. Lawless, E. W., R. von Rumker, T. L. Ferguson, The Pollution Poten-
tial in Pesticide Manufacturing, TS-00-72-04, June 1972.
5. Cotton, F. A. and G. Wilkinson, Advanced Inorganic Chemistry, New
York, Interscience Publishers, 1972.
6. Bailer, J. C., Comprehensive Inorganic Chemistry, Volume 2, New York,
Pergamon Press, 1973.
7. Fezt, C., and K. J. Schmidt, The Chemistry of Organophosphorous Pest-
icides, New York, Springer-Verlag, 1973.
8. Parsons, T., Editor, Industrial Process Profiles for Environmental
Use: Chapter 8, Pesticide Industry, EPA-600/77-023h, Technology
Series, EPA PB-266 225.
9. Marcus, M., J. Spigarelli and H. Miller, Organic Compounds in Organo-
phosphorous Pesticide Manufacturing Vastewaters, Midwest Research
Institute, Kansas City, Missouri, Contract No. 68-03-2343, 1977.
10. Office of Water Programs, Applied Technology Division, The Pollution
Potential in Pesticide Manufacturing, TS-00-72-04.
11. Proprietary information submitted to EPA by Mobay Chemical Corporation
through 1978 response to "308" letter.
12. Office of Water and Hazardous Materials, Effluent Guidelines Division,
Development Document for Interim Final Effluent Limitations Guide-
lines for the Pesticide Chemicals Manufacturing Point Source Category,
Washington, 1976.
13. NIOSH (1978) Registry of Toxic Effects of Chemical Substances.
Pyridene.
-------
IV. References (Continued)
14. Gleason, H.N., et al. Clinical Toxicology of Commercial Products.
Acute Poisoning. (1969) 3rd Ed., p. 61. ~~ ~" "'
15. U.S. EPA (1979) Toluene Ambient Water Quality Criteria.
16. NIOSH (1978) Registry of Toxic Effects of Chemical Substances.
Toluene.
17. U.S. EPA. 1979. Toluene Ambient Water Quality Criteria. (Draft).
i
18. U.S. EPA. 1979. Toluene: Hazard Profile. Environmental Criteria
and Assessment Office, U.S. EPA, Cincinnati, Ohio.
19. Pharmaceutical Journal 185:361 (1960).
20. Toxicol. Appl. Pharmacol. 22:286 (1972).
21. Clinical Toxicology of Commercial Products. Acute Poisoning.
Gleason, M.N. , et al. (1969) 3rd Ed., p. 65.
22. Mallipute et al. J. Agric. Food Chen. 27:463-466 (1979).
23. Fukukto et al. Quarterly Progress Reports to EPA, August 1978 -
November, 1979. EPA Grant No. R804345-04.
24. U.S. EPA. 1980. Physical Chemical Properties of Hazardous
Waste Constituents"(Prepared by Southeast Environmental Research
laboratory; Jim Felco, Project Officer.
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LISTING BACKGROUND DOCUMENT
PRORATE PRODUCTION
Wastewater Treatment Sludges from the Production of Phorate (T)
Filter Cake from the Filtration of Diethylphosphorodithioic Acid
in the Production of Phorate (T)
Wastewater from the Washing and Stripping of Phorate Production (T)
I. Summary of Basis for Listing
The hazardous wastes from phorate production are: (i; wastewater
treatment sludges from the production of phorate, (2) filter cake from the
filtration of diethylphosphorodithioic acid, and (3) wastewater from the
washing and stripping of phorate product.
The Administrator has determined that these solid wastes from phorate
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) Wastes from the production of phorate may contain phorate, for-
maldehyde, esters of phosphorodithioic acid and phosphorothioic
acid.
2) Phorate is extremely toxic and formaldehyde has been evaluated
by the Agency as exhibiting substantial evidence of carcinogen-
icity. The other constituents expected to be present in the
waste are also toxic.
3) Disposal of these wastes in improperly designed or operated
landfills presents a potential hazard due to the risk of
these hazardous compounds leaching into groundwater. As
-------
these hazardous compounds are likely to persist in ground-
water, drinking water supplies derived from these sources
are 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(3).
Phorate is produced in this country by two manufacturers, Amer-
ican Cyanamid at Hannibal, M0(l>6) ancj Mo bay 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 phosphorodithioate with formaldehyde, followed by the addition of
ethyl mercaptan (ethanethiol). The o,o-diethyl hydrogen phosphorodi-
thioate is condensed with formaldehyde and ethyl mercaptan. The reaction
chemistry is as follows (*):
"__ OT The Agency has been informed, however, that
American Cyanamid no longer produces phorate.
All underlined information is from proprietary reports and data.
-S7H
-------
P2S5 + C2H5OH -> 2 (C2H50)2PSH + H2S
phosphorous ethanol o,o-diethyl
pentasulfide hydrogen
phosphorodithioate
(C2H50)2PSH + H2C=0 ~ > (C2H50)2PS-CH2OH
0,0-diethyl formaldehyde dithiophosphate
hydrogen
phosphoro-
dithioate
(C5H50)2P-S-CH2OH + C2H5SH — > (C2H50)2P-SCH2SEt + H20
ethyl
mercaptan 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, phosphorodithioc and phosphorothioc acid
esters, and other main reaction byproducts.
CD
-_ _ m
-------
Figure 1 is Confidential
-576-
-------
(b) Filter Cake: The filter cake is expected to contain
high concentrations of esters of phosphorodithioic
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 50 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 0,0,o-triethyl esters of both phosphoro-
thioic acid and phosphorodithioic acid (as well as other triethyl 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, 0,0,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-
-577-
-------
yzation and biodegradation, will persist for weeks in both surface waters
and ground water (38). o,o,o,-Triethyl esters of phosphorothioic acid
are soluble and persist in both surface water and groundwaters.C38)
Formaldahyde is quite soluble and has great migratory potential. (38) If
disposed of in areas with inorganic or permeable soils, it could become
highly mobile. Formaldahyde also persists in surface and groundwatersC38) .
Based upon estimates of EPA, (?) exposure to these compounds is likely via
i
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,
mobility, 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 landfills can create a potential hazard if landfills are im-
properly 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
-57S-
-------
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 routes of administration [oral rate LD5Q = 1.1 mg/kg].(9~11' Death
in humans has been reported as a result of ingestion of extremely small
doses. (12) Inhalation of phorate by mice caused adverse effects on
reproductive performance at very low concentrations (3.0 ppm), (13) while
the lethal dose by inhalation in rats is also very low [11 mg/kg].(14)
Minute oral dosages of this chemical (in the range of 0.05-1.24 mg/kg)
caused significant depression of a neurotransmitter (cholinesterase) and
mortality. (15) phorate metablites are at least twice as toxic as
phorate.(16,17) 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^) with
-X-
-------
nasal cavity tumors detected in two studies. It has also been mutagenic in
several bacterial and human cell culture assays. (19-22) Formaldehyde is very
toxic to animals by all routes of administration (23-27) } causing death in
humans in small amounts (36 mg/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
can cause- toxic effects to exposed aquatic life.(29) It is lethal to Daphnia
Regulatory Recognition of Hazard - Formaldehyde is a chemical
evaluated by GAG as having substantial evidence of carcinogenicity.(39)
OSHA has set a standard air TWA limit of 3ppm for formaldehyde.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials , lists formaldehyde as highly toxic to skin,
eyes, and mucous membranes.
3. Phosphorodithioic and Phosphorothioic Acid Esters
Health Effects - The phosphorodithioic acid s ,s!-methylene-
0,0,0' ,o'-tetraethyl ester is extremely toxic by various routes of admini-
stration to animals [oral rat LD5Q = 13 mg/kg].(33) Toxic effects
in the blood of humans have been observed at minute doses (100 ug/kg)(34),
while human death from ingestion of this chemical has also occurred at
low doses [50 mg/kg].(35>
The phosphorothioic acid o,o,o-triethyl ester is similar to the
-sso-
-------
o,o,s-triethyl ester, which is very toxic when given orally to rats [LDcn =
80 mg/kgj.^ ' The o,o,s-triethyl ester is extremely toxic to rats [LDsn *
15 mg/kg].(37) Additional information and specific references on adverse
effects of phosphorodithioic and phosphorothioic acid esters can be found in
Appendix A.
Industial Recognition of Hazards - Sax, Dangerous Properties of
Industrial Materials, lists triethyl phosphorothioate (phosphorothioic acid
0,0,0-triethyl ester) as being highly toxic via ingestion, inhalation and
skin absorption.
-x-
-------
IV. References
1. 1977 Directory of Chemical Producers, Stanford Research Institute
Menlo Park, California. *
2. Proprietary information submitted to EPA by American Cyanamid through
1978 response to "308" letter.
3. Farm Chemicals Handbook, 1977; Meister Publishing Company, Willoughby,
Ohio.
4. Lawless, E. W. et al. The Pollution Potential in Pesticide Manufac-
turing USEPA, Office of Water Programs, Technical Studies Report TS-
00-72-04, 1972.
5. NIOSH Registry of Toxic Effects of Chemical Substances, U.S. Depart-
ment of Health, Education, and Welfare, 1978.
6. Personal Communication, S. R. Hathaway, American Cyanamid to D. K.
Oestreich, 11 February 1980.
7. Aquatic Fate and Transport Estimates for Hazardous Chemical Exposure
Assessments. U.S. EPA, Environmental Research Laboratory, Athens, GA.
February, 1980.
8. Martin, H., Pesticide Manual, 4th Edition.
9. Tox. Appl. Pharmacol.
10. American Cyanamide. Cited in USEPA Initial Scientific and Minieconomic
Review of Phorate. 1974.
11. Drinking Water and Health. (1977) National Academy of Sciences,
Washington, D.C.
12. Clinical Toxicology of Commercial Products. Acute Poisoning. Gleason,
M.N., et al., 1969,3rd ed., p. 142.
13. Hazard Profile on Phorate. Greenberg, M. ECAO/RTP NC, 1980, p. 2.
14. National Technical Information Service #PB 277-077.
15. Tusing, T.W. 1956 Unpublished report of American Cyanamid. Cited
in USEPA Initial Scientific and Minieconomic Review of Phorate, 1974.
16. Rombunski, et al. (1958) as cited in Drinking Water and Health. (1977)
National Academy of Sciences, Washington, D.C.
-------
17. Curry, et al. J. Agric. Food Chem. 9:469-477 (1961).
18. U.S. EPA. (1979) The carcinogenic assessments group's Preliminary
Risk Assessment on Formaldehyde. Type I - Air Progrsms. Office of
Research and Development.
19. Auerbach, C., Moutschen-Dahen, M., and Mouytschen, J. Genetic and
Cytogenetic Effects of Formaldehyde and Related Compounds. Mutat.
Res. 39:317-361 (1977).
20. U.S. EPA. (1976) Investigation of Selected Potential Environmental
Contaminants: Formaldehyde. EPA-560/2-76-009-
21. Wilkins, R.J. and MacLeod, H.D. Formaldehyde-Induced DNA Protein
Crosslinks in E_. Coll.. Mutat. Res. 36:110-16 (1976).
22. Obe, G. and Beck, B. Mu.tagenic activity of Aldehydes. Drug Alcohol
Depend. 4:91-4 (1979). ~
23. Union Carbinde Data Sheet. Industrial Medicine and Toxicology Dept.,
Union Carbide Corp., 270 Park Ave., New York, N.Y. April, 1967.
24. J. Ind. Hyg. Toxicol. 23:259 (1941).
25. ACTA Pharmalogica et Toxicologica 6:299 (1950)
26. J. Ind. Hyg. Toxicol. 31:343 (1949).
27. Journal of the National Cancer Institute. (U.S. Governemnt Printing
Office, Supt. of DOC., Washington, D.C.) 30:31 (1963).
28. Practical Toxicology of Plastics. (1968) Lefaux, R. Cleveland, Ohio
Chemical Rubber Company, p. 328.
29. Chemical Industry Institute of Toxicology. 1979. Statement concerning
research findings.
30. Dowden, B.F. and M.J. Barrett. 1965. Toxicity of Selected Chemicals to
Certain Animals. Jour. Water Pollut. Control Fed. 3:1308.
31. Fairchild, E.J. and Stokinger, H.E. Toxicologic Studies on Organic
Sulfur Compounds. 1. Acute Toxicity of Some Aliphatic and Aromatic Thiols
(Mercaptans). Am. Ind. Hyg. Assoc. J. 19:171-189 (1958).
32. ACGIH (American Conference of Governmental Industrial Hygienists) (1971),
Documentation of Threshold Limit Values for Substances in Workroom Air—
Ethyl-Mercaptan. Cinicnnati, Ohio, p. 107.
33. Pharmaceutical Journal 185:361 (1960)
34. Toxicol. Appl. Pharmacol. 22:286 (1972).
-Vf-
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35. Clinical Toxicology of Commercial Products. Acute Poisoning.
Gleason, M. N., et al.(1969) 3rd ed., p. 65.
36. Mallipute et al. J. Agric. Food Chem. 27:463-466 (1979).
37. Fukuto et al. Quarterly Progress Reports to EPA, August 1978—
Nov., 1979. EPA Grant No. R804345-04.
38. Dawaon, English, Petty, 1980, "Physical Chemical Properties of
Hazardous Waste Constituents."
39. GAG List of Carcinogens, April 24, 1980.
-S'S'-J-
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LISTING BACKGROUND DOCUMENT
TOXAPHENE PRODUCTION
Wastewater Treatment Sludge from the Production of Toxaphene (T)
Untreated Process Wastewater 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
r
concentrations of toxaphene, and wastewater treatment sludges that contain
approximately one percent of toxaphene by weight.
The Administrator has determined that process wastewater 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 is also
a potent teratogen and has 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 Georgia. (5)
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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.(1)
.(2,3)
Toxaphene is a complex mixture of polychlorinated camphenes
containing 67 to 69 percent chlorine and has the approximate composition
of CiQH]_QClg. 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 emulsifiable 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
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B. Manufacturing Process
Toxaphene is produced in essentially the same manner by both domestic
manufacturers. The reaction chemistry is as follows:
Ob
CATALYST.
JVORCAT.
CHa
•CAMPHENE
TOXAPH&NE
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).
_ (2)
(3)
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 . (4»5)* ^he sludge 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.
-y-
-587-
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SOUTMCniSI
E STUMPS
"| =S 1
REACTOR
WASTES
MAIN
WASTE
|
CAMPHENE
CHLORINE
SOLVENT -
H,O
LIME
NaOH
LIME-
STONE'
SURFACE
WATERS '
t
I
CHLORINATOR-
r
HCI GAS
ABSORBER
I
SCRUBBERS
(2)
I
NEUTRALIZER
I
PRIMARY
WASTE.
TREATMENT
PLANT
T
DISCHARGE TO
TIDAL CREEK
TOXAPHENE-
SOLUTION
SPILLS
LEAKS
WASHDOWNS
RECOVERED
MURIAMC ACID
MIXED
XYLENES
L
STRIPPER-*- TOXAPHENE-
j
90% TOXAPHENE
SOLUTION
TO SOLID
WASTE
DUST
FORMULATION
BAGHOUSE DUST
COLLECTOR
ATMOSPHERE
SHIPMENTS
i
Oo
Co
VO
I
Figure 1. HERCULES' PRODUCTION AND WASTE SCHEMATIC FOR TOXAPHENE
(A)
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and lime to the wastewater as sorption agents for the removal of toxaphene
from the wastewater.(5) The solids are allowed to settle in holding
11
ponds and may remain there for months at a time.(^) After the basin
is filled with solids it is taken off line and the sludge is allowed to
dry to approximately 50% 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
stream.(^ • »?)
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 the
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.
(3).
(5)
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(3,5)
(3)
* This pond, or lagoon, is .unlined.' The treated waste-
water is discharged to the Mississippi River.
Ill, 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.(4,5)
The toxaphene content in the waste sludge is approximately at one percent
by weight or 10,000 mg/Kg sludge. High 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
cancer in laboratory animals. It is also a potent teratogen and has been
shown to be miitagenic. Toxaphene is regulated as a toxic pollutant
under §307(a) of the Clean Water Act. After an adjudiciative
*No data is currently available on the amount of wastewater treatment
sludges (settled solids) generated at the Vertac plant. Nor is any data
available on the concentrations of toxaphene in these sludges.
-v-
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proceeding, a discharge concentration 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. Cir 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 mg/1 for toxaphene. (That administrative 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.(18) Existing waste management methods could
lead to release of waste toxaphene. Wastewaters 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 or operated.
This can result in leaching of hazardous compounds and subsequent
contamination of ground water. 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.
-------
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., 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^), 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.^) 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-containing
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 have
not always been adequate, as Hercules has conceded that its past effluent
discharge "'had an adverse effect upon the ecology1 of local waters." (18)
-------
B. Health and Ecological Effects
1. Toxaphene
Health Effects - Toxaphene is extremely toxic [oral rat LD^Q
= 40 mg/kg].(8) Death in humans from ingestion of this dosage has also
been reported. (9) Toxaphene is also lethal to animals by inhalation and
skin absorption at dosages of 1 g/kg or less. (10)
This chemical is teratogenic in mice when administered orally
at a relatively small dose (350 mg/kg) .(H) Toxaphene is carcinogenic in
rats and mice, causing a significant .increase in the, incidence of thyroid
and liver cancers when administered in the diet. (12) A significant in-
crease in liver cancer has been reported in mice at dietary levels of 50
Toxaphene and its subfractions have been found mutagenic in the
standard bacterial assay (S_. typhimuriumm, strain TA100). (16)
Ecological Effects - Toxaphene is extremely toxic to fish, and
toxic to lower aquatic organisms, birds, and wild animals. The 11)50
(96-hour) of toxaphene in static bioassays is 3.5, 5.1 and 14 ng/1 for
bluegills, fathead minnows, and goldfish, respectively. (7) Toxaphene
is also capable of producing deleterious effects in fish at levels as
low as 0.39 ng/1, and bio accumulates by factors of as much as 300, 000. (?)
Regulations - Toxaphene has an OSHA standard for air, TWA =
500 mg/m3 (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
j Dangerous Properties of Industrial Materials(15) 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.
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IV. References
1. 1977 Directory of Chemical Producers. Stanford Research Institute.
Menlo Park, California.
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. Mamma, T. L. Ferguson, and G. L. Kelso.
Westwater Treatment Technology Documentation for Toxaphene Manu-
facture. Report prepared by the Midwest Research Institute for the
U.S. Environmental Protection Agency. EPA-400/9-76-013. . ;February
1976.
5. Telephone communication to: Ms. Jennifer Kaduck, State of Georgia,
Land Protection Division, Department of Natural Resources, Atlanta,
Georgia (404-656-2833), February 28, 1980 (Edward Monnig, TRW).
6. Telephone communication to: Ms. Jennifer Kaduck, State of Georgia,
Land Protection Branch, Environmental Protection Division, Depart-
ment of Natural REsources, Atlanta, Georgia, 12 February 1980- (S.
Quinlivan, TRW).
7. Criteria Document for Toxaphene. U.S. Environmental Protection
Agency. EPS-440/9-76-Okl4. June 1976.
8. Special Publication of Entomoligcal Society of America. College
Park, MD, Vol. 74:1 (1974).
9. Clinical Memorandum on Economic Poisons. U.S. Dept. HEW, PHS.
COG, Atlanta, GA. p.l, 1956.
10- Council on Pharmacy and Chemistry. Pharmacologic Properties of
Toxaphene, a chlorinated Hydrocarbon insecticide. JAMA 149:1135-
1137, July 19, 1952.
11. Chernaff, N. and Carber, B.D. Fetal toxicity of toxaphene in rats
and mice. Bull. Environ. Contarn. Toxicol. 15:660-664, June, 1976.
12. National Cancer Institute. (1977) Guidelines for Carcinogensis Bio-
assays in Small Rodents. Tec. Rep. No. 1 Publ. No. 017-042-00118-8.
U.S. Govn. Print. Office, Washington, D.C.
-------
IV. References (Continued)
13. Telephone Communications to: Ms. Jennifer Kadinck, et al., State
of Georgia, Land Protection Division, Department of Natural Resources,
Atlanta, Georgia, 8 April 1980. (Robert Karmen, EPA)
14. Telephone Communication: John King (EPA) to Edward Monmig (TRW),
8 April 1980.
15. Litton Bionetics, 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. (1977) Mutagenicity Testing of Toxaphene Memo dated Dec. 15,
1977, to Fred Hageman. Off. Spec.;Pestic. Rev. U.S. Environmental Pro-
tection Agency, Washington,'D.C.
17. Sax, N. Irving, 1975. Dangerous Properties of Industrial Materials.
Fourth Edition, Van Nostrand Reinhold, New York.
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.
Washington, U.S. GPOV> 1972.
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LISTING BACKGROUND DOCUMENT
2,4,5-T PRODUCTION
0 Heavy Ends or Distillation Residues from the Distillation of
Tetrachlorobenzene in the Production of 2,4,5-T(T)
I. Summary of Basis for Listing
The hazardous waste from 2,4,5-Trichlorophenoxyacetic acid (2,4,5-j)
production consists 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 transportedy-treated, stored, disposed of or otherwise man-
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.
4. Volatilization of the waste constituents 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
*(l,5,6)f
The 2,4,:5-trichlorophenol (TCP) salts.and esters, including
2,4,5-T, are selective herbicides used to control woody plants, es-
pecially on range land and rights-of-way, where 2,4-D is not effective.
The properties and actions of these compounds are similar to 2,4-D for-
mulations. These compounds are used extensively in forest conifer
control and for weed control, and for rice crops.^°'
B. Manufacturing Process
Figure 1 is the process flow diagram of the manufacture of
2,4,5-T (2,4,5-trichlorophenoxyacetic Acid).^7^ The first step in
2,4,5-T manufacture is the reaction of chlorobenzene with chlorine
to form tetrachlorobenzene (TCB). Distillation is then used to sep-
arate the TCB from other chlorobenzenes. The waste of concern is gen-
erated at this point in the process, and consists of the distilla-
tion residues. Following this, the distilled TCB is hydrolyzed to
form TCP and then esterified to form 2,4,5-T.
*The underlined data are those obtained from proprietary reports and
data files.
TSome of the companies listed above may no longer produce 2,4,5-T
-------
•*- TETRACHLOROBENZENE
MONOCHLOROBENZENE-
-J?
CHLORINE
REACTOR
TETRACHLOROBENZENE
DISTILLATION
COLUMN
HEAVY ENDS
(DISTILLATION RESIDUE)
TO LANDFILL
Figure 1. GENERATION OF HEAVY ENDS (DISTILLATION BOTTOMS) FROM
TETRACHLOROBENZENE MANUFACTURE IN THE 2, 4, 5-T PROCESS (7)
-------
C. Waste Generation and Management
The heavy ends or distillation residues generated in separating
TC3 from other chlorobenzene make up the hazardous waste stream
of 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.
Based 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.
Ill. Discussion of Basis for Listing
A. Hazards Posed by the Waste
improperly managed or disposed. Among the compounds expected to be
The heavy ends discussed above contain hazardous compounds
which can be expected to pose a serious threat to the environment if
ini]
present are hexachlorobenzene and ortho-dichlorobenzene.
Hexachlorobenzene is believed to be carcinogenic and terato-
genic, while o—dichlorobenzene may pose a chronic toxicity 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 if
improperly managed, and that these constituents will not persist if
they are released into the environment.
* It is projected that o-dichlorobenzene could create a chronic tox-
icity hazard if it migrated at several orders of magnitude less than
its solubility limit in water.(38)
-------
Indications are that these waste constituents are capable
of migration, mobility and persistence to cause substantial hazards.
The groundwater exposure pathway is of principal concern. Hexachloro-
benzene, while relatively insoluble, has been detected to have
migrated via a groundwater pathway from Hooker Chemical Corpora-
tion's S area, Hyde Park, and 102d St. landfills in Niagra, New York.O7)
Orthodichlorobenzene is relatively soluble (App. B), and thus may be
available for environmental release.
Present waste disposal practices may be inadequate to prevent
waste migration. Certainly, improper management may result in re-
lease of harmful constituents. Thus, uncontained landfill burial
would not impede leachate migration in areas with relatively or high-
ly permeable soils, or where the water table is so high that ground-
water acts as a leaching medium.* Containerization in landfilled
drums could still result in contaminant release, since all drums have
a limited life span as 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 and operated. Improper disposal techniques in surface
containment sites may also present the possibility of surface runoff
contamination. A break in a pond dike or rainwater flowing over an
improperly covered landfill containing the process wastes may allow
migration to surface soils and surface water.
^Laboratory studies of the behavior of chlorinated benzenes in soil
that is high in sand and low in organic content indicate that hexa-
chlorobenzene would be likely to exhibit slow but measureable mobility
in these soils again indicating that soil attenuation will not
prevent environmental release of migrating contaminants A
-------
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 May, 1976, hexachloroben-
zene-containing wastes from a Vulcan plant in Louisiana volatilized
and resulted in the death of cattle gra_zing in contaminated areas.(39)
A similar case history of environmental damage in which air, soil,
and vegetation over an area of 100 square miles were contaminated by
hexachlorobenzene (HCB) occurred in 1972.(39) There was volatiliza-
tion of HCB from landfilled wastes and subsequent bioaccumulation 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. Hexachlorobenzene
is very persistent.* (App. B) 0-dichlorobenzzene is subject to cer-
tain degredative 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)
B. Health and Ecological Effects
1 . Hexachlorobenzene
Health Effects - Hexachlorobenzene has been shown to be
carcinogenic in animals (^, 20) an^ |1£s 'oeen identified by the Agency
to be carcinogenic. This chemical is reportedly teratogenic, known
^Evidence of mobility and resistance to degradation has been shown
by identification of chlorobenzene isomers in ground water in Florida.
Chlorinated benzenes are likely to persist in the environment and to
bioaccumulate.(^')
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to pass through placental barriers, producing toxic and lethal effects
in the fetus.(2I) Chronic exposure to RGB in rats has been
shown to result in damage to the liver and spleen.(22) It has
been lethal in humans when ingested at one-twentieth the known oral
(23}
LD5Q 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. C2^) Additional informa-
tion and specific references on the adverse effects of hexachloroben-
zene can be found in Appendix A.
Ecological Effects - Hexachlorobenzene is likely to con-
taminate accumulated bottom sediments within surface water systems and
bio accumulate in fish and other aquatic organises . ^°)
Regulatory Recognition of Hazard - Hexachlorobenzene is a
chemical evaluated by CAG as having substantial evidence of carcinogen-
icity. Ocean dumping of hexachlorobenzene is prohibited. An interim
food contamination tolerance 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. Ortho-dichlorobenzene
Health Effects - Ortho-dichlorobenzene is very toxic in
rats [oral LD5Q = 500 mg/Kg].^25^ Human death has also occurred at
this level.(26) Chronic occupational exposure to this chemical and. its
isomer has resulted in toxicity to the liver, central nervous system
and respiratory system.C27) Chronic oral feeding of ortho-dichloro-
-GOB-
-------
benzene to rats in small doses has caused anemia as well as liver
damage and central nervous system depression.\2o) Additional infor-
mation and specific references on the adverse effects of ortho-dichloro-
benzene can be found in Appendix A.
Regulatory Recognition of Hazard - Ortho-dichlorobenzene
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-dichlorobenzene under the Clean Water
Act and the Safe Drinking Water Act. Under section 311 of the Clean
Water Act3 regulation has been proposed. The Office of Research and
Development has begun;; pre-r egulatory 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.
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IV. References
1. Proprietary information submitted to EPA by Thompson-Hayvard' Chemi-
cal Co., Kansas city, Kansas in 1978 Response to "308" Letter.
2. U.S. Department of Health, Education and Welfare, National Institute
for Occupational Safety and Health, Registry of Toxic Effects of
Chemical Substances, Cincinnati, Ohio, January 1979 in Radian Cor-
poration Hazardous Waste Background Document, 1979.
3. U.S. Department of Health, Education and Welfare, National Insti-
tute for Occupational Safety and Health, Suspected Carcinogens,
A Subfile of the NIQSH Toxic Substances List, Rockville, Maryland,
June 1975 in Radian Corporation Hazardous Waste Background Docu-
ment, 1979.
4• Identification of Organic Compounds in Effluents from Industrial
Sources, PB-241641, Versar, Inc., Springfield, VA, April 1975 in
Hazardous Waste Background Document, 1979-
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. Sittig, Pesticides
Process Encyclopedia, Noyes Data Corporation, Park Ridge, New
Jersey, 1977.
8. Farm Chemicals Handbook, 1977, Meister Publishing Company, Willough-
by, Ohio.
t
-------
9. Midwest Research Institute, The Pollution Potential in Pesticide
Manufacturing, Washington, B.C., EPA, June 1972, in Pesticide
Process Encyclopedia, Noyes Data Corporation, Park Ridge, New
Jersey, 1977.
10. Assessment of Dioxin-Forming Chemical Processes. Walk, Haydel-
and Associates, 600 Carondolet, New Orleans, LA, for USEPA/IERL-
Cincinnati, EPA Contract No. 68-03-2579, 179 pp., undated.
11. Dow Chemical Company. The Trace Chemistries of File - A Source
of and Routes for the Entry of Chlorinated Dioxins into the En-
vironment. The Chlorinated Dioxin Task Force, the Michigan Divi-
sion, Dow Chemical, USA, November 15, 1978.
12. Stehl, R. H, and L. L- Lamparski. Combustion of Several 2,4 ,5-T
Compounds: Formation of 2,3,7,8-Tetrachlorodibenzo-p-dioxin. Sci-
ence, 1^:1008-1009, September 1, 1977.
13. Rappe, C., S. Marklund, H. R. Buser, and H. P. Bosshart. Forma-
tion of Polychlorinated Dibenzo-p—dioxins (PCDDs) and Dibenzofurans
(PCDEs) by Burning or Heating C'nlorophenates. Chemo sphere, 7(3):26S
281, 1978.
14. Crosby, D. G., land A. S. Wong, 1977. Environmental Degradation
of 2,3,7,8-Tetrachlorodibenzo-p-dioxin. Science, 195:1337.
15. Crosby, D. B. et al, 1971. Photodecomposition of Chlorinated
Dibenzo-p-dioxin. Science, 173:748.
16. International Agency for Research on Cancer. IARC Monographs on
the Evaluation of Carcinogenic Risk of Chemicals to Han. Some
Fumlgants, the Herbicides 2,4-D and 2,4,5-T, Chlorinated Diben-
zodioxins, and Miscellaneous Industrial Chemicals. World Health
Organization, Lyon, France. Volume 15, August 1977.
-------
17. IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals
to Man (International Agency for Research on Cencer, Lyon, France
World Health Organization.
18. Technical Support Document for Aquatic Fate and Transport Estimates
for Hazardous Chemical Exposure Assessments. 1980. U.S. EPA,
Environmental Research Lab., Athens, GA.
19- Cabral, J. R. P. et al. Carcinogenic activity of Hexachlorobenzene
in hamsters. Tox. Appl. Pharmacol. 41:155 (1977).
20. Cabral, J. R. P. et al, 1978. Carcinogenesis study in mice with
hexachlorobenzene. Toxicol. Appl. Pharmacol. 45:323.
21. Grant, D« L. et al. 1977. Effect of hexachlorobenzene on repro-
duction in the rat. Arch. Environ, contain. Toxicol. 5:207.
22. Koss, G. et al, 1978. Studies on the toxicology of hexachloroben-
zene. III. Observations in a long-term experiment. Arch. Toxicol.
40:285.
23. Clinical Toxicol. of Commercial Products - Acute Poisoning. Gleason,
M. N. et al (1969) 3rd Ed., p. 76.
24. Carlson, G. P., 1978. Induction of cytochrome P-450 by halogenated
benzenes. Biochem, Pharmacol. 27:361.
25. Clinical Toxicology of Commercial Products. Gleason, M. N. et al.
(1969), 3rd Ed., p. 49.
26. U.S. EPA (1979). Dichlorobenzenes: Ambient Water Quality Criteria.
27. Varshavsakaya, S. P. Comparative toxicological characteristics of
chlorobenzene and dichlorobenzene (ortho- and para-isorners) in re-
lation to the sanitory protection of water bodies. Gig. Sanit.
33:17 (1967).
-------
35
28. Ben-Dyke, R., Sanderson, D. H. and Noakes, D. N. Acute toxicity
for pesticides. World Rev. Pest Control 9:119-127 (1970).
29. NCI Carcinogenesis Bioassay, National Technical Information Serrlrp
Rpt. PB223-159, Sept. 1978.
30. Clinical Toxicology of Commercial Products. Gleason et al, 3rd Ed,
Baltimore, Williams and Wilkins, 1969.
31. Fahrig, R. et al. Genetic activity of chlorophenols land chloro-
phenol imparities, pp. 325-338. In Pentachlorophenol; Chenistry.
Pharmacology and Environmental Technology. K. Rango Rao, Plenum
Press, New York.
32. Weinback, E. C. and Garbus, J. The interaction of uncoupling
phenols with mitochondria and with raitochondrial protein. Jour.
Biol. Chem. 210:1811 (1965).
33. Hitsuda, H., et-'al. Effect of chlorophenol analogues on the osi-
dative phorphorylation in rat liver mitochondria. Agric. Biol.
Chem. 27:366 (1963).
34. U.S. EPA, 1972. The effect of chlorination on selected organic
chemicals. Water Pollut. Control Res. Agr. 12020.
U.S. EPA, 1978. In-depth studies on health and environmental im-
pacts on selected water pollutants. Contract No. 68-01-4646.
36. Wilson, J. T., and C. F. Enfield, 1979. Transport of Organic Pol-
lutants Through Unsaturated Soil. Presented at American Geophysi-
cal union Fall Meeting, December 3-7, San Francisco, California.
37. Complaint in Civil Action No.
38. Dawson, English, and Petty, I960 "Physical Chemical Properties of
Hazardous Waste Constituents."
VI
-------
39. OSW - Hazardous Waste Management Division - "Hazardous Waste
Incidents", Unpublished Open Fie Data, 1978.
40. The Carcinogen Assessment Group's List of Carcinogens,
April 22, 1980.
-------
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
po1ymer s.
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-dichlorophenol, and 2,4,6-tri-
chlorophenol. 2,6-Diehloropheno1 waste contains
substantial concentrations of 2,6-dichloropheno1,
2,4,6 -trichlorophenol and 2,4-dichlorophenol.
2. 2,4,6-Trichlorophenol has been identified by EPA's
Carcinogen Assessment Group as a substance which
has exhibited susbtantial evidence of carcinogeni-
city. It has also been sited in literature as
being mutagenic. 2,4-Dichloropheno1 is a reported
animal carcinogen and 2,6-dichlorophenol is toxic,
3. Management of these wastes in treatment lagoons or
landfills creates the potential for soil or ground-
water contamination via leaching if mi smanag eiaent
o c cur s .
-------
II. Sources of Wastes and Typical Disposal Practices
A. Profile of the Industry
2,4-D is a selective herbicide registered for use on
grasses, barley, corn, oats, sorghum, wheat and non-crop areas
for post-emergent control of weeds. (?)
1.
2 .
3.
B . Manufacturing Process
In the 2 , 4-D._jnanuf ac tur ing process, benzene is
chlorinated to produce monochlorobenzene, which is hydrated to
produce phenol.(2a) 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.
Chlorination of phenol inevitably leads to the genera-
tion of by-product 2,6-dichlorophenol and other chlorophenols. ( 2a)
(8,10) AS shown in
i
-------
SOLVENT
OR
CATALYST
I I
— PHENOL -*-
i - i
CIILORO
PHENOL
UNIT
15-40°
f
. • '• •• fr
2,6-DICHLOROPHENOL •
2,4-OICHLOROPHENOL
NEUTRALIZER
NEUTRALIZER
J_ SODIUM —
CHLOROACETATE
1
CONDENSATION
REACTOR
LIQUID
WASTE
_J
ACID -.. — , >
NaCI ^
-* M '- • • ' -
2,4-D
RECOVERY
EXCESS
*" CeHjCljOH
••4 «
SCRUBBER
y
TRICKLING
FILTER
\
TO PENTACHLOROPUCNOL
MANUFACTURE (DOW)
i
TO WASTE DISPOSAL
(RHODIA AND TRANSVAAL)
DUST
COLLECTOR
BIOLOGICAL
TREATMEMT
n
f DISCHARGH
TREATED SLUDGE
WASTEWATER
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 is used in the production of pentachlorophenols
in one 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-dichloropheno1, 2,4,6-trichlorophenol,
2,4-dichlorophenol, 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.
-------
(8) Process wastewater is removed
for treatment. This wastewater, prior to treatment, is listed
as hazardous. 2,4-Dichlorophenol 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
(10)
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
-------
(8,10)
(The waste constituents of concern are 2,4,6 trichloro-
phenol and 2,4 dichlorophenol . )*
Dis posal 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 small
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
*0~tfher waste constituents are not deemed present in sufficient
concentrations to be 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 have been found to be contaminated with toxic chloro-
phenols from 2,4-D manufacture.**
As this incident illustrates, waste constituents may wel!
prove mobile and persistent. As to mobility, the chlorinated
phenols present in the waste may undergo bio-degradation in
*This 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
provide that the solid wastes discharged from a' hazardous
waste treatment facility are not also considered hazardous
unless the generator demonstrates otherwise.
**OSW Hazardous Waste Division, Hazardous Waste incidents, un-
published open file 1978.
-------
s
soil if present in low concentrations.(25) It seems
likely, however, the rates of degradation of these compound
in the soil profile would be low because of repression of
soil microbial activity by these and other waste components.
(Also, 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 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
by a case history in California, where long-term pollution
of groundwater by phenolic substances occurred because of
release into the soil of water containing 2,4-dichlorophenol
from 2,4-D manufacture.(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,A-Dichlorophenol is very toxic
in rats [oral LD5Q = 580 mg/kg].(12^ This chemical is
carcinogenic when applied to the skin of mice in small doses.(13
It is also reported to adversely affect cell metabolism,(1^>15 /
An isomer, 2,6-dichlorophenol , is also toxic in animals.(16)
Additional information and specific references on adverse
effects of 2,4-dichlorophenol and 2,6-dichlorophenol can be
-6/7-
-------
found in Appendix A.
Ecological Effects - Small doses of 2,4-dichloro-
phenol have been lethal to fresh water fish and invertebrates . (17)
Regulatory Recognition of Hazard -
2,4-Dichlorophenol 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-dichlorophenol
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-dichloropheno1 under the
Clean Wa ter Act.
Indus trial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, designates a toxic hazard rating of
moderate toxicity for 2,4-dichloropheno1 . However, chlorinated
phenols are designated as highly toxic local and systemic
compo und s .
2. 2,4,6-Trichlorophenol
Health Effects - 2,4,6 -trichloropheno1 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 car-
cinogen icity.(27) jt has been acutely lethal to humans
by ingestion at 60 percent of the oral LD5Q dose in rats
[500 rag/Kg]. (19) This chemical is reportedly mu t ag eni c (20)
-------
and adversely affects cell metabolism . (21>22) Additional
information and specific references on the adverse effects of
2 4-trichlorophenol can be found in Appendix A.
Ecological Effects - Very small concentrations
of 2,4,6-trichlorophenol have been lethal to freshwater fish
[LC50 = 426 ng/lj. This chemical is also lethal to freshwater
invertebrates at very low c one en t r a t io ns . ( 2 4 )
Regulatory Recognition of Hazard - 2,4,6-Tri-
chlorophenol has been designated as a Priority Pollutant
under Section 307(a) of the CWA.
Industrial Recognition of Hazard - Sax, in
Dangerous Properties of Industrial Materials, lists 2,4,6-
trichlorophenol as moderately toxic via the oral route.
-------
IV. REFERENCES
1. U.S. Environmental Protection Agency, Office of Water
Programs, The Pollution Potential in Pesticide Manufac-
turing, Contract 69-01-0142, June, 1972.
2a. U.S. Environmental Protection Agency, Office of Pesticide
Programs Production, Distribution, Use and Environmental
Impact Potential of Selected Pesticides,EPA540/1-74-001
Washington, B.C., 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. Environmental Protection Agency, Industrial Process
Profiles for Environmental Use, Chapter 8: Pesticides^"
EPA-600/77-023h, Research Triangle Park, North Carolina,
January , 1977.
4. U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health, Registry of
Toxic Effects of Chemical Substances, Cine inna ti, Ohio ,
January, 1979.
5. U.S. Environmental Protection Agency, "Hazardous Waste
Guidelines and Regulations," Fed. Reg. 43 (243): 58960,
December 18, 1979 .
6. Proprietary information submitted in 1978 to EPA in
response to "308" letter by Thompson-Hayward Chemical
Company.
7. Farm Chemicals Handbook, 1977, Meister Publishing Company,
Willoughby, Ohio.
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.
-------
j_2. Deichmann, W. The toxicity of chlorophenols for rats.
Fed. Proc. (Fed. Am. Soc. Exp. Biol.) 2:76 (1943).
13. Boutwell, R. K. and Bosch, D. K. The tumo r- pr omo ting action
of phenol and related compounds for mouse skin* Can Res
19:413-424 (1959). L
14. Farquharson, 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 phosphorylation in rat liver mitochondria.
Agric. Biol. Chem. 27:366 (1963).
16. Marhold, J. V. (1972). Sbornik Vysledku Toxikologickeho
Vysetreni Latek a Pripravku, p. 79.
17. U.S. EPA (1978). In-depth studies on health and environ-
mental impacts of selected water pollutants. Contract
No. 68-01-4646. U.S. Environ. Prot. Agency.
18. NCI Carcinogenesis Bioassay, National Technical Information
Service, Rpt. PB223-159, Sept. 1978.~
19. Clinical Toxicology of Commercial Products. Gleason et al.,
3rd Ed., Baltimore, Williams and Wilkins, 1969.
20. Fahrig, R. et al. Genetic activitiy of chlorophenols and
chlorophenol impurities. Pp. 325-338. In Pentachlorophenol;
Chemistry, Pharmacology and Environmental Technology.
K. Rango Pvao , Plenum Press, New York.
21. Weinback, E. C. and Garbus, J. 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. U.S. SPA, 1972. The effect of chlorination on selected
organic chemicals. Water Pollut_. Control Res. Agr.
12020.
24. U.S. EPA, 1978. In-depth studies on health and environmen-
tal impacts on selected water pollutants. Contract
No. 68-01-4646.
-------
25. Kozak, V. P., G. V. Simmons, G. Chesters, D. Stevsby,
and J. Harkins. 1979. Reviews of the Environmental
Effects of Pollutants: XI Chiorophenols. EPA-600/I-79-01 2 .
U.S. EPA, Washington, D.C. 492 pp.
26. Sinenson, H. A., 1972. The ~'Mon t eb el lo Incident. P r o c .
Assoc. Water Treatment and Exam. 11:84-88.
27. Carcinogen Assessment Group's List of Carcinogens, April
22, 1980.
-------
LISTING BACKGROUND DOCUMENT
METHOMYL PRODUCTION
Wastewater from the Production of Methomyl (T)
I. Summary of Basis for Listing
The Administration has determined that the process wastewater
from methoniyl 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 content of the process wastewater from each plant will
vary but the toxic substances which may be found in the
wastewater include methomyl, methylene chloride, and pyridine.
Methomyl is extremely toxic and a mutagen and methylene chloride
has been shown to be carcinogenic and inutagenic. Pyridine is
toxic.
(2) Placement of these wastes in lagoons creates the potential for
either groundwater or surface water contamination via leaching
or overflow. Disposal by incineration, if mismanaged, could
result in substantial hazard via an air exposure pathway through
the release of toxic fumes due to incomplete combustion.
(3) Hazardous compounds in the waste are persistent and mobile and
pose a risk of exposure to humans and the environment.
(4) The industry generates at least 100,000 Ibs./year (dry weight)
of wastewater treatment sludges, indicating that substantial
amounts of process wastewater are generated annually, and
that substantial amounts of hazardous constituents may be
available for environmental release,
11' Sources_of Waste and Typical Disposal Practices
A. Profile of the Industry
According to the SRI Directory of Chemical Producers/
-------
me thorny 1 is produced by E.I. duPont Nemours and Company at its Houston
plant (La Porte, Texas)* and by Shell Chemical Company at its Denver,
Colorado plant.
(2)
Methomyl is an insecticide used for broad-spectrum control of insects
in many vegetables, field crops, certain fruit crops and ornamentals,^) Metho-
was developed by duPont in 1969 and its commercial use is relatively new.
B. Manufacturing Process - Methomyl synthesis may involve the
following steps: ^)
ETHER
1. CH3 - C - N + CH3SH -f HC1 -------- > Methyl Thiolacetimidate
SOLVENT (MTH)
PYRIDINE
2. MTH + HO NH2'HC1 -------- > Corresponding Hydroxamates
3. Fydroxamate + CH3 NCO > CH3 - C = NOCNHCH3
CH2C12 I
0
Methomyl
The duPont plant also produces bromacil, diuron and several other
chemicals,
(5)
:he underlined data are obtained from proprietary reports and data files
-------
Process-details for the commercial production of methorny1 are not
known beyond those shown in Figure l.(5) The waste of concern is the
wastewater from the pesticide reactor. No information is available on
the Shell or Vertac production processes.
C. Waste Generation and Management - Process wastewater from
methomyl production will contain methomvl, and is also expected to contain
*
methylene chloride (a process solvent), and pyridene, -a process reactant.
Nitrosomethomyl, a reaction intermediate, may also be present.
(5)
(5)
The plant itself is located very close to
the Houston ship channel, near Galveston Bay.
(5)
-------
(6).
(2)
III, Discussion of Basis for Listing
A. Hazards Posed by the Waste
As stated above (p.3), the raethomyl production process waste waters
are expected to contain methorny1, and probably its reaction intermediate
nitrosoraethomyl3 methylene chloride (a process solvent), and pyridene
(a process reactant) as well.
Methorayl is mutagenic and extremely toxic and its potential
metabolite, nitrosomethomyl is extremely carcinogenic and mutagenic,
Methvlene chloride is very toxic and has been shown to be mutagenic.
There is also evidence that methylene chloride is carcinogenic, Pvridene
is toxic. In fact, both methomyl and pvridene can pose an acute toxiciiiy
threat if they migrate at an order of magnitude less than their solubility
limit, and thus can reach lethal levels in water at one-tenth their
The underlined data are obtained from proprietary reports and data files
-------
limit of solubility.Methyl chloride would exceed the proposed
human health criteria for water quality if it solubilizes at less than.
one ten thousandth of its solubility limit.(34)*/
Furthermore, large quantities of process wastewater containing
these harmful constituents are generated annually (see p.3), posing an
increased likelihood of large-scale contamination should mismanagement
occur, and making increased amounts of hazardous constituents available
for environmental release. Therefore, the Agency would be justified in
not listing these waste streams only if it were assured that hazardous
waste1constituents would not migrate and persist. Such assurance does
not appear possible.
All of these compounds are capable of migration. They are all
extremely soluble (solubility ranging from 20,000 pptn (methylene chloride)
to 100% solubility for pyridene) . (-^) Methylene chloride may also migrate
by volatilizing (vapor pressure 350 mm Eg, quite volatile).(34)
The waste constituents, once released from the waste matrix, are
expected to be mobile and persistent. Methonyl would undergo soma degrada-
tion in the soil, but it is substantially more stable than most carbanate
insecticides. The reported half life of methomyl is 50 days.W This,
coupled with the high solubility of this compound in water(') (34) £n^ ^ts
tendency to move readily through the soil with infiltrating waterC10),
would likely result in its entering groundvater with little attenuation
in concentration. Once in the groundwater environment, it would be
Agency is not using the proposed Water Quality Criteria as .a
regulatory benchmark, but is referring to them here to illustrate^ethylene
chloride can create a potential hazard substantial hazard if immigrates
from the waste at a rate far less than its water solubility limit.
-------
expected to be persistent and mobile (App. B ). Hence, it could move to
wells providing drinking water or to points of discharge of groundwater
into surface water, resulting in exposure of humans and aquatic ecosystems
to this compound (App. B).
Methylene is also very soluble in water vllK34;j ancj voui^ ^e ex_
pected to move readily through the soil profile into and through groundwater
based on the demonstrated mobility of closely related halomethanes such
as chloroform in subsurface environments, v.12,13,14; Methylene chloride
has been found in groundwater in Massachusetts, probably as the result of
leakage of nearby chemical waste lagoons, strongly suggesting potential
mobility and persistence. ^^ Methylene chloride is also stable in air
(34), and so could persist after volatilizing.
Pyridine sorbs to clay soils, but desorbs in acidic pH conditions.^)
Mobility, thus could be high in non-clay soils, on where soils are acidic.
It also biodegrades moderately quickly (34), but would be exptected to persist
in the abiotic conditions of most aquifers.
The pyridine in this waste might also enter groundwater under
these conditions as indicated by a recorded case of the movement of this
and related compounds from a chemical waste lagoon through an unsaturated
soil into groundwater and thence to nearby domestic wells. ^-^
Treatment ponds could be improperly designed or managed
(i.e., located in areas with highly permeable soils, lacking proper
leachate control systems, and where site runoff or lagoon washout is not
controlled) ,*
"Methylene chloride may also volatilize from a sludge, so that uncovered
disposal sites may create a hazard via an air exposure pathway.
-------
(5)
Disposal by incineration, if mismanaged, can result in substantial
hazard to human health via an air inhalation pathway. If incineration
facilities are operated in such a way that combustion is incomplete (i.e.,
improper conditions of temperature, mixing and/or residence time), the
release into the air of hazardous vapors containing undestroyed waste
constituents and/or their toxic degradation products could present a
significant opportunity for exposure of humans to hazardous constituents,
In any case, it should be noted that in making a determination as
to the hazardousness of this waste, the Agency is not limited to
-------
consideration of existing waste management methods, since absent regulation
there is no guarantee a particular method will be adopted. Thus, less
satisfactory management of this waste could be adopted, resulting in even
greater potential for constituent release.
Thus, waste constituents appear capable of migration, mobility and
persistence. Mismanagement of the wastes is also possible. Under these
circumstances, and in light of the hazards associated with waste con-
stituents, the Agency believes that substantial hazard could follow
waste mismanagement,
^* Health and Ecological Effects
1. Methomy1
Health Effects - Methonyl is an inhibitor of the nerve trans-
mitter (cholinesterase), and is extremely toxic in rats [oral LD5Q ~
20 mg/kgj.(2-O The acute inhalation toxicity of this chemical is also ex-
tremely high [rats L^Q = 0.30 - 0.45 mg/L), depending on formulation.
Methomyl is mutagenic v-^) and a potential metabolite nitrosomethomyl is
extremely mutagenic (*•' ' and carcinogenic.(^8) jn animals, methorayl reduced
growth and hemoglobin levels.(29)
Additional information and specific references on adverse effects
of Methomy1 can be found in Appendix A.
Regulations - The Office of Water and Waste Management is in the
process of conducting preregulatory assessment of methomyl'under the Safe
Drinking Water Act. The Office of Toxic Substances has promulgated regula-
methonyl under Section 3 of the Federal Insecticide, Fungicide
t. __>-'- ip _ ^ L.
?\.3denticiie Act
-(o
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2. Hethylene Chloride
Health Effects - Methylene chloride (dichloromethane) has been
shown to be mutagenic. '16>17) Inhalation of this chemical in an occupa-
tional setting has reportedley caused gynecologic problems in women^18),
and been toxic to fetuses and embryos of rats and mice. ^9, 20) Methylene
chloride is very toxic [oral rat LD5Q = 167 eg/kg] ^2i^ with acute sublethal
exposures resulting in central nervous system disfunction and reduced
oxygen-binding in red blood cells.(22)
There is evidence in animal studies that nethylene chloride is
carcinogenic. {*••*) Additional information and specific references
on adverse effects of inethylene chloride can be found in Appendix A.
EC olog i c al E f f e c ts - For nethylene chloride, the criterion values
for protection of freshwater^aquatic life protection is 4 mg/1 and for salt
water aquatic life is 1.9 nig /I. (24) Sensitivity of lover aquatic life
forms (e.g., algae was less than that of animal life).^2 '
Regulatory Recognition of Hazard. - Methylene chloride is desig-
nated as a priority pollutant under section 307(a) of the CWA. OSHA
regulations designate a TWA of 500 ppm for an 8-hour period of exposure.
Industrial Recognition of Hazard - 2a2l!_L2i£iiI°Hl_Z£°2££~
lies of Industrial Materials lists nethylene chloride as being moderately
toxic via oral and inhalation routes.
3. Pyridene
Health Effects - Pyridene is toxic in rats<30) and humans^31),
-------
causing central nervous system depression, skin and respiratory tract
irritation in snail doses.(-^) Small doses administered chronically to
animals also interfere with platelet production and cause damage to the
bone narrow, liver and kidneys. (-*->)
Additional information and specific references on adverse effects
of pyridene can be found in Appendix A.
Regulatory Recognition of Hazard - Pyridine has an OSHA standard
air TWA of 5 ppm (SCL-P). DOT requires a label warning that the chemical
is a flammable liquid.
Industrial Recognition of Hazard - Sax, Dangerous Properties
of Industrial Materials, lists pyridines as having a moderate toxic hazard
rating via oral, dermal and inhalation routes.
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IV. References
1. 1977 Directory of Chemical Producers, Stanford Research Institute
Metilo Park, California. *
2. Proprietary information submitted to EPA by duPont and Eagle River
Chemical Corporation in response to "308" letters.
3, Farm Chemicals Handbook, 1977, Meister Publishing Company,
Willoughby, Ohio.
4. Sittig, Pesticides Process Encyclopedia Noyes Data Corporation.
Park Ridge, new Jersey, U.S.A., 1977.
5. Proprietary plant report; E.I. duPont de Nemours and Co., Houston,
Texas, EPA Pesticide BAT Review; IKS, EPA IERL-RTP, 1979.
6, Proprietary information submitted to EPA by Shell Chemical Company,
1978, in response to "308" letter.
7. Warner et al. Identification of Toxic Impurities in Technical
Grades of Pesticides Designated as Substitute Chemicals, EPA-600/1-
78-031, Hay 1978.
8. Gubler, K, , V. Flu'eck, and H. Brechbaehler. 1970. In: Insecticides
Proceedings of the Second International IUPAC Congress of Pesticides
Chemistry, Vol. 1, A, Tahari, ed. Gordon and Breach Science Publisher,
New York,
9. Lawless, E.W., T.L. Ferguson, and A.F. Meivers. 1975, Guidelines
for the Disposal of Small Quantities of Unused Pesticides. SPA-670/
2-75-057. U.S. EPA, Washington, D.C.
10. Fung, K,H. and G.L. Briver. 1977, Leaching of Methomyl from Some
Australian Tobacco Soils, Tob. Sci. 21:120-121,
11. Verschueren, Karl. 1977. Handbook of Environmental Data of Organic
Chemicals, Van Nostrand Reinholt Co., N.Y.
12. Water Quality Issues in Massachusetts: Chemical Contamination Special
Legislative Commission on Water Supply. September, 1979.
13. Wilson, J.T. and C.G. Enfield. 1979, Transport of Organic
Pollutants Through Unsaturated Soil. Presented American Geophysical
Union, Fall Meeting. December 3-7. San Francisco, CA.
14. Roberts, P.V.P.L, McCarty, M. Rinhardt, and J. Schriner. 1978.
Organic Contaminant Behavior During Ground Water Recharge. Presented
at 51st Annual Conference of the Water Pollution Control Federation.
October 1-6, Anaheim, CA.
-------
15. Burttschell, R.H. , A,A. Rosen, and F.M. Middleton. 1961. Proceedings
of 1961 Symposium on Ground Water Contamination. Technical Report
W61-5. R.A. Taft Sanitory Engineering Ctr. U.S. DREW,
16. Simmon, V. F. , et al. Mutagenic Activity of Chemicals Identified, in
Drinking Water. (1977) (S. Scott, et al., eds) In Progress in Genetir
Toxicology.
17. Jongeiij W. M. F,, et al. Hutagenic Effect of Dichloromethane on
Salmonella typhinmriuin. Mutat. Res. 56:245 (1978).
18. Vozovaya (1974) as cited by ECAO Hazard Profile (1980).
19. Schwetz, B. A., et al. The Effect of Maternally Inhaled Trichloro-
ethylene, Perchloroethylene, Methyl Chloroform, and Methylene
Chloride on Embryonic and Fetal Development in Mice and Rats. Toxicol,
Appl» Pharaacol. 23:84 (1975).
20. Kat'l. Inst. Occup. Safety and Health. (1976) Criteria for A Recom-
mended Standard: Occupational Exposure to Hethylene Chloride. HEW
Pub. No. 76-138. _IL S. Dept. HEW, Cincinnati, Ohio.
21. DOW Chemcial U.S.A. Material Safety Data Sheet, (Dow Chemical U.S.A,,
Midland, MI 48640). Jan., 1976,
22. Nat7! Acad, Sci. (1978) Non-Fluorlnated Halomethanes in The Environ-
ment. Washington, D.C.
23. Theiss, J.C., et al. Test for Carci-ogencity of Organic Contaminants
of United States Drinking Waters by Pulmonary Tumor Response in Strain
A ilice. Cancer Res. 37:2717 (1977).
24. U.S. EPA. 1979. Halomethanes. Anbient Water Quality Criteria.
PB 296797. Criteria and Standards Division, Office of Water
Planning and Standards, Washington, D.C.
25. Toxic Substances List, 1974.
26. Guerzoni, M., et al. Riv. Sci. Technol., Alimenti. Nutri. Ib. 6:161
(1976). '~
27, Lijinsky, W. ar.d Schmael, D. Ecotoricol, Environ. Saf. 2:413 (1978).
2S. Lijinsky, W. and Slespury, R. K. IAKC Scientific Pub. No. 14 (1976).
29. Kaplan, A. and Sherman, H. Tox. Appl. Pharmacol. 40:1 (1977).
-------
30. BIFAX Industrial Bio-Test Laboratories, Inc. Data Sheets. (1810
Frontage Rd., Northbrook, 111.), 1970.
31. Gleason, M.N., et al. Clinical Toxicology of Commercial Products
Acute Poisoning. (1969) 3rd ed., p. 69. ~~ ~~
32. Merck Index.
33. AGIGR (1976) TLV Documentation.
34. Dawson, English, Petty, 1980, "Physical Chemical Properties of
Hazardous Waste Constituents."
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Explos ives
-------
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)
Wastewater Treatment Sludges from the Manufacture, Formulation
and Loading of Lead-Based Initiating Compounds (T)
Pink/Red Waste from TNT Operations (R)
I. SUMMARY OF BASIS FOR LISTING
Explosives manufacturing produces wastewaters 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.
Under Subtitle C of RCRA. This conclusion is based on the
following considerations:
!• Wastewater treatment sludges from the manufacturing and^
processing of explosives contain significant concentrations
of explosive compounds which could pose an explosion hazard
-------
If improperly managed, this waste could thus present a
substantial hazard to human health and the environment.
Therefore, this waste meets the reactivity characteris-
tic (§261.23).
2. Spent carbon columns from the treatment of 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).
3. 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 .
4. 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, r esu 11 ing - -rn- 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, propellants, 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
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military sectors. Those companies (approximately 40) that
commercially manufacture explosives are situated geographically
in 104 facilities* located in 30 states throughout the country.
The 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 explosives
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 Propellants 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 expl
sive manufacturers, including licensees and permittees for
manufacture of explosives, distributors, users and mix and
blend operators (LAP).
-y-
O
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the military sector is not currently available.
In terras of growth, total commercial consumption of
explosives and blasting agents has increased each year over
the 1973-1978 period. Consumption has risen from approximately
1.3 million metric tons in 1973 to 1.8 million metric tons in
1978, representing an increase of 38 percent.
Out of the total 1978 consumption figure, consumption of
"permis s ib les11* 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 satiTlry energy demands. Over the same
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 (permissibles
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
mine s .
**This document describes only a few processes in the explosives
industry. For a more detailed description, see Reference 22.
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RDX), explosives processing (for example, dynamite and
Qitrocellulose-base propellants) 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 nitric 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 dinitrate (NG/EGDN), pent aerythrito1
tetranitrate (PETN), nitrocellulose (NC), trinitrotoluene (TNT),
cyclotrimethylene trinilramine (RDX), and cyclotetramethylene
tetranitramine (HMX) (see Table 1). Figures 1 and 2 represent
typical production diagrams for NG and RDX, respectively.
Explosives Processing (Dynamite and Propellants)
Two types of explosive processes will be discussed below
as examples; dynamite and nitrocellulose-base propellants.
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
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houses where they are loaded into waxed cardboard boxes
or plastic tubes.16
Nitrocellulose-Based Propellants
Nitrocellulose-based propellants can be divided into single
double, and multi-based propellants. These propellants 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 p1 asticizers, 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 nitrate
materials such as nitrocellulose., ni t r og ly c er in , ni t roguanidine
trie thyleneglycol dinitrate, with stabilizers and the like.26
Initating 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, trinitroresorcino1 (TNR), lead azide, lead
styphnate, lead monomitroresoreinate (LMR), tetry and nitro-
raannite. Figures 4 and 5 are typical flow diagrams for the
production of initiating compounds, illustrating typical
lead azide and lead mononitrorescorcinate production schema-
tics respectively.
-ff-
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B. Waste Generation and General Description
Five 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^Jligures 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.
-------
contaminated with extraneous material to be reused. These
sludges constitute the first listed waste stream and are
marked I 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 propellants, 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;
e Wet milling of propellant castings;
0 Operation of air pollution control devices which
employ wet scrubbers to control emissions and
dust inside production buildings;
Loading, as"~s"emb 1 ing and -packaging of ordinance.
Treatment of these wastewaters also produces a wastewater
treatment sludge.^^"^
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 thes
spent acids are hazardous as defined in Subpart C of Part 261, the
generator would be responsible for managing these wastes under th*
Subtitle C regulatory control system.
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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 absorbant 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.
-X-
-C.N5"-
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Pink/Red Water from TNT Operations
During the production and formulation of TNT and TNT-
containing formulations and products, an alkaline, red-colored
aqueous waste is generated. This waste stream is composed 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 contamination 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 five 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.
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. (4) 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.
-CW7-
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Disposal practices that have been used include
the placing of pink/red water in evaporation ponds.*
V. DISCUSSION 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, HMX,
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-
plosives in the sludges pose a substantial explosive
*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
o f and manag ed .
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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) .(27 )
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 solubilized 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 systems.
-------
Compounding this problem, and an 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 a 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 both 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 bioaccumulates 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
Occupational Safety and Health Act of 1970, a final standard
-------
for occupational exposure to lead has been established.(23>2ZO
Also, a national ambient air quality standard for lead has
teen announced by EPA pursuant to the Clean Air Act.(2^)
In addition, final or proposed regulation of the states of
California, Maine, Maryland, Massachusetts, Minnesota,
Missouri, New Mexico, Oklahoma and Oregon define lead con-
taining compounds as hazardous wastes or components thereof,(2^)
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Figure 1. Schematic Flow Diagram for NG Production
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(60X ACtllC ACID;
2-3%
ACtTIC AflllYnnilJt
(10 Rr.ust)
CYAPOnAIIOH
do ntust)
I •irASUUAUft
do nimi
IM lAGOOM)
MCUIRAUIATIOH
"CRACK MIC'
'."K AUUC
ACM)
Aitoiiippic
DIM IUAT KHI
6U I WO
AiuiYimnus AIMHIIA
(H) HUM)
dot ACt11C
AC 111
(101 AC 1.11C AC III
HtUinAli/.AIlOU
CAUSIIC IIA1IOS
AIVKIIIIA
IU.COYUIY
SICOMUART
IVAPOMAriOII
tYAPOHATION
CYClOllt
StPARATIOM
iDLMMtlllUCl/
runiFito ROX
iron ust IH
CW.0SIYC
FORHUIA1IOH)
(conTAiNims nox)
ROX
ROX
ICRYSTAUIZATIOII
(son
ron rtnTitiun)
•nccovcnco ROX
(TO riURAnOfl/IIASUtllG)
Figure % Schematic Flew Diagram for HDX Produchion.
Source (5); Figure 5-32, pg. 5-123.
-------
Ill
CO
vi'i
-J
INC
SOLVENTS
MIX
DEMY
ULOCK
PNESS
AND
CUT
SOLVENT
RECOVERY
PROCESS
FINISHING
PROCESS
FINISHED
SINGteUASG
PROPELLANV
UJ
CO
•
p
-J
2
5
NC
NO
PREMIX
PROCESS
SOLVENTS
NITROr.UANtOINE
TRIPLEOASE
[TRIPLE UASE CHEMICALS j
[ DOUOLE DASE CHEMICALS
I
OEHY PROCESS
MIX
BLOCK
PRESS
AND
CUT
FINISHED
OOUOLE& TRIPLI
DASE PROPELlAf
SOLVENT
RECOVERY
PRQCESS
FINISIUNQ
PROCESS
tc
III
z
IU
X'
o
NC
[NO
1 • "
UP-
*».
\ SOLVENT
* '
1 Ml
PREMIX
IMIOCESS
i
n
ii
rnnmiANlDtNE 1
JH5GH ENERGY CHEMICALS |
.
.
1
I OUHY PROCliSS
MIX
>-
UtCNO
"" \ l~~V
ULOCK
PIVIISS
AND
CUT
FINSIHEO HIGH ENERGY PKOPE
SOLVENT
RECOVERY
PROCESS
1 1
FINISHING
PROCESS
I AMMONIUM PERCIjLORATE .]
I I.P«lllll •«•« .1 ••'» ' mi • I • '••! •""• ••
Figure 3 • Solvent Propellant Production Scheiratic
Sources (1) Figaro XV-6r pg. 50.
-------
WATER
NUN-
LEAD
AZ1DE
PbNc
PRECJP
NITRIC ACID
NiN0
•%
i
KILL TANK
Pb
DISCHARGE
WATER
.PPT LEAD CARBONATE
?icure 4. SVpical lead Aside Prooucticn Schismatic,
Source: (2); Figure 1V-8/ pg. 53.
-------
NaOH
MNR
I
LEAD NITRATE
REACTOR TUB
REACTOR TUB
EXCESS WATER
•5 WATER WASH '
2 ACETONE WASH
1
3 AMYLACETATE WASH
WASH-FILTER
•*— AMYLACETATE WASH
CAUGHT AND BURNED
WATER WASH WASTE
ACETONE WASH WASTE
SVoicai Lead
Source: (2); Figure IV-10, pg. SI
^s'i^> Prccucticn Schematic
-------
VII. TABLES
-CS7-
-------
IN
OF
Haw Material (s)
Nitratin? Add Additives
nitric *^'" and ethyl acetate
NG/ECSN
glycerine
glycol
nitric »n^ and ethyl acetate
sulfuric aci£
PEIN
pentaerythritol nitric acid
acetone
NC
nitric prid diiutyl phthalate
and sulfaric acid phenylsmine
SDX/HMX
hexsmine
nitric acid and
acetic ?ci.d
acetic
annxDnium nitrate
cyclcihexanaris
acetone
TNT
nitric ?cid
and sulfuric acid
sodinn sulfite
-------
Source: (4) page 32-2,
Nitroglycerin
sulf ate
nitarate
Chloride
Sodium nitrate
Sodium chloride
Calciuiir stearats
'Sulfur
*
Nitrocellulose •
Phenolic resin or glass beads
Bagasse
Sawdust and wood flour
Coal
(Vyrri Tr-ve^l and com starch
Inorganic _salts
-Grain" and seed h"i.ie and flours
3. TCPICAL OPPOSITION CF
t>
lium nitrate
nitroglycerine *
sodium nitrate ' 0-17
t«zce jngrg^J-gnt'S 10—35
Source: (11) Table 7, pg.30,
-------
S 4. KM? fcSSSHIALS FOR
CDMPCONDS
CcTuouno.
Tetracene
Nitrcraarmite
XMR
Tetryl
Startling
sodixza nitrate
f sulfuric scid.
Besorcinol, sulfuric acidf nitric acid
Sodium azics, lead nitrate or lead acetate
nitric acid, sodium nitrate
•
TNR, magnesium oxide, lead nitrate
Mannitol, sulfuric acid, nitric acid
sodium hydroxide,,
lead nitrate
Nitric acid, sulfuric acid, di
-------
TABLE 5; - EXPLOSIVES*1
Industrial Hazardous Waite Quantities by OlsposaT Helhod
fUeferenco 5
bPredomlnantly onslte, >90 percent
Includes chemical detoxification and subsequent disposal! usually landfill, deep well disposal, spray Irrigation,
dIncludes spent activated carbon from processing aqueous hazardous wastes (open burned), red water from THT
purification (evaporated and sold), organic solvents from propollant manufacture, and wastewatort containing
dissolved and suspended RDX/HMX
*0ry Basis • Met BasU
Ooutrooi (1) Table 6-9, page 35.
I Industry Segment . • 1
1 * 1
1 Private Explosives Industry! I
1 Government Owned. Contractor I
1 Operated (GOCO) 1
I Explosives Industry: I
1 Explosives Industry
1 Grand Totals
Waste Type
fined high explosive waste
Blasting agents
Subtotals
Explosive wastes
Explosive contaminated
Inert wastes
Other hazardous wastes
Subtotals
.•
Total Hazardous Waste
Tonnes/Year, 1977 (Dry Basis)
-460
-1,700
(J5,500-Wet Basts)
4.900 •
14,700
240
* 19. 000*
-21.500
(-25,400-Wet Basis)
-
Disposal Methods
Tonnes/Year, 1977 (Dry Basis)'
Open Burned
>430
>1,100
>1,500
4,000
•
13,700
90
10.690
20,100
UndMUed
Negligible
Negligible
Negligible
.--
1,000
140
1,140
1,140
Sold
<5
51?
140
».
/20
160
-100
Olherc
.<«
<100
—
mm
I
-------
IS 6
.rry 3OORS FOR EXPIOSTCS;
Ccrrrxxirjd
NG
KDX
lead aside
Nitrccannite
Solution
water
vater
water
water
0.14 gAOOg
0.24 g/lOOg
water 0.68 g/lOOg
acetone vs^y soluble
ethyl ether very soluble
insoluble
insoluble
styphhate
water
0.04 g/lOOg
Temperature
25eC
-60°C
20eC
25CC
V^t^-T
water""
water .
ethsnol
ether
' 0.02 g/lOOg
— _ M^* ^
0.09 g/lOOg
insolubl e
2.9 g/100g
4 g/100g
18°C
70°C
13°C
9°C
-------
TABLE 7.
Wastewater treatment sludges from the manufacture
and processing of explosives (R)
Proc_es_s_
Nitration of cellulose
(Note: nitrocellulose
is used in a number of
industries)19
Nitrocellulose
(NC) Production^
Nitroglycerin (NG) production^
o
Nitroglycerin production^.
TNT production^
Nitrocellulose production^'
Batch Nitroglycerin Production'7
Combined wastewater of Radford
AAP continuous NG Nitration and
Spent Acid7
Waste (Concentration)
Sludge (25% water and
75% 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 0.072%
of NC output.
NG lost to wastewater at
0.006 kg per Kg NG produced
NG discharges in wastewater:
as high as 1000 mg/1
100 mg/1 of TNT to wastewater
NC fines can produce levels of
solids from 1000 to 10,000 mg/1
Wastewater (315 to 12,700 ppm)
Nitroglycerin in wastewater
(800 to 1,800 ppm)
RDX/HMX production7
Catch basins remove 33
percent of RDX and 62
percent of HMX from
-yf-
-------
TABLE 8.
3. Spent carbon from the treatment of wastewater containing
explosives (R)
Proces s
LAP Melt loading of
105mm Cartridge-*
LAP 40mm Cartridge5
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. 39% TNT, 1% Wax
-GC.H-
-------
TABLE 9.
Wastewater treatment sludges from manufacture, formu-
lation and loading of lead based initiating compounds (T)
Process
Initiating Compounds19
Initiating compounds
19
Initiating Compounds1^
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 CO-,
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
-------
TABLE 10.
5. Pink/red water from TNT operations (R)
Proces s
TNT Production5
(bat ch process )
TNT Production5
(continuous process)
LAP
TNT Production
Evaporator Condensate'
(A source of pink water)
Waste (Concentration)
Red water solids are
produced at a rate of
(0.2398 kg per Kg TNT
produced)
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 kg
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.1
-yf-
-------
VI. References
1§ Van Noordwyk, H., L. Schalit, W. Wyss, H. Atkins.
Quantification fo Municipal Disposal Methods for
Industrially Generated Hazardous Wastes. USEPA-
600/2-79-135, Municipal Environmental Research
Laboratory, Cincinnati, Ohio, August 1979.
2. U.S. Environmental Protection Agency. Development
Document for Interim Final Effluent Limitations,
Guidelines and Proposed New Source Performance Standards.
Effluent Guidelines Division, Office of Water and
Hazardous Materials, USEPA 440/1-76-060, Washington, D.C.,
March 1976.
3. Bureau of Mines, U.S. Department of the Interioor.
Mineral Industry Surveys. Explosives Annual. 1978.
4. Patterson, James, Norman I. Shapira, John Brown,
William Duckert, and Jack Poison. State-of-the Art:
Military Explosives and Propellants Production Industry.
Volume II, Waste Characterization. EPA-600/2-76-213b,
August 1976.
5. TRW Systems Group. Assessment of Industrial Hazardous
Waste Practices, Organic Chemicals, Pesticides, and
Explosives Industries. PB 251-307, April 1975.
6. Hudak, Charles E., and Terry B. Parsons. Industrial
Process Profiles for Environmental Use. Chapter 12,
The Explosives Industry. PB 291-641, February 1977.
7. Patterson, James, J. Brown, W. Duckert, J. Poison,
and N.I. Shapira. State-of-the-Art: Military Explosives
and Propellants Production Industry. Volume III,
Wastewater Treatment. EPA-600/2-76-213c, October 1976.
8. Process Research, Inc. Alternatives for Hazardous
Waste Management in the Organic Chemical, Pesticides,
and Explosives Industry. EPA Contract No. 68-01-4127,
September 2, 1977.
9. U.S. Department of Health, Education, and Welfare.
Registry of Toxic Effects of Chemical Substances,
June 1975.
0. U.S. Environmental Protection Agency. Disposal of
Hazardous Wastes. Office of Solid Waste Management
Programs, 1974.
-------
11. Patterson, J.W., and R.A. Minear. State-of-the-Art
for the Inorganic Chemicals Industry Commercial
Explosives. EPA-600/2-74-009b , March 1975.
12. Ottinger, R.S. J.L. Bluraentahl, D.F. DalPorto,
G.I. Gruber, M.J. Santy, and C.C. Shih. Recommended
Methods of Reduction, Neutralization, Recovery,
or Disposal of Hazardous Waste. Volume VIII. EPA-
670/2-73-053g, U.S. EPA, Washington, D.C. August 1973.
13. Patterson, James, Norman I. Shapira, John Brown,
William Duckert, and Jack Poison. State-of-the-Art:
Military Explosives and Propellant Production Industry.
Volume I, The Military Explosives and Propellants Industry.
EPA-600/2-76-213a, October 1976.
14. Hydroscience, Inc. Draft Development Document for Proposed
Effluent Limitations Guidelines, New Source Performance
Standards and pretreatment Standards for the Explosives
Manufacturing Point Source Category, April 1979.
15. Griffin, T.B., and J.H. Knelson. Environmental Quality
and Safety, Supplement Volume II. Academic Press,
New York, 1975.
16. U.S. Environmental Protection Agency. The Health and
Environmental Impacts of Lead and an Assessment of the
Need for Limitations. Office of Toxic Substances,
EPA-560/2-79-001, 1979.
17. Sax, Irving, Dangerous Properties of Industrial Materials.
Third Edition. Van Nostrand Reinhold Company, New York,
1968.
18. U.S. Environmental Protection Agency. The Prevalence of
Subsurface Migration of Hazardous Chemical Substances at
Selected Industrial Waste Land Disposal Sites. EPA-530
SW-634, October 1977.
19. State of New Jersey. Unpublished Data, Waste Ch ar ac t erizati
Data from the State file of "Industrial Waste Surveys" to
Claire Welty of OSW. 8/31/79 and 9/4/79.
20. Sax, Irving. Dangerous Properties of Industrial Materials.
Fifth Edition. Van Nostrand Reinhold Company, New York.
1979 .
21. Searle, C.E. (editor) Chemical Carcinogens ACS Monograph
173. Washington, D.C. 1976.
-vi-
-------
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. U.S. Department of Health, Education and Welfare,
National Institute for Occupational Safety and Health.
Registry of Toxic Effects of Chemical Substances. 1977.
25. U.S. EPA States Regulation Files, January, 1980.
26. U.S. EPA, State-of-the-Art: Military Explosives and
Propellants Production Industry, Volume 1 - The Military
Explosives and Propellants Industry, Industrial Environ-
mental Laboratory, PB 265-3885 c.l, October, 1976.
27. Pourbaix, Marcel. Atlas of Electrochemical Equilibria
in Aqueous Solutions, London, Pergamon Press, 1966.
-yS-
-------
Petroleum Refining
-------
LISTING BACKGROUND DOCUMENT
PETROLEUM REFINING
API Separator Sludge (T)
j
Dissolved Air Flotation (DAF) Float (T)
Slop Oil Emulsion Solids (T)
Heat Exchanger Bundle Cleaning Sludge (T)
Tank Botton (Leaded) (T)
Summary of Basis for 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., API separator
sludge, dissolved air flotation (DAF) float and slop oil
emulsion solids) or from the clean-up of equipment / s to r-age
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 human health
or the environment when improperly transported, treated,
stored, disposed of, or otherwise managed, and therefore
should be subject to management under Subtitle C of RCRA.
This conclusion is based on the following considerations:
1. These wastes contain significant concentrations of
the toxic heavy metals, lead and chromium.
*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.
I-
-------
In some waste streams the concentrations of lead and
chromium exceed 1,000 mg/kg (dry weight). In addition
to being toxic, lead has been shown to be potentially
carcinogenic and bioaccumulative .
2. Large quantities (a combined total of approximately 66,610
metric tens (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 water-washing step
which simulates leaching activity. Furthermore, if the
last three listed wastes are disposed of in an acidic
environment, the solubility of the lead and chromium
waste constituents will certainly be enhanced, since
these toxic heavy metals' solubilities are pH dependent
(i.e., solubility increases as the pH decreases).
.Therefore, these metals could potentially migrate from
the waste into the environment. Additionally, if these
wastes are incinerated without proper air pollution
control equipment, the possibility exists that lead
will be released into the environment and create an air
pollution problem.
4. Current disposal methods such as landfilling, land-
farming, lagooning and incineration, if not properly
designed and operated, can lead to the contamination of
surface water and groundwater either by the overflowing
of wastes or the leaching of harmful constituents from
the disposal sites into the environment thereby constituting
a potential substantial hazard to human health and the
environment.
Profile of the Industry
Industry Structure
The petroleum refining industry is perhaps one of the
most complex and technically sophisticated in the United
States. There are some 250 to 300 refineries in the United
States, ranging in size from about 400,000 BPD* to only a few
hundred BPD. These refineries vary from a fully Integrated,
high-complexity plant capable of producing a complete range
*BPD = Barrels per day
i
-------
of petroleum products and some petrochemicals, to very simple
plants capable of producing only a very small number of
products. Some refineries are modern and of recent construc-
tion, while others contain at least some operating process
units constructed 40 or more years ago. The crude slates
for refineries vary widely. The product mixes, and to
some extent the product properties, also vary from refinery
to refinery. Because of this, each refinery is characterized
by a unique capacity, processing configuration, and product
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 Mines 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
I960 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
* 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 .
-4-73-
-------
SURVEY OF OPERATING REFINERIES IN TIIE UNITED STATES - 1962-1972
~£
I
n««.rB?_.5:.l!r'!?J! Y-_l!^!"/?>l>)
N
Ditte P
1/1/62
1/1/61
1/1/64
1/1/65
1/1/66
I/I/*,/
1/1/68
1/1/69
1/1/70
1/1/71
1/1/72
0|>er«ttnR Refining
, Capic U y '
lnnt« (MMft/
299 10.
291 9.
288 10.
275 10.
265 10.
:i.\ 10.
269 11.
263 11.
262 12.
253 12.
247 13.
C')J (MMn/SD) 01 »l 111 lit lor
01 10.59 1.67
92 10.46 J.'»H
18 10.72 3.75
25 10:76 3.76
25 10.75 1.76
'.-, 10.95 1.M-.
14 11.66 4.0ft
57 12.08 4.12
15 12.65 4.55
68 11.28 4.74
09 11.71 4.85
Cntalyt Ic
Cr/irktnn C.unlyttc Cutnlyllc C*t«lytlc
Thermal Frenh Cntulytlr. Hydro- Hydio- llydro-
i Ojiftrntlon Yr.vil Recycle Reforming crncking reflnlnR trent Ing
1.81 1.75 1.47 2.02 2.
1.75 l.l«'> 1.5^ l.'fl 2.
1.72 1.99 1.62 2.05 - - 2.
1.64 1.99 1.57 2.06 - - 2.
1 . <>'> 1 . 96 1 . 5 .1 7 . 09 - - 1 .
I.I.'. 1. 'I', | . *.', J . I'l - - •).
1.66 4.18 1.60 2.1ft 0.41 - 3.
1.60 /..25 1.55 2.54 0.50 0.55 3.
1.64 4.17 1.49 2.7R 0.60 0.54 1.
1.56 4.51 1.46 2.89 0.73 0.54 1.
1.5) 4.57 1.26 1.17 0.84 0.61 4.
37
54
75
93
10
r,
66
27
51
81
26
Production Cnpacltjr (MMH/SO)
Cntnlyt Ic
Alkyl«- Polymerlt*-
t Inn t li>i\* l.tibv Aiphnlt
0.
0.
0.
0.
0.
O.
0.
0.
0.
0.
0.
46
49
50
51
55
60
65
67
75
78
82
0.14 0.
0.11 0.
0.13 0.
0.11 0.
0.12 0.
o.ll 0.
0.10 0.
+0.25 0.
0.29 0.
0.11 0.
0.29 0.
21
20
20
21 •
21
71
21
20
21
22
22
0.49
0.49
0
0
0
O
0
0
0
0
0
.51
.54
.51
. U
.53
.17
.58
.60
.62
Cuke
^m/sn|
in. 90
19. 70
30.94
71.14
2). 01
7 '..OO
28.43
79.41
35.49
38.77
41.47
Incremental Change
1962-1972
Z Crude
3.
100.
08 1.12 1 . 1 fl
0 101.3 17.R
(0.2H) O.fl2 (0.211 1.15 0.43 0.08 1.
(9.0) 26.) (n.7) 16.9 13.8 2.6 60.
89
6
0.
11.
16
5
0.
0.
01
1
0
4
.13
.2
22.57
-
NjPC_ _Q< i e_it t 1 o.n n « t r it
^ Cxj>.u\tinn IUt« (MMH/rDJ^
1971-1978
1.
100.
fl - 0.50
0 - 2H.O
(0.1M) 0./.0 n.O 0.67 0.11 0.67 0.
(1.0) II. 0 0.0 17.0 6.0 37.0 55.
99
0
0.
7.
11
.0
0.14 0.
8.0 1.
IA
0
0
5
.09
.0
6.4
M))B - ml lllon bnrrels
CD - caleml.ir
-------
C:KOC:UAPIITO m STUI mrrtoN 01--
SOURCE: Reference 5
-------
FIGURE 2
PETROLEUM ADMINISTRATION FOR DEFENSE (PAD) DISTRICTS
S
6^
i
. I At A'.K A V '
,,ri
AND HAWAII)
- _ _ _» I
Reference 5
-------
TABLE 2
SURVEY OF U.S. REFINING INDUSTRY
BY CAPACITY AND NUMBER OF PLANTS
PT.ANT SIZE, BPD:
10,000
10-100,000
Over
100,000
No. of plants
Total Refining Capacity,
74
141
44
J. -v
I
I
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 (1975).
/
-4,77-
-------
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
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
are 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
refinishing, to produce a varied list of intermediate and
finished products, including light hydrocarbons, gasoline,
^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).
-------
diesel 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
for identifying these wastes as hazardous. (A 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 carried out in a
petroleum refinery, a brief description of some of the individual
operations is included as Attachment I.)
Waste Generation and M an a"g e m e n t
1. Was t e S tre ams
The five waste streams listed as hazardous are:
o API Separator Sludge
o Dissolved Air Flotation (DAF) Float
o Slop Oil Emulsion Solids
o Heat Exchanger Bundle Cleaning Sludge
o Tank Bottoms (Leaded)
Lead and chromium are the constituents of concern in
these waste streams. Lead in the waste streams comes predomi-
nantly from the use of tetraethyl lead in the blending of
leaded products. Chromium in the waste stream comes predominantly
-------
from cooling tower blowdown that uses a chromium base corrosion
inhibitor.* Concentration ranges for lead and chromium in
representative samples of each waste are presented in Table 3.
API Separator Sludge - The API Separator provides for primary
refinery wastewater treatment. The separators are usually
connected to the oily water plant sewer. As a result, the
API separator bottoms 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 API 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 heavy metals, chromium and lead.
(Table 3 lists the concentration ranges of the constituents
of concern in each waste stream.)
*The Agency recognizes that refineries not implementing these
systems will have lower concentrations levels of these toxic
metals. The delisting provisions of §261.39 are available
to generators with fundamentally different waste streams to
justify delisting of their wastes.
-------
" Some refineries utilize dissolved air flotation
Allowing primary separation in the API Separator to remove
additional oil and solids. The process brings finely divided
oil and solid particles to the surface where they are skimmed
for disposal.
Water typically constitutes 82% by weight of this waste
stream, while oil and solids constitute approximately 12.5%
and 5.5% respectively. The solids are generally fine silts
which did not have sufficient residence time in primary
separators to settle, but the waste stream also contains the
heavy metals chromium and lead, for which it is listed.
Slop Oil Emulsion Solids - The skimmings from the API 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 combination of the waste stream by
weight is 40% water, 43% oil and 12% solids. Among the
solids are the heavy metals chromium 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 sandblasted, while the tube insides can be wiped,
brushed, or rodded out. Sludge resulting from the cleaning
-------
TABLE 3
RANGE* IN CONCENTRATION** FOR CONSTITUENTS OF CONCERN
Contaminant
No. of Samples
Chromium
Lead
API Sludge
12
.10-6,790
.25-1,290
O f*\ I TV? f^ TV
CJ \^ Ui V \j 1.4
DAF Slop Oil Bundle Sludge
5 9 , 2
r
28-260 1-1,750 310-311
2.3-1,250 .25-580
_ — S
X
Tank Bottoms
2
—
158-1,420
*Range values represent high and low concentrations for samples of each waste stream
**Concentration In mg/kg dry weight, Including Inert solids but excluding oil
SOURCE: Reference 1
-------
process has approximately 53% water, 11% oil and 36% solids.
These solids are composed largely of silt precipitated
from the water. The metals present are mostly corrosion
products or scale deposits from the exchange bundle tubes.
Chromium is present in the waste in substantial concentrations,
and the waste is listed due to the presence of this constituent.
Tank Bottoms (Leaded) - The petroleum products (or fractions)
after being separated in the distillation column have to be
cooled before they are sent out or used for making other by-
products. This is done in product storage tanks. As cooling
occurs, the water separates from the hydrocarbon phase and is
continually drained from the tank,s to the refinery water
treatment system. Solids formed as products of corrosion and
rust in the tanks cont airr---1 oxi c heavy- metals, and are
periodically removed. This waste is being listed because it
cont ains lead .
In summary, the contaminants in these wastes which
caused EPA to identify these wastes as hazardous are as
follows :
API Separator Sludge - chromium and lead
DAF Float - chromium and lead
Slop Oil Emulsion Solids - chromium and lead
Heat Exchanger Bundle Cleaning Sludge - chromium
Tank Bottoms (leaded) - lead
2. Waste Generation Ratio and Composition
There are a wide variety.of factors which can affect the
-------
quantity and quality of individual waste streams. Factors
that affect quality include crude oil characteristics, compo-
sition of process wastewater, occurence of spills and leaks,
composition of cooling water blowdown, use of corrosion
inhibitors and the use of tetraethyl lead for specific pro-
ducts and modifications. Factors 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, each
waste stream varies with regard to lead and chromium
concentrations, but lead and chromium are found generally in
very high concent rations^with some levels exceeding 1000 mg/kg
dry weight.*
The estimated quantities of individual waste streams
range from 600 - 33,000 metric tons per year (dry weight)
(including inert solids but excluding oil). The combined
total estimated quantity is 66,610 metric tons per year (dry
*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 tng/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.
-------
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 are shown in Table 4
and indicate that the API separator, Slop oil and DAF Float
are the major waste generating streams in terms of quantity.
Additionally, the data indicates that chromium and lead are
present in substantial quantities in these wastes.
A second source of data, the American Petroleum Institute
(API), took an extensive survey at the quantities of each waste
component present in two of the waste streams from the Petroleum
Process which concern the Agency.
As shown in Table 5, the API data on the API sludge
and the^ DAF float generally supports the data found in Table
3. (it is important to recognize that the API data reflect
a much larger sampling effort relative to that encompassed
in the EPA survey.)
Current Disposal Practice - There are currently 4 principal
methods for disposing of petroleum refinery solid wastes.
*BPD - Barrels per Calendar Day
-------
TABLE 4
TOTAL QUANTITIES OF EACH WASTE COMPONENT
Metric Tons/Yr (Dry Weight)*,**
API SLUDGE
DAF FLOAT
SLOP OIL
HEAT EXCHANGER SOLIDS
TANK BOTTOMS
TOTAL
Chromium
Lead
17.6
1.2
8.4
.5
17.7 .4
.06
44.2
1.1 2.9
i SOURCE: Reference 1
oO
*Excludes 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.
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TABLE 5
RESULTS OF API SURVEY
TOTAL WEIGHT
METRIC TONS/YR
API DAF
CONCENTRATION
Mg/Kg
API* DAF**
Chromium
Lead
8.6
2.4
5.3
.23
0-10,800
0-6200
0-3000
0-540
I
o
oO
vj
*Sample size ranges from 63-68
**Sample size ranges from 13-15
SOURCE: Reference 3
-------
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 with up to 75 percent of the
refineries relying upon these processes for solid waste
disposal.
Hazards Posed by Waste
As indicated earlier (Table 3), the five waste streams for
the petroleum refining industry contain significant concentrations
of the toxic heavy me t a-l-s- 1 ead and chromium, 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 DAF float) in which a water-wash ing step was
conducted to simulate leaching (see Table 7), indicates that
lead and chromium will leach from the waste in significant
concentrations (between 10 and 100 x the National Interim
Primary Drinking Water Standard) even when these metals are
subjected to mild environmental conditions. 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
-------
TABLE 6
DISPOSAL METHODS FOR REFINERY WASTES*
Method
Landfill
Lagoon
Incinerat ion
Land Treatment
EPA Survey^
APISurveyc
On-Site
5
3
1
10
Off-Site
14
2
0
0
On-Site
47
15
3
27
Off-Site
36
4
0
3
aReported in terms of number of refineries.
^Nineteen refineries reported.
cSeventy-five r e f ineri es--report ed .
^Percent 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)
API* DAF**
Con t aminant S ludge Float
Chromium (total) 1.9 3.3
Lead 2.3 2.1
*Sample size: 60-63
**Sample size: 12-15
SOURCE: Reference 3
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even more of the hazardous constituents would be released
environmental migration.
Although leaching data for the other three waste streams
is not presently available, the Agency believes that the
contaminants found in the waste 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 three remaining 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. Further, lead oxide, the form
in which lead appears in— these wastes, is soluble in moderately
acidic environments (7). The solubility of chromium oxide
is pH dependent and, like lead oxide, will increase as the
pH decreases (8). Thus, disposal of these wastes in acidic
environments is reasonably likely to result in the solubili-
zation of dangerous concentrations of heavy metals.
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 lan.df i 1 ling , land treatment
°r impounding the waste may be inadequate to prevent such an
°ccurrence. While the Agency is presently unaware of all
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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.
An overflow pr ob le"rrf"mi gh t 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 surface
waters 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
vt
-------
.ce
nearby ground and surface waters, thereby increasing the
likelihood of drinking water contamination. Further, on.
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 elemental metals.
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.
A further possibility of substantial hazard arises during
transportation 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 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 chromium constituents,
even though these 'constituents are also measurable by the
characteristic of extraction procedure toxicity. Although,
*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 II8 C. The temperature at which vapor pressure equals 10 mm
Hg for water is 11° C and for lead is 1162° C (11).
-------
concentrations of these constituents in an EPA extract from
waste streams from individual sites might be less than 100
times the National Interim Primary Drinking Water Standards,
the Agency, nevertheless, 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 significant concentrations of chromium
and lead in the five waste streams, the non-degradabi1ity of
these substances-, and the possibility of 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.
-------
_ects of Waste Constituents of Concern
Toxic properties of chromium and lead have been well
documented. 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
numerous and severe. Lead may enter the human system through
inhalation, ingestion or skin contact. Improper management
of these sludges may lead to ingestion of contaminated drinking
water. Additional 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
§307 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
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 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).
-------
Re ferences
1. Jacobs Engineering Company. Assessment of Hazardous
Waste Practices in the Petroleum Refining Industry.
Environmental Protection Publication PB-259-097.
National Technical Information Service. 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, 68-02-1319.
November, 1975.
5. A.D. Little, Inc. Environmental Considerations of
Selected Energy Conserving Manufacturing Process
Options. Vol. IV Petroleum Refining Industry.
EPA 600/7-76/034-d. IERL, December, 1976.
6. Development Document for Effluent Limitations Guidelines
and Standards for the Petroleum Industry. EPA 440/1-79/
014-b. December, 1979.
7. The Merck Index. 8th Edition. 1968.
8. Pourbaix, Marcel. Atlas of Electrochemi c a 1 Equilibria
in Aqueous Solutions, London, Pergamon Press, 1966.
9. U.S. Department of Interior, Bureau of Mines. Mineral
Commodity Summaries, 1979.
10. U.S. EPA State Regulations Files; January 1980.
11. Handbook of Chemistry and Physics, 56th ed. Cleveland:
CRC Press, 1975.
-------
Wastes from Petroleum Refining Process - Response
to Comments
j_4 A number of commenters stated that the proposed listing
"SIC 2911 API separator sludge (T,0)" should not apply to
all wastes from API separators but only to waste generated
from petroleum refineries*. The commenters 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
that the sludge from any use of such a piece of equipment
would be a hazardous waste). Therefore, the commenters want
the listing to be e i the'F"'c 1 ar i f i ed 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.
-------
2. One cotnmenter 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 re fining-coke from asphalt
cracking. Data was submitted along with the suggested
list ings.
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 reccnrisider these' listings at some later
time once sufficient data becomes available.
3. One commenter 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
de c i s ion.
*This waste was listed in the December proposal (43 FR 58959).
-------
Attachment I
The refinery process can be categorized into the following
individual operations which are displayed schematically in
Figure A-l.
o S eparat ion
o Treating
o Conversion
o cracking
o comb inat i on
o rearrangement
o Blend ing
o Auxiliary Process
o Storage
Separat ion
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 distillated
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
-------
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-------
Of producing a broader spectrum of process streams than a
topping unit. For example, these units may either recover
additional gas oil from the reduced crude while producing a
heavy 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.
Treat ing
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 J^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 ainine-b as ed
solvents.
o Hydro treat ing - Hydrotreating involves the catalytic
conversion of organic nitrogen, sulfur, and oxygen compounds
into hydrocarbons and the more readily removable sulfides,
ammonia, and water. Various process streams normally are
-701-
-------
treated separately because of various fuel specifications and
the wide range of catalysts and reactor conditions required
to hydrotreat the various petroleum fractions.
Convers ion
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
pro cess.
Catalytic Cracking - Catalytic cracking involves the
application of catalytic reactions to reduce heavy oils maxi-
-702-
-------
production of light C4 hydrocarbons and C5 and C6
gasoline compounds. This process is primarily employed to
maximum 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
4
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-aroma t ic s .
Isomerization units are used to increase the octane
ratings of pentane and hexane fractions to produce a gasoline-
blending stock having an octane number of 80-85. The reaction
is conducted at elevated temperatures (> 300°F) and pressure
(400 psig) over a chlorinated-platinum-aluminum-oxide catalyst.
-70S-
-------
Blending
The typical in-line blending operations most commonly
involve the final processing of gasoline prior to storage. A
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
demulsify the two-phase aqueous-organic system.
o Hydrogen Generation - Large quantities of hydrogen
are consumed in numerous refinery operations, including
hydro treat ing, 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
-70
u ~
-------
process depends upon the characteristics of the raw feedstock
material.
o Sulfur Recovery - This process involves the application
Of 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 tail 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 over a 1 1 -f-ac i 1 i ty steam balance. Facility
requirements can range from a simple back-up boiler for
operations where there are significant amounts of by-product
steam to other situations where continuous steam generation
is necess ry.
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
-------
pulping through steel or other piping from one process area
directly to the other.
o Tank Storage
Fixed R oof - These cylindrical steel tanks 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.
Float ing 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
c n a n g e s
-------
Pressure - These tanks are especially useful for
storing highly volatile materials. These tanks come in a
vide variety of shapes and are designed to eliminate vapor
emissions by storing the product under pressure. These tanks
may 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.
-707-
-------
Leather Tanning and Finishing
-------
LISTING BACKGROUND DOCUMENT
LEATHER TANNING AND FINISHING INDUSTRY
I. LISTING OF HAZARDOUS WASTE STREAMS
1. Chrome (blue) trimmings generated by the following subcategories
of the leather tanning and finishing industry: hair pulp/
chrome tan/retan/wet finish; hair save/chrome tan/retan/wet
finish; retan/wet finish; no beamhouse; through-the-blue;
and shearlings. (T)
2. Chrome (blue) shavings generated by the following subcategories
of the leather tanning and finishing industry: hair pulp/
chrome tan/retan/wet finish; hair save/chrome tan/retan/wet
finish; retan/wet finish; no beamhouse; through-the-blue; and
shearlings. (T)
3. Buffing dust generated by the following subcategories of the
leather tanning and finishing industry: hair pulp/chrome tan/
retan/wet finish; hair save/chrome tan/retan/wet finish; retan/
wet finish; no beamhouse; and through-the-blue. (T)
4. Sewer screenings generated by the following subcategories of the
leather tanning and finishing industry: hair pulp/chrome tan/retan/
wet finish; hair save/chrome tan/retan/wet finish; retan/wet
finish; no beamhouse; through-the-blue; and shearlings. (T)
5. Wastewater treatment sludges generated by the following subcategories
of the leather tanning and finishing industry: hair pulp/chrome
tan/retan/wet finish; hair save/chrome tan/retan/wet finish;
retan/wet finish; no beamhouse; through-the-blue; and shearlings. (T)
6. Wastewater treatment sludges generated by the following
subcategories of the leather tanning and finishing industry:
hair pulp/chrome tan/retan/wet finish; hair save/chrome tan/
retan/wet finish; and through-the-blue. (T, R)*
7. Wastewater treatment sludges from the following subcategory of
the leather tanning and finishing industry: hair save/non-chrome
tan/retan/wet finish. (R)**
II. SUMMARY OF BASIS FOR LISTING
The first three waste streams listed above (trimmings, shavings and
dusts) are a direct result of processing operations conducted within
* Reactive (R) listing results from the inclusion of tanneries that^
unhair; this process generates reactive solutions containing sulfides.
**Vegetable tanneries generate sludges which are considered reactive.
Data on the metal content of these sludges is not available at this
time. Therefore, these sludges are listed only as reactive.
-------
tanneries. The four remaining waste streams (screenings and sludges)
are a result of tannery wastewater treatment facility operations which
have to comply with proposed categorical wastewater pretreatment standards
for existing sources (PSES) which discharge to publicly-owned treat-
ment works (POTW's), or proposed effluent limitations based upon best
practicable technology (BPT) and best available technology (BAT) for
plants which discharge to surface waters (44 FR 38746, July 2, 1979).
The Administrator has determined that the above listed wastes
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 Sub-
title C of RCRA. This conclusion is based on the following considera-
tions:
1. These first six waste streams contain elevated concentrations
and quantities of the heavy metals chromium and lead;
2. Wastewater sludges (product of the last two listed wastes)
from chrome tanneries which employ unhairing operations also
contain high concentrations of sulfides and sulfates which
can react to form dangerously toxic hydrogen sulfide gas
when subjected to an acidic environment, a condition
typical to landfills;
3. Approximately 190 leather tanneries currently generate 38,500
dry metric tons (dry weight) of hazardous wastes;
4. Approximately 90 percent of the hazardous wastes listed above
are disposed in landfills. If improperly managed, the
potential exists for these metals to migrate from the waste
in a landfill environment and to contaminate surface and
groundwater supplies; this has been demonstrated when
these wastes were subjected to the proposed extraction
procedure and found to meet the final extraction procedure
toxicity characteristic.
-7/O-
-------
III. DISCUSSION
A. Industry Profile
There are approximately 190 leather tanneries which are
responsible for generating the wastes of concern. Production at
these facilities ranges from less than 300 to greater than 2,000
equivalent hides (1 equivalent hide = 40 ft^) per day. Approximately
93 percent of these plants utilize chrome or chrome-tanned hides or
skins in their operations. The leather tanning and finishing plants
identified are located in 34 states. Approximately 30 percent of
the total are located in two states: New York and Massachusetts. In
general, the greatest concentration of tanneries are found in the New
England area and the Middle Atlantic States with approximately 85
percent of all tanneries located east of the Mississippi RiverC^->2,3).
B. Manufacturing Processes
Cattlehides constitute 81 percent (by weight) of the raw material
utilized by tanneries in the United States. Sheepskins and pigskins comprise
15 percent of raw material, while goatskins, calfskins, and other hide and
skin types represent the remaining 4 percent of the raw material (1,2,3).
The three primary processing operations involved in producing leather
from cattlehides are depicted in Figure 1 and described as follows:
1. Beamhouse Operations. Beamhouse operations typically begin
by trimming the perimeter areas of the hide. The hides are
then washed and soaked in water to clean the hides and re-
store their moisture. Attached hair is removed by either a
-7/1-
-------
rigtzre 1
PRODUCT AKD SOLID VASTS TICK TDK TOLL LT?g
LZATHE& TANNING AKD FTJTISBTHC FLASTS
Tatrrard
£etaa, Color,
Facliquor
finish
K*terlil« I
Process*!
Solid W**cc
u»trr
Q^ ^ ^ ^ ji Cory c*^)*!f^ ic* x 9
Vatex
Receive & SCOT* Hide*
Side & TrtH
k
[Weigh & Sort
. ._* So«.k
> Wwh
[il«*tiinj»
Cnhair
Pulp S*ve
Briae ind Acid
Ag eat
Agent
Agentf.
& Pigaent.8
Eaailaifiers
fatliquor*, Water
i.
Slaichicg & Coloring
liquoringj
[Setting Out]
Trin
Unfinished L»»ci«r
|Hanging I
Drying
' Pasting^
Tojeglins;
! ^«cu^ j
DuaC
Solvent b*«e finishes,
Uater b*«« finishes,
Pignects •—•—
fConditioning'
"-£
[Staking i Drr Xil
[Buffing)-
riaishins & Platiag
[MeasurTi
'Buffing Doit
Leather Trixm±&t»
-------
chemical dissolving process or a combination of chemical
and mechanical means in an alkaline medium.
2. lanyard Processes. Tanyard processes involve the chemical
fixation' in an acid medium of organic (primarily vegetable
tanning) or inorganic (primarily trivalent chromium) ma-
terials to the protein structure of the hide to prevent its
deterioration. Chromium tanning is the more prevalent
tanning method because it results in a product which is
preferred for the majority of leather uses and it requires
less process time to generate a tanned product,
3. Retanning and Finishing. Retanning imparts specific char-
acteristics to. the leather which it lacks following the
initial tanning step. The more commmon retanning agents
are chromium, vegetable extracts, and syntans. Additional
wet finishing steps include coloring by a variety of dye-
stuffs, and fatliquoring using primarily sulfonated oils
to restore lubrication to the leather fibers. Finishing
processes include a number of operations which dry, con-
dition, smooth, and apply surface finishes to the leather
according to its end use. Various finishes (primarily
water-base, as well as solvent-base) provide abrasion
and stain resistance, and color enhancement to the final
product.
The manufacture of leather from sheepskin is similar to cattle-
hide tanning except beamhouse operations are typically absent. In addi-
tion, sheepskins require degreasing prior to tanning.
-"7J3-
-------
Shearlings (sheepskins with wool retained) require essentially
the same sequence of processing steps as sheepskins but differences in
individual steps are necessary.
The sequence of pigskin processing steps is essentially the
same as that used for cattlehide tanning; while most skins undergo ex-
ternal removal of most of the hair at the slaughterhouse, additional
unhairing is necessary to remove hair stubble and follicles. Degreas-
ing is also practiced prior to the tanning of pigskins. Solvents and/or
detergents are employed ot degrease the untanned skins.
C. Waste Generation
Approximately 38,500 metric tons (dry weight) of hazardous
waste is currently generated by the leather tanning and finishing
industry. Wastewater sludges represent the largest portion of the
total at 47 percent. The breakdown of the remaining hazardous wastes
is as follows: chrome trimmings and shavings, 45 percent; sewer
screenings, 4.5 percent; and buffing dust, 3.5 percent. The projected
hazardous waste quantities which will be generated when BPT, BAT,
and pretreatment technologies are fully implemented are 43,400 and
58,000 metric tons (dry weight), respectively. The incremental
difference between BAT and BPT quantities is attributed primarily to
the implementation of pretreatment technology by indirect dischargers
(1,2,3).
Facilities which utilize unhairing processes, chrome tanning
processes, and subject chrome tanned hides to further processing are
the primary generators of hazardous waste within the leather tanning
and finishing industry.
-ff-
-7/H-
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The seven hazardous wastes listed above occur at various
points within either the tanning process or wastewater treatment
facilities. Figure 1 is a generic process flow diagram which relates
the input materials and the solid wastes generated by the subprocesses
of a complete ("full line") leather tanning and finishing plant. The
first three listed wastes, namely the trimmings, shavings and
buffing dust, are a product of the tanning processes as shown in
Figure 1. Figure 2 shows the various waste sources and streams
resulting from in-plant controls, preliminary wastewater treatment
and end-of-pipe treatment. The general waste control and treatment
scheme depicted in Figure 2 is a generic control technology diagram
of the wastewater treatment methods that serve as the basis for
proposed pretreatment standards of PSES and BAT effluent limitations^)
The listed waste streams present in this system are screenings and
sludges. It is noteworthy that all of the production and waste
treatment methods which are responsible for the waste streams are
not always used by a single facility. Hazardous waste streams are
described below.
1. Chrome (Blue) Trimmings. Blue trimmings are generated
prior to retanning and finishing when chrome tanned hides
are hand trimmed to remove irregular pieces of hide which
could disrupt the process machinery and which are not de-
sired in the final product. Blue trimmings contain ele-
vated concentrations of chromium (2,200 to 21,000 mg/kg -
wet weight)^1) and are approximately 60 percent water by
weight.
-7/5"-
-------
A 1 1 .i 1 1 it.-
I'nli.il r tiii;
!il rt>;im
Evill M«-
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Oxidation
Setetna
Flut C««
CerbonatIon/
SedIreentatIon
I
I U««levnt«r
I Screening* j Uantcwatar
| , SludR«
uiiiiHiiiiiiiiniiiiiiKUiiueiiiiiiiiiiitMiuttiiiiiiiiiiiiiiitiiuitsstHUiiuiiiuiigiiateitiiiiii
TANVAKD
C.liiiimr
Substitution
tlirotne
Recovery/
fluune
Equal I cation
and
Co«|ulatlon-
S*Jl»«ntatSon
I
Wa»tcv»t«
Treatment
(Ch«pp«l)
rut ended
Active tad
With
r»c
Addition
To R«c«lving Uat«r«
Hultt-
K«dl«
nitration
Secondary W«*t«wat«r
Sludge
Iii-V|uiit Control* and Preliminary
Cnd-of-rip«
riCURK 2
SOLID UASTK BOURCK3 GENERATED FKOH
BAT WASTE COHTHOI.S. AMD EHl>-Or-PIPE TRKATMrMT
FOB A Fin.L LINK CltROMK CATTLEII1DE TAHNERY
-------
2. Chrome (Blue) Shavings. Shaving adjusts the thickness of
a split tanned hide or skin to generate a uniform product.
This operation is accomplished mechanically and generates
very small fibrous pieces of tanned hide which contain
elevated concentrations of chromium (4,000 mg/kg - wet
weight)'!'. Chrome shavings also contain approximately
60 percent water by weight.
3. Buffing Dust. Buffing dust is generated by mechanically
sanding the leather to smooth or correct irregularities in
the grain surface. Buffing dust is usually collected in
a dry form utilizing cyclone collectors and baghouses, al-
though some dust may enter the process wastewater stream.
Buffing dust contains significant concentrations of chromium
and lead (as high as 22,000 and 924 mg/kg - wet weight, re-
spectively)^'. Lead originates from lead-based pigments
in the finishing operation and possibly as impurities in process
chemicals. Because of the fine particle size and large
surface area of the dusts, these elements are more sus-
ceptable to leaching.
4. Sewer Screenings. Coarse and fine screens remove hair particles,
wool, fleshings, trimmings (raw, chrome, unfinished) and other
large particulates. The chemical content of this waste
is a function of the screen(s) location at the specific
tannery. Significant levels of chromium and lead (as high
as 14,000 and 110 mg/kg - wet weight, respectively)^1) have
been found in this waste, which ranges from 10 to 50 percent
solids.
-------
5. Wastewater Sludges. Sludges generated from the treatment of
process wastewaters are typically slurries of from 2 to 3
percent solids. In some instances, these sludges are de-
watered to achieve from 12 to 50 percent solids prior to
ultimate disposal. The three principle types of dewatering
equipment are centrifuge, vacuum filter, and pressure filter
such as plate and frame or belt press. Sludge drying beds
are also used where on-site land is available. Heavy metals
and/or sulfides have been found in these sludges.
As described above, wastewater sludges are classified as being
either toxic wastes, reactive wastes, or toxic and reactive wastes. Sludges
generated by tanneries which utilize the chrome tanning process and tanner-
ies which utilize only retan-wet finishing processes have been found
to be toxic (T) because of heavy metal (i.e., chromium and lead) content.
Sludges generated by tanneries which utilize the chrome tanning
process and which also unhair using concentrated depilatory (sulfide
containing) solutions are considered toxic and reactive because they
contain, in addition to toxic chromium and lead, sulfides which, under
acidic conditions, may react to release poisonous hydrogen sulfide
gas. Vegetable tanneries which use depilatory solutions also generate
sludges which are also reactive.
In general, cattlehides are received with the hair attached to
the hide. Prior to tanning, the hair is removed. Hair removal is usual-
ly accomplished by dissolving the material using depilatory (unhairing)
chemicals. Chemicals used are commonly lime and sodium sulfide or
sodium sulfhydrate. Concentrated depilatory chemical solutions dis-
-yf-
-718-
-------
solve the hair within a few hours. The hair may be saved by using
less concentrated chemical solutions followed by mechanical removal.
D. Waste Management
Based on a study completed prior to the adoption of the Re-
source Conservation and Recovery Act of 1976, approximately 25 percent
of the hazardous waste generated by leather tanneries and finishers is
disposed of in the open'1). Waste dumped in the open may or may not
be burned. This type of facility is relatively uncontrolled, uncovered,
and little if any attempt is made to protect the environment. Approxi-
mately 60 percent of the hazardous waste is disposed of in landfills^) >
with about 10 percent of the landfilled material being disposed in sani-
tary landfills^1).
Certified hazardous waste disposal facilities accept only 6
percent of the hazardous waste generated by tanneries.* Seven percent
of the wastes are disposed in lagoons, trenches, pits, and ponds, and
the remaining 2 percent is spread on the land as a soil conditioner or
amendment(^).
At least three POTWs, which receive a large portion of
their wastewaters from tanneries, are known to utilize incineration
or a similar high temperature and pressure oxidation process to
manage alkaline chromium bearing wastewater treatment sludges. It
is known that the processes can either partially or completely oxidize
chromium from the trivalent form to the hexavelent form^3'. Recovery
of hexavalant chromium from these oxidized residues is technically feasible.
*The facilities defined in the report as "certified hazardous waste dis-
posal facilities" do not necessarily meet the §3004 requirements
such that they may or may not be permitted as hazardous waste disposal
facilities without some modification.
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IV. HAZARDS POSED BY THE WASTE
A. Concentrations and Quantities of Hazardous Constituents
in the Waste Streams
Samples of wastes which are listed as hazardous were digested
and analyzed to determine the total content of the two heavy metals
present in each sample^'. The hazardous constituents found to
be present in the waste streams are listed below:
Waste Stream
Chrome (blue)
trimmings
Chrome (blue)
shavings
Buffing dust
Sewer screenings
Wastewater treatment
residues (sludges)
No. of
Samples
10
12
17
27
Hazardous
Constituents
Cr
Cr
Cr
Pb
Cr
Pb
Cr
Pb
Mean
Concentration
(Wet Weight mg/kg)
7,600
4,000
5,700
150
2,200
30
3,700
60
Additionally, the results of analyses of 16 sludge samples
obtained from two tanneries and four POTWs (which have tanneries
as the major flow contributors) are listed below(4):
-vt-
-71O-
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CONCENTRATIONS OF CHROMIUM AND LEAD IN WASTEWATER SLUDGE SAMPLES
MEAN CONCENTRATION (mg/kg - DRY WEIGHT BASIS)
Element T-l T-2 POTW-1 POTW-2 PQTW-3 POTW-4
Chromium 13,800 5,200 2,750 5,650 6,050 9,350
Lead 160 110 70 100 46 51
Estimates of the total quantities of these heavy metals generated
in tannery wastes have been computed and are shown below:
HAZARDOUS CONSTITUENT (METRIC TONS/YEAR) (1)
Year Chromium Lead
1977 851 10.1
1983 1,106 12.5
Tanneries with unhairing operations also generate wastewater
treatment sludges which are reactive due to their sulfide content.
The waste material (sludge) removed from this process wastewater by
treatment contains relatively high concentrations of sulfide and, if
subjected to an acidic environment, may generate highly toxic concen-
trations of hydrogen sulfide gas. Concentrations of sulfide in the
raw wastewater of tanneries belonging to subcategories hair pulp/
chrome tan/retan/wet finish; hair save/chrome tan/retan/wet finish;
hair save/non-chrome tan/retan/wet finish; and through-the-blue had
mean concentration of 64, 20, 68 and 118 mg/1, respectively. Sulfide
concentrations up to 680 mg/1 have been reported for subcategory
through-the-blue(3). This waste thus exhibits the criteria of
reactivity (see §261.33(a)>C1)>(v)).
-------
Samples of wastewater treatment sludges were obtained from
a POTW, with over 90 percent contribution from a tannery with unhair-
ing operations, and analyzed to determine the constituents which can
contribute to the generation of hazardous gases under reactive conditions
in a disposal site. Analytical results are listed below:
Constituent (mg/1) (12)
Sample
Combined sludge
Secondary sludge
Sulfide
730
47
Sulfate
465
995
Sulfite
21
trace
B. Propensity for the Constituents to Migrate from the Wastes
Samples of process wastes and wastewater treatment sludges
were collected by EPA during the period of December, 1979 through
February, 1980 and, using the acetic acid extraction procedure (EP),
the extracts were analyzed for the toxic heavy metals chromium and
lead. Analytical results for sample sets from five plants are listed
below.
Waste
Stream
Chrome Trimmings
Chrome Shavings
Buffing Dust
Screenings
Wastewater Treatment
Sludges
Hazardous Number of
Constituent Samples
Range and Mean of
Concentrations Found
in Extracts (mg/1)
Cr
Pb
Cr
Cr
Pb
Cr
Cr
9
3
5
4
1
2
10
Range
3.6 - 190
0.53 - 1.17 '
2.15-152
2.96 - 28.7
3.7
14.8 - 23.0
1.15 - 1,740
Mean
46.3
0.78
36.8
12.1
18.9
190
-72.J-
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These data indicate that highly elevated concentrations of
chromium, as well as elevated concentrations of lead, can be leached
from these wastes. These constituents are orders of magnitude above
the National Interum Primary Drinking Water Standard, and thus
strongly indicate a potential to migrate in harmful concentrations.
In fact, in most cases, extract levels would fail the toxicity
characteristic and require irrevocable inclusion in the Subtitle
C management system.
The Tanners' Council of America also conducted leaching tests
of various chromium containing solid wastes. These tests which used
distilled water as the leaching solution indicated that 200 to 400
mg of trivalent chromium is released from 1 kg of trimmings and
shavings in periods ranging from 24 to 72 hours(•*•'. Other research
has shown that chromium is ""relatively unaffected by most organic
acids, but is solubilized slowly by acetic acid(->). Acetic acid
is a major product of anaerobic digestion processes within refuse
containing landfills, comprising an estimated 30 to 60 percent of
the total organic acid produced^^^. These two studies suggest
that chromium could be leached out of the waste material in harmful
concentrations following realistically occur ing types of land disposal.
C. Possible Pathways of Exposure of Improperly Managed Waste
As previously mentioned, use of both distilled water and acetic
acid extraction test data indicates that lead and chromium may leach
from these waste in harmful concentrations unless the wastes are properly
managed. As a result, these wastes may leach harmful concentrations of
the metal constituents even under relatively mild environmental
-723-
-------
conditions (i.e., monodisposal) . If these wastes are exposed to
strongly acidic disposal environments, for example disposal environ-
ments subject to acid rainfall, these acid concentrations in leachate
would be higher since these metals are more soluble in acid than in
distilled water. Strongly acidic conditions are also created if
these wastes are co-disposed with other concentrated acid wastes
or slurries resulting from the process.
Incineration or similar high temperature and pressure heat
treatment and destructive oxidation technologies are known to
oxidize chromium from the trivalent form to the hexavalent form'^).
Uncontrolled disposal of these sludges can lead to serious and
prolonged contamination of groundwater and surface water. An
alternate to disposal of these sludges is recovery of the hexavalent
chromium for subsequent^ eduction and reuse in the tanning process.
Recovery and reuse is technically feasible and is under study within
the industry.
The Agency thus believes that these toxic metals 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. Present industry practice of
disposing of these wastes in the open (25%) or in inadequate land-
fills (60%), lagoons, trenches, pits, ponds, or by landspreading is
not environmentally sound. These disposal sites are relatively
uncontrolled and unsupervised.
The Agency is also concerned that the lagooned wastes could
-vf-
-72.4-
-------
contaminate surface waters if not managed to prevent flooding or total
washout.
Another pathway of concern is through airborne exposure to
lead and chromium particles escaping from buffing dust. These particles
could escape when the waste is piled in the open, or placed in insecure
landfills.
As previously mentioned, when forms of sulfur such as
sulfide and sulfate are subjected to an acid environment, they may
generate highly toxic concentrations of hydrogen sulfide gas. Hydrogen
sulfide gas is an irritant to the eyes and lungs in lower concentra-
tions of exposure, and is highly toxic with inhalation in higher
concentrations.
Additionally, should lead and chromium escape from the disposal
site, they will persist in.,, .the environment for virtually indefinite per-
iods, since they are elemental metals.
D. The Large Quantities of these Generated Wastes are a Further
Factor Supporting a T Listing of These Wastes
The Agency has determined to list six of the waste streams
from the leather tanning and finishing industry as a T hazardous waste
on the basis of lead and chromium constituents, although these consti-
tuents are also measurable by the E toxicity characteristic. Moreover,
in some cases, concentrations of these constituents in an EP extract
from waste streams from individual sites might be less than 100 times
interim primary drinking water standards although the Agency's own
extraction data suggests that extract concentrations may exceed the
lOOx benchmark for some generators. Nevertheless, the Agency believes
-yf-
-725"-
-------
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 lead and chromium
in actual waste streams, the non-degradability of these substances,
indications (including damage incidents described below) of lack of
proper management of the wastes in actual practice, and the reactivity
hazard for certain wastes.
The quantity of these wastes generated is an additional
supporting factor= As previously indicated, the leather tanning and
finishing industry waste streams are generated in very substantial
quantities, and contain high concentrations of lead and chromium.
(See pp. 13 and 14 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 and surface wastes. 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 possibility of exposure to the
harmful constituents in the wastes, and in the Agency's view, support
a T listing,
E. Damage Incidents
Contamination of groundwater has been reported at two sites in
Maine as a result of the uncontrolled land disposal of tannery solid wastes.
-yt-
-726-
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At one site, monitoring wells at two separate disposal locations were
found to contain elevated chromium concentrations. A land disposal
site located adjacent to a tannery had been used for several years for
the disposal of beamhouse sludge, trimmings, shavings and spent
tanning agent. Chromium concentrations of 0.25 and 0.084 mg/1 were
reported in a well approximately 700 ft from the disposal area.
Wastewater treatment sludge, also containing chromium, which was
disposed at a municipal landfill, has contaminated a monitoring well
located 200 ft from the disposal site. Concentrations of chromium
as high as 0.83 mg/1 have been reported in this wellW.
At a second open land disposal site in Maine, large quantities
of sludge have been received since 1973 from a primary treatment fa-
cility at a tannery. Testing of adjacent groundwater was done in 1974
after complaints from nearby property owners. Results showed traces
of chromium were present in the groundwater while surface water of
the adjacent property has been contaminated to an unknown extent^).
In the Johnstown-Gloversville area of New York, plumes of
contaminated groundwater have been identified adjacent to each of
two landfill sites receiving wastes from a large number of tanneries
in the area. While chromium has not yet been found in the ground-
water, the sites have been closed due to contamination of city wells
near one site and stream contamination from runoff at the other site(°'.
V. HAZARD ASSOCIATED WITH LEAD, CHROMIUM, AND HYDROGEN SULFIDE
A. Hazards Associated with Lead and Chromium
The lead and chromium that may migrate from the wastes to the
environment as a result of improper disposal practices are heavy metals
-yS-
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that persist in the environment in some form and, therefore, may
contaminate drinking water sources for long periods of time.
Chromium is toxic to man and lower forms of acquatic life. Lead
is poisonous in all forms. It is one of the most hazardous of the
toxic heavy metals because it accumulates in many organisms, and its
deleterious effects are numerous and severe. Lead may enter the human
system through inhalation, ingest ion or skin contact. Improper man-
agement of these wastes may lead to ingestion of contaminated drink-
ing 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 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 ex-
posure 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^°'.
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^).
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-72S-
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B. Hazards Associated with Hydrogen Sulfide Gas
As a result of the presence of sulfide, two wastewater treat-
ment sludges are being listed as reactive. When sulfide and sulfate
are subjected to an acid environment they can react and generate
hydrogen sulfide gas. Thus, present industry disposal practice,
particularly in lagoons and landfills, are insufficient to prevent
such an occurence. For this reason, the hazards associated with
contacting hydrogen sulfide gas are presented below.
Hydrogen sulfide gas is extremely irritating to the eyes and
mucus membranes and highly toxic via inhalation. Low concentration
of hydrogen sulfide, in the range of 20-150 ppm, causes irritation of
the eyes, while slightly higher concentrations may cause irritation
of the upper respiratory tract, and if exposure is prolonged, pulmonary
edema may result. With higher concentration the action of the gas
on the nervous system becomes more prominent. A thirty minute exposure
to 500 ppm results in headaches, dizziness, excitement, staggering,
gait, diarrhea, and dysurta, followed sometimes by bronchitis or
bronchopneumonia. Hydrogen sulphide asphyxiant action is due to
paralysis of respiratory center^
Repeated exposures to low concentrations will result in
conjunctivitis, photophobia, corneal bulge, tearing, pain and
blurring vision. Exposure to high concentrations results in immediate
death(10).
-731-
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REFERENCES
1. Assessment of Industrial Hazardous Waste Practices - Leather
Tanning and Finishing Industry. U.S. EPA, Office of Solid Waste,
SCS Engineers, Inc. EPA Contract Number 68-01-3261, November 1976.
2. Economic Impact Analysis of Proposed Effluent Limitations Guide-
lines, New Source Performance Standards and Pretreatment Standards
for the Leather Tanning and Finishing Industry, U.S. Environmental
Protection Agency, Report No. 440/2-79-019, July 1979.
3. Development Document for (Proposed) Effluent Limitations Guidelines
and Standards for the Leather and Finishing Point Source Category,
U.S. Environmental Protection Agency, Report No. 440/1-79/016,
July 1979.
4. Correspondence from Clarence L. Haile, Program Manager, Survey
and Assessment, Midwest Research Institute, to Donald Anderson,
Project Officer, Effluent Guidelines Division, U.S. Environmental
Protection Agency. EPA Contract No. 68-01-3861, Task 7, MRI
Project No. 4436-L^7), "Analytical Data for Tannery/POTW Samples".
October 10, 1979.
5. Chromium, National Academy of Sciences, Washington, D.C. 1974.
6. Telephone conversation between Arthur Day (Maine, Department of
Environmental Protection) and Peter Maher (Edward C. Jordan Co.,
Inc., Portland, Maine) on January 25, 1980.
7. Unpublished data, open file, U.S. EPA, 1979.
8. Telephone conversation between Bud Golden (New York State Dept. of
Environmental Conservation, Warrensburg, NY) and Donald F. Ander-
son (EPA, Effluent Guidelines Div., Washington, D.C.) on March 5, 1980.
-vf-
-730-
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9. U.S. EPA Regulations Files, January, 1980.
10, Sax, H. Irving. Dangerous Properties of -Industrial Materials.
Van Norstand Reinbold Co., New York, 1979.
11. Background Document 261.24, Extraction Procedure Characteristic.
12. Correspondence from David B. Erty, E. C. Jordan Co., to
Donald F. Anderson, Effluent Guidelines Div., EPA, "Hartland,
Maine POTW Sludge Analysis. Leather Tanning and Finishing
Industry," March 10, 1980.
-73/-
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Comments - Leather Tanning and Finishing Industry
A number of comnienters argued that the background document issued on
January 8, 1979 which was used by EPA to support the four waste
streams listed from the leather tanning and finishing industry was
based on inadequate data (i.e., the only data presented in the
background document was taken from a report prepared by SCS Engineers,
Inc. entitled, "Assessment of Industrial Hazardous Waste Practices:
Leather Tanning and Finishing Industry" to which the Tanner's Council
of America has previously objected).
Since the end of the comment period (March 16, 1979), the Agency has
collected additional data (i.e., extraction data, damage cases, etc.)
which support the listing and clarification of the waste streams
from the leather tanning and finishing industry; therefore, the
background document has been expanded to make a more compelling
case. Comments will be accepted on this additional data.
Several commenters argued that the Interim Primary Drinking Water
Standard for chromium which is used in §250.13(d) of the proposed
regulation to identify "toxic wastes" should distinguish between
trivalent chromium and hexavalent chromium.* These coramenters indicated
that in a study conducted by the Oak Ridge National Laboratory
(Reviews of the Environmental Effects of Pollutants III Chromium),
trivalent chromium was not found to be an environmental hazard.
Additionally, these comnienters indicated that when EPA promulgated
*Chromiuin was but one of fourteen constituents used in §250.13(d)
(extraction procedure) in defining a toxic waste.
-------
the Interim Standard for chromium in 1975, it responded as follows to
comments that suggested that the Interim Standard should be applied
only to hexavalent chromium:
"The limit for chromium is based on the known toxicity of the
hexavalent form. Since this form is the one most likely to be
found in drinking water, and since the specified analytical
detection method (atomic absorption spectrophotometry) does
not distinguish between the valence states, the MCL is for
total chromium. If part of the chromium present is in a lower
valence state, the MCL provides the additional margin for
safety."
These same commenters pointed out that in Appendix II to §3004 of the
proposed rules (43 FR 59019), hexavalent chromium was cited as the
parameter used in the EPA Interim Primary Drinking Water Standards.
Thus, these commenters suggested that the definition of toxic wastes
in §250.l3(d) should apply only to wastes which contain hexavalent
chromium.
The Agency does not disagree with the commenters with respect to the
toxicity and environmental hazards posed by trivalent chromium.
However, the Agency has evidence which indicates that trivalent
chromium will oxidize to hexavalent chromium under certain conditions
(such as destructive oxidation of alkaline sludges noted .in the
background document) which could then pose a serious hazard both to
human health or the environment (see the EP toxicity characteristic
-------
background document for a more detailed discussion). With respect
to Appendix II to the §3004 regulations, the Agency has corrected
this inconsistency in the final regulations.
A number of commenters argued that the chromium found in the waste
sludge was in such an insoluble form that it would not migrate out of
the waste to present an environmental problem. Monitoring data was
provided by several commenters to support their argument.
The Agency disagrees with the commenters contention. The monitoring
data provided in the comment letters already indicates that groundwater
contamination has occured. For example, at the segregated landfill
in Michigan, which one commenter included as an example in his
comments, the concentration of total chromium found in the ground-
water at just 50 feet from the site was 0.10, 0.14, 0.17 and 0.20
mg/1, all above the drinking water standard and indicating groundwater
contamination (the drinking water standard for total chromium is 0.05
mg/1). At further distances from the site the level of chromium was
lower «0.04 mg/1), however, the Agency's concern is that the
chromium will move as a slug (i.e., no dilution) and eventually
contaminate groundwater at greater distances from the landfill.
Additionally, as demonstrated in the background document, two
disposal sites in the Johnstown-Gloversville area in New York, known
to have accepted large quantities of tannery wastes have been closed
due to contamination of city wells near one site and stream contamina-
tion from run-off at the other. Therefore, the Agency believes that
there is sufficient probability that the contaminants in the tannery
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the Interim Standard for chromium in 1975, it responded as follows to
comments that suggested that the Interim Standard should be applied
only to hexavalent chromium:
"The limit for chromium is based on the known toxicity of the
hexavalent form. Since this form is the one most likely to be
found in drinking water, and since the specified analytical
detection method (atomic absorption spectrophotoinetry) does
not distinguish between the valence states, the MCL is for
total chromium. If part of the chromium present is in a lower
valence state, the MCL provides the additional margin for
safety."
These same commenters pointed out that in Appendix II to §3004 of the
proposed rules (43 FR 59019), hexavalent chromium was cited as the
parameter used in the EPA Interim Primary Drinking Water Standards.
Thus, these commenters suggested that the definition of toxic wastes
in §250.l3(d) should apply only to wastes which contain hexavalent
chromium.
The Agency does not disagree with the commenters with respect to the
toxicity and environmental hazards posed by trivalent chromium.
However, the Agency has evidence which indicates that trivalent
chromium will oxidize to hexavalent chromium under certain conditions
(such as destructive oxidation of alkaline sludges noted .in the
background document) which could then pose a serious hazard both to
human health or the environment (see the EP toxicity characteristic
-------
background document for a more detailed discussion). With respect
to Appendix II to the §3004 regulations, the Agency has corrected
this inconsistency in the final regulations.
A number of cominenters argued that the chromium found in the waste
sludge was in such an insoluble form that it would not migrate out of
the waste to present an environmental problem. Monitoring data was
provided by several commenters to support their argument.
The Agency disagrees with the commenters contention. The monitoring
data provided in the comment letters already indicates that groundwater
contamination has occured. For example, at the segregated landfill
in Michigan, which one commenter included as an example in his
comments, the concentration of total chromium found in the ground-
water at just 50 feet from the site was 0.10, 0.14, 0.17 and 0.20
mg/1, all above the drinking water standard and indicating groundwater
contamination (the drinking water standard for total chromium is 0.05
mg/1). At further distances from the site the level of chromium was
lower «0.04 mg/1), however, the Agency's concern is that the
chromium will move as a slug (i.e., no dilution) and eventually
contaminate groundwater at greater distances from the landfill.
Additionally, as demonstrated in the background document, two
disposal sites in the Johnstown-Gloversville area in New York, known
to have accepted large quantities of tannery wastes have been closed
due to contamination of city wells near one site and stream contamina-
tion from run-off at the other. Therefore, the Agency believes that
there is sufficient probability that the contaminants in the tannery
-
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waste, especially chromium, will migrate out and escape into the
environment so as to present a potential hazard to human health or
the environment.
Several commenters objected to the Agency's listing of the four tannery
waste streams for lead. These commenters argued that the background
document magnified the industries use of lead. These commenters
pointed out that tanneries do not use lead compounds in the wet work
processes including the bearnhouse, the tanning department, and the
retan/color/lubrication processes; small quantities of insoluble
pigments containing lead are used in the finishing department of
certain tanners. The commenters went on to say that the use of lead
in the leather tanning and finishing industry has declined in recent
years due to restrictions on the use of these pigments, due to leather
style changes and due to industry volume decline resulting from the
import/export situation in the hide, leather and leather products
industry.
As presented in the Leather Tanning and Finishing Industry Listing
Background Document, lead has been found present in the buffing
dust, sewer screenings, and two listed wastewater treatment sludges
(sludges listed separately because some contain sulfides and are
therefore listed as reactive). The designated subcategories that
produce these waste streams are as follows: hair pulp/chrome tan/
retan/wet finish; hair save/chrome-tan/retan/wet finish; retan/
wet finish; no beamhouse; through-the-blue; and shearlings (only
sewer screenings and wastewater sludges include this subcatagory).
-------
Clearly, the subcategory "hair save/ non-chrome tan/ retan/wet
finish" is not included as one of the processes used by an industry
that produces these lead contaminated wastes. It is noteworthy, in
response to a particular claim made in an industry comment, that
the subcategory "no beamhouse" is properly included because facilities
using this process would generate lead-contaminated wastes.
From the data presenting the concentrations of lead and chromium
in the four wastestreams, the Agency is aware that lead appears in
concentrations considerably less than that of chromiuim. But, a
consideration of the data from the acetic extraction procedure (EP)
performed by the Agency in December 1979 through April 1980, will
reveal the leachability of the inorganic compounds (namely, lead and
chromium) found in the wastestreams. Lead, as well as chromium, was
found to leach from the waste in noteworthy concentrations (i.e., 75
times the NIPDWS for lead). Therefore, harmful concentrations of
these heavy metals may leach from the waste unless these wastes are
properly managed. As a result, if these wastes are exposed to more
acidic disposal environments, for example disposal sites where
other strongly acid industrial wastes are disposed, or environments
subject to acid rainfall, these metals' concentrations in leachate
would be higher, since these metals are more soluble in acid than
distilled water. The quantity of waste lead generated annually,
and the indications of actual waste mismanagement by the industry
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further support listing on this basis. Therefore, lead constitutes
a potential health hazard as a constituent which is present in these
improperly managed wastes, and the Agency believes, should be managed
as such.
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Iron and Steel Industry
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LISTING BACKGROUND DOCUMENT
•
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 am/nonia 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*.
' Industry Profile and Process Description
The stripping of ammonia during the by-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 45,000,000 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 lime
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 §§261.22 and 262.11, generators of
this waste stream are responsible for testing 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.
-7VO-
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Of the waste 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 (5% 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). Based on process wastewater 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-
-X-
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trations to 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 in
on-site unlined sludge ponds.(1) 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.
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Cooling
Jacket
DEPHLEGMAJOR V* Cooling Waler
SECTION 9- ^Cooling Water Return
E*ce«»
Ammonia Liquor
from Storage-
(See Fig. I)
To Ammonia Absorber
I
•sj
a:
IA>
i
Steam-
Fixed Leg-
Steam-
-Free Lag
LIME
MIXER
«l Lime Slurry
Steam
AMMONIA STILL
WASTE LIQUOR SETTLING BASIN
*»Wook Ammonia Liquor to
Further Treatment.
Lime Still Sludge*
Periodically Removed
(or Disposal.
Hazardous Woslo Source
Requiring Controlled Disposal
ENVIRONMENTAL PROTECTION AGENCY
STEEL INDUSTRY STUDY
BY-PRODUCT COKEMAKING OPERATIONS
HAZARDOUS WASTE SOURCE
AMMONIA STILL LIME SLUDGES
FIGUR6
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ppm of arsenic are present in the ammonia still lime sludge.*
A separate study of ammonia still lime sludge indicated
phenol and cyanide concentrations ranging from 670 ppm to
1910 ppm for phenol and 343 ppm to 1940 ppm for cyanide (2).
Leaching tests (distilled water) were also performed on
this waste sample. Results of these test revealed leachate
concentrations of 198 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 trioxide has a solubility of 12,000
mg/1 at 0°C, and arsenic pentoxide 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
1 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.
-X-
-7H4-
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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 sufficient 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,OOOyUg/l
to 40,OOOyU.g/l. The solubility of naphthalene in water and
its presence in such high concentrations in the waste make
it likely that it will leach from the wastes 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)
-T-l S-
-------
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
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 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)
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In 1971 a. newly drilled industrial well 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, January, 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
Cyani.de
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, Mas sacuse t t s , Minnesota, Missouri,
-747-
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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 swollowing,
excessive salivtion, diarrehea), nervous disorders (headache,
fainting, dizziness, mental disturbances), and skin erupt ions . (^ '
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
-7S'8-
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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 Water Act.
Arsenic is extremely toxic in humans and animals.
Death, in humans has occurred following ingestion ,of very
small amounts (5mg/kg) of ttiis chemical. Several epidemiolog-
ical 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 mutagenic 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
-------
disturbances, red blood cell production, and cardiovascular
disease .
OSHA has set a standard air TWA of 500 mg/rn^ for arsenic.
DOT requires a "poision" warning label.
The Office of Toxic Substances under FIFRA has issued a
pre-RPAR for arsenic. The Carcinogen Assessment Group has
evaluated arsenic and has determined that it exhibits sub-
stantial evidence of carcinogenici t y . 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-r egulatory 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 oncogenicity 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, hematuria, fever,
anemia, liver damage, convulsions and coma. Industrial
exposure to naphthalene appears to cause increased incidence
of cataracts. Also, hemolytic anemia with associated
-750-
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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 ingestion,
inhalation, or possibly by skin contact.
OSHA's standard for exposure to vapor for a time-weighted
industrial exposure is 50 mg/m^.
Sax(^) warns that naphthalene is an experimental neo-
plastic sub.stance :Via the subcutaneous route; that is, it
causes formation of, non-metas tasizing abnormal or new growth(s)
Additional information and specific references on the adverse
effects of naphthalene can be found in Appendix A.
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References
1. Draft Development Document for Proposed Effluent
Limitations Guidelines and Standards for the Iron
and Steel Manufacturing Point Source Category; By-
product Cokemaking Subcategory. Volume II, October
1979.
2. Calspan Corporation. Assessment of Industrial Hazardous
Waste Practices in the Metal Smelting and Refining Industry.
Appendices. April 1977. Contract Number 68-01-2604,
Volume III, pages 97-144. App. 12, 37.
3. Merliss, R.R. Phenol Moras., Mus. Jour., Occup. Med.,
14:55. 1972.
4. Sax, N. Irving, Dangerous Properties of Industrial Materials,
Fifth edition, Van Nostrand'Reinhold Co., 1979
-------
LISTING BACKGROUND DOCUMENT
ELECTRIC FURNACE PRODUCTION OF STEEL
Emission control dusts/sludges from the electric
furnace production of steel*(T)
Summary of Basis for Listing
Emission control dusts/sludges from the 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/s ludges contain signifi-
cant concentrations of the toxic heavy 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 §250.13(d)
of the proposed Subtitle C regulations.
*The listing description has been changed in response to a
comment submitted by the American Iron and Steel Institute
that the previous listing was incorrect. The electric
furnace process is used for steelmaking only, not iron and
steelmaking, as was previously listed.
-7SE-
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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 dispos.al 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
-75-4-
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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. As the process proceeds,
the electrodes are consumed at a rate of about 5 to 8 kg/kkg
of steel, with the emission of CO and CC>2 gases. The hot
gases entrain finely divided particulate, 70% of which
(by weight) is below 5 microns in size, the majority of
this being 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 (1).
III. Waste Generation
The particulate produced during the electric furnace
steelmaking process is removed from the furnace off-gases by
means of baghouse fi1ters, electrostatic precipitat ors, 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 basis) per metric ton
of steel produced.
'Based on an electric furnace steelmaking capacity of
27,000,000 metric tons/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 capacity are 321,000 metric tons/yr,
and 16,000 metric tons/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, make 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 heavy metal 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 to 200 ppm (4), is present in this waste sample at a
concentration of 1,400 ppm.*
*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.
-75-4-
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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 1380 ppm and lead to be present at 24,220
ppm. The analysis of the emission control sludge revealed
chromium to be present in the waste at 2,690 ppm and lead at
7,900 ppm (-1).
The presence of such high concentrations of lead and
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 Procedures
(Samples 1-4) and an industry-conducted water extraction
(Sample 5) which show that lead, chromium and cadmium may
leach from electric furnace dusts in significant concentrations
All of the waste extracts--either by the EPA EP which uses
acetic acid as its leaching solution, or by the industry
test which uses - disti lied 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 2
indicates that these wastes may leach harmful concentrations
of lead, cadmium, and chromium even under relatively mild
conditions .
-75-7-
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Table 1
Composition of an Electric Furnace Dust*
Parameter Weight % (not intended to
total 100%)
Fe (total) 35.34
MnO :8.29
Si02 5.61
A1203 0.62
CaO 12.01
Cr203 2.69
CuO 0.12
Ni 0.59
Pb 0.14
Zn 0.39
F 5.09
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 precipitat ors 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
-------
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 like 150 ppm. 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 ppm and 2.0 ppm,, respectively (1).
If these wastes are exposed to more acidic environments
Uandfills or disposal environments subject to acid rainfall)
these metals' concentrations in leachate would likely be
higher, since lead, cadmium, and chromium (and their oxides)
are more soluble in acid than in distilled water (5,6,7).
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 particulate 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
-------
Table 2.
Leach Test Results (mg/1) on Electric Furnace Emission Dui
National Interim
Primary
Drinking Water Sample Sample Sample Sample Sample Sam],
Contaminant 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
Pb 0.05 0.5 0.06 36.7 <0.2 0.3
*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 steelmaking
processes which produced these waste samples.
***Source: Reference 3 water extraction.
-------
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
i ;
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
and 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
-741-
-------
by wind if waste dusts are piled in the open, placed in
insecure landfills or improperly handled during transportation.
As a result, the health of persons who inhale the airborne
particulates would be jeopardized.
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 of proper management safeguards,
the wastes might not reach the designated destination at
all, thus making them available to do harm elsewhere.
The lead, chromium and cadmium that may migrate from
the waste to the environment as a result of such improper
disposal practices are elemental heavy metals that persist
indefinitely 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 electric furnace production of steel
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,
v*
-7L2-
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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 distilled water leachate samples, the
non-degradability of these substances, and the strong possi-
bility of the lack of proper management of the wastes in
actual practices.
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
heavy toxic metals lead, chromium and cadmium. Large amounts
of each of these metals are available for 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 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
-743-
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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. Chromium is toxic to man and lower forms of
aquatic life. Cadmium is also a cumulative poison, essen-
tially 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 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 and a draft technical standard for chromium has
been 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).
EPA 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 rulemaking
-------
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 e lectroplaters
which specifically limit discharges of cadmium to Public
Owned Treatment Works (15).
-------
References
1. Calspan Report, "Assessment of Industrial Hazardous Waste
Practices in the Metal Smelting and Refining Industry,
"Volume III, April 1977.
2. Development Document for Proposed Effluent Limitations
Guidelines and Standards for the Iron and Steel Manufacturing
Point Source Category, Vol. V., EPA 440/1-79/024a, October
1979.
3. Waste Characterization Data form the State of Pennsylvania
Department of Environmental Resources; letter from
P.Y. Masciantonio to T. Orlando, dated September 8, 1975.
4. U.S. Environmental Protection Agency, Quality Criteria for
Water, Washington, D.C., 1976.
5. Handbook of Chemistry and Physics, 52nd Edition. Cleveland,
The Chemical Rubber Company, 1971-72.
6. The Merck Index. 8th Edition. 1968.
7. Pourbaix, Marcel. Atlas of Electrochemical Equlibria in
Aqueous Solutions, London, Pergamon Press, 1966.
8. MITRE Corporation, "An Integrated Five-Year Research Plan
(FY 79-83) for EPA's Atmospheric Acid Deposition Program11.
(Draft)
9. U.S. Department of Interior, Bureau of Mines. Mineral
Commodity Summaries, 1979.
10. U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health. Registry
of Toxic Effects of Chemical Substances. 1977.
11. U.S. EPA States Regulations Files, January 1980.
12 . 44 JJj. 53449
13 . 42 £R 5434
14. 38 FR, 28610
15. Federal Register Vol. 44 No. 175 Friday, September 7, 1979
(40 CFR Part 413).
-------
LISTING BACKGROUND DOCUMENT
Steel Finishing
Spent Pickle Liquor (C) (T)
Sludge from Lime Treatment of Spent Pickle Liquor (T)
I. Summary of Basis for Listing;
Spent pickle liquor and the sludge resulting from ,lime
treatment of, spent pickle liquor are generated,, respectively,
in the pickling of iron and. steel to remove surface scale, and
in the lime neutralization of spent pickling liquors. The
Administrator has determined that both the spent pickle liquor
and the sludge from the lime treatment of spent pickle liquor
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, there-
fore, 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 heavy metals lead and
chromium.
2. The toxic heavy 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.
3. The sludge resulting from the lime treatment of the
spent pickle liquors has been shown to contain
significant concentrations of the heavy toxic metals
lead and chromium.
-76,7-
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These toxic metals have been shown to leach in
significant concentrations from a sample of the
lime treatment sludge subjected to an extraction
procedure. Thus, the possibility of groundwater
contamination via leaching exists if these waste
materials are improperly disposed.
Current waste management practices, which consist
primarily of land disposal either in unlined land-
fills or unlined lagoons, may well be inadequate
to prevent the migration of lead and chromium to
underground drinking sources.
A very large quantity (approximately 1.4
billion gallons of spent pickle liquor or, if all
spent pickle liquor is treated, 5 million metric
tons of lime treatment sludge (at 5% solids)) is
generated annually. There thus is greater likeli-
hood of large-scale contamination of the environment
if these wastes are not managed properly.
7. Damage incidents have been reported that are
attributable to the improper disposal of untreated
spent pickle liquor and the sludges resulting from
the lime treatment of the spent pickle liquors.
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.(^)
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
-------
Table 1
Number of Annual Capacity,
Pickling Agent Plants* tons of steel/yr
HC1 43 30,000,000
H2S°4 149 28,000,000
Mixed acid
(e.g. HF-HN03) 152 6,000,000
Depending on the type of steel being processed, or the type
of surface quality desired, different types of acids may be
used. After a certain concentration of metallic ions build
up in the pickling bath, the solution is considered spent
or exhausted and must be replaced.
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 second waste of concern in
this document •
*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.
-X-
-------
Approximately 40% of the mills utilizing the sulfuric
5
acid pickling process discharge these and other pickling
>
wastes after treatment to a receiving body of water. Another
45% of these mills have the spent pickle liquor hauled off-
site by private contractors, presumably for subsequent treat-
ment. 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)
Lime treatment neutralization of spent pickle liquors,
shown in diagram 1, results in the formation of a mixed metal
hydroxide sludge. On-site lime neutralization by mills
involves the addition of lime, either in the hydroxide or the
carbonate form, to the pickling wastes (spent pickle liquor,
wastewaters, etc.) in a mixing tank followed by sedimentation
or filtration.(1)
The total quantity of wet sludge (5% solids) generated
annually from the treatment of spent pickle liquors has been
estimated at approximately 5 million metric tons per year.*
*Estimates based on waste generation data contained in
Reference 1.
--no-
-------
This quantity includes sludges from combined treatment of all
spent pickle liquors together with other aqueous waste streams
from the pickling operations. This sludge is usually disposed
of in unlined land disposal f acili ties . ( *) Outside contract
disposal services generally neutralize spent pickle liquors
in unlined lagoons. (2)
IV . Hazardous Properties of the Wastes
1. Spent Pickle Liquor
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 would
meet the corrosivity characteristic (§261.22) and is thus
defined as hazardous. In addition, Agency data indicate that
significant levels of the toxic heavy metals lead and chromium,
in a highly mobile form, are found in the spent pickle liquor
(see Table 2 below).
Table 2
Typical Concentratons of Lead and Chromium in
Parameter
PH
Cr
Pb
Spent Pickle Liquors (mg/1)
H^SO^Bath HCL Bath Mixed Acid Bath
1.0-2.0 1.0-4.5 1.3-1.5
26-269 2-37 3300-4250
ND*-2 2-1550 1-4
*ND = Nonde tec table
Source: Reference 1
-*-
-771
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PICKLE
RINSE
WATER
•
3PEMT
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<
tt
ir»i
• -g*
RAW WASTEWATERS
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OPERATIONS
«H » ^ .„_ _
T T
fy .1 .
V RECYCLE FUME HOOD FRESH WATER
•- - . ,, — .. -._- ..u-fs. -fll • ijAt/f-llf?
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*
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SLUDGES RF-QUIRING CONTROLLED DISPOSAL
FILTER CAKE
SOLIDS
ENVIRONMENTAL PROTECTION AGENC'
STEEL INDUSTRY STUDY
HAZARDOUS WASTE SOURCE
PICKLING TREATMENT SYSTEM SLUDGE
t
-------
Based on the higher concentration levels listed in
Table 2 for chromium and lead (4250 and 1550, respectively),
if only .12% of the chromium and .332 of the lead leach
from the spent pickle liquor, this amount would exceed
the permissible concentrations in the EP extract.* Since
the spent pickle liquor is a highly acidic solution, these
toxic heavy metals are readily available to migrate into
the environment, as they are more soluble in acidic environ-
ments. (6) Thus, disposal of this waste in landfills or
lagoons, if improperly managed, is likely to lead to the
migration of harmful constituents into the environment and
pose a substantial hazard via a groundwater exposure pathway.
2. Sludge from Lime Treatment of Spent Pickle Liquor
Calculations based on data collected by EPA at 45
plants(^) - taking into account the difference in pollutant
mass before and after treatment of the spent pickle liquor
- estimate that, on the average, 22,400 ppm of chromium and
11,380 ppm of lead are present in the lime treatment sludge.**
Furthermore, lead and chromium have been shown to leach
from the sludge resulting from lime treatment of spent pickle
liquor in significant concentrations when subjected to an
*The concentrations of lead and chromium in these wastes can vary,
depending upon the composition of the raw materials used to manu-
facture the steel and the particular type of steel pickled.
**The sludge, since it is a more concentrated waste form
(i.e., the ratio of liquid to solids in the sludge is less
than the liquid/solid ratio in the spent pickle liquor) will
have a higher concentration of the contaminants of concern
than the spent pickle liquor. The above calculations are not
contained in reference 1, but are based on data contained in
reference 1.
-773-
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extraction procedure.(5) Results of an analysis of the
)
leachate (pH and test conditions unspecified) from a
< i
neutralized pickling liquor sludge are shown in Table 3
below. These data clearly indicate that lead and chromium
may leach from the waste in harmful concentrations unless
properly managed since they are many times greater than
the National Interim Primary Drinking Water Standards for
these substances.
Table 3
Analysis of Leachate from a Neutralized
Spent Pickle Liquor Sludge
Metal Leachate Concentration (ppm)
Cr 429.0
Pb 8.2
Source: Reference 5
3. Possible Types of Improper Management and Available
Pathways of Exposure
As shown above, disposal of spent pickling liquors and
the sludge resulting from lime treatment of spent pickling
liquors on land creates the potential for leaching of the
-------
toxic heavy metals chromium and lead to groundwater, a
common source of drinking water. In addition, improper
storage and/or disposal of spent pickling liquor poses
potential 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 heavy metals) from other wastes
disposed in the landfill. If not stored in special
containers, pickle liquo.rs 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
liquors generated to off-site disposal facilities before
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 trans-
portation may result in their not reaching their
designated destination at all, thus making them available
to do harm elsewhere.
Solubility of lead and chromium present in lime
treatment sludges is pH dependent (e.g. solubility
increases as pH deer eases).(6) Thus, co-disposal of the
-775--
-------
sludges with waste acids, for instance, is likely to
)
result in increased solubilization of these heavy metals.
. ,i
Disposal in a surface impoundment or landfill with an
acidic environment will certainly enhance the solubility
of lead and chromium hydroxide. The result of the
leachate test shown in Table 3'*) strongly suggests
that lead and chromium may be released from lime treated
sludges as well.
Once released from the matrix of, the waste, lead and
chromium can migrate from the disposal site to ground and
surface waters used as or constituting potential drinking
water sources. Present practices associated with land-
filling 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 over-flow 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
-774-
-------
control practices. Available information, in fact,
indicates that liners are not presently used in the
landfilling or lagooning of these wastes.^1) 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 con-
taminants from being carried fron the disposal .site to
nearby surface waters.
An additional regulatory concern is the huge quantities
of these wastes generated annually. Spent pickle liquor
and the sludge resulting from line treatment of the spent
pickle liquor are generated in very large quantities. The
large quantities of these wastes and the contaminants they
contain pose a serious 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 capa-
city 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 envirnoment as a result of such improper disposal
-vi-
-777-
-------
practices are heavy metals that persist in the environment in
some form and, therefore, may contaminate drinking water sources
for long periods of time. Chromium is toxic to man and lower
forms of acquatic life. Lead is poisonous in all forms. It is
one of the most hazardous of the toxic heavy 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 infromation on the adverse health effects of chromium
and lead can be fround in Apprendix 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. '^) 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)
-778-
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VI. Damage Incidents*
These damage incidents are 'attributable to the improper
disposal of spent pickle liquor and sludges from the lime
treatment of spent pickle liquors. They are just a few
examples of the damage which may result if these wastes are
mismanaged.
In '1970, neutralized spent pickling liquors dumped
in an abandoned strip mine by a waste disposal
firm leached into the surrounding soil and,
eventually, into streams in Monroe County, Ohio.
Fish were killed as a result in nearby Wilson's Pond.
In 1971, Wilson's Pond overflowed into Little Beaver
Creek, causing a major kill of some 77,000 fish.
The disposal firm was ordered to construct facilities
to contain and treat wastes which were being discharged
into a nearby stream. Extensive pollution of
groundwater persists, however, and there is a threat to
t
the water supply of several homes and a school.
In Washington County, Pennsylvania, leachate from a
landfill has entered the groundwater and has contaminated
*°raft Environmental Impact Statement for Subtitle C,
Resource Conservation and Recovery Act of 1976, Appendices
-yf-
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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.
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
are to be lined.
-7SO-
-------
References
1. Draft Development Document for the Proposed Effluent
Limitations Guidelines and Standards for the Iron
And Steel Manufacturing Point Source Category; Sulfuric
Acid Pickling Subcategory, Hydrochloric Acid Pickling
Subcategory. Volute VIII, November, 1979.
2. Calspan Corporation, Assesment of Industrial Hazardous
Waste Practices in the Metal Smelting and Refining
Industry. Appendices. April, 1977. Contract
Number 68-01-3604, Volume III, pages 6-69.
App. 12, 37.
3. Waste Characterization Data, from the State of Illinois
EPA, as selected from State files by US EPA/OSW on
3/14/79 and 3/15/79.
4. Waste Characterization from the State of Pennsylvania
Department of Environmental Resources, Division of
Solid Waste Management, March 20, 1978, as selected
from State files by US EPA/OSW, on 1/4/79 and
1/5/79.
-731-
-------
5. Waste Characterization Data from the State of Illinois
EPA, as selected from State files by US EPA/PSW on
3/14/79 and 3/15/79.
6. Pourbaix, Marcel. Atlas of Electrochemical Equilibria
in Aqueous Solutions, London, Pergamon Press, 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. U.S. Department of Health, Education and Welfare,
National Institute for Occupational Safety and
Health. Registry of Toxic Effect of Chemical
Substances. 1977.
10. U.S. EPA States Regulations Files, January, 1980.
11. MITRE Corporation, "An Integrated Five-Year Research
Plan (FY 79-80) for EPA's Atmospheric Acid Deposition
Program". (Draft)
-------
Non-Ferrous Smelting and Refining Industry
-7S3-
-------
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 pl.ant blowdown slurry at
facilities where primary copper is smelted in a reverberatory
furnace. The Administrator has determined that these
sludges are solid wastes wh ich 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
be leached from these sludges by even a mild (distilled
water) leaching media. Therefore, even under the mild
conditions, the possibility of groundwater contami-
*For concentrations of other listed toxic heavy metals that
do 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.
Discus sion
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
-------
oxide/si1icate slag that can be separated from the copper.
The product resulting from the reverberatory 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
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CWTtftJUlflDl
DUST TO
RWEft.
VALUIS
IW klLOCRAWMITWCTXSH
COffCRfflOOUCTl
LISTED WASTE
(SLUDGE)
Figure 1 PR.MARV COPPER SMELTING AND
Source: Reference 1
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reverberatory furnace.* The overflow from the thickener -
about 2,200 cubic meters per day, containing 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-
,'j
goon effluent which is discharged to the main tailings p.ond.
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.
-y-
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Table 1
GEOGRAPHICAL DISTRIBUTION AND CAPACITIES OF
PRIMARY COPPER SMELTERS
Company
Location
Smelting
Capacity (MT*/yr)
Anac6nda
ASARCO
Cities Service
Copper Range
Hecla Mining
Inspiration
Kennecot t
Magma
Phelps Dodge
Anaconda, MT
Hayden, AZ
El Paso, TX
Tacoma, 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.
-781-
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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 26% to '3 60 , 360 me trie
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 heavy metals. The concentrations
found are summarized in Table 3.
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
-790-
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TABLE 2
ESTIMATED TOTAL WASTE SLUDGES FROM PRIMARY COPPER SMELTERS
- — • IN 1977*
S_tate
Tennessee
Michigan
Texas
New Mexico
Montana
Utah
Arizona
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
1
7
6
11
13
15
64
2
6
Disposed
,000
,900
,700
,200
,000
,000
,600
,700
,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
-------
TABLE 3
CONCENTRATIONS OF HEAVY METALS IN WASTE
SLUDGES FROM PRIMARY COPPER SMELTERS (PPM)
Metal Sludges
Cadmium 520
Lead 8000
Source: Reference 1
-------
appears in concentrations 150 times the National
Primary Interim 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 heavy 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 solubilizat ion can occur more
readily due to the fine particulate composition of the
sludges suggests that the heavy 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, toxic
heavy 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 be inadequate to prevent such an occurence.
For instance, selection of disposal sites in areas with
permeable soils can permit contaminant-bearing leachate
-------
Table 4
CONCENTRATIONS OF HEAVY METALS IN FILTERED DISTILLED
WATER LEACHATE, PPM
Sludges
Cadmium 8.4
Lead 7.8
Source: Reference 1
-v-
-------
from the waste to migrate to groundwater. This is
especially significant with respect to ponded wastes
because a large quantity of liquid is available
to percolate through the solids and soil beneath
the fill.
i
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 may 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/tailing 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. The 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 a 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 Agency1s 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.
-7
-------
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 6 are summarized below; more detail
on the adverse effects of lead, and cadmium can be
i
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 it's 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, 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 LD50 (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 §307 of the Clean Water Act of 1977. Under
-717-
-------
§& 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 been announced by EPA pursuant to the Clean Air Act
(8). In addition, final or proposed regulation of the State
of California, Maine, Maryland, Massachusetts, Minnesota,
Missouri, New Mexico, Oklahoma and Oregon define cadmium or
lead containing compounds as hazardous wastes or components
thereof (9).
-y-
-------
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
warrent 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 0 . 8
Selenium 30
Source: Reference 1.
-71°!-
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REFERENCES
1. Calspan Corporation, "Assessment of Industrial Hazardous
Waste Practices in the Metal Smelting and Refining
Industry," Volume 2. Calspan Report Number ND-5520-M-1,
April, 1977.
2. U.S. Department of the Interior, Bureau of Mines, "Copper
Mineral Commodity Profiles" September, 1979.
3. P. D. Dougall, "Copper" in M. Grayson and D. Eckoth, eds.
Kirk-Othmer Encyclopedia of Chemical Technology. 3rd. ed.
Volume 6, John Wiley and Sons, New York, 1979.
4. Pourbaix, Marcel. Atlas of Electrochemical Equilibria in
Aqueous Solutions, London, Pergamon Press, 1966.
5. The Merck Index. 8th Edition. 1978.
6. Cleland & Kingsbury. "Multimedia Environmental Goals
Volume 2." EPA Report Number 600/7-77-136B, November,
1977.
7. U.S. Department of Interior, Bureau of Mines, Mineral
Commodity Summaries, 1979.
8. U.S. Department of Health, Education and Welfare, National
Institute for Occupational Safety and Health. Registry of
Toxic Effects of Chemical Substances. 1977.
9. U.S. EPA States Regulations Files, January, 1980.
-------
LISTING BACKGROUND DOCUMENT
PRIMARY LEAD SMELTING
Surface impoundment solids contained in and dredged from surface
impoundments 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 concentra-
tions of the toxic heavy metals, lead and
cadmium.
-------
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 to 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
(more than 49,100 tons in 1978) and that the
typical waste management practices may be
inadequate to prevent substantial environ-
mental 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 - 2,340,000
tons in the year 2000.
-t-
--SO2.-
-------
All domestic smelters and refineries produce lead
by pyrometallurgical 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, pyrite, 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
-------
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WASTE
ATHOSPHCR1C EMISSION
SOLID WASTE
I
Figure i, v Flow chart depicts primary lead smelting
and refining,( umbers correspond to process numbers in text
and also~correspond to step process"in tliis document. The first three
steps produce the hazardous 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
containing 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
dressing (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
-------
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.
Slag granulation water is often transported to surface impound-
ments for settling.
The blast furnace bullion undergoes "dressing" (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 debismuthing 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
-------
smelting plants are settled solids from surface impoundments.
The impoundments are used to collect solids from miscellaneous
slurries, such as acid plant blowdown, slag 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 condstituents 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 ar,e d.redged 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
to the process.
-•309-
-------
plant A
Flow = 1,300,000 gpd (gallons per day)
Metal
Cd
Pb
Inrluent
Concentration
0.89 ppm
17 ppm
Effluent
Concentration
0.044 ppm
0.925 ppm
Difference i
0 . 84 6 ppm
16.075 ppm
Lbs/day in
solids
9.172
174.3
Plant B
Flow = 280,000 gpd
Influent Effluent Ibs/day in|
Metal Concentration Concentration Difference solids |
Cd
Pb
i 111
15 ppm | 0.43 ppm I 14.57 ppm | 34 j
1 III
i iii
50 ppm | 0.39 ppm I 49.61 ppm |115.85 1
! Ill
1 1 1 i
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 accumulates at a rate of almost 64,000
Ibs/ yr,f 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
-SOI-
-------
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 heavy 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 Pb
I 700 | 115,000
Plant I I
I 640 | 140,000
Plant II I
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 heavy 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 heavy metals. This waste leached
- "8/0-
-------
11 ppm of 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 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 monodisposal 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 hazardous constituents to be 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 solubilizing 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.
-X-
-•311-
-------
Thus, improper disposal of surface impoundment solids
may result in contamination of ground and surface waters by
lead and cadmium. 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
V
to settle in unlined and unsealed impoundments in areas
with permeable soils, the solubilized 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 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-
-•311-
-------
the passage of time, but will provide a potential source of
longterm 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 heavy 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
is carcinogenic to laboratory animals, and relatively toxic
-------
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 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.
-•3H-
-------
References
1. USEPA, IERL/ORD and Office of Solid Waste. Assessment
of Solid Waste Management Problems and Practices in
Nonferrouse Smelters. Prepared by PEDCo Environmental
Inc., Contract No. 68-03-2577. November 1979.
2. USEPA, Office of Solid Waste. Assessmet of Hazardous
Waste Practices in the Metal Smelting and Refining
Industry. Prepared by Calspan Corporation. Contract
No. 68-01-2604. April, 1977.
3. USEPA, Office of Water Planning and Standards, Effluent
Guidelines Division., Draft Development Document for
Effulent-Limitations Guidelines and Standards for the
Nonferrous'Metals Manufacturing Point Source Category.
September, 1979.
-------
Response to Comments
1. One commenter 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
reclaimed.
-------
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. o:n 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 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 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 Parts 264 and 265
(as well as 122) or special tailored requirements under
Part 266.
At this time, applicable requirement 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 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.
-------
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)
Cadmium plant leach residue (iron oxide) (T)
Summary of Basis for Listing
The primary zinc industry is comprised of 7,plants that
employ one of two major zinc manufacturing processes--electro-
lytic or pyrometallurgical processing. The five electrolytic
and two pyrometallurgical plants recover zinc metal from ore
concentrates. Cadmium 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 subject to appropriate management
requirements under Subtitle C of RCRA. This conclusion is
based on the following considerations:
1) The wastes contain significant concentrations of the
toxic heavy metals cadmium and lead.
2) Cadmium and lead have been shown to leach from
samples of these wastes in significant concentrations
-------
when the samples were subjected to a distilled water
extraction procedure.
3) Electrolytic anode slimes/sludges and cadmium plant
leach residue are generated at a rate of 2,600 tons/year,
and 200/tons year, respectively. Sludge from the treat-
ment of process wastewater and/or acid plant blowdown is
generated at a rate greater than 11,000 tons/year. Such
large quantities of wastes containing high concentrations
of hazardous constituents increases probability of damage
to human health and the environment under improper dis-
posal conditions.
4) These wastes are currently stockpiled on site and/or
hauled off-site to landfills, in a manner that could
allow the cadmium and lead in the wastes; to leach to
groundwater.
Industry Profile and Manufacturing Process
Five plants produce zinc by the electrolytic process, and
two plants produce zinc by pyrometallurgical techniques (3).
Locations of the plants, capacities and products are given
in Table 1.
Electrolytic plants (not including the one new plant in
Tennessee) account for approximately 9 percent of the total
solid waste generated although they represent about 49
percent of the industry's production of slab zinc. The two
pyrometallurgical plants account for 91 percent of the solid
waste, although they represent only 51 percent of the produc-
tion of zinc (3).
Electrolytic Process
At four of the electrolytic zinc plants, actual production
rates range from 41,800 tons to 82,100 tons of slab zinc per
year. These four plants account for approximately 268,300
tons of the total annual primary zinc production, or about
49 percent of the industry total. The fifth plant has come
-------
LOCATIONS, CAPACITIES AND PRODUCTS OF PRIMARY
ZINC SMELTERS AND REFINERS (3)
Company and Location
Pr oces s
De script Ion
Capaci ty
(tons/year)
Produc t
Araax, Inc.
East St. Louis, 111
Electrolytic
82,000
Slab zinc, cadmium, zinc sulfate,
and sulfuric acid
Asarco, Inc .
Corpus Christ!, Tex
The Bunker Hill Co.
Silver King, Idaho
National Zinc Co.
Bartlesville, Okla
Electrolytic
Electrolytic
ElectrolytIc
108,000
108,000
55,000
Slab zinc, zinc alloys, zinc sul-
fate, cadmium, and sulfuric aci
Slab zinc, zinc alloys, cadmium,
and sulfuric acid
c
0
Zinc dust, zinc slab, zinc alloys,
cadmium, cobalt cake, copper/
lead/nickel cake, and lead silve
res Idue
New Jersey Zinc Co
Palmer ton, Pa.
St. Joe Minerals Corp
Monica, Pa.
Pyrometallurgical
Pyrometallurgical
113,500
250,200
Slab zinc, zinc alloys, zinc dust
and pellets, zinc oxide, ferro-
alloy, and sulfuric acid
Slab zinc, zinc alloys, zinc oxide
cadmium, ferrosi1icon, mercury,
and sulfuric acid
Jersey Miniere Co.
Clarksville, Tenn.
Electrolyt ic
90,000
Slab zinc, cadmium, sulfuric acid
-------
on-line recently, and production figures are not yet avail-
able (3). Electrolytic processing basically involves dissolv-
ing the zinc in a sulfate solution followed by electrolytic
deposition of zinc (3). Process flow (see Figure 1) at the
plants is very similar, with some variation^).
The sources of solid waste generated by the electrolytic
process are: (1) treatment of preleach residue (this
operation occurs at only one plant), (2) the collection and
treatment of acid plant blowdown and miscellaneous slurries,
(3) the cleaning of the electrolysis cells (anode slimes/
sludges), and (4) the filtration of the leach solution.
The preleach process is used by one electrolytic plant
with an annual production of 62,300 tons. Preleaching removes
excess magnesium from the incoming zinc concentrates. Magnesium
is not electrolyzed but accumulates in the system; therefore
the zinc concentrates having high magnesium levels must be
preleached before further processing. The preleach step
involves the reaction of sulfuric acid and a bleed stream
from the acid plant (i.e., acid plant blowdown—a weak acid
stream) with a portion (up to 100%) of the incoming concentrates
to solubilize the magnesium. The insoluble concentrate containing
zinc is separated and continues through the process. The solu-
bilized material containing magnesium and the acidic preleach
solution enter a lined surface impoundment, from which it is
pumped to a wastewater treatment plant (WWTP). The sludge that
settles in the impoundment is periodically removed and placed in
the WWTP. This sludge, together with the sludge produced from
-------
cess
sster
PRELEACH
PLANT
UNDERFLOW
SOLIDS TO
COPPER OR
. LEAD
REFINERY
SOLIDS TO
CADMIUM
PLANT
STORAGE
WATER
GAS
ROASTER
i
DUST
COi_L£CTlON
CLASSIFIER
&
BALL MILL
CALCINE
DUST
I
ACtO
PLAffT
H -SO4
Acid Plant
Blowdown
LEACHING
zmc SOLUTION FROM
CADMIUM PLANT
THICKENERS
&
FILTERS
'Process
Wastewater
ZINC
SOLUTION
PURIFICATION
ELECTROLYSIS
ZINC OXIDE
CATHODE
MELTING
FURNACE
WATER
ZINC DUST
SPEKT CELL ACID
Anode Slimes/Sludges
CASTING
SLAB ,r
BLOCKS
COOUNG TOWER
SLOWDOWN
OTHER
SHAPES
FICBRE j. ELECTROtTTIC ZUC flSBBCTIBU PIOCESS
-------
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 (^).
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 salable
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 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. Therefore, at this time, applicable require-
ments 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 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
passed through earlier process steps but is not plated
out, or electrolyzed, in the electrolysis step. It is
estimated that anode slimes/sludges make up 2,600 tons of
the 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 metal (3).
These plants account for approximately 51 percent of the total
production of zinc metal by the primary zinc industry, but 91
percent of the total soldi 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
generated and in the ultimate disposal or control of the waste (3)
Pyrometallurgical processing entails the following steps:
sintering, retorting, refining and casting. Sintering develops
the desired characteristics for pyr©metallurgical smelting of the
calcine by processing the calcine in a sinter machine where the
*A11 electrolytic plants also generate a leach residue
from filtration of the leach slurry, which is not currently
listed as hazardous and will not be further discussed in this
background document.
-SIS'-
-------
ZINC CONCENTRATES
WATER
1
SLUDGE < COLLECTION *
WASTEWATER
TO TREATMENT
r
CONCENTRATE
DRYING
\
ROA!
CALC
COKE "*>
SINTE
RESIDUE
1
COKE-r *•
RESIDUE ,^ ,
TREATMENT <
i *
• FERROSILICON
ZINC-POOR WATER •*•
RESIDUE TO
LEAD REFINERY
REDU
FURN
i
WATER GAS
! t
» DUST A
>'tH ^ COLLECTION p|
:iNE CADMIUM
r PLANT
niwtj • — ,'P- COLLECTION ^°^
CADMIUM PLANT j j
r 1 i
CTJON >^ZINC OXIDE
r
CASTING 1 COOLING TOWER
CASTING | ^ SLOWDOWN
SLAB
BLO
'
CKS
l '
OTHER
SHAPES
kCID te.H50,
JVNT
^ Acid Pla
Elcwdown
IS
^ By-product
^^ C^T-fJ TT«^.4-A
Solid '/aste
FIGURE 2. PYROMETALLTJRGICAL
ZINC PRODUCTION PROCESS
-------
calcine burns autothermally and is fused into hard, permeable
sinter. Retorting consists of reducing the calcine in the
sinter with .carbon in a retort to produce zinc metal. Pre-
heated feed of sinter and coal or coke is fed into the top of
the retort; the temperature reaches 1300°C-1400°C inside.
Because of the zinc's low boiling point (906°C), it is vola-
tilized as soon as it is formed. In this way the zinc is
purified by separating it from the gangue material in the
calcine.• Zinc from the retort smelting may need further
purification for some commercial uses. The zinc Is purified
by distillation in a graphic retort. Molten zinc from the
graphic retort is either case pure into bars or blocks or is
alloyed with other metals and case.
The sources of solid waste generated by the pyr©metallurgical
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 pyrometallurgical 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 salable sulfuric acid and
a bleed stream (acid plant blowdown) that must be neutralized.
One plant neutralizes the blowdown with lime, which leads to
the generation of an estimated 10,000 tons per year of settled
*Two other wastes generated by this process (i.e., residue
the production of zinc oxide in Waelz Kins (one plant
only) and furnace residue from the operation of retort and
oxidizing furnaces) are not currently listed as hazardous and
will not be further discussed in this background document.
-------
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 pyrometallurgical 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 pyrometallurgical 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,
1 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 "siimes/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 aci-d 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.
-330-
-------
Three of Che 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. (3)*
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
«r
impoundment 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 is also
assumed to generate a solid waste (such as goethite residue)
that is stockpiled on-site.
Control Practices at Pyrometallurgical Plants
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
Qot be sufficient to adequately monitor leaching from the
surface impoundment.
-------
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 c'admium 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.^) Neither do
the plants currently use barriers to prevent seepage from
solid waste stockpiles, or wells to monitor or collect any
seepage or leachate(S).
Hazardous Properties of the Wastes
The Administrator has classified the process wastewater
and/or acid plant blowdown treatment sludge, electrolytic
anode slimes/ sludges, and the cadmium plant leach residue
(iron oxide) as hazardous because of the high levels of
toxic cadmium and lead found in the 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 tests on the wastes using distilled
water as the extraction medium (1). The results are as
follows :
Sludge from acid
plant blowdown
(Electrolytic
Plant)
Waste Analysis (ppm) Extract Analysis (ppm)
Cd
550
Pb
98
1750
18,100
Cd
2.1
1.0
Sludge from acid
plant blowdown
(Pyrometallur-
gical Plant)
Anode slimes/
sludges
Cadmium Plant
Residue
2000
640
4350
4280
<0.01 -
1.3
12
1400
280
170,000
89,000
215,000
12
2.0
<0.01
9.0
Calculations of sludge contents from 1ime-and-settie
wastewater treatment also indicate that significant amounts
and concentrations of lead and cadmium are present in these
wastes (2)
Plant
//I
#2
Contaminants
Cadmium
Lead
Cadmium
Lead
Percent in Sludge
4.0%
2.5%
2.6%
1.7%
Cadmium and lead are always 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 th'at
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 heavy 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
_J 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 to 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.
-------
significant concentrations of toxic heavy metals that have
been shown to migrate from the waste. Surface water can
become contaminated with contaminants from these wastes via
runoff from rainfall. Similar hazards exist if these waste
are disposed of in improperly managed landfills or surface
impoundments; leaching, run-off, or overflow may result in
contamination of surface and groundwaters.
The cadmium and lead that may migrate from the waste to
the environment as a result of improper,disposal practices
are heavy 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 metals because it accumu-
lates in many organisms and the deleterious effects are
numerous and severe. Lead may enter the human system through
inhalation, ingestion or skin contact. Ingestion of contami-
nated drinking water is a possible means 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 I ead-cont'aining
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 limit discharges of cadmium to Public Owned
Treatment Works (12).
-------
References
1. U.S. EPA, Office of Solid Waste. Assessment of Hazardous
Waste Practices in the Metal Smelting and Refining
Industry.. Calspan Corporation, EPA Contract Number
68-01-2604, April 1977, Volumes II and IV.
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.
PEDCo Environmental Inc. Washington, D.C. November,
1979.,
4. Pourbaix, Marcel. Atlas of Electrochemical Equilibria in
Aqueous Solutions, London, Pergamon Press, 1966.
5. Wladbott, G.L. Health Effects of Environmental Pollutants.
St. Louis, C.V. Mosby Company, 1973.
6. Gleason, M., R.E. Gosselin, H.C. Hodge, B.P. Smith. Clinical
Toxicology of Commercial Products. Baltimore, The
Willaims and Wiltkins Co., 1969. 3rd Edition.
7. U.S. Department of Interior, Bureau of Mines. Mineral
Commodity Summaries, 1979.
8. U.S. EPA State Regulations File, January 1980.
9. 44 .FR 53449.
10. 44 _FR 5434.
11. 38 £R 28610.
12. 40 CFR, Part 413.
-------
Response to Comments to Proposed Regulations
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 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 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 with
in to the environment would still prevail and avoiding its regu'
lation, would ,be unjustified.
The key 'question, therefore, is not wnether, 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 in 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 in 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.
-------
Emi
LISTING BACKGROUND DOCUMENT
SECONDARY LEAD SMELTING
ssion 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,
cadmlunij 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 heavy metals lead,
cadmium and chromium.
2) Waste leaching solutions from acid leaching of the
emission control dusts/sludges likewise contain
significant concentrations of lead, cadmium, and
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 concent rat ions
of lead, cadmium, and chromium fr.om 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 chromium to under-
ground 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 (7,151,600 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
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
1978 and the estimate for 1979 is 760,000 metric tons (4).
-------
Table 1 (1)
Distribution of Secondary Lead Smelters by State
State No. of Plants
Alabama 2
California 8
Colorado 2
Delaware 1
Florida 3
Georgia 3
Illinois 7
Indiana 4
Kentucky 1
Louisiana 2
Maryland 1
Massachusettes 2
Michigan 4
Minnesota 1
Mississippi 1
Missouri 2
Nebraska 2
New Jersey 3
New York 4
North Carolina 2
Ohio 6
Pennsylvania 7
Texas 9
Tennessee 2
Virginia 1
Washington 1
Wisconsin 1
-------
Four products are manufactured in the secondary lead
industry: refined lead, lead oxide, antimonal 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. 10 below confirming the presence
of these heavy metals in the waste stream in significant
concentrations.)
-•3HH-
-------
WASTE BATTERIES
I
00
LEAD RESIDUES
WASTE
SOLIDS
DAGHOUSE
EMISSIONS
H,O
BATTERY
CRACKING
H,O
SCRUBBER
\
LIQUOR TO RECYCLE
"^Sludge
to
Lagoon
REVERBERATORY
FURNACK
SLAQ
i
REMELT
KKTTLB
REFINED LEAD
SOFT LEAD
\
BARTON
OXIDATION
LEAD OXIDE
,O -f ELECTROLYTE
TO TREATMENT.
CASINOS TO DISPOSAL
SCRAP IRON
Li
BLAST
FURNACE
EMISSIONS
ANTIMONIAL
LEAD
At.Cu
ANTIMONIAL LEAD
BAQHOUSE
B^MMMBW^^fr
WASTE
SOLIDS
LIQUOR TO RECYCLE
t
Slud)
** to
Lagoon
SCRUBBER
M,O
EMISSIONS
i
RCMELT
KCTTLK
LEAD ALLOY
FIGURE i
SECONDARY LEAD/ANTIMONY SREltlMC PROCESS
-------
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.
2. 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.
With 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 lagoons (3). EPA presently lacks information
on other waste leaching solution generating locations and
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 1967 and 1977 as well as minimum and maximum generation
projections predictions for 1980, 1984, and 1987. The total
dust/sludge generation for 1977 (dry weight basis) was
127,158,700 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.**
These quantities can be expected to incr ease — part icular ly
dust generation. First, New Source Performance Standards
*At this time, 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 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 major percentage of dusts generated
may be recycled. In light of the large quantities of dust
generated, the Agency believes large amounts of these
dusts are managed as wastes, and not recycled.
-------
SECONDARY LEAD INDUSTRY - (dry weight basis) (5)
I
I
I
Illinois |3-04
Kansas |3-04
Pennsylvania|3-04
"T
State
I SCC Code
I
Process
Total Sludge/Dust Generation
(10^ metric tons/year)
Historic
1967
1977
Minimum Scenario
Maximum Scenario
I
1980 | 1984
1
1987 I 1980
1984
1987
Wet Controls
Alabama
Arizona
California
Indiana
Lousisiana
Minnesota
Mississippi
Missouri
Nebraska
N. Jersey
Ohio
Tennessee
Texas
Virginia
Washington
J3-04
13-04
13-04
J3-04
13-04
13-04
13-04
I 3-04
j 3-04
J3-04
J3-04
|3-04
3-04
3-04
3-04
4964.2
-004-02|Reverberatory furnacel 4505
-004-02JReverberatory furnacel 27
-004-02|Reverberatory furnacel 431
I
| Total sludge from
I wet controls
I
|Dry Controls
I
-004-02jReverberatory furnacel
-004-02|Reverberatory furnacel
-004-02JReverberatory furnacel
-004-02 IReverberatory furnacej 1849
-004-02jReverberatory furnacel 2481
-004-02JReverberatory furnacel 1327
-004-03jReverberatory furnacel 541
-004-03|Reverberatory furnacel 2173
-004-02|Reverberatory furnacel 7380
-004-02JReverberatory furnacel 1856
-004-02|Reverberatory furnacel 550
-004-02|Reverberatory furnacel 5403
-004-021Reverberatory furnacel62043
-004-02|Reverberatory furnacel 1187
.5
.5
.2
6490.8
39.6
621.2
6924
42
662
~T
I
I
.31
.21
• 7|
7718.4
47.0
738.7
8314.
50.
795.
T
I
I
0|
61
7|
7755.2
47.3
742.2
8644.6
52.6
827.3
9311.7
56.7
891.2
7151.6
660
8
360
.0
.3
.5
.6
.2
• 3|
.61
.51
.81
• 2|
.0|
.0|
.21
.91
•004-02jReverberatory furnace
I
| Total dust from
| dry controls
340.7|
T
I
7629.21 8504.1
I
I
I
950.8j 1014.31 1130.6
11.9| 12.7J 14.2
519.3J 554.0J 617.5
2664.6| 2842.61 3168.6
3574.5j 3813.21 4250.51
1912.1| 2039.81 2273.71
780.2| 832.31 927.8|
3131.2| 3340.3| 3723.4|
10633.1| 11343.31 12644.2J
2674.1| 2852.71 3179.9J
792.3J 845.2J 942". l|
778.4J 830.4J 925.61
89382.4J 95352.4|106288.1|
1711.4J 1825.7J 2035.1J
490.81 523.61 583.7|
1
9160.31 8544.7
1
1
9524.5
10259.6
1217
15
665
3413
4578
2449
999
4010
13619
3425
1014
997
114489
2192
628
1
1
8J
3|
1|
ij
51
2J
41
.71
.9J
.31
.81
.0J
1136.0
14.2
620.5
3183.7
4270.8
2284.6
932.2
3741.1
12704.5
3195.0
946.6
930.0
9106794. 7
T
88163.81120007.11128022
I I
~~~1
5|142705. | 53716
I I
1|
7J
2044.8
586.4
T
"1
8|143385.1
I
1266.3 1363.9
15.9 17.1
691.6 744.9
3548.8| 3882.7
4760.5J 5127.9
2546.51 2743.1
1039.11 1119.3
4170.21 4492.0
14161.5| 15254.3
3561.51 3836.3
1055.21 1136.6
1036.71 1116.6
119042.7|128228.7
2279.31 2455.2
653.71 704.1
I
159829.5|172162.7
I
T
Total sludge/dust|93128
from wet/dry J
controls
|127158.7 135651
|
II
7 J151209.1 1145319
II
~1
I
8|151929.8
I
1
1
169354. 1274758.7
1
-------
Wl
ill limit particulate emissions from new reverberatory furnaces,
resulting in increased collection of particulate 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 (5). Projected
dust/sludge generation levels (estimated on a minimum/maximum
basis) are 145,319,800 - 274,475,700 metric tons (dry weight)
by 1987 (Table 2).*
Ill. Hazardous Properties of the Wastes
1. Concentrations of Lead, Cadmium and Chromium in the Waste
Stre ams.
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 - 10% of the entire waste stream. Chromium and
lead 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 may, however, lead
to increased generation of waste leaching solution.
-------
Table 3
Emission Control Sludge
From Soft Lead Smelting
Emission Control Dust
From Lead Alloy Smelting
Waste Analysis (ppm)
Cd Pb Cr
340 53,000 30
900 120,000
150
The Agency does not have heavy metal concentration data
for the waste leaching solution. Concentrations of these
heavy metals in the waste leaching solution, however, can be
expected to be significant since the acid leaching medium will
solubilize heavy metals 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, cadmium,
and chromium are more soluble in acid than in distilled water
(7,8), 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.
2. Propensity of Lead, Cadmium, and Chromium'to Migrate From
the Wastes in Dangerous Concentrations and Possible Path-
ways of Exposure of Improperly Managed Wastes.
-------
The presence of such high concentrations of toxic metals
in a waste stream may pose a serious threat to human health
and the environment should these toxic metals be 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 solubilize from the waste in
concentrations several orders of magnitude greater than
Interim Primary Drinking Water Standards. See Table 4 (1).
Emission Control Sludge
From Soft Lead Smelting
Emission Control Dust
From Lead Alloy Smelting
Interim Primary Drinking
Water Standard
Table 4
Distilled Water
Extract Analysis (ppm)
Cd
230
.01
Pb
2.5
24.0
.05
Cr
.05
12 .0
.05
-------
While the Agency has not performed any analyses of the
waste acid leaching solution, as noted above, the Agency
believes lead, chromium and cadmium concentrations in waste
acid leaching solution will probably be higher than in the
distilled water extract of the emission control dust. Further-
more, since the waste leaching solution may be disposed of
in liquid form, i.e., with harmful constituents already solu-
/\
bilized and available for migration into the environment,
there is a corresponding dang.er 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 chromium even under relatively mild environ-
mental conditions. If these wastes are exposed to more acidic
disposal environments, for example disposal environments sub-
ject to acid rainfall, these metals would most likely be
solubilized to a greater degree than in the distilled water
since lead, cadmium and chromium (and their oxides) are more
soluble in acid than in distilled water (6,7,8). (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,
-ve-
-------
and increasing the probability for leaching of hazardous
conBtituents 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 sludge/dust,
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 pp. 5 and 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 particular 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.
-vf-
-------
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. Although the Agency is not aware whether waste
dusts are managed in this manner, this type of improper manage-
ment situation appears plausible in light of the large quantitiei
of emission control dust generated annually.
Should lead, cadmium, 'or 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 bioaccumulated and passed along the food
chain but not biomagnified. (Although bioaccumulation of
chromium occurs, the process does not play a major role in
determining the fate of chromium.)
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, chromium, and cadmium constituents, although these
constituents are also measurable by the EP toxicity character-
istic. 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
-vf-
-SSH-
-------
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, and especially lead in actual waste streams, the
non-degradability of these substances, and indications of lack
of proper management of the wastes in actual practice.
The quantity of these wastes generated is an additional
supporting factor.
As indicated above, secondary lead emission control
sludge/dust is generated in very substantial quantities, and
contains very high lead concentrations, as well as elevated
concentrations of cadmium and chromium. (See p. 10 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. Contamination could also occur
for long periods of time, since large amounts of pollutants
are available for environmental loading. All of these consid-
erations 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 of the toxic metals because it accumulates in many
-------
organisms. Its deleterious effects are numerous and severe.
Lead may enter the human system through inhalation, ingestion
or skin contact.
Chromium is toxic and poses a hazard if contaminated
drinking water is ingested by humans. It is also toxic to
lower forms of aquatic life. Cadmium is toxic to practically
all systems and functions of human and animal organism (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 304 of the Clean Water
Act, and under National Interim Primary Drinking Water Stand-
ards 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.
In addition, several states that are currently operating
hazardous waste management programs specifically regulate
cadmium, chromium, and lead containing compounds as hazardous
-vt-
-•356-
-------
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).
-yf-
-------
Refer ences
1. U.S. EPA, Office of Solid Waste. Assessment of Hazardous
Waste Practices in the Metal Smelting and Refining
Industry. Calspan Corporation. EPA Contract Number
68-01-2604, April 1977, Volumes II and IV.
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. PEDCo Environmental, Inc. EPA Contract
Number 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
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.
10. Gleason, M., R.E. Gosselin, H.C. Hodge, B.P. Smith.
Clinical Toxicology of Commercial Products. Baltimore,
The Williams and Wilkins Co., 1969. 3rd Edition.
------- |