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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 when it is improperly treated, stored,
transported, disposed of or otherwise managed).
The Agency considered several approaches for formulating
the list. The approaches can be broken down into three main
types:
0 Hazardous Waste from Non-Specific Sources - these
are wastes which are generated from a number of
different sources (i.e., electroplating, etc.)
° Hazardous Waste from Specific Sources - these are
wastes which would be generated from a very specific
source (i.e., distillation bottoms from aniline produc-
tion , etc . )
-ii-
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0 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 intermediate
unless decontaminated; or any residue or contaminated
soil, water or other debris resulting from the
clean-up of a spill into or on any land or water,
of these commercial chemical products or manufacturing
chemical intermediates are hazardous wastes.
i
(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." This background document was
made available to the public when Phase IA of Part 261 was
promulgated (May 19, 1980).
HAZARDOUS WASTE FROM NON-SPECIFIC AND SPECIFIC SOURCES
Testing of pure substances is the traditional approach
-iii-
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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
noted above).
In order f^.j 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 classes, such as halogenated 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 :he eighteen waste streams promulgated (interim final)
under Phase ~B of the hazardous waste regulations. (The
technical suborn for the .85 waste streams promulgated interim
final (45 FR 2.;. !3 - 33124) and 11 waste streams (45 FF 33137)
proposed on May 19, 1980, under Phase IA has been available
*Pure substa- ce 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 benzen- raust be handled according to the DOT flammable
liquid regulations.
-iv-
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for review and comment since May 19, 1980.) This document
also includes the technical support for the seven new wastes
proposed today. This listing (both interim final and proposed)
includes two waste streams from non-specific sources and 23
wastes from specific sources. The background data used to
support these listings comes primarily, from two sources.
The majority of this data or information comes from studies
undertaken by the Agency or data available to the Agency
(i.e., industry assessment studies conducted by the Office
of Solid Waste, effluent guidelines studies conducted by the
Office of Water Planning and Standards, health effects and
fate and transport data compiled by the Office of Research
and Development and Office of Water Planning and Standards,
damage assessments and incidents compiled by the Office of
Solid Waste, etc.). 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 interim final today, and the changes
subsequently made.
-v-
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Table of Contents
Background Document Page
1. Paint Application Processes Used in the Mechanical 1
and Electrical Products Industry
Paint residues/sludges from industrial painting in
the mechanical and electrical products industry(T)
Wastewater treatment sludges from industrial painting
in the mechanical and electrical products industry(T)
2. Chlorine Production/Mercury Cell Process 45
\ - Brine purification muds from the mercury cell
process in chlorine production, where separately
prepurified brine is not used (T)
- Wastewater treatment sludge from the mercury cell
process in chlorine production (T)
3. Chlorine Production/Diaphragm Cell Process .. ... 64
Chlorinated hydrocarbon wastes from the diaphragm
cell process using graphite anodes in chlorine
production (T)
4. Titanium Dioxide Production 78
Wastewater treatment sludge from the production
of Ti02 pigment using chromium bearing ores by the
chloride process (T)
5. Paint Manufacturing , 102
Solvent cleaning wastes from equipment and tank
cleaning from paint manufacturing (I,T)
Water or caustic cleaning wastes from equipment
and tank cleaning from paint manufacturing (T)
Wastewater treatment sludges from paint
manufacturing (T)
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Page
Emission control dust or sludge from paint
manufacturing (T)
6. Nitrobenzene/Aniline Production 163
Distillation bottoms from aniline production (T)
Process residues from aniline extraction from the
production of chlorobenzenes (T)
Combined wastewater streams generated from nitro-
benzene/aniline production (T)
7. Chlorobenzenes Production 185
Distillation or fractionating column bottoms from
the production of chlorobenzenes
Separated aqueous stream from the reactor product
washing step in the batch production of chlorobenzenes
8. Ink Formulation 228
Solvent washes and sludges, caustic washes and
sludges, or water washes and sludges from cleaning
tubs and equipment used in the formulation of ink
from pigments, driers, soaps and stabilizers
containing chromium and lead (T)
9. Veterinary Pharmaceuticals 249
Waatewater treatment sludges generated during the
production of veterinary Pharmaceuticals from
arsenic or organo-arsenic compounds (T)
Distillustion tar residues from the distillation
of aniline-based compounds in the production of
veterinary Pharmaceuticals from arsenic or
organo-arsenic compounds (T)
Residue from the use of activated carbon for
decolorization in the production of veterinary
Pharmaceuticals from arsenic or organo-arsenic
compounds (T)
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Page
10. Coking Operations .... . 265
Decanter tank tar sludge from coking
operations (T)
11. Primary Aluminum Reduction 274
Spent potliners from primary aluminum
reduction (T)
12. Ferroalloys Production 287
Emission control dust or sludge from ferrochromium-
sllicoa production (T)
Emission control dust or sludge from ferrochromium
production (T)
Emission control dust or sludge from ferro-
manganese production (T)
13. Gray Iron and Ductile Iron Foundries 306
Emission control dust from gray and ductile
iron foundry cupol- furnaces (T)
-viii-
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Generic
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LISTING BACKGROUND DOCUMENT
PA1..T APPLICATION PROCESSES USED IN THE MECHANICAL
AND ELECTRICAL PRODUCTS INDUSTRY
o Paint Residues/Sludges* Generated from Industrial Painting
in the Mechanical and Electrical Products Industry (T)**
^
o Wastew-.er Treatment Sludges from Industrial Painting
in the Mechanical and Electrical Products Industry (T)
I. SUMMARY OF BASIS FOR LISTING
The waste streams listed above contain excess paint solids
generated in industrial painting operations in the mechanical
and electrical products industry. The waste streams contain
elevated concentrations of toxic heavy metals and toxic organics.
Under Subtitle C of RCRA, the Administrator has determined
that the above waste streams pose a threat to human health and
the environment when improperly transported, treated, stored,
disposer! of or otherwise managed, and has designated these
wastes as hazardous. This determination is based on the follow-
ing considerations:
I - The paints used by the mechanical and electrical prod-
acts industry contain numerous toxic constituents.
These same constituents are also present In the excess
--•a* -'/• wastes discharged in the subject waste streams.
J.'"•••-• specific toxic constituents of concern are:
c?.f..mium, chromium, lead, cyanides, toluene, and
te.rachloroethylene. Chromium and tetrachloroethylene
ar=* believed to posses substantial evidence of carcino-
ge'icity by the Agency's Carcinogen Assessment Group.
* The r :-rm 'sludge' in this context refers to oversprayed
painr. solids that are disposed of in a wet form.
**These wastes may often be ignitable, but at this time EPA
does not have sufficient data to indicate that this is
typicalJ cr frequently the case. Generator's are responsible
for det- Ining whether the waste meets the ignitability
charac 11 r ... s t ic .
-------
2. The toxic constituents of concern are all capable
of migration, mobility, and persistence. Improper
management of these wastes may result in the release
of toxic constituents in these wastes to groundwater
and to surface waters, resulting in substantial po-
tential for hazard.
II. INDUSTRY PROFILE AND MANUFACTURING PROCESS.
There are more than 88,700 individual manufacturing
facilities associated with the Mechanical and Electrical
Products Industries (M&EP).(!) These facilities are distributed
throughout the 50 states with concentrations in the heavily
industrialized areas. Painting is a common operation throughout
the M&EP and is present at practically all facilities (1).
The paint consumption for a portion of the M&EP industry is
given below and is expected to increase at an annual rate of
7.5 percent (1).
Industry Million Gal/Yr
Manufacture of Transportation Equipment 100
Manufacture of Metal Furniture 25
Manufacture of Prefinished Metal Stock 25
Manufacture of Machinery & Equipment
(including electrical) 35
Manufacture of Appliances 20
Metal Decorating 50
Total ITF
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Paint Application Processes
Paints are uniform dispersions of inorganic and organic
substances, which, after application to a surface, convert
to a solid film. They may be used for protection, decoration
or identification. All paints contain binders and most
contain solvents, pigments and additives. Paint may be
applied in several physical states: as a liquid (waterborne
or organic solventborne); as a high solids coating (a form
of liquid coating in which the liquid portion is small and
the solids content is high); or as a powder (where there
is virtually no solvent).
Paint application methods are by either spray or dip,
or some variation thereof. Application may be manual or
automatic. The major quantities of hazardous wastes are
generated in the spray application method. Other techniques
may generate minor quantities of wastes from clean-up
between paint batches, spills, accidents and paint overspray.
There are six basic paint application techniques(1):
1. Spray Painting: Liquid spray painting is presently
the most common application method and may be used
with almost all varieties of paint to coat almost
all types of materials. Varieties of spray appli-
cation include air spray, airless spray, hydraulic
spray, electrostatic spray and disc spray. All of
these methods are amenable to automation and are
currently in widespread use. In all cases, the
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painting is accomplished by driving finely divided
particles onto a workpiece. The particles may be
atomized from a liquid by an atomizing spray gun,
or they may be finely divided solid particles that
are electrostatically charged at the spray gun
and attracted to the piece to be coated.
Spray painting may also be done with powder. Pow-
der overspray is generally collected and returned
to the paint supply. However, powder overspray is
occasionally intercepted by a water curtain, or col-
lected dry and discarded.
2. Flow Coating; Flow coating is used to apply paint
to materials of simple shape hung from conveyor
lines. Paint flows under low pressure onto the
parts. Excess paint is collected and recycled.
3. Dip Coating: Dip coating consists of submerging
and withdrawing parts from a paint tank. Paint
deposited on areas where it is not desired is re-
moved with a water spray. The resultant waste
may then be directed to the plant central waste-
water treatment system, where it is removed along
with sludge from other manufacturing processes.
4. Electrodeposition Coating: Electrodeposition (EDP)
coating is used primarily to apply primer coats
in the auto industry. It is a fast process which
gives a fairly thick, highly uniform corrosion
resistant coating.
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The finishes produced by electrodeposition are
not glossy. Therefore, spray painting is gen-
erally used for the final coat* In electrodeposi-
tion, parts which are immersed in a paint/water
emulsion bath are coated by electrochemical action.
The emulsion bath is continuously recirculated
through an ultrafilter to remove impurities
(which pass through the membrane into the permeate)
and to provide rinse water. The permeate is
split into a blowdown stream and a rinse water
supply stream. The permeate stream is free of
suspended solids, but if the blowdown portion is
treated for dissolved heavy metals removal before
discharge, some heavy metal sludge will result.
After painting, the parts are rinsed first with
ultraf iltratir .1 permeate and then usually with
deionized water. The permeate rinse drainage is
usually recirculated to the EDP paint bath, but
the final, deionized rinse drainage is usually
discharged. If treated before discharge, a very
small quantity of paint solids may be removed
from the water.
5. Fluidized Bed; The fluidized-bed process is used
to apply powder coating. In this process, powder
is first placed on a-perforated plate forming the
-5-
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bottom of a coating enclosure. Air is then blown
into a chamber under the plate, fluidizing the pow-
der. Coating occurs through heating or electro-
static means. In heating, the workpiece to be
coated is heated, to temperatures above the fusion
point of the powder. The part is then dipped in-
to the powder cloud and becomes coated as the
powder melts on the surface of the workpiece. In
an electrostatic fluidized bed, an electrode con-
nected to a variable de-voltage source is im-
mersed in the powder. The charged particles of
powder are attracted to the grounded workpiece
and coat the surface.
6. Barrel Coating; Barrel coating is a means of coating
batches of small objects, such as buttons or hard-
ware. The parts are placed in a small cement mixer-
like hopper and a carefully measured amount of paint
is added. Fast drying paints, such as nitrocellulose
lacquers are generally used. Drying is usually
carried out in the hopper by continuing rotation
with air injection.
III. WASTE GENERATION AND MANAGEMENT1)
A. General Source of Waste
In the above paint application techniques, the rate of
generation of hazardous waste will vary with the process
used, while the actual contaminants generated will vary with
the type of coating selected.
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The paint use efficiency of several application methods
is shown below(l):
Method Efficiency
Conventional air spray 20 - 75%
t
Powder application up to 99%
Dip coating 75 - 90%
Electrodeposition 90 - 96%
Electrostatic spray up to 90%
Powder Boatings are most efficient and have several advan-
tages over liquid coatings. In powder coatings, virtually
no solvents are used. Therefore, exhaust to the outside
can be eliminated and instead, the air can be filtered and
returned to the paint room. In addition, the dry powder
overspray may be filtered out, eliminating the need for
water or oil curtains. In some instances, the reclaimed
powder coat can be reused after filtering and screening(1).
Liquid spray painting accounts for the majority of
solid waste discharges within the industry. The source
of wast- solids in this process is overspray -- the paint
which mi ~"s the object being painted. Overspray is intercepted
by paper c irtains or liners, by dry filter arrestors (which
pass vent:! '.ating air), by water curtains, or by oil curtains.
The pap^r curtains and dry filter arrestors are periodically
dispos-:?. of as trash. Water and oil curtain interceptors
rely o.. the circulation of water or oil continuously from,
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and back to, sumps under the spray paint booths. The oversprayed
paint solids are periodically removed from the sumps either
manually or automatically. These wet solids are disposed of
with the plant trash for removal by a contractor.
A
Some facilities discharge solids from paint booth sumps
to an on-site wastewater treatment system. The paint solids,
along with solids from other manufacturing processes, are
then settled out as sludges in solids separating chambers
such as clarifiers, settling tanks, and lagoons. All
sludges are removed by contact haulers and disposed of
in landfills.
B. Collection of Paint Residues
Paint booths are used to catch the excess paint over-
spray from a spray painting operation and to remove solvents
in the air exhausted from the booth. The four common types
of spray booths used in the spray painting industry and the
associated wastes are described below.
1. Water-Wash Booths; Water-wash booths are common
where there is a large volume of exhaust and over-
spray. Water reservoirs and water curtains are
used to collect the excess paint and solvents.
These booths are often tunnels, i.e., enclosed on
the bottom, top, and sides. In a down-draft
booth, where air flow is'from toj> to bottom, the
overspray is sucked down through a metal grating
and into the water flowing below. Down-draft
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booths are useful for large objects painted on
more than one side, e.g. auto bodies. Through
the addition of chemicals called paint killers,
the overspray caught by th'e water may be made to
float or sink in the reservoir located below the
spray area.
When it is not feasible to float or sink the
paint in the reservoir, the wastewater may be sent
through an ultrafilter to remove the paint pig-
ments in ths liquid. This technique is most ap-
plicable to waterborne paints.
Electrostatic treatment also has been success-
fully used to treat the recirculating wastewater.
The electrostatic treater incorporates an electrode
to create an electric field through which the
wastewater flows. The suspended paint particles
are repelled by grounded piping or tanks, thus
reducing buildup. Collected paint is disposed of
or, in rare cases, may be reused.
2. Oil Wash Booths; In this type of booth, a special oil
is used in place of chemically treated water. The
oil facilitates recovery of the paint overspray
and solvents that can be subsequently collected
for disposal and/or reclaimed.
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3. Powder Coating Booths; A typical powder coating
booth has a wall with a steep, sloping bottom'to
collect the bulk of the powder overspray. The ex-
haust air from the booth is often sent to a centri-
fugal separator which separates the overspray from
the air. Powder is discharged through the bottom
of the chamber, and the cleaned air from the first
stage separator is then sent to a bag filter to
remove smaller suspended particles. Some plants
then use an absolute filter and return the clean
air to the plant. Recovered powder generally is
blended with new powder and reused.
4. Dry Booths; In manual spray operations, the dry
booth is usually enclosed on all but one side.
Air is exhausted through the back after passing
through disposable filters or around a series of
staggered plates intended to catch most of the
paint overspray. Exhaust rates are high enough
to draw overspray paint away from the operator.
The filters or paint scrapings are usually disposed
of with plant trash.
Table 1 provides disposal data for paint residues/sludges
from paint booths for 10 typical industrial plants. These
were the only plant files, out of 56 examined, which contained
sludge data. Listed are sludge volumes (or weight), disposal
frequencies, the painting process and the number of paint
-10-
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booths (or other source) for each plant(l). The frequency
of disposal listed does not indicate the frequency of pai'nt
booth sludge skimming (which is often daily) but rather the
disposal of accumulated sludge.
TABLE 1
QUANTITIES OF PAINT RESIDUES/SLUDGES GENERATED AT 10 PLANTS
EPA Plant
Identification
Number
Painting
Process
Waste
Volume Disposal Waste
(Or Weight) Frequency Source
1002
1007
1014
1022
1024
1025
1028
1030
1033
1034
Electrostatic Spray 3,680 yd3 Annually
(water curtain booths)
6 Booths
Airless Spray
Autodeposition
Electrostatic Spray
(water curtain booths)
Spray Painting
(water curtain booths)
Electruless Spray
Dip Coating
Electrostatic Disc
Powder Spray
Electroless Spray
(water curtain booths)
2.97 yd3 Annually 2 Booths
600 yd3 Annually 2 Produc-
tion lines
49 yd3 Annually 2 Booths
25 yd3 Biweekly 9 Booths
1.38 yd3 Monthly
0.27 yd3 Monthly
20 Ibs* Weekly
1,000 Ibs Weekly
4 Booths
2 Tanks
Electrostatic Spray 792.24 yd3 Annually
(water curtain booths)
Electrostatic Spray
(oil curtain booths)
Electrostatic Spray-
(water curtain booths)
1 yd3 Monthly
24.75 yd3 Annually
7 Booths
6 Booths
1 Booth
(Approximately 5,830 yd3; average of 1,416,000 Ib per plant)
*Weight includes disposable filter plus adhering paint overspray.
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IV. HAZARDS POSED BY THE WASTE
1. Paint Residues/Sludges
These wastes are believed to frequently contain sig-
nificant concentrations of the toxic metals cadmium, chromium,
and lead, and the organic compounds 'toluene and tetrachloroethylene,
and cyanides. The source of these toxicants is the paint
itself. The primary source of data supporting this conclusion
is data compiled from state hazardous waste manifests.^)
This data shows these substances present in paint residues*,
generally in very high concentrations (in some cases over 1%
of the total waste, as in manifest numbers 3, 4, 5, 6, 7, 9,
10, 12, 17, and 19). Furthermore, in many cases, accompanying
leachate extraction data shows that the toxic constituents
are present in the waste in a highly mobile form, in some
cases several orders of magnitude greater than the applicable
National Interim Primary Drinking Water Staandard. See
manifests numbers 9, 10, 16, 17 and 19. It should also be
noted that the generators of these wastes themselves consider
their wastes to present "high ingestion toxicity", "high
dermal toxicity", as in manifests numbers 11, 12, 14, 15,
16, 17, 20, 21, 22, 23, 24 and 25.
These data are presented below:
*Terraed "sludges" in many of the manifests, although it
is clear from the context that the wastes in question
are paint residues, not wastewater treatment sludges.
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1. State; Illinois
Source; Special Waste Disposal Applications
SIC3: 3573
Waste Name; Solvent based paint sludge from the manufacture of
electric computer equipment
Quaal. i.ty ; 1500 gallons (semi-solid)
Percent Analysis; 39% water
Leachate
Chemical Analysis; Total concentration (ppm) concentration (ppm)
Cd 2.0 0.2
Cr 150 2.0
2. State; Iowa
S jurce; Reports of Special Waste, Iowa Department of
Environmental Quality
Waste Name; Wall water spray booth paint sludge
Quantity; 365,200 Ibs/year (sludge)
Chemical Analysis;
Leachate Leachate
Concentration (mg/1) Concentration (mg/1)
Metal (Deionized water) (pH =• 5.5)
Pb 5.805 5.33
3. _S_i-at_ : Kansas
Source*. Industrial Waste Disposal Requests, Kansas
Department of Health and Environment
Was'3 Name; Paint Sludge from overspray in spray
booth in the manufacture of office furniture.
'•uantity; 15-20 drums/mo.
: Total
Quantitative Analysis; Metal Concentration (ppm)
Cd 10,400
Cr 2,900
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State; Kansas
Source; Industrial Waste Disposal Requests, Kansas
Department of Health and Environment
Waste Name; Paint solids from water wash booths
Quantity; 400 bbls./year
Total
Chemical Analysis; Metal Concentration (ppm)
~Cr 750
Pb 3,490
State; Kansas
Source; Industrial Waste Disposal Requests, Kansas
Department of Health and Environment
Waste Name; Paint booth waste
Quantity; 5 bbls/week (slurry)
Total
Chemical Analysis; Metal Concentration (ppm)
Pb 216,000
Cr 49,000
State; Kansas
Source; Department of Health and Environment, Industrial
Waste Disposal Requests.
Waste Name; Paint booth and machinery clean-up sludge
Quantity; 3000 gallons/month (slurry)
Toxic
Constituent Total
Chemical Analysis; Metal Concentration (ppm)
Sample #1
Pb 352
Sample #2
Toluene 420,000
Sample #3
Toluene 420,000
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State; Illinois
Source; Special Waste Disposal Applications', Illinois. EPA
SIC; 3631
Waste Name; Paint Sludge from microwave oven manufacturing
Quantity; 40,000 gallons/year (solid)
Percent Analysis; 85% paint pigments
Flashpoint; 100°F
Chemical Analysis; Metal
Total
Concentration (ppm)
Leachate
Concentration (pm)
Cr+6
Pb
2,670
130,000
0.1
0.1
8. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 2591
Waste Name; Paint Sludge from the manufacture of porch shades
and Venetian blinds
Quantity; 1100 gallons/year (semi-solid)
Percent Analysis: 83% water
17% naptha
20% paint pigments
Flashpoint; 80°F
Other properties; High ingestion toxicity
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State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3519
e
Waste Name; Paint Sludge from spray curtain
Quantity; 25,000 gallons/bi-weekly (semi-solid)
Percent Analysis; 36% solids
10% water
54% volatile solids
Chemical Analysis; Metal
Cr
Pb
Total
Concentration (ppm)
2,500
16,500
Leachate
Concentration (ppm)
15.0
5.0
10. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3523
Waste Name; Paint Sludge from tractor cab manufacturing
Quantity; 17,600 gallons/year (solid)
Percent Analysis; 72.5% paint pigments
27.5% water
Chemical'Analysis; Metal
CN
Cr+6
Pb
Total
Concentration (ppm)
150.0
1500.0
9200.0
Leacha te
Concentration (ppm)
1.3
5.4
Other properties; High ingestion toxicity
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11. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3523
Waste Name; Paint sludge from farm machinery manufacturing
Quantity; 2000 gallons/year (sem'i-solid)
Percent Analysis; 85% pigments and filler
15% organic solvent
Flashpoint; 69°F
Other properties; High ingestion toxicity
12. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3531
Waste Name; Waste paint from spray booth from tractor manufacturing
Quantity; 24,000 gallons/year (semi-solid)
Percent Analysis; 66.5% water
30% paint pigments
2% lead
0.5% chromium
Chemical Analysis; Metal
Pb
Cr
Total
Concentration (ppm)
19,870
4,914
Leachate
Concentration (ppm)
1.2
1.8
Other properties; High ingestion toxicity
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13. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3661
Waste Name; Oil Sludge with solvent and paint form the manufacture
of telephone and telegraph parts.
Quantity; 100,000 gallons/year (liquid)
Percent Analysis; 37.6% oil and paint
58.2% solvents
Flashpoint; 100°F
14. State; Illinois
Source; Special Waste Disposal Applications, Illionois EPA
SIC; 3661
Waste Name; Caustic and paint waste from the manufacture of
telephone switching equipment
Quantity; 39,000 gallons/year (liquid)
pH; 14.0
Percent Analysis; 7.6% sodium hydroxide
0.5% zinc
Total
Chemical Analysis; Metal Concentration (ppm)
CN
200.0
Other Properties; High dermal toxicity, high ingestion toxicity
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15. State: Illinois
Source; Special Waste Disposal Applications,'Illinois EPA
SIC; 371
Waste Name; Caustic Cleaning Waste from spray booth—paint
stripping operations
Quantityy 66,000 gallons/year (liquid)
Percent Analysis; 13.3% sodium hydroxide
44.7% water
pH; 12.5
Other properties; High dermal toxicity
16. State; Illinois
Source; Waste Disposal Applications, Illinois EPA
SIC; 3312
Waste Name; Paint sludge from steel manufacturing
Quantity; 8,000 gallons/year (liquid)
Percent Analysis; 82.8% paint thlnners
Flashpoint; 85°F
Total Leachate
Chemical Analysis; Metal Concentration (ppm) Concentration (ppm)
Pb 1015.0 6.8
Oi-her properties; High ingestion toxicity
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17. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3713
Waste Name; Paint sludge from manufacture of truck and tractor
cabs •
Quantity; 17,600 gallons/year (semi-solid)
Percent Analysis; 61.0% paint pigments
21.0% thinner
18.0% water
Total Leachate
Chemical Analysis; Metal Concentration (ppm) Concentration (ppm)
Pb 58,200 28
Cr 8,370.0 0.1
Other properties; High ingestion toxicity
18. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3442
Waste Name; Paint waste from production of aluminum screens
and doors
Quantity; 17,000 gallons/year (serai-solid)
Percent .Analysis; 62.4% paint thinners
Flashpoint; 70°F
Total
Chemical Analysis; Metal Concentration (ppm)
Cr 322.6
-20-
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19. State: Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3443
Waste Name: Paint and thinners from water heaters and
steel drums
Quantity; 20,000 gallons/year (liquid)
Percent Analysis; 62.4% paint thinners
0.3% chromium
1.7% lead
0.8% copper
Flashpoint; 70°F
Total
Chemical Analysis; Metal Concentration (ppm)
Leachate
Concentration (ppm)
Cr
Pb
2,975.0
17,393.0
0.2
182.6
20. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 2431
Waste Name; Paint pigment sludge from window from manufacturing
Quantity; 27,500 gallons/year (semi-solid)
Percent Analysis; 50% polyured resin
15% xylene
5% cellosulde acetate
29.2% pigments
Flashpoint; 80°F
Other properties; High dermal and ingestion toxicity
-21-
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21. State: Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3579
Waste Name; Waste paint sludge from the manufacture of office
copying machines
Quantity; 11,000 gallons/year (liquid)
Percent Analysis; 74.6% solvents
25.1% pigments
Flashpoint; 70°F
Other properties; High dermal and ingestion toxicity
22. State; Illinois
Source; Special Waste Disposal Applications, Illinois SPA
SIC; 3612
Waste Name; Dry paint solids from the manufacture of stores
and refrigerators
Quantity; 6,600 gallons/year (solid)
Percent Analysis; 15.7% high boiler solvent
84.3% paint pigments
Total
Chemical Analysis; Metal Concentration (ppm)
Pb .. 449.9
Other properties; High ingestion toxicity
-22-
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23. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 2552
Waste Name; Paint sludge from the manufacture of steel office
furniture
Quantity; 150,000 gallons/year (semi-solid)
Percent Analysis; 23.1% paint thinners
63% paint pigments
Flashpoint; 100°F
Total
Chemical Analysis; Metal Concentration (ppm)
Pb 2649.0
Cr 214.0
Other properties; High ingestion toxicity
24. State; Illinois
Source; Spe.-ial Waste Disposal Applications, Illinois EPA
SIC; 2541
Waste Name; Paint sludge from the manufacture of store furniture
Quantity; 50,000 gallons/year (solid)
Percent Analysis; 85% polyester
7% solvents
8% pigments
Flashpoint; 73°F
Other,properties; High ingestion toxicity
-23-
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25. State: Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 2792
Waste Name; Paint sludge from the manufacture of paint charts
and color cards
Quantity; 19,800 gallons/year (semi-solid)
Percent Analysis; 78% paint pigments
22% lacquer thinner
Flashpoint; 79°F
Other properties; High ingestion toxicity
26. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
SIC; 3352
Waste Name; Paint waste from the manufacture of aluminum coils,
plates, and sheets
Quantity; 33,000 gallons/year (semi-solid)
Percent Analysis; 51.9% pigments
29.5% paint solvents
Flashpoint; 90°F
Tetrachloroethylene is not listed as a waste constituent
in these manifests, although it is a constituent of concern.
The presence of this constituent is shown by its presence in
significant levels in untreated wastewater in a study of 14 plants
undertaken by EPA (1) (see Table 2 ). It is believed
that tetrachloroethylene would be present in solid residues
in substantially higher concentrations, since the solid
-24-
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TABLE 2
PRIORITY POLLLUTANTS IN WASTEWATER FROM INDUSTRIAL
Number of Maximum
Times Analyzed Value (mg/1)
Cadmium 49 0.095
Chromium 50 101.0
Lead 50 103.5
Cyanides 41 63.0
Toluene 41, 4.16
Tetrachloroethylene 41 52.0
-25-
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residues are not diluted.
2. Wastewater Treatment Sludge
As described above, some generators send their process
paint residues to wastewater treatment, where a sludge is
generated. These sludges are expected to contain most (or
all) of the contaminants found in the paints themselves. The
particular constituents of concern are cadmium, chromium,
lead, cyanides, toluene, and tetrachloroethylene, since as
just shown, these constituents have been demonstrated to be
present in significant concentrations in paint residues.
Additional data throwing some light on the constituent
concentrations in these wastewater treatment sludges is
presented in Table 2. This data shows the maximum concentrations
of the constituents of concern in wastewater samples from 14
industrial plants performing various types of painting. This
data shows chromium, lead, and cyanides present in substantial
concentrations, and cadmium and the organic contaminants
present in lesser concentrations. These constituents would
probably be found in the treatment sludges, for the following
reasons. The heavy metals are not degradable and so would be
present in the sludge. Cyanides and toluene are biodegradable
ordinarily only in low concentrations (although some toluene
would probably volatilize and therefore would not be in the
sludge).(6) Tetrachloroethylene is subject in theory to
biodegradation,(6) and thus might be present in lesser
concentrations in the sludge than the other constituents of
-26-
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concern. However, each of these constituents would undoubtedly
be present in the wastewater treatment sludge in higher concen-
trations than in the wastewater since the sludges that contain the
toxic constituents removed from the wastewater are dewatered,
and therefore, th,. constituents are concentrated, before disposal.
Finally, the constituents of concern are typically expected
to be present in these wastes. Table 3 shows toxic
constituents present in the raw materials used by the paint
industry, and shows lead, chromium, cyanides, and toluene in
very wide use. The use of cadmium is less prevalent, but it is
still utilized by roughly 20% of paint manufacturers.
It should be noted that the Agency possesses data'^)
suggesting that a great many other toxic substances are present
in these wastes, specifically the toxic constituents listed
in the paint manufacturing listing background document-. The Agency
however presently lacks reliable data as to these constituents'
concentrations in industrial painting wastes. Further
information as to the presence and concentrations of additional
toxic constituents in thesa wastes is solicited.
3. Migratory Potential of Waste Constituents
The Administrator has classified these two wastes as
hazardous because the Agency has reason to believe that they
contain substantial concentrations of the toxic raw materials
used in the formulationof paint products and therefore that
the wastes pose a substantial threat to human health and the
environment. Specifically, these wastes are being listed as
-27-
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TABLE 3
TOXIC CONSTITUENTS IN RAW MATERIALS
USED BY THE PAINT INDUSTRY^)
Responders Indicating Usage of Raw Materials Containing
Specific Constituents of Concern
Priority Minimum Maximum
Pollutant No. of Plants Percent No. of Plants Percent
Cadmium 260 18.9 312 22.7
Chromium 1042 75.8 1083 78.8
Lead 833 60.6 1016 73.9
Cyanides 860 62.6 1064 77.4
Toluene 961 69.6 998 72.6
*Data generated from 1374 responses to paint industry "308" survey.
Since many of the raw materials included in the "308" Data Collection
Portfolio can contain more than one toxic pollutant, the Agency was
unable to obtain unambiguous conunts for the occurence of particular
toxic pollutants. A conservative approach was taken because of this.
When the Data Collection Portfolio response did not indicate clearly
which toxic pollutant was in use, the Agency mad two counts - one
including neither, one including both. This gave a maximum and
minimum count for toxic pollutants. Twenty-eight plants did not check
any boxes in the survey. It is not clear whether the respondents use
none of the listed raw materials or whether they did not fil out the
questionaire completely. Finally, within the group of respondersto the
raw materials survey, it was found taht each raw materials question was
answered poitively at least once. This indicates that the raw materials
questions represented appropriate paint raw materials.
-28-
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hazardous because of the presence of the following toxic
constituents:
cadmium
chromium
lead
cyanides
toluene
tetrachloroethylene
Of these constituents, hexavalent chromium and
tetrachloroethylene have been Identified by the Agency's
Carcinogen Assessment Group as possessing substantial evidence
of carcinogenic!ty, Increasing Agency concerns as to the
potential of these wastes to cause substantial harm if mismanaged.
Cadmium, lead
-------
150 mg/1 at 25°c(8)). The heavy metals are likewise known
to be capable of migration, as shown by waste extraction data
(see State Manifest Data Number 9, 10, 16, 17, 19). These
compounds thus present a danger of migration via a groundwater
exposure pathway if exposed to a leaching media.
Toluene and tetrachloroethylene are also significantly
volatile (toluene - 28.4 mm at 25°C,(4) tetrachloroethylene -
150 mm at 25°c(°)) and could pose an air Inhalation hazard to
environmental receptors in the vicinity of improperly disposed
wastes.
These constituents are likewise capable of mobility and
persistence upon environmental release. Many constituents
have in fact been involved in damage incidents resulting from
improper waste management, empirically demonstrating their
mobility and persistence. For example, among other contaminants,
tetrachloroethylene was involved in the contamination of
drinking water sources in New Hanover, North Carolina.(6)
Toluene and tetrachloroethylene are among the constituents
present in water and air samples taken in the Love Canal area.(^)
Heavy metals -and cyanides likewise have been involved in
numerous damage incidents from improper waste disposal.(6)
These waste constituents thus have the capacity for
migration, mobility and persistence, raising the possibility
of potential hazard if the wastes are mismanaged.
-30-
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Ground water or surface water contamination could result,
for example, if sites are selected improperly
i.e.(in areas with permeable soils) or if no leachate control
measures are utilized. Lagoon-disposed wastes (such as treatment
sludges prior to dredging) also pose a potential for hazard
because a large quantity of liquid is available to percolate
through the solids and soil beneath the fill. Further, the
Agency is also concerned that the lagooned wastes could
contaminate surface waters if not managed to prevent flooding
or total washout.
An additional consideration favoring hazardous waste
status for these wastes is that they are transported to off-
site disposal facilities. This increases the likelihood of
their being mismanaged, i.e., uncontrolled transportation may
result either in their not being properly handled during
transport or their not reaching their destination at all. A
transportation and manifest system combined with designated
standards for the management of these wastes will greatly
reduce their availability to harm to humans and the environment.
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V. Health and Environmental Effects (9)
The following contaminants of paint wastes are designated
as priority pollutants under Section 307(a) of the Clean
Water Act:
cadmium
chromium
lead
cyanides
toluene
tetrachloroethylehe
Lead is also regulated under the Clean Air Act. Proposed
or final standards have been issued for most of these chemicals
under the Occupational Safety and Health Act of 1970. EPA's
Carcinogen Assessment Group (GAG) has evaluated several constit-
uents of these waste streams and found sufficient evidence to
indicate that chromium (Cr+6) an(j tetrachloroethylene are
carcinogens. More specific information on the health
effects of these chemicals are summarized below. Additional
information on the adverse health and environmental effects
of these constituents can befound in Appendix A.
Cadmium
Cadmium is an extremely dangerous cumulative toxicant,
causing progressive chronic poisoning in mammals, fish, and
probably other organisms. The metal is not excreted.
Toxic effects of cadmium on man have been reported
-32-
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from throughout the world. Cadmium may be j. factor in the
development of such human pathological conditions as kidney
disease, testicular tumors, hypertension, arteriosclerosis,
growth inhibition, chronic disease of old age, and cancer.
Cadmium is normally ingested by humans through food and
water as well as by breathing air contaminated by cadmium
dust. Cadmium is cumulative in the liver, kidney, pancreas,
and thyroid of humans and other animals. A severe bone and
kidney syndrome known as itai-itai disease has been documented
in Japan as caused by cadmium ingestion via drinking water
and contaminated irrigation water. Ingestion of as little
as 0.6 mg/day has produced the disease. Cadmium acts syn-
ergistically with other metals. Copper and zinc substantially
increase its toxicity.
Cadmium is concentrated by marine organisms, particularly
molluscs, which accumulate cadmium in calcareous tissues
and in the visera. A concentration factor of 1000 for
cadmium in fish muscle has been reported, as have concentration
factors of 3000 in marine plants and up to 29,600 in certain
marine animals. The eggs and larvae of fish are apparently
more sensitive than adult fish to poisoning by cadmium, and
crustaceans appear to be more sensitive than fish eggs and
larvae.
For the protection of human health from the toxic
properties of cadmium ingested through water and through
-33-
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contaminated aquatic organisms, the ambient water criterion
is determined to be 0.010 mg/1.
Data show that cadmium can be incorporated into crops,
including vegetables and grains, from contaminated soils.
Since the crops themselves show no adverse effects from
soils with levels up to 100 mg/kg cadmium, these contaminated
crops could have a significant impact on human health. Two
Federal agencies have already recognized the potential
adverse human health effects posed by the use of sludge on
cropland. The FDA recommends that sludge containing over
30 mg/kg of cadmium should not be used on agricultural
land. Sewage sludge contains 3 to 300 mg/kg (dry basis)
of cadmium; mean = 10 mg/kg; median = 16 mg/kd. The USDA
also recommends placing limits on the total cadmium from
sludge that may be applied to land.
Chromium
The two chromium forms most frequently found in industry
wastewaters are hexavalent and trivalent chromium. Some of it
is reduced to trivalent chromium- as part of the process reaction.
The raw wastewater containing both valence states is usually
treated first to reduce remaining hexavalent to trivalent
chromium, and second to precipitate the trivalent form as the
hydroxide. The hexavalent form is not removed by lime treatment.
Chromium, in its various valence states, is hazardous to
man. It can produce lung tumors when inhaled, and induces skin
-34-
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sens!tizations. Large doses of chromates have corrosive effects
on the intestinal tract and can caue inflammation of the kidneys
Hexavalent chromium is a known human carcinogen. Levels of
chromate ions that show no effect in man appear to be so low as
to prohibit determination, to date.'
The toxicity of chromium salts to fish and other aquatic
life varies widely with the species, temperature, pH, valence
of the chromium, and synergistic or antagonistic effects,
especially the effect of water hardness. Studies have shown
that trivalent chromium is more toxic to fish of some types
than is hexavalent chromium. Hexavalent chromium retards
growth of one fish species at 0.0002 mg/1. Fish food
organisms and other lower forms of aquatic life are extremely
sensitive to chromium. Therefore, both hexavalent and
trivalent chromium must be considered harmful to particular
fish or organisms.
For the protection of human health from the toxic
properties oJ: chromium (except hexavalent chromium) ingested
through water and contaminated aquatic organisms, the
recommended water quality criterion is 0.050 mg/1. For
the maximum protection of human health from the potential
carcinogenic effects of exposure to hexavalent chromium
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero.
Chromium is not destroyed when treated by wastewater
treatment (although the oxidation state may change), and will
either pass through to the wastewater treatment effluent or be
-35-
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cyanide.
The toxic mechanism of cyanide is essentially an
inhibition of oxygen metabolism, i.e., rendering the tissues
incapable of exchanging oxygen. The cyanogen compounds are
true noncumulaive protoplasmic poisons. They arrest the
activity of all forms of animal life. Cyanide shows a very
specific type of toxic action. It inhibits the cytochrome
oxidase system. This system is the one which facilitates
electron transfer from reduced metabolites to molecular
oxygen. The human body can convert cyanide to a non-toxic
thiocyanate and eliminiate it. However, if the quantity of
cyanide ingested is too great at one time, the inhibition
of oxygen utilization proves fatal before the detoxifying
reaction reduces the cyanide concentration to a safe level.
Cyanides are more toxic to fish than to lower forms of
aquatic organisms such as midge larvae, crustaceans, and
mussels. Toxicity to fish is a function of chemical form
and concentration, and is influenced by the rate of metabolism
(temperature), the level of dissolved oxygen, and pH. In
laboratory studies free cyanide concentrations ranging from
0.05 to 0.15 mg/1 have been proven to be fatal to sensitive
fish species including trout, bluegill, and fathead minnows.
Levels above 0.2 mg/1 are rapidly fatal to most fish species.
Long term sublethal concentrations of cyanide as' low as
0.01 mg/1 have been shown to affect the ability of fish to
function normally, e.g., reproduce, grow, and swim.
For the protection of human health from the toxic
properties of cyanide ingested through wate:: and throguh
-38-
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contaminated aquatic organisms, the ambient water quality
criterion is determined to be 0.200 mg/1.
Tetrachloroethylene
Tetrachloroethylene is highly toxic via ingestion and
moderately toxic via inhalation and skin absorption as well as
being carcinogenic. Tetrachloroethylene has a vapor pressure
of 19 mm Hg at 20°C. It is insoluble in water but soluble
in organic solvents. Because tetrachloroethylene is
volatile disposal of this waste is an uncontrolled manner
poses risks to human health by all routes of exposure.
The prinicipal toxic effect of tetrachloroethylene on
humans is central nervous system depression when the compound
is inhaled. Headache, fatigue, sleepiness, dizziness and
sensations of intoxication are reported. Severity of
effects Increases with vapor concentration. High integrated
exposure (concentration times duration) produces kidney
and liver damage. Very limited data on tetrachloroethylene
ingested by laboratory animals indicate liver damage occurs
when PCS is administered by that route. Tetrachloroethylene
tends to distribute to fat in mammalian bodies.
One report found in .the literature suggests, but does not
conclude, that tetrachloroethylene is teratogenic. Tetrachloro-
ethylene has been demonstrated to be a liver carcinogen in
B6C3-F1 mice.
For the maximum protection of human health from the
-39-
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potential carcinogenic effects of exposure t-> tetrachloroethylene
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero. Concentrations of
^tetrachloroethylene estimated to result in additional life-
time cancer risk levels of 10~7 , 10~6, and 10~5 are 0.000020
mg/1, 0.00020 mg/1, and 0-.0020 mg/1, respeeLively.
Toluene
Toluene is moderately toxic by ingestiou and inhalation.
Because toluene is both water soluble and volatile, it may pose
»
a threat to human health by both exposure routes, respectively.
Toluene is volatile (vapor pressure of toluene is 36.7 mm at
30°C); handling and disposal of the waste may thus pose an
inhalation hazard. If the waste is disposed in an unsecured
landfill the toluene may be solubilized from the waste (the
water solubility of toluene is 535 mg/1, and it is miscible
with a variety of organic solvents) by rainfall and contami-
nate underlying potable groundwater sources with may pose
a hazard to human health when the water i ingested.
Most data on the effects of toluene ii human and other
mammals have been based on inhalation expr. :.• are or dermal contact
studies. There appear to be no reports of .. .1 administration
of toluene on human subjects. A long term tcxicity study on
female rats revealed no adverse effects on ?. owth, mortality,
appearance and behavior, organ to body weight ratios, blood-
urea nitrogen level, bone marrow counts, peripheral blood
counts, or morphology of major organs. The effects of inhaled
-40-
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toluene on the central nervous system, both at high and low
concentrations, have been studied in humans and animals.
However, ingested toluene is expected to be handled differently
by the body because it is absorbed more slowly and must first
pass through the liver before reaching the nervous system.
Toluene is extensively and rapidly metabolized in the liver.
One of the principal metabolic products of toluene is benzoic
acid, which itself seems to have little potential to produce
tissue injury.
Toluene has been found in fish caught in harbor waters in
the vicinity of petroleum and petrochemical plants. Bioconcen-
tration studies have not been conducted, but bioconcentration
factors have been calculated on the basis of the octanol-water
partition coefficient.
For the protection of human health from the toxic properties
of toluene ingested through water and through contaminated
aquatic organisms, the ambient water criterion is determined to
be 12.4 mg/1.
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REFERENCES
1. Centec Corporation, Contractor Report for Development of
Effluent Limitations Guidelines for Paint Application Proc-
esses Used in the Mechanical and Electrical Products Indus-
. tries, July, 1979.
2. Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the Oil Base
Solvent Wash Subcategories of the Paint Formulating and
the Ink formulating Point Source Category, July, 1975, EPA
440/1-75/050-a.
3. U.S. EPA, Effluent Guidelines Division, Development Document
for Proposed Effluent Limitations Guidelines, New Source
Performance Standards, and Pretreatment Standards for the
Paint Formulating Point Source Category, December, 1979.
4. Karel Verschueren, Handbook of Environmental Data on Organic
Chemicals, Copyright 1977, Litton Educational Publishing.
5. U.S. EPA, Office of Solid Waste, Open Files—State Manifest
Data, 1980.
6. Resource Losses from Surface Water, Groundwater, and
Atmospheric Contamination: A Catalog; prepared by the
Environment and Natural Resources Policy Division of
the Congressional Research Service of the Library of
Congress for the Senate Committee on Environment and
Public Works, Serial No. 96-9, 96th Congress, 2nd Session
(1980).
7. Love Canal Public Health Bomb, A Special Report for the
Governor and Legislature, New York State Department of
Health, 1978.
8. Gosselin, Rober E., et al, Clinical Toxicity of Commercial
Products, Fourth Edition, The Williaras and Wilkin
Company,•Baltimore, 1976.
9. U.S. EPA, Effluent Guidelines Division, Development
Document for Effluent Limitations Guidelines and
Standards for Foundries Metal Molding and Casting Point
Source Category, Section VI--Pollutant Parameters,
April 1980.
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VI. Rv iponse to Comments to the Proposed Rule
Several commenters responding to the proposed Hazardous
Waste Guidelines and Regulations (43 FR 58946, December
18, 1978) objected to the category "paint wastes" which
appeared in §250.14(a) as a hazardous Waste. The main
objection was that the category was overly broad. In
response, EPA has been more specific in its listing of
paint wastes. The two wastes listed in this document are
generated by a. number of industries engaged in industrial
painting. As EPA obtains more information on paint wastes,
additional generic categories may be added to the hazardous
wast a list.
-------
Inorganic Chemicals
-------
LISTING BACKGROUND DOCUMENT
CHLORINE PRODUCTION
BRINE PURIFICATION MUDS FROM THE MERCURY CELL PROCESS
IN CHLORINE PRODUCTION WHERE SEPARATELY PREPURIFIED
BRINE IS NOT USED (T).
WASTEWATER TREATMENT SLUDGES FROM THE MERCURY CELL
PROCESS IN CH70RINE PRODUCTION (T).V
I. SUMMARY OF BASIS FOR LISTING
The solid wastes of concern in this document are muds
from brine purification and wastewater treatment sludges
from the mercury cell process in chlorine production. The
toxic constituent of concern in these wastes is the heavy
metal mercury.
The Administrator has determined that mercury-bearing
sludges and muds resulting from the mercury cell process in
chlorine production are solid wastes which may pose a substantial
present or potential hazard to human health or the environment
when improperly transported, treated, stored, disposed of or
otherwise managed, and which therefore should be subject to
appropriate management requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations:
1. These wastes are generated in large quantities and
contain significant concentrations of mercury. At the
present time approximately 42,000 kkg of hazardous
mercury-bearinc wastes are generated each year.
These wastes are calculated to contain about 600 kkg of
mercury. Large quantities of this highly toxic pollutant
are thus available for environmental release.
2. These wastes have been involved in a number of serious
damage incidents, demonstrating empirically that improper
waste management may result in substantial environmental
hazard.
^/ This waste stream was not included in the initial listing,
and is being initially proposed in the present document.
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II. SOURCES OF THE MERCURY AND TYPICAL DISPOSAL PRACTICES
A. Industry Profile
Twenty-seven facilities, located in 16 states, are
engaged in chlorine and either sodium hydroxide or potassium
hydroxide manufacture using the mercury cell process. ( 1 '2)
These facilities are identified in Tables 1 and 2. In 1979,
their mercury cell production capacity was reported as ranging
from 36,000 to 272,000 kkg per year.(2)
B. Manufacturing Process (Modified from Reference 1)
In the mercury cell process, rock or evaporated salt
is dissolved in recycled brine or in fresh water in agitated
tanks to form a saturated salt brine. In plants, not using
I/
prepurified salt--most of the plants using this process--
this brine is purified by adding soda ash and sodium hydroxide,
and in some cases barium salts, precipitating barium sulfate,
and calcium and magnesium impurities of the salt as the
carbonate and hydroxide, respectively. These are removed by
settling and filtration; these filtered muds (A in Figure 1)
constitute one of the wastes of concern. The purified brine is
then fed to"the electrolytic mercury cells, where it is decomposed
V Six facilities (listed in Table 2) use evaporated rock
salt already purified in on-site diaphragm cell operations;
thesa plants do not perform significant purification, and
therefore do not generate mercury-containing brine muds.
-2-
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TABLE 1
FACILITIES PRODUCING MERCURY-BEARING BRINE PREPARATION/PURIFICATION MUDS.
STATE
Alabama
Delaware
Georgia
Illinois
Kentucky
Louisiana
Maine
New Jersey
New York
No. Carol.
Ohio
Tennessee
Texas
Washington
West Va.
Wisconsin
FACILITY
Diamond Shamrock, Mobile
Diamond Shamrock, Mus.Sho.
Stauffer Chem., LeMoyne
Diamond Shamrock, Del. City
Linden Prods., Brunswick
Olin Corp., Augusta
Monsanto Co . , Sauget
B.F. Goodrich, Calvert City
Pennwalt Corp., " "
Stauffer Chem., St. Gabriel
International Minerals, •
Orrington
Linden Products, Linden
Hooker Sobin, Niag. Falls
Olin Corp., Niag. Falls
Linden Products, Acme
International Minerals,
Ashtabula
Olin Corp., Charleston
Alcoa , Point Comfort
Georgia Pacific, Bellingham
Linden Products, Moundsville
BASF Wyandotte, Port Edwards
ROCK SALT CHLORINE CAPACITY
SOURCE 103 kkg/yr (2)
Louisiana
Louisiana
Louisiana
New York
Louisia 'ia
T >uisiana
Kansas
Louisiana
Ohio
Louisiana
New ;'ork
New York
New York and
Sask.KCl(b>
New York
Louisiana
Sask. KC1
Tennessee
Louisiana
Prepurif. evap.
W.Va.
Michigan
38
142
50
139
98
100
40
116
109
150
72
131
59
80
54
36
227
153
83
87
64
2028
HAZARDOUS BRINE MUDS
/CHLORINE CAPACITY TOTAL, DRY BASIS
(kg/kkg)*10'1) (kkg/year)
10
10
10
20
10
10
20
10
30
10
20
20
25
20
10
30
30
10
0.7
45
45
380
1,420
500
2,775
980
1,000
800
1,160
3,265
1,500
1,440
2,620
1,474
-
1,600
540
1,088
6,803
1 , 530
58
3,918
3,020
37,871
(c)
(c)
(c)
(0
(c)
a) The amounts of hazardous brine muds generated were calculated by multiplying the plant annual capacity
(Reference #2) by the amount of brine muds generated per kkg of chlorine produced.
b) This facility uses New York rock salt and Saskatchewan potassium chloride salt in approximately equal proportions.
These salts generate 20kg and 30 kg of hazardous brine muds respectively per metric ton of chlorine produced. An
average value of 25 kg was used.
c) These facilities segregate the two waste streams A and B of Figure 1.
.L| 7..73-
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Table 2
FACILITIES WHICH DO NOT PRODUCE MERCURY-BEARING BRINE MUDS.(a>
STATE
Alabama
Louis iana
New York
Texas
West Va.
FACILITY
MERCURY CELL
CHLORINE CAPACITY
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-------
by electrolysis to produce chlorine and sodium amalgam. The spent
brine from the mercury cells is dechlorinated and approximately
94% is returned (recycled) to the initial brine make-up for
resaturation-; the remainder is discharged to wastewater treatment.
Since some of the feed of the brine purifier is a mercury
bearing recycle stream from the electrolytic cell/ the muds (A
in Figure 1) resulting from brine purification are contaminated
with mercury.
In all plants, the depleted purged brines from the electro-
lytic cell/ together with two other waste streams generated from
ancillary processes/ are channeled to waste treatment. Wastewater
treatment generates sludges (B in Figure 1) in amounts averaging 2
kg of sludge per kkg of chlorine product.'D These wastes, which
;
contain about 15%* mercury (as mercuric sulfide) constitute the
second waste of concern.**
The mercury leaving the cells in the form of sodium mercury
amalgam is sent to denuders where the amalgam is decomposed at 80°C
by the addition of deionized water. Water reacts with the sodium
mercury amalgam to produce a 50 percent solution of sodium
*This conclusion is estimated from the following factors:
(1) approximately 52 kkg of brine are used per kkg of
chlorine produced^3'; about 3100 kg (6%, Figure 1)
are purged^). These brines contain about 20 ppm of
mercury^3'. ' Thus, 3,100 kg brines/kkg Cl2/x20xlO~6 kg
mercury/ kkg brine = 0.06 kg mercury. Since these are
crude estimates, this figure is rounded to 0.1.
(2) It is estimated that about 0.3 kg of mercury are
- spilled per kkg of chlorine produced.(23)
(3) It is estimated that about "1". 7 kkg^of filter residues
and occluded water are generated per kkg of chlorine
produced.
Thus the treatment sludges total about 2.0 kg per kkg of
chlorine? of this total 0.3 kg, or 15%, is mercury contami-
nated.
**The waterborne waste stream does not contain sufficient
mercury to be of regulatory concern.
-.6-
-------
hydroxide* essentially free of sodium chloride. This solu-
tio.n is filtered to recover entrained mercury. The waste..
from the filtration step is sent to wastewater treatment,
where mercury precipitates into the treatment sludge (stream
B). Entrained mercury is removed from the hydrogen generated
in the denuders, and returned to the electrolytic process.
After removal of mercury/ the hydrogen is either compressed
for sale, used on-site, or used as a fuel. The chlorine gas
collected in the electrolytic cells is cooled to condense out
excess water vapor. This stream, which is essentially free
of mercury, is sent to waste treatment. The partially dried
chlorine is then scrubbed with 98 percent sulfuric acid to
remove the rest of the entrained water vapor and is collected,
compressed and liquified.
C. Waste Generation
The wastes of interest in this document are muds that
result from the treatment of rock salt and recycled depleted
brine, and sludges generated by the treatment of purged,
depleted brines and ancillary waste streams. Twenty one
facilities generate both of these wastes. Six other facilities,
(those which use prepurified salt) do not generate brine
purification muds (waste A, Figure 1).
*Potassium hydroxide is produced in plants using potassium
chloride as raw material.
-7-
-------
The source of mercury in the brine purification muds is
the recycled brine from the electrolytic cell (which mercury
is removed in the purification process step).
These brine preparation muds contain substantial con-
centrations of mercury, either in elemental form or as the
complex ion, HgCl4=3. Available data, in fact, indicate that
the concentration of mercury in these muds ranges from 500(12)
to 2000 ppm (13/14) of mercury. Total potential mercury
loadings are likewise substantial: the 38,000 tons of hazardous
brine preparation and purification muds generated each year
(Table 1) are calculated to contain 19 to 76 kkg of mercury.
It should be noted that the amount of muds produced
depends on the source of the salt used as raw material.(H•12)
As indicated in Table 1, facilities using salt from the
Texas-Louisiana salt dome generate about 10 kg of brine mud
per kkg of chlorine. Plants using other salt sources generate
brine muds in amounts ranging from about 20 kg per kkg of
chlorine (salt from Kansas and New York) to 45 kg per kkg
chlorine (salt from Michigan and West Virginia deposits).
All the above "quoted figures are on a dry-weight basis.(^'1°'^*
The sludges resulting from .wastewater treatment
consist mainly of mercuric sulfide. Approximately 4,300*
^Calculated from mercury cell chlorine production data for
197?(3) and treatment sludge data in Figure 1: 2128xl03 kkg
chlorine produced/year x 2 kkg sludge waste/ 103 kkg chlorine
= 4256 kkg sludge waste.
-8-
-------
kkg of this waste containing 15% mercuric sulfide (equivalent
in total to 645 kkg of mercury) are generated each year.
Therefore, a total of approximately 42,000 kkg of hazardous
mercury-bearing wastes containing as much as 620 kkg of mercury
are generated annually from the mercury cell process. This
estimate is reasonable in view of the reported 846 kkg of
mercury lost to the environment as wastes and air emissions.
for this industry in 1965.<15)
D. Waste Management (1,11,12)
Of the 21 plants generating both listed waste streams, all
but five combine their wastes prior to treatment. One plant
retorts all mercury-containing wastes, eight others retort
only the mercury-rich wastes, and of these eight, four store
these wastes in drums until decisions are made on final
disposal. One plant sends sludges to contractors for recovery.
This latter disposal method is occasionally used by other
facilities. Nine plants now use on-site pond storage of
sludges, and seven use on-site landfill. Four plants send
wastes to contractors for secured landfilling. Several plants
employ combinations of these treatment and disposal techniques.*/
J^/ One plant utilizes a relatively new system for recovery
of mercury from virtually all mercury bearing wastes. Treat-
ment of contaminated wastes with sodium hypochlorite leaves
wastes with a residual mercury content of less than 40 ppm.
This treated waste is then disposed of by landfilling. This
waste recovery process is capable of treating both brine mud and
treatment sludges, and of recycling recovered mercuric chloride.
However, its applicability is limited by cell design and water
balance considerations.
-9-
-------
II. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Waste
The two listed wastes are of regulatory concern because
of their contamination with the toxic heavy metal mercury.
Brine preparation and purification muds are reported to contain
as much as 2000 ppm of mercury, and treatment sludges contain
about 15.0% mercury. Moreover/ very large amounts of these
wastes (42,000 kkg) are generated. Mercury is highly toxic
to a wide variety of organisms, including man, and can accum-
ulate in biological organisms in its various forms.
These wastes have been involved in a number of damage in-
cidents ,. demonstrating empirically that improper management
of these wastes may cause substantial harm. These damage
incidents are described below.
0 The Olin 102nd Street Landfill, Niagara Falls, Niagara
County, New York. (4)
From mid 1948 to September, 1970 Olin Chemical Cor-
poration utilized a landfill for the disposal of chemical
wastes from its Niagara Falls plant. These wastes
include brine sludge from a mercury cell chlor-alkali
plant plus other wastes such as chlorinated organics,
lime wastes, r"mv wastes, fly ash, black cake wastes
(sodium chloride, sodium chlorite, sodium chlorate,
carbon, calcium carbonate, calcium hydroxide), graphite
from electrolytic cells and concrete cell bodies, together
-10-
-------
with a limited amount of research materials. This land-
fill is located in a suburban section of Niagara Falls,
New York, contiguous to the northern shore of the Niagara
River. When it was closed, the landfill was "secured" by
covering the waste with a soil cover, establishing vegetation,
and by constructing a dike along the Niagara River.
..n 1978, a surface and groundwater sampling program was
initiated at the landfill site by RECRA Research Inc. and
WEHRAN Engineering Corporation^) to provide both baseline
water quality data and sufficient information to assess the
impact of previous disposal operations at the site. The
program included the analysis of waters from the various
groundwater regimes encountered on site, and of grab samples
of surface waters from the Niagara River. In view of the
fact that the EPA National Interim Primary Drinking Water
Standard for mercury "is 2 ug/1, pertinent results indicated
serious mercury contamination:
1) On one of the two dates on which samples were
taken, all readings for the six Niagara River
surface grab samples (taken downstream from the
furthest upriver point where the landfill borders
the river) contravened the Drinking Water Standard
in every case, with values ranging from A*7 to 15
ug/1. On the second date, there was no significant
-11-
-------
difference in concentrations up- and down stream
from the landfill site. On this date, stormy conditions
prevailed, and the river flow was much above normal.
2) Water samples were taken from the fourteen piezo-
meters located in the saturated water zone in the
landfill. Soluble mercury readings ranged from
non-detectable values to 40 ug/1, with the bulk of
the readings ranging from 3.9 ug/1 to 11 ug/1.
Out of 14 samples taken, 13 contravened the Drinking
Water Standard.
3) Contiguous to the saturated water zone of the land-
fill is a semi-confined aquifer of alluvial deposits.
Water samples were taken from piezometers located
in the alluvial deposits aquifer. Soluble mercury
readings ranged from non-detectable to 35 ug/1.
These data are believed to indicate that leachate
from the landfill has migrated to this zone.
The Newco Solid Waste Management Facilities, Niagara
Falls, New York (5,6)
At this disposal site, Olin is currently disposing
of brine sludges emanating from its mercury chlor-alkali
process. (This site has been used as a waste disposal
area for over 80 years.) An evaluation was performed of
the presence, movement, and quality of groundwater at
this facility, and the data were incorporated in a
Draft Environmental Impact Statement for the State of
-12-
-------
New York.(5/6) Elevated levels of mercury (6.6 ug/1)
have been found in the leachate of mercury-contaminated
sludges that have been disposed of in the landfill.
In another damage incidental®' (involving an inactive
chloralkali facility not otherwise identified in the
literature), leaching of mercury from the solid wastes
from the facility caused elevated levels of mercury in
downstream water, suspended matter, and bottom sediment.
About 39 kg of morcury are lost to water from this
unlined lagoon each year. Concentration of mercury in
water and suspended matter immediately downstream from
the plant site are about 20 times higher than immediately
upstream. The silt-clay fraction of bottom sediment
immediately downstream of the plant site contains up to
200 times as much mercury as the similar sediments collected
immediately upstream from this facility.(16)
Contamination of Surface Water from an Alkali Processing
Plant in Saltville, Virginia(21> :
In another damage incident involving the Clin
Corporation, an alkali processing plant generating the wastes
listed in this document (and other industrial waste) disposed
of these wastes in a series of lagoons located on the North
Fork of the Huston River in Saltville, Virginia. Although
the site (presently owned by Olin) ceased operating in 1972,
wastes continue to leach from the disposal lagoons. Mercury
-13-
-------
continues to enter the Holston River both from the site of
the chlorine plant and from disposal lagoons used for disposal
of chlorine production wastes. The grounds where the cell
building once stood are estimated to contain some 220,000
Ibs. of mercury. Cleanup costs are estimated at $32-$40
million.
The incidents described, as stated, demonstrate that
mercury will migrate from this waste in harmful concentrations
and reach environmental receptors causing substantial harm
unless proper management is assured.
There are also other factors which warrant listing these
wastes as hazardous. Transportation of these wastes to off-site
disposal facilities, a management practice utilized by several
manufacturers, increases the likelihood of mismanagement of
these hazardous wastes, for example, due to improper handling
during transport, or failure to reach the intended destination.
A transport manifest system, combined with designated standards
for the management of these wastes will greatly reduce their
availability to do harm to human beings and the environment.
The quantity of these wastes generated is an additional
factor of concern. As indicated above, these wastes are gene-
rated in large quantities (42,000 kkg of waste per year,
containing 700 kkg of mercury). Under improper disposal conditions,
large amounts of mercury are thus available for environmental
release. The large quantities of this contaminant poses the
danger of polluting large areas of ground and surface waters.
-14-
-------
Contamination will also occur over long periods of time,
since elemental mercury persist indefinitely. Since large
amounts of pollutants are available for environmental loading,
the attenuative capacity of the environment surrounding the
disposal facility could also be reduced or used up due to the
large quantities of pollutants available. All of these con-
siderations increase the possibility of environmental exposure
to the harmful constituents in the wastes.
B. Health and Ecological Effects
The various forms of mercury are interconvertible under
most environmental conditions. They are toxic to a wide
variety of organisms, including man, (^) an(j are known to
accumulate in biological organisms.(^) In humans, mercurials
have been associated with neurological disorders, sensory
impairment and tremors. Prenatal exposure can result in
impaired brain development and psychomotor disorders.
Organic mercury compounds inhibit fertility, and are more
toxic than inorganic forms; 0.1 ug mercury/1 is toxic to fresh-
water crayfish.(17) Mercury is bioconcentrated 63,000-fold
in fathead minnows foraging under laboratory conditions
resembling those in the field.(18) EPA estimates 200
ug/day as the acceptable daily intake and, in 1973, recommended
2 ug/1 as a drinking water standard (19); in 1979 a ten-fold
reduction was further recommended (2°). EPA has also recommended
•>•
fresh water criteria as follows: 0.064 ug/1 for inorganic
mercury and 0.016 ug/1 for methyl mercury t19). Additional
-15-
-------
information on the adverse effects of mercury on human health
and the environment are documented in Appendix A.
-16-
-------
REFERENCES
1. Versar Inc./ June 13, 1979. Assessment of Solid Waste
Management Problems and Practices in the Inorganic
Chemicals Industry. Final Report. Contract Number
68-03-2604, Task 2, prepared for U.S. Environmental
Protection Agency, Industrial Research Laboratory,
Cincinnati, Ohio 45268, p. 85.
2. SRI International, Directory of Chemical Producers,
Menlo Park, California. 1979
3. Currey, J.E., Pumpkin, G.G., 1978. Chlor-alkali.
Encyclopedia of Chemical Processing and Design, J.J.
Mcketta, ed., John Wiley and Sons, New York, N.Y.,
Vol. 7, pp. 304 - 450.
4. RSCRA Research Inc. and WEHRAN Engineering Corporation,
May 18, 1979. Hydrogeological Investigation: OLIN 102nd
Street Landfill, Niagara Falls, Niagara County, New
York. Prepared for Olin Chemical Corporation.
5. Roy F. Weston, Inc., July 25, 1978. Hydrogeologic
Investigation of the Newco-Niagara Recycling Site,
Niagara Falls, New York.
6. Ecological Analysis Inc., April 1979. Draft Environmental
Impact Statement - Newco Solid Waste Management Facilities,
Niagara Falls, New York, prepared for New York State
Department of Environmental Conservation, 584 Delaware
Avenue, Buffalo, New York 14202.
?. U.S. Environmental Protection Agency. 1978. Draft Water
Quality Criteria Document Mercury. p. 16.
"3» Ib i d. p • 1 9 .
9 N.A.S. 1978. An Assessment of Mercury in the Environment.
10. U.S. Environmental Protection Agency. 1977. Federal Guide-
lines; State and Local Pretreatment Programs. EPA 430/9-
76-017a. PB 266 781
1 .. Versar, Inc.,October 1979. Assessment of Solid Waste
Management Problems and Practices in the Inorganic
Chemicals Industry. Final Report, contract no.68-03-2604,
prepared for U.S. EPA, Office of Solid Waste (SW-180c)
-17-
-------
12. Versar, Inc., October 1979 Multi-media Assessment of
the Inorganic chemicals Industry/ Draft Final Report.
Contract number 68-03-2604, Task * . Prepared for U.S.
EPA, Industrial Research Laboratory, Cincinnati, Ohio
45268, volume III.
13. Versar, Inc., June 1977. Alternatives for Hazardous
Waste Management in the Inorganic Chemicals Industry,
Final Report. Contract No. 68-01-4190. Prepared for
U.S. EPA Office of Solid Waste, Hazardous Waste Management
Division.
14. Versar, Inc, 1975 Assessment of Industrial Hazardous
Waste Practices, Inorganic Chemicals Industry. Contract
number 68-01-2246, prepared for U.S. EPA Office of
Solid Waste Management Programs (SW-104c).
15. Nelson, N. 1971. Hazards of mercury. Env. Res.
16. Turner, R.R. and Lindberg, S.E. 1978. Behavior and
Transport of Mercury in River - Reservoir System Downstream
of Inactive Chloralkali - Plant. Envir. Sci. and Technol.
12(8)918-923.
/
17. K.E.Beisinger and G.M. Christensen, 1972. Effects of
various metals on survival, growth, reproduction and
metabolism of Daphnia Magna . J.Fish. Rev. Board Can.
29: 1691.
18. G.F. Olsen, et.al., 1975. Mercury residues in fathead
minnows, Pimephales promelas Rafinesque, chronically
exposed to methylmercury in water. Bull . _ Environ .
Contamin Toxicol .14:129.
19. U.S. EPA 1973. Water Quality Criteria, 1972. Ecol.
Res. Ser. Rep. Comm. on Water Quality Criteria,
Natl. Acad'.- Sci. EPA/R3/73/033. U.S. Government
Printing Office, Washington. D.C.
20. U.S. EPA 1979, Mercury: Ambient Water Quality
Criteria (draft).
21. U.S. EPA 1980, Damages and Threats Causes by Hazardous
Material Sites, EPA/430/4-80/004.
-18-
-------
22. Draft Development Document. Effluent Limitations
Guidelines (BATEA), New Source Performance Standards
and Pretreatment Standards for the Inorganic Chemicals
Manufacturing Point Source Category Contract No.
68-01-4492 April, 1979.
23. Personal communication, June 23, 1980. E. Risman, Versar
Inc., to J.S. Bellin, EPA.
-19-
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CHLORINATED HYDROCARBON WASTE FROM THE PURIFICATION STEP
OF THE DIAPHRAGM CELL PROCESS USING GRAPHITE ANODES IN
CHLORINE PRODUCTION (T)
I. SUMMARY OF BASIS FOR LISTING
Chlorinated hydrocarbons are generated during production
of chlorine in diaphragm cells with graphite anodes.
Purification results in separation of the chlorinated
hydrocarbon waste from the product. The Administrator has
determined that this waste is a solid waste which may pose a
substantial hazard to human health and the environment when
improperly transported, treated, stored, disposed of or
otherwise managed, and which therefore should be subject to
appropriate management requirements under Subtitle C of RCRA.
This conclusion is based on the following considerations:
1. The waste contains significant concentrations of the
toxic compounds chloroform, carbon tetrachloride,
hexachloroethane, trichloroethane, tetrachloroethylene,
dichloroethylene, and 1,1,2,2-tetrachloroethane. The
Agency's Carcinogenic Assessment Group has found that
chloroform, carbon tetrachloride, tetrachloroethylene
and 1,1,2,2-tetrachloroethane exhibit substantial
evidence of carcinogenicity.
2. Typical management practices include deep well injection
and incineration. Landfilling has also been employed as
a disposal method. If these practices are unregulated,
hazardous substances could be released to the environ-
-------
merit. Improper construction or operation of a deep
well could cause leakage of the waste from the well
into usable aquifers; Inadequate Incineration can result
In the generation of highly toxic combustion products
such as phosgene. Uncontrolled landfilling may result
in migration of hazardous substances to air and ground
and surface waters.
3. Most of these compounds have significant migratory
potential and have proven mobile and persistent in
actual damage incidents caused by imp roper waste
a.
managment•
II. SOURCES OF WASTE AND TYPICAL DISPOSAL PRACTICES
A. Industry Profile
Chlorine is produced by electrolysis of brine. It
is used in the pulp anij paper industry, plastics, water
treatment and r-.nufacture of organic and inorganic chemicals.
About 75 percent of all chlorine manufactured in the United
States is produced by the diaphragm cell process, (i) Approxi-
mately 32 plants use diaphragm cells; of these, six plants
that utilize graphite anodes generate chlorinated hydrocarbon
contaminants.*^) Locations and production capacities of the
six are given in Table 1.(2)
B . .Manufacturing Process^ ^ » 3 )
Brine is purified by precipitation of metals before
being sent to the diaphragm cell. Separation of solids during
*Graphite anodes predominated in the past, but in recent
years most plants have replaced them with metal anodes.
-------
Table 1
FACILITIES GENERATING CHLORINATED HYDROCARBON BEARING WASTES
PLANT/LOCATION
ICI Americas
Baton Rouge, LA
Dow Chemical
Midland, Mich.
Vulcan Materials
Denver City, Tex.
Champion Production
Canton, N.C.
Pasedena, Tex
PGG Industries
Barberton, Ohio
PRODUCTION
CAPACITY
103 KKG/YR
156
256
121
26
20
100
-3-
-------
purification generates waste brine muds; the Agency has no
data at this time to indicate that the brine muds are hazardous(
The purified brine is heated, brought to saturation by the
addition of salt and acidified. The saturated salt solution
is then electrolyzed in the diaphragm cell to form chlorine,
hydrogen and sodium hydroxide. Chlorine is liberated at the
anode, and hydrogen and sodium hydroxide are produced at the.
cathode. Reaction of chlorine with carbonaceous materials
in the graphite anode results in the presence of chlorinated
hydrocarbon contaminants in the chlorine product.
The hydrogen is purified and either sold, vented to the
atmosphere or burned. The salt solution, which has been
decomposed to approximately half its original concentration,
is partially evaporated to increase the sodium hydroxide
concentration. During evaporation, most of the sodium chloride
precipitates from the solution and is recovered in salt
separators. After filtration and washing, the salt is recycled
to initial brine preparation.
Chlorine is recovered from the cell and cooled to remove
water and other impurities. The condensates are discharged
or recycled to the brine purifier. After cooling, the chlorine
gas is scrubbed with acid to remove residual water vapor.
The gas is then compressed and cooled to -30°C to -45°C. At
these temperatures the chlorine liquefies and is pumped to
steel storage tanks. Some further purification is performed
during the cooling and liquefaction process. The chlorinated
hydrocarbon waste of concern is liquefied from the chlorine
-4-
-------
gas stream during purification. Figure 1 illustrates the
process.
The Agency is concerned that wastewaters from clean-out
of the diaphragm cell and from caustic evaporation and salt
recovery operations and sludges resulting from treatment of
these wastewaters may also be hazardous because they contain
significant amounts of lead. The Agency currently does not
have sufficient information on the concentrations and the
migratory potential of the lead in these wastes, but they may
be listed as hazardous at some time in the future. Generators,
however, must determine whether this waste is hazardous pursuant
to §262.11 of the Subtitle C regulations.
C. Waste Generation and Management (4)
As mentioned previously, chlorinated hydrocarbon
contaminants arise primarily from the reaction of chlorine
with carbonaceous materials in the graphite anode. Reaction
of chlorine with oils and greases in the equipment and other
hydrocarbons present in the system also contributes slightly
to the generation of these contaminants. The chlorinated
hydrocarbon contaminants are liquified from the chlorine gas
stream during purification in amounts up to 1 kg per kkg of
chlorine product.
Management practices vary. Vulcan Materials Co.
disposes of the chlorinated hydrocarbon waste by deep well
injection^ and ICI Americas Ltd. incinerates its
-5-
-------
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Champion International Corp. and PPG Industries, Inc., which
landfilled part of their wastes in sealed drums prior to
1977, apparently do not remove the chlorinated hydrocarbon
contaminants from the chlorine product at this time. Dow
Chemical's management practices are not known.
III. DISCUSSION OF BASIS FOR LISTING
A. Hazards Pose by the Waste
The constituents of the chlorinated hydrocarbon
waste include the following (1):
Compound Identified Weight (%)
chloroform 73.7
carbon tetrachloride 10.8
hexachloroethane 8.0
pentachloroethane 1.3
trichloroethane 1.0
tetrachloroethylene 0.6
dichloroethylene 0.3
1,1,2,2-tetrachloroethane 0.5
Clearly, the waste contains substantial amounts of organic
compounds believed to be toxic and carcinogenic. Thus, in
light of these constituents' high migratory potential and
their ability to persist in the environment, improper
management of this waste is likely to lead to substantial
hazard.
Many of the constituents of concern have high vapor
pressures and thus could pose a substantial hazard to human
health and the environment via an air exposure pathyway if
the waste is improperly managed. Evidence available to
-7-
-------
EPA's Carcinogen Assessment Group indicates that chloroform,
carbon tetrachloride, a trichloroethane isomer, tetrachloro-
ethylene, and 1,1,2,2-tetrachloroethane are carcinogenic. The
A
Agency believes that the severity of'the adverse health effects
associated with exposure to these constituents provides a
sound basis for listing the waste as hazardous. The high
concentration of chloroform alone justifies the listing of
this waste as hazardous, in the Agency's judgment. EPA's
decision to list the waste is supported further by case
histories which reveal that the hazardous constituents can
migrate and persist in the environment.
Carbon tetrachloride, a major component of the waste,
has been identified in school and basement air in the vicinity
of Love Canal (8) and has been implicated in groundwater
contamination incidents in Plainfield, Connecticut, where
drinking water sourc -s were adversely affected (9).
Chloroform h^s been found in drinking water wells near a
Jackson Township, New Jersey landfill in which chemical wastes
were dumped- ..and is known to have migrated from the Love Canal
disposal site (10). Hexachloroethane, another major constituent
of the waste of concern, has also migrated from at least
one chemical waste disposal site (Table 7.2, Ref. 9). In
addition, damage incidents compiled by EPA reveal numerous
instances of environmental contamination due to migration
of trichloroethane and tetrachloroe thylene . (^-® )
-8-
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An estimated 75 kkg of waste per year is disposed of
in deep wells or by incineration* (2); either method may
unfavorably affect human health and the environment by con-
taminating ground and surface waters'or polluting the atmosphere
A deep well injection system that is not properly designed
or operated can release hazardous constituents from the well
to aquifers used as drinking water sources. Improper inciner-
ation of chlorinated hydrocarbons can result in the generation
and emission of highly toxic combustion products such as
phosgene (5,6,7).
Landfilling of drummed waste has been practiced in the
past. This disposal method presents obvious hazards; drums
are likely to corrode in the landfill and release the waste
to the surrounding area. Waste contituents could then
volatilize and enter the atmosphere or migrate to ground and
surface waters.
Health and Environmental Effects (From App. A unless
otherwise noted.)
Chloroform
Chloroform has been identified by the EPA Carcinogen
Assessment Group as exhibiting substantial evidence of being
carcinogenic. Due to its highly volatile nature, (App. B),
improper disposal of chloroform-containing wastes may pose
an air pollution hazard. Long range exposures have caused
*This number was derived by multiplying 90% of the plant
nameplate capacity by 0.5, on the assumption that, on
average, 0.5 kg of chlorinated hydrocarbon wastes are
generated per kkg of chlorine.
-9-
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both physical and neurological disorders in humans, with
liver and kidney toxic responses representing the most pre-
valent physical pathology. FDA prohibits the use of chloroform
in drugs, cosmetics or food contact material. . Additional
information on this substance can be found in Appendix A.
Carbon Tetrachloride
Carbon tetrachloride (tetrachloromethane) has been
identified by EPA's Carcinogen Assessment Group as exhibiting
substantial evidence of being carcinogenic. Its toxic effects
include neurological damage and damage to the kidney and
lungs. It is volatile and highly soluble in water and is
therefore expected to migrate readily in the environment (11).
Additional information on carbon tetrachloride can be found
in Appendix A.
Hexachloroethane
Hexachloroethane is moderately toxic to humans and is
one of the more toxic chlorinated ethanes to aquatic species.
It appears to have the potential to bioaccumulate (App. B).
Humans expos.ed to hexachloroethane may suffer central nervous
system depression and liver, kidney and heart degeneration.
It has also been shown to be carcinogenic to laboratory
animals. Little information is available on its environmental
fate and transport, but, due to the nature of the adverse
affects associated with exposure to this compound, the Agency
believes that improper disposal of a waste containing a
-10-
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significant amount of hexachloroethane may pose a hazard to
human health and the environment. Additional information on
hexachloroethane can be found in Appendix A.
Trichloroethane
The trichloroethanes (1,1,1-trichloroethane and 1,1,2-
trichloroethane) are toxic to humans, animals and aquatic
organisms and have been shown to be carcinogenic in laboratory
animals. Due to the toxic and carcinogenic effects of these
compounds, the Agency believes that improper management of
wastes which contain them may pose a hazard to human health
and the environment. Additional information on trichloroethanes
may be found in Appendix A.
Dichloroethylenes
Exposure to dichloroethylenes can result in adverse human
health effects. The three isomers appear to have similar
toxic effects, including depression of the central nervous
system and liver and kidney damage (App. A). Two isomers
are mutagenic in bacterial sytems and one isomer has been
shown to be carcinogenic in laboratory animals (App.A).
Information on environmental fate and transport is scarce
but, due to the nature of the health effects resulting from
exposure to dichloroethylenes, the Agency has determined
that improper management of wastes containing these compounds
\
poses a hazard to human health and the enviroment. Additional
information on dichloroethylenes can be found in Appendix A.
-11-
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Tetrachloroethylene
Tetrachloroethylene has been identified by EPA's Carcinogen
Assessment Group as exhibiting substantial evidence of being
carcinogenic. It is also toxic to aquatic species, and
repeated exposure is implicated in mammalian liver and kidney
damage (App.A). Little information is available concerning
environmental fate and transport processes. Additional
information on tetrachloroethylene is given in Appendix A.
1,1, 2,2-Tetrachloroethane
1,1,2,2-tetrachloroethane has been identified by EPA's
Carcinogen Assessment Group as exhibiting substantial evidence
of being carcinogenic. Occupational exposure has produced
neurological symptoms, liver and kidney damage, pulmonary
edema and fatty degeneration of heart muscle. 1,1,2,2-
tetrachloride is highly soluble in water (2900 ppra) and thus
has high migratory potential (11). Although environmental
fate and transport processes are not well-defined (microbial
degradation appears to be the only known degredation mechanism
(App. B), and this process is not likely to occur under the
abiotic conditions prevailing in most aquifiers), the Agency
believes that, due to the severity of the health effects
associated with exposure to this compound, improper disposal
of the wastes in which it is contained poses a substantial
«.
hazard. See Appendix A for additional information.
-12-
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The waste also contains a significant amount of pentachloro-
ethane, a toxic chlorinated organic. At this time the Agency
has not compiled data on specific health effects or environmental
persistence and mobility; when the data are obtained, a
document will be prepared for Appendix A.
-13-
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1. USEPA Industrial Environmental Research Laboraory.
Draft Final Report-Multimedia Assessments of the
Inorganic Chemical Industry, Vol. III. Prepared
by Versar, Inc. Contract No. 68-03-2604. October 1,
1979.
2. Versar, Inc. Written communication to J. Bellin, USEPA
June 3, 1980.
3. USEPA, Effluent Guidelines Division. Draft Development
Document. Effluent Limitations Guidelines (BATEA),
New Source Performance Standards and Pretreatment
Standards for the Inorganic Chemicals Manufacturing
Point Source Category, Contract No. 68-01-4492.
April, 1979.
4. Draft Background Document - Chlorinated Hydrocarbon
Bearing Wastes from the Diaphragm Cell Process
in Chlorine Production. Prepared by Versar, Inc.
for USEPA, Office of Water Planning and Standards.
May 21, 1980. Contract No. 68-01-5948 Task 2.
5. "Combustion Formation and Emission of Trace Species",
John B. Edwards, Ann Arbor Science, 1977.
6. NIOSH Criteria for Recommended Standard: Occupational
Exposure to Phosgene, HEW, PHS, COG, NIOSH. 1976.
7. Chemical and Process Technology Encyclopedia, McGraw
Hill, 1974".
8. New York State Departement of Health. 1978. "Love Canal,
Public Health Bomb", a Special Report to the Governor
and Legislature.
9. Acurex Corp., 1980, "Chlorinated Hydrocarbon Manufacture:
An Overview." Draft Report
10. USEPA. "Oil and Special Materials Control Division. Damages
and Threats Caused by Hazardous Material Sites. EPA/
430/9-80/004. January, 1980.
11. Verschueren, K. Handbook of Environmental Data on Organic
Chemicals, Van Nostrand Reinhold, 1977.
-14-
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LISTING BACKGROUND DOCUMENT
TITANIUM DIOXIDE PRODUCTION
Wastewater Treatment Sludge From the Production of
Titanium Dioxide Pigment Using Chromium Bearing Ores
by the Chloride Process (T)
Summary of Basis for Listing
s
Process wastewaters from the production of titanium
dioxide (Ti02) by the chloride process contain oxides
and chlorides of chromium and other metals that are present
in the ore as contaminants. Treatment of these wastewaters
prior to discharge generates a sludge that is usually dis-
carded. The Administrator has determined that this wastewater
treatment sludge 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
w
be subject to appropriate management requirements under Sub-
title C of RCRA. This conclusion is based on the following
considerations:
1. The waste contains significant quantities and concen-
trations of the toxic heavy metal chromium. It is
estimated that raore than 600 kkg of chromium are
contained in the 800,000 kkg of these water treatment
sludges produced each year, and that chromium concen-
tratons in the sludge range from 500-12,000 ppm.
2. Chromium is capable of migrating from the waste if
improper management occurs, and may be highly mobile
upon release. Improper disposal of this waste thus
may result in the release and migration of the chromium
which may then contaminate ground or surface waters.
3. Five of the eight plants generating this waste
currently dispose of their wastes in uncontrolled
landfills '!)-, thus posing a realistic possibility
of migration of chromium to underground drinking
-------
water sources. Further, chromium persists virtually
indefinitely so that the danger of contamination
is long-term should migration occur.
4. Very large quantities of this waste (800,000 kkg)
are generated annually and are available for disposal
as solid waste. There is thus greater likelihood of
large scale contamination of the environment if the
waste is not properly managed.
II. Sources of Waste and Typical Disposal Practices
A. Industry Profile
Ti02 is a high volume chemical, ranking in the first
fifty of U.S. chemicals production. More than fifty percent of
the Ti02 produced is used in paints, varnishes and lacquers.
About one-third is used in the paper and plastics industries.
Other uses are found in the manufacturing of ceramics, ink
and rubber. About 610,000 kkg were produced in 1972.(2)
It is manufactured by either the sulfate or chloride process;
the latter accounts for 65% of production capacity (see
Table 1). This document discusses the wastes generated by
the chloride process, wastewater treatment sludge being the
waste of concern.
The chloride process uses rutile or upgraded ilraenite
ores as raw materials. The chromium content of these ores
varies considerably. Australian rutile typically contains
0.19% chromium oxide (6,7) and those ilraenite ores used in
U.S. Ti02 production (New York, Florida and Canadian ores)
contain up to 0.15% chromiura oxide.(6,7) However, the ores
have been reported to contain as much as 4.0% chromium.(*5)
-2-
-------
Table 1 TITANIUM DIOXIDE PRODUCERS (CHLORIDE PROCESS)^1)
Manufacturer
Location
Capacity
kkg/yr
E.I. DuPont de
Nemours Co., Inc
Kerr-McGee Corp.
SCM Corporation
Glidden-Durkee
Division
New Jersey Zinc
American Cyanamid
Antioch, California 27,200
New Johnsonville,
Tennessee 207,000
Edgemoor, Delaware 99,000
Hamilton, Mississippi 45,000
Baltimore, Maryland 26,300
Ashtabula, Ohio 24,500
Ashtabula, Ohio 27,200
Savannah, Georgia 36,400
Total 492,600
-3-
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B. Manufacturing Process (1»8) (see Figure 1 for Flow Chart)
In the manufacturing process, the raw ore is first
dried. Dried ore, dried coke and gaseous chlorine are then
charged to a heated continuous fluidlzed bed chlorination
reactor, converting the titanium oxide in the ore to titanium
tetrachloride by the following reaction:
800-1000°C
3C + 2T102 + 4C12 > 2TiCl4 + C02 + 2CO
The gases leaving the chlorinator consist of titanium tetra-
chloride, unreacted chlorine, carbon dioxide, carbon monoxide
and volatile heavy metal chlorides generated by the reaction
of chlorine with metallic impurities in the ore. These
gases are subjected to a purification step involving cooling,
condensation, and separation of the heavy metal impurities,
specifically the chlorides of vanadium, zirconium, chromium
and other trace heavy metals, silicon, and titanium. This
process stream is labeled "A" in Figure 1.
This purification step is of special importance for
purpose of this document, because it is the point in the
process where chromium enters the solid waste stream. More
importantly, virtually all of the chromium impurities in the
raw ore are removed at this point in the process and, as
explained below, are therefore likely to be present in the
wastewater treatment sludge. The residual uncondensed gases
consisting of unreacted chlorine, hydrochloric acid, traces
-4-
-------
JLCI conca«c or various was t^ s 1 1 cams £s composite
supplied by industry plants, based on 1974 production,
verified on a follow-up basis for accuracy through 1977;
(iACa j.or S
Information
and
'"'the quantity of chromium
is approximately the
in waste streatn A (as chromium chloride)
same regardless of orejtype, due to the
different quantities of each ore type requir/e.d to produce the
same quantity of product, and the differing percentages of chromium
(as chromium oxide) in each type of ore
1
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tlWA
JALIXA1ION AND 5EIILIHO
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' Rolldo from W.nabowaLer Trentnt3nt, 'to Landfill
FIGURE 1
TIlTtfttlM DIOX1DF! MWIJP/CTUHE
nv "nie airoium? rnocESS USINO m/ritE ORE on ILUKNITE one* *
WSCI
IARCC
NOTE: figures in parentheses are for. ilmenite ores
-5-
-------
of phosgene, carbon monoxide, carbon dioxide, titanium
tetrachloride and nitrogen pass to the scrubber (stream B,
Figure 1), where they are scrubbed (cleaned) by a two-step
process. The waste resulting from this process is labelled
"D" in Figure 1.
This stream (D) is not reported to contain chromium,
this element having been removed by the purification ste.p.
The Agency believes, however, that trace amounts of chromium
are present in this stream, but (as stated below) since this
stream is combined with stream A prior to sludge generation,
the fact is not of regulatory significance.
The remaining reactor condensate (stream C, Figure 1)
is purified, vaporized and reacted in special burners with
oxygen (or air) to form the product titanium dioxide:
02 ---- > Ti02 + 2C12
The resulting gas-solid mixture is cooled to near ambient
temperature, and the solid titanium dioxide is separated from
the eas phase by proprietary dry collection methods. The re-
sidual gas stream is further cooled to recover chlorine,
which is recycled to the chlorinator. The tail gases are
released to the atmosphere after chlorine recovery is completed.
*_lThere is a product washing step (labelled 'treatment' in Fig.
1) which deacidifies the,product. A separate waste stream
is generated at this point, which is not believed to be
hazardous, and further is believed to contain only
insignificant amounts of chromium.
-6-
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C. Waste Generation
"The waterborne waste streams A and D are typically
combined (equalized) and neutralized, then lagooned to settle
the suspended solids prior to effluent discharge.'"' The
resulting sludge (E in Figure 1) is the waste of concern in
this document. Chromium is the wastp "onstituent of concern.
Chromium is present in the process wastewater mostly as the
chloride (some unreacted 0^03 is also present), both pre-
dominantly as the trivalent species. When the wastewater
is neutralized, chromium hydroxide is formed. Unreacted
chromium chloride is expected to be entrained by the hydroxide
precipitate. The relative concentrations of the two chromium
compounds will depend in part on the efficiency of the neutra-
lization step.
The Agency believes chromium concentrations in the waste
:o be substantial. Estimated chromium concentrations for
sludges from processes using rutile and ilmenite ores are
presented in Table 2 below, and indicate that elemental
chromium concentrations in the treatment sludge are signi-
ficant: approximately 12,000 ppm when rutile ore is the
feed material, and approximately 500 ppm when ilmenite ore is
used. These are derived figures, and the full basis for the
derivation-is set out in Appendix 1. The assumptions made
for this derivation are as follows:
—The chromium oxide content of the feed ores are 0.15%
for ilmenite ores, based on typical values (see p. 3 above).
-7-
-------
Since significantly higher chromium concentrations have
been reported (ld_.), this is believed to be a conservative
assumption.
—Virtually all of the chromium in the ore will be
removed during the process purification step. This
assumption is somewhat agressive, but is believed to be
realistic, since the purification step is designed to
remove heavy metal impurities, and moreover, available
sampling data (1, as presented in Fig. 1) indicates all
chromium being removed at this point in the process.
Although small amounts of chromium may remain in the
product, or are removed in the product washing step of
the process, these amounts are believed to be insubstantial,
and not of regulatory significance.
--All of the chromium present in the process wastewater
(combined streams A and D in Fig. 1) will precipitate
and will therefore be present in the wastewater treatment
sludge. This assumption is also somewhat aggressive,
since some traces of chromium may be discharged in the
effluent. The overwhelming percentage, however, will
not be so discharged (because of the relative insolubility
of chromium hydroxide). Since elemental chromium is
non-degradable, it will persist in the treatment sludge
and in leachates therefrom.
-8-
-------
Using these assumptions, chromium concentrations in the
treatment sludge are derivable by first determining the
respective total Ti02 production from ilmenite and rutile
ores, by determining the quantity of each ore required to
generate this amount of product, determining the quantity of
chromium oxide in this amount of ore and by converting this
value into chromium (since virtually all chromium in the ore
is assumed to be present in the wastewater treatment sludge).
Total potential waste loadings are quite substantial.
It is estimated that rutile ores generate approximately
0.055 kkg of waste per kkg of product whereas ilmenite ores '
generate between 2.23 and 3.40 kkg of waste per kkg of product
(1,7). As shown in Table 2, the total quantity of wastewater
treatment sludge generated from this process is estimated to
contain over 600 kkg of chromium. Another report (8) estima.ds
the generation of 1.4 kkg chromium per 10^ kkg of product re-
sulting'in a similar figure for total chromium in the waste.
D. Waste Management
Current practices in this industry for the management
of this waste are as follows:(1)
0 One plant disposes of the waste on-site in lined la-
goons (with monitoring).
0 One plant disposes of most of the waste by deep well
injection (with monitoring).
0 Two plants transport the waste off-site to a common
unlined landfill (no monitoring).(7)
-9- ..
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Table 2
QUANTITY OF WASTEWATER TREATMENT SLUDGE GENERATED BY THE TITANIUM DIOXIDE CHLORIDE
PROCESS AND CHROMIUM CONTENT OF THE WASTEWATER TREATMENT SLUDGE
Number
State Plants
California 1
Delawar_- 1
Georgia 1
Maryland 1
Mississippi 1
Ohio 2
Tennessee 1
Totals 8
of Capacity
kkg/yr
27,
99,
36,
26,
45,
51,
207,
492,
200
000
400
300
000
700
000
600
Sludges Generated (Dry basis
Chromium
O) in Sludge
Ore Used (kkg/yr)(x) (dry basis)%*
Rutile 1,500 1.23
Ilmenite 337,000** 0.051
Rutile 2,000 1.23
Rutile 1,800 1.23
Rutile 2,500 1.23
Rutile 9,700 1.23
Ilmenite 461,000 0.051
815,500
)(7)
Total Chromium in
Wastewater Treat-
ment Sludge (Dry)
(kkg/yr)
18
171
24
22
30
116
235
616
* See Appendix I for calculations.
** Of this quantity, up to 150,000 kkg per year is sold as FeCl3
-10-
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8 One plant transports the waste off-site to an unlined
landfill.
0 Two plants combine the chloride process wastewater
with that from ticanium dioxide sulfate process
operations. One plant neutralizes this combined
wastewater prior to discharge and disposes of the
solids in an on-sice landfill. The other facility
neutralizes only part of its wastewater and uses
•
contractors to transport the formed solids off-site
to a landfill.
0 One plant sells a portion of its waste as ferric chlor-
ide (as much as .150,000 kkg per year) and disposes
I/
of the remainder by ocean barging.
III. Discussion Basis for Listing
A. Hazards Posed by the Waste
As shown above, chromium may be present in this
waste in substantial conrontrations, from roughly 500-12,000
ppm. Chromium is presen.. in the wastewater treatment sludge
primarily as the t rdvalen-.. sps ies, principally the hydroxide
and also as the chloride. D..pending on the presence of
other metal ions, and the acidity or alkalinity of the specific
* / U n" d e r §261.6 (which ap-'ies to sludges which fail 2
characteristic, as well as to listed wastes) this reused
hazardous waste is sub;ect to the requirements of Subtitle
C up to the point of ar-tual reuse. (See also 45 Fed. Reg.
at 33092-094 (May 19, 1"TO) for a more detailed explanation
of the current regulator, regime for reused hazardous wastes).
-11-
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environment, oxidation to higher valence states will occur.
Thus, these wastes may, after storage or disposal, contain
chromium generally in the most .stable tri- and hexavalent
states. Both forms of chromium are*toxic, though hexavalent
-I
chromium is more toxic and is an animal carcinogen.(^)
Section III B of this document discusses more fully the
health and ecological effects of chromium.
The chromium components of this waste are capable of
migration, mobility and persistence. Neutralization of the
TiC>2 wastewater stream results in the precipitation of chromium
as the hydroxide. Chromium hydroxide has limited migratory
potential due to its low solubility (see Water Related Environmental
Fate of 129 Priority Pollutants, supra, Vol. 1, Ch. 10).
However, chromium was shown to be extractable f.rom. an electro-
plating wastewater treatment sludge (in which chromium is
present in the hydroxide form). Chromium leached from waste
samples subjected to the proposed extraction procedure in
concentrations as high as AOO mg/1, demonstrating ability to
migrate in .relatively mild acidic environments. (see listing
background document, "Electroplating and Metal Finishing
Operations . ")
See EP Toxicity Background Document at pp. 109-112 summarizing
data showing that trivalent chromium is likely to oxidize v
to the more dangerous hexavalent chromium upon environmental
release, even in mild environmental conditions. Thus,
exposure to hexavalent chromium is possible even if chromium
migrates in the trivalent state. To the same effect,
see Water-Related Environmental Fate of 129 Priority
Pollutants, Vol. 1, U.S. EPA 1979, Ch. 10, at 10-3.
-12-
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In addition, chromium .was shown to be extractable from a
neutralized spent pickle liquor sludge sample (in which
chromium is present in the hydroxide form), in concentrations
(429 ppm) sufficient to create substantial hazard (18)
*y
(see listing background document "Steel Finishing").
Thus chromium, even when present as the relatively insoluble
hydroxide, is capable of migrating from neutralized sludges.
An acidic environment can reasonably be expected to occur in
the waste management practices for titanium dioxide wastewater
treatment sl;udges. Such an environment could result from
inadequate neutralization of the acidic waste stream, from
co-disposal of neutralized sludges with acidic wastes, or as
a consequence of disposal in areas subject to rainfall.
Seven of the eight Ti02 facilities are located east of the
Mississippi, in areas where rainfall is becoming more acidic.(4
An additional consideration is the probable presence in
the waste of chromium as the chloride. It is expected to be
entrained by the precipitated chromium hydroxide, and may,
in fact, be present in high concentration if the wastewater
is not efficiently or adequately -neutralizr d.. Chromium chloride
is extremely soluble (430,000 mg/1), and thus has very
high migratory potential.(16)
*pH and test conditions unknown
-13-
-------
Improper management of this wastewater treatment sludge
may consequently result In ground- and surface water contami-
nation. Sludges accumulate in the bottom of wastewater
treatment lagoons and remain there until dredging and final
disposal. Chromium could leach out and contaminate groundwater
if lagoons are unlined or lack adequate leachate collection
systems; moreover, as shown on p.11 supra, few facilities use
liners or collection devices in managing this waste. In
addition, migratory potential of the waste would increase
under acidic conditions. The solubilities of the different
species of chromium differ but in general increase with
acidity.(3) Thus, though chromium has the ability to
migrate under mild conditions, its ability to do so increases
significantly with a decrease in pH. Accordingly, if the
wastewater -- which, as Figure 1 illustrates, contains significant
concentrations of HC1 — is poorly neutralized, the soluble
chromium constituents in the waste are likely to remain in
solution or be entrained in the precipitated sludges, resulting
in increased migratory potential of chromium ions.
There is also a danger of migration into and contamination
of surface waters if lagoons are improperly designed or
managed. Thus, inadequate flood control measures could result
in washout .or overflow of ponded wastes.
As previously stated, five of the eight facilites which
produce titanium dioxide via the chloride process ultimately
-14-
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dispose of their wastewater treatment sludges in off-site
unlined landfills. This practice could also lead to the
release of chromium from the waste and subsequent groundwater
conta'mination. Rainfall percolating through unlined landfills
may cause the chromium constituents to migrate from the
matrix of the waste into the environment. This is especially
likely in areas where acid rainfall is prevalent, since, as
previously discussed, chromium is more soluble in acid environ-
ments. Seven of the eight plants manufacturing titanium
dioxide are located east of the Mississipi, in area of the
country where rainfall is becoming more acidic. ( »^) If these
unlined treatment or disposal facilities are located in areas
with permeable soils, the potential for groundwater contami-
nation would be even greater.
In addition to difficulties caused by improper site
selection, uncontrolled landfills are not likely co have
leachate control practices or surface run-off diversion
systems that are sufficient to diminish or prevent leachate
percolation- through the soil underneath the site to ground-
water. It should also be noted that two of the sites currently
employ groundwater monitoring at existing on-site disposal
facilities, which would indicate their concern for the manage-
ment of these wastes (i.e., the fact that they may pose a
hazard of groundwater contamination).
With regard to the fate of chromium, the heavy metal
contaminant present in the waste is an element which persists
-15-
-------
indefinitely in some form and therefore may contaminate
drinking water sources for long periods of time.
The Agency has determined to list wastewater treatment
sludge from the production of T102 pigment using chromium
bearing ores by the chloride process as a T hazardous waste,
even though the waste may be evaluated by the E characteristic,
and even though chromium concentrations in the EP extract
from this waste from individual sites may not always be 100
times the national interim primary drinking water standard.
The Agency believes that there are other factors in addition
to the metal concentrations in a waste extract which justify
the T listing. Some of these factors already have been
identified, namely that chromium is believed to be present
in the waste in high concentrations, that present industry
disposal practices may sometimes be improper* that the location
of most of the disposal sites are in areas of acid rainfall
and so may increase the potential of chromium'to leach from
the waste, and that chromium will persist indefinitely in
some form in the environment.
The quantity of the waste, is an additional supporting
factor in the listing of this waste as hazardous. As Indicated
above, these wastewater treatment sludges are generated in
large quantities (800,000 kkg/yr) and contain large amounts
of the constituent of concern (>600 kkg). These large quantities
of chromium pose the danger of large scale contamination of
ground and surface water should mismanagement occur. Addi-
-16-
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tionally, since these wastes are disposed of at relatively
few disposal sites, the chance for environmental insult
increases in these are.is. For example, it is calculated
that approximately 230 kkg of chromium will txe disposed of
annually at a single site. Further, should contamination
occur, it will be for Ion.? periods of time, since chromium
persists virtually indefinitely. Attenuative capacity of
the environment surrounding the disposal facility could also
be reduced or used up uue to the large quantities of pollutant
available. All of these considerations increase the possibility
of exposure to the harmful constituent in the waste, and, in
the Agency's view, support a T .listing.
B. Health and Ecological Effects of Chromium
The hexavalent forms of chromium are more toxic than the
trivalent species. Although trivalent chromium is the pre-
dominant species in tl-o waste sludges of concern in this
document, conversion o an unknown extent to the hexavalent
species is expected tc occur.
Hexavalent chromii-r. J. an animal carcinogen,(9) ancj
there is some epidemiolog.'.c avidence that it may be a human
carcinogen as well;(9) E?/.'s Carcinogen Assessment Group has
listed it as such. Bac.serial mutagenic effects have been
reported as well as cy'ogenetic effects in exposed workers
using hexavalent chromium compounds .(*•*•' Trivalent
chromium has not shown to be either mutagenic or carcinogenic.
A single study, of doubt • I significance, reported teratogenic
-17-
-------
effects of both forms of chromium to chick embryos.(9) Other
chronic effects of chromium compounds occur at very high dose
levels in some industrial situations. (H)
The acute toxic effects of trivalent chr.omium for fish
are more pronounced in soft than in hard water._>10)
Hexavalent chromium, at low concentrations, is toxic to many
aquatic species. For the most sensitive aquatic species,
Daphnia magna, a chronic no-effect level of less than 10
ug/1 has been derived.O Hexavalent chromium (chromate)
has been reported not to bioconcentrate in freshwater fish.C10)
EPA has estimated 800 ug/1 as the concentration of
hexavalent chromium in ambient water whi~h will result in a
/
10~6 risk level of human cancer. The proposed freshwater
standard for hexavalent chromium is 10 ug/1, not to exceed
110 ug/1. (12)
OSHA has established 1 mg/m^ (8 hr TWA) as the workplace
exposure limit in air for chromium metal and insoluble salts,
and 0.5 mg/ra^ for soluble chromium compounds.(^) Additional
information, on the adverse health and environmental effects
of chromium are described in Appendix A.
-18-
-------
References
1. Versar, Inc. 1979. Assessment of Solid Waste Manage-
ment Problems and Practices in the Inorganic Industry.
Tasks 2 and 4, Final Report. Prepared for U.S.
Environmental Protection Agency - Industrial Environ-
mental Research Laboratory. Contract Number 68-03-2604.
2. U.S. EPA, April 1979. Draft Development Document In-
cluding the Data Base for Effluent Limitations Guide-
lines (BATEA), New Source Performance Standards, and
Pretreatment Standards for the Inorganic Chemicals
Manufacturing Point Source Category. Contract Number
68-01-4492. Prepared for Effluent Guidelines Division,
Office of Water and Hazardous Materials, Washington,
D.C. 20460.
3. Pourbaix, Marcel. Atlas of Electrochemical Equilibria
in Aqueous Solutions, London, Pergamon Press.
4. Likens, Gene E., Wright, Richard F., Galloway, James N.,
Butler, Thomas J., 1979. Acid Rain, Scientific American,
241:43-51.
5. Cowling, E. B., 1980. Acid precipitation and its effects
in terrestrial and aquatic ecosystems. Ann. N.Y. Acad.
Sci. 338;540-555.
6. Barksdale, J. 1966. Titanium, Its Occurence, Chemistry
and Technology, Ronald Press, New York.
7. Versar, Inc. 1977. Alternatives for Hazardous Waste
Management in the Organic Chemicals Industry, prepared
for the U.S. Environmental Protection Agency, Office
of Solid Waste. Contract Number 68-01-4190.
8. Versar, Inc. 1979. Multi-media Assessment of the
Inorganic Chemicals Industry. Contract Number 68-03-
2604. Task 4. Draft Final Report, Prepared for U.S.
EPA - Industrial Environmental Research Laboratory,
Cincinnati, Ohio 45268. Volume IV, Chapter 15, p. 19.
9. U.S. EPA, 1979. Chromium: Ambient Water Quality Criteria
10. U.S. EPA. Fate and Transport Potential of Hazardous
Constituents; Appendix B to listing background documents.
11. NIOSH, 1975. Criteria for a recommended standard-Occu-
pational Exposure to Chromium (VI). US DHEW Pub. 76-129.
-19-
-------
12. FR 43: 29028 (July 5, 1978).
13. U.S. EPA, 1979. Subtitle C, Resource Conservation and
Recovery Act of 1976. Draft Environmental Impact
Statement. Appendices.
14. 29 CFR 1910.1000
15. Industrial Minerals and Rocks. American Institute of Mining,
Metallurgical Petrochemical Engineers. J. B. Gillson, ed.
3rd. ed. N.Y., N.Y. 1960. p. 871.
16. W. F. Linke, ed., Solubility of Inorganic and Metal Organic
Compounds, American Chemical Society, Washington, D.C.,
1958.
17. "Resources Losses from Surface Water, Groundwater and
Atmospheric Contamination; a Catalogue", prepared for the
Senate Committee on Environmental and Public Works, serial
number 96-9, 96th Congress, 2nd Session (1980), p. 156.
18. Waste Characterization Data from the State of Illinois EPA,
as selected from State files by USEPA/OSW on March 14, 1979
and March 15, 1979.
-20-
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APPENDIX I
ESTIMATE OF CHROMIUM CONCENTRATION IN WASTEWATER
TREATMENT SLUDGE FROM Ti02 PRODUCTION (Chloride Process)
The amount of chromium in the wastewater treatment sludge
is dependent upon the amount of chromium in the ore. The
amount of chromium in both ilmenite and rutile ore is highly
variable. In the United States, the chromium content of the
ilmenite ores that are used ranges from less than 0.001% to
0.15% (1). Australian rutile ore, which is used domestically,
contains about 0.19% chromium as the oxide (1). An estimate
of the chromium content of the waste can be generated using
these data, but it should be noted that plants can change ore
source and thus their waste load. The following estimate is
based upon a chrome oxide content of rv.15% for ilmenite ore
and 0.19% for rutile ore. Chromium concentration in the
treatment sludge can be estimated as follows:
1978 Ti02 production = 615,853 kkg (*)
Ti02 Chloride process capacity = 492,600 kkg (1)
Ti02 Sulfate process capacity = 263,800 (1)
492,600
Chloride process production - x 615,853 kkg
492,600 + 263,800
401,070 kkg Ti02
*Chemical and Engineering News, June 12, 1978, p.48.
-------
From Tables 1 and 2:
306,000
ilmenite production - _/<401,070
492,600
= 249,142 kkg T102
thus rutile production = 401,070 kkg - 249,142 kkg
= 151,928 kkg T102
A. For Ilmenite ore:
1600 kkg ore
ore required^3' - _^X249,142 kkg Ti02
1000 kkg Ti02
= 398,627 kkg
Cr203 content = 0.0015 x 398,627 kkg ore = 598 kkg
Cr content - 598 x 104/152 = 409 kkg Cr
Treatment sludge from Ilmenite plants = 798,000
409 x 100
Cr concentration in sludges -
798,000
0.051%
B . For rutile ore:
1090 kkg ore
ore required^7' - 151,928 kkg Ti02
. 1000 kkg Ti02,
= 165,600 kkg
Cr203 content = 0.0019 x 165,600 kkg ore = 315 kkg
Cr content = 315 x 104/152 = 215 kkg
-------
Treatment sludges from rutile plants = 17,500 kkg
Cr concentrati.ons in sludges =» 215 x 100 = 1.23%
17,500
-------
Paint Manufacturing
-------
LISTING BACKGROUND E3CUMENT
PAINT MANUFACTURING
Solvent Cleaning Wastes from Equipment and Tank Cleaning (I,T)
Water and/or Caustic Cleaning Wastes from Equipment and
Tank Cleaning (T)*
Wastewater Treatment Sludge (T)**
Emission Control Dust/Sludge (T)
I. SUMMARY OF BASIS FOR LISTING
The main source of hazardous wastes generated by the
paint manufacturing industry is from the cleaning of mixing
tanks and filling equipment. Floor and spill cleanup,
i
cleano'ut of raw material supply tank cars and trucks,
wastewater treatment and air pollution control are addi-
tional sources of hazardous waste.
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
*The spent caustic and its associated solids may also be
corrosive due to the high pH of the caustic cleaning solution.
At the present time, however, the Agency has insufficient
data to substantiate listing this waste for this characteristic
Therefore, it will be the responsibility of individual
manufacturers to determine whether the waste also exhibits
this characteristic.
**In addition to being toxic, the wastewater treatment
sludge may also be corrosive when caustic is used for tank
cleaning and the caustic wash water (which may be corrosive)
flows to the wastewater treatment plant. Since available
data indicates that the sludge will be corrosive in only a
few instances, the Agency is leaving it up to the individual
generators to determine whether their waste also exhibits
this characteristic.
-------
appropriate management requirements under Subtitle C of
RCRA. This conclusion is based on the following considerations
1. The four solid waste streams listed above are
deemed toxic because each contains high concen-
trations of organic and/or inorganic contaminants.
Specific contaminants contained in each waste may
be summarized as follows:
0 Solvent cleaning wastes - lead and chromium
0 Water and/or caustic cleaning waste - lead,
mercury, benzene, carbon tetrachloride, methylene
chloride, tetrachloroethylene, naphthalene, di-
(2-ethylhexyl)phthalate, di-n-butylphthalate and
toluene.
0 Wastewater treatment sludges - chromium, lead,
mercury, nickel, methylene chloride, and toluene.
o
Emission control dust/sludge - antimony, cadmium,
chromium, lead, nickel, silver, cyanides, phenol,
mercury, pentachlorophenol, vinyl chloride,
3,3-dichlorobenzidene, naphthalene, di(2-ethylhexyl)
phthalate, di-N-butyl phthalate, benzene, toluene,
carbon tetrachloride, methylene chloride and
trichloroethylene.
In addition, solvent cleaning wastes are deemed
hazardous because they consist of spent mineral
spirits which are ignitable as defined by 40 CFR
Part 261.21.
Present management of these wastes may be inadequate
to prevent the toxic constituents in these wastes
from migrating to groundwater and nearby surface
waters.
The various physical forms of these wastes (e.g.,
liquid form, sludges, and dust of fine particulate
composition) could allow the release of the hazardous
constituents from their disposal environments.
Exposure to an acidic environment could also
encourage the solubilizing of the heavy metals
-2-
-------
in the wastes (many plants are located in regions
known to be subject to acid rainfall), subsequently
increasing their concentrations in leachate.. Many
of the constituents of concern are also volatile
and pose an inhalation hazard to persons coming
in contact with the waste.
5. The transportation of these wastes to off-site
facilities increases the possibility of exposure
of these wastes to humans and the environment, should
mismanagement occur.
6. Approximately 590,000 tons per year of hazardous
wastes are generated by an estimated 1,500 paint
manufacturing facilities. Such large quantities of
wastes containing high concentrations of hazardous
constituents increases the probability of damage
to human health and the environment under improper
disposal conditions.
7. These paint wastes have been mismanaged in the
past, causing potential substantial hazard to
human health and the environment.
II. INDUSTRY PROFILE AND MANUFACTURING PROCESS
Overall, the paint industry consists of an estimated
1,500 manufacturing plants. Table 1 presents an approximate
breakdown of paint plants by state (1). Faint products
manufactured at these sites fall * \to two general categories:
solvent-thinned or water-thinned products. These products
are also referred to as solvent-base or water-base formulations
Relatively few plants produce exclusively solvent-base or
water-base paints (about 5.1 percent and 4.8 percent
respectively). Common practice for paint plants is to
manufacture both solvent and water-thinnned products.
-3-
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TABLE 1
GEOGRAPHICAL DISTRIBUTION OF PAINT PLANTS^1)
EPA Region I
Connecticut
Maine
Massachusetts
New Hampshire
Rhode Island
Vermont
Total
EPA Region IV
Alabama
Florida
Georgia
10
3
54
3
5
_2
77
12
69
35
SEPA Region II
New Jersey
New York
Puerto Rico
Virgin Islands
EPA Region V
Illinois
Indiana
Michigan
112
109
6
0
227
106
34
47
Kentucky 22
Mississippi 5
North Carolina 20
South Carolina 5
Tennessee 17
Total 185
Minnesota
Ohio
Wisconsin
19
103
34
EPA Region III
Delaware
D.C.
Maryland
Pennsylvania
Virginia
West Virginia
EPA Region VI
Arkansas
Louisiana
New Mexico
Oklahoma
Texas
3
0
20
66
13
4
106
7
15
3
9
58
343
92
-4-
-------
EPA Region VII
Iowa
Kansas
Missouri
Nebraska
13
10
76
EPA Region VIII
Colorado 11
Montana 3
North Dakota 0
Utah 4
Wyoming 1
20
EPA Region IX
Arizona • 6
California 196
Hawaii 0
Nevada 1
203
EPA Region X _
Alaska 1
Idaho 2
Oregon 20
Washington 22_
Total 45
-5-
-------
Figures 1 and 2 illustrate typical solvent-base..and
water-base paint manufacturing operations. Virtually all
paint is made in batches. For solvent-base paints (see
Figure 1), the mixing and grinding of raw materials (pigments,
oils, solvents and resins) is accomplished in one production
step. For high gloss paints, the pigments and a portion
of the binder and vehicle are mixed into a paste of a
specified consistency. This paste is fed to a grinder,
which disperses the pigments by breaking down particle
aggregates rather than by reducing the particle size. Two
types of grinders are ordinarily used for this purpose:
pebble or steel ball mills, or r;oll-type mills. Other
paints are mixed and dispersed in a mixer using a saw-toothed
dispersing blade, which is commonly referred to as a high
speed disperser.
In the next stage of production, the paint is transferred
to tinting and thinning tanks, occasionally by means of
portable transfer tanks, but more commonly by gravity feed or
pumping.'- Here, the remaining binder and liquid, as well
as various additives and tinting colors, are incorporated.
The finished product is then transferred to a filling
operation where it is filtered, packaged and labeled.
Water-base paints are produced in a slightly different
manner from solvent-base paints (see Figure 2). The pigments
and extending agents are usually received in proper particle
size, and the dispersion of the pigment, surfactant and
binder into the vehicle is accomplished with a saw-toothed
-6-
-------
III! !
1 1 1 1 1
I I I Oils I 1 Tints
(Pigments 1 1 and 1 Resins 1 and
| I j Solvents I JThinners
III 1 1
1
1
j
1
i
\lr 4, J,
|
I
1 Mixing Tank
j
I
I
j
1
1
J,
1 1
Stone Pebble | I
or or i Dispersing I
Roller Ball I Tank I
Mill Mill I 1
II 4 IvL
....
1
j
i
i
1
v
\ \
I Thinning and I
I Tinting Tank U
1 I' >
, v
— /
X
1 *
1
4
r
i
1 Solvent,
1 Caustic or
I Water
1
J
* 1 1
1 1
1 1
1 1
i i
Disposal 1
!
I
1
1
1
1
1
,1-
1 1 1
1 Filling J .
I Packaging I Wastewater
• | and | . Treatment
I Shipment |
Figure 1 - Flow Diagram of Manufacturing Process for Solvent Base Paints
-7-
-------
1 II 1
(Pigments | | Resins I
1 1 1 Oils I
1 1 | Surfactants I
1 1
1 1
1 1
1 1
1 1
1
1 1
Water or | |
Caustic I I
Cleaning L I
Waste r 1
1 1
III
III
1 1 I
1 1 1
Lsposal |
\
\ II 1
1 1 1 II
I Water | | Tints 1 1
1 1 1 II
1
1
,
1
1
Dispersing |
- Tank |
1
-------
high speed disperser. In small plants, the paint is thinned
and tinted in the same tank, while in larger plants, the
paint may be transferred to special tanks for the final
thinning and tinting. Once the formulation is correct, the
paint is transferred to a filling operation where it is
filtered, packaged and labeled in the same manner as solvent-
base paints.
III. GENERATION AND MANAGMENT OF LISTED WASTE STREAMS (1,2)
The four hazardous waste streams of concern are
generated primarily as a result of the clean-up of tanks and
other equipment. Table 2 summarizes the hazardous waste
generation rates in the paint manufacturing industry.
Three specific methods of paint tank cleaning are
commonly used in the Paint Industry. These cleaning methods
include (1) solvent wash, (2) caustic wash and (3) water
wash. Solvent wash is used exclusively i ;r cleaning tanks
used for solvent-based paint formulation. Caustic wash
techniques may be used to clean solvent-base and water-base
paint manufacturing tanks. Water washing techniques are
also used in both the solvent-based and water-based segments
of the Paint Industry. For solvent-base operations, water
washing is usually used only to follow caustic washing of
solvent-based tanks. For water-base operations, water
washes often constitute the only tank cleaning operation.
Periodic caustic cleaning of water-base paint tanks is also
a common practice.
-9-
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TABLE 2
HAZARDOUS WASTE GENERATION RATES
IN THE PAINT MANUFACTURING INDUSTRY (1,2)
Waste Tons Per Year
Wastewater and Caustic Rinse Water 520,000(a)
Wastewater Treatment Sludge 39,200(b)
Solvent Cleaning Wastes (not reclaimed) 29,000
Air Pollution Control Residues 1,700
TOTAL 589,900
(a) Wash water and spent caustic that is disposed untreated
as of June, 1980.
(b) Includes 42 plants that currently treat wash water and
spent caustic generating 15 percent sludge, by volume.
-10-
-------
1. Solvent Cleaning Wastes; Solvent-base paint mixing
tanks and other accessory equipment are cleaned with either .
solvent (primarily mineral spirits), caustic or a combination
of the two. The used solvent is normally handled in one
of three ways: (I) used in the next compatible batch of
product as part of the formulation; (2) collected and
redistilled either by the plant or an outside company; or
(3) reused with or without settling until it loses its
"cleaning ability, or is "spent". When spent, the waste
solvent is drummed and removed for disposal. If solids
are settled out of the used solvent, the resultant sludge
is also drummed and removed for disposal. The category
"solvent cleaning wastes" thus includes both spent solvent
and solids contained in the spent solvent. Sometimes the
two are disposed of separately—i.e. the solids are settled
out of the snent solvent and disposed of as a sludge, in
which case b.:.th are deemed hazardous.
Approxib,.!!:^ ly 29,000 tons of solvent cleaning wastes
(not reclaim 1) are generated per year.(2)
2. Water" and .-•' •'r Caustic Cleaning Wastes ; Tanks and equip-
ment used to marufacture water-based paint are generally
washed with water. Rinse water is usually handled in one
of four ways: (1) used in the next compatible batch of
paint as par', of the formulation; (2) discharged with or
without trec^i:ment as wastewater; (3) removed for off-site
disposal; oc •;'4) reused either with or without treatment
-11-
-------
to clean tanks and equipment until spent. If sludge is
settled out of the spent rinse water, it is disposed .of as
a solid waste.
Caustic (NaOH) is used to clean tanks and equipment
used in the manufacture of both solvent and water based
paints. Most plants using caustic reu-se the solution until
it loses some of its cleaning ability. At that time, it is
disposed of as either a solid waste or wastewater with or
without neutralization of other treatment. Following
caustic cleaning, tanks and equipment are usually rinsed
with water. This wastewater is handled in one of three
ways: (1) recycled to the caustic solution as make-up water;
(2) drummed for disposal as a, solid waste; (3) discharged
as wastewater with or without pretreatment—sometimes first
combined with other plant wastewater prior to treatment or
disposal. Caustic cleaning techniques can also create a
sludge when a recirculating caustic system is employed.
The sludge is comprised of paint solids which often accumulate
at the bottom of the caustic reservoir and must periodically
be removed when caustic make-up is required.
The category "water and/or caustic cleaning wastes"
thus includes spent rinse water, spent caustic, and any
solids associated with wastes generated by water cleaning
and caustic cleaning of equipment and tanks. Sometimes
the two phases are disposed of separately—the solids
are settled out of the spent rinse water and/or caustic
-12-
-------
wash and disposed of as sludges, In which case both phases
are included in this listing. Approximately 520,000 tons
per year of wastewater and caustic rinse water are currently
generated per year.
3. Wastewater Treatment Sludges are generated by the paint
industry primarily by the physical/chemical treatment of
equipment and tank rinsewater, caustic cleaning waste, and
other miscellaneous wastewater streams generated at various
parts of the plant.
The sludge produced from wastewater treatment is
;generally 15 precent by volume of the plant wastewater
quantity (1). Proposed pretreatment standards may eliminate
the generation of these wastewater treatment sludges (1).
Instead, 20% of the wastewater generated may be hauled to
disposal sites. This could result in up to 156,000 tons of
wastewater being hauled to disposal sites annually.
4. Emission Control Dust/Sludge; Air pollution control
devices are usually applied to plant ventilation exhausts
to prevent outside air contamination. The purpose of
in-plant ventilation is to remove airborne dusts and
solvent fumes that pose either a health hazard to workers
or create an explosive atmosphere. The residues from the
control dusts consist of dust and particulate matter
collected in filter systems xjhich are usually associated
with emptying bags into process mixers (2). Some plants
-13-
-------
use a wet emission control system, in which case a sludge
(rather than dust) is generated. (Small plants do not
normally employ emission control equipment.(2)) Approximately
1,700 tons of air pollution control residues are generated
per year.(2)
Disposal Practices
Treated and untreated wastewaters (water and/or caustic
cleaning wastes) are discharged to POTWs or placed in
drums for disposal in landfills.(1) About 19.7 percent of
all paint plants engage contract haulers to remove paint
wastewater.^' Table 3 summarizes the major wastewater
disposal methods used in the paint industry. As shown by
the table, discharge to POTWs is the most frequently used
disposal method.
The 29,000 tons per year of unreclaimed solvent are
disposed primarily in landfillsC^) in 55-gallon drums.
Still bottoms from solvent reclaiming operations are also
sealed in drums and disposed of in landfills.(1)
Sludges generated during physical/chemical wastewater
treatment processes are disposed of in one of two general
ways—by contract hauling and by landfill. At least one
large paint producer stores paint wastewater treatment
sludge in an on-site impoundment.(^) Most contract
haulers dispose of the sludge in landfills, although a
small number incinerate or reclaim it (1). Approximately 19%
of all paint plants do not know what the contract hauler
does with the waste.(1)
-14-
-------
Emission control dusts/sludges are generally disposed
of by contract hauling.(2)
IV. HAZARDOUS PROPERTIES OF THE WASTE
A. Waste Composition
In general, the EPA has designated the wastes generated
by water and/or caustic or solvent rinsing of paint manufacturing
equipment as hazardous wastes because they are contaminated
with toxic chemicals found in paint. The products and raw
materials of the paint industry have been shown to contain
at least 21 organic and inorganic priority pollutants(*)
(see Table 4). Since the purpose of these cleaning operations
is to remove unusable paint product, these contaminants
necessarily will be found in the various cleaning wastes.
The sludges resulting from settling of these wastes are
also expected to contain some of these toxic constituents,
as are the wastewater treatment sludges and air pollution
control dusts/sludges. The spp-.ific constituents and
hazards associated with each listed waste are described in
greater detail below. The health and environmental hazards
associated with the specific constituents in the listed
wastes are described on pp. 33-57 and in Appendix A.
-15-
-------
TABLE 3
WASTEWATER DISPOSAL METHODS (1)
AH Plants
Disposal Method
Complete Reuse
Partial Reuse
Evaporation
Discharge to City Sewer
Discharge to Storm Sewer
Discharge to Receiving Stream
Impoundment on Plant Property
Incineration
Contract Hauling
Landfilled
Well or Septic Tank
Spray Irrigation
*Some plants indicated multiple disposal methods
Number of
Plants*
88
262
125
475
68
13
87
5
271
107
13
8
Percent of
Total
6-4
19.1
9.1
34.6
4.9
0.9
6.3
0.<4
19.7
7.8
0.9
0.6
-16-
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TABLE 4
TOXIC CONSTITUENTS IN RAW MATERIALS
USED BY THE PAINT INDUSTRYC1)
Responders Indicating Usage of Raw Materials Containing
Specific Priority Pollutants*
Priority
Pollutant No.
Antimony
Cadmium
Chromium
Lead
Nickel
iSilver
Cyanides
Phenol
Mercury
Pentachlorophenol
Vinyl Chloride
3 , 3-Dichlorobenzidena
Naphthalene
Di-(2 Ethylhexyl)Phthalate
Di-N-Butyl Phthalate
Benzene
Toluene
'Carbon Tetrachloride
1,1,1 Trichloroethane
Methylene Chloride
Trichloroethylene
Minimum
of plants Percent
166
260
1042
833
156
250
860
665
627
190
550
409
772
338
354
' 66
961
9
140
305
77
12.1
18.9
75.8
60.6
11.4
18.2
62.6
48.4
45.6
13.8
40.0
29.8
61.6
24.6
25.8
4.8
69.9
0.6
10.2
22.2
5.6
Maximum
No. of Plants
243
312
1083
1016
395
440
1064
765
627
190
563
412
772
338
354
66
998
8
140
305
77
Percent
17.7
22.7
78.8
73.9
28.7
32.0
77.4
55.7
45.6
13.8
41.0
30.0
56.2
24.6
25.8
4.8
72.6
0.6
10.2
22.2
5.6
(*) Data generated f
Since many of d;
Portfolio can c -•
was unable to "
particular toxi.
because of this
not indicate 'cle
made two counts - .ie
a maximum and minLimtn
rom 1374 responses to paint industry "308" survey.
e raw materials included in the 308 Data Collection
ntain more than one toxic pollutant, the Agency
tain unambiguous counts for the occurence of
pollutants. A conservative approach was taken
Whf.n the Data Collection Portfolio response did
•r? which toxic pollutant was in use, the Agency
including neither, one including both. This gave
count for toxic pollutants.
-17-
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Solvent Cleaning Wastes
Solvent cleaning wastes are considered hazardous
because they have been documented to contain significant
concentrations the two toxic heavy metals lead and chromium.
In addition to posing a toxicity hazard, the solvent cleaning
waste is also considered hazardous because the solvents
employed in the cleaning process, primarily mineral spirits,
are ignitable. The flash point of mineral spirits is
104°F (4) and therefore meets the §261.21 characteristic
of ignitability (i.e. <140°F for liquids). The following
data from state manifests illustrates both the significant
heavy metal concentrations in these wastes, and the fact
that the wastes' flashpoint meets the criteria for ignitability
(5,6):
-18-
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1. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
Waste Name; Still bottoms and thinner sludge
Quantity; 120,000 gallons (liquid)
Percent Analysis; 68.2% Solvents
31.8% Pigments and Resins
Chemical Analysis;
Metal
Cr
Pb
Total
Concentration (ppm)
27.6
112.9
Flashpoint; 70°F
2. State; Illinois
Source; Special Waste Disposal Applications, Illinois EPA
Waste Name; Paint Sludges
Quality; 458,000 gallons
Percent Analysis; 53% Solvents
45% Pigment and Binder
2% Inorganic Residue
Flashpoint; 110°F
Chemical 'Analysis;
Metal
Cr
Pb
Total
Concentration (ppm)
166
1203
-19-
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3. State; New Jersey
Source; Industrial Waste Surveys, New Jersey Department
of Environmental Conservation
Waste Name; Dirty Wash Solvent
Quantity; 37,000 gallons/year (liquid)
Percent Analysis; 85% Solvents
10% Resins
5% Pigments
Chemical Analysis; Contaminant
Chromates
Lead
Total
Concentrations
(ppm)
7000
3000
Waste Properties! Flammable, Toxic (reported by generator)
In summary, solvent cleaning wastes are being listed
as hazardous because (1) the solvents used to clean tanks
and equipment are ignitable; and (2) the solvent cleaning
wastes have been documented as containing the toxic compounds
lead and chromium, in significant concentrations.
-20-
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Water and/or Caustic Cleaning Wastes
The Administrator has classified water and/or caustic
cleaning wastes as hazardous because of the levels of ten
toxic constituents found in samples of the waste. Table 6
summarizes data which substantiate EPA's listing of these
wastes as hazardous. These data were selected from EPA's
Development Document for Effluent Limitations Guidelines
and Standards for the Paint Formulating Point Source Category.
(Note that "untreated wastewater" samples are representative
of water and/or caustic cleaning wastes before treatment.)
These data indicate that lead, mercury, benzene, carbon
tetrachloride, methylene chloride, tetrachloroethylene,
naphthalene, di(2-ethylhexyl) phthalate (DEHP), di-n-butyl-
phthalate and toluene are typically found in water and/or
caustic cleaning wastes. Concentrations of these toxic
pollutants in the was tewa*- srs exceed 10 or even 100 times
the existing drinking water or ambient water quality standards
Wastewater Treatment Sludge
The Administrator has classified wastewater treatment
sludges f-rom paint manufacturing as hazardous because of the
levels of six toxic constituents found in samples of the
waste. EPA tested samples of this waste from several plants
and found that it contained inorganic and organic priority
pollutants.(1) The data shown in Table 7 from EPA's
Development for Effluent Limitations Guidelines and
Standards for the Paint Formulating Point Source Category
-21-
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TABLE 6
UNTREATED WASTEWATER* DATA — SELECTED POLLUTANTS
1977/1978 SAMPLING PROGRAM (1)
HAZARDOUS
CONSTITUENT
Lead
Mercury
Benzene
Carbon tetrachloride
Methylene chloride
Tetrachloroethylene
Naphthalene
Di (2-Ethylhexyl)
Phthalate
Dl-N-Butyl-Phthalate
Toluene
NUMBER
SAMPLES
ANALYZED
60
55
31
31
31
31
31
31
31
31
OF
TIMES ABOVE
DET. LIMIT
45
44
18
7
17
16
8
9
13
27
AVERAGE
(mg/1)
6.300
5.161
1.933
3.770
31.878
.567
2.950
.418
5.745
17.966
MEDIAN
(mg/1)
.805
.500
.370
.014
.620
.175
.054
.140
.160
2.500
MINIMUM
(mg/1)
.022
.001
.020
<.010
X.010
<.010
<.010
<.010
<.oio
.073
MAXIMUM
(mg/1)
80.000
62.000
9.900
30.000
210.000
4.900
18.000
2.810
69.000
259.700
MASS LOADING
(KG/YEAR)**
4,475
3,650
800
675
13,100
232.5
600
105
2,475
11,075
* Representative of water and/or caustic cleaning wastes before treatment.
**Assuraes production 250 days per year.
-22-
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TABLE 7
WASTEWATER TREATMENT SLUDGE DATA SUMMARY
1977/1978 SAMPLING PROGRAM (1)
CONSTITUENT
Chromium
Lead
Mercury
Nickel
Methylene chloride
Toluene
— — Number
SAMPLES
ANALYZED
39
39
36
39
9
9
r\t . ____
or — — — —
TIMES ABOVE
DET. LIMIT
37
37
31
27
8
8
AWT7TJ API?
AVCjlvAXjC*
(MG/L)
7.050
10.770
15.061
10.443
120.201
44.740
UOT\T AM
ran. LI IAW
(MG/L)
.700
3.000
.640
.200
1.735
.905
MTXTTMTTKf
Pl-LJN iClUW
(MG/L)
<.50
<.100
.005
.020
.300
.130
MAYTKfTTM
P1AA J.C1UP1
(MG/L)
90.000
80.000
220.000
200.000
900.000
350.00
i
MASS
(KG/ YEAR)*
767.5
1065
1687.5
1132.5
12,764.25
4650
*Assumes production 250 days/year
-23-
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indicate that chromium, lead, mercury, nickel, methylene
chloride and toluene, are typically found in wastewater
treatment sludge from paint manufacturing.
In addition to the EPA data, the following data from Illinois
and New Jersey(5,6) indicate that, wastewater treatment sludge
from paint manufacturing contains elevated levels of chromium
in both cases, and lead in one case. Further, an acid
leaching test performed on one of the samples indicates
that the chromium and lead can, in fact, be extracted at
levels which exceed 10 and 100 times (respectively) the
drinking water standards for these metals.(5,6)
1. State; Illinois
Source: Special Waste Disposal Applications, Illinois EPA
Waste Name: Paint Sludge
Quantity; 50,000 gallons
Percent Analysis; 50% Resins
45% Pigments
<1% Xylol, toluol, isopropyl alcohol
Concentration Concentrations
Chemical "Analysis; Metal in Waste (ppm) in Leachate (ppm)
Cr+6 1500 1.3
Pb 9200 5.4
-24-
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2. State: New Jersey
Source; Industrial Waste Surveys, New Jersey Department of
Environmental Protection
Waste Name; Emulsion Paint Sludge
Quantity; 70,000 gallons/year (sludge)
Percent Anayais; 60% Water
20% Ti02
20% Latex Solids
Concentration
Chemical Analysis; Metal in Waste (ppm)
Pb 300
Waste Properties; Irritant, toxic (reported by generator)
Emission Control Dusts/Sludges
The Administrator has classified emission control
dusts/sludges as hazardous because the Agency has reason to
believe that these wastes contain substantial quantities of
the toxic raw materials used in the formulation of
paint products (see Section III, Generation and Management
of Listed Waste Streams), and therefore that the wastes
pose a substantial threat to human health and the environment.
Specifically, this waste ii being listed as a hazardous
waste because of the presence of the following toxic consti-
tuents which are constituents of raw materials used in
paint manufacturing;
-25-
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antimony
cadmium
chromium
lead
nickel
s i 1 v.e r
cyanides
phenol
mercury
pentachlorophenol
vinyl, chloride
3,3'-dichlorobenzidene
naphthalene
di(2-ethylhexyl) phthalate
di-N-Butyl phthalate
benzene
toluene
carbon tetrachloride
1,1,1-trlchloroethane
methylene chloride
trichloroethylene
If emission control residues are collected wet,
scrubber water is often diverted to the wastewater treatment
plant for treatment before disposal. In this case, the
scrubber water becomes a source of the wastewater treatment
sludge, which has already been demonstrated as being
hazardous.
B. Potential for Substantial Hazard from Improper Waste
Management
As shown above, these wastes contain a wide range of
toxic organic and inorganis constituents, in many cases in
significant concentrations. Many of these constituents,
namely benzene, hexavalent chromium, carbon tetrachloride,
tetrachloroethylene, 3 , 3'-Dichlorobenzidine, and trichloro-
ethylene have been identified by the Agency's Carcinogen
-26-
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Assessment Group as possessing substantial evidence of
carcinogenicity, increasing Agency concerns as to the
potential of these wastes to cause substantial harm if
mismanaged. Under these circumstances, the Agency requires
assurance that waste constituents will not migrate and
persist should mismanagement occur.
Such assurance does not appear possible here since
most waste constituents appear quite capable of migration
in substantial concentrations, and of mobility and persistence
upon environmental release. As shown in Table 8, most of
the organic compounds in these wastes are very water soluble,
and some (such as phenol) extremely so. The heavy metals
are likewise known to be capable of migrations in leachate.
These compounds thus present a danger of migration via a
groundwater pathway if exposed to a leaching medium.
Other compounds, particularly benzene, vinyl chloride,
toluene, trichloroethylene, 1,1,1'-trichloroethane, and
methylene chloride, are significantly volatile and could
pose an inhalation hazard to environmental receptors in
the vicinity of improperly disposed wastes.
These constituents are likewise capable of mobility
and persistence upon environmental release. Many constituents
have in fact been involved in damage incidents resulting
from improper waste management, empirically demonstrating
mobility and persistence of waste constituents. For example,
-2.7-
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Table 8*
Compound
Vapor Pressure
(mm Hg)
Solubility
in Water
Antimony
Cadmium
Chromium
Lead
Nickel
Silver
Cyanides
Mercury
Varies, depending on which salt of
of the metal is present-in the waste.
Phenol
Pentachlorophenol
Vinyl Chloride
3,3'-Dichlorobenzidene
Naphthalene
Di-2-Ethylhexylphthalate
Di-n-Butylphthalate
Toluene
Benzene
Trichloroethylene
1,1,1-trichloroethane
Methylene Chloride
Tetrachloroethylene
0.2mm at 20°C8
.00011mm at 20°C8
2,660mm at 25°C8
low
1mm at 53°C8
1.2mm at 200°C8
O.lmm at 115°C8
28.4 at 25°C8
76mm at 20°C8
77 at 25°C7
100 at 208C
350 at 20°C
19 at 25°C7
82 g/1 at 15°C8
14 mg/1 at 20°C8
1.100 mg/1 at 25°C8
4 ing/l1*
30 mg/18
50 mg/l9
400 mg/1 at 28°C8"
470 mg/1 at 258C8
1,780 mg/1 at 20°C8
1,000 mg/1 at 20°C7
950 mg/1 at 25°C
20,000 mg/1 at 25°C7
150 mg/1 at 25°C7
*Table compiled from data given in "Physical/Chemical Properties of Hazardous Waste
Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
-28-
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trichlo rot: chylene, benzene, vinyl chloride, raethylene
chloride, and tetrachloroethylene were all involved in the
contamination of drinking water sources in New Hanover,
North Carolina. (Muskie report) Toluene and benzene are
among the constituents present in water and air samples
taken in the Love Canal area. ("Love Canal Public Health
Bomb", a Special Report to the Governor and Legislature,
New State Department of Health (1978)). Trichloroethylene
and phenol were involved in a damage incident in Sehigh
Co., Pa. where industrial wastes contaminated drinking
water walls. (Muskie) Heavy metals and cyanides likewise
have been involved in numerous damage incidents from improper
waste disposal. (Muskie) Pentachlorophenol has been detected
in surface water and finished drinking waster (Appendix B),
and is only moderately degradable. (Id.)
The remaining compounds likewise appear capable of
mobility and persistence. The two phathalate esters present
are rac-lle (particularly in soils low in organic content),
and ar- capable of persistence in most environments, although
subject to I: .©degradation. Both esters are also bioaccumulative,
so that exposure to small concentrations may still prove
dangerous. (H)
3,''-dichlorobenzidene has limited mobility in clay,
or in '-oils high in organic content (11), but could be
mobile in other media. Photolysis is the most significant
degrad.tion mechanism (11), and so would not effect this
compound ••; persistence in groundwater.
-29-
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Napthalene is likewise capable of migration through
soils (11), and since it is not subject to hydrolysis
(although it is biodegradable) (11), could persist in the
abiotic conditions of most aquifers. These constituents
thus have the capacity for migration, mobility and persistence,
raising the possibility of potential hazard if the wastes
are mismanaged.
Additionally, present management and disposal practices
(see Section III) for these hazardous wastes may be inadequate
to protect human health and the environment from exposure
to the toxic constituents shown to be present in the wastes.
Landfilling of any of the listed wastes in unsecure landfills
could contaminate underlying groundwater or nearby surface
water as the waste releases toxic constituents.
In particular, landfilling of liquid wastes such as
the water and/or caustic cleaning waste, solvent cleaning
waste, or a sludge which has not been dewatered, may pose a
threat to water supplies because many of the toxic constituents
present in the liquid waste are already solubilized in the
liquid and would tend to pass more quickly through a landfill,
even without the percolating action of rainwater on the
landfill. The state manifest information presented above
indicates that some of these toxic constituents will indeed
be released from the waste. These-, was tes thus could contaminate
drinking water supplies and pose a threat to human health
and the environment through ingestion of water contaminated
with the toxic constituents of concern.
-30-
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Dewatered sludges--wastewater treatment sludges or air
pollution (emission) control sludges—also pose a threat to
human health and the environment if mismanaged. Extraction
data have shown that the wastewater treatment sludges
sometimes leach contaminants in excess of ten times the
drinking water standard for chromium and lead. These data
indicate that the sludges contain chromium and lead in a
soluble form and thus could he released in harmful
concentrations.
In general, if these wastes should be exposed to an acid
environment, for example, disposed in landfills containing
organic refuse or disposed in areas subject to acid rainfall,
these constituents' concentrations in leachate would be
similar to concentrations shown by the leaching data from
the state manifests. As indicated in Table 1, many of
these plants are located in regions known to be subject to
acid rainfall (east of the Mississippi).
The dry air pollution (emission) control residue
could pose an additional hazard. These emission control
dusts are of a fine particulate composition, and therefore
a large surface area is exposed to leaching action of any
percolating medium. Dusts can pose a hazard in addition
to that of ground and surface water contamination. Airborne
exposure to, for instance, lead and chromium compounds
escaping from air pollution control dusts poses an Inhalation
-31-
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hazard. These minute particles could be dispersed by the
wind if waste dusts are piled in the open, placed in unsecure
landfills or improperly handled during transportation. As
a result, the health of persons who inhale the airborne
particles would be jeopardized.
A further consideration in the regulation of these hazard-
ous wastes is that they are transported to off-site disposal
facilities. This increases the likelihood of their being
mismanaged, i.e., uncontrolled transportation may result
either in their not being properly handled during transport
or their not reaching their destination at all. A transpor-
tation and manifest system combined with designated standards
for the management of these wastes will greatly reduce
their availability to harm to humans and the environment.
In fact, many generators of these wastes actually indicated
that at the present time they are ignorant of the ultimate
disposition of the wastes they give to contract haulers
(see pp. 14-15 above). In fact, in a recent damage incident,
a number of 55 gallon drums of paint sludge were haphazardly
dumped on- a house farm north of Richmond, Virginia. These
drums were traced back to a Maryland paint company.
(Washington Post, June 23, 1980, at B 1.) The danger of
improper transport of these wastes thus appears very high.
These wastes are generated in very substantial quantities
(See Table 2) and contain significant concentrations of the
-32-
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toxic constituents of concern (see previously sited data).
Large amounts of these contaminants pose the danger of
polluting large areas of ground and surface waters near
an unsecure landfill. Contamination could also occur for
any long periods of time, since large amounts of pollutants
are available for environmental loading. Attenuative
capacity of the environment surrounding an inadequate
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.
V. Health and Environmental Effects (10)
The following contaminants of paint wastes are designated
as priority pollutants under Section 307(a) of the Clean
Water Act:
antimony
cadmium
chromium
lead
mercury
nickel
silver
cyanides
phenol
pentachlorophenol
vinyl chloride
3 ,3-dichlorobenzidene
benzene
carbon tetrachloride
methylene chloride
tetrachloroethylene
naphthalene
di (2-ethylhexyl) phthalate
di-N-butyl-phthalate
toluene
t richloroethylene
-33-
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Lead is also regulated under the Clean Air Act. Proposed
or final standards have been Issued for most of these chemicals
under the Occupational Safety and Health Act of 1970. More
specific information on the health effects of these chemicals
are summarized below. For further information on the health
effects of all of these constituents, see Appendix A.
Antimony
Essentially no information on antimony-induced human
health effects has been derived from community epidemiology
studies. The available data are in literature relating effects
observed with therapeutic or medicinal uses of antimony
compounds and industrial exposure studies. Large therapeutic
doses of antimonial compounds, usually used to treat
schistisomiasis, have caused severe nausea, vomiting,
convulsions, irregular heart action, liver damage, and skin
rashes. Studies of acute industrial antimony poisoning
have revealed loss of appetite, diarrhea, headache,
and dizziness in addition to the symptoms found in studies
of therapeutic doses of antimony.
For-the protection of human health from toxic properties
of antimony ingested through water and through contaminated
aquatic organisms, the ambient water criterion is determined
to be 0.145 mg/1.
-34-
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Antimony compounds remaining in wastewater treatment
sludge under anaerobic conditions may be connected -to...
stibine (SbH3), a very soluble and very toxic compound.
Antimony is not known to be essential to the growth of
*
plant;-, and has been reported to be moderately toxic.
Therefore, sludge containing large amounts of antimony
could Ve detrimental to plants if it is applied in large
amounts to cropland.
Cadr'. turn
Cadmium is an extremely dangerous cumulative toxicant
(tha metal is not excreted), causing progressive chronic
poisoning in mammals, fish, and probably other organisms.
Toxic effects of cadmium on man have been reported
from throughout the world. Cadmium may be a factor in the
development of such human pathological conditions as kidney
disease, testicular tumors, hypertension, arteriosclerosis,
grcvth inhibition, chronic disease of old age, and cancer.
Cadiui =.ita is normally ingested by humans through food and
wa<:-r as well as by breathing air contaminated by cadmium
dust- Jadmium is cumulative in the liver, kidney, pancreas,
and th -roid of humans and other animals. A severe bone and
kidney syndrome known as itai-itai disease has been documented
in ."apan as caused by cadmium ingestion via drinking water
an- contaminated irrigation water. Ingestion of as little
as 0.6 mg/day has produced this disease. Cadmium acts syn-
-35-
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ergistically with other metals. Copper and zinc substantially
increase its toxicity.
Cadmium is concentrated by marine organisms, particularly
molluscs, which accumulate cadmium in calcareous tissues
and in the visera. A concentration factor of 1,000 for
cadmium in fish muscle has been reported, as have concentration
factors of 3000 in marine plants and up to 29,600 in certain
marine animals. The eggs and larvae of fish are apparently
more sensitive than adult fish to poisoning by cadmium, and
crustaceans appear to be more sensitive than fish eggs and
larvae.
For the protection of human health from the toxic
properties of cadmium ingested through water and through
i
contaminated aquatic organisms, the ambient water criterion
is determined to be 0.010 mg/1.
Data show that cadmium can be incorporated into crops,
including vegetables and grains, from contaminated soils.
Two Federal agencies have already recognized the potential
adverse human health effects posed by the use of sludge on
cropland. The FDA recommends that sludge containing over
30 mg/kg of cadmium should not be used on agricultural
land. Sewage sludge contains 3 to 300 mg/kg (dry basis)
of cadmium; mean = 10 mg/kg; median = 16 mg/kg. The USDA
also recommends placing limits on the total cadmium from
sludge that may be applied to land.
-36-
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Chromium
The two chromium forms most frequently found in industry
wastewaters are hexavalent and trivalent chromium. Some of it
is reduced to trivalent chromium as part of the process reaction.
The raw wastewater containing both valence states is usually
treated first to reduce remaining hexavalent to trivalent
chromium, and second to precipitate the trivalent form as the
hydroxide. The hexavalent form is not removed by lime treatment.
Chromium, in its various valence states, is hazardous to
man. It can produce lung tumors when inhaled, and induces skin
sensitizations. Large doses of chromates have corrosive effects
on the intestinal tract and can cause inflammation of the kidneys.
Hexavalent chromium has been identified by the Agency's
Carcinogen Assessment Group as exhibiting substantial
evidence of being carcinogenic. Levels of chromate ions
that show no effect in man appear to be so low as to prohibit
determination, to date.
The toxicity of chromium salts to fish and other aquatic
life varies widely with the species, temperature, ?H, valence
of the chromium, and synergistic or antagonistic effects,
especially the effect of water hardness. Studies have shown
that trivalent chromium is more toxic to fish of some types
than is hexavalent chromium. Hexavalent chromium retards
growth of one fish species at 0.0002 mg/1. Fish food
organisms and other lower forms of aquatic life are extremely
-37-
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sensitive to chromium. Therefore, both hexavalent and
trivalent chromium must be considered harmful to particular
fish or organisms.
For the protection of human health from the toxic
properties of chromium (except hexavalent chromium) ingested
I
through water and contaminated aquatic organisms, the
recommended water quality criterion is 0.050 mg/1. For
the maximum protection of human health from the potential
carcinogenic effects of exposure to hexavalent chromium
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero.
Chromium is not destroyed when treated by wastewater
treatment (although the oxidation state may change), and will
either pass through to the wastewater treatment effluent or be
incorporated into the wastewater treatment sludge. Both
oxidation states can cause wastewater treatment inhibition and
can also limit the usefulness of municipal sludge.
Chromium not passed through a. wastewater treatment plant
will be retained in the sludge, where it is. likely to build up
in concentration. Disposal of sludges containing very high
concentrations of trivalent chromium can potentially cause
problems in secure landfills. Incineration, or similar
destructive oxidation processes can produce hexavalent chromium
from lower valence states. Hexavalent chromium is potentially
more toxic than trivalent chromium. In cases where high rates
of chrome sludge application on land are used, distinct growth
inhibition and plant tissue uptake have been noted.
-38-
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Lead
Lead ingested by humans produces a variety of toxic effects
including impaired reproduction ability, disturbances in blood
chemistry, neurological disorders, kidney damage, and adverse
cardiovascular effects. Exposure to lead in the diet results
in permanent increase in lead levels in the body. Most of the
lead entering the body eventually becomes localized in the
bones where it accumulates. Lead is a carcinogen or cocarcinogen
in some species of experimental animals. Lead is teratogenic
in experimental animals. Mutagenicity data are not available
for lead.
For the protection of human health from the toxic properties
of lead ingested through water and through contaminated aquatic
organisms the ambient water criterion is 0.050 mg/1.
Mercury
Mercury can b* introduced into the body through the skin
and the respiratory system as the elemental vapor. Mercuric
salts are highly toxic to humans and can be absorbed through
the gastrointestinal tract. Fatal doses can vary from 1 to 30
grams. Clironic toxicity of methyl mercury is evidenced primarily
by neurological symptoms. Some mercuric salts cause death by
kidney failure.
Mercuric salts are extremely toxic to fish and other
aquatic life. Mercuric chloride is more lethal than copper,
hexavalent chromium, zinc, nickel and lead towards fish and
aquatic life. In the food cycle, algae containing mercury up
-39-
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to 100 times the concentration in the surrounding sea water are
eaten by fish which further concentrate the mercury. Predators
that eat the fish in turn concentrate the mercury even further.
For the protection of human health from the toxic properties
of mercury ingested through water and through contaminated
aquatic organisms the ambient water criterion is determined to
be 0.0002 mg/1.
In sludges, mercury content may be .high if industrial
sources of mercury contamination are present. Little is known
about the form in which mercury occurs in sludge. Mercury may
undergo biological methylation in sediments, but no methylation
has been observed in soils, mud, or sewage sludge.
The mercury content of soils not receiving additions of
POTW sewage sludge lie in the range from 0.01 to 0.5 mg/kg. In
soils receiving POTW sludges for protracted periods, the
concentration of mercury has been observed to approach 1.0
mg/kg. In the soil, mercury enters into reactions with the
exchange complex of clay and organic fractions, forming both
ionic and covalent bonds. Chemical and microbiological
degradation of mercurials can take place side by side in the
soil, and the products - ionic or molecular - are retained by
organic matter and clay or may be volatilized if gaseous. Be-
cause of the high affinity between mercury and the solid soil
surfaces, mercury persists in the upper layer of soil.
Mercury can enter plants through the roots, it can readily
move to other parts of the plant, and it has been reported to
-40-
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cau.se injury to plants. In many plants mercury concentrations
range from 0.01 to 0.20 mg/kg, but when plants are supplied
with high levels of mercury, these concentrations can exceed
0.5 mg/kg. Bioconcentration occurs in animals ingesting mercury
i n f o o d .
Nickel
The toxicity of nickel to man is thought to be very low,
and systemic poisoning of human beings by nickel or nickel
salts is almost unknown. In non-human mammals nickel acts to
inhibit insulin release, depress growth, and reduce cholesterol.
A high incidence of cancer of the lung and nose has been reported
in humans engaged in the refining of nickel.
Nickel salts can kill fish at very low concentrations.
However, nickel has been found to be less toxic to some fish
than copper, zinc, and iron. Nickel is present in coastal and
open ocean water at concentrations in the range of 0.0001 to
C.006 mg/1 although the most common values are 0.002 - 0.003
r •:/!. Marine animals contain up to 0.4 mg/1 and marine plants
c-.ntain up to 3 mg/1. Higher nickel concentrations have been
re no---, d • to cause reduction in photosynthetic activity of the
gian" kelp. A low concentration was found to kill oyster eggs.
For the protection of human health based on the toxic
pr ^erties of nickel ingested through water and through
c.-ntaminated aquatic organisms, the ambient water criterion is
determined to be 0.133 mg/1.
Nickel toxicity may develop in plants from application of
-41-
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sewage sludge on acid soils. Nickel has caused reduction of
yields for a variety of crops including oats, mustard, turnips,
and cabbage. In one study nickel decreased the yields of oats
significantly at 100 mg/kg.
Whether nickel exerts a toxic effect on plants depends on
several soil factors, the amount of nickel applied, and the
contents of other metals in the sludge. Unlike copper and
zinc, which are more available from inorganic sources than from
sludge, nickel uptake by plants seems to be promoted by the
presence of the organic matter in sludge. Soil treatments such
as liming reduce the solubility of nickel. Toxicity of nickel
to plants is enhanced in acidic soils.
Silver /
Metallic silver is not considered to be toxic, but most of
it salts are toxic to a large number of organisms. Upon
ingestion by humans, many silver salts are absorbed in the
circulatory system and deposited in various body tissues,
resulting in generalized or sometimes localized gray
pigmentation of the skin and mucous membranes know as
argyria. " There is no known method for removing silver from
the tissues once it is deposited, and the effect is
cumulative.
Silver is recognized as a bactericide and doses from
0.000001 to 0.0005 mg/1 have been reported as sufficient to
sterilize water. The criterion for ambient water to protect
-42-
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human health from che toxic properties of silver ingested
through water and through contaminated aquatic orgnisms is
0.010 mg/1.
The chronic toxic effects of silver on the aquatic
environment have not been given as much attention as many
other heavy metals. Data from existing literature support the
fact that silver is nearly the most toxic of the heavy
metals, there are insufficient data to adequately evaluate
even the effects of hardness on silver toxicity. There are
no data available or. the toxicity of different forms of
silver.
Cyanides
Cyanides are among the most toxic of pollutants commonly
observed in industrial wastewaters. Introduction of cyanide
into industrial processes is usually by dissolution of
potassium cyanie (KCN) or sodium cyanide (NaCN) in process
waters. However, hydrogen cyanide (HCN) formed when the
above salts are dissolved in water, is probably the most
acutely lethal compound.
The ..relationship of pH to hydrogen cyanide formation
is very important. As pH is lowered to below 7, more than
99 percent of the cyanide is present as HCN and less than 1
percent as cyanide ions. Thus, at neutral pH, that of most
living organisms, the more toxic form of cyanide prevails.
Cyanide ions combine with numerous heavy metal ions
to form complexes. The complexes are in equilibrium with
-43-
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HCN. Thus, the stability of the metal-cyanide complex and
the pH determine the concentration of HCN. Stability of
the metal-cyanide anion complexes is extremely variable.
Those formed with zinc, copper, and cadmium are not stable—
they rapidly dissociate, with production of.HCN, in near
neutral or acid waters. Some of the complexes are extremely
stable. Cobaltocyanide is very resistant to acid distillation
in the laboratory. Iron cyanide complexes are also stable,
but undergo photodecomposition to give HCN upon exposure to
sunlight. Synergistic effects have been demonstrated for
the metal cyanide complexes making zinc, copper, and cadmium,
cyanides more toxic than an equal concentration of sodium
cyanide .
The toxic mechanism of cyanide is essentially an
inhibition of oxygen metabolism, i.e., rendering the tissues
incapable of exchanging oxygen. The cyanogen compounds are
true noncumulative protoplasmic poisons. They arrest the
activity of all forms of animal life. Cyanide shows a very
specific type of toxic action. It inhibits the cytochrome
oxidase 'system. This system is the one which facilitates
electron transfer from reduced metabolites to molecular
oxygen. The human body can convert cyanide to a non-toxic
thiocyanate and eliminiate it. However, if the quantity of
cyanide ingested is too great at one time, the inhibition
of oxygen utilization proves fatal before the detoxifying
reaction reduces the cyanide concentration to a safe level.
-44-
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Cyanides are more toxic to fish than to lower forms of
aquatic organisms such as midge larvae, crustaceans, and
mussels. Toxicity to fish is a function of chemical form
and concentration, and is influenced by the rate of metabolism
(temperature), the level of dissolved oxygen, and pH. In
laboratory studies free cyanide concentrations ranging from
0.05 to 0.15 mg/1 have been proven to be fatal to sensitive
fish species including trout, bluegill, and fathead minnows.
Levels above 0.2 mg/1 are rapidly fatal to most fish species.
Long term sublethal concentrations of cyanide as low as
0.01 mg/1 have been shown to affect the ability of fish to
function normally, e.g., reproduce, grow, and swim.
For the protection of human health from the toxic
properties of cyanide ingested through water and throguh
contaminated aquatic organisms, the ambient water quality
criterion is determined to be 0.200 mg/1.
Phenol
Phenol exhibits acute and sub-acute toxicity in humans
and laboratory animals. Acute oral doses of phenol in
humans cause sudden collapse and unconsciousness by its
action on the central nervous system. Death occurs by
respiratory arrest. Sub-acute oral doses in mammals are
rapidly absorbed then quickly distributed to various organs,
then cleared from the body by.urinary excretion and
metabolism. - Long term exposure by drinking phenol contaminated
water has resulted in statistically significant increase in
-45-
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reported cases of diarrhea, mouth sores, and burning of the
mouth. In laboratory animals long term oral administration
at low levels produced slight liver and kidney damage. No
reports were found regarding carcinogenicity of phenol
administered orally - all carcinogenicity studies were skin.
tests.
For the protection of human health from phenol ingested
A"
through water "and through contaminated aquatic organisms
the concentration in water should not exceed 3.4 mg/1.
Fish and other aquatic organisms demonstrated a wide
range of sensitivities to phenol concentration. However,
acute toxicity values were at moderate levels when compared
to other organic priority pollutants.
Pentachlorophenol
Although data are available on the human toxicity
effects of pentachlorophenol, interpretation of data is
frequently accompanied by exposure to other wood preservatives
Additionally, experimental results and occupational exposure
observations must be examined carefully to make sure that
observed effects are produced by the pentachlorophenol
itself and not by the by-products which usually contaminate
pentachlorophenol.
Acute and chronic toxic effects of pentachlorophenol
in humans are similar: muscle weakness, headache, loss of
appetite, abdominal pain, weight loss, and irritation of
skin, eyes, and respiratory tract. Available literature
-46-
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indicates that pentachlorophenol does not accumulate in
body tissues to any significant extent. Studies on lab-
oratory animals of distribution of the compound in body
tissues showed the highest levels of pentachlorophenol in
liver, kidney, and intestine, while the lowest levels were
in brain, fat, muscle, and bone.
Toxic effects of pentachlorophenol in aquatic organisms
are much greater at pH of 6 where the ionic form predominates
Similar results were observed in mammals where oral lethal
doses of pentachlorophenol were lower when the compound was
administered in hydrocarbon solvents (un-ionized form) than
when it was administered as the sodium salt (ionized form)
in water.
For the protection of human health from the toxic
properties of pentachlorophenol ingested through water and
through contaminated aquatic organisms, the ambient quality
criterion is determined to be 0.140 mg/1.
Vinyl Chloride
Vinyl chloride is a well-known human and animal
carcinogen. Several occupational epidemiology studies in
highly exposed workers have reported excess rates of liver
angiosarcoma and tumors at other organ sites. Animal
experiments using both inhalation and oral routes of exposure
have also induced liver angiosarcona. Because there is no
recognized safe concentration for a human carcinogen, the
-47-
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recommended concentration of vinyl chloride in water for
maximum protection of human health is zero.
Because of its high vapor pressure vinyl chloride
volatilizes rapidly from the aquatic environment. " r:ause
it is so readily volatilized, it does not undergo
bioaccumulation except under extreme exposure conditions.
Existing evidence indicates that it is resistant to microbial
»
degradation.
3,3'-dichlorobenzidene
DCB has been shown to be a carcinogen in non-human
mammals under controlled laboratory conditions. Exposure
to DCB results in various types of sarcomas and adenocarcinomas
Tumors have been induced both locally (at the site of
injection) and remotely (multi-system involvement' after
feeding). Experiments shown DCB to be a much lei-s potent
carcinogen in animals than the unsubstituted base (benzidene).
U.S. EPA's Carcinogen Assessment Group (CAG) has evaluated
3,3'-dichlorobenzidine and has found sufficient evidence to
indicate that this compound is carcinogenic. DCB . • found
to be acutely toxic to bluegill sunfish at levels or 0.5
mg/1 or greater in the water.(12)
-48-
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There are few data available on the bioconcentration,
bioaccumulation, and biomagnificatlon of DCB in the aquatic
environment. DCB has been shown to be experimentally
bioconcentrated by fish to a significant degree —
approximately 1150 fold. However, no DCB was detected in
fish sampled from the vicinity of a DCB contaminated waste
lagoon using analytical methods with sensitivities of 10 to
100 mg/kg.
Benzene
The chronic, rather than acute toxicity of benzene is
important in industry. It is a recognized carcinogen of
the blood-forming tissues. The exposure routes of concern
are ingestion, inhalation and skin absorption through
repeated exposures.
Benzene is harmful to human health according to numerous
published studies. Most studies relate effects of inhaled
benzene vapors. These effects include nausea, loss of muscle
coordiantion, and excitement, followed by depression and coma.
Death is usually the result of respiratory or cardiac failure.
Two specific blood disorders are related to benzene exposure.
One of these, acute myelogenous leukemia, represents a
carcinogenic effect of benzene.
Oral administration of benzene to laboratory animals
produced leukopenia, a reduction in number of leukocytes
in the blood. " Subcutaneous injection of benzene-oil solutions
-49-
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has produced suggestive, but not conclusive, evidence of benzene
carcinogenisis.
Benzene demonstrated teratogenic effects in laboratory
animals, and mutagenic effects in humans and other animals.
For maximum protection of human health from the potential
carcinogenic effects of exposure to benzene through ingestion
of water and contaminated aquatic organisms, the ambient water
concentration is zero. Concentrations of benzene estimated to
result in additional lifetime cancer risk at levels of 10"?,
10~6, and 10~5 are 0.00015 mg/1, 0.0015 mg/1, and 0.015 mg/1,
respectively.
Carbon Tetrachloride
Carbon tetrachloride produces a variety of toxic effects
in humans. Ingestion of relatively large quantities - greater
than five grams - has frequently proved fatal. Symptoms are
burning sensation in the mouth, esophagus and stomach, followed
by abdominal pains, nausea, diarrhea, dizziness, abnormal pulse,
and coma. When death does not occur immediately, liver and
kidney damage are usually found. Symptoms of chronic poisoning
are not as well defined. General fatigue, headache, and anxiety
have been observed, accompanied by digestive tract and kidney
discomfort or pain.
Data concerning teratagenicity and mutagenicity of carbon
tetrachloride ace scarce and inconclusive. However, carbon
tetrachloride has been demonstrated to be carcinogenic in
laboratory animals. The liver was the target organ.
-50-
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For the maximum protection of human health from the
potential carcinogenic effects of exposure to carbon tetra-
chloride through ingestion of water and contaminated aquatic
organisms, the ambient water concentration is zero. Concen-
trations of carbon tetrachloride estimated to result in
additional lifetime cancer risk at risk levels of 10"?,
10~6, and 10~5 are 0.000026 mg/1, 0.00026 mg/1, and
0..0026, respectively.
Methylene Chloride
Methyleno chloride is highly toxic by the inhalation route
of exposure over a short period of time.
Inhaled methylene chloride acts as a central nervous
nervous depressant. There is also evidence that the compound
causes heart failure when large amounts are inhaled.
Methylene chloride does produce mutation in tests for this
effect. In atdition a bioassay recognized for its extremely
high sensitiv:icy to strong and weak carcinogens produced results
which were ma:.?inally significant. Thus potential carcinogenic
effects 'of ,me t. •-. 7]' ;~ . chloride are not confirmed or denied, but
are under continuous study. Difficulty in conducting and
interpreting the test results from the low boiling point (40°C)
of methylene cVijride which increases the difficulty of main-
taining the c-v-upound in growth media during incubation at 37°C;
and from the Difficulty of removing all impurities, some of
which might t". ?mselves be carcinogenic.
-51-
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For the protection of human health from the toxic properties
of methylene chloride ingested through water and contaminated
aquatic organisms, the ambient water criterion is 0.002 mg/1.
Trichloroethylene
Data on the effects produced by ingested TCE are
limited. Most studies have been directed at inhalation
exposure. Nervous system disorders and liver damage are
frequent results of inhalation exposure. In the short term
exposures, TCE acts as a central nervous system depressant -
it was used as an anesthetic before its other long term
i
effects were defined.
TCE has been shown to induce transformation in a highly
sensitive in vitro Fischer rat embryo cell system (F1706)
that is used for identifying carcinogens. Severe and per-
sistant toxicity to the the liver was recently demonstrated
when TCE was shown to produce carcinoma of the liver in
mouse strain B6C3F1. One systematic study of TCE exposure
and the incidence of human cancer was based on 518 men
exposed to TCE. The authors of that study concluded that
although the cancer risk to man Cannot be ruled out, exposure
to low levels of TCE probably does not present a very serious
and general cancer hazard.
-52-
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TCE is bioconcentrated in aquatic species, making the
consumption of such species by humans a significant source
of TCE. For the protection of human health from the
potential carcinogenic effects of exposure to trlchloroethylene
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero. Concentrations of
trichloroethylene estimated to result in additional lifetime
cancer risk of 1 in 100,000 corresponds to an ambient water
concentration of 0.00021 mg/1.
Only a very limited amount of data on the effects of
TCE on freshwater aquatic life are available. One species
of fish (fathead minnows) showed a loss of equilibrium at
concentrations below those resulting in lethal effects.
Tetrachloroethylene
Tetrachloroethylene is highly toxic via ingestion and
moderately toxic via inhalation and skin absorption as well as
being carcinogenic.
The prinicipal toxic effect of tetrachloroethylene on
humans is central nervous system depression when the compound
is inhaled". Headache, fatigue, sleepiness, dizziness and
sensations of intoxication are reported. Severity of
effects increases with vapor concentration. High integrated
exposure (concentration times duration) produces kidney
and liver damage. Very limited data on tetrachloroethylene
ingested by laboratory animals indicate liver damage occurs
-53-
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when PCE is administered by that route. Tetrachloroethylene
tends to distribute to fat in mammalian bodies.
One report found in the literature suggests, but does not
conclude, that tetrachloroethylene is teratogenic. Tetrachloro-
ethylene has been demonstrated to be a liver carcinogen in
B6C3-F1 mice.
For the maximum protection of human health from the'
potential carcinogenic effects of exposure to tetrachloroethylene
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero. Concentrations of
tetrachloroethylene estimated to result in additional life-
time cancer risk levels of 10"?, 10~6, and 10"^ are 0.000020
mg/1, 0.00020 mg/1, and 0-.0020 mg/1, respectively.
Naphthalene
Naphthalene, ingested by humans, has reportedly caused
vision loss (cataracts), hemolytic anemia, and occasionally,
renal disease. These effects of naphthalene ingestion are
confirmed by studies on laboratory animals. No carcinogenic!ty
studies are available which can be used to demonstrate carcinogenic
activity for naphthalene. Naphthalene does bioconcentrate in
aquatic organisms.
For the protection of human health from the toxic properties
of naphthalene ingested through water and through contaminated
aquatic organisms, the ambient water criterion is determined to
be 143 mg/1.
-54-
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Only a limited number of studies have been conducted to
determine the effects of naphthalene on aquatic organisms. The
data from those studies show only moderate toxicity.
Pi (2-ethylhexyl) phthalate
Di (2-ethylhexyl) phthalate is insoluble in water. For
the protection of human health from the toxic properties of
di(2-ethylhexyl) phthalate ingested through water and through
contaminated aquatic organisms, the ambient water quality
criterion is determined to be 10 mg/1.
Di-n-butyl phthalate
The water solubility of di-n-butyl phthalate at room
temperature is reported to be 0.4 g/1 and 4.5 g/1 in two
different chemistry handbooks.
For protection of human health from the toxic properties
of di-n-butyl phthalate ingested through water and through
contaminated aquatic organisms, the ambient water quality
criterion is determined to be 5 mg/1.
Toluene
Toluene is moderately toxic by ingestion and inhalation.
Because to'luene is both water soluble and volatile, it may pose
a threat to human health by both exposure routes, respectively.
Toluene is volatile (vapor pressure of toluene is 36.7 mm at
30°C); handling and disposal of the waste may thus pose an
inhalation hazard. If the waste is disposed in an unsecured
landfill the toluene may be solubilized from the waste (the
-55-
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water soluhilif.y of toluene is 535 mg/1, and it is miscible
with a variety of organic solvents) by rainfall and contami-
nate underlying potable groundwater sources with may pose
a hazard to human health when the water is ingested.
Most data on the effects of toluene in human and other
mammals have been based on inhalation exposure or dermal contact
studies. Ther^ appear to be no reports of oral administration
of toluene on human subjects. A long term toxicity study on
female rats revealed no adverse effects on growth, mortality,
appearance -ind behavior, organ to body weight ratios, blood-
urea nitrogen level, bone marrow counts, peripheral blood
counts, or morphology of major organs. The effects of inhaled
toluene on the central nervous system, both at high and low
concentrations, have been studied in humans and animals.
However, ingested toluene is expected to be handled differently
by the bod- because it is absorbed .more slowly and must first
pass through the liver before reaching the nervous system. .
Toluene is <_:>:£ 2 naively and rapidly metabolized in the liver.
One of the principal metabolic products of toluene is benzole
acid, which \':.K?.if seems to have little potential to produce
tissue injury,
Toluene has been found in fish caught in harbor waters in
the vicinity of petroleum and petrochemical plants. Bioconcen-
tration studies have not been conducted, but bioconcentration
factors have been calculated on the basis of the octanol-water
partition coefficient.
-5.6-
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For the protection of human health from the toxic properties
of toluene ingested through water and through contaminated
aquatic organisms, the ambient water criterion is determined to
be 12.4 mg/1.
1,1,1-Trichloroethane
Most human toxicity data for 1,1,1-trichloroethane
relates to inhalation and dermal exposure routes. Limited
data are available for determining toxicity of ingested
1,1,1-trichloroethane, and those data are all for the
compound itself not solutions in water. No data are
available regarding its toxicity to fish and aquatic
organisms. For the protection of human health from the
toxic properties of 1,1,1-trichloroethane ingested through
the consumption of water and fish, the ambient water
criterion is 15.7 mg/1. The criterion is based on bioassy
for possibly carcinogenicity.
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References
1. U.S. EPA, Effluent Guidelines Division, Development
Document for Proposed Effluent Limitations Guidelines,
New Source Performance Standards, and Pretreatmeut
Standards for the Paint Formulating Point Source
Category, December, 1979.
2. U.S. EPA, Office of Solid Waste. Assessment of
Hazardous Waste Practices: Paint and Allied
Products Industry, Contract Solvent Reclaiming
Operations, and Factory Application of Coatings.
WAPORA. 1976.
3. U.S. EPA, RCRA Docket, Section 3001. Comments to
proposed regulations, letters #0355, #0817.
4. N. Irving Sax, Dangerous Properties of Industrial
Materials, Fourth Edition, Van Nostrand Reinhold
; Company, New York, 1975.
5. U.S. EP,A files, Illinois Waste Disposal Applications
6. U.S. EPA files, N.J. Industrial Waste Surveys
7. Gosselin, Robert E. at al., Clinical Toxicilogy of
Commercial Products, Fourth Edition, The Williams and
Wilkin Company, Baltimore, 1976.
8. Verschueren, Karel, Handbook of Environmental Data on
Organic Chemicals, Van Nostrand Reinhold Company, 1977.
9. Peakall, D.B. 1975 Phthalate esters: occurence and
biological effects. Residue Reviews, Vol. 54.
Springer-Verlag New York Inc., p. 1-41.
10. U.S. EPA, Effluent Guidelines Division, Development
Document for Efflent Limitations Guidelines and
Standards for Foundries, Metal Molding and Casting
Point Source Category, Tection VI--Pollutant Parameter^,
April 1980.
11. U.S. EPA, Water - Related Fate of 129 Priority Pollutants,
EPA-440/4-79-0296 (1979; (2 volumes).
12. Sikka, H.C., et al., 1978. Fate of 3 ,3'-Dichlorobenzidene
in Aquatic Environments. U.S. EPA 600/3-8-068.
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Response to Comments to the Proposed Rule
Two commenters responding to the proposed Hazardous Waste
Guidelines and Regulations (43 FR 58946, December 18, 1978)
objected to the classification of paint wastes, stating that
EPA had been "overly broad" in its classification (5). Dupont
commented that the diversity of products, product types, and
different chemical formulations makes the listing of paint
wastes (specifically "water-based paint wastes") impossible
without a detailed listing of the waste generated by the
manufacture of various paint products.
Based on the information presented in this document,
the Agency believes these listed wastes are typically or
frequently hazardous. Individual generators can, of course,
petition to delist their waste. In further reponse, EPA
cites information considered by Effluent Guidelines Division
for subcategorization of the paint industry (1):
EPA considered the following factors in determining
whether differences within the paint industry might
require separate limitations:
1. Raw materials and products
2. Production Methods
3. Size and age of production facilities
4. Wastewater characteristics
5. Tank cleaning techniques.
The Agency concluded that tank cleaning techniques offer
appropriate basis for subcategorization; examination of the
other four factors proved to be inappropriate for subcategori-
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zation. (See Reference 1, pp. 53-55).
A second comment was that wastewater treatment sludge from
i
latex paint production is not hazardous because extracts of the
waste do not exceed 10 times the drinking water standards.
National Paint and Coatings Association submitted extraction
data on seven samples of latex sludge using the TEP ("Toxicant
Extraction Procedure"—-an extraction test which was a pre-
proposal version of the EP). Test results show heavy
metals in the extract to be less than 100 times the drinking
water standard for those metals.
As far as differentiating latex paint wastewater treatment
sludge from other wastewater treatment sludge in the industry,
EPA cannot do so because 1) only 4.8% of paint manufacturers
produce exclusively water-based paint and 2) when evaluating
factor #4 listed above, EPA found that no specific segment
of the industry has a sig-.if icantly different quality or
quantity of wastewater, and therefore concludes the same
for the wastewater treatment sludge. In addition, EPA is
listing wastewater treatment sludge for factors other than EP
toxicity,' including levels of heavy metals in the sludge, total
quantities of the waste produced and disposed per year, and,
perhaps most significantly the presence of toxic organics
in the sludge.
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Organic Chemicals
-------
LISTING BACKGROUND DOCUMENT
NITROBENZENE/ANILINE PRODUCTION
Distillation Bottoms from Aniline Production (T)
Combined Wastewater Streams Generated from Nitrobenzene/
Aniline Production (T)*
Process Residues from Aniline Extraction (T)*
I. Summary of Basis for Listing
The first listed waste is the distillation bottom residue
from the purification of aniline by distillation. The second
listed wa^te is the combined process wastewater streams from
the co-production of nitrobenzene and aniline. These waste
streams contain toxic nitrogenous organic materials/ and the
wastewater stream is likely to contain benzene as well. The
third listed waste stream results from the extraction step in
aniline p . oductior., and may or may not be combined with other
process waters. This listing covers the uncombined waste
stre ams.
- The ;'V..!miri itrator has determined that still bottoms from
aniline distillation, process residues from aniline extraction
(when generai ad as a separate waste stream and not combined
with other ? ocess wastewater streams), and wastewater generated
from nitr>- oenzene and aniline production are solid wastes
which may pose a substantial present or potential hazard to
*These wast streams were not included in the initial listing,
and are in -.ally proposed in the present document.
-------
human health or the environment when improperly transported,
treated, stored, disposed of or otherwise managed, and there-
fore should be subject to appropriate management requirements
under Subtitle C of RCRA. This conclusion is based on the
following considerations:
1) The distillation bottoms contain aniline, diphenyl-
amine, nitrobenzene, and phenylenediamine while the
combined wastewater stream contains these constituents
and usually contains benzene as well.* The process
residues from aniline extraction, if disposed of
separately, contains aniline, nitrobenzene and
phenylenediamine. All of these constituents are
toxic. Benzene is a known human carcinogen.
Aniline, diphenylamine and phenylenediamine are
carcinogenic to laboratory animals. Diphenylamine
is expected to bioaccumulate.
2) Current disposal practices of these wastes are not
well documented. However, there is a high potential
for contaminating groundwater by leaching from
waste treatment lagoons or landfills that are not
properly designed or operated, since these constituents
have high migratory potential, and some have proven
mobile and persistent in actual waste management
practice. In addition, under certain conditions,
release to the atmosphere by volatilization poses
a risk of inhalation of aniline and nitrobenzene.
3) In a damage incident involving improperly managed aniline
distillation bottoms, waste oils were contaminated with
nitrobenzene from the distillation residues and spread
over roads, posing the risk of human exposure to dangerously
high, concentrations of nitrobenzene. This waste has thus
proven capable of posing a potential substantial
hazard in actual waste management practice.
4) The State of Texas regulates distillation bottoms
from aniline production as a hazardous waste.
* Aniline, diphenylamine and plienyl enediamine are not presently
listed in Appendix VIII to Part 261. An amendment to
Appendix VIII to add these constituents is being prepared
concurrently with this listing document.
-2-
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5) Total potential loadings of benzene and aniline in the
wastewater stream from the production of nitrobenzene and
aniline could be as high as 9.5 kkg and 150 kkg annually,
quantities believed by the Agency to be quite significant in
view of these compounds' adverse health effects.
II. Sources of the Waste and Typical Disposal Practices
A. Profile of the Industry
Nitrobenzene and aniline are major chemical inter-r
mediates; the actual nameplate capacity was reported as
557,000 kkg(25) and 313,000 kkg respectively.(2) The U.S.
International Trade Commission lists aniline as the sixth
largest volume intermediate in terms of 1978 production.(^)
Table 1 lists the facilities producing nitrobenzene and
aniline, and their production capacities. As is indicated,
most facilities produce both nitrobenzene and aniline. In
fact, 97% of nitrobenzene produced is used for the synthesis
of aniline. The balance is purified for use chiefly as a
solvent, or in the manufacture of Pharmaceuticals, dyes and
photographic chemicals.
United States production of aniline is increasing.
Production levels were 151,000 kkg in 1969, 186,000 kkg in
1972, 187,000 kkg in 1975,<3> and 270,000 kkg in 1978.(D
Aniline production capacity is anticipated to reach 450,000
kkg in 1980. Most aniline (about 40%) is used for the prod-
uction of methylene diisocyanate, an intermediate used in
the manufacture of urethanes; another 35% is used in the
-3-
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Table 1
PRODUCER LOCATIONS AND PRODUCTION CAPACITIES
MANUFACTURER
American Cyanamid Co.
American Cyanamid Co.
E. I. Dupont de Nemours
& Company, Inc.
E. I. Dupont de Nemours
& Company/ Inc.
First Mississippi Corp.
Mallinkrodt Corp.
Mobay Chemical Corp.
Rubicon Chemicals, Inc.
PRODUCTION CAPACITY (103kkg)
1978
1977
FACILITY
Bound Brook, NJ
Willow Island
Beaumont, TX
Gibbstown, NJ
Pascaqoula, MS
Raleigh, NC
New Martinsville, WV
Geismar, LA
Nitrobenzene*25^ Aniline^2*
48
33
140
90
151
0
61
34
557
27
28
104
59
45
10
45
27
340
-4-
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synthesis of rubber chemicals.^) The remainder is mainly
used in the manufacture of dyes and drugs.
B. Manufacturing Process(2)
1. Manufacture of Nitrobenzene
Nitrobenzene is made by the direct nitration of
benzene using a sulfuric-nitric acid mixture. In the most
common continuous phase process, benzene is nitrated with an
aqueous mixture of sulfuric acid (53 to 60 mole percent) and
nitric acid (39 to 32 mole percent) at atmospheric pressure
and temperatures between 45 to 90°C. Yields are typically
better than 98 percent. This process (see Figure 1) is
carried out in vented stainless steel vessels equipped with
high speed agitators and cooling coils. Average residence
time is approximately 8 to 10 minutes. Nitrobenzene is
continuously drawn from the side of the reactor and separated
in a decanter. Once separated, this "crude" nitrobenzene is
reportedly used directly in the manufacture of aniline.
If pure nitrobenzene is required, the product is washed
first with water and subsequently9 with an alkaline solution
(generally either a sodium carbonate or sodium hydroxide
solution) in small vessels equipped with high speed mechanical
agitators, and then distilled. The wastewater resulting
from the washing operation (stream 3 in Figure 1), is one
component of the waterborne waste stream of concern in this
document.
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FIGURE 1
SIGNIFICANT POLLUTANTS FROM
NITROBENZENE/ANILINE MANUFACTURE (MODIFIED FROM (2))
NITROBENZENE MANUFACTURE
ANILINE MANUFACTURE
Sulfurlc Acid ^Tp
(Recycle to < I
Still Bottoms
- -fWastes to
Incineratoi
(Recycl
Reactor)
Point 1* -
Benzene, Nltroalkanes, Nitrobenzene, Nitrogen Oxides
Point 2*
Benzene, Nitroalkanes, Nitrobenzene, Nitrogen Oxides
Point 3
Benzene, Benzoic Acid, Carboxylic Acids, Nitrates, Nitrites,
Nitrobenzene, Nitrophenol
Point 4**
Dinitrobenzene, Nitrobenzene, Nitrophenol, Nitrogen Containing
High Molecular Weight Polymers, Polycarboxylic Acid, Dinitro-
toluene
-------
FIGURE 1 CONTINUED
Point 5
Benzene, Nitrobenzene, Nitrophenol, Polycarboxylic Acid, Nitro-
gen Containing High Molecular Weight Polymers
Point 6*
Aniline, Carbon Monoxide, Hjrdrogen, Methene, Nitrobenzene
Point 7* ._ . • •
Cyclohexylamine, Volatile Amines, Water
Point 8*
Aminophenols, Azepins, Diphenylamine, Nitrobenzene, Phenyl-
enediamine, Nitrogen Containing High Molecular Weight Polymers
Point 9
Aminophenol, Aniline, Nitrobenzene, Phenylenediamine, Water
Soluble Amines
* Emitted to air and therefore not subject to RCRA.
**This waste was listed in the May 19, 1980 promulgation (see
"Nitrobenzene Background Document" for details).
-------
Figure 1 to be inserted here.
Recovery of spent acid (A in Figure 1), is essential,
from the standpoint of economical operation. Generally/
unreacted nitric acid is extracted from the spent acid by
steam stripping (denitrating tower). The bottom product/
dilute sulfuric acid (60 percent by weight), is then concen-
trated by distillation (sulfuric acid concentrator) and
recycled to the reactor as shown, or used in other manufacturing
operations. Nitric acid removed overhead from the denitrating
tower is bleached with air to remove nitrogen oxide and
subsequently recycled to the reactor. The overhead nitrogen
oxides from the bleacher are scrubbed with water and recycled
to the denitrating tower.* The waste resulting from acid
recovery (number 5 in Figure 1) is another component of
the aqueous waste stream of concern in this document*
2. Production of Aniline(2'3)
In the U.S., aniline production is based almost exclusively
on vapor phase reduction of nitrobenzene in the presence of a
copper catalyst. This process is also illustrated in Figure 1.
With the exception of one facility (Mallinkrodt, Inc.), the
nitrobenzene feedstock is produced on site.(2) The nitrobenzene
is vaporized in a stream of hydrogen and introduced into the
reactor. The crude product mixture (aniline, hydrogen and
water) leaving the reactor is condensed and separated from
*Another approach to spent acid recovery uses benzene, rather
than steam, to strip nitric acid from spent acid in the de-
nitrating tower. The nitric acid is thus dissolved in the
benzene and fed to the reactor. The remaining sulfuric acid
is concentrated as before.
-6-
-------
the gas stream. Most of this gas stream is compressed and
recycled to the reactor, but, to prevent build-up of gaseous
impurities in the reactor, some gas is purged. The two-phase
(aqueous and organic) reactor product mixture is separated.
The lower organic phase (stream B, Figure 1), consisting
principally of aniline, up to 5 percent nitrobenzene, and 5
percent water,(2) is purified by two stage distillation.
In the crude still, aniline and water are removed overhead,
while higher boiling organic impurities, such as nitrobenzene,
remain in the still bottoms (noted as 8, Figure 1). In a finishing
distillation step, the overhead product from the crude still
is purified to 99% specification, and the bottoms from
this finishing distillation step are combined with the crude
distillation bottoms. (This process is shown as a single
distillation in Figure l.)(3)
Several methods are used to recover aniline from the
aqueous phase of the separator (C in Figure 1). Aniline may
for instance be concentrated from this stream by steam stripping.
The resulting enriched aniline/water mixture is then incinerated.
This latter waste stream is not included within the present
listing, although it may be listed in the future. The Agency
solicits information as to the composition of this waste and
risks associated with its improper disposal.
At some facilities aniline is recovered by countercurrent
extraction with nitrobenzene. Recovered aniline and nitrobenzene
are recycled to the reactor. In either case (i.e., if either
-7-
-------
extraction or steam stripping is used), the residual waste
stream (9 in Figure 1) ordinarily is directed to wastewater
treatment with other process wastewater streams. This is
the third component of the waterborne waste stream of concern
in this document. In some facilities/ the residues from the
extraction step are not combined with other process wastewaters.
In such cases/ the listing includes the separate wastewater
stream from the extraction step.
C. Waste Generation and Management
The\listed wastes consist of still bottoms from the
distillation of aniline (Point 8, Figure 1) and the wastewater
streams generated from nitrobenzene/aniline manufacture
(points 3, 5 and 9 of Figure 1), which are most often combined
before wastewater treatment. (Wastes from the aniline extrac-
tion step are listed when disposed of separately/ as discussed
above . )
On the basis of process chemistry assumptions set forth
in (2), the aniline distillation bottoms are expected to
contain nitrob.enzene, aniline, diphenylamine, and phenylenediamine
While precise concentrations are unknown, concentrations of
nitrobenzene are expected to be quite high, since the organic
phase prior to distillation consists of 5 percent nitrobenzene,
most of which would be expected to be (and is intended to be)
removed .by distillation. A damage incident involving this
waste (described at pp. 14-15 below) likewise suggests that
nitrobenzene concentrations may be quite substantial.
-8-
-------
The volume of aniline still bottoms and the present
practices of the industry with regard to their disposal are
not well defined. The most common disposal method for
distillation bottoms is storage in drums in private landfills.(2
Some of these wastes are apparently utilized for their acid-
neutralizing capacity in drilling operations.(*'
The wastewater stream components from nitrobenzene/aniline
manufacture include: the nitrobenzene washwater (Point 3),
the acid distillation column overhead (point 5) and the
aniline recovery stream (point 9). Based on a knowledge of
process chemistry, these streams are estimated to contain
the pollutants indicated in Figure 1. Most manufacturers
combine these waste lines prior to treatment.^) Table 2
lists typical concentrations of selected pollutants found in
combined nitrobenzene/aniline waste streams, as reported by
two manufacturers.(2^
A variety of wastewater treatment methods are applied,
and it is not known to what extent these are successful in
removing the toxic chemicals from the listed waste. The
following treatment methods have been reported:^) steam
stripping, carbon adsorption, aerated lagoon, biological
contact, clarification, equalization, activated sludge,
stabilization pond, land application, and subsurface disposal.
As.noted above, the waste waters from the extraction
step of aniline production are not always combined with other
process wastewater streams. When disposed of separately,
j
mm Q —
-------
Table 2
Characterization of Raw Waste Loading From
Nitrobenzene/Aniline Manufacture(2)
kg/kkg aniline product kkg/yr*
Avg. Min. Max* Max.
Aniline 0.067 0.005 0.49 150
Benzene 0.005 0 0.031 9.5
Nitrobenzene 0.002 0 0.012 3.7
In addition to the above pollutants whose identity was
quantitatively confirmed, animophenol, benzoic acid,
nitrophenol, and phenylene diamine as well as nitrates and
nitrites are estimated^) to occur. Of these constituents
the wastewater loading data shcv that at least aniline,
benzene and nitrobenzene are present in substantial
concentrations, and generated in significant quantities
annually .
*Obtained by multiplying the maximal value by the 340,000
kkg by 90% of annual aniline nameplate production capacity
(since plants rarely operate at 100% of capacity).
-10-
-------
this waste stream is expected to .contain aniline, phenylenediamine
and nitrobenzene as constituents of concern.(2)
III. Discussion of Basis for Listing
A. Hazards Posed by the Waste
On the basis of available information, it is apparent
that the listed wastes contain toxic organic materials, including
nitrobenzene, aniline, diphenylamine and phenylenediamine, and
(for the combined wastewaters) benzene. These constituents
are all toxic, and all but nitrobenzene are experimental or
(in the case of benzene) known carcinogens. All of these
constituents are projected to have migratory potential and
to be mobile and persistent in ground and surface water
(Appendix B), so that they can create a substantial hazard
if disposal facilities are not properly designed and operated.
Aniline, nitrobenzene and phenylenediamine are quite soluble
(solubility 34,000, 38,000 ppm and 1900 ppm respectively),(6)
and thus can easily migrate through unsaturated sandy soils.
Diphenylamine is also significantly soluble for purposes of
risk of chronic exposure (300 ppm (6)). Furthermore, the
solubility of amines such as aniline and phenylendiamine
increases significantly under conditions which are more
acidic than their acid dissociation constant (pKa is 6.0 for
phenylenediamine). Since the pH of the rainfall in the
United States presently ranges from 4.0 - S.O^9'22),
residues of aniline and phenylenediamine can be expected to
-11-
-------
leach to surface and groundwater if these wastes are improperly
transported/ treated, stored, disposed of, or otherwise
managed.
Present waste disposal practices may be inadequate to
prevent waste migration. Certainly, improper management may
result in release of harmful constituents, particularly in
view of the properties of the waste constituents as described
above. For instance, if this waste should be exposed to an
environment subject to acid rainfall, disposed residues
containing phenylenediamine contacted by acid rainfall can
be expected to leach and to migrate to surface and groundwater.
Further, if this waste is treated in a lagoon, even
under relatively mild environmental conditions, the harmful
constituents can be expected to leach from the waste, as a
result of their moderate to extreme water solubility properties.
Once released from the matrix of the waste, these constituents
could migrate from the waste and contaminate groundwater.
Nitrobenzene, for example, has proven mobile and persistent
in two major damage incidents involving waste disposal at the
Monsanto Chemi'cal dump in East St. Louis and at the LaBounty
dump in Charles City, lowa.(lO)
Another potential hazard associated with lagoon treatment
of this waste would be the volatilization of compounds with
appreciable vapor pressure such as benzene into the atmosphere/
thus posing a hazard via inhalation. Benzene has proven
capable of migration and persistence via an air exposure
-12-
-------
pathway in many actual damage incidents, Love Canal being the
most notorious.
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 many of the subject production facilities are
located in regions of significant rainfall (LA, NJ, WV), so
that ample percolating liquid is available for leachate
formation. (In any case, there is no reason to believe that
wastes will be containerized at all, since, absent Subtitle C
regulation, wastes could be landfilled in a variety of improper
ways.)
A special hazard posed by these subject wastes is the
poss.-bility of the formation over time of highly carcinogenic
nitrosamines from some of their constituents.^) Aniline and
other amines (most importantly secondary amines) as well as
nitrites are thought to be present in these wastes (Figure
1). These substances may react to form nitrosamines, especially
under acidic conditions. Such conditions might result as a
consequence of co-disposal of the listed wastes with acidic
wastes, "or under conditions of continued acid rainfall.
Improperly managed aniline distillation bottoms have
been involved in at least one damage incident.(23) From 1976
-13-
-------
through November 1978, contaminated waste oils were used as
dust suppressants on roads throughout East Texas. The chief
source of contamination were aniline tars (still bottoms)
from aniline production*, generated by Dupont's Beaumont
facility. These still bottoms were sent to Browning-Ferris
Industries Chemical Services/ Inc./ a state permitted waste
management facility, which proceeded impermissibly to mix the
wastes with waste oil, which oil was used indiscriminately as
a road dust supressant. Nitrobenzene levels in contaminated
soil varied, and were as high as 21,000 ppm. Most of the
concentrations were deemed by state environmental officials
as more than sufficient to cause substantial harm. The danger
was discovered before occurence of known harm, and Browning-
Ferris was ordered to remove approximately 10,000 cubic yards
of contaminated material from one subdivision, and additional
amounts of material from four additional subdivisions.'23)
This incident not only illustrates the potential for
substantial harm if this waste is disposed of improperly, but
also suggests strongly that the aniline distillation residues
may contain very high concentrations of nitrobenzene, in
light of the substantial concentrations found in the contaminated
road oil. Furthermore, aniline distillation bottoms are
* The waste oils were heavily contaminated with nitrobenzene,
and the only source of nitrobenzene in wastes accepted by
Browning-Ferris were aniline distillation wastes. (23 at p. 17.)
-14-
-------
regulated as hazardous wastes (termed 'Class I wastes' under
the state waste management system) by the State of Texas
(23), another indication of their potential for hazard.
B * Health and Ecological Effects of Waste Constituents
of Concern
Benzene
Acute exposure to high concentrations of benzene causes
central nervous system depression (euphoria, nausea, staggering
gait and coma). Inhalation of lower amounts produces dizziness,
headache and nausea. EPA's Carcinogen Assessment Group has
designated benzene as a human carcinogen (leukemogen).
Benzene demonstrated teratogenic effects in laboratory
animals. Chromosomal changes have also been demonstrated in
workers exposed to benzene.(28)
For maximum protection of human health from the potential
carcinogenic effects of exposure to benzene through ingestion
of water and contaminated aquatic organisms, the ambient
water concentration is zero. Concentrations of benzene
estimated by the Agency's Carcinogen Assessment Group to
result in additional lifetime cancer risk at levels of 10~7,
10"6, and 10~5 are 0.00015 mg/1, 0.0015 mg/1, and 0.015
mg/1, respectively.(29)
Because benzene is soluble in water, it could be leached
from the wastewater treatment sludge which would be generated
from treatment of the combined wastewaters, in a landfill
situation and pose a threat to groundwater supplies. Because
-15-
-------
it is also volatile (vapor pressure = 100 mm at 26.1°C .
(Appendix B.)), it may pose an inhalation hazard during
handling in transportation and disposal. Additional information
on the adverse health and environmental effects of benzene
can be found in Appendix A.
Nitrobenzene
Nitrobenzene has toxic reproductive effects: in rats it
delays embryogenesis, alters normal placentation, and produces
abnormal fetuses (14); changes in the tissues of the chorion
and placenta have been reported in women exposed to nitrobenzene
(15). Nitrobenzene has been listed as a Priority Pollutant
in accordance with §307(a) of the Clean Water Act of 1977.
With present data, it is not possible to fully estimate
its aquatic fate. Hydrolysis and volatilization from water
are considered unlikely. Adsorption onto humus and clay,
and subsequent production by weathering and biological action,
of (carcinogenic) benzidine and diphenylhydrazine could be
a major fate pathway (12) Nitrobenzene is neither stored
nor ecologically magnified, but is resistant to degradation
by soil microflora (11, 12). In mammalian systems nitrobenzene
is metabolized to aniline, nitrophenol, p-hydroxyaniline
and other metabolites, which are excreted in urine, but such
metabolism in man is slower by an order of magnitude than in
~~x
animals (13).
The criterion to protect freshwater aquatic life is 480
ug/1 (24 hour average). The occupational exposure limit
-1 6-
-------
(OSHA) is 5 rng/m^ (skin, 8 hr TWA). The American Conference
of Governmental Industrial Hygienists (ACGIH) threshold
limit for industrial exposure to nitrobenzene is 1 ppm.(23)
Additional information on the adverse health e'ffects of
nitrobenzene can be found in Appendix A.
Aniline
Aniline is an experimental carcinogen (18). Its absorption
causes anoxia due to the formation of methemoglobin, but
significant chronic problems (other than animal carcinogencity)
have not been demonstrated. Human exposure to vapor
concentrations of mm has been observed to cause slight
symptoms. (^") Rapid absorption through the intact skin is
frequently the route of entry.(1&'3°) Cyanosis is the most prominent
outward symptom of aniline intoxication.(8) At 0.4 mg/1
aniline is toxic to Daphnia (8). OSHA's PEL for aniline is
19 mg/m-* (skin, 8 hr TWA) (17). Additional information on
the adverse health effects of aniline can be found in Appendix A.
P h e ny1en e di am i ne
Phenyl en'ediamine is a highly toxic substance (18), con-
tinued exposure to which can cause liver injury. It is a
suspected carcinogen and teratogen (18). Of the three isomers,
the p-substituted compound is by far the more toxic (19).
The relative concentrations of these isomers in the listed
waste are not known. The oral toxicity for human beings is
high (LDlo= 50 rag/kg (19)), so the high water solubility
of this compound is worr some. Phenylenediamine is listed
-17-
-------
by DOT as a hazardous substance (ORM-A), and the OSHA PEL is
0.1 mg/m3(8 hr TWA) (17).
Diphenylamine
Diphenylamine is an experimental carcinogen.and teratogen
(19). Chronic exposure to diphenylamine induces cystic lesions
in the chicken(20) an
-------
References
1. D.B. Beck et al./ United States International Trade Commission,
Synthetic Organic Chemicals; United States Production and
Sales, 1978, US ITC Publication 1001, 1979.
2. W. Lowenbach and J. Schlesinger, Nitrobenzene/Aniline Manufacture;
Pollutant Prediction and Abatement, Mitre Corporation Report
No. MTR-7828 on EPA Contract 68-01-3188, May 1978.
3. J. Northcott, "Aniline and Its Derivatives" in M. Grayson and
D. Ekroth, Eds., Kirk-Othmer Encyclopedia of Chemical Technology,
3rd ed., Vo1 2. Wiley Inter science, 1978.
4. Arthur D. Little, Inc. information (D. Ennis)
5. Handbook of Chemistry and Physics, 47th ed, Chemical Rubber
Co., Cleveland, OH 1966.
6. P.A. Patty, Industrial Hygiene and Toxicology, Vol II
Interscience Publishers, New York 1963.
o-
7. C. Hansch and A. Leo, Substituent Constants for Correlation
Analysis in Chemistry and Biology John Wiley and Sons, NY 1979.
8. K. Verschueren, Handbook of Environmental Data on Organic
Chemicals. Van Nostrand Reinhold Company, N.Y. 1977.
9. G.E. Likens, R.F. Wright, J.N. Galloway, and T. Butler.
Acid Rain, Scientific American 241(4): 43-51(1979).
10. Mitre Associates, Draft Environmental Impact Statement for
Subtitle C RCRA, January 1979. OSW Hazardous Wastes Management
Division, Hazardous Waste Incidents. Unpublished, open file
data .
11. Federal Register, Vol. 43 , No. 243, 59025-27, "Bioaccumulation
Potential Test." . - , , -
12. M.A. Callahan et. al. Water-related Environmental Fate of 129
Priority Pollutants, Vol II. EPA 440/4-79-0296. December 1979.
13. J. Piotrowsky, Exposure Tests for Organic Compounds in Industrial
Toxicology. NIOSH 77-144 USDHEW 1977.
14. Kazanina, S.S. Morphology and histochemistry of hemochorial
placentas of white rats during poisoning of the maternal organism
by nitrobenzene, Bull. Exp. Biol. Med. 65: 93 (1978).
-19-
-------
15. J. Dorigan and J. Hushon. Air Pollution Assessment of
Nitrobenzene U.S. EPA. 1976.
16. C.W. Chin et. al Mutagenicity of some commercially available
nitro compounds for Salmonella typhimurium, Mutat. Res.
58: 11 (1978).
17. 29CFR1910.1000.
18. N.I. Sax, Dangerous Properties of Industrial Materials/ Van Norstrand
Reinhpld, N.Y. 1979.
19. Registry of Toxic Effects of Chemical Substances
N.I.O.S.H. - USDHEW, 1978.
20. F. Sorrentino/ A. Fella and A-Porta, 1978. Dipherilauine-
Induced Renal Lesions in the Chicken. Urol. Res 6/2:71-5
21. Threshold Limit Values for Chemical Substances in Workroom Air
with Intended Changes for 1979. American Conference of
Govermental Industrial Hygienists, Cincinnati, OH 45201
22. Cowling, E. B., Acid Precipitation and its Effects on Terrestial
and Aquatic Ecosystems. Annals, N.Y. Acad. Sci. 338: 540-556,
(1980).
23. C. J. Oszman, EPA, June 21, 1980, Personal Communication with
J. S. Bellin, EPA.
24. K.D. Ganier Jr., S. Solomon, W.W. Fitzgerald and A.P. Evan,
1976, Function and Structure in the dipherzlaurine exposed
kidney. J. Clini. Invest. 57(3): 796-806.
25. Directory of Chemical Producers, 1979, Stanford Research
Institute.
26. Lowensteim and Moran, Faith, Key's and Clark's Industrial
Chemicals, 4th ed., New York, 1975.
27. Recommended Methods of Reduction, Neutralization, Recovery,
or Disposal of Hazardous Wastes, Volume XI: Industrial and
Municipal Disposal Candidate Waste Stream Constituent Profile
Reports, Organic Compounds (continued) EPA 670/2-73-053-k,
TRW Systems Group, August 1973.
28. Trough, I. M. and Brown, W. M., 1965. chromosome Aberrations
and Exposure to Ambient Benzenes. Lancet 1:684.
-20-
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HAZARDOUS WASTE LISTING BACKGROUND DOCUMENT
Di8tillation or Fractionating Column Bottoms from Production
of Chlorobenzenes (T)
Separated Aqueous Stream from the Reactor Product Washing Step
in the Batch Production of Chlorobenzenes (proposed) (T)*/
Distillation or fractionation column bottoms from the
**/
production of Chlorobenzenes, and the separated aqueous
waste stream from the reactor product washing step in the
batch production of Chlorobenzenes, are composed of a vary-
ing mixture of Chlorobenzenes (dichlorobenzene through hexa-
chlorobenzene) and benzyl chloride, and may also contain
benzene and monochlorobenzene. The Administrator has deter-
mined that these waste streams are solid wastes and as solid
wastes may pose a substantial present or potential hazard to
human health or the environment when improperly treated,
stored, disposed of, transported or otherwise managed. There-
fore, these wastes, should be subject to appropriate management
requirements under Subtitle C or RCRA. This conclusion is
based on the following considerations:
1. Distillation or fractionating column bottoms from
chlorobenzene production are likely to contain 'sig-
nificant concentrations of dichlorobenzenes, tri-
chlorobenzenes, tetrachlorobenzene, pentachloroben-
j^/This waste stream was not included in the original waste
listing, and thus is being initially proposed in the present
document.
j*j*/Throughout this background document, the terms 'chlorobenzene'
and 'chlorinated benzene' are used synonoraously.
-------
zene and hexachlorobenzene. Benzyl chloride is
also expected to be present in significant concen-
trations. Benzene and monochlorobenzenes may also
be present in lesser concentrations depending on the
efficiency of distillation . The dichlorobenzenes,
trichlorobenzenes and tetrachlorobenzenes are all
toxic. Hexachlorobenzene and benzene have been
Identified as having substantial evidence of carcin-
ogenicity by the Carcinogen Assessment Group. Penta-
chlorobenzene has been reported to induce cancers
in some animal species. Benzyl chloride is report-
edly carcinogenic. Monochlorobenzene is toxic.
All of the chlorobenzenes are also highly bioaccu-
malative.
2. The separated aqueous waste stream from the batch
production of chlorozenzenes is believed to contain
significant concentrations of benzenes, and also
contains the various chlorobenzenes, and probably
phenols and chlorinated phenols, some of which are
carcinogens, and all of which present acute and
chronic toxicity hazards.
3. These waste constitiuents are capable of migration,
mobility and environmental persistence if managed
Improperly, and have caused substantial hazard in
actual damage incidents. Disposal of these distil-
lation bottoms and the aqueous waste in uncontrolled
landfills, therefore, could allow migration of con-
taminants to ground and surface waters and release
of volatile toxicants to the air, while improper
incineration may result in the generation of ex-
tremely hazardous compounds such as phosgene.
I. Industry Characterization and Manufacturing Process (1)
There are twelve chlorinated benzene compounds that can
be formed during the chlorination of benzene including mono-
chlorobenzene, three isomers of dichlorobenzenes, three of
trichlorobenzenes, three of tetrachlorobenzenes, pentachloro-
benzene and hexachlorobenzene.
— Monochlorobenzene is the dominant commercial product; in
"-. •
1978, production was approximately 134,000 metric tons.(l)
-2-
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Production of orthc- and para-dichlorobenzene was estimated
at 10,000 metric tons each for that same year.(l) Production
of 1,2,4-trichlorobenzene was 13,000 metric tons in 1973.
It is estimated that approximately the same amount was
s
produced in 1977.(1) Statistics for other chlorobenzenes are
unavailable because they have limited commercial value and their
production is limited to their formation as by-products.(1)
Major producers of chlorobenzenes in the United States include:
Allied Chemical Corporation (Syracuse, New York); Dow Chemical
Company (Midland, Michigan); Monsanto Company (Sauget, Illi-
nois); Montrose Chemical Corporation of California (Henderson,
Nevada); PPG Industries, Inc. (Natrium, West Virginia);
Specialty Organics, Inc. (Irwindale, California); and Standard
Chlorine Chemical Company, Inc. (Delaware City, Delaware).(2)
Chlorobenzene, dichlorobenzenes, and higher chlorinated
benzenes are produced in batch and in continuous processes by
direct chlorination of benzene in the presence of a Friedel
Craft catalyst, such as ferric chloride, as shown in the
following reaction for monochlorobenzene:
Ci
V
+ !
1,3-Dichlorobenzen*, 1 , 3 , 5-trichlorobenzene and 1,2,3,5-
tetrachlorobanzene are not produced by the method discussed
below.
-3-
-------
Because higher chlorinated benzenes always result from the
direct chlorination of benzene, chlorobenzene production, is a
multiple product operation, i.e. a whole range of chlorinated
benzenes may be produced. Product ratios are influenced by
temperature, mole ratios of the feedstocks, residence time,
and the catalyst. Additionally, the crude reaction product
of a continuous process may be recycled to the process to
achieve the desired final product mixture. Depending on the
final product mixture, chlorobenzenes are purified by frac-
tional distillation and/or crystallization. Continuous
chlorination processes, in contrast to batch processes,
minimize the amount of higher chlorinated products,
thereby maximizing monochlorobenzene yields.
A. Production of Monochlorobenzene
1. Continuous Process (modified from Reference 1,6,7)
As shown in Figure 1 (p. 5A), in a typical continuous
process for the production of chlorobenzenes, anhydrous benzene
and chlorine are introduced into a reactor operating at a
bottom temperature of 90-125°C and a top temperature of
about 808C. -Benzene is introduced near the top of the column,
and an equimolar amount of chlorine is introduced near the
midpoint of the reactor. A variety of catalysts may be
used, usually iron or ferric chloride impregnated on a suitable
carrier.
-4-
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CONDENSER
BENZENE;
DRIER I
CHLORINE-
RECYCLE
BENZENE!
oc
O
oc
g
o
01
Q
L
H2O-
VENT
A
SCRUBBER
HCI SOLUTION
CARBON COLUMN
(OPTIONAL) '
RECOVERED
ORGANICS
SEPARATOR
>r.CHLOROBENZENEi
FRACTIONATING
COLUMN
DICHLOROBENZENES
TO FRACTIONAL
CRYSTALLIZATION
REACTOR
DICHLOROBENZENES \
AND HIGHER
CHLORINATED BENZENES
FRACTIONATING
COLUMN
V
SOLID WASTES
(HIGHER BOILING
CHLORINATED BENZENES AND
FEEDSTOCK! iNPu RITI ES)
FIGURE 1
CONTINUOUS PRODUCTION OF CHLOROBENZENE (MODIFIED FROM 7)
-------
The overhead reactor effluent consisting of hydrogen
chloride and benzene passes through a condenser which condenses
the benzene for recycle. Hydrogen chloride is recovered by
passing the uncondensed gas through a scrubber tower contain-
ing a chlorination catalyst, thereby removing unreacted..
chlorine. The mixture is then passed through one or more.
towers in which chlorobenzenes are used to remove organic
contaminants. The resultant hydrogen chloride is then recov-
ered as either an anhydrous product or as a 30-40% aqueous
solution. (If the hydrogen chloride must meet a low j>rganic
specification, a carbon column may be used prior to or after
the water absorption tower.)
The bottom effluent from the reactor corn-prises an
equilibrium mixture of benzene and mixed chlorobenzenes. To
maximize monochlorobenzene production, a high recycle rate of
benzene is maintained (20:1). Chlorobenzene is withdrawn at
a rate equal to that at which benzene is fed and chlorinated,
and flows to a fractionating column which operates at a bottom
temperature of aproximately 190°C and top temperature of
140°C. The higher boiling bottom products (mostly dlchlofb-
benzenes) are continuously bled at approximately 2% of the
product feed to a fractionating column for recovery of the
di- and trichlorobenzenes. The wastes of concern are the
bottoms from the two fractionating columns.*/
^7Insomeprocesses, this further fractionating step for
recovery of higher chlorobenzenes will not occur, in which
case the waste of concerns are the column bottoms from the
first fractionating column.
-5-
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2. Batch Process
Chlorobenzenes may also be manufactured by a batch
process as shown in Figure 2. Dry benzene is charged into an
agitated glass-lined or iron (steel) agitated reactor.
Either iron turnings or anhydrous ferric chloride are used
as a catalyst and remain in the chlorinator after each batch.
Chlorine is added to the reactor at a rate to keep the tem-
perature between 20° to 60°C. If monochlorobenzene is the
desired product, the reaction temperature is maintained in
the range of 20° to 30°C for 10 to 16 hours and about 60
percent of the stoichiometeric requirement of chlorine used.
If poly-substituted Chlorobenzenes (generally dichlorobenzenes)
are desired in addition to monochlorobenzene, the reaction
is run at a temperature of 55° to 60°C for approximately six
hours.
Hydrogen chloride is recovered in a manner similar to
that of continuous processes by scrubbing with chlorobenzene
to remove organic contaminants and absorbing the product gas
in water to give hydrochloric acid. The chlorobenzene prod-
uct is washed in an agitated reactor with an aqueous solution
of sodium hydroxide (10 percent by weight). The separated
aqueous layer is a separate waste stream, and is the second
waste stream included in this listing.*/
such aqueous stream is expected to be present in continu-
ous processes, since during the stripping step in the contin-
uous process (see Fig. 1) the temperature at the bottom of
the condenser column already removes residual hydrogen chloride
and benzene, and makes a product washing step unnecessary.
-6-
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CHLOROBENZENE-
BENZENE
CHLORINE
HoO-
VENT
A
SCRUBBERS
V
REACTOR
iNEUTRALIZER
SEPARATOR
BENZENE & WATER
BENZENE & CHLORO-
j BENZENE
CHLOROBENZENE
FRACTIONATING
COLUMN
V
POLYCHLOROBENZENES
TO RECOVERY OF
! HIGHER
i CHLORINATED
I BENZENES
i AQUEPJJSWASTE <
{{CHLORINATED ORGANICS)
i TO DISPOSAL
V
DISTILLA-
TION
COLUMN
SOLID WASTE
TO DISPOSAL
FIGURE 2 :
BATCH PRODUCTION OF CHLOROBENZENES (MODIFIED FROM 6)'
-------
After the neutralized organic layer is separated, it is
sent to a fractionation column for product separation. A
typical product distribution from fractionation is shown in
Table 1 for a fully chlorinated batch for which 100 percent
of the theoretical amount of the chlorine requirement for
monochlorobenzene has been consumed'is given..
TABLE 1
PRODUCT DISTRIBUTION OF A CHLOROBENZENE BATCH REACTION (6)
Component % by weight
Benzene and water 3
Benzene and chlorobenzene 10
Chlorobenzene 75
Chlorobenzene and dichlorobenzene 10
Tar (trichlorobenzene and higher) 2
Most batch processes will include a further distillation
step to separate higher chlorinated benzenes, particularly o-
l/
and p-dichlorobenzcne and trichlorobenzene. The chlorobenzene
and dichlorobenzene fraction is usually further distilled to
recover p-dichlorobenzene and o-dichlorobenzene. Trichloro-
benzene may also be recovered. The tarry residue—the solid
waste of concern-- consists chiefly of trichloro and higher
chlorinated benzenes.
1 is a product mix prior to thij/s second distillation
s tep.
-7-
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B . Production of Polychlorobenzenes
As noted previously, aromatic chlorination is a multiple
product process; most polychlorobenzenes can be produced via
processes similar to those described above. Reaction conditions
are, however, likely to be somewhat different. Higher reaction
temperatures, and longer reaction times and higher chlorine
to benzene ratios are likely modifications. A process
configuration for production of dichlorobenzenes is shown
in Figure 3.
Dichlorobenzenes
Dichlorobenzenes are co-products of the production of
monochlorobenzene using a ferric chloride catalyst. Separation
of o- and p-dichlorobenzene is difficult by fractional dis-
tillation ( bp-6°C), and so is accomplished by fractional
crystallization.
Trichlorobenzenes
As noted previously, both 1,2,4-and 1,2 ,3-trichlorobenzene
are produced as co- or by-products of the catalytic chlorination
of benzene. Isoraers may be separated by fractional
crystallization.
-8-
-------
CHLOROBENZENE-
BENZENE
CHLORINE
REACTOR
H2O-
VENT
A
SCRUBBERS
RECYCLE
BENZENE
CRYSJALLIZER CENTRIFUGE
MONOCHLOROBENZENE
DISTILLATION
COLUMN
SOURCE: MODIFIED FROM (8)
ORTHODICHLOROBENZENE
P-DICHLOROBJENZENE.
DICHLOROBENZENE-
• SOUD WASTE-
(TRICHLORO &
: HEAVIER! '
FIGURE 3
PRODUCTION OF HIGHER CHLOROBENZENES
-------
Tetrachlorobenzenes
There are three isomeric tetrachlorobenzenes: 1,2,3,4-
tetrachlorobenzene; 1,2,3,5-tetrachlorobenzene; and 1,2,4,5-
tetrachlorobenzene. Of these isomers, the 1,2,4,5- isomer is
a chemical and pesticide intermediate (hexachl'orophene, Isobac
20, Ronnel, Silvex, and 2,4,5-T). Each isomer can be produced
by catalytic chlor.ination using an aluminum chloride catalyst.
1,2,4,5-Tetrachlorobenzene may also be produced via the
Sandmeyer reaction:
GI ;
• Reduction
. Cl
2 Cl
-9-
-------
Pentachlorobenzene and Hexachlorobenzene (8,9)
Pentachlorobenzenes are formed by the chlorination of
benzene in the presence of ferric or aluminum chloride at
temperatures of 150 to 2008C, or by the chlorination of any
of the lower chlorobenzenes.
Hexachlorobenzene is reported not to be produced
commercially via catalytic (ferric chloride) chlorination of
benzene. When generated as a by-product of the processes
described in this document, it is not recovered and is found
in the fractionating column bottoms.
II. Waste Composition and Management
1. Fractionation Bottoms
The distillation or fractionation bottoms from the
production of monochlorobenzene consist primarily of the
higher polychlorinated benzenes (trichlorobenzenes and higher),
*/
benzyl chloride and chlorotoluenes resulting from the chloro-
nation of toluene impurities in benzene feedstock, and lesser
concentrations of feedstock benzene, product chlorobenzene,
and dichlorobenzenes (depending on the efficiency of the
fractionating step). The relative concentrations of the
various chlorobenzenes in these wastes vary according to
reaction conditions and the efficiency of fractionation. In
general, when monochlorobenzene is the favored by-product,
dichlorobenzene will probably be the most prevalent of the
*/Both o- and p-chlorotoluene also are expected to be present.
These constituents are not considered to be of regulatory
concern because of their low chronic toxicity. Further
information as to the validity of this conclusion is solicited,
however.
-10-
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chlorinated benzenes in the distillation residue (and in the
waste if there is no subsequent distillation step to recover
dichlorobenzenes as product) since benzene is being chlorinated
for less time, so that smaller concentrations of tetra- to
hexachlorobenzene are formed. If dichlorobenzenes are
recovered as product, then trichlorobenzenes will represent
the greatest fraction in the waste. When the reaction is
pushed in the direction of polychlorinated benzenes, there
will be more trichloro through hexachlorobenzene in the waste
stream.
Waste composition, and especially the concentrations of
the various chlorinated benzenes, also will vary quantitatively,
although not qualitatively, depending on whether a continuous
or batch production process is used. Batch processes would
tend to have somewhat higher concentrations of higher
e
chlorinated benzenes, since benzene chlorination occurs for a
longer period.
Table 1 (p. 8 above) gives an estimate of wastes resulting
from a batch reaction favoring monochlorobenzene production.
As noted, distillation tars are estimated to consist principally
of the higher chlorinated benzenes (trichlorobenzene and
higher). These tars would comprise roughly 2% by weight of
the total reaction products and byproducts.
Table 2 gives a second estimate of waste composition
^•Nk
from a batch process favoring monochlorohenzene. The
polychlorinated tars are the listed hazardous wastes. Benzene
and chlorobenzene would be vented to the atmosphere, since
-11-
-------
they have lower boiling points, though small concentrations
of these constituents would be expected to remain in the
distillation bottoms. In addition, some dichlorobenzenes would
be present from the recovery of dichlorobenzenes by subsequent
distillation.
Table 2
ESTIMATED LOSS OF MATERIALS DURING CHLOROBENZENE MANUFACTURE
(BATCH PROCESS)
Chemical
Source
Quantity Produced
(Kg/kg monochlorobenzene)
Hydrogen Chloride
(catalyst; nonhazardous)
Monochlorobenzene
Dichlorobenzenes
(isomers not specified)
Monochlorobenzene
Dichlorobenzenes
Polychlorinated
Distillation Tars
Hot scrubber vent
Dichlorobenzene
Column
Fractionating
Towers
Distillation
Residues
0.0014
0.00088
0.0037
0.004
0.0001
0.044
A third reference (shown in Table 3) taken from the
patent literature and involving a continuous process, shows
monochlorobenzene present in fairly substantial concentrations
in the solid waste, as well as the same ranges of heavier
chlorinated be;.:enes.
-12-
-------
TABLE 3
ESTIMATED EMISSIONS FROM CHLOROBENZENE MANUFACTURE:
Chlorination of Benzene, Continuous Process
Emmissions kg/Mg
Species Air
Benzene
Chlorobenzene
Aqueous Solid
trace
2.6
Polychlorinated
benzenes
31
33.6
Source: Derived from Hunter, W. K., Combination Reaction-Fraction-
ation U.S. Patent 3,366,457, January, 1968.
These wastes (from both continuous and batch processes)
are also expected to contain significant concentrations of
benzyl chloride and o- and p-chlorotoluene resulting from
chlorination of toluene impurities in benzene feedstock.^/
(As noted above, the chlorinated toluenes are not waste
constituents of concern). The specific reaction pathways for
these constituents are given below:
Cf
~Lr
~*J Toluene is believed to be the most significant feedstock
impurity. Benzene may typically contain up to 1% toluene
Mellan, I. Industrial Solvents Handbook, 2nd Ed., Noyes
Data Corp., Park Ridge,NJ,1977.
-13- -
-------
These side reactions are believed to be those most
likely to occur under usual conditions of benzene chlorination.
Virtually all of these substances would be present in the
distillation bottoms since they are high boiling chemicals that
the distillation process is designed to eliminate.
2. Separated Aqueous Stream from the Reactor Product
Washing Step (batch process)
The aqueous stream from the reactor product washing
step in the batch production of chlorinated benzenes will con-
tain benzene, and all of the chlorinated benzenes in solution
(along with water and caustic soda used in the washing opera-
tion). Since this is an aqueous waste, concentrations of these
constituents will depend on..their solubilities in the somewhat
alkaline wash solution. While the Agency does not presently
have precise information on these compounds' solubility in basic
solutions, it is not believed to differ significantly from
their solubilities in water (if anything, solubilities would be
slightly higher in basic solutions). Thus, the highly soluble
benzene (water solubility reported at up to 1,780 ppm) would
probably be the principal waste constituent, and monochloro-
benzene and o- and p-dichlorobenzene would also be present
in fairly significant levels (water solubilities from 79 ppm
to 488 ppm respectively) would also be present in significant
concentrations. The remaining chlorinated benzenes would
be present at much lower levels, since their solubilities
are quite low. (Solubility data is from App. B.) Phenols
-14-
-------
could also be formed if temperatures are sufficiently high to
create hydrolysis conditions, and a highly alkaline wash mix-
ture is used. Chlorinated phenols could also be present from
the phenolization of the di- and tri-chlorobenzenes, although
concentrations of phenols and chlorinated phenols would probably
be small.
Table 4 below shows organic contaminants found in the waste-
water stream from chlorobenzene manufacture at a Dow plant.
TABLE 4
PRIORITY POLLUTANTS IDENTIFIED IN AQUEOUS WASTESTREAM FROM
PRODUCT WASHING STEP IN PRODUCTION OF CHLOROBENZENES(29)
Concentration mg/1 Loading kg/day
*The underlined data are those obtained from proprietary reports
and data files.
-15-
-------
3. Waste Management
Waste management practices for the distillation residues
generally involves disposal in on-site and off-site landfills (1).
Incineration is also practiced to destroy toxic constituents (9).
The separated aqueous stream generally is sent to waste-
water treatment.(1) The most feasible treatment method is acti-
vated carbon preceded by sand filtration.(1) A wastewater treat-
ment sludge is generated which is assumed to be hazardous unless
generators show otherwise. (See §261. 3(a) (2)(ii).)
III. Hazards Posed by the Waste
As: noted above, the distillation wastes are expected to
contain significant concentrations of tri- through hexachloro-
benzene, and benzyl chloride, lesser concentrations of dichloro-
benzenes, and some monochlorobenzene and benzene. Furthermore,
the waste stream will consist almost completely of these organic
contaminants. Hexachlorobenzene and benzene have been identified
as having substantial evidence of carcinogenicity by the Carcinogen
Assessment Group. Pentachlorobenzene is reported to induce
cancers in some animal species. Benzyl chloride is reportedly
carcinogenic. The remaining constituents present acute and
chronic toxicity hazards. All are priority pollutants.
In addition, all of the chlorinated benzenes are very bio-
accumulative (based on extremely high octanol/water partition
coef.ficents (see pp. 23 - 28 below)) and so could pose an additional
hazard even if exposure is only to small concentrations of the
pollutant.
-16-
r
-------
The aqueous wastestream will contain benzene, chloroben-
zenes through trlchlorobenzene, and (under certain conditions)
certain phenols and chlorinated phenols. 2,4-dichlorophenol
and 2,4,6-trichlorophenol have been identified by the Carcinogen
Assessment Group as having substantial evidence of carcinogenicity.
In addition, both compounds present acute and chronic toxicity
hazards. 2,4,6-trichlorophenol is also mutagenic.
In light of the reported concentrations of these hazardous
constituents, these waste streams are clearly of regulatory
concern. Indeed, for the carcinogens in the wastes, there is no
known safe level of exposure, every exposure likely giving
rise to at least one cancer in a defined portion of population,
regardless of exposure concentration. (EPA Water Quality Criteria,
44 Fed. Reg. 15926, 15930 (March 15, 1979).) The Agency thus
requires strong assurance that these waste constituents are
incapable of migration, mobility, and persistence in the event
of improper management to justify not listing this class of
wastes. Such assurance does not appear possible.
All of the waste constituents have proved capable of
migration, of mobility through soils, and of environmental
persistance in the course of actual waste management practice,
creating a substantial potential for hazard. Benzene and all
of the chlorinated benzenes through pentachlorobenzene have
been detected in air, basement sump and solid surface samples
collected in the vicinity of the Love Canal waste disposal
-17-
-------
site in Niagra, New York.(5) Benzyl chloride has been identified
as leaching from Hooker's Hyde Park site in Niagra, New York
(OSW Hazardous Waste Division, Hazardous Waste Incidents, Open
Files, 1978), and has been shown to persist in the atmosphere
in the New Jersey area for considerable periods of time (Altshuller,
A. P., Lifetimes of Organic Chemicals in the Atmosphere,
Environmental Scientific Technology, 1980, in press).
Hexachlorobenzane has likewise been shown to migrate
via air and groundwater pathways and to persist following
migration. One notorious damage incident involving hexachloro-
benzene occured in Louisiana in the early 1970s. Exposure to
hexachlorobenzene resulted via inhalation from transport of
hexachlorobenzene-contaminated wastes, resulting in dangerously
elevated hexachlorobenzene concentrations in humans and animals
along the route. (OSW Hazardous Waste Management Division,
Hazardous Waste Incidents, unpublished, Open Files, 1978.)
Hexachloro'benzene has also been detected in concentrations
exceeding background levels in many groundwater monitoring
samples taken, at various locations at a chosen chemical company
dump. (1 at Table 7.2.)
The phenols and chlorinated phenols present in the waste
water stream also are capable of migration, mobility, and per-
sistence. Phenol and 2-chlorophenol are extremely soluble in
water (App. B) and, although subject to biodegradatlon (id.),
-18-
-------
could persist for long periods of time in the abiotic conditions
characteristic of most aquifers. Both 2,4-dichlorophenol and
2,4,6-trichlorophenol are likewise quite soluble in water and
Vo
do not exhibit a high propensity to adsorb -i-n soils.(30) Mi-
gratory potential is thus substantial, and if migration occurs,
these chlorinated phenols are mobile and persistent. For
example, in a damage incident at Montebello, California, involving
wastes from 2,4 dlchlorophenol manufacture, 2,4-dichlorophenol
and other phenolic compounds proved capable of passing through
soils and causing longterm pollution of groundwater. (Sinenson,
H.A., 1962. The Montebello Incident., Proc. Assoc. Water Treatment
and Exam. 11:84-88.) Contamination of groundwater by 2,4-dichloro-
phenol and other hazardous compounds has also been reported in
East St. Louis, 111. The source of the compounds was the
Monsanto chemical dump. (EPA Office of Solid Waste, Hazardous
Waste Division, Hazardous Waste Incidents, unpublished, open
file 1978.)
Since all of the waste constituents of concern have
proven capable of migration, mobility, and environmental persistence,
anu have in fact caused substantial hazard in acutual waste mana-
gement practice, the Agency believes that the waste constituents
could migrate and reach environmental receptors if the wastes
are improperly managed. Landfilling the waste without adequate
cover could easily result in volatilization of hexachlorobenzene
and benzene. Solubilization of hazardous compounds could occur
-19-
-------
if rainwater is allowed to percolate through the waste or run
off the surface of exposed waste. Waste constituents could
then be released if landfills are improperly designed (built
without leachate control in areas with permeable soil or located
in areas where soils have low attenuative capacity), or managed.
Improperly designed wastewater treatment ponds pose the same risk,
In the case of improperly managed landfills, surface run-off
might also transport compounds that have adsorbed to suspended
particulates. Contaminant-bearing leachate and surface run-off
may eventually enter ground and surface waters, polluting valu-
able water supplies and adversely affecting aquatic organicsras.
Improper incineration of the distillation residues pro-
vides another means by which toxic compounds can be generated
and introduced into the environment. If incineration is inade-
quate (for instance, if temperatures are insufficient or resi-
dence time incomplete), inadequate combustion can result in the
formation of substances (such as phosgene) that are even more
toxic than the original waste.(1) These contaminants can be
emitted from,the incinerator to the atmosphere and dispersed
in the environment.
IV. Health and Ecological Effects
Health and ecological effects and potential transport
mechanisms for the constituents of concern that might be found
in the distillation bottoms and the separated aquaeous waste
stream from manufacture of chlorobenzenes are described below:
-20-
-------
Benzene
Health Effects Benzene is a human carcinogen. Exposure
to benzene as a result of inhalation induces abnormalities in
the blood and causes leukemia.(31-3) Benzene administered
subcutaneously has been teratogenic in mice at extremely low
doses [3 ml/Kg].(34) Chronic inhalation of this chemical in
low doses by rats has caused both inhibition and resorption of
embryos.(35) Benzene is also mutagenic when administered
orally to mice at extremely low doses [1 mg/Kg].(36)
Exposure of humans to benzene has resulted in the reduction
of blood cells, impairment of the immunologic system, aplastic
anemia and a variety of mutagenic effects in lymphocytes and
bone marrow.(37-42) Oral ingestion of benzene in small amounts
(50 mg/Kg), or one-seventieth of the oral LD5Q in rats, has been
lethal in humans.(43)
Regulatory Recognition of Hazard - OSHA has set a revised
TLV for benzene at 10 ppm with a maximum permissible exposure
of 30 ppm for 10 minutes, within EPA the Offices of Water and
Waste Management, and Air Quality Planning and Standards and Toxic
Substances are performing a pre-regulatory assessment of benzene
based on its environmental effects, high-volume production, spill
reports and other health effects. Additionally, benzene has
been identified by the Agency as having substantial evidence of
being carcinogenic. The Consumer Product Safety Commission
requires benzene to carry special labelling.
-21-
-------
Industrial Recognition of Hazard - Benzene is designated
as highly toxic in handbooks used by industry, such as Plunkett,
Handbook of Industrial Toxicology.(44) According to Sax, Dan-
gerous Properties of Industrial Materials(45), benzene repre-
sents a fire and moderate exposure hazard.
In addition, benzene is a priority pollutant in accordance
with §307 of the Clean Water Act of 1977 and is listed as a
hazardous waste or hazardous waste constituent in final or
proposed regulations of California, Maine, New Mexico and
Oklahoma.
i
Additional information on the health and ecological
effects of benzene may be found in Appendix A.
Chlorobenzenes; Chlorobenzenes are products of the main
reaction. Their acute toxic effects are moderate but, because
they bioaccumulate to a significant degree, Chlorobenzenes may
pose a substantial hazard if chronic exposure occurs. They are
relatively mobile in the environment and likely to persist for
long periods of time.
Chlorobenzene (Monochlorobenzene, MCB)
Health effects - Monochlorobenzene is a central nervous
system depressent, with the typical anesthetic effect(46); de-
generation of the liver and kidney may develop concurrently w^th
anesthesia produced by this chemical. Acute inhalation of mono-
chlorobenzene has induced narcosis, neuropathy and death in ani-
mals during acute inhalation studies.(47) The metabolism of
monochlorobenzene may lead to the formation of carcinogenic active
-22-
-------
intermediates.(48) Monochlorobenzene is also very bioaccumula-
tive with an octanol/water partition coefficient of 690 (App. B).
Regulatory Recognition of Hazard - The OSHA standard for
chlorobenzene is a TWA of 75 ppm. E?A's Office of Water and Waste
Management provides technical assistance data and regulation
for chlorobenzene under Section 311 of the Clean Water Act. They
are also involved with pre-regulatory assessment under the Safe
Drinking Water Act. The Office of Air, Radiation and Noise and
the Office of Research and Development are involved with pre-
regulatory assessment under the Clean Air Act. The Office of
Toxic Substances is involved with test rule recommendations un-
der Section 4(e) of the Toxic Substances Control Act.
Monochlorobenzene also is listed as a priority pollutant
in accordance with §307 of the Clean Water Act of 1977, and
final or proposed regulations of Maine, New Mexico, Oklahoma
and California list chlorobenzene as a hazardous waste or a
component of hazardous wast*>. The American Conference of
Governmental Industrial Hygienists (ACGIH, 1971) threshold
o
limit value for monochlorobenzene is 350 mg/mj.
A more detailed discussion of monochlorobenzene may be
found in Appendix A.
Dichlorobenzenes; Ortho- and paradichlorobenzene are
products of the main reaction. They are very bioaccumulative,
each having an octanol/water partition coefficient of 2500
-23-
-------
(Appendix B). A discussion of each isotner follows.
ortho-Dichlorobenzene
Health Effects - Ortho-dichlorobenzene is very toxic in
rats [oral LD5Q a 500 mg/Kg].(49) Human death has also occurred
at this level.(50) Chronic occupational exposure to this chemi-
cal and its isomer has resulted in toxicity to the liver, central
nervous system and respiratory system.(51) Chronic oral feed-
ing of ortho-dichlorobenzene to rats in small doses has caused
anemia as well as liver damage and central nervous system de-
pression. (52)
Regulatory Recognition of Hazard - Ortho-dichlorobenzene
has been designated as a priority pollutant under Section 307(a)
of the CWA. The OSHA standard for o-dichlorobenzene is 50 ppm
for an 8-hour TWA. It was selected by NCI for Carcinogenesis
Bioassay, September 1978. o-dichlorobenzene is listed as a haz-
ardous waste or a component thereof in final or proposed regula-
tions of the States of California, New Mexico and Oklahoma.
The Occupational Safety and Health Administration standard and
the American Conference of Government Industrial Hygienists
threshold values for o-dichlorobenzene is 300 mg/m^. The
U.S. EPA draft water quality criterion for total dichloroben-
zene is 0.16 mg/1. U.S. EPA has also established criteria for
freshwater and marine aquatic life.
-24-
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para-Dichlorobenzene
Health Effects - Para-dichlorobenzene is very toxic in
rats (oral LD5Q = 500 mg/kg](53)), having lethal effects in hu-
mans ingesting similar amounts.(54) Adverse effects are exerted
on the liver and kidney function in humans at a smaller [300 mg/Kg]
dose level.(55) This chemical has induced growth depression,
liver cell necrosis and death in animals exposed by inhalation.(56)
Regulatory Recognition of Hazard - Para-dichlorobenzene has
been designated as a priority pollutant under Section 307(a) of
the CWA. p-Dichlorobenzene has an OSHA standard for air TWA of
75 ppm (SCP-T). It is listed as a hazardous waste or a component
thereof in final or proposed regulations of the states of California,
New Mexico, and Oklahoma. The Occupational Safety and Health
Administration Standard and the American Conference of Government
Industrial Hygienists threshold values for p-dichlorobenzene
is 450 mg/m^. A more detailed discussion of dichlorobenzene can
be found in Appendix A.
Tetrachlorbenzene
Health Effects - There is some evidence of liver damage
occuring with prolonged exposure of rats and dogs to tetrachloro-
benzene. (11,18). Tetrachlorobenzene has an oral rat LD5Q of
1500 mg/kg.(14) It is reported to be acutely toxic in varying
degrees to some fresh- and saltwater organisms, and chronically
toxic to saltwater organisms.(19) The octanol/water partition
coefficient for 1,2 , 4,5-tetrachlorobenzene is extremely high,
47,000.(14) The predominant disposition site for tetrachloro-
benzene is suspected to 1.3, or shown to be, in the llpi:.1 tissues
of the body.(16)
-25-
-------
Tetrachlorbenzene is designated by Congress as a priority
pollutant under §307 of the Clean Water Act of 1977.
Additional information on the toxic effects of tetrachloro-
benzene can be found in Appendix A. ' .
Pentachlorobenzene
Health Effects - Pentachlorobenzene was reported to be
carcinogenic in mice, although not in rats or dogs.(21) It
was also reported to have caused bone defects in the offspring
of rats which had received doses of pentachlorobenzene during
gestation.
Pentachlorobenzene is quite acutely toxic at low
concentrations (ranging from 160 ug/1 to 6,780 ug/1) to both
salt- and freshwater organisms, including plants.
Pentachlorobenzene has an extremely high octanol/water
partition coefficient of 154,000, indicating a dangerously high
bioaccumulation potential.(14)
Pentachlorobenzene is designated as a priority pollutant
under §307 of the Clean Water Act.
Additcnal information on the adverse health effects of
pentachlorobenzene can be found in Appendix A.
Hexachlorobenzene
Health Effects - U.S. EPA's Carginogen Assessment Group
(GAG) has evaluated hexachlorobenzene and has found sufficient
evidence to indicate that is is carcinogenic. It has also
been demonstrated to be fetotoxic to rats.(23) The distribution
of hexachlorobenzene is apparently the same in the fetus as in
-26-
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the adults, with the highest concentration in fatty tissue.
(23) This is expected because of its extremely high octanol/water
partition coefficient of 168,000.(14)
Chronic exposure of rats to hexachlorobenzene has caused
histological changes in the liver and spleen (24), and in humans,
has caused porpyrinuria.(25)
Hexachlorobenzene is designated as a priority pollutant
under §307 of the Clean Water Act.
Additional information on the adverse health effects of
hexachlorobenzene can be found in Appendix A. ;'
\
Benzyl Chloride
Health Effects - Benzyl chloride has been identified as a
carcinogen(16), and is also mutugenic(27).
The OSHA TWA for benzyl chloride is 1 ppm. DOT requires
labeling as a corrosive. The Office of Water and Waste
Management, EPA, has regulated benzyl chloride under Section
311 of the Clean Water Act. Preregulatory assessment has been
completed by the Office of Air, Radiation and Noise under the
Clean Air Act. The Office of Toxic Substances has requested
additional testing under Section 4 of the Toxic Substances
Control Act.
Benzyl chloride is listed in Sax's Dangerous Properties
of Industrial Materials as highly toxic via inhalation and
moderately toxic via the oral route.
Additional information and specific references on the
adverse effects of benzyl chloride can be found in Appendix A.
-27-
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2, 4-Dichlorophenol
Health Effects - 2,4-Dichlorophenol is very toxic in rats
[oral 1050 = 580 mg/Kg].(61) This chemical is carcinogenic when
applied to the skin of mice in small doses.(62) It is also re-
ported to adversely affect cell metabolism.(63,64) An isomer,
.j
2,6-dichlorophenol is also toxic in animals.(65)
2,4-Dichlorophenol has been designated as a priority .pol-
lutant under Section 307(a) of the CWA.
Ecological Effects - Small doses of 2,4-dichlorophenol
have been lethal to freshwater fish and invertebrates.(66)
Regulations - The Office of Water and Waste Management
has completed a pre-regulatory assessment of the proposed
water quality criteria under sections 304(a) and 311 of the
Clean Water Act. The Office of Research and Development is
presently conducting a pr-eregulatory assessment under the
Clean Water Act.
Industrial Recognition of Hazard.- Sax, Dangerous Properties
of Industrial Materials(45), designated a toxic hazard rating of
moderate toxicity of 2,4-dichlorophenol. However, chlorinated phe-
nols are designated as highly toxic local and systetric compounds.
Additional information and specific references on the
adverse effects of 2,4-dichlorophenol can be found in Appendix A.
2,4,6-Trichlorophenol
Health Effects - 2,4,6-trichlorophenol induced cancer in
mice during long-term oral feeding studies.(67) It has also
been acutely lethal to humans by ingestion of 60% of the oral
-28-
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243 641. 1975.
9. Gruber, G. I., "Assessment of Industrial Hazardous Waste
Practices", Organic Chemicals, Pesticides, and Explosives
Industries", TRW Systems Group, PB 251-307, 1975.
10. Dawson, English and Petty, Physical Chemical Properties
of Hazardous Waste Constituents, 1980.
11. Irish, D. D. 1963. Halogenated Hydrocarbons: II Cyclic.
Industrial Hygiene and Toxicology, Vol. II, 2nd Ed. (F. A.
Patty, ed.) Interscience, N.Y., p. 1333.
12. Knapp, W. K., Jr. et. al. 1971. Subacute Oral Toxicity of
i
Monbchlorobenzens in Dogs and Rats. Toxicol. Appl. Pharmacol.
19: 393.
13. U.S. EPA, 1979. Chlorinated Benzenes Ambient Water
Quality Criteria (Draft).
14. U.S. EPA. 1978. In-Depth Studies on Health and Environmental
Impacts of Selected Water Pollutants.
15. U.S. EPA. 1980. Physical Chemical Properties of Hazardous
Waste Constituents. (Prepared by Southeast Environmental
Reasearch Laboratory; Jim False, Project Officer.)
16. Jondorf, W. R., et. al. 1958. Studies in Detoxification.
The Metabolism of Halogenobenzenes 1,2,3,4-, 1,2,3,5- and
1,2,4,5-Tetrachlorobenzenes. Jour. Biol. Chem. 69:189.
17. U.S. EPA. 1979. Chlorinated Benzenes: Ambient Water
Qualtiy Criteria Document. (Draft)
18. Fomenko, V. N. 1965. Determination of the Maximum Permissible
Concentrations of Tetrachlorobenzene in Water Basins. Gig.
Sait 30:8 .
-32-
-------
19. Broun, W. H., et. al. 1978. Pharmacokientics and
Toxicological Evaluation of Dogs Fed 1,2,4,5-Tetrachloro-
benzene In the Diet for,Two Years. Jour. Environ. Pathol.
Toxicol. 2:225.
20. U.S. EPA. 1978. In-depth Studies on Health and Environmental
- Impacts of Selected Water Pollutants. U.S. EPA, Contract no.
68-01-4646.
21. U.S. EPA. 1980. Generic Chlorinated Organic Waste Streams.
Background Document, Appendix D. (Draft)
22. Preussman, R. 1975. Chemical Carcinogens in the Human
Environment. Hand. Allg. Pathol. 6:421.
23. Khera, K. S., and D. C. Villeneuva. 1975. Teratogenicity
Studies on Halogenated Benzenes (Pentachloro-, pentachloronitro-
and hexabromo-) in Rats. Toxicol. 5:117.
24. Grant, D. L., et. al. 1977. Effect of Hexachlorobenzene on
Reproduction in the Rat. Arch. Environ. Contam. Toxicol.
5:207.
25. Koss, R., and W. Koransky. 1975. Studies on the Toxicology
of Hexachlorobenzene. I. Pharmacokinetics• Arch. Toxicol.
34:203.
26. Cam, C. and G. Nigogosyan. 1963. Acquired Toxic Porphyria
Cutaneatarda Due to Hexachlorobenzene. Jour. Am. Med.
Assoc. 183:88.
27. Druckrey. H., H. Druse, R. Pruessmann, S. Ivanovic, C.
Landschutz. [Carcinogenic Alklating Substances — II.
-33-
-------
Alkyl-Halogeni^es, -Sulfates, -Sulfonates and strained
Heterocyclic Compounds.] Z. Krbsforsch. 74:241-70,
1970. (Ger.)
28. McCann, J., E. Choi, E. Yamasaki, B. N. Ames: Detection
of Carcinogens as Mutagens in the .Salmonella/Microsome
Test—Assay of 300 Chemicals. Proc. National Academy ov
Science VSA 72:5135-39, 1975.
29. Proprietary Plant Report, Dow Chemical U.S.A., Midland,
Michigan. EPA Pesticides BAT Review, USEPA IERL-RTP, 1979.
30. Kozak, V.P., Simmons, G.V. et al. 1979. Reviews of the En-
vironmental Effects of Pollutants: XI Chlorophenols, EPA-
600/1-79-012. U.S. EPA, Washington, D.C.
31. Aksoy, M. et al. Acute Leukemia in Two Generations Following
Chronic Exposure to Benzene. Hum. Hered. 24:70 (1974a).
32. Aksoy, M. et al. Leukemia in Shoe Workers Exposed Chronically
to Benzene. Blood 44:837 (1974b).
33. Natinal Academy of Sciences/National Research Council. (1976)
Health Effects of Benzene: A Re Lew. Nat'l Acad. Sci. Wash-
ington , D.C.
34. Wanatabe, G.I. & Yoshida, S. The teratogenic effects of ben-
zene in pregnant mice. Act. Med. Biol. 19:285 (1970).
35. Gofmekler, V.A. Effect in embryonic development of benzene
and formaldehyde. Hyg. Sanit. 33:327 (1968).
36. Ehling, U.K., et al. Standard protocol for the dominant lethal
test on male mice set up by the work group on dominant lethal
mutations of the ad hoc committee on cheraogenetics. Arch.
-34-
-------
Toxicol. 39: 173-185 (1978).
37. Goldstein, G.D. Hematoxicity in Humans. Jour. Toxicol. Environ
Health Suppl. 2:69 (1977).
38. Snyder, R. & Kocsls, J.J. Current concepts of chronic ben-
zene toxicity. CRC Grit. Rev. Toxicol. 3:265 (1975).
39. Lange, A., et al. Serum immunoglobin levels in workers ex-
posed to benzene, toluene and xylene. Int. Arch. Arbeitsmed.
31:37 (1973).
40. Wolf, M.A., et al. Toxicological studies of certain alky-
lated benzenes and benzene. Arch. Ind. Health 14:387 (1956).
41. Kissling, M. & Speck, B. Chromosomal aberrations in experi-
mental benzene intoxication. Helv. Med. Acta. 36:59 (1971).
42. Pollini, G. L& Colombi, R. Lymphocyte Chromosome Damage in
Benzene Blood Dyscrasia. Med. Lav. 55:641 (1964).
43. Gleason, M.N., et al. Clinical Toxicology of Commercial Prod-
ucts; Acute Poisoning. (1969) 3rd Edition, p. 49.
44. Plunkett, E.R. Handbook of Industrial Toxicology.
45. Sax, N. Irving, Dangerous Properties of Industrial Materials,
Fourth Edition, Van Nostrant Reinhold Company, New York, 1975.
46. Irish, D.D. (1963) Halogenated Hydrocarbons: II Cylic. I_n
Industrial Hygiene and Toxicology, Vol. II, 2nd Ed., (ed.
F.A. Patty), Interscience, New York. p. 1333.
47. Flury, F. and Zernick, F. (1931) Schadliche Case, Springer,
Berlin.
48. Kohli, I., et al. The metabolism of higher chlorinated ben-
zene isomers. Can. J. Biochem. 54:203 (1976).
-35-
*•*, "s
-------
49. Jones, K.H., 5a~ lerson, D.M. and Noakes, D.N. Acute toxicity
data for Pesticides. World Rev. Pest Control. 7:135-154
(1968).
50. Clinical Toxicology of Commercial Products. Gleason, M.N., et
al. (1969), 3rd Edition, p. 49.
51. U.S. EPA (1979). Dichlorobenzenes: Ambient Water Quality
Criteria.
52. Yarshavskaya, S.i'. Comparative toxicoloical characteristics
of chlorobenzeae and dichlorobenzene (ortho- and para- isomers)
•
in relation to the sanitary protection of water bodies. Gig.
Sanit. 33:17 (1967).
53. Ben-Dyke, R., Sauderson, D.M. and Noakes, D.N. Acute Toxicity
for Pesticides. World Rev. Pest Control 9: 119-127 (1970).
54. Clinical Toxicology of Commercial Products - Acute Poisoning.
Gleason, et al. 3rd Ed., Baltimore, Williams and Wilkins,
1969.
55. Association of American Pesticide Control Officials, Inc.
(1966) Pesticide Chemical Official Compendium, p. 851.
56. Hollingsworti R.L., et al. Toxicity of para-dichloro-
benzene. De t;; riuinr f.ions on experimental animals and human
subjects. AMA A :h. Ind. Health 14:138 (1956).
57. U.S. EPA (1977). Investigation of Selected Potential Environ-
mental Containing ,ts: Halogenated Benzenes. EPA 560/2-77-004.
58. Brown, V.K.H... Muir, C. and Thorpe, E. The Acute Toxicity and
Skin Irritant Properties of 1,2,4-trichlorobenzene. Ann.
Occup. Hyg. 12:209-212 (1969).
-36-
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59. Coate, W.B. et al. Chronic inhalation exposure of rats,
rabbits and monkeys to 1,2,4-trichlorobenzene. Arch. Environ.
Health. 32:249 (1977).
60. Smith, C.C., et al. Subacute toxicity of 1,2,4-trichloroben-
zene (TCB) in subhuman primates. 'Fed. Proc. 37:248 (1978).
61. Deichmann, W. The toxicity of Chloroph.enols for rats. Fed.
Proc. (Fed. Am. Soc. Exp. Biol.) 2:76 (1943).
62. Boutwell, R.K. & Bosch, D.K. The tumor-promoting action of
(^
phenol and related compounds for mouse skin. Can. Res.
19:413-424 (1959).
63. Farquharson, M.E. et al. The biological action of chloro-
phenols. Br. Jour. Pharmacol. 13:20 (1958).
64. Mitsuda, W. et al. Effect of chloropl analogues on the oxi-
dative phosphorylation in rat liver mitochondria. Agric.
Biol. Chem. 27:366 (1963).
65. Marhold, J.V. (1972) Sbornik Vysledku ToxiKologicKeho Vyse-
treni Latek a Pripravku p. 79.
66. U.S. EPA (1978) In-depth studies on health and environmental
impacts of selected water pollutants. Contract No. 68-01-4646.
U.S. Environmental Protection Agency.
67. NCI Carcinogenesis Bioassay, National Technical Information
Service, Rpt. PB223-159, Sept. 1978.
68. Clinical Toxicology of Commercial Products. Gleason, et al.,
3rd Ed., Baltimore, Williams and Wilkins, 1969.
-s.
69. Fahrig, R. et al. Genetic activity of chlorophenols and chloro-
phenol impurities. pp. 325-338. In Pentachlorophenol Chemistry,
-37-
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Pharmacology and Environmental Technology. K. Rango Rao,
Plenum Press, New York.
70. Weinback, E.G. and Garbus, J. The interaction of uncoupling
phenols with mitochondria and with mitochondrial protein.
Jour. Biol. Chem. 210:1811 (1965)'.
71. Mitsuda, H., et al. Effect of chlorophenol analogues on the
oxidative phosphorylation in rat liver mitochondria. Agric.
Biol. Chem. 27:366 (1963).
72. U.S. EPA 1972. The effect of chlorination on selected organic
chemicals. Water Pollut. Control Res. Ser. 12020.
73. |U.S. EPA, 1978. In-depth studies on health and environmental
impacts on selected water pollutants. Contract No. 678-01-4646.
74. Merliss, R.R. 1972. Phenol MorAS. Mus. Jour. Occup. Med.
14:55.
75. U.S. EPA. 1979. Phenol: Ambient Water Quality Criteria. (Draft)
76. Harden, E. and H. Niggli. 1946. Mutations in Drosophila
after chemical treatment of gonads in vitro. Nature 157:162.
77. Dickey, F.H., et al. 1949. The role of organic peroxides
in the induction of mutations. ?roc. Natl. Acad. Sci. 35:581.
78. Heller, V.G. and L. Pursell. 1^38. Phenol-contaminanted
waters and their physiological action. Jour. Pharmacol.
Exp. Ther. 63:99.
79. Boutwell, R.K. and D.K. Bosch. 1959. The tumor-promoting
action of phenol and related compounds for mouse skin.
Cancer Res. 19:413.
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80. U.S. EPA 1978. In-depth studies on health and environmental
impacts of selected water pollutants. Contract No. 68-01-4646.
U.S. Environ. Prot. Agency.
-39-
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Ink Formulation
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SJ-39-1
SOLVENT WASHES AND SLUDGES, CAUSTIC WASHES AND SLUDGES
AND WATER WASHES AND SLUDGES FROM THE CLEANING OF TUBS AND
EQUIPMENT USED IN THE FORMULATION OF INK FROM PIGMENTS, •••••
DRIERS, SOAPS AND STABILIZERS CONTAINING CHROMIUM AND LEAD
(T).
I. SUMMARY 0-F BASIS FOR LISTING
Tubs and equipment used in ink formulation are washed by
solvents, caustics and/or water. The Administrator has
determined that the spent washes and wash sludges generated
after ink formulation in which pigments, driers, soaps and
stabilizers containing chromium and lead are used 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 appropriate
management requirements under Subtitle C of RCRA. This
conclusion is based on the following considerations:
1. The washes and sludges typically contain significant
concentrations of lead and chromium. Lead is highly
toxic to a variety of species and is reportedly
carcinogenic in laboratory animals. Chromium is
also toxic and the hexavalent form is a suspected
carcinogen.
2. Present management practices may be inadequate to
prevent the migration of chromium and lead from a
disposal site. Disposal practices subject to SCRA
include landfilling, impoundment and removal by
contract haulers. Such practices, if uncontrolled,
can result in contamination of ground and surface
waters by lead and chromium.
II. INDUSTRY DESCRIPTION AND MANUFACTURING PROCESsC1)
An EPA survey of the ink formulating industry indicates
that there are approximately 460 ink manufacturers in the
United States (excluding captive ink producers that manufacture
ink in a printing plant solely for use in that plant). The
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distribution of i~k manufacturing plants by state is given in
Table 1. In 1972, total ink production was greater than one
billion pounds.
The variety of inks used today is broad, ranging from
ordinary writing inks to specialized magnetic inks.— Inks
manufactured for the printing industry, which utilizes a
major portion of ink production, fall into four major
categories: letterpress inks, lithographic inks, flexographic
in4cs, and gravure inks.
Letterpress inks are viscous, tacky pastes using vehicles
that are oil and varnish-based. They generally contain resins
and dry by the oxidati'ou of the vehicle.
Lithographic or off-set inks are viscous inks with a
varnish-based vehicle, similar to the letterpress varnishes.
The pigment content is higher in lithographic inks than letter-
press ink becsuse the ink is applied in thinner films.
Flexographic inks are liquid inks which dry by evaporation,
absorption intL the substrate, and decomposition. The^e are
two main types of flexographic inks: water and solvent.
Water inks are -jsc.-l on absorbent paper and the solvent "inks are
used on nonabsorbint surfaces.
Gravure inks are liquid inks which dry by solvent evapora-
tion. The ink;; have a variety of uses ranging from printing
publications ".o food package printing.
Inks are either water, oil or solvent-based. The
"average" plan-- produces approximately 60 percent oil base
-2-
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Table 1 (1)
DISTRIBUTION OF INK MANUFACTURING PLANTS BY STATE
State Number of Plants Percent of Plants
California
Illinois
New Jersey
New York
Ohio
Pennsylvania
Texas
Massachusetts
Georgia
Missouri
Florida
Wisconsin
Michigan
Tennessee
North Carolina
Louisiana
Maryland
Minnesota
Virginia
Indiana
Oregon
All Others
47
46
39
34
28
24
22
21
20
16
14
14
13
13
10
9
9
'9
9
7
7
49
10.2
10.0
8.5
7.4
6.1
5.2
4.8
4.6
4.3
3.5
3.0
3.0
2.8
2.8
2.2
2.0
2.0
2.0
2.0
1.5
1.5
10.7
-3-
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Ink, 25 percent solvent base ink and 5 percent water ba?e ink.
In the manufacture of inks, the major ingredients
(vehicles, pigments and driers) are mixed thoroughly
to form an even dispersion of pigments within the vehicle.
The mixing is accomplished with the use of high-speed mixers,
ball mills, three-roll mills, saad mills, shot mills, and/or
colloid mills.
Most inks are made in a batch process in tubs ranging in
sizes from 19 liters (five gallons) to over 3,750 liters (1,000
gallons). The number, of steps needed to complete the
manufacture of the ink depends upon the dispersion characteristics
i
of the ingredients. Most inks can be completely manufactured
in one or two steps since many of the pigments used can be
obtained predispersed in a paste or wetted -form.
III. GENERATION AND MANAGEMENT OF HAZARDOUS WASTED)
Ink is manufactured by blending raw. materials; chemical
reactions generally do not occur and no by-products are
formed. When required, production tub^s and manufacturing
equipment are washed clean of residue or clingage from the
formulation process. The spent cleaning solutions become
impregnated with tank residue composed of the residual raw
materials.
There are four broad types of raw materials use4 in ink
manufacture:
-4-
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0 Pigments and Dyes, Flushes and Dispersions
0 Chemical Specialties (including driers, plasticizers,
soaps and stabilizers)
0 Resins
0 Solvents
Inorganic pigments are the primary source of chromium and
lead in ink industry wastewaters, although chemical specialties
are also reported to contain lead. Survey data obtained by
EPA show that the ink formulation 'industry relies on inorganic
pigments for about 40% of the total production. The two most
widely used lead and chromium-containing pigments are chrome
yellow and molybdate orange, although many other pigments are
sources of lead and chromium in the waste.
Particular chemical specialties are another significant
source of lead and chromium in these wastes. For example,
driers containing lead are used by approximately 30% of the
industry.* Stabilizers containing lead and phenol, and
metallic soaps and flatting agents containing lead are also
in use and are expected to contribute significant
concentrations of lead to process wastes.**
* Examples are Shephard-Lead Tallates, Lead Linoleates, Hexogan,
Aduasol and Catalox.(^)
**Industry survey data indicate that approximately 70% of
the manufacturers use chromium-containing raw materials, and
55% use lead-containing raw materials. Thus, use of materials
containing these pollutants is widespread in the industry.
-5-
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The ink industry commonly uses three methods of ink tub
cleaning: (1) Solvent-wash; (2) Caustic-wash; and (3)
Water-wash.
(1) Solvent-Wash Wastes
Solvent-wash is used exclusively to clean tubs used for
formulating solvent-based and oil-based ink. The dirty solvent
generally is handled in one of three ways:
1. used in the next compatible batch of ink as part
of the vehicle;
2. collected and redistilled, either by the plant or
by an outside contractor for subsequent resale or
reuse; or
3. reused with or without settling to clean tubs and
equipment un'til spent, and then .drummed for
disposal. If sludge is settled out it is also
drummed. These spent solutions and sludges are
usually disposed of by contract hauling.
(2) Wash-Water Wastes
Water-washing techniques are used in both the solvent-
base and water-base segments -f the ink industry. For solvent-
base operations, water-washing usually follows caustic
washing of solvent-base tanks. For water-base operations,
water washes often constitute the only tub cleaning operation,
although wate'r-base ink tubs may be cleaned periodically with
caustic.
Wastewater generated by rinsing tubs or equipment used
for manufacturing water-base ink is usually handled in one of
four ways:
1. reused in the next compatible batch of water-base
ink as part of the vehicle;
-6-
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2. reused either with or without treatment to clean
tubs and equipment until spent and disposed. If
sludge is settled out it is disposed by contract
hauling; :
3. discharged with or without treatment as wastewater;
or
4. disposed of immediately by contract hauling.
The water rinse following a c'austic-wash is rarely reused
in a subsequent batch of ink. The most common methods for
disposal of this rinse are:
1. recycling it back into the caustic as make-up water;
2. drumming it for contract hauling;
3. discharging it as wastewater, with or without pre-
treatment. Combination with other wastewater
prior to treatment or disposal is sometimes practiced.
Discharge of this wastewater is currently prohibited
by some states and municipalities and may be prohibited
in other areas in the future.
(3) Caustic-Wash Wastes
Caustic wash techniques are used to clean bot^i
solvent-base and water-base ink manufacturing tanks. Plants
using caustic rinse or washing systems usually rinse the
caustic residue with water, although a few plants allow the
caustic solution to evaporate in the tubs. There are several
types of caustic systems commonly used by the ink industry.
For periodic cleaning of fixed tubs two methods are popular:
1. maintaining the caustic in a holding tank (usually
heated) and pumping through fixed piping or flexible
hose to the tub to be cleaned. After cleaning,
the caustic is returned to the holding tank; and
2. preparing the caustic solution in the tub to be
cleaned, and soaking the tub until clean. The
caustic solution is either transferred to the
next tub to be cleaned, stored in drums or a
tank for subsequent use, or is discarded.
-7-
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For cleaning small portable tubs, three common methods are used
by the ink industry:
1. pumping caustic from a holding tank (usually heated)
to nozzles in a fixed or portable hood which is
placed over the tub to be cleaned. The caustic
drains to a floor drain or sump and is pumped back
to the tank, or is pumped back directly from the
tub; . '
2. maintaining an open top caustic holding tank. Small
tubs are put into "strainers" and dipped into these
tanks until clean,; and
3. placing the tubs in a "dishwasher-like" device (which
circulates hot caustic), and a subsequent water rinse
These devices ca'n handle tubs up to about 1900 liters
(500 gal).
Most: plants using caustic recycle the caustic solution
until it loses some of its cleaning ability. The spent
caustic is then disposed of either by contract hauling or as
a wastewater, with or without neutralization or other treatment
The most common methods of wastewater disposal are
discharge to a sewer, contract hauling, evaporation, and land-
fill or impoundment. Most contract haulers discharge the-
sludge t. a landfill, although a few incinerate or reclaim
it. " .
Although orecise figures on the amount of waste covered
by this liSiing are not available, the quantity is expected.
to be signi :ica-nt, and, furthermore, is expected to increase
in the fut-.-.a. Final regulations issued by EPA's Effluent
Guidelines Division impose zero discharge requirements for
certain pollutants on all ink manufacturers in the solvent
wash category of the industry except existing
-.8-
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pre-treaters; proposed regulations would impose zero discharge
requirements on existing pre-treaters in the Solvent Wash
category and all others in the Caustic and/or Water Wash
category. Implemementation of these regulations will increase
the amount of hazardous waste requiring disposal in accordance
with the RCRA Subtitle C regulations.^
V. DISCUSSION OF BASIS FOR LISTING
A. HAZARDS POSED BY THE WASTE
Solvent washes and sludges, caustic washes and
sludges and water washes and sludges from cleaning equipment
used in the formulation of ink from raw materials containing
chromium and lead are listed as hazardous because they
/
typically contain significant concentrations of lead and
chromium.* Lead is poisonous in all forms. It is one of" the
May 19, 1980 (45 FR 33063), and if these solvent's are used
in ink formulation and are disposed of, they are" "considered
hazardous wastes under the earlier listing as well as the
most hazardous of the toxic metals because it accumulated in
* Other toxic,heavy metals and various toxic organics are
also known to be present in some of the wash wastes, but
sufficient data are not yet available to list the wastes for
those contaminants. It also should be noted that the tub-
cleaning wastes can exhibit hazardous characteristics other
than toxicity; the Agency has information which indicates
that the listed wastes can be ignitable or corrosive (3,4,5,6).
In addition, a number of spent solvents are listed as hazardous
in §261.31 of the hazardous waste regulations published
May 19, 1980 (45 FR 33063), and if these solvents are used
in ink formulation and are disposed of, they are considered
hazardous wastes under the earlier listing as well as the
present listing. Listed solvents presently
in use by the ink formulation industry are: toluene, 1,1,1-
trichloroethane, carbon tetrachloride, methylene chloride
and trichloroethylene^1). Delisting petitions by ink
formulators' using these solvents must address not only the
presence of the spent solvent itself in the waste, but the
presence of lead and chromium as well.
-------
many organisms and its deletrious effects are numerous and
severe. Epidemiology studies implicate occupational exposure
to chromium in the induction of lung tumors. Impairment of
pulmonary function is also reported to result from chronic
exposure to chromium. (For further information on Health
and Ecological Effects of Chromium and Lead, see Appendix A.)*
The following data substantiate the presence of significant
concentrations of lead and chromium in the wash wastes:.
0 EPA has determined that the average concentrations
of lead and chromium per day in ink industry caustic
wash and water-wash wastewaters are 151 mg/1 and
35 mg/1, respectively. Concentrations as high as
900 mg/1 of lead and 200 mg/1 of chromium were
reported. C1)**
0 A summary of industrial waste composition data
taken from the manifests required by the State
of California for transportation of hazardous
wastes lists the following wastes from the
manufacture of printing ink as hazardous:^)
1. Ink wastewater which contained 1000 ppm of lead.
2. Equipment cleaning washwater which contained
10,000-20,000 ppm of lead chromate.
0 "Special Waste Disposal Applications" were submitted
to the State of Illinois for the following wastes
from ink manufacture^-^)
1. Solvent waste containing 120 ppm of chromium
and 770 ppa of lead.
2. Solvent waste containing 291 ppm of lead.
0 ~A "Hazardous Waste Disposal Request" was submitted
to the Missouri Department of Natural Resources for'
disposal of printing ink sludge (wash waste) con-
taining 260 ppm of chromium and 1,340 ppm of
The "Industrial Waste Surveys" file of the State of
New Jersey contained a description of ink manufacturing
wash water with 260 ppm of lead (^).
*It should be noted that even if chromium migrates in the
trivalent form, it is capable of oxidation to the far more
dangerous form under normal environmental conditions. See
Background Document for Extraction Procedure Toxicity
Characteristic at pp. 109-112.
**These .figures may be conservative in light of the higher
concentrations contained in state manifests, given below.
-10-
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Clearly the concentrations of lead and chromium in the
wastes may be very substantial.
The presence of such high concentrations of toxic metals
in a waste in and of itself raises regulatory concerns. Lead
and chromium have proven capable of migration, mobility and
persistence in many waste management settings(28)t raising
the concern that, if these wastes are improperly managed,
the lead and chromium may be released from the waste in
harmful concentrations and adversely effect human health and
the environment. Because lead and chromium do not degrade
with the passage of time, they will provide a potential source
of long-term contamination if they are permitted to escape
from the disposal site.
Current disposal methods do not appear.adequate to
prevent migration of these toxic heavy metals from the waste
into the environment. Toxic metal-bearing liquid wastes
placed in an impoundment can release those hazardous consti-
tuents to the surrounding area if seepage and overflow
are not controlled, or measures are not taken to prevent total
washout. Without regulation, proper containment of the
impounded wash wastes cannot be assured.
Clearly, if measures to retard migration of liquids
from impoundments and landfills are not employed, ground and
surface waters could easily become contaminated. Improper
landfilling of sludges settled from the liquid wastes could
also result in release of the hazardous constituents. The
-11-
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heavy metal compound might already be solubilized or may
solubilize as a result of disposal conditions (co-disposal
with acids, alkalis or decomposing organic matter, for instance)
and could then migrate from the disposal site to ground and
surface waters. As a result, ground and surface
drinking water supplies may become contaminated, and the
existence of wildlife and various aquatic species could be.
threatened by exposure to the toxic heavy metals.
Unregulated contract hauling of wastes by private disposal
services, scavengers or purveyors in tank trucks — a waste
management method frequently used for these wastes -- creates
additional hazards. There have been innumerable damage
incidents involving unregulated contract hauling,.resulting in
substantial environmental harm. (Some examples are collected
in Reference 28.) Thirty-one percent of the ink plants
surveyed by EPA did not know what the contract hauler does
with their waste.(1) There is obvious potential for abuse in
this system since there is no way to determine whether these
wastes are properly managed during transportation, treatment
or disposal; irresponsible handling at any point could ultimately
endanger human health and the environment. Therefore, it is
essential that wastes of this nature be subject to regulation
from "cradle to grave".
B. Health and Ecological Effects
1. Lead
Health Effects
Lead is poisonous in all forms. It is one of
-12-
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the most hazardous of the toxic metals because It accumulates
in many organisms, and its deleterious effects are numerous
and severe. Lead may enter the human system through inhalation,
ingestion or skin contact* The hetnatopoietic system is the
most sensitive target organ for lead in humans, although
subtle neurobehavloral effects are suspected in children at
similar levels of exposure.(8)
Lead exposure has been reported to decrease reproductive
ability in men(^) and women.(10) 'It has also been shown to
cause disturbances of blood chemistry,(11) neurological
disorders , (12 ,13 ) t kidney damage(l4) an(j adverse cardiovascular"
effects.(15) Lead has been shown to be teratogenic in animals.
Although certain inorganic lead compounds are carcinogenic to
some species of experimental animals, a clear association
between lead exposure and cancer development has not been
shown in human populations.
Additional information and specific references on adverse
effects of lead can be found in Appendix. A.
Ecological Effects
In the aquatic environment, lead has been reported to be
acutely toxic to invertebrates at concentrations as low as
450 ug/1 and chronically toxic at less than 100 ug/l.(l^)
The comparable figures for vertebrates are 900 ug/1 for acute
toxicity(18) and 7.6 ug/1 for chronic toxicity.(19)
Lead is bioconcentrated by all species tested - both marine
and freshwater - including fish, invertebrates and algae.
-13-
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The mussel, Mytilus edulis, concentrated lead 2,568: times
that found in ambient water. Two species of algae concentrated
lead 900-1000 fold. Algae reportedly can concentrate lead in
their tissues to levels as much as 31,000 times ambient water
concentrations •(20) Lead does not degrade with the passage
of time and may be expected to persist indefinitely in the
environment in some form.
Regulatory Recognition of Hazard
As of February 1979, the U.S. Occupational Safety and
Health Adcinistration has set the permissible occupational
exposure limit for lead and inorganic lead compounds at 0.05
mg/m^ of air as an 8-hour time-weighted average. The U.S.
EPA (1979) has also established an ambient airborne lead
standard of 1.5 ug/m^.
The U.S. EPA has derived a draft criterion for lead of
50 ug/1 fcr ambient water.(21) This draft criterion is based
on empiric..! observation of blood lead in human population
groups consuming their normal amount of food and water daily.
In add ;'. M jii, final or proposed regulations of—the States
of California, Maine, Massachusettes, Minnesota, Missouri,
New Mexico, Oklahoma and Oregon define lead containing compounds
as hazardous wastes or components thereof.(22)
Indu'.- '.-rial Recognition of Hazard
Lead is rated as highly toxic through ingestion, inhalation
and skin absorption routes in Sax, Dangerous Properties of
Industrial >•: erials .
-14-
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Chromium
Health Effects
Hexavalent chromium is an animal carcinogen and there is
some evidence that it may be a human carcinogen as well.(23)
EPA's Carcinogen Assessment Group has listed it as such.
Mutagenic effects in bacteria have been described. Cytogenetic
effects in workers using hexavalent chromium compounds have
been reported.(24)
Teratogenic effects of chromium have been reported in a
single study and have not been confirmed.
Impairment of pulmonary function has been described in
chrome electroplating workers subject to chronic chromium
exposure.(25)
Additional information and specific references on the
adverse effects of chromium can be found in Appendix A.
Ecological Effects
Hexavalent chromium, at low concentrations, is toxic to
many aquatic species. For the most sensitive aquatic species,
Daphnia magna-, a final chronic no-effect level of less than
10 ug/1 has been derived by the U.S. EPA. For trivalent
chromium, toxic effects are more pronounced in soft than in
hard water.(26)
Regulatory Recognition of Hazard
Based on animal data indicating carcinogenic effects of
chromium VI and estimates of lifetime exposures from consump-
tion of both drinking water and aquatic life forms, the U.S.
-15-
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' has estimated levels of hexavalent chromium in ambient
water which will result in specified risk levels of human cancer:
Exposure Assumptions (per day) Risk'Levels and Corresponding Criteria
£ 10"7 10"6 10-5 .
2 liters of drinking water and 0 0.08 ng/1 0.8 ng/1 8 ng/1
consumption of 18.7 grams fish
and shellfish
Consumption of fish and shell 0 8.63 ng/1 86.3 ng/1 863 ng/1
fish alone
The OSHA time-weighted average exposure criterion for
chromium (carcinogenic compounds) is 1 ug/m3; for the "non-
carcinogenic" classification of chromium compounds the cri-
terion is 25 ug/3 TWA.
For the protection of aquatic species, proposed water
criteria for both trivalent and hexavalent chromium in fresh-
water and marine environments have been prepared in accordance
with the Guidelines for Deriving Water Quality Criteria.(27)
Industrial Recognition of Hazard '" .
Sax, Dangerous Properties of Industrial Materials,
4th Ed. 1975, rates chromium as having a high pulmonary
toxicity.
-16-
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References
1. USEPA Effluent Guidelines Division. Development Document'
for Proposed Effluent Limitations Guidelines and Standards
for the Ink Formulation Point Source Category. EPA-440/1-79/
090-b. December, 1979.
2. Storm, D.L. Handbook of Industrial Waste Compositions in
California - 1978. California Department of Health Services.
Hazardous Materials Management- Section. November, .1978. . ....
3. State of Illinois, Environmental Protection Agency. Special
Waste Disposal Applications. Obtained by USEPA March 13-14,
1979.
4. State of Missouri, Department of Natural Resources.
Hazardous Waste Disposal Request. Obtained by USEPA
March 16, 1979.
5. USEPA Effluent Guidelines Division. Development Document
for Proposed Effluent Limitations Guidelines and New
Source Performance Standards for the Paint Formulating
and the Ink Formulating Point Source Categories. EPA
440/1-75/050.
6. Personal Communication. National Association of Printing
Ink Manufacturers to John P. Lehman, Office of Solid
Waste, U.S. EPA, March 15, 1979.
7. State of New Jersey, Department of Environmental Protection.
State Files of Industrial Waste Surveys. Obtained by
USEPA August - September, 1979.
8. ECAO Hazard Profile: Lead (1980) SRC, Syracuse, N.Y.
9. Lancranjan, I. et al. 1975. Reproductive Ability of
Workmen Occupationally Exposed to.Lead. Arch. Environ.
Health 30: 396.
10. Lane,'R. E. 1949. The Care of the Lead Worker. .Er. .
Jour. Ind. Med. 6: 1243.
11. Roels, H. A., et al. 1978. Lead and Cadmium Absorption
Among Children Near a Nonferrous Metal Plant. A Follow-
up Study of a Test Case. Environ. Res. 15: 290.
12. Perlstein, M. A. and R. Atlala. 1966. Neurologic
Sequelae of Plumbism in Children. Clin. Pediat. 6: 266.
13. Byers, R. K. and E. E. Lord. 1943. Late Effects of Lead
Poisoning on Mental Development. Am. Jour. Child. 66: 471.
-17-
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14. Clarkson, T. W. and J. E. Kench. 1956. Urinary Excretion
of Amlno Acids by Men Absorbing Heavy Metals. Biochem.
Jour. 62: 361.
15. Dingwall-Fordyce, J. and R. E. Lane. 1963. A Follow-
up Study of Lead Workers. Br.-Jour. Ind. Mech. 30: 313.
16. McLain, R. M. and B. A. Baker. 1975. Teratogenicity,
Fetal Toxicity and Placental Transfer of Lead Nitrate in
Rats. Toxicol. Appl. Pharmacol. 31: 72.
17. Biesinger, K. E. and G. M. Christensen, 1972. Effects
of Various Metals on Survival, Growth, Reproduction and
Metabolism of Daphnia Magna. Jour. Fish. Res. Board Can.
29: 1691.
18. Brown, V. M. 1968. Calculation of the Acute Toxicity of
Mixtures of Poisons to Rainbow Trout. Water Res. 2: 723.
19. Pavies, P. H., et al. 1976. Acute and Chronic Toxicity
of Lead to Rainbow Trout, Salmo Gairdneri, in Hard and
Soft Water. Water Res. 10: 199.
20. Trollope, D.R., and B. Evans. 1976. Concentration of
copper, iron, lead, nickel, and zinc in freshwater
algae blooms. Envirom. Pollut. 11: 109.
21. U.S. EPA. 1979. Lead: Ambient Water Quality Criteria.
U.S. Environ. Prot. Agency, Washington, D.C.
22. USEPA Office of Solid Waste, States Regulations Files,
January, 1980.
23. National Academy of Sciences. 1974. Medical and Biological
Effects of Environmental Pollutants: Chromium. Washington™"
D.C.
24. Hedenstedt, A., et. al . 1977. -Mutagenicity of Fume Particles
From Stainless Steel Welding. Scand. J. Work. Environ.
Health 3: 203.
25. Bovett, P., et al. 1977. Spirometric Alterations In
Workers in the Chromium Electroplating Industry. Int.
Arch. Occup. Environ. Health 40:25.
26. ECAO Hazard Profile; Chromium (1980) SRC Syracuse,
N.Y.
27. U.S. EPA 1979. Chromium Ambient Water Quality Criteria.
28. U.S. EPA 1980. Damages and Threats Caused by Hazardous
Material Sites. EPA 430/9-80/004.
-18-
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Comments
The National Association of Printing Ink Manu-
factures (NAPIM) commented that the proposed
listing is too broad and that all wash wastes
should not be considered hazardous.
A
The listing of the above waste has been clarified.
After reviewing available information, the Agency has narrowed
the listing to cover waste wastes from tub in which ink is
formulated from raw materials containing chromium and lead.
Data- show that chromium and lead containing raw materials are
widely used in the industry, and the wash wastes generated
when these raw materials are used are likely to exhibit
substantial concentrat'ions of the toxic metals. The Agency
concluded that these wash wastes present a potential hazard
to human health and the environment because improper disposal
may result in the contaminatipn of ground and surface waters
used as drinking water sources (see the background document
for a more detailed discussion).
The NAPIM comments stated that wash.wastes
should not be listed as corrosive'since the
corrosive waste streams can be neutralized.
The fact that the wastes can be neutralized does not
mean that they are not hazardous when generated. In order to
make sure that corrosive wastes are managed properly, corrosivity
must be determined before treatment by neutralization or any
other means (see §261.3(b)(3).
-19-
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For the final listing, the Agency has decided not to
characterize the wash wastes as corrosive because adequate data
are not available to indicate that the wastes are typically
corrosive as defined in §261.22. In addition, the Agency
believes that the corrosivity of the wastes can easily be
determined by the generator. Such a determination is, of
course, required for all wastes not included in this listing,
and for all wastes addressed by individual petitions for
delistif*. (See §§ 262.11, 260.22.)
NAFIM stated that classification of all wash
wastes, as hazardous because some might contain
toxic organic substances is arbitrary.
The Agency has narrowed its proposed listing, although
the unsubstantiated comments submitted by NAPIM are not
particularly persuasive. The revised listing does not address
toxic organic substances in the waste and may be changed
shortly to include ink formulation wastes containing organic
contami. *nts. In this regard, the Agency is particularly
concern -;i with the USP «f phthalates in .plas t iciz ers used in
ink formula ion, and use of phenols in chemical specialties.
Information is solicited as to concentrations of these
materials in ink formulation wastes, and potential mass
loadings of these pollutants. As mentioned previously,
certain spent solvents are already listed as hazardous wastes
due to uheir toxicity.
-20-
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Veterinary Pharmaceuticals
-------
CON-13
LISTING BACKGROUND DOCUMENT
Wastewater treatment sludges generated during the production
of veterinary Pharmaceuticals from arsenic or organo-arsenic
compounds (T).
Residue from the use of activated carbon for decolorization in
the production of veterinary Pharmaceuticals from arsenic or
organo-arsenic compounds (T) (proposed)^/
Distillation tar residues from distillation of aniline-based
compounds in the production of veterinary Pharmaceuticals from
arsenic or organo-arsenic compounds (T) (proposed)^/
I. SUMMARY OF BASIS FOR LISTING
Treatment of wastewater from the production of veterinary
Pharmaceuticals from arsenic or organo-arsenic compounds generates
a wastewater treatment sludge containing arsenic or organo-
arsenic compounds. The production of this class of veterinary
Pharmaceuticals likewise generates other arsenic-containing
wastes, proposed for listing in this document.
The Administrator has determined that these wastewater
treatment sludges and other arsenic-containing wastes from
the production of veterinary Pharmaceuticals are solid
wastes which pose a substantial present or potential hazard
to human health or th.; environment when improperly transported,
treated, stored, disposed of or otherwise managed, and,
therefore, should be subject to appropriate management require-
ments under Subtitle C of RCRA. This conclusion is based on
the following considerations:
*_/These waste streams were not included in the initial listing,
and are being initially proposed in the present document.
-------
1) These wastes have been shown to contain high concen-
trations of arsenic. Arsenic is highly toxic and has
been identified by the Agency as a substance which has
demonstrated substantial evidence of being carcinogenic.
It has also been shown to be mutagenic to bacteria and
teratogenic to laboratory animals.
2) Disposal of these wastes in improperly designed or
operated landfills has resulted in arsenic contamination
of ground and surface water, providing empirical proof
that the arsenic in this waste is soluble and may migrate
from disposal sites into soil, groundwater and surface
water in concentrations sufficient to create a substantial
hazard. Further, since arsenic persists in the environ-
ment, any contamination caused by mismanagement of these
wastes will be long-term.
3) These wastes are generated in large quantities, so that
large amounts of arsenic are potentially available for
environmental release, an additional hazard posed by this
waste. _ . ... .
II. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Profile of the Industry
Three companies produce veterinary pharmaceuticals
containing arsenic: Salsbury Laboratories in Charles City,
Iowa; Whitmoyer Laboratories in Meyerstown, Pennsylvania; and
Fleming Laboratories in Charlotte, North Carolina.(^>2)
B. Manufacturing Process and Waste Generation
Manufacture of arsenic-containing pharmaceuticals
requires the reaction of an organic compound with inorganic
arsenic to form the organic arsenical product. Arsenic-
containing solid wastes generated during the production
process include tars from the distillation of aniline-
based compounds, and residue from the use of activated carbon
in the decolorization of pharmaceuticals.(^) Whitmoyer
-2-
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reported that it generates these wastes in annual quantities
of 100 55-gallon drums and 630 55-gallon drums, respectively.(
Salsbury Labs also generates arsenic-containing tars from
production processes.(5)
Production of veterinary Pharmaceuticals from arsenic
compounds generates wastewaters which contain organic
and inorganic arsenic. Treatment of these wastewaters produce
arsenic-bearing sludges. Figure 1 summarizes the wastewater
treatment system at Salsbury Laboratories, which produces
organic arsenicals marketed as feed additives for chickens,
turkey and swine.(1) Process wastewaters at Salsbury are
segregated into two sewer systems, of which only the second
generates a listed hazardous waste. As a point of clarifica-
tion, the first sewer system (the source of a non-listed
waste) carries waste acid washwater (10,000 gallons per day)
from the nitration processes; this washwater is neutralized
and clarified. These jolids are not believed to contain
arsenic, and are not listed in this document.jV
The second sewer system —the source of the listed waste
collects approximately 25,000 to 30,000 gallons per day of
arsenic-containing process wastewaters which originate from
^/Generators must still determine, however, whether this
waste stream meets any of the characteristics of hazardous
waste contained in §§261.21-24 of the regulations.
-3-
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Magr
Flow
.
Influent Saiin
pH adjujsent
(if necessary)
•
'•.
ClaHHer
(ISO, COO cal)
•
etic p
Meter L_
Waste Acid Uafh Hater
_____ pll adjuss^nt -• — -{frc" lltrat'O'* Process)
_ • (fiaOtl) plus otftfr acidic ccntri-
. fuqites (10.000 «jad)-
Other process vastr-tters (contact cooiina.
water, floor wash anC sr.ill cltin-.-o. jacket
drains frca jacte:sd ressels - 0.4 nod)
1
1 -
1
1 Arsenic Tres^tr.; Arsenic wastss
1 • (30,000 gp«) -
-~ __ i
1
Vacuum filter ^Htrate/j Filtrate
•-• i X ' iluete X
! Slo«igex • *
Equa
fl
i :_--
i X H.
• - Corjnprcial
' | Vacuum Fi'te-sl -Oisnosal Site
1 ™ "" "" (Listed Waste)
*
mi 11 ion- gal) ' aell
Lift Station
• .• »
R I A Building Discharge
Force Ha in t
Figure 1. Umewat^r Tr»auwrt System ^(j City Sani^r
Silsbury Laboratories. Ovaries City. lo-J
-4-
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the manufacture of Salsbury's arsenical compounds, 3-nitro-4-
hydroxyphenylarsonic acid and 4-nitrophenylarsonic acid.
Tha waste treatment process, indicated in Figure 1 by a
dashed line, is operated on a batch,basis and consists of
two parallel systems of treatment basins. The first set of
treatment basins works within the box marked "arsenic treat-
ment"; the second set of treatment basins works within the
two vacuum filter boxes located below the arsenic treatment
box in Figure 1. During "arsenic treatment", slaked lime
anG a flocculating agent are added to each batch, resulting
in pH adjustment to 11.2 - 11.4, and subsequent precipitation
of inorganic arsenic. The supernatant liquor is decanted——
and the precipitate [Ca3(As04)2 and 033 (As03 )_2-.] is f-iltere-d—
(vacuum filter box I, Figure 1) on a pre-coated rotary drum
vacuum filter. The filtrate and decant liquors are combined
an^. re-introduced into the arsenic treatment box for treatment
wi-.h MnS04 and a flocculating agent. The pH is lowered to
7... with HC1 or H2S04 to form a precipitate which is then
dra -n of'' to the second precoated rotary drum vacuum filter
(filt«-.: box II, Figure 1). The filtrate and decant liquors
are m;: xed with clarifier overflow, which presumably contains
no a. '•: . snic .
The remaining manufacturers of arsenic-containing
veterinary Pharmaceuticals also produce arsenic sludges.
Wbicmoyer L.a.boratories generates approximately 1,260 drums
per "ear of sludge from the evaporation, volume reduction
-5-
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and centrifugation of waste salt solutions.'^) Fleming
Laboratories reported the production of arsenic sludges, but
did not describe the process by which they are generated (24).
The wastewater treatment sludges are believed to contain
large amounts of arsenic. A sample of fresh sludge from the
Salsbury Laboratories disposal site, the LaBounty landfill,
contained 28,000 ppm of arsenic. In addition, the fact that
significant concentrations have been released from the waste
at the LaBounty site indicates that the contaminant is present
in substantial amounts thus, borings from underlying soils ex-
hibited a mean arsenic concentration of 700 ppm and borings from
surrounding soils exhibited a mean concentration of 2200 ppm.
;
Samples obtained from a well located between the site and the
river showed an arsenic concentration of 590 ppm in groundwater.
That these sludges typically contain a large quantity of the
contaminant is further supported by a report that Whitmoyer's
sludges contain 1-7% arsenic.(4)
Arsenic concentrations in the other listed wastes are
also substantial; distillation tars are reported to contain
10-15% arsenic, and residues from activated carbon decplori-
zation contain 4-14% arsenic.(^'
C. Waste Management
From 1953 to December, 1977, Salsbury Laboratories
disposed of its solid wastes in the LaBounty Dump, located
on the west bank of the Cedar River. (1) Prior to 1953,
-6-
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solid wastes were disposed of across the river at the municipal
dump, but quantities are estimated to be relatively minor
compared to those at the LaBouhty site. The wastewater treat-
ment sludge presently is stored in drums and shipped by rail
to Waste Management, T.nc., a commercial disposal operation
in Livingston, Alabama.'^)
Whitmoyer Laboratories' treatment sludges were stored
in on-site lagoons until groundwater contamination was detected
(this was also the disposal practice under prior ownership).
Off-site disposal has been utilized since that time. Since
1975, Whitmoyer Laboratories has drummed all of its arsenic-
containing wastes, and has shipped these wastes to landfills
specially designed to impede release of hazardous constituents
to the environment.(^)
III. DISCUSSION OF BASIS FOR LISTING
A. Hazards Posed by the Waste
These treatment sludges, distillation tars, and
activated carbon residues contain high concentrations of
arsenic, an extremely toxic substance. Arsenic and arsenic
compounds have been identified by the Agency as a substance
which has demonstrated substantial evidence of carcinogenicity.
Arsenic is mutagenic '-o bacteria and teratogenic to laboratory
animals. See Appendix A for further information.
It is quite obvious that improper management of these
wastes can result in substantial hazard, since substantial
harm has in fact occurred from their faulty management. The
-7-
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most notorious example of this damage caused by mismanagement
of this waste at the LaBounty landfill.
Various wastes, including large amounts of arsenic sludges,
were disposed of at the LaBounty site. In January, 1978
approximately 7.5 cubic meters of arsenic sludge were disposed
per day. (1) At one time it was estimated that the site
contained more than six million pounds of arsenic'^). Th.e site
is located over a major aquifer. As noted above, substan-
tial arsenic contamination of soil and groundwater resulted
when the arsenic compounds leached from the waste site. As
a result of surface run-off and groundwater discharge, the
Cedar River picked up an average load of 53 kg of arsenic
per day in the vicinity of the LaBounty Site.(l) The Iowa
Department of Environmental Quality issued an order that
required Salsbury to cease disposal of wastes at the LaBounty
landfill. (77-DQ-01, Dec. 14, 1977).
A report on this damage incident concluded that arsenic
in the wastewater treatment sludge is "fairly easily solu-
'hilized even if it is' precipitated with calcium as the
arsenate (Ca,(AsO/)~)"•' ' The presence of arsenic in
ground and surface waters in the vicinity of the LaBounty
Site likewise clearly indicates that, once released from the
waste, it is highly mobile and persistent.
The migratory potential of the arsenic contained in
these wastes is also substantiated by the groundwater
-8-
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contamination resulting from the storage of the listed waste
and similar wastes by Whitmoyer Laboratories in holding
lagoons (4). When the groundwater contamination was discovered
in the late 1960's, the company began disposing of the sludges
at a number of different sites; presently, these wastes are
transported by truck to hazardous waste landfills or a
specially designed vault disposal operation (4). Again,
this demonstrates the potential hazard posed by the migration
of waste constituents from a disposal site and the generator's
subsequent recognition of this hazard.
An additional demonstration of the necessity for proper
management occurred when Salsbury Laboratories, as a result
of a cease order, began disposing of solid wastes in a tem-
porary on-site holding basin.(1) This disposal method was quickly
terminated because leachate was detected in the underdrain
system within 24-hours af'er disposal.(1) The 1977 court
action, coupled w: :h the present management of these wastes
in chemical waste landfills, substantiates the concern by
both the state and the generator for the proper management
and disposal of this hazardous waste.
These damage incidents show that arsenic may easily
migrate from these wastes and persist in the environment
upon release . Indeed, because, arsenic is an element, and
does not degrade with the passage of time, it will persist
in some form virtually indefinitely.
There are a number of additional reasons to impose
hazardous waste status on this waste. Unregulated transpor-
-9-
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tation of this waste to off-site disposal facilities also
increases the likelihood of harmful exposure to human beings
and the environment. Without proper means to track the
waste from the point of generation to its ultimate destination,
the waste might not reach its designated destination at all,
thus making it available to do harm elsewhere.
Furthermore, as previously indicated, arsenic sludges
from the production of veterinary Pharmaceuticals are generated
in very substantial quantitites (in January 1978, approximately
7.5 m^/day at Salsbury plant (1)). Large amounts of arsenic
are thus available for potential environmental relelase. The
large quantities of this contaminant pose the danger of pol-
luting large areas of ground or surface waters. Contamina-
tion could also occur for long periods of time, since large
amounts of this pollutant are available for environmental
loading. Attenuative capacity of the environment surrounding
the disposal facility could also be reduced or exhausted due
to the large quantities of pollutant available. All of
these considerations increase the possibility of exposure to
this harmful constituent.
B. Health and Ecological Effects
Health Effects
Arsenic is very acutely toxic to animals and humans
(6). Death in humans has occurred following ingestion of
very small amounts (5mg/kg) (7). Several epldemiological
studies have associated cancers with occupational exposure
-10-
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to arsenic (8-10), including those of the lung, lymphatics
and blood (11,12). Skin cancer has been associated with the
presence of arsenic in drinking water (13), while liver
cancer has developed in several cases following ingestion of
arsenic (14). The human carcinogenic potential of arsenic
is supported by animal studies.
Occupational exposure to arsenic has also resulted in
chromosomal damage (15), and several different arsenic
compounds have demonstrated positive mutagenic effects in
laboratory studies (16-18). The teratogenicity of arsenic
and arsenic compounds is well established (19-21); observed
defects include those of the skull, brain, kidneys, gonads,
eyes, ribs and genitourinary system.
The effects of chronic arsenic exposure include skin
diseases progressing to gangrene, liver damage, neurological
disturbances (22), disturbances in red blood cell production
and cardiovascular disease (8).
Additional information and specific reference on adverse
effects of arsenic can be found in Appendix A.
Ecological Effects
The data base for the toxicity of arsenic to aqua.tic
organisms is more complete for freshwater organisms; con-
centrations as low as 128 ug/1 are acutely toxic to fresh-
water fish. Based on one chronic life cycle test using
Daphnia magna, a chronic value for arsenic was estimated at
853 ug/1 (21).
-11-
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Regulatory Recognition of Hazard
OSHA has set a standard 8-hr air TWA in air of 0.5 mg/m^
for occupational arsenic exposure. 0.05 mg/m^ has been proposed
<
for arsenic trioxide (23). DOT requires a "poison" warning
label.
EPA's Office of Toxic Substances under FIFRA has issued
a pre-RPAR. The Carcinogen Assessment Group has identified
arsenic and its compounds as a substance which has demonstrated
substantial evidence of being carcinogenic. Arsenic is
designated as a priority pollutant under Section 307(a) of the
CWA. The Office of Drinking Water has regulated arsenic
under the Safe Drinking Water Act and the Office of Air
Quality Planning and Standards has begun a preregulatory
assessment of arsenic based on its suspected carcinogenic
effects. The Office of Water Planning and Standards under
Section 304 (a) of the Clean Water Act has begun development
of a regulation based on health effects other than oncogenicity
and environmental effects. Finally, the Office of Toxic
Substances has completed Phase I assessment of arsenic
under the Toxic Substances Control Act.
Industrial Recognition of Hazard
Arsenic is rated as highly toxic through intra-muscular
and subcutaneous route in Sax, Dangerous Properties of
Industrial Materials (22). Arsenic is rated as highly toxic
through ingestion, inhalation, and percutaneous routes in
-12-
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Patty, Industrial Hygiene and Toxicology.
A ten-fold reduction (to 0-.05 mg/m^) of the present QSHA
standard for arsenic trioxide has been proposed (23).
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REFERENCES
1. Dahl, Thomas 0. "NPDES Compliance Monitoring and
Water/Waste Characterization. Salsbury Laboratories/
Charles City, Iowa. (June 19-30, 1978)" National
Enforcement Investigations Center-Denver and Region
VII-Kansas City. EPA-330-2-78-019. November 1978,
pp. 35, 101, 103, 128.
2. Directory of Chemical Producers, 1978 and 1979 editions.
3. Personal communication with Martha Steincamp. Enforce-
ment Division. EPA Region VII. Kansas City, MO".
March 2, 1980.
4. Personal communication to Arthur D. Little, Inc., from
Chemical Area Manager. Whitmoyer Laboratories.
Meyerstown, PA. April 3, 1980.*/
5. Report of Investigation. Salsbury Laboratories. Charles
City, Iowa. U.S. Environmental Protection Agency.
Region VII. Surveillance and Analysis Division.
February 1979.
6. Gleason, M. N., et al. Clinical Toxicology of Commercial
Products. Acute Poisoning. (1969) 3rd ed., p. 76.
7. Lee, A. M. and Fraumeni, J. F., Jr. Arsenic and respira-
tory cancer in man: An occupational study. Jour.
Natl. Cancer Inst. 42:1045 (1969).
8. Pinto, S. S. and Bennett, B. M. Effect of arsenic
trioxide exposure on mortality. Arch. Environment.
Health 7:5883 (1963).
9. Kwratune, M., et al. Occupational lung.cancer among
copper swelters. Int. Jor. Cancer 13:552 (1974).
10. Oh, M. G., et al. Respiratory cancer and occupational
exposure to arsenicals. Arch. Environ. Health
29.250 (1974).
j^/The Agency acknowledges and appreciates the cooperation of
Whitmoyer Laboratories in furnishing data for this document.
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11. Baetjer, A. M., et al. Cancer and occupational exposure
to inorganic arsenic. 18th Int. Cong. Occup. Health
Brighton, England, p. 393 in_ Abstracts, September 14-
19 (1975).
12. Tseng, W. P., et al. Prevalence of skin cancer in an
endemic area of chronic arsenicism in Taiwan. Jour.
Natl. Cancer Inst. 40-453 ' (1968).
13. ECAO Hazard Profile; Arsenic. (1980) SRC, Syracuse, NY.
14. Nordenson, I. et al. Occupational and environmental
risks in and around a swelter in northern Sweden..
II. Chromosomal aberrations in workers exposed to
arsenic. 88:47 (1978).
15. Petres, J., et al. Zum Einfluss a norgan ischen Arsens
auf die DNS-Synthese menschllcher Lymphocyten in
vitro. Arch. Derm forsch. 242:343 (1972).
16. Paton, 6. R. and Allison, A. C. Chromosome damage in
human cell cultures induced by metal salts.
Mutat. Res. 16 : 332•(1972).
17. Moutshcen, J. and Degraeve, N. Influence of thiol-
inhibiting substances on the effects of ethyl methyl
sulphonate on chromosomes. Experientia 21:200 (1965).
18. Hood, R. D. and Bishop, S. L. Teratogenic effects of
sodium arsenate in mice. Arch. Fnvirn. Health
24:62 (1972).
19. Beandoin, A. R. Teratogenicity of sod'urn arsenate in
rats. Teratology 10:153 (1974).
20. Perm, V. H., et al. The teratogenic profile of sodium
arsenate in the golden hamster. Arch. Environ.
He-alth 22:557 (1971).
21. U.S. EPA. 1979. Arsenic: Ambient Water Quality
Criteria. Environ. Protection Agency, Washington,
D.C.
22. Sax, N. Irving, 1975. Dangerous Properties of Industrial
Materials. Fourth Edition, Van Nostrand Reinhold,
New York.
23. Threshold"Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with
Intended Changes for 1979. ACGIH, Cincinnati, OH 45201
24. Personal Communication to Arthur D. Little from Mr. George
Fleming, Fleming Labs, April 3, 1980.
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Coking
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LISTING BACKGROUND DOCUMENT
. COKING
Decanter Tank Tar-Sludge*(T)
I. Summary of Basis for Listing
The spray cooling of coke oven gases during the by-
product recovery process results in the generation of a de-
canter tank tar-sludge. Tha Administrator has determined
that decanter tank tar-sludge may pose a present or po-
tential hazard to human health or the environment when im-
properly transported, t?:eated, stored, disposed of or other-
wise managed, and therefore should be subject to appropriate
management requirements under Subtitle C of RCRA. This con-
clusion is based on the following considerations:
1) The tank tar-sludge contains significant concentrations
of phenol and naphthalene. Phenol is highly toxic, and an
animal carcinogen. Naphthalene is also toxic and is a demon-
strated neoplastic substance in experiments done on labora-
tory animals.
2) Phenol has lead. :d in significant concentration from
a waste sample tested i. a distilled water extraction proce-
dure. Although no leae -ite data is currently available for
naphthalene, the Agency ;>el.l^-ras that, due to its presence
in the tar "in high conce^'v Lions and due to its relative solu-
bility, naphthalene also ;».•_/ leach from the waste in harmful
concentrations if the wastf is improperly managed.
3) These tar-sludges are often land disposed in on-site
landfills or dumped in the open. These methods may be inade-
quate to impede leachate migration and resulting groundwater
contamination.
*The listing description has been amended from that originally
proposed on December 18,. 1978 (43 PR 58959) which included two
waste listings [i.e., CoV'r.g: Decanter tank tar and Coking: De-
canter tank pitch/sludge]
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II. Waste Generation, Composition and Management
Coke, the residue from the destructive distillation of
coal, serves as both a fuel and as a reducing agent in the
making of iron and steel. Some coke plants recover by-products
given off or created during the coke production process, and
the recovery of by-products generates the sludge which is
listed in this document. There are 66 by-product coke plants,
which generate an estimated 72,300 tons/yr of decanter tank
tar-sludge. During the recovery of chemicals in the by-prod-
uct coke production process, tar separates by condensation
from coke oven gas and drains to a decanter tank. Recover-
able oil fractions are decanted off the top and the tar sludge
settles to the bottom.
Approximately .97% of this tar-sludge is elemental carbon.
The remaining 3% consists of condensed tar materials. These
condensed tar materials contain the waste constituents of con-
cern, namely phenolic compounds and naphthalene, which are
formed as a result of the destructive distillation of coal.
•• \
Rased on a published reference, the condensed tar compo-
nent contains, by weight, 2.2% naphthalene and 0.1% phenolic
compounds(^). With an estimated 2,169 tons/yr of condensed
tar contained in the amount of tar-sludge generated annually
(i.e., 3% of the 72,300 tons/yr of tar-sludge), approximately^
47.7 tons of naphthalene and 2.2 tons of phenolic compounds
will be contained in the waste generated each
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Of the 66 coke p.lants generating decanter tank tar-sludge,
30 plants use the tar-sludge as a raw material in either the
sintering process or open hearth furnace operation. The re-
maining 36 plants dispose of this waste in unsecure on-site
landfills(*•) , or by dumping in the open(-!\
III. Hazardous Properties of the Waste
Phenol and naphthalene are present in the tar component
of this waste in significant concentrations: 0.1% by weight
(1000 ppm) and 2.2% by weight (22,000 ppm), respectively(2).
Phenol is highly toxic and is also an animal carcinogen,
while naphthalene is tpxic. Thus, the Agency believes that
the concentrations of these materials in the waste are quite
significant, in light of the constituents' known health
hazards. Further, these waste constituents appear capable
of migrating in significant concentrations if mismanaged,
and are likely to be mobile and persistent so that waste
mismanagement could result in a substantial human health or
environmental hazard.
Phenol's potential for migration from this waste In sig-
nificant concentrations has been demonstrated empirically.
Phenol leached in significant concentration (approximately
500 ppm) from a decanter tar-sludge wast.i sample subjected
to distilled water extraction procedure.(3) in addition,
phenol is extremely soluble, about 67,000 ppm @ 25°c(5),
indicating high potential for migration. Phenol biodegrades
at a moderate rate in surface water and soil but moves very
-3-
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readily (App. B). Even with a persistence of only a few day,
the rapid spreading of phenol could cause widespread contamina-
tion of the eco-system and contamination of potable water supplies
The migratory potential of phenol and its ability to move
through soils is further confirmed by the fact that it has been
detected migrating from Hooker Corporation's S Area, Hyde Park,
and 102nd St. landfills in Niagara, New York (OSW Hazardous
Waste Division, Hazardous Waste Incidents, Open File, 1978).
The compound's persistence following migration is likewise
shown by these incidents.
Although no comparable leachate data is currently avail-
able for naphthalene, the Agency believes that this constituent
also may leach in harmful concentrations from the waste if not
properly managed. Naphthalene is very water soluble, with solu-
bilities ranging from 30,000 ug/1 to 40,000 ug/1. In addition,
naphthalene has been identified in finished drinking water,
lakes, and rivers, demonstrating its ability to persist and
to be mobile(^). This information, naphthalene's solubility
in water, and its presence in the tar in such high concentra-
tions (22,000 ppm) make it likely that it will leach from the
waste in potentially harmful concentrations if the waste is
mismanaged, and will then be mobile and persistent, and so
poses the potential for causing substantial hazard to human
health and the environment.
Current practices of disposing of this waste in fact ap-
pear inadequate. Disposal of decanter tank tar-sludge in un-
secured landfills or by dumping in the open makes it likely
-------
that the hazardous constituents in the waste will leach out
and migrate into the environment, possibly reaching and con-
taminating drinking water sources. Siting of waste manage-
ment facilities in areas with highly permeable soils could
facilitate leachate migration. As demonstrated above, the
waste constituents appear capable of migration, mobility and
persistence. Thus, if disposal sites are improperly managed
or designed (e.g., lack adequate leachate collection systems),
waste constituents could leach into soils and contaminate
groundwater.
Health and Ecological Effects
Phenol
Congress designated phenol a priority pollutant under
§307(a) of the Clean Water Act.
Phenol is readily absorbed by all routes. It is rapidly
distributed to mammalian tissues. This is illustrated by
the fact that acutely toxic doses of phenol can produce
symptoms within minutes of administration regardless of the
route of entry. Repeated exposures to phenol at high concen-
trations have resulted in chronic liver damage in humans.(3)
Chronic poisoning, following prolonged exposures to low
concentrations of the vapor or mist, results in digestive
disturbances (vomiting, difficulty in swallowing, excessive
salivation, diarrhea), nervous disorders (headache, fainting,
dizziness, mental disturbances), and skin erupt ions(^).
Chronic poisoning may terminate fatally in some cases where
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there has been extensive damage to the kidneys or liver.
OSHA has set a TLV for phenol at 5 ppm. Phenol is listed
in Sax's Dangerous Properties of Industrial Materials as high-
ly toxic via an oral route.(4) gax also describes phenol as
a co-carcinogen and a demonstrated carcinogen via a dermal
route in studies done with laboratory animals. Additional
information and specific references on the adverse effects
of phenol can be found in Appendix A.
Naphthalene
Naphthalene is designated as a priority pollutant under
Section 307(a) of the CWA.
Systemic reaction to acute exposure to naphthalene in-
cludes 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 jaundice and occasion-
ally renal disease from precipitated hemoglobin has been des-
cribed in newborn infants, children, and adults after exposure
to naphthalene by ingestion, inhalation, or possibly by skin
contact.
OSHA's standard for exposure to vapor for a time-weighted
industrial exposure is 50 mg/m^.
Sax lists naphthalene as moderately toxic via the oral
route and warns that naphthalene is a demonstrated neoplastic
substance via the subcutaneous route in experiments done on
-.6-
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laboratory animals^'. Additional information and specific
references on the adverse, effects of naphthalene can be found
in Appendix A.
-7-
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References
1. Draft Development Document for Proposed Effluent Limitations
Guidelines and Standards for the Iron and Steel Manufactur-
ing Point Source Category; By-Product Cokemaking Subcate-
gory. Volume II October 1979.
2. Desha, Lucius. Organic Chemistry. McGraw-Hill Book Company,
New York, New York 1946.
3. Calspan Corporation. Assessment of Industrial Hazardous
Waste Practices in the Metal Smelting and Refining Industry.
Appendices. April 1977. Contract No. 68-01-2604, Volume
III.
4. Sax, N. Irving. Dangerous Properties of Industrial Materials,
Fifth edition, Van Nostrand Reinhold Co., 1979.
5. Dawson, English, Petty. Physical Chemical Properties of
Hazardous Waste Constituents, Southeast Environmental Re-
search Laboratory, March 5, 1980.
-8-
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Primary Metals
-------
LISTING BACKGROUND DOCUMENT
PRIMARY ALUMINUM REDUCTION
Spent potliners from primary aluminum reduction (T)
I. SUMMARY OF BASIS FOR LISTING
Primary aluminum metal is produced by the electrolytic
reduction of alumina, an aluminum oxide. This process takes
place in carbon-lined cast iron electrolytic cells known .as
"pots". After continued use, the carbon pot lining ("pot-
liner") cracks, and must be removed and replaced with a new
potliner.
The Administrator has determined that these used potliners
("spent potliners") are a solid waste 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. Spent potliners from primary aluminum reduction
contain significant amounts of iron cyanide complexes.
EPA has detected iron .cyanide complexes (expressed as
cyanides) in spent potliners in significant
concentrations.
Note: The Agency is aware that there are other solid wastes
generated by the primary aluminum reduction process, and is
currently investigating these wastes to determine whether to
list them as hazardous in the future.
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2. The aluminum reduction industry typically either
stores spent potliners in unprotected piles outside
(prior to reprocessing) or dumps them in the open.
Part or all or the cyanide contained in the spent
potliners can be expected to be released into the
environment if spent potliners are dumped in the
open, stored without protection in the open or
otherwise improperly managed. Available data
indicates that significant amounts of free cyanide
and iron cyanide will leach from potliners if the
spent potliners are stored or disposed of in unpro-
tected piles out-of-doors and exposed to rainwater.
In addition, in the presence of sunlight, the iron
cyanides may decompose to release highly toxic
hydrogen cyanide into the environment. Iron cyanide
complexes are toxic and free cyanide is extremely
toxic to both humans and aquatic life if ingested.
3. One major damage incident has been reported which is
attributable to the improper disposal of spent pot-
liners, demonstrating migration, mobility and persist-
ence of waste constituents, and demonstrating as
well that substantial Jiazard can result from improper
management of this waste.
4. In 1977, the primary aluminum reduction industry
generated an estimated 191,000 MT of spent pot-
liners per year (approximately 6,366 MT per average-
sized plant). This figure is expected to increase
to 243,000 MT (approximately 8,100 MT per plant)
by 1983. Generation of such large quantities of
waste increases the potential for hazard if mis-
managment should occur and is a further justification
for listing these wastes as hazardous.
II. SOURCES OF THE WASTE AND TYPICAL :ISPOSAL PRACTICES
A. Profile of the Aluminum Reduction Industry
Primary aluminum plants convert aluminum oxides into
aluminum metal. Currently, there are 30* primary aluminum
plants, located in 16 states, operating in the United States.
The primary aluminum industry currently produces approx-
imately 5 million MT of primary aluminum per year, (100,000
to 150,000 tons per year for an average-size plant). Pro-
*0ne other plant operates on a stand-by basis.
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duction has been increasing for many years and is expected to
reach 7 million MT per year by 1985.(7)
B. Manufacturing Process
Aluminum metal is produced almost entirely by the Hall- .
Heroult process. In this process, alumina, an aluminum oxide
is reduced to aluminum metal in carbon-lined cast iron
electrolytic cells known as "pots". The carbon potlining
("potliner") acts as the cathode of the cell; petroleum coke
and pitch act as the anode; and cryolite, calcium fluoride,
and aluminum fluoride are used as the electrolyte. When an
electric current is passed through the pots, the alumina is
reduced to aluminum metal. The molten aluminum is periodically
drawn off as it accumulates in the bottom of the pots.
During the reduction process, iron cyanide complexes
form in the potliners. The chemical/physical mechanism by
which these compounds are produced is poorly understood(4);
however, it is generally agreed that the iron cyanide compounds
are produced in all cases(7).
C. Waste Genration and Management
After continued use, potliners crack, causing the molten
aluminum in the pots to become contaminated with iron from the
cast iron pots. At this point, the cracked potliners ("spent
potliners") must be removed from the pots and replaced with
new carbon pot liners(1).
In 1974, the primary aluminum industry generated
approximately 159,000 MT of spent potliners (approximately
5,300 MT for an average sized plant). By 1977, the industry
-------
was generating an estimated 191,000 MT of spent potliners
per year (6,366 MT per average facility)(1) . This figure is
expected to increase to 243,000 MT by 1983(1).
Spent potliners are either processed to recover cryolite
(which saturates the potliners during the redu.ction process)^/
or disposed of immediately.(1,7) Those spent potliners
which are reprocessed are usually stored on-site out-of-doors
in uncovered piles(1,3,4 , 7) , sometimes for periods of up to
five years or more before reprocessing.(7) Spent potliners
which are disposed c.C immediately are generally dumped in the
open, either off-site or on-site.(1,3,4,7) No site preparation
other than tree and shrub removal is commonly practiced(7).
One company also has been reported to dispose of spent pot-
liners in a lagoon, along with industrial sludge.(7)
D. Hazardous Properties of Spent Potliners
Spent potliners contain iron cyanide complexes. As
noted above in Sectxon B, these complexed cyanides are
generated during the reduction process, and are believed to be
present in all spent potliners. Analyses of leachate from
piles of spent potlii:<-r: .discussed below) confirm the
presence of iron cyanide and free cyanide in the spent
potliners(2,3,4,5). Thise concentratins are indicative of a
potential for hazard; since these complexed cyanides are
capable of migratior as highly toxic free cyanides. Furthermore,
iron cyanides themselves are toxic.
j^/The Agency has inr-rmation indicating that the wastewater
from the cryolite recovery process contains high concentrations
of cyanide. This wast-, stream is, therefore, being considered
by the Agency as a ca?. date for future listing. Further
information is solici-T e .i .
-4-
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The following discussion demonstrates that cyanides are
present in these wastes in substantial concentrations, and
that, if the wastes are mismanaged, cyanide may migrate as
both free and complexed cyanide, and may be mobile and
presistent enough to reach environmental receptors via
groundwater, surface water and air exposure pathways in
concentrations sufficient to create a substantial hazard.
Indeed, one damage incident involving spent potliners confirms
that these wastes can cause substantial hazard if mismanaged.
A. Waste Composition and Migratory Potential of Waste
Constituents
The Agency does not presently possess reliable data on
iron cyanide concentrations in spent potliners themselves,
but concludes that the concentrations of cyanide in potliners
are substantial, based on cyanide concentrations in leachate
from potliners. These data further demonstrate that-the
iron cyanide in the waste may migrate as highly toxic free
cyanide in high concentrations in leachate or surface runoff.
Monitoring samples taken by Kaiser Aluminum and Chemical
Company in 1976 (10) confirm that free cyanide may migrate
from this waste in high concentrations upon exposure to
leaching media. These data indicate 2500 mg/1 of free cyanide
(13,000 mg/1 total cyanide) in potlining slab liquor samples
(the runoff from concrete slabs on which spent potliners are
placed during open storage), and 1200 rag/1 free~"cyanide (9000
mg/1 total cyanide) in pot soaking pit liquor sample (liquor
-5-
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left after spraying pots to facilitate removal of the liner)(lC).
That these concentrations pose very high potential for hazard
is indicated by the fact that exposure to 300 ppm of cyanide
will cause death to humans in minutes (see p. 9 below). .
Furthermore, in a paper entitled "Development of a Method
for Detoxificaiton of Spent Cathode (potliner) Leachates",
Comalco Aluminum personnel stated, " The storm water leachate
from spent reduction cell cathodes (spent potliners) stored
uncovered in the open typically contains unacceptably high
levels of cyandies."(4). Table 1 of this paper shows spent
potliner leachate to contain 200 mg/1 *y of free cyanide and
2000 mg/1 complexed cyanides prior to leachate treatment.
A third source likewise identifies substantial concen-
trations of complexed cyanides in leachate from spent potliners.
The Kaiser Aluminum and Chemical Company collected and analyzed
samples of pondwater from a pond that collects rainwater
runoff from spent potliners which are discarded in a 10-acre
dump next to its Chalmette, LA plant. Kaiser reported that
pond liquor contains complexed cyanide in concentrations
ranging from 50-700 ppm.(3,9) The chemical analyses of the
pond liquor samples show concentrations of 100-350 ppm cyanide.(9)
Thus, both extremely toxic free cyanide and less toxic iron
cyanides are capable of migrating from spent potliners in
*_/The table, in fact, does not give units of measurement, but the
actual values indicate that the units are mg/1.
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substantial concentrations if the waste is exposed to leaching
media. Migration of free cyanides may also occur via an
airborne route. Iron cyanide has long been known to undergo
photodecomposition leaving extremely toxic hydrogen cyanide
and free cyanide decomposition byproducts . (8 ,13 ,14 ,15 ,16)j^/
Hydrogen cyanide will then enter the atmosphere, where it is
both mobile and persistent.(17) **/
Once free cyanide migrates from the waste it is likely to
be quite mobile in soils. Cyanide has been shown to move
through soils into groundwater.(12) Disposal of these wastes
in the open, a present waste management method, could therefore
lead to release of free cyanides and subsequent migration through
soils to groundwater. (Migrating iron cyanide, on the other
hand, has limited mobility in soils, but, as shown above,
can photolyse to form mobile cyanide and hydrogen cyanide.)
Thus, these wastes may potentially release high
concentrations of cyanide into water and (to a lesser extent)
air, should mismanagement occur. Current waste management
practices appear to allow a strong possibility of migration
of cyanide, i.e., spent potliners are often simply dumped in
the open. Spent potliners being stored for cryolite recovery
are also piled in the open without cover, sometimes for
periods of up to five years (see p. 4 above). The Agency
believes that substantial hazard could result from these
]J|_/These sources do not indicate a degradation rate constant.
j^/Hydrogen cyanide is reported to be resistant to naturally
occuring wavelengths reaching the earth's surface.(17)
-7-
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types of waste management practices, in light of this waste's
potential to release free cyanide, and cyanide's mobility
and persistence following release.
An actual damage incident involving spent potliners
confirms this judgement. Kaiser Aluminum's Mead Works is
situated 150 feet above the Spokane aquifier which is used
for private wells and which drains into the Little Spokane.
River.(5) Leachate from a lagoon containing potliners and
sludge leached through the ground and contaminated the aquifier
with cyanide.(5) Eighteen wells were contaminated, some
having cyanide levels in excess of 1,000 ppb.(5) Kaiser had
to provide alternative, sources of drinking water to the
affected owners and to upgrade and seal the leaking lagoon.(5)
A further reason for listing spent potliners as hazardous
is the quantity of waste generated. Approximately 191,000 MT
of spent potliners were generated by the aluminum industry in
1977 and this figure is expected to increase substantially
(see p. 3). Thus, large amounts of cyanide are available
(in light of the high concentrations in leachate) for
environmental release. These large quantities pose the
danger of polluting large expanses of ground and surface
waters, and an increased likelihood of reaching environmental
receptors, in light of cyanide's mobility in water and air.
Contamination also could occur for long periods of time,
since large amounts of pollutants are available for environ-
mental loading. Attenuative capactiy of the environment
-8-
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could also be reduced or exhausted by large quantities of
pollutants released from the waste. All of these considerations
increase the possibility of exposure to harmful constituents
in the waste and, in the Agency's point of view, further
justify a "T" listing.
Hazards Posed by Harmful Constituents
Cyanide is extremely toxic when it is ingested in free
form and less toxic when ingested in complex form. (Appendix
A). Free cyanide can cause death in humans and aquatic
life. In its most toxic form, cyanide can be fatal to humans
in a few minutes at a concentration of 300 ppm. While
recovery from non-fatal poisonings is generally rapid and
complete, fatal exposure levels are low. (App. A)
The Public Health Service recommends 0.2 mg/1 as the
acceptable level of cyanide for water supplies and EPA has
recommended that this level be used as the ambient water
quality standard under the Clean Water Act. The Canadian
government has set a similar criterion. OSHA has regulated
exposure levels for the workplace. Finally, final or pro-
posed regulations of the states of California, Maine, Mary-
land, Massachusetts, Minnesota, Missouri, New Mexico and Oregon
define cyanide-containing compounds as hazardous waste or
components thereof. See Appendix A for references and addi-
tional information on cyanide.
-9-
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Response to Comments
On August 22, 1979, EPA proposed to list spent potliners
as a hazardous waste (44 FR 49404). No information was sub-
mitted during the public comment period that disagreed with
the conclusion that spent potliners are hazardous as defined
by the proposed regulation. The Anaconda Company stated
however, that the particular disposal practices, coupled
with the physical and geologic conditions at its two primary
aluminum smelters produce "no significant release of any
constitutent from che spent potliners into an underground
water supply." (6). Anaconda indicates that coal (not water)
underlies its Kentucky disposal site, that there is little
rain at its Montana site. It concludes that the standards
for each disposal site should be established separately.
The conditions at any particular disposal site do not,
however, change ti a initial determination of whether or not
a waste is hazardc >s. A waste is listed as hazardous if it
may pose a substar'.lal threat to human health and the environ-
ment if it i.s misnu; '-.s.a ^ . Anaconda implicitly concedes
that if the constituents released from spent potliners
entered a drinking wa:er reservoir, such a threat would
exist. The individ:\-.l circumstances of a particular disposal
site will be addr^'-.sed when a permit is issued, and are other-
-10-
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wise taken into account in many of the standards contained
in the recently promulgated Parts 264 and 265 (see, e.g. ,
§265.90(c), which provides for a waiver of the groundwater
monitoring requirement if a facility owner/operator demonstrates
"that there is a low potential for migration of hazardous
waste or hazardous waste constituents from the facility via
the uppermost aquifer to water supply wells ... or to surface
water").
-11-
-------
References
U.S. EPA, Office of Solid Waste. Assessment of Hazardous
Waste Practices in the Metal Smelting and Refining Indus-
try. 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 Seg-
ment of the Nonferrous Manufacturing Point Source Category.
Washington, D.C., September 1979. "
3. Trachtenberg, J. J., and M. A. Murphy. Removal of Iron Cya-
nide Complexes from Waste Water Utilizing an Ion Exchange
Process. Kaiser Aluminum and Chemical Corporation, Chal-
mette, La.
4. Dojlbey, D. H. and D. A. Harrison. Development of a Method
for Detoxification of Spent Cathode Leachates. Comalco
Aluminum (Bell Bay) Limited, Georgetown, Tasmania, Aus-
tralia.
5. U.S. EPA, Region 10 - Seattle, Washington, Status of Cya-
nide Contamination of Spokane Aquifers in the Vicinity
of the Kaiser Aluminum Company Mead Works. Memo from
Lloyd A. Reed to Terrell Hunt, January 2, 1979.
6. U.S. EPA, RCRA Section 3001 Docket, Comment Number A
4 W-004, Anaconda Company to John P. Lehman, September
25, 1979.
7. U.S. EPA, Assessment of Solid Waste Management Problems
and Practices in Nonferrous Smelter. PEDCo Environmental,
Inc. EPA Contract Number 68-03-2577, November 1979.
8. Ecological Analysts, Inc. Cyanide an overview and analysis
of the literature on chemistry, rate, toxicity, and detec-
tion in surface waters. Prepared for; The Inter-Industry
Cyanide Group. June 1979.
9. U.S. EPA, Open Files - Primary Aluminum Industry, 1980.
10. Technical Memorandum from T.A. Palmer to B.P. Leber re:
Analysis of Ravens Wood Samples. October 20, 1976.
-12-
-------
11. Cruz, M., Et al. 1974. Absorption and Transformation of
HCN on the Surface of Copper and Calcium Montmprillanite
Clay Minerals 22: 417-425.
12. 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.
13. EPA Quality Criteria for Water, EPA-440/9-76-023 (1976).
14. Burdick, G. E., and M. Lipschuetz. 1948. Toxicity of
ferro- and ferricyanide solutions to fish, and determination
of the cause of mortality. Trans. Amer. Fish., Soc. 78;192-202.
15. Baudisch, 0., and L. W. Bass. 1972. Eisen als licht-chemischer
Katalyzator, I Uben die Zursetzung von Ferrocyankalium in
Tageslicht. Ber-Deut. Chem. Gesell. Bd. 55, Ab. B, S.
2698-2706.
16. Schwarz, R. and K. Tede. 1927. Uber die Photochemical der
Komplexverbindungen. III. Die Hexachayokomplexe des drei-
wertigen Eisens, Kobalts, Chroms and Mangans. Ber. Deut.
Chem. Gesell., Bd. 60, Ab. B.S. 69-72.
17. Frank, S. N. and Baid, D. J. Heterogeneous photocatalytic
oxidation of cyanide ion in aqueous solution of titanium
dioxide powder. Journ. Amer. Chem. Soc. 99( 1) : 303^-304 .
-13-
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LISTING BACKGROUND DOCUMENT
PRIMARY SMELTING AND REFINING OF FERROALLOYS*
Emission control dust/sludge from ferromanganese (FeMn)
production in electric furnaces (T) •
Emission control dust/sludge from ferrochromium (FeCr)
production in electric furnaces (T)
Emission control dust/sludge from ferrochromium-
silicon (FeCrSi) production in electric furnaces (T)
I. Summary of Basis for Listing
The emission control dusts/sludges from the production of
ferromanganese, ferrochromium and ferrochromium-silicon are
generated when particulates entrained in the reaction gases
given off by electric furnaces during the smelting process
are removed by air pollution control equipment. Dry collection
methods generate dust; wet collection methods result in
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 environment when improperly
transported, treated, stored, disposed of or otherwise
managed and therefore should be ;, Abject to appropriate manage-
ment requirements under Subtitle C of RCRA. This conclusion
is based on the following considerations:
1) The emission control dusts/sludges from ferromanganese
and ferrochromium production contain significant
concentrations of the toxic heavy metals chromium
and lead, and emission control dusts/sludges from
production of ferrochromium silicon contain
significant concentrations of chromium.
*The Agency has recently obtained information indicating
that wastes generated by the ferroalloys industry are likely
to contain substantial concentrations of polycyclic organic
several carcinogenic compounds (5). For this reason, EPA
will expand the listing for the ferroalloys industry if
further studies show that such wastes pose a hazard to
human health and the environment.
-------
2) Significant concentrations of chromium and lead
have been shown to leach from various samples of
ferromanganese and ferrochromium wastes subjected
to extraction procedures, while significant
concentrations of chromium have been shown to leach
from samples of ferrochromium/silicon waste subjected
to the same extraction procedures.
3) A large quantity (a combined total of approximately
120,000 tons) of these wastes is generated annually.
There is thus a risk of large scale contamination
of the environment if the wastes are mismanaged.
Lead and chromium persist virtually indefinitely in
the environment, posing the further threat of long-
term contamination.
4) The wastes typically are disposed of by dumping in
the open, in landfills or in unlined lagoons.
Thus, the possibility exists for the migration in
harmful concentrations of lead and chromium to
groundwater or surface water.
II . Sources of the Waste and Typical Disposal Practices
A. Industry Profile and Manufacturing Process The
ferroalloys industry produces a variety of ferroalloys
for use in the manufacture of iron, steel and non-ferrous
metals (1). In May, 1980, eight companies produced ferrochromium,
ferrochromium-silicon or ferromanganese in electric furnaces.
Those producers are listed in Table 1 (5). It should be
noted that- companies may frequently change their product
lines and put furnaces in or out of service according to
product demand or operating requirements.
Ferrochromium, ferrochromium-silicon and ferromanganese
are generally produced by carbothermal smelting in electric
submerged-arc furnaces (some ferromanganese is also produced
in blast furnaces). The raw materials used most often include
-.2-
-------
Table I - Producers of FeMn, FeCr or FeCrSi in
in the United States May, 1980 (5)
Producer
CHROMASCO
Woodstock, TN.
INTERLAKE
"Beverly, OH.
MACALLOY
Charleston, SG
OHIO FERROALLOYS
Philo, OH.
SAMANCOR
Rockwood, TN.
SATRALLOY
Steubenvills, OH.
SKW ALLOYS
Calvert City., KY.
Niagara Pal]••>, NY
UNION CARBIDE
Marietta, Oh.
Portland, OK.
Products
FeCr
FeCrSi, FeCr
FeCr
FeMn
FeMn
FeCr, FeCrSi
FeMn
FeCrSi
FeMn, FrCr
FeMn
-.3-
-------
mineral ores and concentrates of manganese, chromium and
silicon, steel turnings and reducing agents such as coke,
coal and wood chips (2). Feed materials are charged to the
furnace on either a continuous or intermittent basis. The
molten alloy collects at the bottom of the furnace and is
removed to a cooling area.
B. Waste Generation
The process of reducing metallic ores to a metallic
state generates large quantities of carbon monoxide along
with other gases from moisture in the charge materials,
reducing agent volatile matter, thermal decomposition products
of the raw ore and intermediate products of the reaction (1).
The gases carry fumes from the high temperature regions of the
furnace and entrain fine particles of the charge materials.
Particulate matter, which contains lead and chromium originally
present in the charge materials, is removed from the gases
by baghouse collection systems, electrostatic precipitators,
or scrubbers. Wastes are collected from baghouses and
precipitators as dusts and from scrubbers as sludges (2).
These emission control dusts/sludges are the waste streams of
concern. The Ferroalloys Association estimates that approximately
120,000 tons of these wastes are generated annually (2).
C. Current Disposal Practices
Dusts typically are dumped directly on..land or disposed
x^
of in landfills (2,3). Dusts from the production of different
-4-
-------
ferralloys are generally mixed and disposed of together.
(Comments of the Ferroalloys Association, January 9, 1979.)
Sludges usually are sent to unlined lagoons for settling;
the sediments are dredged periodically and dumped on land
(3). Waste piles in disposal areas can approach 250 feet in
places, and the depth of dispose1 lagoons may approach 25
feet (2).
III. Hazardous Properties of the Waste
Ferroalloy production emission control dusts and sludges
consist primarily of sub-micron particles composed of oxides
of various elements, including lead and chromium (3). The
Agency has data from two sources which indicate that sub-
stantial amounts of lead and chromium are contained in ferro-
manganese and ferrochromium dusts/sludges, while dusts and
sludges from ferrochromium-silicon production contain substantial
concentrations of chromium. The data are presented in Tables
2 and 3.
Table 2. Concentrations of Lead and Chromium in Ferroalloys
Dusts/Sludges (3).
Product
Sample Source
Cr(ppm) Pb(ppm)
Ferromanganese
Ferrochromium
Ferrochromium-
s ilicon
Baghouse (dust)
Scrubber (sludge)
Electrostatic
precipitator (dust)
Baghouse (dust)
32
18
3,390
6000
5000
300
-5-
-------
Table 3. Concentrations of Lead and Chromium in Particulate Matter
Generated During Production of Ferroalloys! (!)•
Product
Sample Source
Cr(ppm) Pb(ppm)
Ferromanganese
Ferrochromium
Ferrochromium-
s ilicon
Scrubber stack outlet- <80 1,130
Furnace 140,000
Electrostatic
precipitator (dust) 40,000 1,000
Furnace I 14,100 <10
Baghouse inlet I 4,400
tMost of the samples are of particulate matter collected
from the furnace emissions prior to cleaning in an air pollu-
tion control device. These samples should be similar to the
dust or sludge generated by these types of furnaces since
emission control equipment removes 95-99% of these contaminants
prior to air emission. (Comments of Ferroalloys Association,
June 7, 1977, App. B.) The sample of particulate matter from
the FeMn scrubber stack outlet should indicate which pollutant
species are present in the sludge or dust, although relative
quantities may be different from those in the solid waste.
Simulated leaching data also indicate that lead and
chromium are capable of leaching from these wastes in concen-
trations sufficient to create a potential for substantial
hazard. Table 6 below shows distilled water and acetic acid
extract ion .data supplied by the Ferroalloys Association for
selected emission control dusts. In most cases, contaminant
levels in leachate are one to two orders of magnitude in
excess of drinking water standards.
The Agency also has extraction data showing high concen- "
trations of the constituents of concern in a distilled water
extract of the waste:
-6-
-------
Table 6 - Waste Extraction Data for Ferroalloys Waste (2)
Waste from FeMn Production
Extract Concentrations
EPA EP Using H?0
Emissions Control Dust (Sx #1)
Emissions Control Dust (Sx #2)
EPA EP per 9/12/78 Draft (Acetic Acid Extractant)
Emissions Control Dust
Waste from FeCr Production
EPA EP Using H?0
Emissions Control Dust (Sx #1)
Scrubber Dust (Sx #2)
EPA EP per 9-12-78 Draft (Acetic Acid Extractant)
Scrubber Dust (Sx #2)
Waste from FeCrSi Production
EPA EP Using H?0 Only
Emissions Control Dust
EPA EP per 9-12-78 Draft (Acetic Acid Extractant)
Emissions Control/Dust
Drinking Water Standard
.05
Cr
1.4
1.0
.40
.65
2.0
Pb
2.0
7.6
14.0
2.4
.30
Source: Comment of the Ferroalloys Association, January 9, 1979.
-------
Table 7 (3)
Product
FeMn
FeCr
FeCrSi
1
1
1 Sample
1
I Baghouse dust
1
I ESP dust
1
1
1 Baghouse dust
1
ppm i n
water
Cr
0.2
710
190
di
ext
1
1
1
1
1
1
1
1
stilled
rac t
Pb
560
0.7
1.5
The Agency frankly entertains some doubts as to the
probity of the data in Table 7. For example, the chromium
value for the FeCrSi baghouse dust waste extract exceeds the
value given for the raw waste sample in Table 2 above (which
was obtained during the same study.) Such a discrepancy can
only be attributable to an error in the calculation or in
the recording of data, or to the use of faulty,analytical
techniques. Since high concentrations (14,000 and 4,400
ppm) of chromium in the particulate matter given off during
the production of ferrochromium-silicon are reported in Table 3,
the Agency believes it likely that the 41 ppm chromium value
shown in Table 2 is grossly understated. In any case, the
Agency views this data, while hardly determinative, as at
least corroborative of other data submitted by industry
showing waste constituents capable of migration in potentially
harmful concentrations.
Furthermore, groundwater monitoring performed by an
independent laboratory for the Ferroalloys Association
-8-
-------
indicates that lead, one of the two waste constituents of
concern, can migrate from ferroalloy waste disposal sites
and reach groundwater in harmful concentrations. Thus,
groundwater monitoring in the vicinity of an "unlined disposal
lagoon" on the site of an unidentified ferroalloy company
revealed lead concentrations in groundwater exceeding the
National Interim Primary Drinking Water Standard of .05 mg/1,
as shown in Table 4. In the second test, apparently only one
well was measured; no contamination was detected.
Table 4 - Monitoring Data From Groundwater Wells Surrounding
An Unlined Disposal Lagoon Showing Lead Concentrations In
Groundwater (Reference: Comments of Ferroalloys Association,
June 29, 1979.)
Monitoring Location
T e s t #1 Distance from Lagoons,(Ft.) Pb Concentration(mg/l)
Lagoon Analys;s .03
#1 Well 100 .085
#2 Well 500 .105
in Well 200 .190
#4 Well " 100 .085
#4 Well 1600 .090
Test #2
Lagoon Analysis .160
#8 Well '375
-9-
-------
Without groundwater background monitoring data, it cannot
be said with assurance that the disposal lagoon is the source
of lead contamination. However, the comments do not indicate
any other source of contamination, and the fact that monitored
lead levels in groundwater levels appreciably exceeded levels in
the lagoon could indicate that concentrated solids from the
lagoon are leaching into groundwater.* Certainly, this data
fails to support the Ferroalloys Association's claim that of
an absence of environmental problems from current disposal
practice. (Comments of Ferroalloys Association, June 29, 1979,
p.3).
Ferroalloys Association also supplied monitering
data obtained from wells in the vicinity of a ferroalloy
waste landfill (2). These data are shown in Table 5.
Although the monitoring results might indicate that
this landfill does not contribute substantially to groundwater
contamination (measurements from wells located downgradient
from the landfill are similar to background levels), the
Agency is unable to determine whether this is a valid inter-
pretation of the data without considerably more information
on the hydrogeological characteristics of the site, the
placement, construction and operation of the monitoring
wells, the types and compositions of the wastes in the land-
fill and the protocols utilized to obtain and analyze the
groundwater samples. Sampling over a longer period is probably
*Thus, the unexplained "lagoon analysis" could be of liquid
in the lagoon rather than settled solids.
-10-
-------
Table 5 - Monitoring Data from Groundwater Wells Surrounding
a "Typical Landfill" Showing Lead Concentrations in Groundwater
Location Test
T e s t # 1
Upgradient
Groundwater Background
Well #3
Well #4
Downgradient of Landfill
Well #1
Well #2
Well #5
Test #2
Pb in Groundwater (mg/1)
<.03
.08
.08
.06
.03
(1 month after #1)
Upgradient
Well #3
Well #4.
Downgradient
Well //I
Well #2
Well #5
Test #3
.07
.05
.08
.10
<.03
(2 months after #1)
Upgradient.
Well #3
Well #4
Downgradient
Well #1
Well #2
Well #5
Pb in Groundwater (mg/1)
.08
.08
.05
.03
.04
Note: Chromium was also monitored at these locations (although
not at the wells surrounding the lagoon in Table 4), but
chromium concentrations did not exceed the National Interim
Primary Drinking Water Standard.
-11-
-------
also necessary. Based on the information provided, the
Agency can only observe that lead concentrations in groundwater
in the vicinity of this landfill frequently exceed the National
Interim Primary Drinking Water Standard of 0.05 mg/1. Therefore
a potential hazard appears to exist unless proper management
of these wastes is assured.*
It should be noted that some of the wastes included in
this listing may not fail the toxicity characteristic (even
though leachate data indicates that lead and chromium in
these wastes have substantial migratory potential). This does
not preclude listing of the wastes. The Agency believes that
there are factors in addition to metal concentrations in
leachate which justify this listing. As indicated above,
these wastes are generated in very substantial quantities and
may contain high concentrations of lead and chromium. Industry
data indicate that groundwater contamination from ferroalloy
waste disposal may already have occurred. In addition,
large amounts of these metals are available for potential
environmental release. The large quantities of these contaminants
pose the danger of polluting large areas of ground or surface
waters if waste mismanagement occurs. Contamination could
also occur over long periods of time since large amounts of
pollutants, which, as heavy metals, persist virtually indefinitely,
are available for environmental release. Attenuative capacity
* The Ferroalloys Association indicated that the waste dusts
are believed to exhibit sealant properties when wetted,
thereby reducing leaching. This data (particularly that in
Table 4), however, suggests that any sealant properties of
the waste are insufficient to prevent waste constituent
migration.
-12-
-------
of the environment surrounding the disposal facility could
also be reduced or exhausted due to the large quantities of
pollutants available.
Furthermore, current management practices may not be
adequate to prevent leachate migration and subsequent ground-
water and/or surface water contamination. Industry submissions
indicate that disposal lagoons and landfills are generally
unlined, and that no special steps are taken to impede leachate
formation (although the dusts are reported to exhibit a sealant
effect when wetted, this appears insufficient to prevent leachate
formation and migration). As a result, these waste management
practices may have the potential to allow release of harmful
concentrations of contained toxicants, particularly if disposal
occurs in areas with highly permeable soils, or where waste
is directly exposed to groundwater due to the height of the
water table. If wastes are disposed of where acid rain is
prevalent, solubilization oi toxic heavy metals is even more
likely to occur. Uncontrolled surface run-off from the
waste piles and overflow from lagoons might disperse the
wastes and/or their toxic constituents in the surrounding
area. If control practices are nonexistent or inadequate,
contaminant-bearing leachate, run-off or impoundment overflow
may reach ground and surface waters, polluting valuable drinking
water supplies.
IV. Hazards Associated With Constituents of Concern
Ingestion of drinking water from ground and surface
waters contaminated by lead and chromium threatens human
-13-
-------
health; aquatic species exposed to the heavy metals may also
be adversely effected. Chromium is toxic to man and lower
forms of aquatic life. Lead is poisonous in all forms, and
is one of the most hazardous of the toxic metals because it
bioaccumulates in many 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, (see Appendix A)
It also bioaccumulates in many species.
Contact with chromium compounds can cause dermal ulceration
in humans. Data also indicate 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 Appendix A.
The hazards associated with lead and chromium-containing
compounds have been recognized by other regulatory 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 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
-14-
-------
under the Clp-in 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 (4).
-15-
-------
References
1. Dealy, James 0., and A. M. Killin. .Engineering and Cost
Study of the Ferroalloy Industry. EPA-450/2-74-008,
May, 1974.
2. U.S. EPA, RCRA Section 3001 Docket, Attachment to
Communication from George A. Watson to Claire Welty,
June 29, 1979.
3. U.S. EPA, Office of Solid Waste. Assessment of Hazardous
Waste Practices in the Metal Smelting and Refining
Industry. Calspan Corporation. EPA Contract No. 68-01-2604.
April, 1977. Volumes III and IV.
4. U.S. EPA States Regulations Files, January 1980.
5. Westbrook, C.W. and D.P. Daugherty. Environmental
Assessment of Electric Submerged Arc Furnaces
for Production of Ferroalloys (DRAFT). USEPA,
RTI/1434/04-02f, March 1980.
-16-
-------
Comments a..d Responses
o One comment stated that ferrochromium-silicon emission
control dusts/sludges should not be listed because a
discrepancy between the chromium concentrations
reported in the original sample and the extract of
that sample exists; 190 ppm were found in leachate
but only 41 ppm in fhe original waste sample.
The Agency agrees that an error was made. The error
might be due to faulty analytical techniques or to a mistake
in calculating or recording data. As stated in the background
document, however, data from another source indicates that
chromium concentrations in ferrochromium silicon emission
control dusts/sludges might be much higher. For this reason,
EPA believes that the value of 41 ppm is understated and
will continue to list this waste as hazardous.
o The Ferroalloys Association stated that the extracts
.of ferroalloys emission control dusts/sludges which
they obtained by performing the proposed extraction
procedure were only slightly above the limits defined
as hazardous in the proposed regulations and therefore
the wastes should not be classified as hazardous.
It is unusual that the data supplied by the Ferroalloys
Association shows significantly less leaching using the pro-
posed Extraction Procedure than other data from a distilled
water extraction since the Ef is the more rigorous of the two
methods. Because such large quantities of these wastes are
generated and samples of the wastes leached chromium in
excess of 100 times the National Interim Primary Drinking
Water Standard when subjected to a distilled water extraction,
the Agency has decided that the wastes pose a potential threat to
-17-
-------
human health and the environment and therefore should remain
on the hazardous waste list.
o One comment indicated that the wastes are not
hazardous because they are properly managed.
The purpose of the regulations developed pursuant to
§3001 of RCRA is to define hazardous waste. The hazard posed
by a waste due to potential mismanagement is only one factor
in the determination that a waste should be listed as hazard-
ous. Other factors such as the nature of the hazard must be
considered. The Agency believes that the waste listed above
contain significant amounts of lead and chromium which may
leach from the waste matrix and migrate to ground and surface
waters; therefore the waste poses a threat to human health
and the environment.
o One comment included ground water monitoring data
which show that the hazardous constituents of the
waste do not migrate from the waste.
The data were acquired over a short period of time
(2 months) and may not be representative of contaminant
migration over a period of years. In addition, no informa-
tion on the site conditions in the lagoon and landfill which
were monitored was included in the comment so the Agency is
unable to determine whether these are typical disposal sites.
The Ferroalloys Association stated that emissions control
dust behaves as a sealant when it attains a sufficiently high
moisture content and therefore provides a barrier to migration
of hazardous constituents.
No data were submitted to support this contention so the
-18-
-------
Agency is unable to respond in detail to the comment. EPA
solicits additional information on the overall effectiveness
of emissions control dust/sludges as sealants, the amount of
moisture required to make the wastes behave as sealants and
the moisture content of landfilled dusts.
-19-
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PS-24-01
LISTING BACKGROUND DOCUMENT
GRAY AND DUCTILE IRON FOUNDRIES
Emission Control Dust from Gray and Ductile Iron Foundry
Cupola Furnaces (T) (Proposed)*
I. SUMMARY OF BASIS FOR LISTING
Emission control dusts from gray and ductile iron foundry
cupola furnaces are generated when the heavy metal contaminants
found in the raw material scrap are entrained .in the cupola
furnace fumes as metal oxides and are subsequently collected
*The present proposed listing is limited to gray and ductile
iron foundries collecting emission control dust from cupola
furnaces. The Agency also has information Indicating that
gray iron foundries using electric arc furnaces generate
an emission control dust with high concentrations of
heavy metals, particularly lead. See U.S. EPA, Office of
Air Quality Planning and Standards, Electric Arc Furnaces
Foundries/Background Information for Proposed Standards,
(Draft Environmental Impact Statement), EPA-450/3-80-020a
(1980), pp. 726-27 (available from EPA Office of Solid Waste).)
EPA thus may broaden the listing in the future to include
electric arc furnaces. Further, in the sampling study
described in the note below, EPA will sample some emission
control dusts from electric arc furnaces to determine
whether these wastes should be listed as hazardous.
NOTE: The Agency has made two prior proposals to list iron
foundry process wastes. The first proposed listing, undertaken
largely in 'r-esponse to comments received by the State of
New York and Chem-Nuclear Systems, Inc., was of "lead/phenolic
sandcasting waste from malleable iron foundries". This
proposal was later altered (and the comment period extended)
to cover "lead-bearing wastewater treatment sludges from
gray iron foundries", 44 Fed. Reg. 674451, November 26,
1979). The present document expands the November, 1979
proposed listing to encompass a limited class of iron
foundry emission control dusts.
These changes in the proposed listings have prompted
industry complaints of having to respond to a moving target,
making it difficult to comment responsively to the successive
proposals.
-------
The / 'minis trator has determined that the emission control
dust collected from gray iron and ductile iron foundry cupola
furnaces is a solid waste 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 or RCRA.
This conclusion is based on the following considerations:
1. Waste extracts from gray and ductile iron emission
control dusts have been shown to release high con-
centrations of the heavy metals lead and cadmium.
In all cases the concentration exceeded 100 times
the drinking water standards for lead and cadmium,
and in some cases exceeded 1000 times the standard.
2. Large quantities of these wastes are generated
annually, increasing the quantity of lead and
cadmium available for environmental release.
3. These wastes may be disposed of in wetland or dis-
charge type areas, increasing the hazardous con-
stituents' migratory potential.
Tbo
the Age -c
study Oi
wastes -
a final -1
control -»
hazardous
for listi
industry
appreciat
Agency is sensistive to these concerns. Moreover,
y presently is undertaking a sampling and analysis
the gray iron foundry industry's emission control
Data from the sampling study will be used to make
etermination of the regulatory status of emission
lud"-->.s (which wastes have already been proposed for
•*,.ste identification), as well as the dusts proposed
ec
in this document. The
undertaking this study
by the Agency.
assistance of the foundry..
is acknowledged and
therefore, is not promulgating either listing
The AO
(i.e. ei..Uer emission control dusts or wastewater treatment
sludges'' in interim final form. Rather, both listings are
proposals, and no final regulatory action will be undertaken
until completion of the sampling study.
These wastes are of concern due to the presence
of lead ?.nd cadmium in a form capable of migration in high
concentra-ions.
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II. SOURCES OF THE WASTE AND TYPICAL DISPOSAL PRACTICES
A. Profile of Gray and Ductile Iron Foundry Industry
Approximately 1166 gray iron foundries and 81
ductile iron foundries comprise these two industries (1).
Although the foundries are located throughout the United
States, a large portion of the plants are found in the Great
Lakes area. Geographic distribution of gray iron and ductile
iron foundries is shown in Table 1.
Gray iron is characterized by the presence of most of
the contained carbon as flakes of free graphite in the as-
cast iron. Gray iron is classified into ten classes based on
the minimum tensile strength of a cast bar. The tensile strength
is affected by the amount of free graphite present as well as
the size, shape and distribution of the graphite flakes.
Flake size, shape and distribution are strongly influenced by
metallugical factors in the melting of the iron and its
subsequent treatment while molten, and by solidification
rates and cooling in the mold (1).
Ductile iron (also known as nodular iron, spherulitic iron,
etc.) is similar to gray iron composition with respect to
carbon, silicon and iron content, and in the type of melting
equipment, handling temperatures, and general metallurgy. The
important difference between ductile and gray iron is that the
graphite in ductile iron separates as .spheroids or nodules
"x,
(instead of flakes as in gray iron) under the influence of a
few hundredths of a percent of magnesium in the composition.
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Table 1 (1)
Distribution o'f Total Gray and Ductile Iron Foundries
New England
Mid-Atlantic
Great Lakes
Plains
South Atlantic
East South Central
West South Central
Mountain
Pacific
Gray Iron
77
188
386
141
101
89
80
27
7_7_
1166
Ductile Iron
3
9
20
8
7
13
9
1
11
81
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The presence of minute quantities of sulfur, lead, titanium
and aluminum can interfere with and prevent the noduling
effect of magnesium. Although the molten iron for conversion
to ductile iron must be purer than for gray iron manufacture,
a small quantity of cerium added with' the magnesium minimizes
the effects of impurities that inhibit nodule formation and
make it possible to produce ductile iron from the same raw
materials used for high grade gray iron manufacture d).
Single foundries therefore are capable of producing both
gray and ductile iron. Furthermore, since the same types
of raw materials are used to produce each type of iron,
waste composition also tends to be similar.
The general procedure for manufacturing ductile iron is
similar to that of gray iron, but with more precise control
of composition and pouring temperature. Prior to pouring of
metal into the molds (and in some cases during pouring) the
metal is innoculated with the correct percent of magnesium,
usually in a carrier alloy, to promote the development of
spheroids of graphite upon cooling (1).
B. Manufacturing Process (1)
1. Overall Process Description
While specific procedures vary from foundry to
foundry, the overall operations for producing iron castings
are essentially the same. These procedures include sand -
preparation, mold and core making, metal melting and pouring,
casting shakeout and cleaning and finishing.
-5-
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In all types of foundries, raw materials are assembled
and stored in various material bins. From these bins, a
furnace charge is selected by using various amounts of the
desired materials. This material is charged into a melting
furnace and made molten through a hea-ting process.
Simultaneously, molds are prepared. This process begins
by forming a pattern (usually of wood) to the approximate
final shape of the product. This pattern is usually made in
two pieces that will eventually match to form a single piece,
although patterns may be 3 or more pieces. Each part of the
pattern is used to form a cavity in a moist sand media, and
the two portions of the mold (called "cope" and "drag") are
matched together to form a complete cavity in the sand media.
An entrance hole (called a "sprue") is cut to provide the
proper paths of molten metal introduction into the cavity.
The mold is then ready to receive the molten metal. In die
casting operations the mold cavity is formed in metallic die
blocks which are locked to; ether to make a complete cavity.
The molten metal i.= then "tapped" from the furnace into
the ladle. .The ladle and molds are moved to a pouring area
and the metal is poured into the molds. The molds are then
moved to a cooling area where the molten metal solidifies
into the shape of the pattern. When sufficiently cooled, the
sand is removed by a process known as "shake.out". By violent
shaking, the sand surrounding the metal is loosened and falls
to the floor or conveyor that returns it to the sand storage area.
-6-
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The cast metal object (casting) is further processed by
removing the excess metal, and cleaned by various methods
that complete the removal of the sand from its surface. In
the case of die casting, where no sand is used, the cast
object is removed from the die casting machine after cooling
sufficiently to retain its shape. The casting is either
further cooled by a water bath or is allowed to cool by air
on a runout or cooling table. Depending on the final use of
the casting, further processing by heat treatment, quenching,
machining, chemical treatment, electroplating, painting or
coating may take place. After inspection, the casting is
then ready for shipping.
2. Types of Furnaces used in Gray and Ductile
Iron Production (1)
Three types of melting furnaces are used for the
production of gray iron and ductile iron; cupola, electric
arc, and electric induction furnaces. EPA estimates that
95% of the furnaces used for producing gray iron and ductile
iron are cupola furnaces, and the present document covers
emission control dusts only from this type of furnace. The
differences among the types of melting furnaces are discussed
below.
a) Cupola Furnaces
The cupola furnace is a vertical shaft furnace
consisting of cylindrical steel shell lined with refractories
and equipped with a wind box and tuyeres for the admission of
air. A charging opening is provided at an upper level for
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the introduction of melting stock and fuel. Near the bottom
are holes and spouts from removal of molten metal and slag.
Air for combustion is forced into the cupola through
tuyeres located above the slag well. The products of combustion,
i.e., particles of coke, ash, metal, sulfur dioxide, carbon
monoxide, carbon dioxide, etc. and smoke comprise the cupola
emissions. Air pollution emission standards require that
these emissions be controlled, and both dry and wet control
systems are utilized for this purpose.
b) Electric Arc Furnaces
An electric arc furnace is essentially a refractory
hearth in which material can be melted by heat from electric
arcs. The molten metal has a large surface area in relation
to its depth, permitting bulky charge material to be handled.
Arc furnaces generally are not used for nonferrous metals as
the high point of the arc tends to vaporize the lower melting
temperature metals. Arc furnaces are operated in a batch
fashion with tap-to-tap times of 1-1/2 to 2 hours. Power,
in the -nnge of 500-600 kwh/ton, is introduced through three
carbon t'af< jdes. These electrodes are consumed in the
process ot passing the electic current through the scrap and
metal into the molten batch. They oxidize at a rate of 5 to
8 kg per a-acric ton of steel (10.5 to 17 Ibs/ton).
Th ; waste products from the process are smoke, slag,
carbon monoxide and dioxide gases and oxides of iron emitted
as sub:;-'cron fumes. Dry collection air pollution control
-8-
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equipment (usually baghouse) is generally used to control
electric arc furnace emissions (1).
c) Induction Furnaces
Induction melting furnaces have been used for many
years to produce nonferrous metals. Innovations in the power
application area during the last 20 years have enabled them to
compete with cupolas and arc furnaces in gray iron and steel
production. This type of furnace has some very desirable
features. There is little or no contamination of the metal
bath, no electrodes are necessary, composition can be accurately
controlled, good stirring is inherent and, while no combustion
occurs, the temperature obtainable is theoretically unlimited.
There are two types of induction furnaces: (a) coreless,
;
which is a simple crucible surrounded by a water-cooled copper
coil carrying alternating current, and (b) core or channel,
in which the molten metal is channeled through one leg of a
transformer ore. The induction furnace provides good furnace
atmosphere control, since no fuel in introduced into the
crucible. As long as clean materials such as castings and
clean-metal scrap are used, no air pollution control equipment
is necessary. If contaminated scrap is charged or magnesium
is added to manufacture ductile iron, air pollution control
devices are required to collect the fumes that are generated.
C. Waste Generation and Management (1)
The cupola furnaces in gray and ductile iron foundries
require emission control systems. Both wet and dry systems
are utilized. Venturi scrubbers are used exclusively for wet
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crubbing of cupola furnace fumes and baghouses are used
exclusively for dry collection of emissions. The waste
collected by dry systems (baghpuse dust) is the waste of
concern in this document.
The use of a baghouse involves the collection of
particulate matter by entrapment of the particles in the
fabric of a filter cloth that is placed across a flowing gas
stream. These dust particles are removed from the cloth by
shaking or back-flushing the fabric with air. The resulting
dry dust is usually collected in bins or open trucks (2).
It is then often mixed with other foundry wastes prior to
ultimate disposal in landfills.
It is estimated that for gray and ductile iron foundries,
10-22 Ibs. of emission control dust is generated for every
ton of metal produced (14). Approximately 95% or 1185 foundries
use cupola melting furnaces. A known 392 foundries use wet
collection systems and therefore SPA assumes that the remaining
793 (~65%) use dry dust collection systems. In 1979, 16,741,000
tons of metal were produced by the industry (3). If 65% of
this amount is assumed to be produced by the 65% of the gray
and ductile iron plants that generate a dry dust, then a
range of 54,000 to 120,000 tons of dust will be generated by
the industry per year. This estimate is probably low (2).
Foundry wastes are land disposed (1). Wastes from many
foundries are monofilled. but others are disposed at municipal
or private sanitary landfills which also accept other types
of solid waste (2). Disposal procedures include random dumping
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and grading, .combination with other municipal and industrial
wastes, and grading upon deposition followed by application of
earth and topsoil cover (2). The physical setting of the disposal
sites varies; locations are generally selected on the basis of
availability of land at an appropriate cost within a reasonable
haul distance from the foundry. It has been a fairly common
practice to dispose of foundry wastes in wetland or discharge
type areas where waste materials can become saturated with
surface waters or shallow groundwaters (2).
D. Hazardous Properties of the Wastes
1. Waste Composition
The Agency believes that these emission control dusts
ordinarily contain high concentrations of lead and cadmium,
and that these toxic metals are capable of migration in
quantities sufficient to create a substantial hazard if the
wastes are managed improperly.*
The following data support this conclusion. Gray and
ductile iron foundry cupola furnace emission control dusts
from three foundries operated by the Mead Corporation were
tested using the EPA extraction procedure, and in all cases
the extract contained lead and cadmium significantly in
excess of 100 times the National Interim Primary Drinking
Water Standard. These data are presented in Table 2 below.
* The raw materials used as charge account for the lead
and cadmium present in the emission control dust. Automotive
scrap is thought to be one principal source of heavy metal
contaminants (14). If engine block is used as scrap charge,
the source of lead may be paint, tetraethyl lead deposits
or engine bearings. If auto bodies are used as scrap, the
source of lead may be attributable to paint or, more likely,
to solder used to fill in joints (15).
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TABLE 2
FOUNDRY EP TOXICITY TEST SUMMARY
Level Detec-
of EP tion
Toxicity Limit
Location
Date Sampled
Parameters
Cadmium (mg/1) 1.0 0.01
Lead (mg/1) ' 5.0 0.05
Green
Sand
Cu po la
Dust
LB
5-8-79
6.9
16.5
Shell
Mold
Cupola
Dust
LB
5-8-79
4.8
12.8
Cupola Dust
Dry Dust
AC
8-22-79
2.5
11.5
Dry Dust
RD
10-30-78
19.6
96.0
Wet Dust
RD
10-30-78
6.6
68.0
Dry Dust
LD
10-78
12.9
2.3
LB = Lower Basin Foundry (Gray and Ductile Iron)
AC = Archer Creek Foundry (Gray and Ductile Iron)
RD = Radford Foundry (Ductile Iron)
Note: Analysis for other heavy metals and the 129 priority pollutants revealed no
significant concentrations of any of these parameters.
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The charge for these foundries is believed to consist
primarily of fairly high grade (clean) metal scrap from a number
of sources (14). Facilities accepting lower grade scrap (such
as automotive body scrap) could have higher concentrations of
these metals in their emission control dusts.
These leachate extract results indicate strongly that
improper management of the wastes could lead to migration of
dangerous concentrations of cadmium and lead from the waste.
A further concern in assessing potential hazards posed by
these wastes is the possibility that existing disposal
practices may not always be adequate, since disposal in
wetlands and municipal landfills is said (in an industry .
publication) to occur. Since lead and cadmium appear to be
present in these wastes in leachable form, waste disposal
under conditions where leaching media are readily available
could well lead to migration of contaminant-bearing leachate
which can then migrate to ground or surface water. Disposal
in acidic environments, such as landfills containing municipal
refuse (another waste management practice known to occur (2)),
could als.o lead to environmental release of dangerous
concentrations of lead and cadmium. Improper disposal of
these dusts can therefore result in contamination of ground
and surface waters with 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.
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j..! addition an inhalation hazard may be posed by management
of this waste due to its fine particulate nature and due to
the inhalation toxicity of the particulates. The dust could
easily become airborne and cause damage to humans if the
waste Is not properly buried at the time of disposal. The
waste also could pose an inhalation hazard during transportation
if it is transported in open trucks and no precautions are
taken to prevent dust from blowing freely.
These wastes also are believed to be generated in substantial
quantities (see page 10 above). This is further cause for
concern, since large amounts of the toxic constituents cadmium
and lead 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.
Contaminantion could also occur for long periods of time,
since large amounts of pollutants are available for environmental
loading. The attenuative capacity of the environment surrounding
di.-:. \5osal facilities could also be reduced or exhausted by such
lar.-;e quantities of pollutants. All of these considerations
inc.- -as-1, the possibility of exposure to harmful constituents
in the waste and further justify a hazardous designation.
2 , Hazardous Properties of Waste Constituents
The cadmium and lead that may migrate from the waste
to he environment as a result of improper disposal practices
are heavy metals that persist in the environment and may
contaminate- drinking water sources for extremely long periods
of ti c:. Cadmium is toxic to practically all systems and
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functions of the human organism (6). Acute poisoning nay
result from the inhalation of cadmium dusts and fumes (usually
cadmium oxide) and from ingestion of cadmium salts (7).
Lead is poisonous in all forms; it is one of the most hazardous
of the toxic metals because it accumulates in many organisms
and the deleterious effects are numerous and.severs. Lead
may enter the human system through inhalation, ingestion or
skin contact. Ingestion of contaminated drinking water is a
possible means of exposure to humans as a result of improper
management of these wastes. Inhalation hazards are also
possible through exposure to the airborne dust which contains
lead oxide and cadmium oxide. 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 Waster Act of 1970. Under §6 of the
Occupational Safety and Health Act of 1970, a final standard
for occupational exposure to lead has been established (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 regulations of the States
of California, Maine, Massachusets, Minnesota, Misouri,
New Mexico, Oklahoma' and Oregon define cadmium and lead-
'"X
containing compounds as hazardous wastes or components thereof (9)
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EPA has proposed regulations that will limit the amount
of cadmium in municipal sludge which can be landspread on
crop land (10). 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)
(11). EPA has prohibited ocean dumping of cadmium and
cadmium compounds except as trace contaminants (12). EPA has
also promulgated pretreatment standards for electroplaters
which specifically limit discharges of cadmium to Public
Owned Treatment Works (13).
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References
1. U.S. EPA Draft Development Document for Effluent Limitations
Guidelines and Standards for the Foundries (Metal Molding
and Casting) Point Source Category. April, 1980.
2. American Foundrymen's Society. Foundry Landfill Leachates
from Solid Wastes, 1978.
3. The Metal Casting Industry Directory. Foundry Management
and Technology Magazine, Penton Publications. July, 1977.
4. U.S. EPA, RCRA Section 3001 Docket. Letter from Russell E. Kross
(Mead Corporation) to John P. Lehman, January 23, 1980.
5. U.S. EPA, RCRA Section 3001 Docket. Memorandum of phone call
from Claire Welty to Mead Corporation.
6. Waldbolt, G.L. Health Effects of Environmental Pollutants.
St. Louis, C.V. Mosby Company, 1973.
7. 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.
8. U.S. Department of Interior, Bureau of Mines. Mineral
Commodities Summaries, 1979.
9. U.S. EPA, Office of Solid Waste, State Regulations File,
January, 1980.
10. 44 FR. 53449.
11. 44 FR_ 5434.
12. 38 FR. 28610.
13 . 40 CFR, Part 413.
14. U.S. EPA, RCRA Section 3001 Docket. Memorandum of meeting
with Mead Corporation, June 25, 1980.
15. U.S. EPA, RCRA Section 3001 Docket. Memorandum of phone
call from Russell Frye of Mead. Corporaton to Claire
Welty. July 8, 1980.
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V. Response to Comments
A number of comments have been received which address
the Agency's proposed listing of wastewater treatment sludges
from gray iron foundries. As noted above, the Agency is
undertaking (with industry assistance), a sampling study of
selected foundry wastes and does not plan to proceed to
finalize this listing or to abandon the listing until the
study is completed. The Agency does feel that it is necessary
to restate its justification for proposing to list these
i
wastewater treatment sludges, both to respond to criticism
that the proposal lacks justification and to indicate our concern
that these wastes could pose a very real hazard if disposed
of improperly.
First, these waste sludges could contain large quantities
of lead, a toxic element. EPA analyzed raw and treated wastewater
samples from five plants. These data and resultant lead
levels found in the sludge at these five plants are summarized
as follows (1):
Lead Lead Lead Total
Concentration Concentration . - Concentration Flow Lead
in Raw in treated removed from (gal/ (pounds
Plant Wastewater (mg/1) Wastewater (mg/1) wastewater(mg/l) day) year)
A •• 40 2.2 . 37.8 4.8xl04 3,800
B 54 - .'."0.9 53.07 3.86xlQ5 42,700
C 29 1.4" ' 27.6 4.24xl05 24,400
D 100-— — ;---.r.-8-'.;5•--•-• --;-:-- -••-*•" 91.5 1.13xlo6 216,000
E 140 " " '"'"'.-..•" 0.87 .. " . : 139.13 7.49xl04 21,700
Note: This type of mass balance approach "provides an accurate
indication of amounts of lead in the wastewater treatment sludge,
since lead neither degrades nor volatilizes.
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Thus, total potential environmental loadings of lead from
these wastes appear to be high. Further, over 5 million wet
tons of these wastes are generated annually on a national
basis (1), increasing concern about total potential
lead loadings.
Second, lead will be present in these wastes in higher
concentrations than concentration of lead removed from the
waste water, since the sludge will be dewatered, and- the lead
therefore .concentrated, before disposal.
Third, an industry publication indicates that "(Ot has
been a fairly common practice in disposal of foundry solid
wastes ... to use wetland or discharge type areas. In areas
such as these, waste material is often water-saturated from
the presence of surface water or shallow groundwater".
("Foundry Landfill Leachages from Solid Wastes", American
Foundrymen's Society, 1978.) Under these conditions, dangerous
concentrations of lead could leach into ground and surface
waters and reach environmental receptors.
o Industry has indicated that although lead is present in
these sludges, it is present in a substantially immobile
T ' _
•\ . - ~. . - - • - -
.form. One of the purposes of the sampling study is assess
'! * "
the potential mobility of waste constituents. Although this
\ - - •..•"
:j,s not .the sole determinant of a waste's toxicity (see
j£61.11), it is certainly a significant factor in making a
'A' -.:••"• - •• • . •
--sting determination. Thus, the results of. waste extract
\a from the upcoming sampling study will be taken into
sideration in making a final listing determination.
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