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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)
                             -vi-

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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)
                               -vii-

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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 .

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     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
                             -2-

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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






                             -3-

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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.






                     -4-

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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.


                             -6-

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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,
                             -7-

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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




                                -8-

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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.
                     -9-

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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.
                             -11-

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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.
                             -12-

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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
                             -13-

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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
                         -14-

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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
                             -15-

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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
                              -16-

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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
                              -17-

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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
                              -18-

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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
                              -19-

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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 
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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.
                             -31-

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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.
                            -41-

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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.

-------
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-

-------
                                                             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-

-------
                                      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
  103 kkg/yr
-------
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                                          YD
                               TtUiATMENT SLUDGE
                               Z riLTT-ll All) AND
WATF.ll nof\NE WASTE
Di::i'i'Aiu;nD AS  EPFLUENT  TO  NAVIGABLE : WATERS
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                                                  -.5-
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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-

-------
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-

-------
                                                                                                               VENT
                                                                                         CAUfflTC
                                                                                         GOUmOM
                                                                                12(6-3S)lljSGv
                                                                                (9B»-104»)
                                DaCli
                                HaOII
                                SODA ASH
                      CEU.
                      O.S ASUES106
                      3 OllEnS
                                     20.5 III
urn niutiB
1.000(1,663-2,150)riaCl.
mm Mj, Co,  SO»
UFUIUTIES
    DIVD IE

PURIFICATICN
                                                       1          1
                                CELL

                            EICCWDLYSIB
                                             SM.T
                                                         OOOUtC
                                                          nm
                                                         DIVING
PURIFICATION
     m>
                                                      U(6-35)U,GO»
                                                      (701-93%)
                                                                                               VOTT
15 (TO 30)
   DRUE
                                                       vmrrr.i
                                             3 CAmON MI0 [DUnUU!
                                                 0.4 KSDESTC6
                                                                   r
                                                            CAUSTIC
                                                          EVAPOiuvnoN
                                                           N1D SALT
                                                           VECCMS.VX
   1,OCO
-*"aux«ujnj
   prooocr
                                                                                                                                     2256
                                          i^TF.ni»xini
                                              35-265 Had
                                                15 tloCU
                                              0-20 HniSO,
                                             0-0.01 COTPGR
                                                                                                                                     150»)
                 1 NrOCJ
                 3 NflUCOt
                 IN
                             MUlll
                      (IVj(ai), CnCOi
                          HHW, ir -noxuts)
                        0.2 FIMKI. AID
                            1 NnCl \
                           3 H/iXEIt  '
                                                                                                                 (0-1.0)
                                                                                                           attOlUNMBD
                                                                                                           IIYOKXVUinCMS
                                                                               (6
                                                          ciaon-AUCAU
                                                        niMiuwai CEII. PIKCESS
                                                                                                                        AMobcS

-------
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-

-------
     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-

-------
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-

-------
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-

-------
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-

-------
     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-

-------
 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-

-------
                 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-

-------
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
ciLoimc nccycte
w;
ez cwvrn on
to 11,3 ua — i
KonoANics 1
•160(090)
ITEfl C€L> CO VENT
1 I
MJMU,
f»
\*mji,|
M3(30O)COKE'— — •»• CIB OfUNATmj •» CONDtNSE
ywoo tooionc "-11 *~ n'"
1

one nccvac wAitn-iM
1
^o
IIFY
A


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VAPORIZE
ANU
OXIDIZE
D


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ViiJif j tVftVtH
^^.^ 1 m u.^vi

COOL
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COLLECr


'
4

-*•* TnEATMCNT — *• MILLINO
V • r
                                                                                               WOO TIO,
                                                                                              'rnccucr
                                                jcnuo
                                                                      11JAKUM
                                                                               rtANT
                                     1C (25) OIIC
                                     3M60) COKE
                                     3(6) SIO,
                                     10(1) 1,0,
                                      29 TICI,
                                      •1 CrCI, '.<•
                                     • AS rid, < r«ci,
                                        v,o,
                                         1,0,
                                    «z cncif n oil
                                      10 n,s on
                                     is oonAii(cs
                                      130 IICI
                                      WArcn
                                                  29 Tia
                                                  so imi
                                                                              10 TIO,

                                                                            10 Nod I Na, SO,
                                      tlWA
                                         JALIXA1ION AND 5EIILIHO
                                            E ^
                              ' 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-

-------
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-

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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-

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     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-

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     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-

-------
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-

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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-

-------
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-

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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-

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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-

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     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-

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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-

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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-

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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-

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 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-

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     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-

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                            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-

-------
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-

-------
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-

-------
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-

-------
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-

-------
                          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-

-------
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-

-------
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.
                            -57-

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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.
                             -58-

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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-
                            -59-

-------
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.
                            -60-

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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.
                              -5-

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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-

-------
          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-

-------
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-

-------
     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-

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      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

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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-

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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-

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  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-

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                            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- -

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     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-

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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-

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       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

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       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-

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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-

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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-

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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-

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         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-

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       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-

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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-

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(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-

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       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-

-------
    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.
                              -38-

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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-

-------
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-

-------
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-

-------
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-

-------
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-

-------
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).
                             -13-

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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.
                              -14-

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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.
                              -15-

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Coking

-------
                 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]

-------
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
                             -2-

-------
     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-

-------
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






                             -5-

-------
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-

-------
laboratory animals^'.  Additional information and specific




references on the adverse, effects of naphthalene can be found




in Appendix A.
                             -7-

-------
                          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.

-------
     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.

                             -2-

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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-

-------
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.
                             -6-

-------
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-

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                           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-

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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-

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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-

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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-

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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-

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    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.

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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-

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     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-

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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-

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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-

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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-

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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-

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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-

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                          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-

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                 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-

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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-

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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.
                             -2-

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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.
                             -3-

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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
                             -4-

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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
                             -7-

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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-

-------
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




                             -9-

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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
                             -10-

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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).

                          -11-

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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.
                                                    -12-

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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.






                             -13-

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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







                             -14-

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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)
                             -15-

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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).
                             -16-

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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.
                              -17-

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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.


                             -18-

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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.
                               -19-

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