BACKGROUND DOCUMENT
          RESOURCE CONSERVATION AND RECOVERY ACT
SUBTITLE C  -  IDENTIFICATION AND LISTING  OF  HAZARDOUS WASTE
    §§261,31  and  261.32 - Listing of Hazardous  Wastes
                                              May 2,  1980
           U.S.  ENVIRONMENTAL PROTECTION  AGENCY




                   OFFICE OF SOLID WASTE

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          Hazardous Waste Listing Background Document





INTRODUCTION





      Subtitle  C of the Solid Waste Disposal Act,  as  amended



by the  Resource Conservation and Recovery Act  of  1976  creates



a comprehensive "cradle-to-grave" management control  system



for  the  disposal of hazardous wastes designed  to  protect  the



public  health  and the environment from the improper  disposal



of such  waste.   Section 3001 of that Subtitle  requires  EPA to



identify the  characteristics of and list hazardous wastes.
                                       /


Wastes  identified or listed as hazardous will  be  included in



the  management  control system created by Sections 3002-3006



and  3010.   Wastes not i,d,ent i f ied or listed will be subject to



the  requirements for non-hazardous waste imposed  by  the States



under Subtitle  D.





Hazardous Waste List





      The  purpose of the hazardous waste list as required  by



Section  3001  of RCRA is to identify those wastes  which  mav



present  a potential hazard to human health or  the environment.



The waste so  identified is considered hazardous (unless it'



has been  excluded from the list under §§260.20 and 260.22)



and subject to  the Subtitle C regulations.  A  solid  waste,



or class  of solid wastes  is listed if the waste:



      (1)  exhibits any of the characteristics  identified  in



          Subpart C of the final regulations;  or




                               «
                              -i-

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     (2)  meets  the  definition  of  § 261.11(a)(1) of the regu-




          lations  (i.e.,  may  cause  or  significantly contri-




          bute to, an  increase  in  mortality or an increase




          in serious irreversible,  or  incapacitating rever-




          sible,  illness)  and  thus,  presents  an acute hazard




          to humans; or




     (3)  contains any of  the  toxic  constituents listed in




          Appendix VIII  of Part  261  unless, after considering




          any of  a number  of  factors,  the Administrator con-




          cludes  that  the  waste  will not meet the criterion




          of §261. 11(a)(2)  (i.e.,  may  pose  a  substantial




          present  or potential  hazard  to human health or the




          environment  w-h-en it  is  improperly treated, stored,




          transported, disposed  of  or  otherwise managed) of




          the regulations  (see  Criteria  for Charazcteristics/




          Listing/De 1 isting background  document for a discussion




          of the  various  factors).






     The Agency  considered  several  approaches for formulating




the list.  The approaches  can  be  broken  down  into three main




types:




          Hazardous  Waste  from  Non-Specific Sources - these




          are wastes which  are  generated from a number of




          different  sources  (i.e.,  electroplating, etc.)




          Hazardous  Waste  from  Specific  Sources - these are




          wastes  which would  be  generated from a very specific
                              -11-

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           source  (i.e.,  distillation bottoms from  the  produc-




           tion  of  acetaldehyde from ethylene, etc.)




           Commercial  Chemical Products - these are a  list  of




           commercial  chemicals or manufacturing chemical




           intermediates  which if discarded either  as  the




           commercial  chemical or manufacturing chemical




           intermediate itself; off-specification commercial




           chemicals  or manufacturing chemical intermediates;




           any  container  or inner liner removed from a  container




           that  has  been  used to hold these commercial  chemical




           products  or manufacturing chemical intermediates




           unless  decontaminated; or any residue or contaminated




           soil, water.0x^.0ther debris resulting from the




           clean-up  of a  spill into or on any land or water,




           of these  commercial chemical products or manufacturing




           chemical  intermediates are hazardous wastes.







(This listing  background document will cover the first two




categories; the third category of hazard waste is discussed in




the background  document  entitled, "Hazardous Waste from Dis-




carding of Commercial Chemical Products and the Containers




and Spill  Residues  Thereof".)






HAZARDOUS  WASTE FROM  NON-SPECIFIC AND SPECIFIC SOURCES







     Testing of pure  substances is the traditional approach
                             -ill1

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used by  regulatory agencies to control toxic/hazardous  chemicals*

The purpose  of  RCRA,  however,  is to control waste  materials;

these  are  not  normally pure substances (except  as  in  the  case

not ed  above) .

     In  order  for  a regulation to be effective,  it  should be

structured  so  that it reflects the organization  of  the

regulated  community.   Since waste process streams  are  often

the units  of  the  solid waste regulated by the Act,  these  same

waste  process  streams can be used to provide a  ready means

of identification; such that,  for our purposes,  it  is more

useful  (for  identification purposes) to list "still bottoms

from the XYZ process  - ignitable".   Likewise,  there are

certain  waste  c las s es , —soich as halog.enated solvents which,

if classified  as wastes,  would be unambiguously  identified

by such  a  designation.

     In  this document,  the Agency is providing  the  technical

support  for  the 85 waste  streams promulgated (interim  final)

today.   This document also includes the technical  support for

the eleven new wastes proposed today.   This listing (both

interim  final and  proposed) includes 16 waste streams  from

non-specific sources  and  80 wastes  from specific sources.
*Pure substance  listings  work well for many agencies,  since
 their responsibilities  lie  with some aspect of the  pure
 substance.  The Department  of Transportation, for example,
 uses this approach.   Benzene is listed by DOT as a  flammable
 liquid.  A transporter  knows, after consulting the  DOT  listing,
 that benzene must  be  handled according to the DOT flammable
 liquid regulations.
                              -iv-

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The background  data  used to support these listings comes pri-

marily from  two  sources.  The majority of this data or infor-

mation comes  from  studies undertaken bv the Agency or data

available  to  the Agency (i.e., industry assessment studies

conducted  by  the Office of Solid Waste, effluent guidelines

studies  conducted  by the Office of Water Planning and Standards,

health effects  and fate and transport data compiled by the

Office of  Research and  Development and Office of Water Planning

and Standards,  damage assessments and incidents compiled by

the Office of  Solid  Waste, etc.)*.  The second source of

data came  from  information collected from State Agencies

(i.e., manifest  data, etc.).

     In  addition,  this Document discusses the comments received

on the proposed  listings (43  FR 58957-58959 and 44 FR 49402-49404)

which are  promulgated today,  and the changes  subsequently made.
*It should be noted  that  a  number of these documents (e.g.,
 pesticide waste  background documents)  contain confidential
 information.  This  data  has  been removed from the^document
 and will not be  made  available  to the  public.  This data,
 however, is part  of  the  Administrative record and is included
 in the Agency's  case  to  support  the listing.
                              -v-

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                       Table of Contents
Background  Document                                          Page

1.   Wastes  From  Usage of Halogenated Hydrocarbon  	 2
     Solvents  in  Degreasing Operations

          The  spent  halogenated solvents used in
          degreasing,  tetrachloroethylene,  methylene
          chloride,  trichloroethylene, 1,1,1-tri-
          chloroethane, carbon tetrachloride, and
          the  chlorinated fluorocarbons; and sludges
          resulting  from the recovery of these sol-
          vents  in degreasing operations (T)

2.   Wastes  From  Usage of Organic Solvents  	 30

          The  spent  halogenated solvents, tetrachloro-
          ethylene,  methylene chloride, trichloroethy-
          lene,  1,1,1-trichloroethane, chlorobenzene,
          1,1,2-trichloro-1,2,2-trifluoroe-thane, o-
          dichlorobenzene, trichlorofluoromethane, and
          the  still  bottoms from the recovery of these
          solvents (T )

     -    The  spent  non-halogenated solvents, xylene,
          acetone, ethyl acetate, ethyl benzene,
          ethyl  ether, n-butyl alcohol, eyelohexanone,
          and  the still bottoms from the recovery of
          these  solvents (I)

     -    The  spent  non-halogenated solvents, cresols
          and  cresylic acid, nitrobenzene,  and the still
          bottoms from the recovery of these solvents (T)

          The  spent  non-halogenated solvents, methanol,
          toluene, methyl ethyl ketone, methyl isobutyl
          ketone, carbon disulfide, isobutanol,  pyridine,
          and  the still bottoms from the recovery of
          these  solvents (I,T)

3.   Electroplating  and Metal Finishing Operations 	 82

          Wastewater  treatment sludges from electroplating
          operations

4.   Spent Waste  Cyanide Solutions and Sludges 	 102

          Spent plating bath solutions from electroplating
          operations  (R,T)


                              -vi-

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                                                              P_ag e

           Plating  bath sludges from the bottom of
           plating  baths from electroplating
           operations  (R,T)

           Spent  stripping and cleaning bath solutions
           from  electroplating operations (R,T)

           Plating  bath and  rinse water treatment
           sludges  from electroplating operations (T)*

           Quenching  bath  sludge from oil baths from
           metal  heat  treating operations (R,T)

           Spent  solutions from salt bath pot cleaning
           from metal  treating operations (R,T)

           Quenching  wastewater treatment sludges from
           metal  heat  treating operations (T)

           Flotation  tailings from selective flotation
           from mineral metals recovery operations  (T)

     -     Cyanidation wastewater treatment tailing pond
           sediment  from mineral metals recovery opera-
           tions  (T)    -"-"

     -     Spent  cyanide bath solutions from mineral
           metals recovery operations (R,T)

     -     Dewatered  air pollution control scrubber
           sludges  from coke ovens and blast furnaces  (T)

5.   Wood  Preserving  	  141

     -     Bottom sediment sludge from treatment of
           wastewaters from  wood preserving processes
           that use creosote or pentachloropheno1 (T)

     -     Wastewater  from wood preserving processes
           that use creosote or pentachloropheno1 (pro-
           posed) (T)

6 .   Chromium Pigments and  Iron Blues	  171

           Wastewater -treatment sludge from the pro-
           duction  of  chrome yellow and orange pigments  (T)


-Same as "Wastewater  treatment sludges from electroplating
 opera tions .
                             -vii-

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                                                              Page

          Wastewater  treatment sludge from the pro-
          duction  of  molybdate orange pigments (T)

          Wastewater  treatment sludge from the pro-
          duction  of  zinc yellow pigments (T)

          Wastewater  treatment sludge from the pro-
          duction  of  chrome green pigments (T)

          Wastewater  treatment sludge from the pro-
          duction  of  chrome oxide green pigments
          (anhydrous  and hydrated) (T)

          Wastewater  treatment sludge from the pro-
          duction  of  iron blue pigments (T)

          Oven  residue from the production of chrome
          oxide green pigments (T)

7.   Acetaldehyde  Production 	 204

     -    Distillation bottoms from the production of
          acetaldehyde from ethylene (T)

     -    Distillation side-cuts from the production
          of  acetaldehycfe from ethyl'ene (T)

8.   Acrylonitrile Production	 224

          Bottom stream from the Wastewater stripper
          in  the productionof acrylonitrile (R,T)

          Still bottoms from final purification of
          acrylonitrile in the production of
          acrylonitrile (T)

     -    Bottom stream from the acetonitrile column
          in  the production of acrylonitrile (R,T)

     -    Bottoms  from the acetonitrile purification
          column in  the production of acrylonitrile (T)

9.   Benzyl Chloride  Production 	 245

          Still bottoms from the distillation of benzyl
          chloride (T)

10.   Carbon Tetrachloride Production 	 260

          Heavy ends  or distillation residues from the
          production  of carbon tetrachlor ide (T)
                             -viii-

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                                                               ") Q £
11.  Epichlorohydrin  Production 	•	

          Heavy  ends  (still bottoms) from the puri-
          fication  column in the production of
          epichlorohydrin (T)

12.  Ethyl  Chloride Production 	  312

          Heavy  ends  fromt  he  fractionation column
          in  ethyl  chloride production (T)

13.  Ethylene  Bichloride  and Vinyl Chloride Monomer Pro-  ...  326
     due tion

          Heavy  ends  from the  distillation of ethylene
          dichloride  in  ethylene dichloride production  (T)

          Heavy  ends  from the  distillation of vinyl
          chloride  in vinyl chloride monomer production  (T)

14.  Fluorocarbon Production 	  357

     -    Aqueous spent  antimony catalyst waste from
          fluoromethane's" production '(1)

15.  Phenol/Acetone Production	  373

     -    Distillation bottom  tars from the production
          of phenol/acetone from cumene (T)

16.  Phthalic  Anhydride  Production 	  386

          Distillation light ends  from the production
          of phthalic anhydride from naphthalene (T)

          Distillation bottoms from the production
          of phthalic anhydride from naphthalene (T)

          Distillation light ends  from the production
          of phthalic anhydride from ortho-xylene
          (propos ed)  (T)

          Distillation bottoms from the production
          of phthalic anhydride from ortho-xylene
          (proposed)  (T)
                              -ix-

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                                                             Page

17.  Nitrobenzene  Production 	.	 403

           Distillation bottoms from the production of
           nitrobenzene by the nitration of benzene (T)

18.  Methyl  Ethyl  Pyridine Production  	 416

           Stripping  still tails from the production
           of methyl  ethyl pyridine (T)

19,.  Toluene Diisocyanate Production	 431

     -     Centrifuge residues from toluene diisocya-
           nate  production (R,T)

20.  Trichloroethane Production 	 444

           Waste  from the product stream stripper in
           the  production of 1,1 ,1-trichloroethane (T)

           Spent  catalyst from the hydrochlorinator
           reactor  in the production of 1,1,1-tri-
           chloroethane_y_ia the vinyl chloride
           proces s  (T)

           Distillation bottoms from the production
           of 1,1,1-trichloroethane (proposed) (T)

     -     Heavy  ends from the production of 1,1,1-
           trichloroethane (proposed) (T)

21.  Trichloroethylene and Perchloroethylene Production .... 475

     -     Column  bottoms or heavy ends from the com-
           bined  production of trichloroethylene and
           perchloroethylene (T)

22.  MSMA  and Cacodylic  Acid Production 	 500

           By-product  salts generated in the production
           of MSMA  and  cacodylic acid (T)

23.  Chlordane  Production 	 523

           Wastewater  and scrub water from the chlori-
           nation of  cyclopentadiene in the production
           of chlordane (T)
                              -x-

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                                                              Page
           Wastewater  treatment sludges from the  pro-
           duction of  chlordane (T)

           Filter  solids from the filtration of hexa-
           chlorocyclopentadiene in the production
           of  chlordane (T)

     -     Vacuum  stripper discharges from chlordene
           chlorinator in the production of chlordane
           (propsed)  (T)

24.  Creosote Production 	 544

           Wastewater  treatment sludges generated in
           the production of creosote (T)

     -     Process wastewater from creosote production
           (proposed)  (T)

25.  Disulfoton Production  	 560

           Wastewater  treatment sludges from the  pro-
           duction of  disulfoton (T)

           Still bottoms from toluene reclamation
           distillation in the production of disulfo-
           ton (T)

26.  Phorate  Production 	 573

     -     Wastewater  treatment sludges from the  pro-
           duction of  phorate (T)

           Filter  cake from  the filtration of diethyl
           phosphorodithioic acid in the production
           of  phorate  (T)

     -     Wastewater  from the washing and stripping
           of  phorate  production (T)

27.  Toxaphene Production 	 585

     -     Wastewater  treatment sludge from the pro-
           duction of  toxaphene (T)

           Untreated  process wastewater from the  pro-
           duction of  toxaphene (proposed) (T)
                              -xi-

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28.   2,4,5-T Production
                                                             .Page
597
          Heavy  ends  or  distillation residues from
          the distillation of tetrachlorobenzene in
          the productionof 2,4,5-T (T)

29.  2,4-D Production 	 610

     -    2,6-Dichloropheno1 waste from the produc-
          tion of  2,4-D  (T)

          Untreated wastewater from the production
          of 2,4-D  (proposed) (T)

30-  Methomyl Production	 623

          Wastewater  from  the production of methomyl
          (proposed)  (T)

31.  Explosives  Industry	, 637

     -    Wastewater  treatment sludges from the manu-
          facturing and""~pr ocessing of explosives (R)

     -    Spent  carbon  from the treatment  of waste-
          water  containing explosives (R )

     -    Wastewater  treatment sludges from the manu-
          facture,  formulation and loading of lead-
          based  initiating compounds (T)

          Pink/red  water from TNT  operations (R)

32.  Petroleum Refining  	 671

          Dissolved air  flotation  (DAF)  float from the
          petroleum refining industry (T)

          Slop oil  emulsion solids from the petroleum
          refining  industry (T)

          Heat exchanger bundle cleaning sludge from
          the petroleum  refining industry  (T)

          API separator  sludge from the petroleum re-
          fining industry  (T)

          Tank bottoms (leaded)  from the petroleum re-
          fining industry  (T)

                             -xii-

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33.   Leather Tanning  and  Finishing Industry
                                                              Page
709
          Chrome  (blue)  trimmings generated by the
          following  subcategories of the leather
          tanning  and  finishing  industry: hair
          pulp/chrome  tan/re tan/wet finish; hair
          save/chrome  tan/retan/wet finish; retan/
          wet finish;  no  beamhouse; through-the-
          blue; and  shearlings  (T)

          Chrome  (blue)  shavings  generated by the
          following  subcategories of the leather
          tanning  and  finishing  industry: hair
          pulp/chrome  tan/retan/wet finish; hair
          save/chrome  tan/re tan/wet finish; retan/
          wet finish;  no  beamhouse; through-the-
          blue and shearlings  (T)

          Buffing  dust generated  by the following
          subcategories  of  the  leather  tanning
          and finishing  industry; hair  pulp/
          chrome  tan/retan/wet  finish;  hair save/
          chrome  tan/refan/wet  finish;  retan/wet
          finish;   no beamhouse;  and through-the-
          blue (T)

          Sewer screenings  generated by the following
          subcategories  of  the  leather  tanning and
          finishing  industry: hair pulp/chrome tan/
          retan/wet  finish; hair  save/chrome tan/
          retan/wet  finish; retan/wet finish;  no
          beamhouse;  through-the-blue;  and shearlings  (T)

          Wastewater treatment  sludges  generated by
          the following  subcategories of the leather
          tanning   and  finishing  industry: hair pulp/
          chrome  tan/retan/wet  finish;  hair save/chrome
          tan/retan/wet  finish;  retan/wet finish; no
          beamhouse;  through-the-blue;  and shearlings  (T)

          Wastewater treatment  sludges  generated by
          the following  subcategories of the leather
          tanning   and  finishing  industry: hair pulp/
          chrome  tan/r e tan/we t  finish;  hair save/chronie
          tan/re tan/wet  finish;  and through-the-blue (R,T)
                            -xiii-

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                                                              Page


          Wastewater  treatment sludges from the
          following  subcategory of the leather
          tanning  and finishing industry: hair
          save/non-chrome tan/retan/wet  finish (R)

34.  Coking	  739

          Ammonia  still lime sludge (T)

35.  Electric  Furnace Production of Steel 	  753

          Emission control dusts/sludges from the
          electric furnace production of steel (T)

36.  Steel Finishing  	  767

          Spent  pickle liquor from steel finishing
          operations  (C,T)

          Sludge from lime treatment of  spent pickle
          liquor from steel finishing operations (T)

37.  Primary Copper  Sm'eTting and Refining 	  784

     -    Acid plant  blowdown slurry/sludge resulting
          from the thickening of blowdown slurry from
          primary  copper  production (T)

38.  Primary Lead  Smelting 	  801

     -    Surface  impoundent solids contained in and
          dredged  from surface impoundments at pri-
          mary lead  smelting facilities  (T)

39.  Primary Zinc  Smelting and Refining  	  819

          Sludge from treatment of process wastewater
          and/or acid plant blowdown from primary
          zinc production (T)

          Electrolytic anode siimes/sludges from primary
          zinc production (T)

          Cadmium  plant leach residue (iron oxide) from
          primary  zinc production (T)
                             -xiv-

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                                                             .Page
40.   Secondary Lead Smelting
                                                              841
          Emission control  dust/sludge  from
          secondary lead  smelting  (T)

          Waste leaching  solution  from  acid
          leaching of  emission  control  dust
          from secondary  lead smelting  (pro-
          posed) (T)
                             -xv-

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Generic Listings

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                  LISTING  BACKGROUND  DOCUMENT

         Wastes  from  Usage  of  Halogenated  Hydrocarbon
               Solvents  in Degreasing Operations


The  spent  halogenated  solvents used  in  degreasing,  tetra-
chloroethylene,  methylene chloride,  trichloroethylene,
1,1,1-trichloroethane,  carbon  tetrachloride and  the chlorinated
fluorocarbons; and  sludges  resulting from  the  recovery of
these  solvents in degreasing operations.   (T)*,**,***
I.  SUMMARY OF BASIS  FOR  LISTING

     Solvent degreasing operations  remove  grease,  wax, dirt,

oil, and other undesirable  substances  from various materials.

All degreasing facilities which use  the  halogenated hydro-

carbon solvents listed above  generate  spent  solvent solutions

which are either discarded  or  processed  to recover the

solvent from the spent solution.  The  recovery  operations

invariably generate solvent sludges.
*   In December, 1978, the Agency  proposed  a  generic listing
    for this class of wastes.

**  These solvents are often marketed  under trade names; the
    listing obviously includes all  trade  name solvents
    which containt he enumerated constituents of  concern.
    Another point of consideration  is  that  different names
    may be used to refer to the  same  solvent:
         tetrachloroethylene = perchloethylene
         1 ,1 ,1-trichloroethane = methyl chloroform
         carbon tetrachloride =  tetrachloromethane
         methylene chloride = dichloromethane
         trichloroethylene = 1,1,2-trichloroethylene

*** In response to industry comments,  it  should  be noted
    that the Agency is no longer listing  these wastes on
    the basis of ignitability, or  EP  toxicity.   However, these
    solvents may be contaminated with  heavy metals (i.e., lead
    and chromium) in the degreasing operations;  therefore, the
    generator will be responsible  for  determining whether the
    waste would also meet the EP toxicity characteristic.

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The Administrator  has  determined that spent halogenated

solvents from degreasing  and  the sludges that result from

associated solvent reclamation operations are solid wastes

which may pose a substantial  present or  potential hazard to

human health or  the  environment when improperly transported,

treated, stored, disposed of,  or otherwise managed;  therefore,

these wastes should  be subject to appropriate management

requirements under  Subtitle C  of RCRA.

     For all of  the  listed waste solvents,  this conclusion

is based on the  following considerations:

     1.  The chlorinated  waste hydrocarbons are toxic  and, in
         some cases, genetically harmful, while chlorofluoro-
         carbons may remove the ozone layer following  environ-
         mental  release.

     2.  Approximately 99,000  metric tons of waste halogenated
         solvents  from degreasing operations are generated
         each year(l).  There  are approximately 460,000
         facilities  dispersed  throughout the country that
         use halogenated  solvents and generate these wastes(l).
         It is estimated  that  about  30,000  metric tons  per year
         of halogenated hydrocarbons from these facilities are
         either  disposed  of annually in  landfills or by open-
         ground  dumping,  either as crude spent solvents
         or as sludges.   The remainder of these wastes  are
         usually incinerated.   The large quantity of wastes
         generated and  the large number  of  disposal  sites
         utilized, increases  the possibility of waste  mis-
         management and environmental release of harmful
         cons ti tuents .

     3.  Since a large  majority of the spent solvents  and
         sludges are in liquid  form,  the potential for  these
         wastes  to migrate from land disposal facilities
         is high.  Further, the solubility  of these  solvents
         is uniformly  high, increasing their migratory
         po tential.

     4.  The spent solvent solution  from degreasing  operations
         contains up to 90 percent of the original solvent.
         Depending on  the recovery technique,  sludges  that result
         from reclamation processes  can  contain up ,t o  50 percent
         of the original  solvent.  Such  high concentrations

                             iO —

                             -J -

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          of  hazardous  constituents increases the chance of
          waste  constituents  escaping in harmful concentrations-

      5.   Spent  solvents  can  create an air  pollution problem
          via  the  volatilization of the solvents from the
          wastes.

For  the  five  chlorinated  solvents  (not including chlorofluoro-
carbons)  found  in the  waste  streams, this  conclusion is
based  on  the  following considerations:

      6.   Incomplete  combustion  of  the spent  chlorinated
          hydrocarbon solvents during incineration can
          cause  emissions  of  the solvent and  generate
          toxic  degradation products  (e.g.  phosgene).

      7.   These  spent halogenated  solvents  can  leach from
          the  waste  to  effect adversely human health and
          the  environment  through  the resulting contamination
          of   groundwater.

      8.   Current  waste management  practices  have resulted
          in  environmental damage.   These incidents  serve to
          illustrate  that  the mismanagement of  these wastes
          does occur  and can  result in substantial environmental
          and  health  hazards.

      9.   A number of these solvents  are carcinogenic or
          mutagenic,  or are suspected carcinogens or mutagens,
          and  are  lethally toxic to humans  and  animals.

For  the chlorofluorocarbons, the Agency is basing the listing
on the following  consideration:
                                                            •
     10.   Chlorofluorocarbons, after  release  at the  surface of
          the  earth,  mix with the atmosphere  and rise into
          the  stratosphere where they are decomposed by  ultra
          violet radiation to release chorine atoms.  These
          atoms catalytically remove  ozone, leading  to adverse
          effects,  including  skin cancer and  climate changes.

II.   OVERALL  DESCRIPTION OF  INDUSTRY USAGE
     Degreasing operations are not  industry  specific.   Degreasing

operations are prevalent  in  twelve  major  SIC (Standard Industrial

Classification) categories,  numerous  subcategories ,  and auto-

motive maintenance shops.  The pertinent  industries  where

halogenated hydrocarbons  are used primarily  are  presented in

Table 1.  A summary of  the number and  types  of  plants  that

conduct degreasing operations is presented  in Table  2.

                             -V

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                           Table 1



          Industries Using Halogenated Hydrocarbons



                   in Degreasing Operations
Source                                  SIC Code



Metal Furniture                            25



Primary Metals                             33



Fabricated Products                        34



Non-electric Machinery                     35



Electric Equipment                         36



Transportation Equipment                   37



Instruments and Clocks                     38
                       «


Miscellaneous Industry                     39



Automotive Repair Shops                    75



Automotive Dealers                         55



Automotive Maintenance  Shops



Texitile Plants (Fabric  Scouring)          22



Gasoline Stations

-------
                                                                c B L JL la u L u u  11 u in u t:
;j o u r c e


Material Degreasing


    Metal Furniture

    Pr ima ry Me tale

    Fabricated  Products

    Non-electric  Machinery

    Electric  Equipment

    Transportation  Equipment

    Instruments and  Clocks

    Mis eellaneous


 Automo t ive


    Auto Repair Shops

    Automotive  Dealers

    Gasoline-Stations

    Maintenance Shops

 Textiles
     Textile  Plants (Fabric Scouring)   22
                            Total
SIC
25
33 ,
34
35
36
37
38
39

.75
55
55

Number of of V'a p o r D e g r e a 8 i u g
Plants , Operations
9,
6,
29,
.40.
12,
8,
5,
15.

127,
121,
226,
320,
233 492
792 1,547
525 5,140
792 5,302
270 6,302
802 1,917
t
983 \ 2,559
187 886
i
1
203
369
445
701
of Cold Cleaning
Operat tons
22,
17,
76,
105,
31,
22,
15.
39,

141,
135,
869
5.58
329
456
720
756
467
262

977
463
277,440
252,735
  7,201
931,513
24,145
1,230,006
 *Includes  facilities which do not use halogenated solvents
                                                   -V

-------
III.  OVERALL PROCESS  DESCRIPTION, WASTE GENERATION LEVELS
      AND GEOGRAPHIC DISTRIBUTION OF DECREASING FACILITIES'

     1.  Solvents  Used in Degreasing Process

          As indicated in Table 3, out of the more than 1,230,000

     non-halogenated and  halogenated degreasing operations

     (see Table 2),  approximately 460,000 use halogenated

     solvents(l).   Table  3 breaks down the number of plants

     which use halogenated solvents to show the' estimated number

     of these plants using a particular halogenated solvent by

     their type of degreasing operation.  As the table indicates,

     the largest  number of these plants use cold cleaning and open

     top vapor degreasing operations (see next section for more

     detailed discussion  of specific degreasing operations).

     In both of these  operations, the largest number use trichloro-

     ethylene and  trichlor ethane.  Of the industries with conveyor-

     ized vapor degreasing operations., the largest number use

     trichloroethylene;  fabric scouring operations use principally

     tetrachloroethylene  (perchloroethylene) .  Overall, trichloro-

     ethylene is  the solvent used most prevalently.

     2 .  Process  Description

          Degreasing operations may be classified into

     four basic categories: cold cleaning, vapor degreasing

     (open top),  vapor degreasing (conveyorized), and fabric

     scouring .

          In cold  cleaning operations, the solvent is

     maintained well below its boiling point. The item

     to be cleaned  is  either immersed in agitated solvent
                                 -1-

-------
       Table 3 - Estimated Number of  Plants  using  Halogenated

             Solvents  by Type of Degreasing  (1974)  (1)

Solvent
bon tetrachloride
or ocar bons*
hylene Chloride
rachloroethylene
chloroethylene
c h 1 ofoethane
Total
Vapor
(open top )

2,130
298
3,121
11,440
4, Oil

21, 000
Cold Cleaning
10,568
66,932
21,136
45,795
149,715
137, 386

431, 532
Vapor Fabric
Conveyorized Scouring

319
45
467
1, 713
601

3,145



2,522
693


3,215

Note:  Blanks indicate no use of specified solvent  in  that  type
       of degreasing operation.

*This refers to all fluorocarbons,  some of which are chlorinated.
                                -V

-------
     or suspended  above  the solvent where it is systematically

     sprayed in  a  manner  similar to that of an automatic

     dish washer.   Simple cold cleaning operations may

     even consist  of  a container of solvent in which

     items are manually  immersed, as is the case in small

     auto repair shops and in service stations.

          Simple vapor degreasing (open top) is achieved by

     suspending  the  item  to be cleaned above the boiling

     solvent in  a  vat.   Condensation continues until the

     temperature of  the  object approaches that of the solvent

     vapors.  Often  the  suspended item is sprayed with liquid

     solvent to  facilitate further degreasing.   In order to

     control vapor emissions, a layer of cold air is often

     maintained  above the^open top degreaser.

          The conveyorized vapor degreaser operates in much

     the same manner, except  that the objects to be cleaned
                                                     •
     are continuously conveyed through the vapor zone.

     Auxiliary solvent sprays are also used to improve the

     cleaning efficiency  of the operations.

          Fabric scouring  operations are slightly more complex.

     Generally,  the  fabric is conveyed through the degreasing

     machine, where  it is  sprayed with solvents.   The solvents

     are then removed with an aqueous solution of alcohol.


     3.  Waste Generation  Levels and Projected Levels

          The annual growth rate for the use of the listed

halogenated solvents in degreasing applications is expected to
                                 -V

-------
 be  4  percent(l).   Growth is expected to be uniform  among

 the various  solvents, except for trichloroethylene,  which

 has been  banned in several states for use in occupational

 settings  because  it is a carcinogen. (1,2,21).   In  Cali-

 fornia,  the  use of trichloroethylene has been  restricted by

 legislation,  but  tetrachloroethylene and 1,1,1-triehloroethane

 are exempt(l)  from the restrictions and are still used  in

 degreasing operations.   Rhode Island has completely  banned

 the use  of trichloroethylene(2).

 4 .   Geographic  Distribution of  Degreasing Operations

      The  location  of  the vapor  degreasing operations has

 been  determined by identifying  the  industries with which

 the operations  are associated.   There are about  24,145

 vapor degreasing operations in  the  United States, which

 consume about 52 percent of the total halogenated solvents

 used(l).  More  than 63  percent  of these operations are

 found in  nine states  (California, Illinois,  Massachusetts,

 Michigan, New Jersey,  New York,  Ohio, Pennsylvania and

 Texas).   Figure 1  and  the associated Table 4  present the

 geographic distribution  of these plants.

     There are  about  431,532  operations that perform

 cold cleaning using about 35  percent of the total

 halogenated solvent consumption,  while  approximately

 3,125 fabric scouring  operations consume about 13 percent

 of  the total halogenated solvent(l).   Assuming an equal

distribution of halogenated solvent  use among cold

cleaning  and fabric scouring  operations, over 59 percent

                            -V
                            -10-

-------

                                                  ^ '::?|||ferj-;i: 'i'::r-i.^;:T :;,.:;•'\;; !'••' ^O^
                                                          ..i-.'~';:' ;"::•!""•'.:.-';:'=:.	t:;iif
                      Figure   1
                                                                > 1.000
         3HIC DISTRIBUTION  OF
VAK5R DECREASING OPERATIONS   (1)
Table  4
• t 	 ^ i_,W^ . W^A H~\~
CONVEYORIZ
State
*
. , . , 	
Alaska ' ^ -
Arizona

California
Colorado
Ccr.;-.*cticut
Delavare
District of Colu.-iia
Florida
Georgia
Hawaii

Idaho
Illinois

* ~<- Ic..--
Tcva
Kar.sas
Kc-r.tucky

louisiaria
.
'.-'.& me
t>. ^, . • - — /j
•'•- - .v A -'"-
,'•'.; oh i can
'•'. i r.r. £ s o t a
:•'•' isii's irci
«.. .- ^ . . • • • »• i
ED)' DSGRSAS
Nuroer
of slants

247
0
1S9
147
3,313
212-
€43
29
11
730
315
29
39
1,737
6S3
225
217
193
174

6 5

227
S23
1,539
^ t 0
IIS
455
••^ in 1 ^^ ^ r t * •• *^ * >•
«*• iN *• i? y^j £f ^— , i\i^™% JK • ^»
St =te

Xcr.tar.a
N'ebraska
'tavada
New Hi-t shire
N"«w Jersey
N'ow :-:-=xloo
**ew York
North Carolina
North D'kcta
Ohio
Creccn
•• G "* * **^ ^** ^ " -^ r*i i 2.
".hoc a 1 3] and
* •« ^» T *
South Circlir.a
South Dakota
Texas
\j ^ ."; [^
» * «. ,» ^
'« C^ « ..••w' • * ^
; . .• ^ „ : . ; -
• »-';-•••
'-•-"£ shine ton
Wiscor.sin

Wycrir.g
^* *• 4. - *
» -* V — ^
NS (1).
N'u.-.cer
of clints

25
102
30
36
1,200
54
i , :14
20
1 C T ^
1,5-5
^ C. ~
25^
246
i * ' i
I , - in
221
* - 1

25
356
1,119
Ci G
-? J
"> Q
**" ^
213
^ •» *

33
—
'
24,145

-------
      of  the  total halogenated solvent used  for  degreasing

      occurs  in ten states (California, Illinois,  Massachusetts,

      Michigan, New Jersey, New York, Ohio,  Pennsylvania,  Texas

      and  North Carolina).

 IV.   WASTE STREAM SOURCES AND DESCRIPTION

      The  usefulness  of a solvent decreases  with time  as  contami-

 nants  adulterate  and become concentrated in the solvent.   When the

 boiling  point  of  the solution (i.e., solvent and  contaminants)

 increases to  about 30°C above that of the pure  solvent,  the  solvent

 is discarded.   Halogenated solvent use pattern  by  type of degreasing

 operation is  presented in Table 5.  Approximately  527,520 metric

 tons  of  halogenated  solvents are used each  year for degreasing

 operations(1).

      Spent solvent solutions are either disposed  of,  reclaimed

 and recycled  by the  waste generator, or processed  by  a contract

 solvent  reclamining  operator.*   Reclamation is achieved via

 settling and/or batch  distillation.   The listed sludge results

 from  this reclamation  process.

     The composition of the spent solvent is dependent on the

application of the degreasing operation.   The spent solvent
*At this time, applicable  requirements of Parts 262 through'
 265 and 122 will apply  insofar  as the accumulation, storage
 and transportation  of hazardous wastes that are used,  reused,
 recycled or reclaimed.  The  Agency believes this regulatory
 coverage is appropriate for  the subject wastes.  These wastes
 are hazardous insofar as  they  are being accumulated,  stored  or
 transported.  These wastes may  not pose a substantial  hazard
 during their recycling  and,  even though its listed as  hazardous,
 this  aspect of their management is not presently being regulated
                                 -13. ~

-------
                       USE  PATEERN  OF  HALOGENATED  SOLVENTS  IN DEGREASING AND

                                FABRIC SCOURING  OPERATIONS  IN 1974
    Chemical



 Halogenated hydrocarbons:

  Carbon t e trachlor Ide

  Fluoro carbons*

  Methylene  Chloride

  Perchloroethylene

  Trlchloroethylene

  Trichloroethane
Total U.S.
Consump tion
(103 kkg)
    U.S.  Consumption
    for  Degreasing
    (103  kkg)
                     Cold
                Vapor
534.
428.
235.

330.
173.
236
8
6
4

2
7
.3
0
6
46

11
43
7
.72

.2
1
.4 ;
.8 '
i
8

1
1

5
1.
0


1


43
11

2.
90
7

          U.S.  Consumption
          for Fabric Scouring
          (103 kkg)
                                                       54.6

                                                       15
               Total U.S.
               Consumption
               for Degreasing
               and Scouring
               (103 kkg)
                                                       5.72

                                                     17.1-

                                                     56.2

                                                    109

                                                    171.5

                                                     168
        TOTAL
 1939.0
186.12
271.8
69.6
527.52
*Thls refers~to all fluorocarbone ,  a percentage of which are chlorinated.
                                                        -12--

-------
 solution contains up to 90 percent  of  the  original solvent(A)*




 Depending on the recovery technique, sludges  which result from




 reclamation processes contain from  1 to  50  percent of the




 original hydrocarbon ' solvent(5).  However,  because of the




 economic considerations of the reclaiming  process, the solvent




 content  of the sludge is seldom reduced  below 10  percent.




 Heavy  metal fines and other organics are also present in




 these  wastes,  in addition to the original  solvent(3).






 V.   QUANTITIES OF THE WASTE AND TYPICAL DISPOSAL  PRACTICES




     Disposal  practices include overt open  ground  dumping,




 containerized  landfilling, and incineration (3).   Approximately




 99,000 metric  tons  of waste halogenated  solvents  from degreasing




 operations are generated annually(l).  It  is  estimated that




 about  30,000 metric  tons of these are either  landfilled  or




 open ground dumped.   The remaining quantity of waste  halogenated




 solvents  from  degreasing operations are incinerated.   The




 rationale and  derivation of this estimated  quantity  is presented




 in Ap pend ix I.






 VI.  HAZARDOUS  PROPERTIES  OF THE WASTES
     As indicated  earlier,  the spent halogenated  solvents  and




sludges from  the  reclamation of these solvents contain  very




significant concentrations  of the solvent itself  —  the




spent solvent  solution  contains up to 90 percent  of  the original




solvent and the sludge  contains a minimum of 10 percent of




•jih-a original  solvent.   The  landfilling or open ground  dumping




of these wastes in  an unsecure land disposal facility  may

-------
result in the migration of the toxic halogenated solvents




into the surrounding  environment, thus becoming a potential




contaminant of  groundwater.  For example, since a large




majority of these  wastes are in liquid form — including all




of the spent solvents -- these wastes' physical form makes




them amenable to migration from a the land disposal facility.




Additionally, the  solubility in water of these halogenated




solvents is quite  high (13): 1 ,1 ,1-trichloroethane - 950




mg/1, tetrachloroethylene 45,000 mg/1, methylene chloride -




20,000 mg/1, carbontetrachloride 800 mg/1, and trichloroethy-




lene - 1,000 mg/l(36).  Again, these high solubilities demon-




strate a strong  propensity to migrate from inadequate land




disposal facilities  in substantial concentrations.  Thus,




improperly constructed or managed landfills (for example,




landfills located  in  areas with permeable soils, or landfills




with inadequate  leachate control practices) could easily




fail to impede  leachate formation and migration.  Haphazard




dumping of the  wastes is even more likely to result in migration




of waste constituents.




     Once released  from the matrix of the waste, the halogenated




solvents could  migrate through the soil to ground and surface




waters utilized  as  drinking water.  In the National Organics




Monitoring Survey,  the Agency detected a number of these solvents




in drinking water  samples tested over the past several years, thus




demonstrating the  propensity of these solvents to migrate from the

-------
 waste disposal  environment and to persist  in  drinking water follow-

 ing migration*  (14 a,  14b,  14c, 14d, 14e).   In  addition, a number

 of actual documented  damage incidents show  the  potential for a

 very common halogenated  solvent,  trichloroethylene,  to leach

 from disposal sites into  groundwater.  (See Damage  Incidents

 Resulting from  the Mismanagement  of Halogenated Hydrocarbons,

 p.  17.)

      These actual damage  incidents confirm  literature data  points

 indicating the  environmental  persistence of these compounds.   Thus,

 1 ,1 , 1-trichloroethane, methylene  chloride, and carbon tetrachloride

 are all  likely  to persist  in  the  environment long enough to  reach

 environmental receptors (1,1,1-trichloroethane is subject  to

 hydrolysis,  but has a half-life in groundwater of 6 months)(37).

      Another problem which  could  result  from improper  landfilling

 of these wastes is the potential  for  the contaminants  to volatilize

 into  the surrounding atmosphere.   All  of the listed chlorinated

 solvents are volatile and thus could  present an air pollution

 problem  if they are improperly managed  (for example,  disposed of

 in  the open,  or  without adequate  cover),  since they are  uniformly

 toxic via  inhalation.

     A special  problem is posed by chlorofluorocarbon  solvents.

 These solvents  are also highly volatile,  but instead  of  posing a

 direct toxicity  hazard, they may  be released at the surface of the

 earth, mix with  the  atmosphere and rise  slowly into the  stratosphere,
*The specific  solvents detected in  these  samples were methylene
 chloride, carbon  tetrachloride, trichloroethylene ,  and tri-
 chloroethylene  and  trichlorofluoromethane .

-------
        Damage Incidents  Resulting From The Mismanagement of




                          Trichloroethylene






1.   In one incident  in  Michigan,  an automotive parts manu-




     facturing plant  routinely dumped spent degreasing solu-




     tions on the  open ground  at a rate o-f about 1000 gallons




     per year from 1968  to  1972.  Trichloroethylene was one




     of the degreasing solvents present in the spent solutions.




     Beginning in  1973,  trichloroethylene was detected at levels




     up to 20 mg/1 in neary residential wells.  The dump site




     was the only  apparent  source  of possible contamination (10)




2.   In a second  incident,  also in Michigan,  an underground




     storage tank  leaked  trichloroethylene which was detected




     in local groundwater up to four miles away from the




     land C11).




3.   In April of  1974, a  private water well in Bay City, Michi-




     gan became contaminated by trichloroethylene.   The only




     nearby source of this  chemical was the Thomas Company




     (which replaced  the  well  with a new one).  The company




     claimed that,  although it had discharged trichloroethylene




     into the ground  in  the past,  it had not  done so since




     1968.  Nevertheless,  in  May  of 1975, two more wells




     were reported  to be  contaminated with trichloroethylene




     at concentrations of 20 mg/1  and 3 mg/1, respectively





     (12).

-------
vhere  they  are decomposed by ultra violet  radiation  to r e-




laase  chlorine atoms.   The chlorine atoms  catalytically




remove  ozone,  thereby reducing the total amount  of ozone in




the  stratosphere,  leading to an increase in skin  cancer,




climatic  changes  and other adverse effects (33,34).




     In March,  1978, EPA banned the use of chlorofluoro-




carbons in  aerosol propellants.  The primary concern  in the




enactment of  this  ban  was the ozone depletion effects  resulting




from chlorof1uorocarbons entering the stratosphere and




reacting  with  the  ozone.  The Agency's concern, however,  is




with chlorofluorocarbon use  in general, due to the present




or future health  and environmental hazards resulting  from




their  use.  Therefore,  the Agency has proposed the regulation




of non-aerosol  uses  of  chlorofluorocarbons(8) .




     Additionally,  the  U.S.  EPA is expecting to propose  regu-




lations controlling  the airborne emissions of  these solvents




and other volatile organics  so as to reduce the air pollution




problems  presented when these solvents are used or disposed.




These proposed  regulations will apply certain  standards  to




a number of the Volatile Organic Compounds (VOC) which have




been demonstrated  to be percursors of the  to the formation




of ozone and other  photochemical oxidants in the atmosphere.




Ozone air pollution  endangers the public health and welfare




and is  thus reflected in the  Administrator's promulgation  of  a




National Ambient Air Quality  Standard for Ozone (February  8,




1979, 44 FR 8202).   Additionally,  1 ,1,1-triehloroethane  and
                                 -X-

-------
methylene chloride, which  are  not  ozone percursors, are




being regulated under the  proposed rule since under EPA's




proposed airborne carcinogen policy,  a compound which shows




evidence of human carcinogenicity  is  a candidate for regulation




under Section 111 as a pollutant  "reasonably anticipated to




endanger public health and  welfare".   Finally, trichlorofluoro-




methane, as indicated in the earlier  discussion of chlorofluoro-




carbons in general, has been implicated in the depletion of




the stratospheric ozone layer,  a  region of the upper atmosphere




which shields the earth from harmful  wavelengths of ultra




violet radiation, that would increase skin cancer risks in




h urn ans.(^^»^'




     If these wastes are incinerated, as a large percentage




are, and the wastes are not subject  to proper incineration




conditions (i.e., temperature  and  residence times), pollution




of the environment may result  from the airborne disposal of




uncombusted halogenated organics,  partially combusted organics




and newly formed organic compounds.   Phosgene is an example




of a partially combusted chlorinated  organic which is produced




by the decomposition or combustion of chlorinated organics




by heat(15,16,17).  Phosgene has  been used as a chemical




warfare agent and is recognized as extremely toxic.




     The large quantities  of the  spent solvent and sludges re-




sulting from the recovery  of these solvents, a combined total




of 99,000 metric tons per  year, are  another area of concern.

-------
As  previously indicated, these wastes  are  generated in

substantial  quantities and contain very  high  concentrations

of  the  original solvent (the spent solvent  solution contains

up  to  90  percent and the sludges contain up to  50  percent

of  the  original solvent).  The large quantities  of these

contaminants  pose the danger of polluting  large  areas  of

ground  or  surface waters. Contamination  could also occur

for  long  periods of time, since large  am-ounts of  pollutants

are  available for environmental loading.   All of  these

considerations  increase the possibility  of  exposure to the

harmful constituents in the wastes.

VII .  HEALTH  AND ECOLOGICAL EFFECTS ASSOCIATED  WITH THE
      CONSTITUENTS  IN THE WASTES

     The  toxicity of t e tr achloro e thylene , methylene chloride,

1 , 1 , 1-trichlor ethane , t ric hlo roe thylene , carbon  t e trachlor ide

and  chlo ro f luo rocarbons has been well  documented.   Capsule

descriptions  of  the adverse health and environmental effects

are  summarized  below;  more detail on the adverse effects of

these solvents  can  be found in Appendix A.

     Te trachloroethyl ene has been included on EPA ' s list of

chemicals which  have demonstrated substantial evidence of

car cinogenic i ty . ( 21)   jn addition,  repeated exposure in

rats and mice  to  t e trachl oro ethyl ene in  air or  in  the  diet

has resulted  in  central fatty degeneration in the  liver,

increased kidney  weights and toxic nephr opa thy . ( 18 , 19 , 20 ) .

Additionally,  t e tr ac hlo r oe t hyl ene has demonstrated toxicity

to freshwater  f ish( 14 b , 22 , 23 ) .
                                 -30-

-------
     Methylene chloride has been  shown  to  be mutagenic(24).




 In addition, acute exposure to methylene  chloride in




 humans is a central nervous system  depressant resulting




 in narcosis in high concentrations  and  is  metabolized




 to carbon monoxide and causes an  increase  in carboxy-




 hemoglobin(25 ) •



     1,1,1-trichloroethane has been shown  in an NCI bioassay




 for carcinogenicity to induce a variety of neoplasms(26).   A




 high incidence of deaths in test  animals  has led to retesting




 of this  compound by NCI(26).  Human toxic  effects seen after




 exposure to 1,1,1-trichloroethane include  several central




 nervous  system functions, including reaction time,  perceptual




 speed, manual dexterity and equilibrium(27).  In addition,




 animal studies have prod-uced toxic  effects in the central




 nervous  system,  cardiovascular system,  pulmonary system,  and




 induced  liver and kidney damage(27).




     Trichloroethylene has been included  on  EPA' s list of




 chemicals which  have demonstrated substantial evidence of




 carcinogenicity.(21)  Trichloroethylene has  also been




 shown, both through acute and chronic exposure, to  produce




 disturbances of  the central nervous  system and  other neuro-




 logical  effects(28,29,30).




     Carbon tetrachloride has been  included  on  EPA's list of




 chemicals  which  have demonstrated substantial evidence of




 carcinogenicity.(21)  In addition,  toxicological data for




non-human mammals are extensive and  show  carbon tetrachlor ide




to cause  liver and kidney damage, biochemical changes in







                                -K-

-------
liver  function  and  neurological damage(32).




     The  hazards  associated with exposure to the above




halogenated  solvents  have been recognized by other regulatory




programs.  Tetrachloroethylene, methylene chloride, 1,1,1-




trichloroethane,  trichloroethylene,  carbon tetrachloride and




the  two fluorocarbons,  trichlorofluoromethane and dichloro-




difluoromethane,  are  listed as priority pollutants in accordance




with §307  of  the  Clean  Water  Act of  1977.  Under §6 of the




Occupational  Safety and Health act of 1970,  final standards




for  occupational  exposure have been  established and promulgated




in 29  CFR  1910.1000 for carbon tetrachloride, methylene




chloride  and  1,1,1-trichloroethane.   On March 17, 1979,




fully  halogenated fluorocarbons were banned  by the Consumer




Products  Safety Commission as  propellants in the United




State, except for essential uses because of  their threat to




the ozone.  In  addition,  final or proposed regulations in




the States of California,  Louisiana, Maryland,  Massachusetts,




Minnesota, Missouri, New  Mexico,  Oklahoma and Vermont define




compounds  containing one  or more of  the solvents tetrachloro-




ethylene,   methylene chloride,  1,1,1-trichloroethane,  trichloro-




ethylene,   carbon  tetrachloride and trichlorofluoromethane




as hazardous wastes or  components thereof.^5

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                            ATTACHMENT I

     DERIVATION OF THE ESTIMATED QUANTITIES OF THE WASTE

I.   ANNUAL  QUANTITIES OF WASTES

     Total  amount  of spent solvents (Halogenated and non-
     halogenated)C1) « 425,560 kkg

     Total  amount  of spent solvents from vapor degreasing^
     = 54,560  kkg

     Vapor  degreasing units only use halogenated solvents  so all
     of the  54,560 kkg from this source are halogenated solvents.
     Cold  cleaners-and fabric scourers use both halogenated and
     non-halogenated solvents.  Assume that the spent solvent
     solutions contain solvents in the same proportion as  their
     use.   About  12 percent of solvent use in applications other
     than  vapor degreasing is halogenated(1).

     .'.  (425,560  kkg - 54,560 kkg) (0.12)(1)
        =  44,250  kkg of halogenated solvents contained in wastes
           from sources other than vapor degreasing

        54,560 kkg + 44, 520 kkg = 99,000 kkg of halogenated
        solvents                            yr

ii.   DISPOSITION OF WASTE"

     The disposition of about 30 percent of these wastes can be
     derived  from  information which is documented in the litera-
     ture.   The disposition of the remaining 70 percent is based
     upon  extrapolations and economic consideration of waste
     management alternatives.

     A.   DISPOSITION OF 30 PERCENT OF THE WASTE

          0     Vapor degreasers only use halogenated solvents(l)

          0     Virtually all metal finishing shops (SIC 35, 36,
               37,  and 39), and by implication vapor degreasing
               operations,  either reclaim their spent solvents
               or  sell them to solvent refiners . (1,3)

         0     Between 50-99 percent of the solution is recovered(4,5)

         0     Approximately 37 percent of the plants which recover
               these solvents on site dispose of their waste sludges
               in  landfills(3).

               (amount of waste) (1-percent recovery)(percent  of
               plants  with  on site recovery) x (percent of plants
               that landfill) = Amount of waste landfilled.

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     1.   Assume 50 percent  of  the  solution is  recovered

          (54,560 kkg)  (0.50)(0.37)(0.70)  - 7,065 kkg

     2.   Assume 99 percent  of  the  solution is  recovered

          (54,560 kkg)  (0.01) (0.37)(0.70)  =  140  kkg

          140 kkg to 7,065 kkg  of halogenated  solvents
          disposed of in landfills.

     About 20 percent of the solvent  reclaimers which process
     the remaining 63 percent of the  solvents  from this  source
     also landfill their waste.  The  remaining  80 percent
     of the solvent reclaimers  reportedly  incinerate their
     sludges(4,5).  Therefore an additional 109 to 5,456
     kkg' of halogenated solvents are  landfilled by solvent
     reclaimers.

B .    DISPOSITION OF THE REMAINING 70  PERCENT OF THE  WASTE

     The wastes generated by the plants in  the SIC cate-
     gories delineated  above represent about 60 percent
     of all vapor degreasing operations and  about  30
     percent of all wastes generated  by all degreasers.
     Reportedly, a facility which generates  at least 350
     gallons of spent halogenated solvents  anually has
     economic incentive to implement  a recovery strategy(4,9) .
     Virtually all vapor degreasers meet this criteria.

     The disposition of spent solutions from cold  cleaning
     and fabric scouring operations is not  as well defined.
     In order to account for these wastes,  some economic
     factors have been  considered.  In general, it is  expected
     that a  plant or industry which has a high incidence
     of  use  of a relatively expensive solvent will probably
     have some kind of  recovery strategy, assuming the scale
     of  operations permits an acceptable payback  period.
     In  cold cleaning and fabric scouring operations,  the
     following factors  are pertinent:

     0     Cold cleaning and fabric scourers  use halogenated
          solvents in conjunction with inexpensive non-
          halogenated solvents.   It has been estimated
          that these operations must  have  six to  twelve
          times the solvent throughput of plants  which
          only use halogenated  solvents in  order  to
          economically  justify  a recovery  strategy.

     0     Cold cleaning and fabric scouring  operations
          represent about 94.7  percent of all facilities
          that use halogenated  solvents but  only  use about
          48 percent of the total supply of  these  solvents

-------
          that  are used for degreasing.  The implication  is
          that,  on the average, the solvent throughput
          rate  is much lower in this segment of the
          degreasing industry than that of the vapor
          degreasing segment.

     Although  some cold cleaning and fabric scouring
     operations  probably operate on a scale that would
     make  a  recovery strategy economically attractive,
     it  is not  possible to estimate the extent of recovery-
     operations  in this segment of the industry.  The
     economics  seem to indicate that the incidence of
     recovery  from these operations is probably very low.

C.    THE GROSS  ESTIMATE
     In  estimating  the disposition of all the wastes,
     the best  and worst cases pertaining to the portion
     of  the  waste which cannot be documented in the
     literature  are considered.   The ideal case is where
     all of  the  wastes from cold cleaning and fabric
     scouring  operations are processed by contract re-
     claimer using  maximum efficiency recovery techniques
     (i.e.,  99  percent recovery).  The worst case would
     be  where  all of this waste  is simply disposed of.
     The following  is  the basis  for the estimate.

     From Section A

          249  kkg to 12,521 kkg  of halogenated solvents are
          landfilled.

     Best Case  for  Cold Cleaning and Fabric Scouring

          (amount of waste)(percent recovered)(percent
          landfilled)  = amount landfilled

          (44,520 kkg)(0.01)(0.2) = 90 kkg of waste land-
          filled

          Worst  case for cold cleaning and fabric scouring
          is when all  44,520 kkg of waste is landfilled

     The estimated  best and worst cases for the disposition
     of  halogenated solvents from all types of degreasing
     operations  are 339-57,041 metric tons per year.  It
     is  unlikely that  either the best or worst case is
     representative of reality.   In this case, about half
     of  the  waste is generated by vapor degreasers where
     it  is likely that the incidence of recovery is high.
     The remaining  half is generated in environments where

-------
the incidence of recovery is probably very low.  A
reasonable inference and prudent estimate based on
available data would be about 30,000 metric tons
per year of halogenated solvents disposed of on land.

-------
REFERENCES

1.   United States Environmental Protection  Agency.   1979.
     Source Assessment:  Solvent Evaporation -  Degreasing
     Operations.

2.   Mansville Chemical Products.   1976.   Chemical Products
     Synopsi s-Trichloroethylene.

3.   United States Environmental Protection  Agency.   1976.
     Assessment of Industrial Hazardous Waste Practices
     Electroplating and Metal Finishing Industries -  Job
     Shops Pb-264-349.

4.   United States Environmental Protection  Agency.   1979.
     Organic Solvent Cleaners-Background  Information  for
     Proposed Standards.  EPA-45/12-78-045a .

5.   United States Environmental Protection  Agency.   1978.
     Source Assessment:  Reclaiming  of Waste  Solvents.   State
     of the Art.   Pb-289-934.

6.   United States Environmental Protection  Agency.   1977.
     Assessment of Industrial Hazardous Waste Practice  Special
     Machinery Manufacturing Industries.   PB-265-981.

7.   Scheflan, L. , Jacobs^ M.B., 1953.  The  Handbook  of  Solvents,
     D. Van Nostrand Company, Inc.,  New York.

8.   March 17, 1978, 43 FR 11301.

9.   United States Environmental Protection  Agency.   1977.
     Control of Volatile Organic Emissionf From  Solvent  Metal
     Cleaning.  EPA-450/2-77-022.

10.  Michigan Department of Natural  Resources -  Geological  Survey
     Division.  Case History #48.

11.  Shellenbarger, P.  1979.  "New  Charge Hits  Air Force."  The
     Detroit News, May 17, 1979.

12.  Mitre Corporation.  1979.   Draft Report in  Support  of  Sub-
     Section C.  Prepared for U.S.  Environmental Protection Agency.

13.  Technical Support Document for  Aquatic  Fate and  Transport
     Estimates for Hazardous Chemical Exposure Assessments.  1980,
     USEPa,  Environmental Research  Laboratory, Athens,  Georgia

14a.  U.S.  EPA. 1979.  Trichloroethylene:  Ambient Water  Quality
     Criteria. U.S. Environmental  Protection Agency.

14b.  U.S.  EPA. 1978.  In-depth Studies on Health and  Environ-
     mental  Impacts of Selected Water Pollutants.   Contract
     No.  68-01-4646.  U.S. Environmental  Protection Agency.

-------
14c. U.S.  EPA.   1975.   Preliminary Assessment of Suspected
     Carcinogens  in  Drinking Water, and Appendices.  A
     Report  to  Congress,  Washington, D.C.

14d. U.S.  EPA.   1977a.   Determination of Sources of  Selected
     Chemicals  in Waters  and Amounts from These Sources.
     Draft Final  Report.   Contract No.   68-01-3852.  U.S.
     Environmental Protection Agency.

14e. U.S.  EPA.  1978b.   The. National Organic Monitoring  Survey.
     Rep.  (unpublished),  Tech.  Support  Div.,  Off. Water
     Supply, Washington,  D.C.
15.  "Combustion  Formation and  Emission of Trace Species",
     John  B. Edwards, Ann Arbor Science, 1977.

16.  NIOSH Criteria  for Recommended Standard:  Occupational
     Exposure  to  Phosgene,  HEW, PHS, CDC, HIOSH, 1976.

17.  Chemical  and Process Technology Encyclopedia, McGraw
     Hill, 1974.

18.  National  Cancer  Institute.  1977.   Bioassay of  Tetrachloro-
     ethylene  for Possible  Carcinogenicity.   CAS No. 127-18-4
     NCI-CG-TR-13  DHEW Publication No. (N1H) 77-813.

19.  Rowe, V.K.,  et  al.   1952.   Vapor Toxicity of Tetrachloro-
     ethylene  for Laboratory Animals and Human Subjects.  AMA
     Arch. Ind. Hyg.  Occup.  Med.  5:566.

20.  Klaassen,  C.D.,  and  G.L.  Plaa.  1967.   Relative Effects
     of Chlorinated  Hydrocarbons  on Liver and Kidney Function
     in Dogs.   Toxicol.  Appl.  Pharmacol. 10:119.

21.  The U.S. EPA.   Carcinogen  Assessment Groups.  List of Car-
     cinogens.  April 22,  1980.

22.  Alexander, H.,  et  al.   1978.   Toxicity of Perchloroethylene,
     Trichloroethylene,  1,1,1-Trichloroethane, and Methylene
     Chloride  to  Fathead  Minnows.   Bull Environ. Contam. Toxicol.
     20:344.

23.  U.S. EPA.  1979.   Tetrachloroethylene:   Ambient Water
     Quality Criteria (Draft).

24.  Simmon, V.F.  et  al.   1977.  Mutagenic Activity  of Chemicals
     Identified in Drinking  Water.   S.  Scott, et al . , eds . J_n_
     Progress in  Genetic  Toxicology.

25.  National Academy of  Sciences.   1978.  Nonfluorinated
     Halomethanes  in  the  Environment.  Washington, D.C.

-------
26.   National  Cancer Institute.  1977.  Bioassay  of  1,1,1-
     Trichloroethane for Possible Carcinogenic!ty.   Carcinog.
     Tech.  Rep.  Ser. NCI-CG-TR-3 .

27.   U.S.  EPA.   1979.   Chlorinated Ethanes:  Ambient  Water
     Quality Criteria. (Draft)

28.   Nomiyama,  K.,  and H. Nomiyama.  1971.  Metabolism  of
     Trichloroethylene in Human Sex Differences in Urinary  ,
     Excretion  of  Trichloroacetic Acid and Trichloroethanol.
     Int.  Arch.  Arbeitsmed.  28:37.

29.   Bardodej,  A.,  and J. Vyskocil.  1956.  The Problem  of
     Trichloroethylene in Occupational Medicine.  AMA Arch.
     Ind.  Health 13:581.

30.   McBirney,  B.S., 1954.  Trichloroethylene and Dichloro-
     ethylene  Poisoning.  AMA Arch. Ind. Hyg. 10:130.

31.   U.S.  EPA.   1979a.  Carbon Tetrachloride: Ambient Water
     Quality Criteria  Document. (Draft)

32.   Von Oettingen,  W.F.  1964.  The Halogenated  Hydrocarbon
     of  Industrial  and Toxicological Importance.  In  E.
     Browning,  ed.  Elsevier Monographs on Toxic Agents.
     Elsevier  Publishing Company, New York.

33.   National  Academy  of Sciences, National Research  Council.
     1976.   Halocarbons:  Environmental Effects of Chloromethane
     Release.

34.   National  Academy  of Sciences, National Research  Council.
     1979.   Stratospheric Ozone Depletion by Halocarbons:
     Chemistry  and  Transport.

35.   U.S.  EPA  States Regulations Files; January 1980.

36.   U.S.  EPA.   1979.   Trichloroehylene Ambient Waste Quality
     Criteria  Draft.

37.   Dawson, English,  Petty,  1980, "Physical Chemical Properties
     of  Hazardous  Waste Constituents".

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             WASTES  FROM USAGE OF ORGANIC SOLVENTS
I.   LISTING




     The  listed  wastes  are those major streams which result




from usage  of  organic  solvents  and which contain a significant




concentration  of one  or more organic solvents.  The solvents




referred  to include both halogenated and non-halogenated




organic compounds.  The specific wastes listed are presented




b elow.






The spent halogenated  solvents  tetrachloroethylene , methyl




chloride, trichloroethylene,  1,1,1-trichloroethane , chlorobenzene,




1,1,2-trichloro-1,2,2-trifluoroethane,  o-dichlorobenzene, tri-




chlorofluoromethane,  and the  still bottoms from the recovery




of  these  solvents (T);






The spent non-halogenated  solvents xylene, acetone, ethyl




acetate,  ethyl benzene,  ethyl ether, n-butyl alcohol,  cyclo-




hexanone  and the still  bottoms  from  the recovery of these




solvent s  (I);






The spent non-halogeanted  solvents,  cresols and cresylic acid,




nitrobenzene and  the  still bottoms from the recovery of these




solvents  (T);  and






The spent non-halogenated  solvents,  methanol,  toluene,  methyl




ethyl ketone,  methyl isobutyl ketone,  carbon disulfide,




isobutanol,  pyridine and the  still bottoms from the recovery




of  these solvents (I,T).

-------
     Listing codes for the most  widely  used halogenated

organic solvents are presented on  Table 1-1, and codes for

widely-used non-h'alogenat ed organic  solvents are on Table 1-2.


II.  SUMMARY OF BASIS FOR LISTING

     Wastes resulting from usage of  organic solvents typically

contain significant concentrations of  the  solvent.   Examples

of wastes from usage of organic  solvents  include still-bottoms

from solvent recovery and spent  solvents  from dry cleaning

operations and maintenance and repair  shops.

     The Administrator has determined  that  waste from usage

of the 24 organic solvents listed  in Tables 1-1 and 1-2 may

be a solid waste, and as a solid waste, may pose a  substantial

present or potential hazard to human health or the  environment

when improperly transported,  treated,  stored,  disposed of or

otherwise managed, and therefore should be  subject  to appropriate

management requirements under Subtitle  C  of RCRA.  This

conclusion is based on the following considerations*:

     1.   Of the list of 24 solvent  types  presented in Tables
          1-1 and 1-2, each solvent  exhibits one or more
          properties (i.e., ignitability  and/or toxicity)
*The Agency is presently aware that  these  solvents may contain
 concentrations of additional toxic  constituents  listed in
 Appendix VIII of the regulations.   For  purposes  of this
 listing,  however, the Agency is only  listing  those wastes for
 the presence of the halogenated and non-halogenated solvents.
 The Agency expects to study these  listings  further to deter-
 mine whether the waste solvent and  still  bottom  listings
 should  be amended.


                             -X-

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                           TABLE 1-1


       LISTING  CODES  FOR  HALOGENATED ORGANIC SOLVENTS*
                 (in.  order of  usage as solvent)
S olvents
Listing
 Codes
  Flash
Point (°F)
Perchloroethylene

Methylene chloride

Trichloroethylene

1,1,1,-Triehioroethane
Chlorobenzene
1,1,2-Triehloro-l,2,2-
  Trifluoroethane
o-Dichlorobenzene
Trichlorofluoromethane
   T

   T

   T

   T

   T

   T
   T

   T
*A11 data in this table  are  based  on information contained in
 Reference (!)•  Dashes  in place  of  data mean either the values
 were not available  or (in the  case  of flash points) not
 applicable.
                              -v

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                          TABLE  1-2

     LISTING CODES FOR NON-HALOGENATED  ORGANIC SOLVENTS*
                (in order of usage  as  solvent)
Toluene
Acetone
Ethyl acetate

Ethyl benzene

Ethyl ether
Isobutanol
Cyclohexanone
Nitrobenzene
Pyridine




yl ketone

butyl ketone
ulf ide
ate
ene
r
cohol

d cresylic acid
one
ne

Listing
Codes
x**
I,T**
I,T**
I,T**
I**
I>T**
I,T**
x**
x**
x* *
x**
I,T**
T
x* *
T
I,T**
Flash
Point (°F)
84(2)
54
39
22(3)
3
61
-25
45(2)
59
-49(2)
115
82
-
111(3)
—
68
* All data on this table are based  on  information contained in
  Reference (1)  except as noted.  Dashes  in  place of data mean
  either that the values were not available  or (in the case of
  flash  points)  not applicable.
**Because the listed waste would contain  a large percentage of
  these  solvents, the listed wastes  would fail the ignitability
  characteristic for liquids--a flash  point  less than 60 °C
  (140°F).

-------
      which  pose  a potential hazard.  These  solvents
      represent  approximately 95 percent or  more  of
      organic  solvent usage in the United States  (see
      Table  II-l).

2.    The  use  of  organic solvents is widespread throughout
      the  United  States, and the quantities  involved  are
      large;  according to Table II-l the total annual
      usage  of  the  listed materials as solvents is over
      2.8  X  106 kkg.

3.    Of the  twenty-four solvents listed in  Tables I-
      1 and  1-2,  seven are listed for meeting only the
      ignitability  characterisitc.   These seven spent
      solvents  all  have a- flash point below  60°C  (140°F)
      and  are  thus  considered hazardous.

          The  seventeen solvents listed as  either toxic
      or toxic  and  ignitable pose a further hazard to
      human health  and the environment.   If  improperly
      managed,  these  solvents could migrate  from  the
      disposal  site  into ground and surface waters,
      persist  in  the  environment for extended periods
      of time,  and  cause substantial hazard  to environ-
      mental  receptors.

          The  two  fluorocarbons, 1, 1,2-1richloro-1,2 , 2-
      trifluoroethane and trichlorof1uoromethanes present
      a different  type of hazard.  Due to their high
      volatility,  these two organics can rise into the
      stratosphere  and deplete the  ozone, leading to
      adverse health  and environmental effects.

4.    Damage  incidents resulting from the mismanagement of
      waste solvents  have been reported.   These damage
      incidents are  of three types:

      (a)  Fire/explosion damage resulting from ignition
          of  the  so Ivent s;

      (b)  Contamination of wells in the vicinity of in-
          adequate  waste storage or disposal (with re-
          sulting  illness in at least one instance); and

      (c)  Direct entry  of solvent  into  a waterway, resulting
          in fish kills.

5.    These damage  incidents  show that  mismanagement
      occurs and  that  substantial hazard to human health
      and the environment may result therefrom.
                       -53-

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                          Table  II-l
        RANKING AND AMOUNTS  OF  THE  LISTED SOLVENTS^1)
Chemical Name
Amount Used As
Solvent (kkg/yr)
Xylenes
Methanol
Toluene
Perchloroethylene
Methylene chloride
Methyl ethyl ketone
Trichloroethylene
1,1,1-Trichloroethane
Acetone
Methyl isobutyl ketone
Chlorobenzene
Carbon disulfide
Ethyl acetate
Ethyl benzene
Ethyl ether
n-Butyl alcohol
l,l,2-Trichloro-l,2,2-tri-fluoroethane
Isobutanol
o-Dichlorobenzene
Cresols & cresylic a
Cyclohexanone
Nitrobenzene
Trichlorofluoromethane
Pyridine
    489,900
    317,500
    317,500
    255,800
    213,200
    202,300
    188,200
    181,400
     86,200
     78,000
     77,100
     77,100
     69,900
     54,430
     54,430
     45,360
     24,040
     18,600
     11,800
     11,800
      9, 072
      9,072
      9,072
        907
   Consumption amounts for cresol  and  cresylic acid were
   combined.
                             -V

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Ill.  SOURCES  OF  THE WASTE AND TYPICAL DISPOSAL  PRACTICES

      A.    Overall Description of Industry Usage*

           The primary solvent-using industries  and  the quantity

of  solvents  they use annually are as follows:'  '

Paint  &  Allied Products and Industrial          1,153,500 kkg/yr
  Operations

Surface  Cleaning                                  610,600 kkg/yr
       ^
Pesticide  Production                              266,700 kkg/yr

Laundry  and  Dry  Cleaning Operations               214,550 kkg/yr

Pharmaceuticals  Manufacture                         34,740 kkg/yr

Solvent  Recovery Operations (Contract and         499,000 kkg/yr
  in-house)                                          (feedstock)


      Table III-l summarizes the use pattern of  the  10  most

widely used  solvents in the industrial categories listed

above.   These data illustrate the distinct difference  between

halogenated  and  non-halogenated solvents in industrial usage;

the chlorinated  and other halogenated solvents  in Table

III-l  are  used almost exclusively in the surface cleaning,

laundry  and  dry  cleaning categories, whereas the non-halo-

genated  solvents  are used primarily in the production  cate-

gories (paint, pesticides and pharmaceuticals).  The  ten

specific solvents  included  in this table are believed  to

account  for  about  80 percent of all organic solvent usage. (-*-)
*Large amounts  of  chemicals  listed on Table II-l  are  used  in
 such non-solvent  applications as chemical feedstock  so  that
 the total production  of  specific solvent chemicals  for  all
 applications is often many  times larger than the  amount
 used specifically as  a solvent.

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                                Table III-l
     USE DISTRIBUTION OF THE 10 MOST WIDELY USED ORGANIC SOLVENTS
                  (All data in units ©f 103 kkg/yr)
                                                                  05
















Paint & Allied Products
Surface Cleaning
Pesticides
Pharmaceuticals
Laundry & Dry Clean.


TOTAL
Listed Use Level
in Reference (1)












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      The composition of the spent  solvent  is  dependent on its

 application,  but the spent solvent  contains  up to 90 percent

 of  the  original solvent*.  Depending  on  the  recovery techniques,

 sludges  which result from reclamation  processes  contain from 1

 to  50%  of  the original solvent.**   However,  because of the

 economic considerations of the reclaiming  process,  the solvent

 content  of  the sludge is seldom reduced  below 10  percent.***

      B .    Solvent  Usage in Paint &  Allied  Products  and

           Industrial Operations

          The category of Paint & Allied Products  and  Industrial

 Operations  is taken  here to  include the  following  solvent-use

 industrial  operations:

      0    Paint &  Allied Products Manufacture

      0    Roll  Coatings	

      0    Paper Coatings

      0    Dye Manufacture

      0    Ink Manufacture

      0    Adhesive Manufacture

      0    Printing Operations
  *United States  Environmental Protection Agency.  1976.
   Assessment of  Industrial  Hazardous Waste Practices
   Electroplating  and  Metal  Finishing Industries - Job
   Shops  PB-264-349.
** United States  Environmental Protection Agency.  1979.
   Organic Solvent Cleaners-Background Information for
   Proposed Standards.   EPA-45/12 - 78-045 a.
***United States  Environmental Protection Agency.  1978.
   Source Assessment:  Reclaiming  of Waste  Solvents.  State
   of the Art. PB-289-934.

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     The Paint and Allied  Products and Industrial operations

category accounts for about  half  of all organic solvent  utili-

zation by industry.  The Paint  and Allied Products portion

of this category is the largest  solvent-use subcategory, with

printing Operations being  the  second largest use subcategory.

     For the Paint & Allied  Products Industry, there are

about 1200 paint manufacturing  companies that operate more

than 1500 plants.  Solvents  are  important ingredients in

formulations for soIvent-thinned  paints, lacquers, and factory-

applied coatings.

     Solvent containing wastes  arise from the use of solvents

to clean equipment, and still bottoms  from the recovery  of the

solvents used in production*.   It  is estimated^' that approxi-

mately one-third of the ^solvents  used  for equipment cleaning

are reclaimed, and that 7  x  10°  gallons of solvent are

disposed of yearly from this source.

     The total quantity of solvent-containing wastes from

the paint industry is estimated  to contain 14,300 kkg/yr of

solvents.(^) These are primarily  non-halogenated solvents

such as xylenes, methanol, acetone, toluene, MEK, etc.

     The remaining industrial processes included in this over-

all category (manufacture  of inks, adhesives, dyes, and

various types of coatings) utilize organic solvents (primarily

non-halogenated) in much the same  manner as the paint industry;

that  is,  as an important component of  formulations and for
* Additional  waste streams from  these  industrial categories  (such
 as  off-specification product and  spills  of finished product)
 are expected  to be covered by  future listings.

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equipment  cleaning.(1)   Printing operations also  use  sol-




vents  for  cleaning  operations and as dye or pigment  carriers.




The  types  of  waste  generated from these industries  should be




generally  similar  to  those from the paint industry  and  include:




     Equipment  cleaning wastes;




     Still  bottoms  from solvent recovery.






     Spent  solvents used for equipment cleaning,  if not  re-




claimed, are  drummed  and land filled(^).  Most paint companies




contract for  waste  disposal  services.  Solvent recovery  still




bottoms are incinerated, landfilled,  or injected  into deep




walls. (5)




     C.    Surface Cleaning




          The Surface Cleaning  category consists  of two




important  subcategories:




           0     Industrial  Degreasing




           0    Repair work




                  Industrial Maintenance and Repair




               -  Commercial Service  and Repair




                  Consumer-performed  Maintenance  and Repair




     About half  of  the  solvents  used  in Surface Cleaning




Operations, as  shown  in Table III-l,  are used in  Industrial




Degreasing, (see the  Listing Background Document  for Solvent




Degreasing Operations)  with  the  other half being  used in




various types of repair work.(^)   According to Reference




(5), the total number of degreasing operations in the United




States for 1976  was over 1,300,000,  of which nearly half





                              -X-

-------
were associated with manufacturing operations of various




types.  The major solvents  used  are trichloroethylene, 1,1,1-




trichloroethane, and chlorofluorocarbons.   Most of the




solvents used in surface  cleaning  were halogenated, due to




their nonflammable character;  this property is especially




important in high-temperature  degreasing operations.




     Neither surface cleaning  nor  either of its two subcate-




gories can be classified  as industry specific, per se; rather




these operations are conducted  in  a number' of types of indus-




tries (i.e., primary metals,  auto  repair shops, textile




plants) .




     With respect to the  geographic distribution, industrial




degreasing is the most concentrated source of solvent wastes




from the surface cleaning  category since degreasing is asso-




ciated with manufacturing  operations that  involve metal




finishing (including etching,  plating, priming and painting)




and electronic components  manufacture.  The repair




work subcategory is much  more  diffuse in distribution, with




both commercial service and repair and consumer-performed




maintenance and repair being  generally distributed in the




same pattern as the population  itself. (->t)




     The major types of wastes  from solvent usage in the




industrial degreasing subcategory  are used (spent) solvent




and solvent recovery still  bottoms.   Wastes from the repair




work subcategory would include  both halogenated and non-




halogenated solvents, and  would  take the form of relatively

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 small  amounts of used solvent  (typically up to a few  gallons),




 plus  contaminated rags and other  materials.




      D.    Production of Pesticides,  Pharmaceuticals and




           Other Organic Chemicals




           Solvent applications  in  the  production of pesticides,




 Pharmaceuticals and other organic  chemicals include usage  as




 a  reaction (synthesis) medium,  and  usage in equipment cleaning, (




 The  solvents  used are primarily non-halogenated and are




 typically  selected for compatibility  with the  production




 process.   Toluene is the most widely  used solvent in pharma-




 ceuticals  manufacture, methanol is  used  as  the reaction




 solvent  in Nylon 66 production, and  acetone is used as the




 solvent  in the production of cellulose  acetate. ^-^ '




      Wastes  from solvent usage  in  these  industries  take the




 form  of  off-specification product material,  equipment cleaning




 wastes,  and  solvent recovery still  bottoms.  The  destination




 of all solid  wastes is riot known, but  a  large  percentage is




 reclaimed  either in-house or by contract  recovery operations.^'




      Solvent-containing wastes  in  these  industries  are not as




 geographically distributed as in the  other  categories discussed




 herein,  but would be expected to follow  the general geographical




 pattern  of the organic chemical industry.




     E .    Laundry and  Dry Cleaning




           There  are about 25,000 retail  dry cleaning plants




 in the United States,  18,000 of which use between 167,000




 Kkg/yr^7)  and 208,000  kkg/yr^1^ of  perchloroethy lene.  Of  the




other 7000 plants,  6000  use  about 72,700  kkg/yr of  Stoddard's

-------
solvent*,  (which is a petroleum  distillate), and 1000 use  tri-

chlorofluoroethane at a rate  of  about 900 kkg/yr.(7)  The

solvents  are used to remove dirt,  grease and other materials.

It is believed that 8 percent^7)  of  the amount of perchloro-

ethylene  used in dry cleaning  is  disposed of along with still-

bottom and cooker residues, so that  the amount of perchloro-

ethylene  discarded is between  13.4  and 16.6 thousand kkg/yr.

     The  distribution of dry  cleaning plants is uniform with

respect  to population and  is  especially associated with popu-

lation in large urban areas.(7'

     Still bottoms from retail dry  cleaning consist of about

60 percent solvent and 40  percent  oily residue.(7)  "Cooker"**

residues  are 25 percent solvent  and  75 percent spent filter

(mostly diatomaceous earth).(?)

     F .    Solvent Recovery Operations

          Still bottoms from  solvent recovery operations are

the remaining waste streams included in this listing.   Each

of the solvent use industry categories discussed above generates

feedstocks for solvent recovery  operations.   Recovery may be

accomplished either in-house  or  by  contract to a recovery firm.


 *Stoddard solvent is not  specifically included in the waste
  listings,  however,  since this  solvent has a flash point of
  of  105°F (i.e.,  meets the ignitability characteristic),
  it  would also be regulated under  the Subtitle C regulatory
  control  sys tem .

**A "cooker" is a  type of  still  in  which solvent-contaminated
  diatomaceous filter powder is heated to drive off the solvent
  fraction of the  total liquid residue contained in the filter
  powder .

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     With  regard  to contract solvent recovery  operations,


there  are  between 80 and 100 contract solvent  recovery


operations  in  the U.S.(4)   The surface cleaning  category,


and particularly  industrial degreasing operations  is  one of the


largest  sources  of spent solvents sent to contract  reclaimers.


Other  important  sources  of spent solvents are  the  paint,  ink,


and coatings manufacturers and manufacturing processes  where


very pure  solvents are  used in organic synthesis (e.g.,  the


organic  chemical  and pharmaceuticals industries).'°'   Some


contract reclaiming of  solvents is also carried  out on  sol-


vents  from  commercial and  industrial dry cleaning  operations.


The geographic distribution, by state,  of contract  solvent


recovery operations is  presented in Table III-2.


     The volume of feedstock sent to the contract  solvent


recovery industry is approximately 287,000 kkg/yr;   of  this


volume,  about 27  percent are halogenated.(^)


     Although there are  approximately 100 contract  solvent


recovery companies,  the  total number of solvent  recovery


operations  is much larger  due to on-site recovery.   Of  the


total  number of plants  involved in "cleaning operations",


97.89  percent perform on-premises solvent recovery. (8)


     Excluding the dry  cleaning plants,  which are distributed


geographically in  the same pattern as population, the  geographic


distribution of all  solvent recovery operations  is  as  shown


in Table III-3*
                              -1§L-
                              -vv-

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                Table  III-2




GEOGRAPHIC DISTRIBUTION  OF  CONTRACT SOLVENT




           RECOVERY  OPERATIONS^)
New Jersey
California
Ohio
Illinois
Michigan
New York
Indiana
Massachus e 1 1 s
Rhode Island
Maryland
South Carolina
Georg ia
Kent ucky
Tennessee
Mis sour i
Texas
Connecticut
North Carolina
Florida
Kansas
Arizona
9
9
8
8
7
5
4
3
2
2
2
2
2
2
2
2
1
1
1
1
1
74

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                    Table III-3
STATE DISTRIBUTION CF SOLVENT RECLAIMING OPERATIONS
State
Alabama
Arizona
Arkansas
California
Colorado
Connect icut
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Mich igan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
Soudi Carolina
Tennessee
Number
of Plants
72
37
39
424
44
60
12
141
98
14
224
113
59
49
70
83
19
83
85
178
76
45
98
15
30
10
13
153
21
372
105
13
213
56
40
245
21
55
83
Percent
of Total
1.8
0.94
0.99
10.
0.16
1.5
0.35
3.5
2.4
0.4
5.5
2.8
1.4
1.2
1.7
2.0
0.5
2.0
2.0
4.3
1.8
1.1
2.3
0.41
0.77
0.29
0.38
3.7
0.57
8.9
2.5
0.37
5.1
1.3
1.1
5.9
0.57
1.3
2.0
                        -X-

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                  Table  III-3  (cont'ci)
                      Number         Percent
      State          of Plants       of Total
Texas                   242             5.8
Utah                     21             0.56
Vemont                  8             0.24
Virginia                 97             2.3
Washington               72             1.7
West Virginia            41             0.99
Wisconsin                90             2.2
Wyoming                 	6_             0.14

        Total         4,158           100
                         -X-
                         -Y7-

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     Solvent  recovery  still bottoms (sludges)  from  contract

reclaiming  operations  amount to about 73,900 kkg/yr,  of which

between 5 and  50  percent is solvent, or an average  solvent

content of  about  25  percent.(*)  About 27 percent of  the

solvents in still-bottom sludges are halogenated.'4'   Thus,

the total still bottom waste from contract reclaiming  consists

of the following  components:

     18,250 kkg/yr  solvent,  including 13,320 kkg/yr non-

        halogenated  and 4,930  kkg/yr halogenated;

     54,750 kkg/yr  nonsolvent  contaminant, including  oils, waxes,

        metals and  chlorinated and nonehlorinated organics.

     The estimate of 25 percent average solvent content, as

presented above,  can probably  be applied to solvent recovery

still bottoms  for all  of the industries discussed herein,

since the technology used  to reclaim solvents  is roughly

similar throughout  U.S.  industry. (8)

Waste Management Practices*

     The most  widely used  management practices for  spent
*The Agency has concluded  that  it does have jurisdiction
 under Subtitle C of RCRA  to  regulate waste materials  that
 are used, reused, recycled  or  reclaimed.  Furthermore,  it
 has reasoned that such materials do not become less hazard-
 ous to human health or the  environment because they are
 intended to be used, reused, recycled or reclaimed in  lieu
 of being discarded.  Therefore,  at this time, applicable
 requirements of Parts 262 through 265 and 122 will apply
 to the accumulation, storage and transportation of hazardous
 wastes that are used, reused,  recycled or reclaimed.   The
 Agency believes this regulatory  coverage is appropriate to
 the subject wastes.  These  spent solvents and still bottoms
 from the recovery of these  solvents are hazardous in  so far
 as they are being accumulated  or stored in drums or tanks
 prior to recycling.  Therefore,  these wastes will be  con-
 sidered as hazardous whether recycled or disposed.  However,
 at the present time, the  management of these wastes during
 recycling operations will not  be regulated.

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solvents  is  either  recovery/reclamation  (either  on-site




or by  contract  recovery operations), land  disposal (which




may include  anything  from open ground dumping  to  landfilling),




or incineration.  For still bottoms, about  8()(8)  to 86^)




percent  of these  bottoms from contract solvent reclaimers




are incinerated.   Still bottom sludges from both  contract




reclaimers and  from solvent recovery operations  performed




by solvent-using  industries, if not incinerated,  are either




landfilled or  injected into deep wells.(8>5)   Land disposal




of st'ill  bottom sludges from contract reclaimers  is mostly




in landfills  that are covered daily.(^  A  small  amount




of sludge is  used as  asphalt extender (about 0.1  percent). (^)

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IV.  References  to Section III

1.   Lee,  B.  B.,  G.  E.  Wilkins and E. M. Nichols,  "Organic
     Solvent  Use  Study", Final Report, Contract  68-03-2776,
     Work  Effort  1.   Prepared for EPA by Radian  Corporation,
     Austin,  Texas (October, 1979).

2,   Wildholz, M.  (ed.), The Merck Index, 9th Edition.   Merck
     and Company,  Rahway,  New Jersey (1976).

3.   Sax,  N.  I.,  Dangerous Properties of Industrial  Materials,
     Reinhold  Publishing Company, New York, New  York.  (1963).

4.   Scofield, F.,  J.  Levin,  G.  Beeland and T. Laird,  "Assess-
     ment  of  Industrial  Hazardous Waste Practices, Paint  &
     Allied Products  Industry,  Contract Solvent  Reclaiming
     Operations,  and  Factory Application of Coatings."  Pre-
     pared  for EPA by WAPORA,  Inc.,  Washington,  D.C.,  as
     Final  Report,  Contract 68-01-2656.

5.   WAPORA,  Inc.,  "Assessment  of Industrial Hazardous Waste
     Practices -  Special Machinery Manufacturing Industries"
     NTIS  PB-262-981  (March,  1977).

6.   Goodwin, D. R., and D.  G.  Hawkins,  "Organic Solvent
     Cleaners - Background  Information  for  Proposed  Standards".
     EPA-450/2-78-045a.   (October, 1979).

7.   International Fabricare  Institute,  Silver Spring, Maryland.
     Personal communication with  B.  Fisher  (December, 1979).

8.   Monsanto Research Corp.,  "Source Assessment Reclaiming
     of Waste Solvents."   NTIS  PB-282-934 (April, 1978).

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IV.  HAZARDS POSED BY THE WASTES




     A.    Hazardous Properties  of the Solvents




     The major halogenated  solvents exhibit organic  toxic




properties which make them  potentially hazardous  to  human




health and the environment.   In particular, the two  halo-




genated  solvents, perchloroethy 1ene and trichloroethy 1ene




are on CAG's List of Carcinogens.  1,1,1-trichloroethane was




determined to be an animal  carcinogen.  All of the listed




halogenated organic solvents,  except 1,1,2-trich loro- 1, 2 , 2-




crifluoroethane , are priority  pollutants under Section  307(a)




of the C.W.A.




     A number of the non-halogenated organic solvents  also




exhibit  toxicity properties.   Nitrobenzene has been  identi-




fied as  a suspected carcinogen.   These compounds  are  toxic




via one  or more of the  exposure routes inhalation, inges-




tion and/or through the skin.   Short term human exposure




to these compounds can  have  numerous adverse effects.   (For




more information on the adverse health effects of these




halogenated and non-halogenated solvents, see Health  and




Environmental Effects,  pp. 38-46).   In addition,  almost  all




of these non-halogenated solvents also present an ignitability




hazard .




     In  light of the health hazards associated with  the  waste

-------
solvents--particularly those which are genetically  active--




and  the  high  concentrations of hazardous solvents contained




in the  waste,  the  Agency believes a decision not  to  list




these waste  solvents  as  hazardous would be warranted  only if




the  Administrator  were convinced that waste solvents  could not




migrate  and  persist,  reaching human or environmental  receptors




(if  improperly managed).  Such assurance does not appear




possible.  Not only  do all of the waste solvents have




significant  potential for migration,  mobility, and  persistence,




but  many have  been  implicated in actual damage incidents as




well.   The Administrator thus believes the hazardous  waste




listing  to be  warranted.




     In  addition,  almost all non-halogenated solvents  also




present  an ignitability  hazard.   According to Table 1-2,




the  eleven most-used  non-halogenated  organic solvents  exhibit




flash points of  115°F or below,  and are thus well below  the




limit set for  defining an ignitable waste under RCRA  §261.21




(flash point below 140°F);  therefore,  these spent solvents




and  the  still  bottoms from the recovery of these solvents  are




defined as hazardous.




     Based on  the  information in Section III,  most of  the




wastes from usage  of  organic solvents  are landfilled  or  incin-




erated.  Smaller amounts of  these solvent wastes are  either




placed on open land  (or  dumps),  into  storm sewers, and into




deep  wells.  Mismanagement and improper disposal of these
                              -X-

-------
wastes  by  any of these methods  could result in a substantial




health  and environmental hazard.




     Actual damage incidents  (see  pp.  33-35) involving  certain




of these listed wastes confirm  the dangers of ignitability,




and of  leaching of waste constituents  from landfills to




groundwater.   Improper waste  incineration could also lead  to




substantial hazard.  Thus,  inadequate  incineration conditions




(temperature  and residence  time)  can result in emission  of




solvents or toxic degradation products.   Where a chlorinat.ed




solvent is involved, emissions  could be  more dangerous  than




the waste  itself.  For example,  phosgene is a partially




combusted  chlorinated organic (halogenated solvent) which  is




produced by the decomposition or  combustion of chlorinated




organics by heat . ^ •*• a > ^ " » ^c '   Phosgene  has been




used as a  chemical warfare  agent  and is  recognized as  extremely




toxic .




B.   Migratory Potential and  Persistence of Halogenated  And




     Non-Halogenated Solvents




     The following section  of the  document discusses the




migratory  potential mobility, and  persistence of the individual




waste solvents.  In general,  all  of  these solvents appear  •




capable of sufficient migration,  mobility and persistence  to




create  a substantial hazard should waste management occur.




     Environmental fate data  showing the potential for  release




°f the  individual halogenated and  non-halogenated solvents  is

-------
                                                         U-34-01
described  below and  summarized in Table IV-1  and  Table IV-2.




Perchloroethylene




     Perchloroethylene,  if not properly disposed  of,  may




migrate  from  the waste  into the environment via both  air and




groundwater  exposure pathways.




     Having  been detected in several sites away from  the




disposal area (i.e., found in varying amounts in  school




basement air,  in basement sumps,  and on solid surface samples




at  the  Love  Canal  site),  perchloroethylene has indeed been




demonstrated  to be quite  mobile and persistent.^




Methylene  Chloride




     Methylene chloride,  if not properly managed,  may migrate




from the waste into  the  environment.  It is extremely water-




soluble  (20,000 mg/1),  thus could leach into groundwater




and persist  there  due to  its stability.10  It is  also very




volatile (350  mm Hg  at  20°C) and  could present an  air pollu-




tion problem  because of  its high  evaporation rate  (1.8  times




the rate of ether)  and  its stability in air and light.10




Trichloroethylene




     Trichloroethylene,  if not properly managed,  may  migrate




from the disposal  site  into the environment via air and




groundwater pathways.   First,  it  is volatile (77  mg Hg  at




20°C,  141.04  mm  Hg at 40°C8),  so  it may be released from




the waste  into  the air;  it has been detected in school  and




basement air  at  the  Love  Canal site.9

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                                      TABLE IV-1
                                 Halogenated Solvents*
Compound
P erchloroethy lene
Methylene chloride
Trichloroethylene
1,1, 1-Trichloroethane
Chlorobenzene
1,1,2-Trichloro-
1,2 ,2-Trif luoroethane
1,2-Dichlorobenzene
Tr ichlor of luorome thane
Vapor Pressure
(mm Hg)
19 at 25 °C5
350 at 20 °C
77 at 25°C5
100 at 20 °C
10 at 22 °C
270 at 20°C
1.56 at 25°C5
687 at 20 °C11
Solubility in
Water (mg/1)
150 at 25 °5
20,000 at 25°5
1,000 at 20°5
950 at 25 °C
488 at 25 °C
10 at 25°C
145 at 25 °C
1,100 at 25 o11
Octanol/Water
Partition
Coefficient
3392
20 |
1952
158
690
100
24002
3392
* Table compiled from data given in "Physical Chemical Properties of Hazardous Waste
  Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
                                      -5-T-

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                                   Table IV-2
                           Non-Halogenated Solvents'
Compound
Methanol
Toluene
Methyl ethyl ketone      I

                         I

Methyl isobutyl ketone   |
Carbon disulfide
Isobutanol
Cresols and  cresylic


  acid ortho  (1,2)
  meta
  para  (1,4)
 Nitrobenzene
 Pyridine
                   Vapor Pressure

                     (mm Hg)	


                   100 at 21.2°C


                   28.4 at 25°C


                   100 at 25°C


                   16 at 20°C


                   260 at 20°C


                   10 at 25 °C


                   0.24 at 25°C1:L






                   0.04 at 200C1:L


                   0.11 at 250C1;L


                   1  at 44.4°C


                   20 at 25°C
   Solubility

    in Water


  Miscible         I


  470 at 25°C


[1000,000 at 25°C


I  19,000 at 25°C


  2,200 at 25°C


|  95,000 at 18°C
                                                                   Octanol/Water

                                                                Partition Coefficient
131,000 at 40°C1:L  1



I                   !
|  23,500 at 20°C1:L I
I
|  24,000 at 40°C1:L
I
|   1,900 at 25°C   i
I
I   Miscible
117


1


1


100


8


HO2
102'


982


62


5
  Waste
   piled from data given in "Physical Chemical Properties of Hazardous

Constituents" (U.S. EPA, 1980) unless otherwise specified by superscript.
        com

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     It is also relatively water-soluble (1,000 mg/1),  so




 that it may leach  into  groundwaters if not adequately  contained




 Trichloroethylene  has  been detected in a number of  wells and




 residue ponds near  groundwater contaminated by a chemical




 company dump, as well  as  in basement sumps at the Love  Canal




 site, confirming its miblity and persistence in groundwater.^




 1,1,1-Trichloroethane




     1,1 ,1-Trichloroethane is a highly mobile compound, and




 if not properly managed,  could migrate from wastes  into




 the  environment.   It is highly volatile (100 mm Hg  at  20;




 approximately 210  mm Hg at 40°C),  so that it may be released




 from waste sites into  the air.  Once in the air, it will




 only decompose at  elevated temperatures.   Because of this,




 and  the fact that  1,1,1-trichloroethane is reactive to  sunlight




 at high altitudes,  while  stable at low altitudes, it may




 create air-pollution problems if disposed of inadequately.^




 It has been detected in school and basement air at  the  Love




 Canal site.9




     1,1,1-trichloroethane is also quite  water-soluble  and




 mobile,  particularly where soils are low  inorganic  content




 It is also relatively  persistent in groundwater where  it




 reacts slowly, releasing  hydrochloric acid.^




 Chlorobenzene




     Chlorobenzene may  migrate from the disposal site  into




 the environment if disposed  of inadequately.   It is soluble




in water (488 nig/1) such  that it may leach into groundwater




where it  would persist  since  it is unamenable to hydrolyza-

-------
tion.10  Chlorobenzene  is  also  volatile so it could  be




released from wastes into  the  air.1-0   It has been  detected




in  school and basement  air,  basement sumps, and  solid  surface




samples  at the Love Canal  site.^   Because it does not  biodegrade




well,  chlorobenzene is  very  persistent in the environment.




1,1,2-Trichloro-l, 2,2-trifluoroethane/Trichlorofluoromethane




      These two solvents,  if  improperly managed,  can migrate from




the  disposal site into  the environment.   The are  extremely




volatile ( 1 , 1 ,2-Trichloro-1,2,2-trifluoroethane,  270 mm Hg at




20°C,  to over 500 mm Hg at 40°C;i0 trich1 orfluoromethane,




687  mm Hg at 20°C') and very  persistent  in the  environment




due  to resistance to biodegradation, photodecomposition,  and




chemical degradation.^  Because  of their high volatility,  after




release  at the surface  of  the  earth, these solvents rise to




the  stratosphere where  they  may  release  chlorine  atoms  and




deplete  the ozone.  This can  lead  to various adverse health




and  environmental effects  including an increase  in  the  amount




of ultraviolet radiation reaching  the earth, as well as




possible changes in the earth's  climate  induced by  the  "green-




house  effect" . 3 > 4




o -  Dich lorobenzene




      o - Dich lorobenzene,  if  disposed of improperly, may




migrate  from the disposal  site  into the  environment by  both




air  and  water pathways.  Having  been detected at  several




sites  away from the disposal  area  (found in school  and  base-




ment:  air,  in basement sumps,  and  in solid surface samples  at

-------
 the Love Canal  site),  o-dichlorobenzene  have  been demonstrated




 to be mobile  and  persistent.9




     o-Dichlorobenzenes has a very high  octano1/water par-




 tition coefficient  of  2,400, indicating  a  high  bioaccurau1 ation




 potential.  Thus, migration, even in small  concentrations,




 could lead to  a  chronic toxicity hazard  (Appendix A).




 Methano1




     Methanol,  if improperly managed,  can  migrate from the




 disposal site  into  the environment.  It  is  miscible




 (1,000,000 mg/1)  and mobile in soils,  so that  it  may




 leach into groundwater^0.   While biodegradable,  it  would




 persist in the  abiotic environment of  most  aqui f er s . ^




     Methanol  is  also  highly volatile  (100  mm Hg  at  21.2°C)




 so it may migrate via  an air exposure  pathway.   Since, it is




 eliminated slowly from the body, methanol  could  bioaccumu1 ate




 causing numerous  adverse health effects  from  prolonged and/or




 repeated exposure.°




 Toluene




     Toluene,  if  improperly managed,  may migrate  from the




 the disposal  site into the environment.  It is  relatively




volatile (vapor pressure 28 mm Hg at  20°C)  and  so can migrate




via and air pathway.   It is photochemically degraded, but




it can  re-enter the hydrosphere in rain.12  Toluene  is also




capable of migration via a groundwater pathway  since it




is relatively soluble,  and persistent  in abiotic  environments




(such  as  most aquifers).

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     Toluene  has  been detected in school  and  basement air,




basement  sumps,  and solid surface samples  at  the  Love Canal




site, demonstrating its mobility and persistence  in both air




and groundwater.9




Methyl Ethyl  Ketone




     Methyl  ethyl ketone, if disposed  of  inadequately may




migrate  from  the  disposal site into the environment.   It is




very soluble  in  water (100,000 mg/1),  such that  it  could




leach into groundwaters.   It is also very  volatile  (185.4 mm




Hg at 40°c8),  and could present an air pollution  problem




if improperly  contained.




     Methyl  ethyl ketone  has been detected at  several sites




near groundwater  contaminated by an old chemical  company




dump, as  well  as  in school and basement air at  the  Love Canal




site, demonstrating both  its mobility  and  persistence."




Methyl Isobutyl Ketone




     Methyl  isobutyl ketone, if improperly managed,  may




migrate  from  the  disposal site into the environment  through




water and air  pathways.  It is very soluble in water  (19,000




mg/1), and mobile in most soils, so that  it could leach into




the ground water  and persist due to its nonreactivity with




water.10




     It  is also volatile  (vapor pressure  of 16 mm Hg  at 20°C and




known toxicity),  so it could pose an air  pollution  problem if im-




properly  contained.  Methyl isobutyl ketone biodegrades slowly, °




and is demonstrated to be mobile as well  as persistent, having

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 been detected at  the  Love Canal site.°




 Carbon Bisulfide




     Carbon disulfide,  if improperly managed,  may migrate




 from the disposal  site  into  the environment.   It  is extremely




 volatile (260 mm  Hg at  20°C)   and althouth  subject to photo-




 lysis, could present  an air  pollution problem  if  inadequately




 contained.  It is  also  quite  soluble in water  (2200 mg/1),




 and is not known  to attenuate in soils; therefore it could




 leach into the groundwater,  where, being unamenable to hydro-




 lysis, it is likely to  persist for an extended  time period. -^




 Isobutanol




     Isobutanol,  if improperly managed, may migrate from




 the disposal site  into  the environment.  It is  extremely




 water-soluble (95,000 mg/1);  thus, if inadequately contained,




 it may contaminate surface water and adversely  affect its self-




 purification ability.^-0  In  addition, isobutanol  could leach




 into groundwater  if disposal  is inadequate.




 Cresols (and cresylic acid)




     Cresols, if  improperly  managed, may migrate  from the




 disposal site into the  environment.   Cresols are  highly




 soluble (23,500 to 31,000 mg/1) and are not known to attenuate




 significantly in  soils;  thus, they could leach  into groundwater




 if disposal is inadequate.  Once in water, cresols rapidly




 form chlorinated  compounds,  which are more environmentally




objectionable .-^   Cresols are not known to hydrolyze and so




would  be likely to persist in groundwater.^^

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Ni trobenzene




      Nitrobenzene, if disposed  of  inadequately, may migrate




from  the  disposal site into the  environment.   It is water-




soluble  (1900 mg/1) and would be mobile  where soil organic




content  is  low,10 an£i thus could leach  into groundwater if




disposal  is not  adequate.  It is likely  to  be highly per-




sistent  in  groundwater since it is  not  amenable to hydro-




lization  and does not biodegrade well.  ^




Pyridine




      Pyridine,  if disposed of inadequately,  may migrate from




the disposal site.  Because pyridine  is  miscible with water,




it has high migratory potential.   It  would  be mobile as well,




unless soil has  high clay content.^-®  Pyridene also would be




likely to persist in the abiotic environment  of most ground-




wat e r s .




C.    Mismanagement of Wastes Destined for Land Disposal




      Documented  damage incidents resulting  from the mis-




management  of these wastes from usage of organic solvents




are presented below:




Damage Resulting from Ignitability  of Wastes




(1)   A load of used pesticide containers delivered to a




      disposal site in Fresno County,  California, also con-




      tained several drums of an acetone-methanol solvent




     mixture. When the load was compacted  by a bulldozer,




      the waste ignited,  engulfing  the bulldozer in flames




     and dispersed pesticide wastes, v

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(2)  A  large  number of drums containing  organic solvent wastes




    were  deposited in a landfill at  Contra  Costa,  California.




    In the  immediate area were leaking  containers  of concen-




    trated  mineral acids and several bags  of  beryllium wastes




    in dust  form.   The operators failed  to  cover the wastes




    at the  end  of  the day.  The combination of wastes ignited




    during  the  night, starting a large  chemical fire which




    possible dispersed hazardous beryllium  oxide. (^3)




(3)  Two  serious  fires at the Merl-Milam  Landfill,  St. Clare




    County,  Illinois (August, 1973 and  April,  1974)  were




    attributed  to  the presence of  solvent  wastes from plastics



    manufacture.(13)




Contamination of  Groundwaters




(1)  In two  separate instances in Michigan,  trichloroethyl ene




    was  dumped  on  the ground and later  found  to have migrated




    into  groundwater.  In one case,  trichloroethylene dumped




    at a  rate of 1000 gallons per  year  over a  four-year




    period  was  detected in residential  wells  as much as




    1100  feet from the site of dumping.  Concentrations




    ranged  as high as 28 ppm.^1^)




          In  the  other case, the Air  Force  at  a base  near




    Oscoda,  Michigan, had problems with  contaminated




    groundwater  because of a leaking tank  used to  hold




    trichloroethylene.  The problem  was  compounded  when




    a  waste  hauler apparently mismanaged the  trichloro-




    ethylene  that  was hauled from  the leaking  tank,  and




    groundwater  contamination up to  four miles away  was

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      considered one of the results, v 11 '




(2)   A  sump  overflow in 1971 at  the  Superior Tube Company




      allowed  trichloroethylene wastes  to  leak into a cooling




      pond.   Seepage from this pond was  found to contaminate




      a  private  well 75 yards distant  and  a company well  at




      the  s ite . (13 ^




(3)   Open  dumping  of wastes, including  solvent wastes, from




      a  chemical packing plant by U.S. Aviex Company resulted




      in entry  of organic solvents into  the water table and




      contamination of several nearby water wells in 1973.




      One  family reported illness resulting from use of the




      contaminated  well water. '^3 )




      The  damage incidents  presented  above  illustrate the




following  potential hazards  associated with wastes from usage




of organic solvents:




(1)   Ignitability  hazard during mismanagement;




(2)   Potential  toxicity hazard  to humans via groundwater




      exposure  pathways.

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IV•   References to Section  IV  (A,  B and C)

1.   Jacobs,  S.  1957.  The  handbook of solvents.  D. Van
     Nostrand Company, Inc., New York.

la.   Combustion Formulation  and  Emission of Traces Species",
     John B.  Edwards, Ann Arbor  Science, 1977.

lb«   NIOSH Criteria for a Recommended Standard; Occupational
     Exposure to Phosgene,  HEW,  PHS,  CDC,  NIOSH, 1976.

lc.   Chemical and Process Technology Encyclopedia, McGraw
     Hill, 1974.

2.   Leo, A., C. Hansch, and D.  Elkins.  1971  (Updated 1977).
     Partition coefficients  and  their uses.  Chem. Rev. 71:
     525-616.

3.   National Academy of Sciences,  National Research Council.
     1976.  Halocarbons: Environmental Effects of Chloro-
     methane Release.

4.   National Academy of Sciences,  National Research Council.
     1979.  Stratospheric Ozone  Depletion  by Halocarbons:
     Chemistry and Transport.

5.   Patty,  F. A., Editor.   1963.   Industrial hygiene and
     toxicology.  Interscience Publishers, New York.

6.   Sax, N.  I.  Dangerous  Properties of Industrial Material,
     Fifth Edition.  Van Nostrand  Reinhold Company, New York,
     1979.

7.   U.S. EPA.  1975.  Environmental Hazard Assessment of
     One- and Two-Carbon Fluorocarbons.   EPA-560/2-75-003.

8.   U.S. EPA.  1980.  Evaluation  of treatment, storage, and
     disposal techniques for ignitable,  volatile, and reactive
     wastes.   Contract Number 68-01-5160.   (Draft final report)

9.   "Love Canal Public Health Bomb",  A Special Report to the
     Governor and Legislature, New  York State Department of
     Health  (1978).

10.   U.S. EPA.  1980  Physical Chemical Properties of Hazardous
     Waste Constituents.  (Prepared by Southeast Environmental
     Research Laboratory;  Jim Falco,  Project Officer).

11.   Verschueren,  K.  1977.  Handbook of Environmental Data on
     Organic  Chemicals.  Van Nostrand Reinhold Company, New
     York.

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12.  Walker, P.   1976,   Air  pollution assessment of toluene.
     MTR-7215.  Mitre  Corp.  McLean,  Virginia.

13.  U.S. EPA Office  of  Solid  Waste  Division, Hazardous  Waste
     Incidents, Open  File,  1978.

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 D.   Health and Environmental Effects*

 Perchloroethylene  (Tetrachloroethylene)

     Perchloroethylene  (PCE)  was reported  carcinogenic to

 mice. (•'•6)  It has  also  been identified by  the  Agency  as a

 chemical which has  demonstrated substantial  evidence  of being

 carcinogenic.  PCE  is  chronically toxic to rats  and mice, causing

 kidney and liver d amage ; (^ > ^ > 2 1) ancj to  humans,  causing impaired

 liver function.(^'   Subjective central nervous  system complaints

 were noted in workers  occupationa1 ly exposed to  PCE.(^'   PCE

 exposure is reported  to cause alcohol intolerance  to  humans.

 PCE  is also reported  to be  acutely toxic in  varying degrees

 to several fresh-  and  salt-water organisms,  and  chronically

 toxic to some saltwater organisms. (28 , 32 ) (Appendix A)

     PCE is a priority  pollutant under Section  307(a)  of  the

 Clean Water Act .

 Methylene Chloride  ( Dichloromethane )

     Methylene chloride was reported as being  mutagenic to  a

 bacterial strain,  S.  typhimurium.(^)  It  was  also reported  to

 be feto- or embryo-toxic  to rats and mice.(23)   Female workers

 had gynecological problems  after prolonged exposure to methylene

 chloride.(36;  Methylene  chloride is acutely toxic, causing

 central nervous system  depression and elevation  of carboxy-

 hemoglobin levels.  (18)   Severe contamination of  food  or water

 can cause irreversible  renal  and hepatic injury.(30;   Acute

 toxicity values  range  from  147,000 to 310,000  mg/1 for aquatic
*Ethyl  benzene, which  is  only  being listed for  its  ignitability
hazard,  is also considered  a  priority pollutant  under  Section
307(a)  of the Clean Water Act.

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organisms  (Appendix A)




Trichloroethylene




     Trichloroethylene (TCE) has been  reported to be carcino-




genic  to mice.(15)   It has been identified  by the Agency as  a




chemical which  has  demonstrated substantial evidence of




being  carcinogenic.(38) Industrial exposure to TCE caused




some cases  of central nervous system disturbances (headaches,




insomnia,  tremors)  as well as peripheral  nervous  system




impairment  (neuritis, temporary loss of  tactile sense,  finger




paralysis). ( ^> -^ )   Rare cases of hepatic  damage have been reported




following  repeated  abuse of TCE.(6)




     TCE was  also  found to be acutely  toxic in varying  degrees




to several  freshwater o rgani sms; (*• °' there  was a  50% decrease




noted  in -^ C  uptake  by a salt-water algae at  a concentration




of 8,000 mg/1.(2°)(Appendix A)




1,1, 1-Trichloroethane (Methyl Chloroform)




     1,1 , 1-Trichloroethane has  been determined to be carcino-




genic  to all  tested  animals.'^-')   It was  found to cause several




central  nervous  system disorders (changes in  rection time,




perceptual  speed, manual dexterity, and  equilibrium) in




humans, and,  in  animal studies,(34) was  found  to  produce




toxic  effects in  the  central nervous system,  cardiovascular




system, pulmonary  system,  and to induce  liver  and kidney




damage in  tested  animals.   1,1 , 1-Trichloroethane  was reported




acutely toxic in  varying degrees to some  freshwater fish and




some marine organisms.(28,34)(Appendix A)

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     1,1,1-Trichloroethane is a priority  pollutant under




 Section 307(a) of  the  Clean Water Act.




 Chlorobenzene  (Monochlorobenzene, MCB)




     Ch lorobenzene  has been found to  produce  histopatho logica 1




 changes in lungs,  liver,  and kidneys  following  its inhalation




 by rats, rabbits  and  guinea pigs.'?'  Oral  administration of




 raonoch lor obenzene  to  rats  was reported  to  cause  growth retar'-




 dation in males.(11)   >*CB  also appears  to  increase the activity




 of some microsomal  enzyme  systems, which  enhances  the metabolism




 of many drugs, pesticides, and other  xenobiotics.^9;(Appendix A)




     MCB was reported  to  be toxic to  varying  degrees  to




 several fresh- and  salt-water organisms,  including algae.'28;




     MCB is a  priority -pollutant under  Section  307(a) of the




 Clean Water Act.




 1,1,2 Trichloro-l,2,2  trif1uoroethane (Trif 1 uorotri-ch 1 oroethane)




     The Agency's  primary  concern in  listing  this  solvent is




 the air pollution  hazard  resulting from its release  at the




 surface of the earth.   This can have  many  adverse  health and




 environmental  effects  including skin  cancer resulting from




 the depletion  of  the  ozone. ( 39 , 40 )




JD2-Dichlorobenzene (ortho isomer)




     Ortho 1,2-Dichlorobenzene exhibits moderate  toxicity via




inhalation and oral routes.  The major  toxico logica 1  effect




is injury to the  liver and kidneys;  it  can  also  act  as a




central  nervous system depressant after short periods of




exposure.(19,22)(Appendix  A)

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      1,2-dichlorobenzene is designated  a  priority  pollutant




under  section  307(a)  of the Clean Water Act.




Trichlorofluorom ethane




      The Agency's  primary concern in listing  this  solvent is




the air pollution  hazard resulting from its release  at the




surface of  the  earth.   This can have many  adverse  health and




environmental  effects  including skin cancer resulting from




the depletion  of  the  ozone.(39»^'  However,  additional




adverse health  effects have been found  and are  presented




b elow.




      Exposure  of  rabbits to trichlorofluoromethane was reported




to cause cardiac  arrhythmias in all rabbits exposed. (26)  jt




induced cardiac  arrhythmias, sensitized the heart  to  epine-




phrine-induced  arrhythmias, and caused  tachycardia (increased




heart  rate) myocardial depression, and  hypertension  in the




monkey, dog, rat  and  mouse.'26;




      Trichlorofluoromethane is a priority  pollutant  under




Section 307(a)  of  the  Clean Water Act.




Methanol (Methyl  Alcohol)




      The main  toxic  effects resulting from methanol  exposure




to humans are  exerted  upon the nervous  system,  particularly




the optic nerves  and  the retinae.  Upon ingestion  and/or




inhalation  followed  by absorption from  the gastrointestinal




and respiratory  tracts, methanol is slowly elimated.   Because




of this, methanol  should be regarded as a  cumulative  poison.




Though  single  exposures to fumes may cause no harmful effect,




daily  exposure  may result  in accumulation  of  methanol to

-------
cause illness  including intoxication, headache,  weakness,




apathy and convulsions.   Severe exposures may  cause dizziness,




unconsciousness,  cardiac depression, permanent  blindness and




eventual death.^>^2'(Appendix A)




Toluene




     Toluene  is  a  toxic chemical absorbed into  the  body by




inhalation, ingestine,  and through the skin.  The  acute toxic




effect in humans  is  excessive depression of  the  central




nervous system,(45)  and this occurs at low concentrations




[200 ppm].^"'    Chronic occupational exposure  to  toluene




has led to the  development of neuro-muscu1ar disorders.




Occupational  exposure  to female workers to toluene  reported




to cause several  reproductive problems, both to  the woman




and the offspring. ' 25;




     Since toluene  is  metabolized in the body by  a  protective




enzyme system which  is  also involved in the  elimination of




other toxins,  it  appears that over-loading the metabolic




pathways with  toluene  will greatly reduce the clearance of




other more toxic  chemicals.   Additionally, the high affinity




of toluene for  fatty  tissue can assist in the absorption of




other toxic chemicals  into the body.   Thus,  synergistic




effects of toluene  on  the  toxicities  of other contaminants




may render the waste  stream more hazardous (Appendix A).




     Toluene is a priority pollutant  under Section  307(a) of




the Clean  Water Act.

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Methyl Ethyl Ketone


     Methyl  ethyl  ketone is a highly volatile  liquid  whose


chief effect is  narcosis;  it is also a strong  irritant  of the


aiucous membranes  of the eyes and nose.  Additionally,  lethal


doses in animals  (LC50  - 700 ppm) has caused marked  congestion


of the internal  organs  and slight congestion of  the  brains.


Lungs also showed  emphysema (Appendix A).


Methyl Isobutyl  Ketone

     In a  study(^l)  reported on 19 employees who  worked with


methyl isobutyl  ketone  for 20-30 minutes daily during  an 8-


hour shift,  Linari  et.  al . concluded that methyl  isobuty


ketone irritates  the conjuctive and respiratory  tract  and


produces disturbances  of the gastrointestinal  tract  and


central nervous  system.  Other reported effects  due  to  exposure


include weakness,  loss  of  appetite, headache,  eye  irritation,


stomach ache, nausea,  vomitting, and sore throat.


     Further, Linari et. al.^^-) found skin lesions  in  3 of


the 19 workers  exposed  to  methyl isobutyl ketone  at  80-500 ppm


for 20-30  minutes  daily.  Evidence also suggests  that  ketones


in liquid  form  may  cause dermatitis (Appendix  A).


     All of  the  ketones except methyl isomyl ketone  have been


reported to  produce irritation of the eye, nose,  or  throat. (42)


Carbon Bisulfide


     Short term  human  exposure to low atmospheric  concentrations


of carbon  disulfide may result in central nervous  system


depression, headaches,  breathing difficulty and  ga s t r o in t e s t i-
                               /"S -1 _
                                /«*

-------
nal disturbances.   Exposure to short term  but  high atmospheric




concentrations  can  lead  to narcosis and  death.   The symptoms




of humans subjected  to  repeated exposure to  high concentrations




or prolonged exposure  to low concentrations  include insomnia,




fatigue, loss of memory, headache, melancholia,  vertigo and




loss of appetite.   Visual impairment,  loss of  reflexes, and




lung irritation has  been reported . ^ •*•'»^^ '  Rats  and mice exposed




8 hours per day for  20  weeks to an average concentration of 37




ppra carbon disulfide showed evidence of  toxic  effeets.^"^(Appendix A)




Isobut ano 1




     Rats receiving  isobutyl alcohol,  either orally or  subcu-




taneously, one  to  two  times a week for 495 to  643  days  showed




liver carcinomas and sarcomas, spleen  sarcomas  and myeloid




leukemi a . ^^ )




     Ingestion  of  one  molar solution of  isobutyl alcohol in




water by rats for  4  months did not produce any  inflammatory




reaction of the liver.   However,  rats  ingesting  a  two molar




solution for two months  developed Mallory's  alcoholic hyaline




bodies in the liver  and  were observed  to have  decreases in




fat, glycogen,  and  RNA  in the liver.(43)




     Acute exposure  to  isobutyl alcohol  causes  narcotic effects,




and irritation  to  the  eyes and throat  in humans  exposed to




100 ppm for repeated 8 hour periods.    Formation  of facuoles




in the superficial  layers  of the  cornea  and  loss  of appetite




and weight  were reported among workers subjected  to an  undeter-




mined  but  apparently high  concentration, of  isobutyl alcohol.




(Appendix A)

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Pyridine




      Pyridines exhibit moderate toxicity when  introduced into



                                                               (22)
the human  body through oral,  dermal, and inhalation routes.




Liver  and  kidney damage has  been produced in animals  and man




after  oral administration.^)   In small doses,  conjunctivitis,




dizziness, vomiting, diarrhia  and jaundice may  appear;  tremors




and ataxia,  irritation of  the  respiratory tract  with  asthmatic




breathing, paralysis of eye  muscles, vocal cords  and  bladder




also  have  been reported.^^'




      Adverse  taste in fish  (carp, rudd) has been  reported at




5 ppm.  Pyridine causes inhibition of cell multiplication in




algae  and  bacteria at 28 and  340 ppm r e s pe c t ive ly . ^ -* ' (Appendix A)




Nitrobenzene




      Nitrobenzene is a suspected carcinogen.' ^'




      When  administered to  pregnant rats, it caused  abnor-




malities in  some of the fetuses  examined.'"'  Changes were




observed in  the chorionic  and  placental tissues  of  pregnant




workers exposed to nitrobenzene,^'  and menstrual  disturbances




after  chronic  exposure have  been reported.   Chronic  exposure




to nitrobenzene has been found  to cause a variety  of  blood-




variety disorders.




     Nitrobenzene is actually  toxic  in varying  degrees  to




several salt-  and fresh-water  organisms . ( 3 1 )(Appendix A)




     Nitrobenzene is a priority  pollutant under  Section




307(a) of  the  Clean Water Act.

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Cresols  (Cresylic Acid)




     Cresol  exhibits moderate toxicity  via  oral and inhala-




tion  routes.   Acute exposure can lead  to  absorption causing




kidney  and  liver  damage as well as  central  nervous system




disturbances.   Other symptoms include  gastroenteric problems,




severe  depression,  collapse and even death.   In addition,




exposure  to  cresol  can cause severe skin  burns  and derma-




titis . (^ > 22 ) (Ap pendix A)
                            -7.T-

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VII. References  to Section IV, D


1.   Bardodej,  Z., and J. Vyskoch.   1956.   The Problem of
     Trichloroethylene in Occcupational  Medicine.  AMA
     Arch.  Ind.  Health 13:581.

2.   Coler,  H.R.,  and H.  R. Rossmiller.   1953.  Tetrachloro-
     ethylene  Exposure in a Small Industry.   Ind. Hyg . Occup.
     Med .  8:227 .

3.   Deichmann,  W.R.   Toxicology  of  Drugs  and Chemicals.
     Academic  Press Inc.   New York,  1969.

4.   Dorigan,  J.  and  J.  Hushon.   1976.   Air  Pollution Assessment
     of Nitrobenzene.   U.S. Environmental  Protection Agency.

5.   Gosselin, Robert E.  et. al., Clinical  Toxicology of
     Commercial  Products, Fourth  Edition,  The Williams and
     Wilkin  Company,  Baltimore, 1976.

6.   Huff,  J.E.,  1971.  New Evidence on  the  Old  Problems of
     Trichloroethylene .   Ind. Med. 40:25.

7.   Irish,  D.D.   1963.   Halogenated Hydrocarbons:  II. Cyclic.
     In Industrial Hygi en.e and Toxicology,  Volume II, Second
     E~dition  (F.  A. Patty, Editor),  In t er sc i ene e ,  New York
     p. 1333.

8.   Kazanina, S.S.  1968.  Morphology and  Histochemistry of
     Hemochorial  Placentas of White Rats During  Poisoning of
     the Maternal  Organisms by Nitrobenzene.  Bull.  Exp. Biol.
     Med.  (USSR)  65:93.

9.   Kirk-01hmer . ,  Encyclopedia of Chemical  Technology, Third
     Edition,  Volume  9.   John Wiley  and  Sons,  New York.  1980.

10.  Klaassen, C.D.,  and  G.L.  Plaa   1967.   Relative Effects
     of Chlorinated Hydrocarbons on  Liver  and Kidney Function
     in Dogs.  Toxicol.  Appl.  Pharmacol.

11.  Knapp, W. K.,  Jr.,  et al .  1971.  Subacute  Oral Toxici'ty
     of Monochlorobenzene in Dogs and Rats.   Toxicol. Appl.
     Pharmacol.  19:393.

12.  Matsushita,  T.,  et  al.  Hemato logical  and Neuro-muscular
     Response  of  Workers  Exposed  to  Low  Concentrations of
     Toluene Vapor.  Ind. Health 13:115.

13,  McBirney, B.S.  1954.  Trichloroethylene and Dichloroethylene
     Poisoning.   AMA  Arch. Ind. Hyg. 10:130.

-------
14.  Medek, V. and J. Kavarik.   1973.  The Effects of  Per-
     chloroethylene on  the  Health of Workers.  Pracovni
     Lekarstvi.  25:339.

15.  National Cancer Institute.   1976.   Carcinogenesis
     Bioassay of Trichloroethylene.   CAS No. 79-01-6,
     NCI-CG-TR-2.

16.  National Cancer Institute.   1977.   Bioassay of Tetra-
     chloroethylene for Possible  Carcinogenicity. CAS  No.
     127-18-4, NCI-CG-TR-13,  DHEW Publication No. (NIH)
     77-813.

17.  National Cancer Institute,    1977.   Bioassay of 1,1,1-
     Trichloroethane for Possible Carcinogenicity. Carcinog.
     Tech. Rep. Ser.  NCI-CG-TR-3.

18.  National Institute for  Occupational Safety and Health.
     1976a.  Criteria for a  Recommended  Standard:  Occupational
     Exposure to Methylene  Chloride.   HEW Pub. No. 76-138.
     U.S. DHEW., Cincinnati,  Ohio.

19.  Patty, Frank A., Editor.   Industrial Hygiene and  Toxicology,
     Volume II, Interscience Publishers, New York.  1963.

20.  Pearson, C., and G_._Mc Connell .   1975.   Chlorinated GI and
     G£ Hydrocarbons in the  Marine Environment.  Proc. R. Soc.,
     London B. 189 : 302 .

21.  Rowe, V. K., et al., 1952.   Vapor  Toxicity of Tetrachloro-
     ethylene for Laboratory Animal  and  Human Subjects.  AMA.
     Arch. Ind. Hyg.  Occup.  Med. 5:566.

22.  Sax, N. Irving.  Dangerous  Properties  of Industrial Materials.
     Fifth Edition, Van Nostrand  Reinhold Company, New York.   1979.

23.  Schwetz, B. A., et al.   1975.   The  Effects of Maternally
     Inhaled Trichloroethyl ene,  Perchloroethylene, Methyl
     Chloroform, and Methylene  Chloride  on  Embryonal and Fetal
     Development in Mice and  Rats.   Toxicol. Appl. Pharmacol.
     32:84.

24.  Simmon, V.  F., et  al.,  1977.  Mutagenic Activity of
     Chemicals Identified in  Drinking Water.   S.  Scott, et al.,
     Editors: In Progress in  Genetic  Toxicology.

25.  Syrovadko,  0.  N.   1977.  Working Conditions  and Health
     Status of Women Handling Organosiliceous Varnishes Con-
     taining Toluene.  Gig.  Tr.  Prof. Zabol.   12:15.
                              -7'7-

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26.  Taylor,  O.C.,   1974.  Univ. of California,  Riverside.
     Unpublished  Data, (as cited in U.S. EPA,  1976a.)

27.  U.S.  EPA.   1976a.  Environmental Hazard  Assessment
     Report:   Major  One- and Two-Carbon Saturated  Fluoro-
     carbons,  Review of Data.  EPA-560/8-76-003.

28.  U.S.  EPA.   1978.   In-depth Studies on Health  and
     Environmental  Impacts of Selected Water  Pollutants.
     Contract  No.  68-01-4646.

29.  U.S.  EPA.   1979.   Chlorinated Benzenes:  Ambient Water
     Quality  Criteria  (Draft).

30.  U.S.  EPA.   1979.   Halomethanes: Ambient  Water  Quality
     Criteria  (Draft).

31.  U.S.  EPA.   1979.   Nitrobenzenes:  Ambient  Water Quality
     Criteria  (Draft).

32.  U.S.  EPA.   1979.   Tetrachloroethylene: Ambient Water
     Quality  Criteria  (Draft).

33.  U.S.  EPA.   1979.   Toluene: Ambient Water  Quality  Criteria
     (Draft) .

34.  U.S.  EPA.   1979.   Chlorinated Ethanes: Ambient Water
     Quality  Criteria  (Draft).

35.  Verchuerer  K.,  Handbook of Environmental  Data  on  Organic
     Chemicals.   Van Nostrand Reinhold Company.  1977.

36.  Vozovaya.   1974.

37.  Wolf, M.  A.,  et al.   1956.  Toxicological Studies  of Certain
     Alkylated Benzenes and Benzene,  Arch. Ind. Health  14:387.

38.  EPA Carcinogen  Assessment  Group's List of Carcinogens,
     April 22, 1980.

39.  National  Academy  of  Sciences, National Research Council.
     1976.  Halocarbons:  Environmental Effects of Chlorome fhane
     Release .

40.  National  Academy  of  Sciences, National Research Council.
     1979.  Stratospheric Ozone Depletion by  Halocarbons:
     Chemistry and Transport.

41.  Linari, F.,  Perrelu, G., Varese,  D.:  [Chemical Observa-
     tions and Blood  Chemistry  Tests Among Workers  Exposed
     to the Effect of  a Complex Ketone--Methyl-Isobutyl  Ketone,]
     Arch. Sci. Med.,  1964,  pp. 226-237 (Ita).

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42.   Specht, H.,  Miller,  J.  W., Valaer, P. J.,  Sayers R.  R.:
     Acute Response  of  Guinea Pigs to the Inhalation of  Ketone
     Vapors, NIH  Bulletin No. 76.  Federal Security Agency.
     Public Health  Service,  National Institute  of Health,
     pp.  66 •

43.   Gibel, et  al . ,  Exp.  Chir. Forsch.  JL:235,  1974.

44.   Smith  et al. ,  Arch.  Ind. Hyg. Occup. Med .  1Q_:61, 1954.

45.   U.S. EPA.   1979.   Toluene Ambient Water Quality Criteria.

46.   NIOSH  (1978) Registry of Toxic Effects of  Chemical  Sub-
     stances.   Toluene.

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                      Response  to  Comments


     One  commenter objected to the  listing  "Waste non-

     halogenated  solvent (such as methanol,  acetone, iso-

     propyl  alcohol,  polyvinyl alcohol,  stoddard solvent

     and  methyl  ethyl ketone)  and solvent  sludges from

     cleaning,  compounding milling  and other  processes."*

     The  commenter argued that without indicating the con-

     centration  or quantity of the  solvent  in  the waste,

     the  Agency  would be listing wastes  as  hazardous even

     if the  solvent  were present in small concentrations and

     quanti ties .


     In the  listing  promulgated today for waste  solvents,

     the  Agency  is only listing those spent  solvents or

     still  bottoms fro m.__t..h e recovery of  these  solvents

     which would  contain substantial quantities  and  con-

     centrations  of  the solvent.  For example,  spent solvents

     can  contain  up  to  90% of the original  solvent  while

     the  still  bottoms  may contain  up to 50% of  the  spent

     solvent.


     A number of  commenters objected to  the  listing  of poly-

     vinyl alcohol (PVA) as a solvent.   These  commenters

     argued  that  PVA  is not a solvent but is a  solid and

     can  only be  used as a solute.  Therefore,  they  recommended

     that PVA be  removed from the list.
•''This specific  listing  will not be included  in  the  final
 regulation; however,  it  will be covered under  the  generic
 listing "The Spent  non-halogenated solvents...."

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The Agency agrees with  the  commenters and therefore,




has removed PVA from the  listing.







A number of commenters  objected  to  the listing of waste




halogenated/non-halogenated  solvents.  They felt that




the listing was too vague and  ambiguous.






In the listings promulgated  today,  the Agency has




specifically listed only  those solvents for which data




or information are available which  indicates a present




or potential hazard could be posed  to human health and




the environment if improperly  managed.   Therefore, the




listing description promulgated  today should respond




to the commenters1 objection.

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        Electroplating and Metal Finishing Operations


Wastewater Treatment Sludge from Electroplating Operations  (T)


Summary of Basis for Listing

     Wastewater treatment sludge from electroplating operations

are generated by a number of industry categories located nation-

wide.  This waste contains a variety of heavy metals such as

chromium, cadmium/ nickel as well as cyanide.  The Administrator

has determined that waste from these processes may be solid

wastes which may pose a substantial present or potential hazard

to human health and the environment when improperly transported,

treated, stored/ disposed of or otherwise managed/ and therefore

should be subject to appropriate management requirements under

Subtitle C of RCRA.  This conclusion is based on the following

considerations:

     1.   Wastewater treatment sludge from electroplating
          operations contain significant concentrations of
          the toxic heavy metals chromium/  cadmium/ and nickel/
          and highly toxic cyanide.

     2.   Leaching tests using the extraction procedure (used
          in the extraction procedure toxicity characteristic)
          have shown that these metals leach out in significant
          concentrations, with some samples failing the extraction
          procedure toxicity characteristic.  Therefore, the
          possibility of groundwater contamination via leaching
          will exist if these waste materials are improperly
          disposed.

     3.   A large quantity of this waste is generated annually
          (specific quantities have not been calculated at this
          time)  and amounts are expected to increase substantially
          when the pretreatment standards for these sources become
          effective.  Damage incidents (i.e., contaminated wells,
          destruction of animal life, etc,) that are attributable
          to the improper disposal of wastewater treatment sludge
          from electroplating operations have been reported, thus

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          indicating that the wastes may be mismanaged in actual
          practice,  and are capable of causing substantial harm
          if mismanagement occurs.
Sources of the Waste and Typical Disposal Practices


Industry Profile

     The electroplating industry consists of both job shops

and captive platers.  Job shops are small, independent

operations performing electroplating on a contract basis while

captive facilities are part of an integrated manufacturing firm

(i.e.,  electroplating operations carried-out in an automobile

manufacturing facility, aircraft manufacturing facility, etc.).

Of the  approximately 10,000 electroplating facilities in the

United  States, it is estimated that 3,000 are job shops and

6,100 are captive shops including 400 printed circuit board

manufacturers.  Approximately 7 percent of the job shops and

42 percent of the captive shops discharge directly to the waters

of the  United States.(D

Electroplating Process Description

     Electroplating, as defined in this document, includes a

wide range of production processes which utilize a large num-

ber of  raw materials.  Production processes include common and

precious metals,  electroplating, anodizing, chemical conver-

sion coating (i.e.,  coloring,  chromating, phosphating and

immersion plating),  electroless plating, chemical etching and

milling and printed  circuit board manufacturing (5).*  The
"Among  the  industries  included in this listing are segments of
 the  printing  and  publishing category associated with rotogravure
 and  metalic plate manufacture,  continuous electroplating proces-
 ses  of the iron and  steel  industry and chromic acid waste treat-
 ment from magnesium  carbon battery production.

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primary purpose of electroplating operations is to apply a




surface coating, typically by electrode decomposition/ to




provide protection against corrosion, to increase wear or




erosion resistance, or for decorative purposes.  The operation




itself involves immersing the article to be coated/plated into




a bath consisting of acids, bases, salts, etc.   A plating line




is a series of unit operations conducted in sequence in which




one or more coatings are applied or a basis material is removed




Figure 1 illustrates a standard electroplating process.  (For




a more detailed discussion of the electroplating process, see




the Development Document for Existing Source Pretreatment




Standards for the Electroplating Point Source Category, August




1979 (5).)




     The metals used in ...electroplating operation (both common




and precious metal plating) include cadmium, lead,  chromium,




copper, nickel, zinc,  gold and silver.  Cyanides are also




extensively used in plating solutions and in some stripping




and cleaning solutions.  Electroless plating often uses copper,




nickel and tin complexed with cyanide.  Etching solutions are




commonly made up of strong acids or bases with spent etchants




containing high concentrations of spent metal.   The solutions




include ferric chloride,  nitric acid, ammonium persulfate,




chromic acid, cupric chloride and hydrochloric acid.  Anodizing




is usually performed on aluminum parts using solutions of




sulfuric or chromic acid often followed by a nickel acetate




seal.   Chemical conversion coating most commonly involves the




use of chromate or phosphate-containing baths.   A number of

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rai
                           my
                                               j
 L
                                          TVlkallne
                                         G*lorination

                              Chcml cal
                            Precipitation
wast'ewater
                                     Wastewater
                                     Treatment
                                     Sludge
                 Rinse Water
                      to
               Sanitary Sewer*
                    FIGURE 1   TYPICAL  ELFCTROPLATING PROCESS

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acids can also be used  (as in passivating), but are not as




common as the phosphate/chromate baths.  Typical process baths




used in the industry are shown in Table 1.'^0 '




Waste Stream Description



     As indicated in Figure 1, the spent plating/coating




solution and rinse water is chemically treated to precipitate




out the toxic heavy metals and to destroy the cyanide.  The




extent to which plating solution carry-over or drag-out adds




to the wastewater and enters the sludge depends on the type




of article being plated and the specific plating method




employed.




     The composition of these sludges will vary because of




the multitude of production processing sequences that exist




in the industry.  For example, printed circuit board




manufacture involves electroplating,  etching, electroless




plating and conversion coating and would generate one type of




sludge.  A different processing sequence,  on the other hand,




would generate a sludge with a differing composition.  However,




is expected that since most platers conduct a number of differer




electroplating operations,  all sludges will contain significant




concentrations of toxic heavy metals, and may also contain




complexed cyanides in high concentrations if cyanides are not




properly isolated in the treatment process.  Table 2 illustrates




the varying composition of these sludges for two of the heavy




metals in twelve different plating processes.




     The predominant type of wastewater treatment sludge




generated from this industry is metal hydroxide sludge (which
                                 _
                             "~ Q Lo

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                                Table 1
          (10)
      Typical Electroplating Baths and Their Chemical Composition
plating Compound

Cadmium Cyanide
Cadmium Fluoborate
Chromium Electroplate
Copper Cyanide
Electroless  Copper
Gold Cyanide
Acid Nickel
Silver  Cyanide
Sine  Sulfate
Constituents

Cadmium oxide
Cadmium
Sodium cyanide
Sodium hydroxide

Cadmium fluoborate
Cadmium (as metal)
Ammonium 'fluoborate
Boric acid
Licorice

Chromic acid
Sulfate
Fluoride

Copper cyanide
Free sodium cyanide
Sodium carbonate
Rochelle salt

Copper nitrate
Sodium bicarbonate
Rochelle salt
Sodium hydroxide
Formaldehyde  (37%)

Gold (as potassium
  gold cyanide)
Potassium cyanide
Potassium carbonate
Depotassium phosphate

Nickel sulfate
Nickel chloride
Boric acid
      Concentration (g/1)

              22.5
              19.5
              77.9
              14.2

             251.2
              94.4
              59.9
              27.0
               1.1

             172.3
               1.3
               0.7

              26.2
               5.6
              37.4
              44.9

              15
             10
              30
              20
             100  ml/1
Silver cyanide
Potassium cyanide
Potassium carbonate
Metallic silver
Free cyanide

Zinc sulfate
•Sodium sulfate
Magnesium sulfate
               8
              30
              30
              30

             330
              45
              37

              35.9
              59.9
(min.)         15.0
              23.8
              41.2

             374.5
              71.5
              59.9
                                 - si

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                              Table 2

           Heavy Metal Content for Chromium, and  Cadmium_

           in Electroplating Sludges-Dry Weight  (mg/1)  *  '



Primary Plating Process               Cr              Cd

Segregated Zinc                       200            <100

Segregated Cadmium                 62,000         22,000

Zinc Plating and Chromating        65,000          1,100

Copper-Nickel-Chromium
  on Zinc                             500             ND

Aluminum Anodizing                  1,700             ND

Nickel-Chromium on Steel           14,000

Multi-Process Job Shop             25,000          1,500

Electroless Copper on Plastic,
  Acid Copper,  Nickel Chromium    137,000             ND

Multi-Process with Barrel or
  Vibratory Finishing                 570              -

Printed Circuits                    3,500             <100

Nickel-Chromium on Steel           79,200             <100

Cadmium-Nickel-Copper on
  Brass and Steel                  48,900             500

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results  from alkaline  precipation).   Metallic sulfide sludges,




although not widely  used,  are also generated when wastewater is




treated  by  sulfide precipation.   Among those facilities which




discharge to publicly  owned treatment works (POTW's)/ approxi-




mately 80 percent of the job shops and 70 percent of the captive




shops do not presently treat their wastewater and, therefore,




do not currently generate  water  pollution control sludges.




However, compliance  with the electroplate pretreatment standards




for existing job shops will be required by October 1982, and




for captives shortly thereafter.   Thus, when the regulations




are implemented, virtually all electroplaters will generate a




sludge and  drastically increase  the quantity of wastewater




treatment sludge produced.






Typical  Disposal Practices




     A recent  study  '2)  using a  48 plant survey indicated




that approximately 20  percent of the electroplating facilities




dispose  of  their waste on-site while the remaining 80 percent




haul their  waste off-site  to commercial or municipal disposal




facilities.  The actual disposal practices utilized by the




industry varies  greatly (i.e., landfilling, lagooning, drying




beds and drum  burial).   However,  the Agency is aware that




electroplating facilities  are known to be using extremely poor




hazardous waste  disposal practices.   For example, one printed




circuit  board  manufacturer is know to dispose of their waste




sludges  in  a dry river
                            -89 -

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Hazards Posed by the Waste




     As indicated earlier in Table 2 and as shown in Table  3,




wastewater treatment sludges from electroplating facilities




contain significant concentrations of the toxic heavy metals




cadmium, chromium and nickel with some levels exceeding 1,000




mg/kg (dry weight) and cyanide.  Additionally, leaching tests




run by the American Electroplaters'  Society (AES) under a grant




from the Industrial Environmental Research Laboratory (IERL)




U.S. Environmental Protection Agency have shown that these




metals leach out in significant concentrations with some




samples failing the extraction procedure toxicity character-




istic (Table 4).  The leaching tests used in the AES study




were performed on twelve separate samples using the proposed




extraction procedure (43 FR 58956-58957).  A leaching test was




also performed on two samples using the ASTM distilled water




leaching test; the results of this test as indicated in




Table 4 indicate that two of the contaminants of concern




(i.e., chromium and cadmium) may not solubilize in water to




the extent found in the acid leaching test.   However, since




these sludges tend to be disposed of an acid environment




(i.e., sanitary landfill), the acid leach test would closer




replicate what would be expected to  happen under field condi-




tions, and thus is more predictive of potential hazards from




improper management.  Cyanides have  also been shown to leach




from these wastes at a concentration range from 0.5 to




170 mg/l.(6)  <£he public Health Service's recommended concen-




tration limit for cyanide in drinking water in .02 mg/1

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                                Table  3
           Projected Sludge Concentrations For Various Heavy

                     Metals and Cyanides  (mg/1) (5)*
.utant
'n. urn
eel
?mium, Total

lide, Total
Raw Waste Cone
   (mean)	

    0.08

    5.0

    3.8

    0.4
Projected Sludge Cone.
       (mean)
2% Solids     20% Solids
                                                      3.2
  486.2
  369.7
   42.9
                  32.5
4862.0
3697.0
 429.2
DJections of sludge concentrations  are  based on mean raw waste

pled during an effluent guidelines  study.   This study utilized an

plant data base and the data are  derived from analyses of actual

 waste concentration, assumptions of  clarifier removal efficiencies

-98%) and non-dewatered and dewatered sludge solids content (2% and
                                                              t
  respectively).  To estimate pollutant concentrations in sludge, the

uraption is made that:

  1.   1% of the influent flow goes to  the  sludge stream at 2% solids.

  2.   The clarifier removal efficiencies were 96-98%.

refore,

  Mass removed = influent flow x  influent waste concentration -

  (1-.01) x influent flow x effluent  concentration
                                      mass  removed
  Sludge pollutant concnetration  =  .01 x influent flow

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                                      Table 4

              Extract  Concentrations From Electroplating Wastewater

                             Treatment Sludge 0
 Primary Plating Process                        Cr*                  Cd*

 1A  Segregated Zinc                            1.22                 0.2J

 2A  Segregated Cadmium                         1.89                 126

 3A  Zinc Plating and Chromating               85.0                  6,0

 4A  Copper-Nickel-Chromium  on	"•"
       Zinc                                    21.8
 5A  Aluminum Anodizing                        <0.01

 6A  Nickel-Chromium on  Steel                  25.4

 7A  Multi-Process Job Shop**                   0 .24                 2,1{

 8A  Electroless Copper  on Plastic,
      Acid Copper, Nickel, Chromium             400

 9A  Multi-Pocess with Barrel or
       Vibratory Finishing**                    0.32                 O.OJ

10A  Printed Circuits                           0.12

11A  Nickel-Chromium on  Steel                   4.22                <0.01

12A  Cadmium-Nickel-Copper on
       Brass and Steel                          4.85                 268^


Note:  Those concentrations underlined would  fail  the Extraction

       Procedure Toxicity Characteristic

    *  These values were determined  using  the proposed extraction procedl

       contained in the  toxicity characteristic.

   **  The ASTM distilled water extraction procedure was run on these

       samples with the  following  results  obtained:


         Plant                   Cr  (mg/1)                   Cd (i
          7A                        0.63                        0.03

          9A                        0.04

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indicating  that cyanide leaching may also lead to a substantial




hazard.




     Once released from the matrix of the waste, cadmium/




chromium, nickel,  and cyanide could migrate from the disposal




site to  ground and surface waters utilized as drinking water




sources.  Present  practices associated with the landfilling,




dumping  or  impounding of the waste may be inadequate to prevent




such occurences.   Actual damage incidents involving electro-




plating  wastes are presented.-In Attachment I, again showing




that actual mismanagement of electroplating wastes has




occurred.  For instance, selection of disposal sites in




areas with  permeable soils can permit contaminant-bearing




leachate from the  waste to migrate to groundwater.  This is




especially  significant with respect to lagoon disposed wastes




because  a large quantity of liquid is available to percolate




through  the solids and soil beneath the fill.




     The prevalence of off-site disposal creates a further




potential for mismanagement and substantial hazard.   Not only




is there a  danger  of mismanagement in transport, but there is




the further danger of unmanifested wastes never reaching their




destination or of  being disposed with incompatible wastes.




     An  overflow with respect to lagoon disposed wastes might




be encountered if  the liquid portion of the waste is allowed




to reach too high  a level in the lagoon; a heavy rainfall could




cause flooding which might reach surface waters in the vicinity




unless the  facility has proper diking and other flood control



measures.
                            -X-

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     In addition to difficulties caused by improper  site




selection, unsecure land disposal facilities are likely to




have insufficient leachate control practices.  There may be




no leachate collection and treatment system to diminish




leachate percolation through the wastes and soil underneath




the site to groundwater and there may be no surface run-off




diversion system to prevent contaminants from being carried




from the disposal site to nearby surface waters.




     With regard to the fate of these waste constitutents




once they migrate, the heavy metal contaminants present in




the waste are elements which persist indefinitely in some




form and therefore may contaminate drinking water sources




for long periods of time.  Cyanides have been shown to be




extremely mobile in the-soil environment (12),  and have been



shown to move from soils to groundwater.(13)   Thus cyanide




is also available for potential release and transport to




environmental receptors.




     The Agency has determined to list wastewater treatment




sludge from electroplating operations as a T hazardous waste,




on the basis of chromium, cadmium,  nickel and cyanide, although




chromium and cadmium are also measurable by the (E) character-




istic.   Moreover, concentrations for chromium and cadmium in




the EP extract from this waste from individual  sites might be




less than 100 times the national interim primary drinking water




standard as indicated (although the Agency's own extraction




data indicates that extract concentrations have exceeded the




100 x benchmark for some generators).  Nevertheless, the Agency

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believes  that  these  are factors in addition to metal concen-




trations  in  leachates  which justify the T listing.  Some of




these factors  already  have been indentified, namely that




present industry  disposal practices have often proven inade-




quate;  the presence  of nickel and cyanide/ often in high




concentrations/ two  constitutents not caught by the (E)




characteristic; the  nondegradability of the three heavy metals




and the high concentrations of cadmium and chromium in actual




waste streams.




     The quantity of these wastes generated is an additional




supporting factor.   As indicated above/ wastewater treatment




sludge from  electroplating operations will drastically increase




in quantity  when  the pretreatment standards are implemented in




October 1982 and  these sludges will contain extremely high




cadmium,  chromium and  nickel concentrations (see p. 7 above).




Large amounts  of  each  of these metals are thus available for




potential environmental release.   The large quantities of




these contaminants pose the danger of polluting large areas




of ground and  surface  waters.   Contamination could also occur




for long  periods  of  time, since large amounts of pollutants




are available  for environmental loading.   Attentative capacity




of the  environment surrounding the disposal facility could




also be reduced or used up due to the large quantities of




pollutant available.   All of these considerations increase




the possibility of exposure to the harmful constitutents in




the wastes,  and in the Agency's view, support a T listing,

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Health Effects Associated with Hazardous Waste Constitutents




     The toxicity of cadmium, chromium/ nickel and cyanide




has been well documented.  Capsule descriptions on the adverse




health and environmental effects are summarized below; more




detail on the adverse effects of cadmium/ chromium, nickel/




and cyanide can be found in Appendix A.




     Chromium is toxic to man and lower forms of aquatic life.




Contact with chromium compounds can cause dermal ulceration in




humans.  Data also indicates that there may be a correlation




between worker exposure to chromium and development of hepatic




lesions.



     Cadmium shows both acute and chronic toxic effects in




humans.  The LD5Q (oral, rat) is 72 mg/kg.   Excessive intake




leads to kidney damage.  Cadmium and its compounds have also




been reported to produce oncogenic and teratogenic effects.




Aquatic toxicity has been observed at sub-ppb levels.




     Nickel has been found to bring about a carcinogenic




response upon injection in a number of animal studies.  Nickel




has also been demonstrated to present adverse effects in a




three generation study with rats at a level of 5 mg/1 (5 ppm)




in drinking water.  In each of the generations, increased




number of runts and enhanced neonatal mortality were seen,




Chronic exposure to nickel has also resulted in injury to




both the upper and lower respiratory tract in man.  Addition-




ally,  in the aquatic environment, nickel has been found to be




toxic to fish at concentrations of 2,480 mg/1 and chronically




toxic at levels as low as 433 mg/1.

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     Ferrocyanides  exhibit low toxicity, but release cyanide




ions  and toxic hydrogen cyanide gas upon exposure to sunlight.




Cyanide compounds can  adversely affect a wide variety of




organisms.   For  example,  cyanide in its most toxic form can




be fatal to  humans  in  a few minutes at a concentration of




300 ppm.   Cyanide is also lethal to freshwater fish at concen-




trations as  low  as  about 50 mg/1 and has been shown to adversely




affect invertebrates and fishes to concentrations of about




10 mg/1.   The hazards  associated with exposure to chromium/




cadmium/ nickel  and cyanide have been recognized by other




regulatory programs.   Chromium/ cadmium, nickel and cyanide




are listed as priority pollutants in accordance with §307(a)




of the Clean Water  Act.  Under §6 of the Occupational Safety




and Health Act of 1970, .-a-final standard for chromium has been




promulgated  in 29 CFR  1910.1000; permissable exposure limits




have  also  been established for KCN and NaCN.  The U.S.  Public




Health Service established a drinking water standard of




0.02  mg CN/1 as  an  acceptable level for water supplies.  In




addition/  final  or  proposed regulations for the State of




Maine,  Massachusetts/  Vermont,  Maryland, Minnesota -,  New Mexico,




Oklahoma,  and California define chtromium,  cadmium, nickel,  and




cyanide containing  compounds as hazardous wastes or components



thereof.(14)

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                       Attachment  I



       Damage  Incidents Resulting  From the  Mismanagement




                  of Electroplating Wastes'17/
Columbia County,  Pennsylvania  (1965)  - Unlined  lagoons  caused




contamination of  a number of private  wells  in the  area.   The




lagoons contained plating wastes and  were leaking  such




pollutants as cyanide, copper, nickel, alkylbenzenesulfonate




and phosphate.




Illinois - At a farm  site in Illinois used  for  the dumping of




highly toxic industrial wastes (mostly from metal  finishing




operations), three cows died as a result of cyanide poisoning




and extensive danger  occured to wildlife, aquatic biota and




vegetation.  Additionally, crops cannot be  safely grown in




the area again.




Bronson, Michigan (1939) - Since 1939, electroplating industries




in Bronson, Michigan have experienced difficulty in disposing




of their electroplating wastes.  Originally, the wastes were




discharged into the city's sewer system which was subsequently




emptied into a creek.  Contaimination of this water resulted in




the death of fish and cattle below Bronson  from cyanide




poisoning.  All the plating wastes of the company were




subsequently discharged to ponds.




Lawrenceburg, Tennessee - Between 1962 and  1972 in Lawrenceburg,




Tennessee, an industry dumped, up to 5,000 gallons of untreated




metal plating waste daily into trenches near the city dump.

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Significant concentrations of hexavalent  chromium  and  traces




of cyanide were measured in an adjacent stream by  several local




residents as a drinking water supply.




South Farmingdale, New York - An aircraft plant, operating in




South Farmingdale on Long Island during World War  II,  generated




large quantities of electroplating wastes containing chromium,




cadmium and other metals.  It has been estimated that  between




200,000 to 300,000 gallons per day of these wastes were




discharged into unlined disposal basins throughout the 1940's.




A treatement unit for chromium was constructed in  1949, but




discharge of cadmium and the other metals continued.   The




local groundwater flows in three unconsolidated aquifers




resting on crystalline bedrock.  The uppermost aquifer consists




of beds and lenses of fine-to-coarse sand and gravel and




extends to within 15 feet of the land surface.  Groundwater




contamination by chromium was first noted in 1942 by the




Nassau County Department of Health.  Extensive studies in




1962 indicated that a huge plume of contaminated groundwater




had been formed, measuring up to 4,300 feet long,  1,000 feet




wide and extending from the surface of the water table to




depths of 50 to 70 feet below the land surface.  Maximum




concentrations of both chromium and cadmium were about 10




mg/1 in 1962,   (Chromium had been measured as high as  40




mg/1 in 1949.)  This huge contaminated plume cannot be removed




or detoxified without massive efforts and will take many




more years of natural attenuation and dilution before  it

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becomes useable  again.  Meanwhile,  the  plume  is  still slowly




moving, threatenting a nearby creek and other wells  in the




area.




Kent County, Michigan - An aquifer  used for a municipal waste




supply was contaminated by chromium leachate  from a  sand and




gravel pit used  as a landfill.  The landfill had been taken




from a former dumping ground for electroplating wastes.   The




fill material was removed to ameliorate the pollution problem.




Allegan County,  Michigan (1947) - Wells produced yellow water




which contained  high levels of chromium.  About three years




before any contamination appeared,  a metal-plating company




began discharging chrome-plating wastes into an infiltration




pit and the surrounding overflow area.  Discharge of  plating




wastes resulted  in the contamination of the glacial-drift




aquifer.   Health Department personnel estimated it would be




about six years  before the aquifer  in the vicinity of the




wells would be free of chromate.  All private wells in  the




village of Douglas were condemned.




Riverside County, California (1956) - Chrome plating  wastes




were discharged  on the ground and into  a cesspool.   Samples




from four wells  contained concentrations of hexavalent  chromium




of as much as 3 mg/1 and 18 others  contained trace amounts.




The National Interim Primary Drinking Water Standard  for




total chromium is 0.05 mg/1.

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                           References
 1.   Economic Analysis of Pretreatment Standards  for  Existing
        Sources of the Electroplating Point  Source Category,
        U.S.  EPA,  EPA-440/2-79-031, August 1979.

 2.   Assessment of Industrial Hazardous Waste Practices,
        Electroplating and Metal Finishing Industries  -
        Job Shops, U.S. EPA, EPA 68-01-2664,  September 1976.

 3.   Electroplating Category RCRA Review.   Technical  Contractors
        Final Report, October 1979, Contract 68-01-5827.

 4.   Electroplating Wastewater Sludge Characterization  Study.
        AES-EPA  Cooperative Agreement No. R880026-01,  September
        1979.

 5.   Development Document for Existing Source Pretreatment
        Standards for the Electroplating Point Source  Category,
        U.S.  EPA,  EPA/440-1-79/085, August 1979.

 6.   Composite of State Files of  "Special Wastes  Disposal
        Applications."  1976-1979.  Result of Leachate Tests
        on Cyanide Containing Wastes from Illinois,  Iowa,
        Kansas and Pennsylvania.

 8.   Development Document for Pretreatment  Limitations  Guide-
        lines and Standards for the Electroplating  Point Source
        Category;  August 1979.  EPA 440/1-79/085.

10.   Metal Finishing Guidebook and Directory, Volume  77, No,  13
        Metals and Plastics Publications,  Inc., Hackensack, New
        Jersey, January 1979.

11.   U.S.  EPA, Effluent Guidelines On-going BAT Study.

12.   Aiesii, B.A. and W.A. Fuller.  1976.   The Mobility of Three
        Cyanide Forms in Soil.  pp. 213-223.   In Residual Management
        Land  Disposal.  W.H. Fuller (ed.), Environmental  Protection
        Agency, Cincinnati, Ohio.   PB 256768 268.

13,  The Prevalence of Subsurface Migration  of Hazardous  Chemical
       Substances  at Selected Industrial Waste Land  Disposal  Sites.
       1977.   EPA/530/SW-634.  U.S. EPA, Washington, D.C.

14.  U.S.  EPA State Regulations Files,  January 1980.

15.  U.S.  EPA 1979.   Cyanides:  Ambient Water Quality  Criteria.
       (Draft)  EPA ?3 296792.  National Technical  Information
       Service, Springfield,  Virginia.

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                  Listing  Background Document

           SPENT WASTE  CYANIDE  SOLUTIONS AND SLUDGES

 1.    LISTING

      The listed wastes  are  those  major waste  streams,  from

 several  industry segments,  which  specifically contain  either

 cyanide  salts or complexed  cyanide  compounds.  The  specific

 wastes  listed are as follows:

 Cyanide  Salts

      Electroplating

           Plating bath  solutions  (R,T)*

           Spent stripping and  cleaning bath solutions  (R,T)

           Plating bath  sludge  from  the bottom of plating  baths  (R,T

      Metal Heat Treating

           Quenching bath  sludge from oil baths (R,T)

           Spent solutions from  salt  bath pot cleaning  (R,T)

      Mineral Metals Recovery

           Spent cyanide bath solution  (R,T)

 Complexed  Cyanides

      Electroplating

           Plating bath  and  rinse  water treatment sludges  (T)*

      Metal Heat Treating

           Quenching wastewater  treatment sludges (T)

      Mineral Metals Recovery

           Cyanidation wastewater  treatment  tailing pond sediment (?'

           Flotation tailings from selective flotation  (T)

      Coke  Ovens and Blast Furnaces

           Dewatered air pollution control  scrubber sludges  (T)
* S p e n t plating  bath solutions and  plating bath sludge  from  the
 bottom of  placing baths also contain  complexed cyanides, but
 are more significant as sources of  cyanide salts.

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II.  SUMMARY OF BASIS FOR LISTING

     A number of different  industry categories located  nation-

wide dispose of spent or waste  cyanide solutions  and  sludges,

the most prevalent being electroplating,  metal heat treating,

mineral metals recovery, and  coke ovens and blast  furnace

operations.   Cyanide is present  in these  wastes in the  form  of

either (1) alkali-metallic  or  alkaline earth cyanide  salts

such as sodium, potassium,  and  calcium cyanide or  (2) as

heavy metal  cyanides, ferro  and  ferricyanides, and ferric

ammonium ferrocyanide (iron  blue) referred to as  complexed

cyanides . ^ •*•'

     The Administrator has  determined that waste  from these

processes  may be a solid waste,  and as a  solid waste may pose

a substantial present or potential hazard to human health and

the environment when improperly  transported, treated, stored,

disposed of  or otherwise managed, therefore should be subject

to appropriate management requirements under Subtitle C of

RCRA.   This  conclusion is based  on the following  considerations

     1.    Each of the wastes generated exhibits either
          reactive or toxic  properties or both due to their
          cyanide content.

     2.    The land disposal of  cyanide wastes is widespread
          throughout the United  States with 1,940 kkg of
          cyanide (CN~)  contained in  these wastes annually.
          These wastes generally  contain  high concentrations
          of cyanide.  This  large annual  generation rate,
          and high cyanide concentration  level increases the
          likelihood of exposure  and  possibility  of 'substantial
          haz ard.

    3.    Cyanides can migrate  from the wastes to adversely
          affect human health and the environment by  the

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           following pathways,  all of which have  occured in
           actual management  practice:

           (a)  generation  of cyanide gas resulting from the
                reactive  nature of cyanide salts  when mixed
                with acid was t es;

           (b)  contamination of  soil and surface  waters in the
                vicinity  of  inadequate waste disposal resulting
                in destruction  of  livestock, wildlife,  stream-
                dwelling  organisms,  and local vegetation;  and

           (c)  contamination of  private wells  and  community
                drinking  water  supplies in the  vicinity of
                inadequate  waste  disposal.

 Ill.  SOURCES OF CYANIDE  WASTE  AND TYPICAL DISPOSAL  PRACTICES

      A.    Overall Description  of  Industry Sources

           Waste cyanide  solutions and sludges  containing  both

 cyanide  salts and complexed  cyanides are generated  by  a number

 of  different industries  including electroplating, metal heat

 treating  and mineral metals  recovery operations.  Approximately

 20,000  facilities in the United States use one or more  electro-

 plating  or  heat treating processes  in manufacture of primary

 metals,  fabricated metals, machinery,  and electronics  equipment.'"^

 An  additional 73  facilities  use cyanide in the proces  of

 recovering  various metals, particularly gold and silver.

 Complexed  cyanide waste solutions  or sludges containing only

 complexed  cyanide are generated by  a number of other industrial

 processes,  principally iron  blue  manufacturing*, coke  ovens,

 and blast  furnace operations.
*!ron blue manufacturing is discussed  in the chromium  pigments
 background  document and thus is  not  presented here.

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     Table 1 lists  the  equivalent cyanide  (CN~) consumed

 annually by each  of these processes  including the specific

 types of cyanide  salts  and complexed  cyanides used.  Table  2

 indicates the number  of facilities and  types  of waste associated

 with these different  sources.  Industrial  processes which

 generate these waste  cyanide solutions  and sludges are further

 described below.

     B.   Waste Generation,  Waste Stream Description and Waste

          Management  Practices

         The major  processes which generate  cyanide salt-con-

 taining waste include (1) electroplating with cyanide plating

 baths or cyanide  stripping or cleaning  baths,  (2)  metal heat

 treating using cyanide  quenching baths, and  (3)^ mineral metals

 recovery with cyanide plating baths.  Complexed cyanide

 wastes (primarily  ferro and  ferricyanides)  are  generated from

 (1) treatment of  electroplating wastewater,  (2) treatment of

 quenching process wastewater from the metal heat  treating

 industry, (3) selective flotation and cyanidation  for mineral

 and metals recovery and the  air oxidation   and  chemical

 treatment of their  wastewaters, and  (4) coke  oven  and blast

 furnace air scrubbers.

 1.   Electroplating

     a.    Generation  of Spent Plating,  Stripping  and Cleaning
          Bath Solutions


          Electroplating,  as defined  in this  document,  in-

cludes  both common  and  precious metal electroplating, anodizing,

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                       Table 1
   Annual Consunption of Cyanide for Cyanide
Generating Processes (kkg of Of equivalents)
Electro- Heat
plating Treating
Cvanide Salts
NaCN 10,292 1,428
KCN 72 65
CaCN2
Complexed Cyanides
Heavy Metal 2,346
Ferrocyanides - 65
Ferri cyanides - -
TOTAL 12,710 1,558
Mineral
and
Metals
Recovery
1,592
30
90
451
30
2,193
Coke
Cvens
and
Blast
Furnace
0

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                            Table 2
                    CYANIDE  WASTE SOURCES
Source
                      Number  of Facilities
                        Types of Wastes(s)
Electroplating
Minerals  and Metals
  Recovery
Metal Heat Treatment
Coke Ovens and
  Blast Furnac e s
 13,
      73
                                    (b)
   7,000
  287 coke  ovens,
200 blast  furnaces,
48 with both^8)
Cyanide salts  and
complexed cyanides
(Solution and  sludge)

Cyanide salts  and
complexed ferro
and ferricyanide
(s olut i ons and
sludges in tailing
pond s)

Sodium and potassium
cyanide (solution
and sludge)

Iron cyanide com-
plexes (slud ge)
'a'Based on Oct. 1979 Effluent  Guidelines document  estimates.   (U.S.
   Environmental Protection  Agency.  Oct.,  1979.   Draft  Development
   for Effluent Limitations  Guidelines, New  Source  Performance Stan-
   dards and Pretreatment  Standards for the  Photographic Processing
   Point Source Category.  Washington, D.C.).

^'Estimate of facilities  using cyanidation  or  selective flotation
   with cy anide .
                              -107-

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coating  (i.e.,  coloring, chromating,  phosphating and immersion




plating),  chemical etching and milling,  electroless plating,




and  printed  board manufacturing.   The  primary purpose of




electroplating  operations is to  apply  a  surface coating,




typically  by electrode decomposition,  to  provide protection




against  corrosion, to increase wear  or erosion resistance,




to restore worn parts to their original  dimensions, or for




decor at ion. (7'   The operation itself  involves immersing




the  article  to  be coated/p1 ated  into  a bath  consisting of




acids,  bases,  salts,  etc.   A plating  line  consists  of a




series  of  unit  operations  conducted  in a  sequence  in which




one  or more  coatings  are applied or  a basis  material is




removed.   (For  a more detailed discussion  of the electro-




plating  process see the Development  Document for Existing




Source Pretreatment Standards for  the Electroplating Point




Source Category,  August 1979).^)




     Figure  1-1 in Appendix I illustrates  a  standard electro-




plating  process.   Cyanides are used  to make-up the  various




pi at ing/coat ing solutions  and as stripping and cleaning bath




solutions . ^''   For example,  the  electrolytic baths  used




in both  chromium and  precious metal  electroplating  typically




consist  of cyanide salts or sodium,  potassium,  cadmium,




zinc, copper, silver,  and  gold.^'    Seventy-five percent




of those facilities that conduct both common and precious




metals electroplating utilize cyanide.^'  After  extended




use,  plating baths become  deficient  in the specific ion
                             -log-

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being plated/coated,  leaving  cyanides in solution  either as

simple ions or in complexes.   After extended  use  of stripping

and cleaning solutions,  metals begin to accumulate so that

further removal of metal coatings on articles  becomes difficult.

At that point these  solutions are dumped.'''  These plating,

stripping and cleaning  bath  solutions, when discarded,  represent

the major sources of  cyanide  salt containing  wastes generated

in electroplating operations* (and a minor source  of complexed

cyanides) .

     b .   Management  of  Spent Plating, Stripping  and Cleaning
          bath Solutions,  and Generation of Treatment Sludges


          Spent plating,  stripping and cleaning bath solutions

and rinse waters are  chemically treated primarily  with  hypo-

chlorite or chlorine  to  convert cyanide compounds  to carbon

dioxide, metal salts, nitrogen, and water. (?)

     Complexed cyanides  that  are present in hypochlorite-

treated bath solutions  and rinse waters are precipitated as

part of the sludge during  any additional wastewater treatment

(see Figure 1-2 in Appendix  I).  Even though  the  cyanide is

treated, a certain percentage of the complexed  cyanide  is
^Another major source  of  cyanide salt waste  is  the  rinse water
 contaminated by the solution remaining on  the  article that
 has been plated, stripped,  or cleaned.  This  rinsewater is
 either treated and present  in wastewater treatment sludge,
 in which case it is part  of a listed waste,  or  discharged
 directly to a POTW.   Rinsewater which is mixed  with domestic
 sewage that passes through  a sewer system  before  it reaches
 a POTW for treatment  is  excluded from RCRA  jurisdiction
 under § 26 1 .4(a)(1) .   The  Agency is in the  process  of developing
 pre-treatment standards  for the electroplating  industry.

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                                                       ( 1 8 ^
not destroyed  and thus may be present  in  the  sludges.^  >  '

These sludges  are typically disposed of in  a  sanitary

landfill .( 1>8)

     c .    Plating bath sludge from the bottom of cleaning
           baths


           Additionally,  plating solutions  that  have been

restored  several  times often leave a sludge in  the bottom of

the bath  which must  be cleaned out when spent solutions are

discarded.   These sludges often contain cyanide  salts and

complexed  cyanides  and typically are placed in  drums  for

chemical  landfill disposal. (1)

     Available plant information indicates  that  nearly all

of the cyanide containing materials discharged  to  the environ-

ment are  treated, although it is possible  that  some small

plating shops  may either  discharge directly to municipal

sewer system or landfill  spent solutions.^)*

2 .  Metal  Heat Treatment

     a .    Generation of Quenching Bath Sludge and  Spent
           Solutions  from  Salt Bath Pot Cleaning
          Case hardening  by carburizing adds carbon  to  the

surface of steel. ('/   Liquid carburizing uses  cyanides  as'

the source of carbon.   Liquid carburizing is accomplished by
*However, since 60  to  80  percent of these small  plating shops
 have shifted to non-cyanide baths (such as  zinc),  the  quantity
 of untreated cyanide  waste  landfilled from  electroplating
 operations is getting  smaller.(9)
                              -no -

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submerging  the metal in  a molten salt bath containing  sodium




cyanide  (6-23%).  Figure 1-3  in Appendix I illustrates  the




liquid  carburizing process.   Sodium cyanide  is  also  used in




the case hardening of steel  using either the  liquid  nitriding




or carbonitrid ing processes.




     Cyanide salt containing-wastes from this process  arise




generally from two sources:  (1) quenching sludge  and (2) pot




cleanout.  In the quenching  process, oil is  used  as  the




quenching media.  The sodium  cyanide adhering to  the




case hardened steel during  oil  quenching is  not  soluble and




settles  to  the bottom of the  quenching tank  as  a  sludge.  Another




source of cyanide waste  (although generated  in  less  volume




than the quenching sludge)  results from cleaning  out salt  bath




pots.




     b .    Generation of  Quenching Wastewater  Treatment  Sludge







          Where process  wastewaters are chemically




treated, sludges from these  operations are typically disposed




of in landf ills . ( ^-° )  During  waste treatment  some of the




untreated cyanide may complex with heavy metals  and  precipitate




in the  sludge.(? )




3.   Mineral and Metals  Recovery




     Cyanides are used extensively in the extraction and




beneficiation of gold and silver from ore and as  a depressant




in selective flotation processes.

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      a.    Generation and Management  of Cyanidation  Wastewater
           Tailings Pond Sediment
           Use  of cyanide  (cyanidat ion)  in the recovery of

gold  and,  to  a lesser extent,  silver, varies in process

complexity depending on the ore  matrix.   Generally,  the  ore

is pulverized  to expose gold  and  silver  deposits prior to

leaching by  caustic cyanide so lutions. ^^'  The gold  or

silver-laden  caustic cyanide  solution is then e 1 e c t r o ly z ed.,

and the  gold  or  silver is deposited  on  stainless steel wool

cathodes (see  Figure 1-4  in Appendix I).  The cyanide  bath  is

then  chemically  treated with  hypochlorite or chlorine  to

destroy  cyanide  salts and complexes.   The resulting  wastewater

tailings pond  sediment is a listed waste.  Ferrocyanide  and

ferricyanide  complexes formed  in  tailings pond sediment  are

periodically  dredged and  disposed of in  1 andfi 11 s. (^'

      b .    Generation of Spent  Cyani d e B ath So lu tions^'
           This  waste stream also  arises  from the cyanidation

process described  above.  Some minerals  and metals recovery

plants, however,  instead of chemically  treating spent  cyanide

bath solutions,  discharge the waste  directly to tailing  ponds

where oxidation  and sunlight are  relied  upon to convert

cyanide salts  to  complex cyanides  which  precipitate  into  the

pond sediment.   In this case, the  listed waste stream  is  the

spent cyanide  bath solution.

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     c.    Generation  of  Froth Flotation  Tailings






          Froth flotation tailings are also  cyanide-containing



wastes discharged  to  tailings ponds without  prior chemical




treatment.  Inorganic  cyanide salts,  and  calcium cyanides




and sodium ferro-  and  ferricyanides ,  are  extensively used as



chemical additives  in  froth flotation  as  a  depr es s ant . ( !•)



Froth flotation is  a  process by which  desired  mineral (copper,




lead, zinc, silver) attach to air bubbles,  float to the



surface as a foam  or  froth, and overflows  the  flotation



cell.'^-'  Undesirable  ore ("gangue")  is  removed from the



bottom of the cell  and  discharged to  a tailings pond as



shown in Figure 1-5 in  Apendix I.  Cyanides  are often added



to depress the flotation of undesirable  components of the



pulverized ore.  Cyanide-containing wastes  are discharged to



the tailings ponds  along with the gangue.   Tailings pond



sediment containing complexed cyanide  is  disposed of in




landfills similar  to  cyanidation wastes.^1'



^ *   Coke Oven and  Blast Furnace



     a.    Coke Oven Cyanide Waste Generation



          Thermally generated cyanides result  from the  high



temperature reaction  of  carbon and nitrogen  compounds in a
   %


reducing atmosphere.^)   Conditions favorable  to cyanide




generation exist in coking operations, blast  furnace



production or iron  and  ferroallys, and production of ferro-




alloys by means other  than blast furances.

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     During  coke production,  carbon compounds  and ammonia,

both produced by coal breakdown,  combine to  produce hydrogen

cyanide,  some of which is  collected as condensate in de-

su1ferizat ion scrubber sludges. (8)  Desu1furization scrubbers

installed  on many of the coke  oven  stacks  collect an estimated

36,300  kkg  of solids in a  scrubber  solution  per  year of which

3,555 kkg  are cyanide equiva 1 ents. ( 8) The  scrubber solution* is

dewatered,  and  the resulting  scrubber supernatant is filtered

and discharged.**  Solids  from  the  dewatering operation are

then combined with the solids  filtered from  the  scrubber liquor,*'

forming  the  listed waste,  the  dewatered scrubber  sludge.

Most of  the  cyanide (3,553 kkg)  goes to the  scrubber liquor,

and approximately 2 kkg of cyanide  remains in the scrubber sludge,

Estimated  concentrations of  complexed cyanide in  the dewatered

scrubber  sludge  are 55 ppm (2  kkg of cyanide in  36,300  total

solids) .

     b .    B1 as t  Fu_rnace Cyanide Waste Generation


           Hydrogen cyanides  are  also produced in  blast  furnace

operations when  nitrogen, water,  and carbon  react at high
  *The "scrubber  solution referred  to  in the text  is  properly
   referred  to  as  scrubber sludge.   The term "scrubber  solution'
   is used  to  aviod confusing  this  stream with  the  listed waste,
   which is  dewatered scubber  sludge.

 **Discharge of  scrubber supernatant  is usually regulated under
   the NPDES permit program.

 ' * * F i11 e r e d  solids  (filter cake)  may  be recycled back into the
   orocess  for  sintering.

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temperatures.  Although  no data are available on amounts of




hydrogen cyanide  generated in blast furnace  operations, it




is estimated that  scrubber systems remove  in solution 915 kkg




of cyanide equivalents  (CN~).'°'  The  scrubber solution is




then dewatered (much  as  in coking operations).  The resulting




sludge is the  listed  waste stream.




     Based on  limited surveys, blast  furnace scrubber liquor




appears to contain  most  of the cyanide.  Analysis of the




scrubber sludge indicates  that 2,720  kkg of  solid waste produced




annually contain  approximately 1 kkg  of CN~~  or cyanide con-




centrations of about  400
G.    Waste Characteristics  and Quantities




     Waste cyanide  solutions and sludges  are  generated




nationwide with most  disposal occuring  in  EPA Regions I




through IV and in Region  IX. ^^  The quantity and types of




wastes that result  from any of these processes are variable




and depend upon operation conditions at each  facility, but




significant cyanide concentrations in all  of  these waste




streams are anticipated.   Nearly all cyandie  processes include




some form of chemical  treatment which destroys most of the




cyanide prior to precipitaion of solids and heavy metals.  Of




the total 16,400 kkg  equivalent cyanide consumed  annually,




12,710 kkg is used by  the electroplating  industry.^'  A large




percentage of that is  either oxidized by  electrolysis in the

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plating  bath,  destroyed during  alkaline chlorination  or




ozonation  prior to wastewater discharge. ' •*• '  This means




that  approximately 127 kkg of equivalent  cyanide  (CN~)




(probably  in the salt form) is  disposed of annually on  land




by  this  industry.   Of the remaining  3,750  kkg (from the




total  of  16,460 kkg)  equivalent cyanide (CN~) consumed




annually,  about 48 percent (1,940 kkg  - 127 kkg  = 1,813




kkg)  is  disposed of on land as  solutions  or sludges.^'




The balance  is  either recovered or chemically destroyed by




alkaline  chlorination, electrolysis, or ozonation,  Sixty-seven




percent  of  this 1,813 kkg of CN~ disposed  of (by industries




other  than  electroplating) is in complexed cyanide form.




      Table  3 lists the types of cyanide wastes  generated, the




range  of  quantity  disposed of in solid  waste streams by an




individual  facility,  and the total quantity of  waste for each




of  the contributing sources of manufacturing processes.




These  quantities are  considered significant in  light of




cyanide's migratory potential (see p.  24)  and high toxicity.




The fact that disposal occurs nationwide  is  also significant,




since  the wastes are  exposed to many differing  environmental




conditions and  management  situations,  increasing the possibility




of mismanagement.




     Cyanide is  expected to be present  in  most  of these waste




streams in high  concentrations.   Table  3A  contains cyanide




s^lc and complexed cyanide concentration  data from listed




electroplating  and metal heat treating  wastes.   Concentrations

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Source
Electroplat ing
Mineral  and
 Metals
 Recovery
Metal Heat
 Treating
Coke  oven  and
 Blast  Furnac e
                                         Annual Waste
                                        Quanity/Facility
                                              kkg
                                         Cyanide  (CN~)
                                          Quant i ty/
                                           Facility
                                             (kkg)
                                  Total  Annual
                                Waste Quantity
                                     (kkg)
Type of Waste

Spent plating,
 Stripping  and
 Cleaning bath
 solutions;  plating
 bath sludge; plating
 bath and rinse
 water treatment
 sludge

Tailing pond  sedi-
 ment and cyanida-
 tion wastewater
 treatment  sludge

Quenching bath
 sludge and  spent
 bath solution  and
 quenching  waste-
 water treatment
 sludge

Air polluti on
 control  sludge
                     20-300
                            (d)
H-51(f)
                            Cyanide  Salts
                                 (Cn-)
                               Disposed
                               Annually
                                 (kkg)
                                     42,000
                                      0
                 6,125<10>
0.2-l.l
-------
                                                   Table 3  (Continued)
"Total based on mining  capacity and NaCN and depressant consuption  data'-*-'.
C50% of NaCN equivalent consuption^'
^Hange of total annual  waste for facilities included in a composite  of  state  wste  disposal applications
 assuming waste density ^ke/gallon^).  Based on total waste disposal  estimates  average quantity per
 facility is 3.5  kkg/yr^10'.
BTotal based on estimated  25 employees per facility; 7,000  facilities  of  which 25% use cyanide^!);
 0.14 kkg/yr-employee(1^)  ($ee figure 1)
nRunge of content  of waste per facility for facilities iincluded  in  a  composite  of state
 wnate disposal applications assuming waste density and kg/gallon(2)
*Total based on estimate that 13% of waste are cyanide wastes  and 25%  of  all  cyanide waste is
 destroyed.

-------
 Indua L ry
Sou rc e*
Metal Heat  Treating
Metal Heat  Treating
   Cyanide Salts

Quenching Bath  sludge
and Spent Solution
Quenching Bath  sludges
Elec t roplat ing


Elect roplating


Electroplating


Electroplat ing
Electroplating


Elect roplat ing


Electroplating


Electroplating


Metal Heat Treating
Speht Cleaning  Bath
Solution

Spent Cleaning  Bath
Solution

Spent Plating Bath
Solution

Plating Bath Sludge
   Complexed  Cyanides

Plating Bath  Treatment
Sludge

Spent Plating Bath
Solution

Spent Plating Bath
So lut ion

Plating Bath  Treatment
Sludge

Quenching  Wastewater
Treating  Sludge
                                                              Waste/
 Potassium and
 Sodium Cyanide/
 Solid**

 Potassium and
 Sodium Cyanide/
 Sludge

 Sodium Cyanide/
 Solut ion

 Cyanide Salts/
 Solution

.Sodium Cyanide
{Solution

 Metal Salts/Sludge
 Complex Metal
 Cyanide/Solution

 Complex Metal
 Cyanide/Solution

 Complex Metal
 Cyanide/Solution

 Complex Metal
 Cyanide/Sludge

 Coraplea Metal
 Cyanide Solids***
 3,000
13 ,200
92 ,300
 8,530
22
14
6
1
15
6
36
12
6
,500
,000
,600
,000
,600
,•600
,000
,000
,600
350,000
38
14,547
64
80
14,329
2,000
1,681
26,803

-------
Industry
 Source*
                                                        Table  3A
                                                    Cyanide, Wastes^)
                                                     Concentrations
                                                        Continued
Type of
Was t e/Form**
Annual Disposal
   in Gallons
                                                                                                          Cyanide
                                                                                                        Concent ra tions
Metal Heat Treating
Quenching Wastewater
Treatment Sludge
Complex Metal
Cyanides/Sludge
     5,500
8,400
   *Source descriptions  included  in  special waste disposal applications were not always the same as those
    presented  in  the  listing'  ).*  An attempt was made to classify the waste in its approximate category
 ** These descriptions were  taken directly from the special waste disposal applications(2).
*** Solid cyanide wastes  are  placed  in drums and disposed of.   Solid wste quantities are expressed in
    gallons related  to the  size  of the drum used to containerize waste for disposal.
                                                          -X-

-------
range from 38 ppm to 92,300  ppm,  with most concentrations




exceeding 1,000 ppm.  In  light  of  the health dangers associated




with cyanide (see pp.27-29 below),  these concentrations are deemed




to be of regulatory concern.




     The Agency presently  lacks  concentration data on wastes




generated by the mineral  metals  recovery industry, although




concentrations are believed  to  be  high based on the large




quantity of cyanides disposed  of  annually.  (See Ta-ble 3)




     Cyanide concentrations  in  coke ovens  and blast furnace




scrubber sludges are somewhat  less,  probably not exceeding




400 ppm (see pp. 14-15 above).   These concentrations could still




prove significant in light of  cyanide's  migratory potential and




extreme toxicity.




     D.   Typical Disposal Practices




          In general, waste  management of  cyanide solutions




and sludges relies primarily on  disposal in  municipal,




chemical,  or company-owned landfills. '-*•'




     Facilities using only one  process,  sometimes find it




more cost effective to landfill  spent cyanide salt solutions




(without any chemical treatment)  along with  cyanide sludges.'1'




Of course,  as described above,  most  spent  solutions are managed




initially in holding ponds, which  are treatment  facilities




under RCRA.




     Spent  cyanide solutions and  sludges from electroplating




operations  are generally treated  by  alkaline  chlorination




prior to discharge into municipal  sewer  systems  or landfill

-------
disposal.   Data characterizing the disposal  practices in some




states  indicate, however,  that some small plating  shops dispose




of  spent  plating solutions  and sludges which  still  contain




untreated  cyanide in landfills.'!'




     Mineral and metals recovery wastes from  extraction of




gold and  silver (cyanidation)  and selective  flotation of




copper,  lead,  zinc, and silver are diposed of  in tailing




ponds which may be lined  with  clay and are sometimes  constructed




to  control  run-off and dam  seepage.^' The size, construction,




and  location of tailing ponds  and retention of waste  solutions




in  ponds  varies from site  to  site depending on whether  mineral




and metals  recovery wastes  include cyanide containing solutions




or  sludges.   When wastes  are  not  alkaline chlorinated to




destroy  cyanide prior to  disposal,  tailing ponds are  used  as




holding  ponds  whera natural  air  oxidization and sunlight




destroy  the cyanide or where  the  cyanides are  complexed  with




metals  in  solution and by  attachment  to gangue materials. O-'




     Scrubber  sludges from  coke  ovens  and blast furnaces are




generally  dewatered and the  filter cake reused in the sintering




process  feed.   The remaining  solid wastes, which contain




small quantities of complexed  cyanides, are disposed  of  in




company  owned  or off-site  landfills.




     This  data suggests that  cyanide-containing wastes  are




sometimes  managed  properly.  Many damage incidents  involving

-------
cyanide-containing wastes  (set  forth  at  pp.  25-26 below)*

indicate,  however, that waste mismanagement  may occur and

cause  substantial hazard.  Furthermore,  proper management  of

wastes  capable of causing  substantial  hazard if mismanaged

does not make a waste non-hazardous under  the definition of

hazardous  waste contained  in Section  1004(5) of RCRA.  In

fact)  industry management  practice described above suggests

strongly  that industry itself regards  these  wastes as hazardous

and requiring careful management.


IV.  HAZARDS  POSED BY THE  WASTES

     A.    Nature of Hazards

           Cyanide salt-containing wastes exhibit  both reactive

and toxic  properties  which make them  potentially  hazardous to

human health  and the  environment.  If  exposed  to  mild acid
                                            *
conditions,  these wastes can react to  generate toxic hydrogen

cyanide gas.   Cyanide wastes are land  disposed and if improperly

managed, cyanide can  migrate from these wastes as  toxic  hydrogen

cyanide gas  or in a soluble form into  groundwater  or surface

water supplies.   Adverse health effects on landfill  operators

and environmental stress to avian and  possibly human

populations  is possible if hydrogen cyanide  is generated.
*Additional  damage  incidents are described  in  the  electroplating
 vaste background  document.

-------
Indus try
Source *
  Type of
Waste/Form**
Annual
Disposal
In Gallons
                                                                                  Cyanide
                                                                                Concent rat Ions
                   Leachable
                   Cyanide/
                   Metals
                   (pH 5.5
                   Conditions)
                   Within Theae
                   Wastes (ppm)
Electroplating
Electroplating
Metal Heat Treating
Metal Heat Treating
Spent Plating
Bath Solution

Plating Bath
Treatment Sludge

Quenching Waste-
water Treatment
Sludge

Quenching Waste-
water Treatment
Sludge
Complex Metal
Cyanide/Solution
          •
Complex Metal
Cyanide/Solution

Complex Metal     •
Cyanide/Solids*** (
Complex Metal
Cyanide/Sludge
   36,000


   12,000


    6,600



    5,500
 2,000


 1,681

i
26,803



 8,400
 80
170
915
  9.3
  *Source  descriptions  Included in special waste disposal applications were not always the same aa
    those presented  In the Us ting'^'.   An attempt was made to classify the waste Inits appropriate
    category.
 **These descriptions were taken directly from the special waste disposal applicatIonsv*).
***Solld cyanide  wastes are placed In  drums and disposed of.  Solid waste quantities are expressed
    In  gallons  related to the size of  the drum used to containerize waste for disposal.

-------
utilized  in  the  Subtitle  C  EP.*  This data indicates that the

complexed  cyanides  tend  to  be  relatively soluble and the

cyanide salts were  highly  soluble in this environment.  In

all cases, cyanide  leached  from the waste in concentrations

exceeding  the U.S.  Public Health Service recommended standard,

in most cases, by many orders  of magnitude.   Thus,  cyanide is

fully capable of migrating  from disposed wastes.

     Cyanide would  be capable  of migrating from these wastes

if improperly disposed,  for  example,  if  disposal occured in

areas with permeable soils,  or  if adequate leachate control

measures  are not adopted.   The  migrating cyanide is likely to

be highly mobile, since  cyanides have been shown to be

extremely mobile in the  soil environment.   pH  appears to

influence the mobility, with greater  mobility  at high pH.(l^)

Even clay liner  systems may  not  adequately impede migration;

as in the presence  of water, montmorillonite clays  (• which

have high surface areas) sorbed  cyanide  only weakly.(15)

Cyanide has also been shown  to  move through  soils into

groundwater.(1"'  In light  of  the extreme  toxicity  of this

waste constituent in the environment,  its  migratory potential

in both salt and complexed  form,  and  its  environmental

persistence and mobility, it strongly appears  that  waste

mismanagement can result in  substantial  potential hazard.
*In light of the prevalent landfilling  of  these  wastes,  and
 the great number of different  disposal  sites  utilized in
 managing different listed waste  streams,  it  is  certainly
 a plausible assumption that these wastes  may  be disposed
 of in acidic environments.

-------
Certainly the Administrator  cannot with assurance  state that




cyanide will not migrate  from these wastes and  persist  in




the environment; yet  such  assurance is required  to  justify




a decision not  to list  these wastes.




     In any case, actual  damage incidents involving  cyanide-




containing wastes,  including some of the wastes  listed  here,




confirm that cyanide  can  migrate, persist, and  contaminate




groundwater, public drinking water, soil, and vegetation.




For example, a  landfill  site in Gary,  Indiana,  in which large




quantities of cyanide electroplating wastes have been disposed,




has leached into groundwater supplies.(17)




     A total of 1,511 containers (mostly 55 gallon  and  30




gallon drums) of industrial  waste containing cyanides,  heavy




metals, and miscellaneous  other materials were  disposed of




improperly on a farm  near  Bryon, Illinois.  Leachate entering




nearby surface water  was  responsible for the death  of three




cows and substantial  damage  to  wildlife (birds, downstream




aquatic community,  stream  bottom-dwelling organisms) and




local vegetation.   Pathological examinations established




that the cattle died  of cyanide poisoning. ( ^2)




     In 1965,  unlined lagoons  in Columbia County, Pennsylvania,




caused contamination  of private wells  in the area.   The




lagoons were leaking  plating wastes containing cyanide,




copper, nickel al Iky Ibenzenesul f onat e , and pho s ph at e . ' ^2 '




     A landfill in Monroe  County,  Pennsylvania, that accepts




plating process wastes such  as  hydrocyanic acid, has created

-------
a groundwater  pollution problem in the  area.'^J


     Between  1962  and 1972 in Lawrenceburg,  Tennessee, an


industry dumped  up to 5,000 gallons of  untreated  metal plating


waste daily into  trenches near the city dump.   Trace quantitie


of cyanide were  measured in private wells  and  in  an adjacent


drinking water  supply.(12)  More recently,  cyanide  wastes were


disposed down  boreholes in Pittston,  Pennsylvania,  which

                                             / -I O 'J
discharged directly  into a nearby wat e rway . ^ 1J '


2.    Reactivity  Hazard


     Cyanide  salt-containing wastes (although  not  complexed


cyanide wastes)  pose  a  reactivity hazard as  well.   These are


cyanide bearing  wastes  which when exposed  to mild  acidic


conditions react  to  release toxic hydrogen  cyanide  gas,  and


thus possess  the  characteristic of reactivity  (see  §261.23


(a)(5).


     Documented  damage  incidents resulting  from mismanagement


of wastes from  disposal of cyanide salts are presented below:


     Damage Resulting from Reactivity of Wastes


     (1)  A tank  truck  emptied several thousand gallons  of


          cyanide  waste onto a refuse at a  sanitary  landfill


          in Los Angeles County, California.   Another  truck-


          subsequently  deposited several thousand  gallons of


          acid waste  at the same location.    Reaction between


          the  acid and  the cyanide evolved  large  amounts of


          toxic hydrogen cyanide gas.   A potential  disaster


          was  averted when a local chlorine  dealer  was
s

-------
          quickly called to oxidize  the  cyanide  with
                                      i
          hydrogen chlorine solution.(12)   Hydrogen cyanide

          gas can be fatal to humans  in  a  few  minutes  at

          a concentration of 300 ppm.  The  average fatal

          dose is 50 to 60 mg.

     (2)  A standard procedure at a  Southern California dispo-

          sal site for handling liquid wastes  containing

          cyanides and spent caustic  solutions was to  inject

          these loads into covered wells dug into a completed

          section of a sanitary landfill.   Routine air sampling

          in the vicinity of the wells detected  more than

          1000 ppm HCN.  No cyanide was  detected during

          addition of the spent caustic  to  a new well.  On

          the basis of these discoveries, use  of the wells

          was discontinued.  The cyanide gas was apparently

          formed in the well as a result of lowering of the

          pH of the waste by C0£ and  organic acids produced

          in the decomposition of refuse. (12)

V.   HEALTH EFFECTS

     The toxicity of both cyanides and hydrogen  cyanide have

been well documented.  Cyanide in its most  toxic form  can-be

fatal to humans in a few minutes at a concentration of 300

ppm.  Cyanide is also lethal to freshwater  fish  at concen-

trations as low as about 50 mg/1 and  has been  shown to

adversely affect invertebrates and fish  at  concentrations of

about 10 mg/1.   Hydrogen cyanide is also extremely toxic to

-------
humans  and  animals,  causing  interferences with respiration




processes leading  to  asphyxiation  and  damage to several organs




and systems.   Toxic  effects  have  also  been reported at the




very low exposure  level  of less  than  1 mg/kg.(^,lo;




     The hazards associated  with  exposure to cyanide  and




hydrogen cyanide have  also been  recognized by  other regulatory




programs.   Congress  listed cyanide  as  a priority pollutant




under  §307  of  the  Clean  Water  Act  of  1977.   In addition,  the




U.S. Public Health Service established a  drinking  water




standard of 0.2 mg/1  as  an acceptable  level  for cyanide in




water  supplies.  The  Occupational  Safety  and Health Administration




(OSHA)  has  established a permissible  exposure  limit for KCN




and NaCN at 5  rag/m^  as^an eight-hour  time-weighted average.




Additionally,  the  OSHA permissible  limit  for exposure  to  HCN




is 10  ppm (11  mg/m^)  as  an eight-hour  time-weighted average.




DOT requires a label  stating that HCN  is  a poisonous  and




flammable gas.




     Finally,  final  or proposed regulations  of  the states  of




California,  Maine, Maryland, Massachusettes, Minnesota,




Missouri, New Mexico, Oklahoma and  Oregon  define cyanide




containing  compounds as  hazardous wastes  or  components




thereof.(17)




     A more  detailed discussion of  the  health  effects  of




cyanide is  contained in  Appendix A.
                             -130 -

-------
V.   REFERENCES


1.   Midwest Research Institute.   April  1976.   The  Manufacture
     and Use of Selected Cyanides.   Kansas  City,  Mo.   Prepared
     for U.S. Environmental Protection Agency.   EPA 560/6-76-
     012.  Pp. 6-11, 24-99.

2.   Composite of State Files  of  "Special Waste Disposal
     Applications."  1976-1979.   Results  of  Leachate  Tests
     on Cyanide Containing Wastes  from Illinois,  Iowa,
     Kansas and Pennsylvania.

3.   Cotton, F. A. and G. Wilkinson.  1979.  Advanced  Inorganic
     Chemistry.  John Wiley &  Sons,  Inc., New York.   pp.  300-301.

4.   Production and Use of Cyanide,  Draft Report, Contract
     68-01-3852, Task Order 22.   Prepared for EPA-MDSD  by
     Versar, Inc., Springfield, Virginia  (1978).

5.   U.S. Environmental Protection Agency.   July  1976.  Quality
     Criteria for Water.  Office  of  Water and Hazardous Materials.
     Washington, D.C. p. 67.

6.   Webster, W. 1979.  U.S. Environmental Protection Agency.
     Personal communication.

7.   U.S. Environmental Protection Agency.   February, 1978.
     Development Document for  Proposed Existing  Source  Pre-
     treatment Standards for the  Electroplating  Point Source
     Category.  EPA 440/1-78/085.

8.   Radian Corporation.  February 1977.  Industrial  Process
     Profiles for Environmental Use:  Chapter 24  The  Iron and
     Steel Industry.  Austin,  Texas.  Prepared  for  U.S. Environ-
     mental Protection Agency, IERL, Research Triangle  Park,
     N.C.  EPA 600/2-77-023X.

9.   Lancy, L.E.  1979.   Dart  Industries, Inc.   Lancy Labora-
     tory Division,  Elienople, Pa.

10.  Wapora, Incorporated.   March, 1977.  Assessment  of Indus-
     trial Hazardous Waste  Practice  Special  Machinery Manu-
     facturing Industries.   Washington, D.C.  Prepared  for
     the U.S.  Environmental Protection Agency,  Office of
     Solid Waste,  Washington,  D.C.   SW-l41c.

11.  U.S.  Environmental  Protection Agency.   July  1975.  Develop-
     ment Document for Effluent Limitations  Guidelines  and
     New Source Performance Standards for the Iron  and  Steel
     Foundry Industry.

-------
12.  U.S. Environmental Protection Agency.   1978.   Hazardous
     Waste Incidents.  Office of Solid Waste,  Hazardous
     Waste Management Division.  Unpulished,  open  file  data.

13.  Philadelphia Inquirer.  October 15-26,  1979.   Series  of
     Articles Related to Pittston Cyanide Disposal.

14.  Alesi, B.A. and W.A. Fuller.  1976.  The  Mobility  of
     Three Cyanide Forms in Soil.  Pp. 213-223.  In  Residual
     Management by Land Disposal, W. H. Fuller  (ed.),
     Environmental Protection Agency, Cincinnati,  OH
     PB 256768 268.

15.  Cruz, M., Et al.  1974.  Absorption and Trans  Formation
     of HCN on the Surface of Copper and Calcium Montmorillanite
     Clay Minerals 22: 417-425.

16.  The Prevalence of Subsurface Migration  of Hazardous Chemical
     Substances at Selected Industrial Waste Land Disposal
     Sites.  1977.  EPA/520/SW-634.  U.S. EPA, Washington, D.C.

17.  Chemical Engineering News,  Editors Newsletter, November,
     1979.

-------
APPENDIX I
   FLOW DIAGRAMS

-------
Metal
Parts
' Surface
Preparation
and Cleanim


* E1
, "'

V V
ectro- ^
a ting


_
Alkaline
Chlorination
4


Chemical
Precipitation
	 wa
ntncfnn t Single-Coated
Rinsing Electroplated
Parts
i i
1
1 l
i i
i i
i i
i
stewater J
                          Sludge and Solvent
                                to
                          Sanitary Landfill
                   2.5 kkg/yr-Dept. employee (wet)
                   1.0 kkg/yr-Dept. employee (dry)
  Rinse Water
      to
Sanitary Sewer*
  *Due to pending EPA effluent guidelines, rinse water discharge to sewers may
   be prohibited  in  the  future,  lliis wastewater generation rate presently
   amounts to 1.0 kkg/yr-Dept. enployee.
          FIGURE 1-1  SIMPLIFIED TYPICAL EUDCTROPLATING OPERATION
                                                                 (10)

-------
    strong
    acid
     itfong
     olkali
hold
hold
                         gpm
        gpm
     dilute acid      CB6 „
     and alkali
   gpm
                    Neutral*
                     izatlon
                700
                                             gpm
chromium
             Reduction
              225
                              gpm
               MCI
     strong
     cyanide
     WtlH
                 Hold
        gpm
340
360
     cyanide
              ypm
Dtitruo-
 tion
3KO
                      lump
                     25 gpm
                                                                                                      1300
                     1275  1300
                                         gp™
                                Final
                               Neutral-
                               ization &
                             Precipitation
                                 1300 ^
                                                 gpm
                                                                                                      gpm
                                                                         Clarilier
                                                                                               gpm
                gpm
                                                                                                                  "  7 gpm
                                                                                   Filter
                                                                                                                    1.8 gpm
                                                                                                                iludqc
                             FIGURE 1-2  DIAGRAM OF A TYPICAL CONTINUOUS  TREATMENT PLANT
                                                         -/JET-

-------
Metal
Ports
Heating 1n
Furnace

Heating 1n
, Molten Salt
Dath



i
i

Cooling In
flitrtft^r^itinrt
*s ijuCiicii i ny
" Uath
t
i
t
i
i
i
i
: r"""":::::::::;: 	

Metal
f^k f* 1 rk ^t rt • n ri
Ix L 1 Gall 1 liy
1
1
1
1
I
1
1
1
1


  Meat
Trea tod
 Parts
                     Waste Disposal  to Landfills


        Total 2.00 kkg/yr-Dcpt. employee (wet)- 0.07 (dry)
            Quench oils 0.06 kkg/yr-Dept. emp.  (wet)~0.65 (dry)
            Cyanide waste 0.14 kkg/yr-Dept.  emp. (wet)
            Acids/alkalies 1.00 kkg/yr-Dept. emp.  (wet)
                FIGURE 1-3  SIMPLIFIED TYPICAL HEAT TREATING AND CARBURIZING OPERATION
                                                                                    (10)

-------
                           Ore
                         Crushing
                        Rod Milling
                       Bali Milling
                       Launder Traps
                       CJossi flection
                        Cycloning
 Lime
 NoCN
1
Sands  (60%)
         Sand Leach Vats
       I
     Residue
     to Fill
     Mine
     Stopes

  Barren Solution
                        Zinc
                        Dust
          Precipitation
                 Filtration
                    I
                 Bullion
                 to Refinery
Adapted from Gold and Silver
Cyonidotion Plant Practice.
                                    Barrel
                                    Amaloamotion
                                                •To Refinery
                                      r
                                                Carbon m Puio Plant
                                                          Slimes (40%)  '
                                                     Thickeners
                                   NoCN	1
                                     ir
                                   NaCN
                                   NoOH
                                                              Lime
                                                              & Air
Conditioning
                                          Adsorption Agitators
                                                            To Toiling Pond
                                           Desorption
                                                     Carbon Reactivation
                                                Electrolysis

                                           Sponge to
                                           Refinery
                                                              T
                                                          Undersize
                                                          to Refinery
         FIGURE  1-4  GOID  AND SILVER RECOVERY  PROCESS SCHH^ffiTIC
                                                                          (1)

-------
        O
          ie
       Crushing
      Rod Milts
r
Doll Mill*
     Classification
     Conditioning

Copper Ore
-H
<
fe»

<





Flotation

	 ^-Copper Concentrates
Copper - Molybdenum Ore
Bulk 0
Flotation



Copper
Moly 	 •
.Cone.

Copper - Lead - Zinc Ore /Tv
Selective ^-/
Flotation




Selective 	 •
Flotation 	 «

Flotation 	 •

^2\ — «*~ Molybdenum Concentrates
». Selective
Flotation — *- Copper Concentrates

»-Lead Concentrates
•*• Copper Concentrates
»- Zinc Concentrates
Copper - Zinc - Iron - Sulfide Ore
Selective \5)
Flotation

Leod - Zinc Oie
Selective ffr\
Flotation

— *•

—
Leod - Zinc - Silver Oi






Selective /y\
Flotation

Zinc Ore
Selective /g\
Flotation

:luorspar Ore
Selective fi\
Flotation

	 •»-
-*-
— »-
Copper Concenl
Selective ,
Flotation

Lead Conccnlra
Flotation I 	

rales
•*. Zinc Concentrates
cs
^•Zlnc Concentrates
e
Lead Concentrates With Silver
Flotation 	

^" Zinc Concentrates
Lead Concentrates
Flotation 	

•"- Zinc Concentrates
Fluorspar Concentrates
Flotation I 	

•""Zinc Concentrates
Cyanides
Used
NaCN
Ca(CN)2
^ NoCN
{*) Ca(CN)2
NoCN
f) Ferrocyanide
Ferrlcyonide
^y co(CN)2
^ NaCN
^ Ca(CN)2
/Tk NoCN
W Ca(CN)2
©NoCN
Co(CN)2
xrs NoCN
v:/ Ca(CN)2
^~, NaCN
Mojoi Sj>rcies
Dcpresse<<
lion Sulfidcs
,1 J Iron Sulfiilrs
[2) Copper Sulfidn
(3) Zint SuHides
[4) Copper Sulfides
©Zinc Sulfides
Iron Sulfides
(^T\ Zinc Sulfidcs
^^ Iron Sulfidcs
0Zinc Sulfides
Iron Sulfidcs
(O) Zinc Sulfides
© Zinc Sulfidcs
                             FIGLIRE 1-5   GENERALIZED SELECI'IVE  FIOl'ATION  PROCESS SCHEMATIC
                                                                                                              (1)

-------
flaw WoUr
  02OI  IA«c —
  II3.OOO
                   MOISTURE
                  SEPAKAIOR

scnuoeEn
                                            Slnlir Plant
                                                                   020.1 I/MC
                                                                   (13.000 gpm)
                            ALKALINE

                          CIILOnUUTION
               336 I/MC
                   gpm|
                                        onir
                                      CHAMBER
 To
                                                           PLANT5O2T

                                                           PRODUCTIONS 3494 M«Ulc Too* SU«l/Oay

                                                                       (6O37 Tone SU«l/Oay)
                                                                                                 Outfall
   079 f»«c
  13.932  gpm
  PI.ml
                                                                                                      Hot Mttol Dftiulfurliallon
12.«  l/»»c
(200 gpm)
                                   FIGURE  1-6   aiLORINATION  OF BLAST FURNACE  CYANIDE WASTE
                                                                                                       (8)

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                 Response To  Comments

One commenter  suggested  that  the  listings  of  "Spent  or
waste cyanide  solutions  or  sludges"  should  be  modified
so as ot to include solutions or  sludges containing
small amounts  of cyanide formed during  one  or  more
proces operatins.  The following  language  was
recommended:

      "Spent or waste cyanide solutions or  sludges
       resulting from cyanide-based  processes  (R,T)"

     °The Agency agrees with  the  commenter  that  solutions
      or sludges that contain minute quantities  of cyanide
      should not and are not  intended to be included
      in the above listing.   However, to limit the listing
      to just  those processes which  result  from  cyanide-
      based processes may leave out  several waste streams
      from RCRA control wich could present  a problme,
      if improperly managed.  For example,  during blast
      furnace  operations nitrogen, water and carbon combine
      to produce hydrogen cyanide. Desulfurization scrubbers
      installed on many of the blast furnace stacks scrub
      HCN scrubber liquor is rarely  treated.   Thus, if
      the scrubber liquor is dewatered,  the cyanide is
      likely to end up in the sludge at  concentrations
      high enough to be of concern (see  discussion under
      Coke Oven and Blast Furnace, p. 15,  for more
      details ).

A number of comments suggested that  the  definition of
cyanide bearing wstes should distinguish between
"free  cyanide" and "ferro cyanide",  since  the latter
would  not be available to gnerate  hydrogen cyanide
under  mild, acidic, or basic conditions.

      "The Agency agrees  that only cyanide salt-
       containing wastes  pose a  reacivity  hazard,
       and the listing descriptions reflect this
       distinction, since no complex cyanide wastes
       are listed for reactivity.

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Wood Preserving

-------
                  LISTING BACKGROUND DOCUMENT

                          WOOD PRESERVING
      Wastewater  from  wood  preserving processes that use
      creosote  or  pentachloropheno1 (T)

      Bottom  sediment  sludge  from treatment of wastewaters
      from wood preserving  processes  that use creosote and/or
      pentachlorophenol  (T)
I.   Summary  of  Basis  for  Listing*


     Wood  preserving  processes  that  use  creosote or penta-

chlorophenol  as  preserving agents  generate a wastewater,

which contains  toxic  phenolic  compounds  including penta-

and tetrachloropheno1, volatile  organic  solvents such as

benzene and toluene,  and polynuclear  aromatic (PNA) components

of creosote.  Treatment of this  wastewater results  in the

generation  of a  bottom-sediment  sludge that  must be removed

for ultimate  disposal.  The Administrator  has determined

that wastewater  from  these wood  preserving processes  and the

resulting  bottom sediment  sludge are  solid wastes that  may

pose a substantial present or  potential  hazard  to human

health or  the environment  when improperly  treated,  stored,

disposed of or otherwise managed, and therefore  should  be

subject to  appropriate management requirements  under  Subtitle

C of RCRA.
*Based on available data, and in response  to  industry
 comment, the Agency has modified  this  listing.   Waste streams
 from wood preserving processes using waterborne  inorganic pre-
 servatives are not included in the  listings  of  this  document.
 However, although limited data is currently  available on the
 sludges generated from these wood preserving processes (i.e.,
 from work tanks, cylinders or storage  tanks),  the  Agency
 plans to study these wastes in the  future  to determine whether
 they should also be listed.

-------
This conclusion is  based  on  the following considerations:

1)   The wastewater  generated  from wood preserving
     processes using pentachloropheno1 as a preservative
     and the sludge  generated  from the treatment of this
     wastewater will contain  significant concentrations
     of toxic phenolic  compounds  and  volatile organic
     solvents such  as benzene.

2)   The wastewater  from  wood  preserving processes that
     use creosote and the  sludges  generated from the
     treatment of this  wastewater  will contain significant
     concentrations  of  toxic  polynuclear aromatics components
     of creosote and volatile  organic solvents such as
     toluene.  Wastewater  and  resulting sludges  from
     wood preserving operations  that  use both creosote
     and pentachlorophenol as  preservatives will generate
     waste streams  which  contain  all  or most of  the
     above contaminants.

3)   Polynuclear aromatics,  as  a  group,  are known to be
     toxic, rautagenic,  teratogenic  and carcinogenic.
     Phenolics are  toxic  and,  in  some cases,  bioaccumu-
     lative and carcinogenic  substances.   Benzene and
     toluene are relatively  toxic,  and benzene is a
     carcinogen.

4)   Approximately  200,000,000  gallons of wastewater are
     generated annually.  About 90  percent  of this  waste-
     water is treated by  treatment  methods  which generate
     a bottom sediment  sludge.

5)   Treatment of wastewater in evaporation ponds or
     lagoons, could  lead to the environmental release
     of hazardous constituents  and  result  in  substantial
     hazard via groundwater or  surface water  exposure
     pathways.  Evaporation of wastewater  in  ponds,
     lagoons or by other treatment  methods,  if mis-
     managed, could  lead to the release  of  hazardous
     constituents into  the atmosphere  and  result  in
     substantial hazard via an air  exposure  pathway.

6)   Off-site disposal  in landfills is  the  most  commonly
     used  disposal method for these sludges.   This
     presents the possibility of the  toxic  components
     in the sludge migrating to nearby  underground
     drinking water  sources,  if the landfill  is
     improperly designed or operated.

7)   The Agency has been informed that  incineration  is
     another (though less frequently  used)  disposal

-------
           method  for these sludges.   If improperly managed,
           incineration could  result  in the release of hazardous
           vapors  to  the atmosphere,  presenting a substantial
           hazard  via an air  exposure pathway.


 II.   Sources  of the  Wastes and  Typical Disposal Practices


           A.   Industry Profile  and Manufacturing Process


           There are  approximately 415  wood preserving plants

 operated by about 300  companies  in the  United States .  The

 plants are concentrated  in two  areas,  the  Southeast from east

 Texas to Maryland and  along the  Northern Pacific coast.

 These areas correspond  to  the natural  ranges  of the southern

 pine and Douglas  fir-western red cedar, respectively  (2).

           Approximately  240 million  cubic  feet  of wood  are

 treated each  year (1),  principally for  railroad ties, utility

 poles, and lumber for  construction materials.   Of the 250

 million cubic  feet of wood treated annually,  it is  estimated

 that approximately 85  percent is treated with  creosote  or

 pentachlorophenol based  preservatives as shown  in Table  1

 (4).  The  total quantity of preservative consumed in  1975

during these  treatment cycles is shown  in  Table 2.

           B.   Process Description

          At  plants using  creosote or pentachlorophenol-based

preservatives, wood products are treated by chemical  processes

to increase their  resistance to natural decay,  attack by

-------
                            TABLE 1
       VOLUME  OF WOOD  TREATED IN 1975 BY PRESERVATIVE (4)
               Preservative Type
                  I Quantity of
                  (Wood Treated
                  I(million cubic feet)
 I Oil Borne   85%
  Waterborne  15%
                   Creosote and creosote-coal tar
                   Creosote-petroleum
                   Creosote-pentachlorophenol
                   Petroleum—pentachlorophenol
                   Chromated  copper arsenate (A,B,C)|
                   Fluor-chrome-arsenate-phenol
                   Chromated  zinc chloride
                   Acid  copper chrornate
                   All other  preservatives
                         110.5
                          32.1
                           0.9
                          60.8
                          29.9
                           1.8
                           0.5
                           1.4
                           1.8
                            TABLE 2
           QUANTITY  OF  PRESERVATIVES USED IN 1975.
 LIQUIDS:
 Creosote
 Coal  Tar
*Petroleum  (with PCP)
*Petroleum  (with creosote)
96.3 million gallons (0.84 gal/cu ft)
23.6 million gallons (added to above)
48.7 million gallons (0.80 gal/cu ft)
16.7 million gallons (0.52 gal/cu ft
                        plus creosote)
 SOLIDS:

 Pentachlorophenol

 Chromated Copper Arsenate
 Other  Solids  (zinc, fluor,
 chromate, etc.)
35.5 million pounds (0.58 Ib/cu ft
                     plus petroleum)
15.9 million pounds (0.55 Ib/cu ft)
 4.5 million pounds (0.82 Ib/cu ft)
     *The petroleum listed  in  Table  2  acts as a dissolving
 and/or carrying medium  for  the preservatives  with which they
 are used.

-------
 insects,  micro-organisms,  or fire.  Briefly, the treatment  consists



 of  debarking,  forming,  drying,  impregnation of preservative,



 and  s torage  (3).



      The  two  major  wood preserving processes, producing  large



 quantities of  wastewater and sediment sludge, are called steaming



 and  boultonizing.*  Both these processes are pressure processes



 and  differ mainly  in  the way the  wood is conditioned before or



 during  the application  of  the preservative.  Figures la-le present
                                  1        '                 i


 flow diagrams  for  the major  wood  preserving processes  (Source:



 Re ference  19).



      Steaming  is used principally on southern pines.  In this



 process,  the  stock  is normally  steamed for 1 to 16  hours at



 about 120°C  to reduce the  wood's  moisture  content and render



 it more  penetrable  to preservatives.   After steaming, the



 preservative  is added to the same retort.   Condensate removed



 from the  retort after steaming  is contaminated  with  entrained



 oils, organic  compounds,  and wood carbohydrates.



      In  the boulton process,  used principally on  Western



 Douglas  fir,  the wood is  already  immersed  in the  preservative,



 placed under vacuum, and  then heated  in the retort  at approximately



 100°C.  The vapor removed  is  composed  of water,  oils, organic



 compounds and carbohydrates  from  the  wood.   Contaminated



vapors from both the steaming and boultonizing  processes are
     *Vapor drying is another wood  preserving process, also

generating a wastewater and sludge  of  concern.

-------
    WOOD' IN
    WOOD OUT
   PRESERVATIVES
   TO WORK TANK
WORK TANK
                   TREATING CYLINDER
                         STEAM
     PRESERVATIVES
      TO CYLINDER
                                   COOUHO
                                    WATER
                                                            -C COrlO£N5fci\ Jr
                     CYLINDER WATErt
                                    CYLINDER DRIPPINGS
                                     AND RAIN WATER
                       RECOVERED OILS
                                     OIL - WATER
                                     SEPARATOR
                                                                         VACUUM
                                                                          PUMP
                                                                ACCUMULATOR
                                    CONDENBATE
                                    WASTE WATER
                                                                                     AIR AND
                                                                                     VAPORS
                                                                   COOLINd
                                                                    WATER
       FigUr.e la> ,
OPEN STEAMING PROCESS WOOD TREATING PLANT
                                     »s~

-------
    wodo IN
    WOOD OUT
   PRESERVATIVES
   TO WORK TANK
WORK TANK
         I
TREATING CYLINDER
                                           VAPORS
                 J
     CONOCNSATE

     •TEAM

   PRESERVATIVES
    TO CYLINDER
                      RECOVERED O!U
                   CYLINDER
                   WATER
                   STORAGE
CYLINDER DRIPPINGS
 AND RAIN WATER
                                   Oil-WATER
                                   SEPARATOR
                COOLINQ
                 WATER
                                                           CONDENSER >
                                                                     VACUUM
                                                                      PUMP
                                                             ACCUMULATOR
                                CONDEN8ATE
                                  WASTE WATER
                                                               AIR AND
                                                               VAPORS
                                                                                 COOLINQ
                                                                                 WATER
           lb  CLOSED STEAMING PROCESS WOOD TREATING PLANT

-------
    WOOD IK
    WOOD OUT
   PRESERVATIVES
   TO WORK TANK
WORK TANK
   TREATING CYLINDER
                        COMPENSATE
        STEAM


       PRESERVATIVES
        TO CYLINDER
                      CYLINDER WATER
                                   CYLINDER DRIPPINGS
                                    AND RAIN WATER
                       RECOVERED OILS
                                    OIL - WATER
                                    SEPARATOR
                                   WASTE WATER
                                    COOLINO
                                     WATER
                                                            CONDENSER >
                                                                                   AIR AND
                                                                                   VAPORS
                                                                       VACUUM
                                                                        PUMP
COOLING
 WATER
                                                               ACCUMULATOR
                                     COMPENSATE
  Figure Ic
MODIFIED STEAMING PROCESS WOOD TREATING PLANT

-------
    wooo
    WOOD OUT
:
   PRESERVATIVES
   TO WORK TANK
WORK TANK
                                            VAPORS
                  TREATING CYLINDER

         PRESERVATIVES
          TO CYLINDER
                      RECOVERED OILS
CYLINDER DRIPPINGS
 AND RAIN WATER

                                   OIL - WATER
                                   SEPARATOR
                                   WASTE WATER
                COOLINQ
                 WATER
                                                            COOLINQ
( CONDENSER )
                                                                      VACUUM
                                                                        PUMP
                                                              ACCUMULATOR
                                       CONDEN3ATE
                                                                                  AIR AND
                                                                                  VAPORS
                Figure  id  BOULTON WOOD TREATING PLANT

-------
    WUUU IN
    WOOD OUT
   PRESERVATIVES
   TO WORK TANK
WORK TANK
                   TREATINQ
PRESERVATIVES
 TO CYLINDER
                   I
                                              CONDEN8ED VAPORS
            STEAM   SOLVENT
                  VAPORIZER
                   STEAM
CYLINDER DRIPPINGS
 AND RAIN WATER
                       RECOVERED OILS
                                    OIL -f WATER
                                     SEPARATOR
                                    WASTE WATER
                                                                                     AIR AND
                                                                                     VAPORS
                                                            SOLVEN1
                                                            •«—+^+~*~-

                                                            WATER
                                                                        VACUUM
                                                                          PUMP
                                                                ACCUMULATOR
                               CONDENSATE
  Figure le
              VAPOR CONDITIONING PROCESS WOOD TREATING PLANT

-------
 condensed  and  transported to an oil/water separator  to  reclaim

 any  free  oils  and  preserving chemicals before treatment  and/or

 disposal  of  the  wastewater,  usually an oil/water emulsion.'*' »1° '


 II.   Generation,  Composition,  and Management of Listed Waste
      Streams  (17,1ST"  ~"~~

          •. A.   Generation

           Based  on  the  quantity of wood treated with

 creosote  or  pentachloropheno1  preservatives  in 1975, and

 assuming  that  about  one  gallon of wastewater is generated

 per  cubic  foot of wood  treated,  approximately 200 million

 gallons of wastewater will be  generated annually.

           About  90%  of  this  wastewater is  treated by treatment

 methods that generted a bottom sediment sludge.   The remaining

 wastewater is  typically discharged directly,  to POTW's.   The

 listing covers both  of  these instances.*

          Table  3 shows estimates  of  the  amounts  of sludges

 generated by creosote and pentach loropheno1  preserving

 processes, and the amount of hazardous  constituents contained

 in the wastes.
     *The listing does not  include wastewater  discharged from
a point source regulated under  §402  of  CWA.  This  listing also
does not include any wastewater which is  mixed with domestic
sewage and that passes through  a  sewer  system  before it
reaches a pub lielyowned treatment works  (POTW) for treatment.
"Domestic Sewage" means untreated sanitary  wastes  that passes
through a sewer system.

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    TABLE 3.  POTENTIALLY HAZARDOUS  SOLID WASTES FROM THE
              WOOD PRESERVING  INDUSTRY (8)*
 (Source:   American Wood Preserver's  Association (1979)
Total Process
 Solid Waste
metric tons/yr
  Total Potentially
Hazardous Constituents
  met ri c tons/yr
Creosote-oil emulsion
      230-930

Penta-oil emulsion
      600*
        Creosote
         1.1-4.6

    Pentachlorophenol
           3.0
Note:   Although these wastes are  listed  in the table in
terms  of  amounts generated per year,  many of the wastes are
generated on  a periodic basis which  often can be as long as
five years  (8).  Thus, the sludges may be allowed to sit at
the bottom  of wastewater treatment ponds  for five years at a
time.
    *Estimated  maximum amount.

-------
B.   Compos i t ion

     Table  5  presents  a list of some of the typical organic

compounds found in  wood treating plant wastewaters.*  Bottom

sediment  sludge from wood  preserving plants contains primarily

creosote, polynuclear  aromatics (creosote compounds), chlorinated

phenols and volatile organic solvents such as toluene and benzene,

as listed in  Table  6.

     According to data  taken from California State hazardous

waste manifests,  (7) this  waste may  contain 5-20% pentachlofo-

pheno1.

     EPA  has  tested samples  of  bottom sediment sludge and

found that  it contains  polynuclear  aromatic hydrocarbons and

phenolic  compounds.  Many  wood  processing plants, such as the

two listed  below, may use  both  creosote  and pentachloropheno1

based processes and thus treat  the wastewater generated  by these

processes in  a combined  treatment  system.   Thus,  sludge  samples

from one  plant may  contain both creosote  compounds  and phenolic

compounds.  The pertinent  information from two plant's sludge

samples (Plants 10  and  11) is summarized  below:**
     *Approximately  125 wood preserving  plants  use both
organic and inorganic preservatives.  Although  the systems
are kept separate, cross contamination of  chemicals may
occur through exchange of dollies used to  transport the wood
and drippage from the inorganic  into  the organic  operation.
Thus, wastewater from organic wood  treatment  processes often
contains inorganic materials.

    **For details of sampling program and  further information,
see Reference 6.

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 TABLE 5.  HAZARDOUS  ORGANIC  COMPOUNDS FOUND IN WOOD PRESERVING
          PLANT WASTEWATER.(17)
 Using Pentachlorophenol
                             Using  Creosote
 Phenol
 2,4-Dichlorophenol
 2,4,6-Trichlorophenol
 4-Nitrophenol
 4,6-Dinitro o-cresol
 Te.tr achlorophenol
 Pentachlorophe.no 1
 Benzene*
                              Toluene*
                              Fluoranthene
                              Naphthalene
                              1,2-Benz anthracene
                              Chrysene
 TABLE 6 .
HAZARDOUS ORGANIC COMPOUNDS  FOUND  IN  WOOD PRESERVING
PLANT BOTTOM SEDIMENT  SLUDGE  (17)
                Creosote  Polynuclear Aromatics

                          Benz(a)anthracene
                          Benzo(a)pyrene
                          Chrysene

                          Phenolies**

                          Phenol
                          2-chlorophenol
                          Pentachlorophenol
                          2,4-dime thyIpheno1
                          2,4,5-trichlorophenol
     *Certain volatile compounds  in  the  wastewater,  such as
toluene and benzene,may volatilize completely  during the evaporation
process and thus may not appear in the  sludge.

    **A test conducted on a cooling  tower  sludge  at  a plant
treating with pentachloropheno1 revealed the  presence of octa-
chlorodibenzo-p-dioxin as well as phenolics.   The .presence
of this dioxin and the possibility of the  presence  of other
more hazardous dioxins (such as TCDD) is of  great concern to
the Agency since various chlorinated dibenzo-dioxins are
known carcinogens, mutagens and teratogens  (IARC  Monographs
on the Evaluation of Carcinogens Risk of Chemicals  to Man,
Vol.  15).
      However, the Agency is not  listing these  waste streams
for the presence of these constituents until  further information
of the presence and fate of dioxins  in the waste  is  made
available.

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Plant  10
                                 Bottom  Sediment Dry Weight  (mg/kg)(6)
Polynuclear  Aromatics

  Benz(a)anthracene
  Chrysene

Phenolies

  Pheno1
  2,4-dimethylphenol
  2-chlorophenol
  2,4,6-trichlorophenol
  Pentachlorophenol
 Aerated Lagoon

      3,700
      4,500
       9,030
       4,398
     396,000
     No data
     302,000
Final
     149
   2,060
   16,000
    3,418
    1,200
   25,000
   58,000
     One  sediment  waste sample was taken  from  an aerated lagoon;

the analytical  data for this plant are  summarized below:
Plant  11
Polynuclear  Aromatics

  Benzo(a)anthracene
  Benzo(a)pyrene
  Chrysene
Bottom Sediment  Dry  Weight

          Aerat ed Lagoon

                  1,250
                  5 ,980
                  9,280
Phenolics

  Pheno1
  2-chlorophenol
  Pentachlorophenol
                  4,500
                     300
                  4,800
     Additionally,  a  contractor/hauler that disposes  of

bottom sediment  sludge  for  a wood treatment plant  has  provided

an analysis of  the  waste  for EPA (3).  The analysis  is as

fol lows:

-------
  Component                             Concentration,  mg/l(6)

Total phenols                                    5,043
Pentachlorophenol                                   34
Dinitrophenol                                       24
Creosote         .                               10,000


C.   Typical Disposal Practices
                                   I

     These plants typically  dispose  of  their  wastewater
                      - j
streams by .one of two treatment  methods,  namely evaporation

or combined biological and irrigation process.

     In the evaporation  treatment  process,  water  is  evaporated

off, leaving the bottom  sediment sludge.   Currently  there

are four prinicipal evaporative  methods:   still ponds,  pan

evaporators, stripper/cooling  towers  and  spray  ponds.   All

four methods produce bottom  sediment  sludge.

     A still pond depends on the natural  evaporation of water

from the pond surface.   A pan  evaporator  adds heat  to  the

wastewater in order to accelerate  evaporation.   (In  both cases,

a sludge remains in the  evaporation vessels.)

     In a stripper/cooling tower,  wastewater  is pumped  to the

top of the tower and flows down  slatted surfaces  in  contact

with the air.  Sludge accumulates  in  the  base of  the tower  and

is removed when its build-up hinders  tower  performance.

     A spray pond uses a high-pressure  pump and nozzle  assembly

to spray wastewater droplets into  the air.  The resulting

large droplet surface area contacts the air,  promoting

evaporation.   Again, the accumulated  sludge remains  in  the

pond .

-------
     When  sufficient sludge residue has been accumulated,  it




is  removed  from the bottom of the evaporation device  and




transported  to  a dry bed.   The sludge is typically  disposed




of  in  an off-site landfill (6).




     The second (although  less typical) method used by wood




preserving  plants is a combined  biological and irrigation




process.  This  process consists  of (1) settling, (2)  storage,




(3)  aerated  treatment, (4) spray irrigation,  and (5)  runoff




storage.  Rainfall  runoff  water  is collected  in a storage




pond,  recycled  through spray  nozzles,  and then bled into a




settling basin  for  treatment.   The wastewater flow at a




particular  plant  equipped  with this  type of treatment system




averaged approximately 50,000  gallons  a day.^"'   Wastewater




flows  from  the  settling  basin  to a storage pond, and  then




into an aerated lagoon.  The  wastewater remains  in both the




storage pond  and  the aerated  lagoon  for 40 to 60 days.  From




the  aerated  lagoon,  the  wastewater is  intermittently  pumped




and  sprayed  through  spray  nozzles  onto a planted field.




Runoff from  this  field is  collected  in a runoff  storage




pond.  Sludge is  generated in  this treatment  system on the




bottom of the aerated  lagoon  (6);  typically the  sludge is




disposed in  an  off-site  landfill.




     The Agency,  believes  that incineration is  another,




chough less  frequently used,  disposal  practice  for these




s ludges .

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Ill.  Discussion of Basis for Listing


          A.   Hazardous Properties of the Waste


          As  discussed earlier, the most commonly  used  wood


preservatives are pentachloropheno 1 and creosote.   The

                          - ^
principal toxic pollutants in wastewater from  plants  that


treat with these preservatives are phenolic  compounds,  vola-


tile, organic  solvents such as benzene and toluene,  and  poly-


nuclear aromatic hydrocarbon components of creosote.


          Phenolics are toxic and, in some cases,  bioaccumu-


lative and carcinogenic.  Polynuclear aromatics, as a group,


are known to  be toxic, mutagenic,  teratogenic  and  carcinogenic.


Benzene and toluene are relatively toxic, and  benzene is  a


carcinogen.



          B.   Migratory Potential  of Hazardous Constituents


          In  light of the extreme  danger posed by  these waste


constituents, the Agency would require some  assurance that


these waste constituents will not migrate and  persist to  warrant


a decision not to list these waste streams.  No such


assurance appears readily available.


          Many of these waste constituents,  in fact, have


proven capable of migration,  mobility and persistence.


Chrysene,  naphthalene, benz(a)anthracene, and  benzene have


been  detected in rivers,  demonstrating ability to  persist.


Naphthalene and  benzene have  been identified in finished

-------
drinking  water  and  wells,  demonstrating ability to

migrate  to  drinking water  sources and to persist. (20)

          The migratory potential and persistence of phenol,

benzene,  toluene,  trichlorophenol and dichlorophenol is con-

firmed by the fact  that these constituents have been identified

in  samples  taken at the Love  Canal site in Niagra, New York.

Toluene  and  benzene have migrated from the Love Canal site

into  surrounding residential  basements and solid surfaces,

demonstrating ability  to migrate  through soils. Toluene,

benzene  and  dichlorophenol  have also  been  found in school

and basement air at Love Canal, demonstrating ability to

migrate  and  persist in  the  air.   (See "Love  Canal, Public

Health Bomb, a  Special  Report to  the  Governor and Legislature",

New York  State  Department of  Health  (1978).)

      Studies on biodegradability* indicate that under specific

idealized conditions,  pentachlorophenol  is biodegradable

(9,10,11).   Pentachlorophenol has been shown  to be degradable
     *Comments were  received  from  industry  that  the Agency
failed to take into  consideration  the  biodegradability of
waste constituents in  listing wastewater  sludges.   This
document now discusses biodegradability of  constituents of
wastewater and wastewater  treatment  sludge.
      In addition, some comments were  received  stating that
a hazardous waste designation would  discourage  biological
treatment of wastewater.   Where biological  treatment,  in fact,
proves successful in degrading hazardous  constituents, the
delisting mechanism  provides  generators a means  of  avoiding
hazardous waste status for their treatment  sludges.
      Furthermore, the Agency's legal  obligation is to list
wastes based on their  potential to cause  substantial harm if
mismanaged, and the  comment does not  even challenge that
such hazard may result.  Finally,  a  hazardous waste designation
may encourage biological treatment,  since it  may prove easier
to obtain a permit for this type of  waste management.

-------
when composted in permeable  soil  at  pentachlorophenol concen-




trations of 200 ppm or less.  Under  these conditions, at




least 98% of the PGP can be  destroyed  in  about 200 days (12).




However, biodegradation is feasible  only  if the microorganisms




have been acclimated to pent ach lorophenol and  the p'ent ach loro-




phenol concentration is carefully  controlled  (13).  As mentioned




before,  typical concentrations  of  pentachlorophenol in the




s.ludge range.from 5 to, 20 percent  or 5000 to  200,000 ppm,




although concentrations as high as 302,000  have been reported




(see p.  10).  The sludge, therefore, would  need J:_o be combined




with noncontaminated permeable  soil  in  a  ratio of 1:20 in




order to ensure that the reported  level of  degradation




at the disposal site is possible.




     Furthermore, presence of harmful  constituents in such




high concentrations in sludge samples  taken at two plants




which treated wastewater with nutrient  addition (see pp.  10-11)--




with high concentrations being  present  at one  plant in both




the aerated lagoon and final retention  pond — shows that the




constituent may persist in these sludges  even  after biological




treatment (i.e.,  won't fully biodegrade).
     Studies  on pentachlorophenol  leaching have  shown that




water contamination from soil leaching  is  low  (10,12).   Also,




this  contaminant  tend to be bound by the  soil,  limiting the




possibility  for migration (10,12).  In  one laboratory study




on soils  containing between 100 and 300 ppm  pentachlorophenol,




the  leachate,  due  to an equivalent of 1/2  to  1  inch  of rainwater,

-------
contained  less  than  0.01  percent  of the original pent ach lorophenol




in the soil  (4).  Again,  however,  these studies were conducted




on soils with PGP concentrations  well  below the levels reported




in the California State hazardous  waste manifests,  and, as




noted above, phenolic  compounds have demonstrated ability for




mobility and persistence.




     Creosote compounds have  also  demonstrated  ability for




mobility and persistence.  An  actual damage incident of




surface and  grounwater contamination due  to improper manage-




ment of creosote-containing wastes  confirms the migratory




potential, mobility  and persistence of  the  waste constituents




in these wastes.  In the  1950's, waste  chemicals including




creosote and other types  of wood preserving oils were injected




into wells in Delaware County, Pennsylvania.  The  injected




wastes migrated into groundwater,  infiltrated a storm drain




sewer, and discharged into a small  stream,  causing  biological




damage.   Although injection of the wastes into  the  wells




ceased in the 1950's, contamination was  first observed  in




1961. (21)  Thus, the waste constituents  proved  capable




 f migration via both ground and surface  waters,  and were




able to  persist and cause damage for a  long time.




     Since large quantities of bottom sediment  sludge contain-




ing such large concentrations of harmful  constituents are
o
                             -flfS -

-------
disposed of in landfills or  sometimes  allowed to accumulate

at the bottom of ponds and lagoons  for  long periods of time,

attenuative capacity of the  environmental  surrounding these

facilities could be reduced  or used  up.

     Finally, many of the constituents  of  concern are
                                                    i

highly bioaccumulat i'v.e in environmental,  rec.eptors.

Benz (a)anthracene and pentachloropheno1  are extremely bioaccumu-

lative with octano1/water partition  coefficients of 426,579

and 102,000,  respectively.   Tetrachloropheno1,  trich loropheno1

and dichloropheno1 are also  highly  bioaccumulative  with octanol/

water partition coefficients of 12,589,  4,169 and 1,380,

respectively  (App. B).*  Thus, the  possibility  that waste

constituents  could accumulate in harmful concentrations if

they reach a  receptor further supports  a hazardous  waste

listing.

     In light of the above and of the  extreme dangers to

human health  and the environment posed  by  these  constituents,

there is insufficient indication of  environmental degradation

and inability to migrate to  justify  a  failure to list this

waste as hazardous.
       *An  octano I/water coefficient of  100 means, thjat  after an
aqueous  solution  of the test compound is  intimately  mixed with
octanol  and  allowed to separate, there will be  100  times  as
much  of  the  test  compound in the octanol  than  in  the water.
Solubility  of  a  substance in octanol models its  solubility in
body  fat  tissue  and is, therefore, indicative  of  bioaccumu1 at ion
potential.

-------
           C•   Exposure  Pathways




           Mismanagement  of these wastes, therefore, could  lead




to environmental  contamination since constituents are available




for release  and persist  following release.   Thus, as previously




noted,  the wastewaters  generated by wood preserving operations




are typically  treated by  evaporation or by  a combined biological




and irrigation process.   Bottom sediment sludge, generated




by the  treatment  of  the wastewater, is  typically disposed of




in an off-site landfill,  although incineration is another




possible disposal method.




           The  treatment of wastewater  in ponds and/or lagoons,




if mismanaged, could also  lead to the  release  of hazardous




constituents,  particularly in  light of  these constituents'




demonstrated propensity for migration.   These  waste constituents




could thus contaminate groundwater  if  ponds  or lagoons  are




unlined or lack adequate  leachate collection systems.   Siting




of wastewater  treatment facilites in areas  with highly  permeable




soils could  likewise facilitate  leachate migration.   The




bottom  sediment sludges, which form at  the  bottom of wastewater




treatment  ponds or lagoons, could thus  release harmful  consti-




tuents  and contaminate groundwater.   As  previously noted,




these sludges may be allowed to  sit at  the  bottom of ponds




for up  to  five years (8),  thus  increasing the  potential for




release of harmful constituents  and for  eventual groundwater




cont aminat ion.

-------
          There is also  a  danger  of migration into and




 contamination of surface water  if ponds and lagoons are




 improperly designed or managed.   Thus,  inadequate flood




 control measures could result  in  washout or overflow of ponded




 wastes .




          Disposal of bottom  sediment sludge in an-off-site




 landfill, if mismanaged, could  also lead to release of hazardous




 constituents.  The waste constituents of concern may migrate




 from improperly designed or managed landfills and contaminate




 ground and surface waters.




          Transportation of these sludges  off-site increases




 the liklihood of mismanagment  and of their causing harm to




 human health and the environment.   Mismanagement of sludges




 during transportation thus may  result in hazard to human




 and wildlife through direct exposure to harmful constituents.




 Furthermore, absent of proper managment safeguards,  the




 waste might not reach the  designated disposal destination




 at all.




          The harmful constituents  in the  waste also present




 a health hazard via an air inhalation pathway.   Studies on




 actual  pentachloropheno1 and creosote process wastewater




 samples  using a bench scale pan evaporator indicated that a




 large  fraction of the organic constituents were entrained in




 the vapors  given off during the treatment(18).   Benzene and




toluene  have vapor  pressures of 75.1 mm Hg @20°C  and

-------
28.4 mm Hg @25°C and  are  therefore likely to volatilize


(App. B).  Thus, evaporation  of  wastwaters  in ponds, lagoons,


stripper/cooling towers and  evaporation pans could lead to


the release of hazardous  and  volatile  constituents into the


air .
                                          i
          Disposal  of  sludges  by incineration is  another type


of management which could  lead to  substantial hazard.   Improper


incineration might  result  in  serious air  pollution by  the


release of toxic fumes occurring when  incineration facilities


are operated in such  a way that  combustion  is incomplete.


These conditions can,  therefore,  result in  a significant


opportunity for exposure  of humans, wildlife and  vegetation,


in the vicinity of  these  operations, to potentially  harmful


substances.



          D.  Hazards Associated with  Constituents of  the
              Waste


          Phenolics are toxic  and  in some cases bioaccumulative


and carcinogenic.   Phenol, pentachlorophenol,  2,3,4,6-tetra-


chlorophenol, 2,4,6-trichlorophenol, and  2,4-dichlorophenol


are given highly toxic ratings in  N. Irving  Sax's  Dangerous


Properties of Industrial  Materials.  2,4,6-Trichlorophenol


has been identified by the Agency  as a  compound exhibiting


substantial evidence of being  carcinogenic.   In addition,


2,4,6-trichorophenol has  been  reported  to be mutagenic,


and pentachlorophenol  has  shown  mutagenic and teratogenic


effects .

-------
     Polynuclear aromatics, as a group,  are  known  to  be

toxic,  mutagenic,  teratogenic and carcinogenic.

Benzo(a)anthracene and chrysene have been  identified  by  the

Agency  as  compounds exhibiting substantial evidence of being

carcinogenic.   Benzene and toluene organic solvents,  are

relatively toxic,  and benzene is a carcinogen.  Additional

information and specific references on the adverse effects

of the  following substances can be found in  Appendix  A:
           *Benzene
           *Benzo(a)anthracene
           *Benzo(a)pyrene
           *Chrysene
           *Phenol
     *2,4,6-Trichlorophenol
           *Pentachlorophenol
           *2-Chlorophenol
         *4-Nitrophenol
           *Toluene
           *Naphthalene
        4,6-Dinitro-o-cresol
            Tetrachlorophenol
        2,4-Dimethylephenol
*Starred  compounds  are designated as priority pollutants under
 Section  307(a)  of  the CWA.

-------
                           References
 1.  Federal Register, Vol. 44, No.  212.  Wednesday,
     October 31, 1979.

 2.  Development Document for Effluent Limitation.  EPA:
     440/l-74-023a.
                                                          'i
 3.  Federal Register No. 202.  Wednesday, October 18,  1978.

 4.  Ernst and Ernst.  Wood Preservation Stat is tics.  1976.
     American Wood Preservers Association.

 5.  Nicholas.  Wood Deterioration and its Prevention by
     Preservation Treatments.  Syracuse University Press,
     Volume II, 1973.

 6.  Myers, L.H., et al.  Indicatory Fate Study.  EPA:
     660/2-78-175.   August, 1979.

 7.  Handbook of Industrial Waste Compositions in
     California.  1978

 8.  Multimedia Pollution Assessment of the Wood Products
     Industries, Edward C. Jordan Co., Inc.,  for Industrial
     Pollution Control Division,  EPA Contract No. 68-03-2605,
     November, 1979.

 9.  Hartford, W.H., "The Environmental Impact of Wood
     Preservation," American Wood Preservers  Association,
     1976.

10.  Young, A.L. et al, Fate of 2 , 3,7,8-tetrachlorodibenzo-
     p-dioxin (TCDD) in the Environment:   Summary and
     Decontamination Recommendations, United  States Air
     Force Academy, Colorado,  USAFA-TR-76-18, October, 1976.

11.  Kirsch,  E.J.,  and J.E. Etzel.  Microbial Decomposition
     of Pentachlorophenol, Journal of Water Pollution Control
     Federation, Vol. 45, No.  2,  February, 1983.

2.   Arsenault,  R.D., "Pentachlorophenol and Contained
    Chlorinated Dibenzodioxins in the Environment—A
    Study of  Envrionmental Fate,  Stability, and Significance
    when Used in Wood Preservation."  American Wod Preservers
    Association, 1976.

-------
13.  Proceedings:  Technology  Transfer  Seminal on the
    Timber Processing  Industry—March  10,11,  1977.
    Toronto, Ontario.   EPS:   3-WP-78-1,  January, 1978,

14.  Crosby, D.G., et al.   "Environmental Generation and
    Degradation of Dibenxodioxins  and  Dibenzofurans."
    Environmental Health  Perspectives.   September,  1973.

15.  "Army Handling of  Wood  Preservative  is  Questioned",
    Louisville Courier Journal, October  8,  1979.

16*  "Rep. Carter calls for  Faster  Research  on Properties
    of Wood Preservative",  Louisville  Courier Journal,
    October 4, *1979.

17.  Acurex Corporation,  "Solid Waste from Wood Treating
    Processes - a Hazardous Waste  Background  Document",
    December 20, 1979.

18.  Acurex Corporation,  "Fate of Toxic  Pollutants  in the
    Wood Treating Industry".

19.  Development Document  for  Effluent  Limitations,  EPA
    440/l-79/Q23b.

20.  Shakleford and Keith,  "Frequency of  Organic Compounds
    Identified in Water,"  EPA-600/4-76-062, Environmental
    Research Laboratory,  Athens, Ga.,  Dec.  1976.

21.  Damage Incident, U.S.  Environmental  Protection  Agency,
    open file, unpublished  data.

-------
inorganic Chemicals

-------
                 LISTING BACKGROUND  DOCUMENT
               Chromium Pigments  and  Iron Blues
Wastewater treatment sludge from  the  production of chrome
yellow and orange pigments (T)

Wastewater treatment sludge from  the  production of molybdate
orange pigments (T)

Wastewater treatment sludge from  the  production of zinc
•yellow .pigments (T)

Wastewater treatment sludge .from  the  production of chrome
green pigments (T)

Wastewater treatment sludge from  the  production of chrome
oxide green pigments (anhydrous and hydrated)  (T)

Wastewater treatment sludge from  the  production of iron blue
pigments (T)

Oven residue  from the production  of chrome  oxide green pig-
ments (T)
Summary of Basis for Listing


     The above listed Wastewater treatment  sludges  are gen-

erated when wastewaters from chromium pigments  production

are treated to remove heavy metals.  Oven residue  from hydrated

chromic oxide  manufacture is generated when  the  raw materials

are heated together to form the pigment product.   The  Admini-

strator has determined that these wastewater  treatment sludges

and oven residues  are solid wastes which may  pose  a substantial

present or potential hazard to human health  or  the  environment

when improperly  transported, treated, stored, disposed of or

otherwise  managed  and therefore should be subject  to appropriate

-------
management  requirements under Subtitle C of RCRA.  This con-

clusion  is  based  on  the following considerations:


1.   These wastewater ' treatment sludges contain substantial
     amounts  of  the  toxic  heavy metals lead or chromium (and
     often both) and  also  contain ferric ferrocyanide when
     iron blue pigments  are  produced.   The oven residue contains
     a  substantial  amount  of chromium.

2.   If these  wastes  are managed improperly, toxic chromium
     and  lead  may  leach  from the waste and migrate to the envi-
     ronment.  Ferrocyanide  will decompose upon exposure to
     sunlight, releasing cyanide and hydrogen, cyanide gas.

3.   A  significant  quantity  of these sludges is generated
     annually, and  the amount  is expected to increase.  When
     industry  wastewater treatment standards based on best
     practicable technology  are implemented, approximately
     4300 metric tons of sludge will be generated  per year.
     Currently 50-60% of that  amount is generated.

4.   These wastes are frequently disposed of in unlined lagoons
     and  landfills, or dumped  in the open.  These  management
     practices may  not be  adequate to  prevent  toxic constituents
     from being  released to  the environment.


Profile of  the Industry (1,2)

     Chrome  pigments are  used extensively in  paints,  printing

ink, floor covering  products  and  paper.   They may also be

used in ceramics, cement  and  asphalt  roofing.  Eleven plants

currently manufacture chromium pigments;  two  also manufacture

iron blue pigments.  Individual plant production  rates range

from a low of 9 metric  tons per day to a high of  79  metric

tons per day.  Total yearly industry-wide production is

estimated at 64,500 metric  tons;  approximately 60% of that

total is manufactured by  two  plants in the  northeastern

United States.  All other plants  are  located  in the  midwest

and south.

-------
Manufacturing Processes




1.   Manufacture of Chrome Yellow  and  Orange Pigments




     Chrome yellow and orange pigments  are  produced by reacting




sodium dichromate, caustic soda and  lead  nitrate as follows (1):




     (a)   2HNC-3 + PbO ---- > Pb(N03>2 +  H20




     (b)   Na2Cr207 + 2NaOH + 2Pb(N03)2  ----- > 2PbCr04 + 4NaN03 + H20




Lead chromate is formed as a precipitate  and is  recovered by




filtration, then treated, dried, milled and  packaged.  The




filtrate,  containing lead and chromium  compounds,  is  sent to




a wastewater treatment facility.   A  process  flow diagram is




given in  Figure 1 (3).




2.   Manufacture of Molybdate Orange Pigments




     Molybdate orange pigment is made by  the co-precipitation




of lead chromate (PbCr04) and lead molybdate (PbMo04).




Molybdic  oxide is first dissolved  in aqueous sodium hydroxide;




sodium chromate is then added.  This solution is mixed  and




reacted with a solution of lead oxide in  nitric  acid.   The




reactions  proceed as follows (1):




     a.   Mo03 + 2NaOH  ---- >   Na2Mo04 +  H20




     b.   PbO + 2HN03   ---- >   Pb(N03)2+  H20




     c.   Na2Mo04 + Pb(N03)2 ---- >  PbMo04 +  2NaN03




     d.   Na2Cr04 + Pb(N03)2  ---- >  PbCr04 + 2NaN03
     The  precipitate  is  filtered, washed, dried,  milled  and




packaged.   The  filtrate,  containing lead and  chromium compounds,




is  sent to  the  wastewater treatment facility.  A  flow diagram




is  given  in Figure  2  (3).

-------
714
LEAD OXIDE
WATER
403 NITRIC AGIO—
(OH ACETIC ACID)
DISSOLVING
263 60% NoOII—**
490 SODIUM
DICHROMATE
                    DISSOLVING
                                               MIXING
                                                 AND
                                            DEVELOPMENT
                                                FILTRATION
                                                   AND
                                                 WASHING
                                9.911^0,,

                                 9.7 SO,,-

                                2. Ca(OH)e-
                                DRYING,
                                MILLING
                                 AND
                              PACKAGING
,1000
'PRODUCT
                                                                      WASTE
                                                                    TREATMENT
  VALUES WILL DIFFER DU£ TO DIFFERENT
  REACTANTS USED TO MAKE DIFFERENT
  SHADES OF CHROME YELLOW
  SOLIDS

 30 PbCKX,
10.4 Cr{OM)3
26.1 Co SO,
2.6 Pb(OH)2
                                                         EFFLUENT
                                                         544
                                                         14.3
                                                          1.7
                                                         OR Ca(Ac)z)
                                                          WATER
                                                      FIGURE  1
                                        CHROME YELLOW  MANUFACTURE

-------
212
MOLYODIC
WATER
CAUSTIC
SODA
LEAD
OXIDE
NITRIC
ACID
                         255 SODIUM
                         CIIROMATIi
                                 WATER
 I   WAIt
L   I
K;
% 	 *-
•»
—



MIX
TANK



               17.5 NaCI
                                              \
                MIXER
                   9.9 H2f

                    9.7 S02
HOLDING
  TANK
FILTRATION

WASHING
  CHEMICAL TREATMENT
                                                                                            VENT
                                                                 t
  DRYING,
 MILLING
  • AND
PACKAGING
                                                                                                            IOOO
                                                                                                            PbCr
                                                                                                            PRODUCT
          CONTAINED IN MOLYOD/C
  OXIDE «AW MATERIAL
                                SLUDGE SEPARATION
                         SOLIDS TO LANDFILL
                           i.eo uioz*
                            £0 PbCrQ,'PbMoOi4
                            10 Cr(OII)5

                           2.5 Pb{OH)2
                                                                            J
                                                                            17.0 NaCI :
                                                                            502 NaN05
                                                                             14 NajSO^
                                                                             1.7 Ca{N03
                                                                               WATER
                                                     FIGURE
                                      MOLYBDATE  ORANGE MANUFACTURE

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3.   Manufacture  of  Zinc Yellow Pigments

     Zinc  yellow  pigment is  a complex compound of zinc,

potassium  and  chromium.   It  is produced by the reaction of

zinc oxide,  hydrochloric acid, sodium dichromate and potassium

chloride (1):

     a. 2KCL + 2HC1  +  2Na2Cr207  .  H20 	> K2Cr40i3 + 4NaCl + 3H20

     b.  4ZnO  + K2Cr4013 + 3H20	> 4Z,nO .  K20 .  4Cr03  . 3H20

The product  forms  as a precipitate and is filtered,  washed,

dried., milled  and  packaged.   The filtrate, containing chromium,

is sent to  the wastewater treatment facility.  A flow diagram

is given in  Figure 3 (3).

4.   Manufacture  of  Chrome Green Pigments

     Chrome  green  pigments are co-precipitates of chrome

yellow and  iron blues.   They  include a wide variety  of hues,

from very  light to very  dark  green.   Chrome green is produced

by mechanically mixing  chrome yellow and iron blue  pigments

in water.  The  coprecipitate  formation of chrome green is

given by the following  reaction  (1):

     (1)   PbCr04 +  Fe(NH4) [Fe(CN6)J   	>  PbCr04Fe(NH4)  [Fe(CN)6]

     The co-precipitate  is filtered,  dried,  ground,  blended and

packed.  The filtrate, containing  lead and chromium, is sent

to wastewater  treatment  for removal  of suspended pigment

particles.   Figure 4 gives a  process  flow diagram for the

manufacture  of  chrome  green (3).

5.   Manufacture of  Anhydrous  and  Hydrated Chrome Oxide Green
     P igment s.

     Anhydrous   chrome  oxide is produced by the calcination

-------
404 ZnO

105 HCI -

218 KCI —
-H»
7G5 NaftCr£0|-I^O
     REACTION
       TANK
                                 23 HtSOv

                                   71 S0r
                                166 NaOH
                                                                WATER
                                                                VAPOR
                                                                 VENT
 DEWATER,
CENTRIFUGE
    AND
   WASH
                                                         -*,
                                                                  t
 DRYING,
 MILLING
   AND
PACKAGING
                                                    TREATMENT
                                                                                 PRODUCT
                                         SOLID RESIDUE

                                        20 ZINC YELLOW
                                        24 ZnO
                                        40 Cr(OH)B
                                                              LIQUID EFFLUENT

                                                                 44 KCI
                                                                 131 NatS04
                                                                433 NaCl
                                                                   WATER
                                          FIGURE 3
                                ZINC YELLOW MANUFACTURE

-------
                                             WATER
776 LEAD
NITRATE

190 SODIUM.
CIIROMATE

167 SODIUM
SUUFATE
                 WATER
   I
263 IRON BLUE-



     WATER
                                              I
                                           RESLURRY
REACTION
  TANK
                                i
     WASH
SHADE
TANK
, .... , ta «.

FILTER
DRY
••M.ttari

GRIND,
BLEND
AND
PACK
IOOO
CHROME
GREEN
PRODUCT
NOTE:
    INPUT VALVES WILL
    VAHY DEPENDING ON
    SHADE OF GflEEN
    DEStnED.
             LIQUID EFFLUENT
               WATER I
               400 NaNOj
                                                      5 CMROf^E GREEN PIGMENT
                                                   (AS SUSPENDED SOLIDS IN WATER)
                                                 RGURE 4
                                     CHROME  GREEN  MANUFACTURE

-------
of sodium dichromate with sulfur  or  carbon according to




either of the following reactions  (1):




     a.  Na2Cr2Oy + S 	> Cr203  +  Na2804




     b.  Na2Cr207 + 2C	> Cr203 + Na2CC>3 + CO




     The recovered oxide is slurried with water, filtered,




washed, dried, and packaged.  The  washwaters, containing a




chromium compound, are sent to wastewater treatment.  A




process flow diagram is given in  Figure  5 (3).




     .Hyd.rat.ed chrome oxide is made by reacting  sodium dichromate




with boric acid as follows (1):




     2Na2Cr207 + 8H3B03	> 2Cr203 .  2H20 + 2Na2B40y  + 8H20 -I- 302




The raw materials are blended in  a mixer, then  heated in an




oven at 550° C.  Oven residues, which contain chromium, remain




to be disposed of as wastes.  The  reacted material is slurried




with water and filtered.   The filtered  solids are washed,




dried, ground, screened and packaged.   The filtrate and




washwater are treated to  recover  boric  acid.   The waste




stream from the boric acid recovery  unit  and  washwaters from




the filtration step, containing a chromium compound, are




sent to wastewater treatment.  A process  flow diagram is




given in Figure 6 (3).




G.   Manufacture of Iron  Blue Pigments




     Iron blue pigments are produced  by  the reaction of




sodium ferrocyanide with  an aqueous  solution  of  iron sulfate




and ammonium sulfate.   The precipitate  formed is separated




and oxidized  with sodium  chlorate or  sodium chromate to form

-------
O
 i
       1994 SODIUM
       DICIIROMATE
       WATER
       198 SULFUR
        22 WHEAT'
        FLOUR
                      BLENDER
63 C02,CO,S02
 i
KILN
                                                 WATER
SLURRY
 TANK
                                                 33
                                               666
                          WATER
                                                                1
                             FILTER
                                                            TREATMENT

                           VENT
                           1
DRYER
                                                       SOLID RESIDUE  LIQUID EFFLUENT
                   Z?. Cr(OM)
                                                                   993
 GRIND,
 SCREEN
  AND
PACKAGE
JOOO C
VROOU
                                                    FIGURE  S
                             ANHYDROUS  CHROMIC OXIDE PIGMENT MANUFACTURE

-------
1695 SODIUM
DtCHROMATE

1630 BORIC ACID
  exi
BLENDER
258 Ot

_1_
OVEN




SLURRY
TANK

        SOUD WASTE TO LANDFILL
             10 CfjOj- 2H20
                  646SULFURICACiD
                     DORIC ACID
                     RECYCLE
                    BORIC ACID
                    RECOVERY
                      UNIT
                             300
                                     l
                         61
                       76 NoOU	fr*
                    TREATMENT
                                                          WATER
                                                       WATER
WASH
                                                                        1
                           VENT
                                        FILTER
DRYER
 GRIND,
SCREEN
  AND
PACKAGE
1000
•Cr,0s-2l
PRODUCT
                                RESIDUE
                               66Cr(OH)3    IH7
                                           300ttaOu3     p|GURE ^

                                     HYDRATED CHROMIC OXIDE MANUFACTURE

-------
iron blues  (Fe  (Nfy)[Fe(CN)e])•   The product is filtered,




dried and packaged  as  shown in  Figure 7.   The filtrate, con-




taining  ferric  ferrocyanide (and chromium when sodium chromate




is used  as  an oxidizing  agent)  is sent to wastewater treatment.




Waste Generation  and Composition




     Some plants  produce different pigments in sequence, while




others manufacture  several  pigments  concurrently and combine the




wastewaters  for treatment at  a  single facility.  Wastewater treat-




ment generally  involves  precipitation of  heavy metals with lime




or caustic  soda.  This process  generates  a  sludge containing




heavy metal  hydroxides and  pigment particles.   The sludge also




contains ferric ferrocyanide  if  iron blues  are produced, due to




the reaction of feedstock materials.   The remaining listed hazar-




dous waste,  oven  residue from the production of hydrated chrome




oxide green  pigments, is generated when sodium dichromate and




boric acid  are  heated to form the pigment product.  A chromium-




containing  compound is found  in  the  oven  residue  as a result




of chromium  in  the  feed  material.




     The composition of  the wastewater treatment  sludge  from




chromium pigments production  is  dependent upon the pigments




which are being manufactured, as  shown in Table 1  below, and




whether wastes  from multi-process plants  are combined for treat-




tment.   With regard to the  waste  constituents  of  regulatory con-




cern, chromium is usually present and  lead  may also be found.




Ferric ferrocyanide is a component  of  the sludge  when iron




blues are produced.  Table  1  lists  the chromium,  lead and




cyanide-containing compounds  in  the  respective sludges,  and




their amounts relative to the amount  of the sludges.

-------
^v
Reaction
Tank
         L"   ^
          ...s
T
Digestion 	 ^ Oxidalion
Tank Tank
/ /
O •• ,OT
\T- *•
O /•C"
•* O
/
, o
-cm |:«llcr
& Wasli
;.,
1 rr»/"ifii
-------
                            TABLE 1
              Composition of Wastewater Treatment
             Sludge and Oven Residue from Chromium
                      Pigments Production
Source  of  Sludge
Mass Units of
Contaminants in  sludge per
1000 Mass Units  of  Product
Production  of  Chrome
Yellow and  Orange  Pigments
30 PbCr04 (Lead  chromate)
10.4 Cr(OH)3  (Chromium  hydroxide)
2.5 Pb(OH)2   (Lead  hydroxide)
Produc tion  of
Molybdate Orange  Pigments
20 PbCr04  . PbMo04  (Molybdate  Orange
10 Cr(OH>3  (Chromium  hydroxide)
2.5 Pb(OH)2(Lead  hydroxide)	
Production  of
Zinc Yellow Pigments
20 4ZnO.K20.4Cr03.3H20  (Zinc  Yellow)
48 Cr (OH)-3  (Chromium  hydroxide)
Production  of
Chrome Green Pigments
5 PbCr04Fe(NH4)[Fe(CN)6]  (Chrome Gree
Production  of
Anhydrous Chromic  Oxide
P igments     	^^^
22 Cr(OH>3 (Chromium  hydroxide)
Production of Hydrated
Chromic Oxide Pigments
66 Cr(OH)3 (Chromium  hydroxide)
Production of
Iron Blue Pigments
25
      (Fe(CN)5)3  (Ferric  Ferrocyanide
Oven Residue  from
Production of Chromic
Oxide Pigments	
10 Cr203.2H20  (Chromium  Oxide)
* Note:  Iron blue wastewater  treatment sludge will contain
chromium compounds when  sodium chromate is used as an oxidizing
agent.  Generators,  should  they seek to delist their iron
blue waste streams should thus address  chromium concentrations
as well as cyanide concentrations  in their wastes.

-------
     The Agency lacks  data on the precise concentrations  of
            *
hazardous constituents in the sludges.   These concentrations,

however, are believed  to  be substantial.  Data indicates

that  wastewaters  from  all chromium pigments plants accumulate

8,450 Ibs. of  chromium,  2,538 Ibs of lead and 157 Ibs  of

cyanide per day (2).   Because treatment of the wastewaters

is effected by consolidation of contaminants in sludge, the

sludge is expected  to  contain much higher concentrations  of

those contaminants.   Moreover, as shown by the material

balances indicated  on  Figures 1-7 above, chromium and  lead-

containing compounds  are  significant constituents of the

sludge, and thus  obviously are present in substantial

concentrations .

     Furthermore, the  amount of sludge generated is quite

substantial.   The Agency  estimates that approximately  2100  to

2600  metric tons  of  sludge are currently generated per year

by treatment of wastewaters from the manufacture of chromium

pigments (4).  The  amount of wastewater treatment sludge  is

expected to increase  significantly in the near future.

Treatment standards  based on Best Practicable Technology

(BPT)  are being developed for the chromium pigments industry,

and compliance will  result in removal of at least 95%  of  the

chromium and lead from the wastewaters.  Using current produc-

tion  figures,  the Agency  estimates that about 4300 metric

tons  per year  (dry weight)  of sludge will be generated by

the industry when BPT  standards are implemented (1).

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     EPA solicits  information on the composition of wastewater




treatment  sludges  and  concentrations of hazardous constituents




in extracts  of  those  samples.   The  Agency emphasizes, however,




that hazardous  constituent  amounts  in these  sludges appear to




be sufficiently high  to  be  of  regulatory significance.




Current Waste Management Practices




     A report done by  the Versar Corporation in 1975  indicates




that, at that time, eight companies  manufacturing chromium




pigments disposed  of  their  wastewater treatment sludge on




land (3).  Two  companies disposed on-site, one  by ponding and




the other  by landfill  after  treatment.   Six  companies disposed




off-site,  one to a municipal  landfill,  one to a land  dump and




four to private landfills.   Another  company  discharged to the




sewer and  one claimed  to recover its  wastes.(3)




Hazards Posed By These Wastes




     These wastes may  pose  a  substantial  threat to  human




health and the  environment  if  the hazardous  constituents  are




released to the environment, and environmental  release may




occur as a result of waste mismanagement.  Lead and chromium




occur in pigment particles  and  as hydroxides in the sludge




and may be solubilized if the  wastewater  treatment  sludges




are improperly managed.  Solubilization  of the  lead and




chromium hydroxides is pH-dependent  and  will increase as  the




pH of the  solubilizing medium  deereases.(3)jf t^e sludges




are exposed to acidic conditions (which  might occur due to




co-disposal with waste acids,  or in  municipal landfills or

-------
in areas where  acid  rain is prevalent),  the  toxic  heavy
                        ?
metals could be released from the waste  matrix.   Furthermore,
                        o
lead  hydroxide, if  present in sufficient  quantities,  is

soluble enough  in water  alone to exceed  the  National  Interim

Primary Drinking Water  Standard of 0-05  mg/1 (5).   Although

chromium hydroxide  is relatively insoluble in  water,  its

solubility  is enhanced  in  the presence of chloride ions.(3)

Chloride ions .are common in the environment  and  would almost

certainly be found  in many landfills, increasing  the  likelihood

that  chromium could  be  leached by water  from chromium hydroxide

containing  wastes.

     Water  is likely to  come into contact with the waste  in

several ways.   Open  dumping or improper management of a

landfill may permit  percolation of rainwater  through  the

waste pile  or allow  surface run-off to solubilize  hazardous

constituents.   Placement of the waste below  the  water table

could result in leaching of the lead and chromium  by  ground-

water.  Clearly, wastes  that require ponding are already  in

contact with a  substantial amount of liquid, which could
       •
encourage leaching  or form a head, facilitating  leachate

migration to groundwater.   If control practices  are nonexistent

or inadequate,  contaminant-bearing leachate, run-off  or

impoundment overflow may reach ground and surface  waters,

polluting valuable water supplies for a considerable  period

of time.

     Wastewater treatment  sludges from iron  blues  production

-------
may release  cyanides  to  air  or groundwater and thus also
      '                                                    %
create a substantial  hazard  if improperly managed.   Ferric

ferrocyanide  itself has  little migratory potential.  It is

insoluble  in  water and has been observed to be quite immobile

in soil column  studies (Appendix A).   Ferrocyanides, however,

undergo decomposition upon exposure  to  sunlight,  releasing

cyanide and  hydrogen  cyanide gas.   Once released  from the

matrix of  the waste,  hydrogen cyanide  gas  will volatilize

and enter  the atmosphere.  Cyanide,  once released,  appears

to be fairly  mobile in soils  (Appendix  A).   Even  clay liners

beneath a  disposal site  might not  impede cyanide  migration

significantly;  in the presence  of  water,  montmorillonite

clays sorbed  cyanide  weakly  (6).   Cyanide  thus  is capable of

migrating  from  the waste disposal  site  to  ground  and surface

wa ters .

     Should  lead and  chromium escape from  the  disposal  site,

they will  not degrade with the  passage  of  time, but  will

continue to provide a potential  source  of  long-term

contamination.  Lead can be  bioaccumulated  and  passed  along

the food chain  but not biomagnified.

     The Agency has determined  to  list  chromium pigments and

iron blues as T hazardous wastes on  the  basis  of  lead,  chromium,

and ferrocyanide constituents  (for iron  blues), although two

of these constituents are also  measurable  by the  EP  extraction

procedure  toxicity characteristic.  There  are  other  factors  (in

addition to those measured by  the  EP toxicity  characteristic)
                            - /

-------
which justify the T listing.   Some of these factors already

                                     t
have been identified, namely  the  non-degradability of these


substances, indications of  lack of proper management of  the


wastes in actual practice and  the presence of ferrocyanide as


a waste constituent in iron blues.  The quantity of these


wastes generated is an additional supporting factor.


    As indicated above, wastes from the production of chromium


pigments and, iron blues are generated in very substantial


quantities and the amount generated will increase.  Each


waste contains substantial  amounts of lead, chromium,  or


f errocyanides, and several  wastes contain more than one of


these contaminants.  (see Table 1, p. 8 above).   Large amounts


of each of these contaminants  are thus available for potential


environmental release.  These  large quantities pose the danger


of polluting large areas of ground or surface waters.


Contamination could also occur for long periods  of time,


since large amounts of pollutants are available  for


environmental loading.  Attenuative capacity of  the environment


surrounding the disposal facility could also be  reduced or
                  •

exhausted by large quantities  of  pollutants released from the


wa s t e .


    All of these considerations  increase the possibility of


exposure to the harmful constituents  in the wastes, and in


the Agency's view, support  a T listing.
                       (\9o-

-------
Adverse Health Effects  of  Constituents of Concern


     Ingestion of  drinking water  from ground and surface
                   j
waters contaminated  by  lead  and  chromium threatens human


health.  Aquatic species exposed  to  the  heavy metals may


also be adversely  effected.

     The hazards of  human  exposure  to lead  include neurological


damage, renal damage and adverse  reproductive effects.   In


addition, lead is  relatively  toxic  to freshwater organisms


and bioaccumulates in many species.   Contact  with chromium


compounds can cause  dermal ulceration in humans.  Data  also

indicates that there may be a correlation between worker

exposure to chromium and development  of  hepatic  lesions.

Additional information  on  the adverse health  effects  of

these elements can be found in Appendices A.

     Ferrocyanides exhibit low toxicity,  but  release  cyanide

ions and toxic hydrogen cyanide gas upon exposure to  sunlight.

Cyanide compounds can adversely affect a  wide  variety of

organisms because of their inhibition of  respiratory  meta-

bolism.  Adverse health and environmental effects  of  cyanide

are discussed in Appendix  A.


     The hazards associated with  lead, chromium,  and  cyanide  -

containing compounds have  been recognized by  other  regula-


tory programs.  Lead and chromium are  listed  as  priority

pollutants in accordance with §307 of  the Clean  Water Act,


and National Interim Primary Drinking  Water  Standards have
                             -X-

-------
been  established pursuant  to  the Safe Drinking Water Act.

                                                 )
The Occupational Health and  Safety Administration has a


final standard for occupational  exposure to lead and a draft


technical standard for occupational exposure to chromium.


In addition, a national ambient  air quality standard for


lead  has been announced under  the Clean Air Act.  Final or


proposed regulations of the  States of California, Maine,


Massachusetts, Minnesota,  Missouri, New Mexico, Oklahoma and


Oregon define lead and chromium  compounds as hazardous wastes


or components of hazardous wastes (7).


     Cyanide is also listed  as a priority pollutant under


§307  (a) of the Clean Water  Act.   Cyanide compounds are


defined as hazardous waste or  components of hazardous waste


in proposed or final regulations  of California, Louisiana,


Missouri, New Mexico, Oklahoma and Oregon (7).

-------
                           References
(1)  US EPA, Effluent Guidelines  Division.  Draft Development
     Document for Inorganic  Chemicals  Manufacturing Point
     Source Category. US EPA  Contract  No.  68-01-4492.
     April 1979.

(2)  US EPA Effluent Guidelines Division.  Inorganic Chemicals
     BAT Review.  EEM/DH. May  1979

(3)  US EPA, Office of Solid  Waste.  Assessment of Industrial
     Hazardous Waste Practices Inorganic Chemicals  Industry.
     US EPA Contract No. 68-01-2246. March  1975.

(4)  Personal Communication to Virginia  Steiner  from US EPA
     Effluent Guidelines Division. December 1979.

(5)  Handbook of Chemistry and Physics,  48th  Ed.   The Chemical
     Rubber Company.  1967-68.

(6)  Cruz, M., et al.  1974.  Absorption and  Transformation
     of HCN on the Surface of Copper and Calcium Montmorillonite.
     Clay Minerals 22:417-425.

(7)  US EPA Office of Sql^id Waste.   State Hazardous Waste
     Program Files.   January 1980

-------
Organic Chemical.s

-------
                       LISTING BACKGROUND DOCUMENT

                         ACETALDEHYDE PRODUCTION ,
Distillation bottoms from the production of acetaldehyde from ethylene (T)

Distillation side cuts from the production of acetaldehyde from ethylene (T)
I.    Summary of Basis for Listing


      Distillation bottoms and distillation side cuts from acetaldehyde

production from ethylene contain suspected carcinogens such as chloroform,

and formaldehyde and contain other toxic materials as well.


      The Administrator has determined that the still bottoms from

acetaldehyde production from ethylene may pose a substantial present or

potential hazard to human health or the environment when improperly trans-

ported, treated, stored, disposed of or otherwise managed, and therefore

should be subject to appropriate management requirements under Subtitle

C of RCRA.  This conclusion is based on the following considerations:
      1.   The wastes contain chloroform and formaldehyde which have
           been identified by the Agency as exhibiting substantial
           evidence of carcinogenicity, as well as other toxic
           materials, including methylene chloride, methyl chloride,
           paraldehyde, and formic acid.

      2.   The wastes are held in settling ponds prior to deep well injec-
           tion or they are disposed of in lagoons.  While in the settling
           ponds and lagoons, there is the potential for ground and surface
           water contamination by leaching and flooding.  Additionally,
           there is risk of volatilization of the toxic waste components from
           the settling ponds and human exposure via inhalation.

      3.   The wastes are persistent in the environment and tend to bio-
           accumulate so that there is a potential for widespread ex-
           posure through volatilization or drinking water contamination.

-------
II.   Source of the Waste and  Typical Disposal Practices


     A.   Profile of  the Industry


          Acetaldehyde  (CH3CHO)  is  a high-volume production chemical

intermediate used principally  in  the manufacture of acetic anhydride,

butyraldehyde, chloral,  pyridines, and other chemical derivatives.  Most

acetaldehyde is manufactured by the  liquid-phase oxidation of ethylene.

Apetaldehyde is produced in three plants,in the U.S., which ;utilize

ethylene  for starting  material. (*) •


          Table  1 provides a  list of the ethylene-based plants, their

locations, and their production capacities.


                              TABLE  1

     Acetaldehyde Producer Locations, Annual Production Capacities
           and Raw Materials  Used (2)(4)
                                        1978
                                     Production
                                      Capacity                 Raw
Company	Facility	(Gg/Yr)	Material
                              (metric tons/yr x 10-5)
Celanese Corp.
 Celanese Chem. Bay City, Tx.              136                 Ethylene
 Co.  Div.     Clear Lake,  Tx.             277                 Ethylene

Eastman Kodak Co.
 Eastman Chemical
 Products, Inc.,
 subsid. Texas
 Eastman Co.   Longview, Tx.               277                 Ethylene
                                                            (90%); ethyl
                                                           alcohol (10%)

   Total                                   690

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      B.   Manufacturing Process

           The direct liquid-phase oxidation of ethylene is the most

widely used method for the manufacture of acetaldehyde.  Ethylene is

catalytically oxidized with air in a dilute hydrochloric acid solution

containing the chlorides of palladium and copper.(3,4,5;


           The process involves the oxidation of ethylene by palladium chlo-

ride to form product acetaldehyde, palladium metal and hydrogen chloride:


C2H4     +    PdCl'2     + H20	> CH3CHO    +    Pd    +    2HC1

ethylene   palladium             acetaldehyde  metallic    hydrochloric
           chloride                            palladium      acid


      Cupric chloride is used as the second component of the catalyst

system to reoxidize the palladium metal  to palladium chloride:


      2CuCl2  +  Pd°	>  PdCl2   +   2CuCl

      cupric chloride      palladium  cuprous
                           chloride   chloride


      The cuprous chloride thus formed is, in turn,  reoxidized  in the

second stage regeneration unit to cupric  chloride:


      2CuCl   +  1/2 02  +  2HC1  	> 2CuCl2  +  H20

     cuprous                          cupric
     chloride                         chloride

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C.    Waste Generation, Waste  Composition and Waste Management




      1.   Waste Generation and Composition (3,4,5)




      The process which generates the subject waste is shown in Figure 1.




Ethylene feed gas goes to  a tubular reactor where it mixes with palladium




chloride and copper  chloride in solution at 9 atmospheres of pressure




and a temperature of 130°C.   The reaction products are flash evaporated




and the product acetaldehyde passes overhead to the crude distillation




column. The aqueous bottoms go to a reactor where the palladium catalyst




is regenerated and recycled to the acetaldehyde reactor. , The overhead from




the crude distillation column is condensed; unreacted ethylene and light




hydrocarbons (including a  small amount of acetaldehyde) are vented.  The




crude acetaldehyde from the bottom of this column then goes to final




distillation.  Purified acetaldehyde is distilled overhead.  Two wastes




are obtained:  the side-cuts and the bottoms.   The distillation bottoms




(discharge wastewater) containing high-boiling organic impurities leaves




the still at the bottom; and the side-cut stream consists of higher boiling




organic and chlorinated organics is removed as a side stream higher up the



column. (4,7)
      Table 2 shows the analytical  composition of waste discharges for the




two streams.









          Table 3 presents data  on 1978 acetaldehyde production capacity,




estimated production, and estimated generation of still bottom and side




cut wastes for the three plants which  produce acetaldehyde by direct




liquid-phase oxidation of ethylene.

-------
      ETHYLENE
         BLEED
           BOTTOMS
WASTE
                          REGENERATED CATALYST
                        >
                     REACTOR
                      FLASH
                      TOWER
                      CRUDE
                      DISTILLATION
                      COLUMN
                          PRODUCT
                     SCRUBBER
LIGHT ENDS
DISTILLATION
COLUMNS
                      ACETALDEHYDE
                      PRODUCT
                       CATALYST
                       REGENERATION
                                    'SPENT CATALYST
                      BOTTOMS
                      (SCRUBBER
                      MEDIUM)
SIDE CUT TO
CHLOROALDEHYDE
RECOVERY OR
WASTE
 Figure 1. SIMPLIFIED ACETALDEHYDE SCHEMATIC PROCESS FLOW

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                           TABLE  2

            Uncontrolled Waste Discharge Ratio (4)
            (g of discharge per kg of acetaldehyde)
                   Formula
Distillation
  Bottoms
(Discharge    Distillation
 Wastewater)    Side-Cut    Combined  *>
Ethylene C2H4
Acetaldehyde C 2*140 - ,
Acetic Acid ,C2H4°2 13.9
Chloroacetaldehyde C2H30C1
Acetyl chloride C2H30C1 4.2
Chloral C2HOC13 2.1
Paraldehyde (02^0)3 1.6
Other organics (including chloro- 4.0
form, formaldehyde and methylene
and methyl chloride)
TOTAL Volatile Organics: 25.8
Water H?0 795.6
TOTAL STREAM: 821.4
-
7.8
0.6
5.5
5.0
3.4
-
2.0

24.3
25.5
49.8
—
7.8
14.5
5.5
9.2
5.5
1.6
6.0

50.1
821.1
871.2
*>These totals are combined because combination of the two waste streams
  is a known method disposal. (4)

-------
                                                     Table 3
                     Estimated Still Bottom Generation from Acetaldehyde Production - 1978a
Company
Celanese Chemical
Texas Eastman
TOTAL:
Location
Celanese Chemical    Bay City, TX
Clear Lake City,
TX

Longvlew, TX
   1978
Production
 Capacity
(1000 MT/yr)

   136

   277
277
                     690
                          Estimated       Estimated
                            Still-Bottom    Side-Cut
             Estimated       Wastewater        Waste
             Production*3      Generated      Generated0
             (1000 Mt/yr)    (1000 Mt/yr)   (1000 Mt/yr)
                                     97
               197
197
               491
                                            Total
                                           (1000 Mt)
                                111
                 227
227
                 565
10


10
• ••••• ••

25
                                              116
                             237
                                                                237
                             590
aBased on data from reference 4.
bfiased on 1976 industry average of 71% production, 1000 MT/yr

cBased on Figures in Table 2, 1000 MT/yr.

-------
     2.   Waste Management


          Reported disposal of the side  cuts  has been by deep well injec-


tion.^  Waste water from the distillation bottoms has been disposed of both


by deep well injection and in anaerobic lagoons.W  One of the three


domestic plants producing acetaldehyde from ethylene disposes of both


side  cuts and wastewater by deep well injection.^'  This plant combines


the two wastes prior to injection.(^) Deep  well  injection requires

      .'!
waste presettling, and flow equalization via ponding prior to injection


to avoid well obstruction.  So that the wastes from this plant are also


managed at least for a time in holding ponds.






     The waste constituents of concern are chloroacetaldehyde,


paraldehyde, chloroform, formaldehyde, methylene  chloride,  and methyl


chloride and formic acid.  Acetyl  chloride  and chloral,  although dangerous,


are expected to hydrolise rapidly  upon aqueous disposal, so that there


is little possibility of migration and exposure  (App.  B.) (42).

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III.  Discussion of Basis for Listing


      A.   Hazards Posed by the Waste

      The toxic components present in these wastes include the compounds

listed below in Table 4.


               Table 4.  Toxic Components in the Waste
      o  Chloroform                          o  Paraldehyde
      o  Formaldehyde                        o  Formic acid
      o  Methylene chloride                  o  Chlotoacetaldehyde
      o  Methyl chloride
A number of these compounds are known or suspected carcinogens or mutagens

while all exhibit toxic properties.

      These waste constituents are capable of migration by leaching or by

volatilization from lagoons or holding ponds (the management method for

both waste streams, see p. 6 above), and of reaching environmental receptors

should the wastes be improperly managed.

      As to the migratory potential of waste constituents, chloroacetaldehyde,

which is present in high concentrations (4), is highly soluble (App. B.).

Although subject to degredation, the most significant degredation mechanism

for chloroacetaldehyde is biodegration, and thus chloroacetaldehyde would

be expected to persist for long periods in the abiotic conditions of an

aquifer. (42)  Further, chloroacetaldehyde is highly volatile (vapor pressure

100 mm Hg), and thus could migrate via an air exposure pathway. (42) Chloro"

acetaldehyde is in fact an extremely noxious vapor, with a TLV of 1 ppm.

-------
 (42)  Thus, this threshold could be exceeded  in  areas  in  the vicinity of




 the lagoon if chloroacet aldehyde were to volatilize at rates four levels




 of magnitude less than its actual volatility  potential. (42)




      Paraldehyde, another waste constituent  present in high concentrations




 (4), is capable of migrating via ground or surface water, since it is




 extremely soluble (120,000 ppm) . (42)  Bacterial degradation is the chief




 degredation mechanism (42), so this compound  would likely persist in an




 abiotic environment such as that of most groundwaters.




      Other contaminants of concern are likewise .capable of migrating and




 persisting via water or air exposure pathways.  Chloroform, for example




 is highly soluble (8200 ppm) .  Although it adsorbs to organic soil




 constituents and to clay surfaces, management could occur in areas with




 highly permeable soil or soils low in organic content, so that mobility




 would not be significantly impeded.  Chloroform hydrolises slowly, and so




 could persist for substantial periods in ground and surface waters (half




 life of 18 months in dark water).  (42)




      Thus, virtually all chloroform emitted from a lagoon is expected




 to persist in groundwater or reach surface waters via groundwater move-




 ment (App. B.).  Such behavior is likely to result in exposure to humans




 using such groundwater sources as drinking water supplies within adjacent




 areas.  Such movement and persistence of chloroform has been observed. (17)




 Chloroform has been detected in groundwater supplies in Miami,  Florida. (18)




           Movement of chloroform within surface water is likely to result




 in exposure to aquatic life forms in rivers,  ponds, and reservoirs (App.B.).




 Similarly, potential exposure to  humans is likely where water supplies  are




drawn  from surface waters.
                             -j/J-

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      Chloroform is  projected  to  be  released  to  the  atmosphere from

surface water  systems  (App. B.).   Although chloroform  decomposes  slowly in

air when  it  is exposed  to  sunlight,  the  photochemical degradation  products

are carbon tetrachloride,  a carcinogen,  (47)  and phosgene, a highly

toxic gas.   In addition, photochemical degradation mechanisms  result in

chlorine  burden.  At stratospheric levels, atomic chlorine reduces the

levels of ozone which shields  the earth  from  harmful radiation.(20)

      Formaldehyde is also capable of migrating and reaching environmental

receptors via  a groundwater exposure pathway  since it is miscible.

Biodegradation is the most significant degradation mechanism,  so that

formaldehyde would be likely to persist  in groundwater. (33)  Formaldehyde

also oxidizes  to form toxic formic acid, increasing the likelihood of

exposure  to  that substance. (33)^

      Formic acid could itself migrate via both an air and water pathway,

being both highly volatile and miscible. (33)  Formic acid would have

high mobility  so long as soils were not basic and were low in organic

content.  (33)

      Both methylene chloride  and methyl chloride also are capable of

migrating and  persisting via air and water exposure pathways, as both

waste constituents are quite soluble (although methylene chloride is

significantly more soluble than methyl chloride), and also highly volatile

(33).
>Soil attenuation would not significantly impede formaldehyde*s migratory
 potential in areas where soil is highly permeable or low in organic
 constituents (33).

-------
      Virtually all of the methylene chloride and methyl chloride




 discharged from a lagoon is expected to persist in groundwater or reach




 surface waters via groundwater movement (App. B.).  Such behavior is




 likely to result in exposure to humans who use such groundwater sources




 as drinking water supplies within adjacent areas.




      Both methylene chloride and methyl chloride are likely to be




 released to the atmosphere from surface water systems (App. B.).




 Furthermore,, there may be high local concentrations of these compounds




 near disposal sites due to their high volatility which could also result




 in serious adverse effects to individuals residing near such sites,  due




 to exposure to high vapor concentrations.




      The persistence of many of the contaminants of concern has been




 demonstrated through analysis of leachates from actual disposal sites.




 Chloroform has been found in PPM concentrations at Love Canal,  while




 methyl chloride levels reached 180 ppb. (43,44,45)  Leachate from the




 Story chemical site included methylene chloride in the ppm range. (46)




      As demonstrated above, therefore, the waste constituents  of concern




 are capable of migrating and persisting if these wastes are managed




 improperly.  Improper management is certainly reasonably plausible or




 possible.  Thus,  lagoons or holding ponds may be sited in areas with




 highly permeable  soils, and may lack adequate leachate control  features.




 There may be inadequate cover to impede migration of volatile waste




 constituents.   There may also be inadequate flood control measures to




 impede waste washout in the event of heavy rainfall.  Thus, mismanagement




could realistically occur,  resulting in substantial hazard.

-------
      The Agency is aware that most of the waste constituents of concern




(with the exception of chloroacetaldehyde and paraldehyde) are likely to




be present in small concentrations.  In light of the high potential for




substantial hazard associated with these materials, the concentrations




are deemed sufficient to warrant regulation as hazardous.  The Agency's




policy for carcinogens in water, for example, is that any exposure to




a carcinogen will induce an oncogenic response in a human receptor,




and that the greater the concentration of the carcinogenic substance,




the greater the likelihood of response.  .(See 44 FR_ 15926, 15940




(March 15, 1979)).  In light of the carcinogenic potential of many




of these waste constituents, therefore, even small (<100 ppm) concen-




trations are considered significant.




      Furthermore, the wastes are generated in significant quantities




(see Table 3 above) so that large amounts of all waste constituents




are available for environmental release, increasing the likelihood of




exposure.  There is also more chance of a major damage incident should




wastes be mismanaged.  The quantity of waste generated is thus a




further reason supporting the hazardous waste listing of these two




waste streams from production of acetaldehyde.




      B.   Health and Ecological Effects
           1.  Chloroform






               Health Effects - Designated a priority pollutant by U.S.E.P.A.,




chloroform has been judged as having high carcinogenic potential in humans




on the basis of substantial evidence of its carcinogenicity. (10,11,47)




Chloroform also is considered a toxic chemical [oral rat 11)50= 800 mg/Kg].
                                -3.il*-

-------
               Other studies have demonstrated that chloroform can cause




 a variety of  teratological and other effects in animals, such as missing




 ribs, delayed skull ossification, maternal toxicity, and fetotoxicity,




 when it is administered orally or in a vapor phase. (12,13)  Occupational




 exposure situations have resulted in damage to liver and kidneys with




 some signs of neurological disorder. (1^'  Manifestation of the toxic




 nature'of chloroform is, in part, attributable to the observation that




 metabolism results in toxication rather than detoxication. (15., 16)




 Additional information and specific references on the adverse effects of




 chloroform can be found in Appendix A.






               Ecological Effects - Chloroform has been found to be acutely




 toxic at high concentrations to bluegill and rainbow trout.






               Industrial Recognition of Hazard - Chloroform has been given a




 moderately toxic  hazard rating via oral and inhalation routes by Sax in




 Dangerous Properties of Industrial Materials.






               Regulations - OSHA has set the TWA at 50 ppm.






           2.   Methylene chloride and methyl chloride






               Health Effects - Methylene chloride(21) and methyl chloride




 are highly mutagenic.(22,23)  Methylene chloride is very toxic [oral rat




 LD50 a 1,67 mg/Kg].




               Exposures to high vapor concentrations of methylene chloride




 can produce dizziness,  nausea and numbness of  the extremities;(24)




 prolonged  exposure  to  concentrations near 500 ppm could result in central




nervous system  depression and elevated  levels  of carboxyhemoglobin,

-------
levels  that  reduce  the  blood's  ability to carry oxygen and thus cause




asphyxiation.   Similar  toxicological  effects  are expected with exposure




to methyl  chloride.   Severe  contamination of  food or water can result in




irreversible  renal  and  hepatic  injury. (25)




           Exposure  to  high  concentration can cause  death. (*-v) Additional




information  and specific  references on the adverse effects of  methylene




chloride and  methyl  chloride ,can be found, in  Appendix A.




                Ecological Effects  - In laboratory tests,,  high  concentra^




tions of methyl chloride  are acutely  (96-hours)  toxic to  aquatic  organisms,




e.g., the  bluegill. (27)  Similarly, methylene chloride also is actively



toxic. (28, 29)




                Regulations - The  OSHA standard  adopted for methylene chloride




is TWA  500 ppm.   The  OSHA standard for methyl chloride is  100  ppm.






                Industrial Recognition  of  Hazard  -  Sax, Dangerous Properties




of Industrial Materials,  designates methylene chloride as  highly  toxic via




inhalation and  moderately toxic via oral  and  skin  routes.   Methyl chloride




is designated highly  toxic via  inhalation.






           3.   Formaldehyde






                Health Effects -  Formaldehyde has  been reported to be .car-




cinogenic, (3^,31) mutagenic(32) an
-------
              Ecological  Effects - Formalin, an aqueous solution of for-

 maldehyde,  can cause  toxic effects to exposed aquatic life.(35)   jt is

 lethal to Daphnia magna.(36)

           Regulations  -  OSHA has set a standard air TWA limit of 3 ppm

 for formaldehyde.

              Industrial  Recognition of Hazard -  Sax, Dangerous Properties

 of Industrial Materials, lists formaldehyde as highly toxic to skin, eyes

 and mucous  membranes.


           4.  Chloroacetaldehyde


              Health Effects  - Chloroacetaldehyde is a toxic chemical which

 is mutagenic and a  proposed carcinogen.(37,38,39)  jt ^s extremely corrosive

 upon contact and can  cause severe effects to the skin, eyes,  and respiratory

 tract.  Upon decomposition, conversion to methyl chloride takes place

 and, as previously  discussed,  methyl chloride is a known mutagen.   Additional

 information and  specific references on the adverse effects of chloroacetalde-

 hyde can be found in  Appendix  A.


              Regulations - The  OSHA standard for chloroacetaldehyde is

 1 ppm in air.


              Industrial  Recognition of Hazard -  Chloroacetaldehyde is

 dessignated as a highly toxic  irritant in Sax, Dangerous Properties of

Industrial  Materials.
                                -X-
                              -J/1-

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           5.  Paraldehyde






               Health Effects - Paraldehyde is a toxic chemical  [oral




rat LD5Q = 1530 rag/Kg].  It has been implicated in human  fatalities  in




which congestion of the lungs and dilation of the right side of  the




heart occurred following oral ingestion of the chemical.^1'




Additional information and specific references on the adverse effects




of paraldehyde can be found in Appendix A.
           6.  Formic Acid






               Health Effects - Formic acid is toxic   [oral rat LD50 =




1,210 mg/Kg] and ingestion of even small amounts for short periods may




cause permanent injury or severe damage to .skin, eyes, and mucosal




membranes.  Because it is rapidly absorbed through the lungs, chronic




exposure to formic acid vapors can result in blood in urine.  The OSHA




(1976) and ACGIH (1977) standards for the workplace are 5 ppm.  Additional




information and specific references on the adverse effects of formic acid




can be found in Appendix A.






               Regulations -   The OSHA standard for formic acid is a TWA




of 5 ppm.




               Industrial Recognition of Hazard -   Formic acid is designated




as highly toxic via ingestion, moderately toxic via inhalation and moderately




toxic as a skin irritant in Sax, Dangerous Properties of Industrial Materials*

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IV.   References


 1.   Hayes, E.R.  Acetaldehyde.   Klrk-Othmer Encyclopedia of Chemical
     Technology.  2nd Ed.   Volume 1.   Interscience Publishers, New York,
     1963.  pp.77-95.

 2.   Stanford research  Institute.   1978 Directory of Chemical Producers -
     U.S.A.  SRI  International,  Menlo Park, California, 1978.  1127 pp.

 3.   Kirk-Othmer  Encyclopedia of Chemical Technology.  2nd Ed.  Vol. 1
     John Wiley and  Sons,  New York,  1970.  pp. 86, 87.

 4.   Lovell, R.J.  Acetaldehyde  Pro luct Report.  Emissions Control
     Options for,the Synthetic Organic Chemicals Manufacturing Industry.
      Draft.  Prepared  for the U.S.  Environmental Protection,Agency
      under Contract No.  68-02-2577,  January 1979.

 5.   U.S. Environmental Protection Agency.   Industrial Process Profiles
     for Environmental  Use:   Chapter 6.  The Industrial Organic Chemicals
     Industry.  EPA-600/2-77-023f, February 1977.

 6.   Stanford Research  Institute.   1979 Chemical Economics Handbook.
     Acetaldehyde.   SRI International, Menlo Park, California, March 1979.

 7.   Jira, et al.  Acetaldehyde  via  Air or Oxygen.  Hydrocarbon Processing,
     55(3):  97-100, March 1976.

 8.   American Conference  of  Governmental Industrial Hygienists.
     TLV's for Chemical Substances and Physical Agents in the Workroom
     Environment.  Cincinnati, Ohio.   1977.

 9.   Sittig, M.   Pollution Control In the Organic Chemical Industry.
     Noyes Data Corporation,  Park Ridge, New Jersey,  1974.

10.   United States Environmental  Protection Agency.  Carcinogen Assessment
     Group Type II Risk Assessment,  1979.

11.   National Cancer Institute.   Report on Carcinogenesis Bioassay of Chloro-
     form, NTIS PB264018,  1976.

12.   Schwetz et al.  Toxicology  and  Applied Pharmacology 28:  442, 1974.

13.   Thompson et al.  Toxicology and  Applied Pharmacology 29: 348, 1974.

14-   National Institute of Occupational Safety and Health.  Recommended Cri-
     teria for .   . . Occupational  Exposure  to Chloroform, No. 75-114, 1974.

15.   Uett et al.  Exper.  Mol. Pathology, jg: 215, 1973.

-------
References  (cont.)


16.   McLean.   British  Journal  of Experimental Pathology 51: 317, 1970.

17.   Roberts,  P.   Removal  of Trace Contaminants from reclarified water during
      aquifer passage.   NATO-CCMS Conference, Sept. 11-13, 1978, West Germany.

18.   USEPA.  Preliminary Assessment of Selected Carcinogens in Drinking
      Water  EPA-560/4-75-0()3a,  1975.

19.   United States Environmental Protection Agency.   Carbon tetrachloride:
      Ambient tfater Quality Criteria Document, 1979.

20.   National  Academy  of Sciences, Stratospheric Ozone Depletion by Halocarbqn
      Chemistry and Transport,  1979.

21.   United States Environmental Protection Agency.   Unpublished Results of
      the Health Effects  Research Laboratory, 1979.

22.   Andrews et al,  1976.

23.   Simmon et al, 1977.

24.   Pattie, Industrial  Handbook of  Toxicology,  1965.

25.   United States Environmental Protection Agency.   Methyl  Chloride:   Ambient
      Water Quality Criteria.   PB 296797,  1979.

26.   MacDonald, 1964.

27.   Dawson, et al.  The Acute  Toxicity of  47 Industrial  Chemicals  to  Fresh
      and Saltwater Fishes.  J.  Hazard. Materials,  Jj303,  1977.

28.   USEPA.  In-Depth  Studies on Health and Environmental Impacts of Selected
      Water Pollutants.   Contract No.  68-01-4646,  1978.

29.   Alexander et al.  Toxicity of Perchloroethylene,  Trichloroethylene,
      1,1,1-Trichloroethane, and Methylene Chloride to Fathead Minnows.  Bull.
      Environ.  Contam.  Toxicol.  20:344,  1978.

30.   Nelson, N. 1979.  Letter to Federal agencies:  A status report on
      formaldehyde and  HC1  inhalation  study  in rats.   October 19, 1979.
31.
Katanabe, F., et al.  1954.  Study on  the  carcinogenicity of aldehydes;
1st Report.  Experimentally produced rat sarcomes by repeated infections
of aqueous solutions of formaldehyde.   Genn.  45:  451.
32.    Auerbach, C., et al.   1977.  Genetic and  cytogenetical effects of
      formaldehyde and relative compounds.  Mut.  Res.  39:317.

-------
 References (cont.)

 33.   Humi,  H.  and  H.  Olnder.  1973.  Reproduction study with  formaldehyde
      and hexamethylenetetramine in beagle dogs.  Food Cosmet.  Toxicol.
      11: 459.

 34.   Coon,  R.S., et al.  1970.  Animal inhalation studies on ammonia, ethyl-
      ene glycol, formaldehyde, dimethylamine and ethanol.  Tox. Appl.
      Pharmacol.  16: 464.

 35.   U.S. EPA. 1976.   Investigation of selected potential  environmental
      contaminants: Formaldehyde.  EPA 560/2-76-009.
                                                  . \
 36.   Dowden,  B.F.  and M.J. Barrett. •1965.  Toxicity of selected chemicals
      to.certain animals.  Jour. Water Pollut. Control Fed.  37:  1308.

 37.   Rannug et al«  The  Mutagenicity of Chloroethylene Oxide,  Chloroacetaldehyde,
      2-Chloroethanol  and Chloroacetic Acid, Conceivable Metabolites of Vinyl
      Chlloride.  Chem. Biol. Inter. 12(3-4): 251-263, 1976.

 38.   Hussain and Osterman-Golkar.   Comment on the Mutagenic Effectiveness of
      Vinyl Chloride Metabolites.  Chem. Biol. Interact. 12(3-4):265-267, 1976.

 39.   Guengerich et al.  Biochem. L8:5177-5182, 1979.

 40.   Waskell,  L.,  A Study-o-f the Mutagenicity of Anesthetics and their Meta-
      bolites.   Mut. Res.  57(2): 141-154, 1978.

 41.   Browning, 1965.

 42.   Dawson,  English  and Petty, 1980.   Physical Chemical Properties of
      Hazardous Waste  Constituents.

 43.   Barth, E.F.,  Cohen,  J.M., "Evaluation of Treatability of  Industrial
      Landfill  Leachate",  Unpublished report, U.S. EPA, Cincinatti.
      Nov. 30,  1978.

 44.   O'Brien,  R.P, City  of Niagara  Falls, N.Y., Love Canal Project,
      Unpublished report,  Calgon Corp.,  Calgon Environmental Systems
      Div.,  Pittsburgh, Pa.

 45.   Rcera  Research,  Inc., Priority Pollutant Analyses prepared for
      Nuco Chemical Waste  Systems,  Inc., Unpublished report,
      Tonawanda, N.Y.,  April, 1979.

 46.   Sturino,  E.,  Analytical Results:   Samples From Story Chemicals,
      Data Set  Others  336", Unpublished  data U.S.  EPA Region 5, Central
      Regional  Laboratories,  Chicago,  Illinois, May, 1978.

47.   Cancer Assessment Group List of  Carcinogenic Substances,  April 22, 1980.

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                       LISTING BACKGROUND DOCUMENT

                         ACRYLONITRILE PRODUCTION
           Bottom stream from the wastewater stripper in the production of
           acrylonitrile (R,  T)

           Still  bottoms from final  purification of acrylonitrile in the
           production of acrylonitrile (T)

           Bottom stream from the acetonitrile column in the production of
           acrylonitrile (R>t)*

           Bottoms  from the acetonitrile  purification column in tne production
           of  acrylonitrile (T)*
 * *       Summary  of  Basis  for Listing

         The hazardous  wastes generated  in  the  production of acrylonitrile

 contain  the toxic constituents  acrylonitrile,  acrylamide,  acrolein,

 hydrocyanic acid, and  acetonitrile.  The Administrator  has  determined that

 the  subject waste from acrylonitrile production may  pose a  substantial

 present  or potential hazard to  human health  or the environment when

 improperly transported, treated, stored, disposed of or otherwise managed,

 and  therefore should be subject to appropriate management  requirements

 under Subtitle C of RCRA.  This conclusion is  based  on  the  following

 considerations:
        1)   Of the constituents present in these wastes,
             acrylonitrile has been identified by the Agency  as  a
             substance exhibiting substantial evidence of being
             a carcinogen and is extremely toxic.  Acrylamide is
             regulated as a,carcinogen by OSHA.  Acrolein is  extremely
             toxic and a suspected mutagen.  Hydrocyanic acid is
             extremely toxic, as is HCN gas.  Acetonitrile  is also
             toxic.
*These waste streams were originally proposed in a single  listing
 description, and are now listed separately for purposes of  clarity.

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        2)    The  bottom streams from the wastewater stripper and the
             acetonitrile column,  and the bottoms from the acetoni-
             trile  purification column are typically stored and settled
             in ponds  prior to deep well disposal.  If improperly stored,
             leachate  from such systems could persist in groundwater,
             causing potential exposure through drinking water.  Volatili-
             zation of toxic compounds from the pond also poses a risk to
             humans.

        3)    Still  bottoms from the final purification of acrylonitrile
             are  typically incinerated.  Improper incineration could lead
             to dispersion of waste contaminants.

        4)    The  bottom streams from the wastewater stripper and :he
             acetonitrile column contain substantial concentrations of
            .hydrocyanic acid,.which can be released as hydrogen
             cyanide gas, an extremely; toxic gas, if these wastes are
             exposed to mildly acidic conditions.

        5)    The  aqueous wastes from this process are generated in
             substantial quantities, increasing the possibility of
             exposure  should mismanagement occur.

 II.    Sources  of the  Waste and Typical Disposal Practices
       A.     Profile  of  the""Industry


             Acrylonitrile  is  produced  in the U.S.  by four producers oper-

ating six  plants  (Table  1).  All  six plants  use the(SOHIO) Standard Oil of

Ohio process  for  ammoxidation  of  propylene.   The chemical reaction

in the form of acrylonitrile may be  represented by  the following

 equation:


      2CH2 -  CH - CH3 -1-  2NH3 + 302	>  2CH2 -  CH - CN + 6H20


The reaction  of propylene and  ammonia results in acrylonitrile (70-80

percent), acetonitrile (3 percent),  and hydrogen cyanide (HCN)

(8-13  percent).O)W(5)  (Acetonitrile and  hydrogen cyanide would

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                                TABLE 1
                    U.S. Producers of Acrylonitrile
       Producer
        Location
     Capacity
 American Cyanamid Co.

 E.I. duPont de Nemours
   & Company, Inc.

 E.I, duPont de Nemours
   & Company, Inc.

 Monsanto Company

 Monsanto Company

 Vistron Company
  New Orleans,  LA

  Memphis,  TN
  Beaumont,  TX
  Chocolate Bayou,  TX

  Texas  City,  TX

__Lima,  Ohio
  265 MM Ibs/year

  270 MM Ibs/year
  350 MM Ibs/year
  440 MM Ibs/year

  420 MM Ibs/year

  400 MM Ibs/year

2,145 MM Ibs/year
Source:  Reference 2

-------
 result from the reaction of acrylonitrile  and water,  forming

 cyanohydrinacetaldehyde, which decomposes  to form acetaldehyde and hydrogen

 cyanide.  The acetaldehyde reacts with  ammonia and further decomposes to

 form acetonitrile and water.)

             By-product hydrogen cyanide is  currently recovered by American

 Cyanamid, duPont, Monsanto, and Vistron.   Acetonitrile by-product  is  recovered

 by duPont and Vistron.(3)(4)(5)

       B.'    Manufacturing. Process

             A flow sheet of a typical  acrylonitrile  plant is  shown in

 Figure 1.  The hazardous waste streams  of  interest  are described in

 Section C.

       C.    Waste Generation and Management

             1.  Bottom stream from waste  water  stripper  in acrylonitrile
                 production.(Stream 14,  Figure 1)
             Gases from the acrylonitrile reactor  are  cooled  and neutral-

 ized in a quench column with a sulfuric acid solution.   Quenched product

 gases then pass to the absorber where acylonitrile,  acetonitrile and

 hydrogen cyanide are recovered by absorption in water.

             Quench column bottoms are sent to the wastewater  stripper

 column where volatile organics are stripped with steam and recycled to

 the quench tower.   The aqueous bottoms (Stream 14) which contain some

 of the catalyst, ammonium sulfate and heavy organics,  are generated at the

 rate of about 3600 g/Kg.  of acrylonitrile product^7\  Applying this

 ratio to the 1977  production figure for acrylonitrile  gives a  yearly pro-

duction rate of about 6000 MM Ibs/year of waste.  A  typical flow rate is

about 155  gallons  per minute.

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                       WASTE HEAT BOILER
                        /

                         STEAM
PROPYLENE
 STORAGE
   AMMONIA , 0
   STORAGE X2
                                                                CRUDE
                                                              ACRYLONITRILE
                                                                STORAGE
        PROCESS AIR
                                                                                                                        ACRYLONITRILE
                                                                                                                           LOADING
             D
              COMPRESSOR
                                                              ACETONITRIIE
                                                              runiriCATiofi
                                                                COLUMN
ACETONITRILE
  COLUMN
                              WASTE
                              WATER
                              COLUMN
                                                                                                                       HCN
                                                                                                                     LOADING
                          TO DEEP-WELL STORAGE
                             <
     FUGmVE EMISSIONS
      OVERALL PLANT
                                         DEEP-WELL POND
                                                                                           ACETONITRILE
                                                                                             STORAGE
                                                                         ACETONITRILE
                                                                           LOADING
                                Figure 1. FLOWSHEET FOR ACRYLONUBILE PRODUCTION
                                          BY THE SOHIO PROCESSES (6)

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       Table 2 summarizes the composition of  this waste  stream.  The waste

 constituents of concern are acrylonitrile, acetonitrile,  and hydrocyanic

 acid.
                                  TABLE 2
                      Typical Composition of Aqueous Bottom
                        Stream from Wastewater Stripper
                                                    mg/1
       Acrylonitrile                   |             500 or less    :
                                       I
       Acetonitrile                    I           3,000
                                       I
       HCN                             I           7,000
                                       I
       Sulfates                        I          32,000
                                       !
       Ammonia                         I          15,000

      1                   ,              '
      I Additional non-toxrc solids     I •         40,000 approximately
             Wastewater stripper column bottoms are sent to a settling

pond where they are co-mingled with other process wastes.  After the

solids settle,  the liquid waste is injected into disposal wells.(8)

The acrylonitrile facility which deviates from this process is duPont in

Memphis.   At  this facility, the wastes are treated by alkaline hydrolysis.

The biodegradable effluent is disposed of in a municipal sewer.(8)


       2.     Still bottoms from final purification of acrylonitrile.
             (Stream 22,  Figure 1)

             Crude acrylonitrile is purified by successive distillation of

the absorber  bottoms.

             The  absorber bottoms go to a recovery column where crude

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acylonitrile  is  separated from crude acetonitrile and sent to crude



acrylonitrile storage.   The crude acrylonitrile then is sent to the



light  ends  column which  separates the hydrogen cyanide and other light ends.



The bottoms from this  column go to the product column where the heavy



impurities  are removed and disposed of in an incinerator. W(7)  -j^g



still  bottoms from  this  process (Stream 22)  are typically  incinerated. (6)(8)
                                                                       ' i

A typical rate of production for this stream is 8.1  g/Kg.  of product^).



Applying this factor to  the 1977 production  results  in an  estimate  of 13



MM Ib. of this stream produced  per year.   The column bottoms contain



acetonitrile  (25 percent)  and  toxic  materials such as  acrolein  and  acrylamide



(75 percent)^''.  Acrylonitrile is also probably present,  since it  is



unlikely purification will be  complete.'®-'





       3.  Bottom Stream from Acetonitrile Column (Stream  15, Figure 1).



           The crude acetonitrile  obtained as bottoms  from the  recovery



column goes to the  acetonitrile  column  for separation  of water  (which



is recycled to the  absorber).   This  waste  stream is  also aqueous.



This stream is typically  produced  at  a  rate  of 1003  g.  per kg.  acrylonitrile



product.'"J   Applying this  factor  to  the total nameplate capacity of



the acrylonitrile producers who  are  recovering acetonitrile results  in an



upper limit estimate of  675 MM  Ib. of the waste  stream produced per. year.



At the Vistron plant, approximately  180 gallons  per  minute of column



bottoms are produced.
                                   -X-
                                  -J30-

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      A typical composition of  this  waste stream is shown in Table 3
                                  TABLE  3

             Typical Composition of  Bottom Stream from
             Acetonitrile Column (8)
             (waste constituents of  concern only)
                                                      mg/1
            HCN                           I            22.5
            Acrylonitrile     '    .        |            <10
            Acetonitrile                               35
       This waste stream is combined  with other  process  wastes  (streams

14 and 16, Figure 1) and sent  to  a  settling  pond,  followed  by final

disposal, as previously described (see  page  6).


       4.  Bottoms from Acetonitrile  Purification  Column  (Stream 16,  Fig=  1)

          This stream is generated in  the purification  of  crude  acetonitrile

obtained as bottoms from the recovery column, after water  separation in

the acetonitrile column.  This waste  stream  is not expected to  be present

in large quantities, since acetonitrile is a minor by-product of  acryloni-

trile  production.

    The waste is expected to  contain substantial  concentrations  of

acetonitrile (since purification  would  probably  not be complete), and

acrylamide (which as a heavy compound would  be found  in  the purification

residue).  This waste is generally mixed  with aqueous process waste  and

sent to the settling pond, followed by  final disposal (see  page 6).

-------
        Although waste streams 14, 15, and 16 (the two aqueous bottom wastes,

 and  the acetonitrile purification column bottoms) are reported to be mingled

 in process  and co-disposed,  the Agency has determined to list each waste

 stream separately for purposes of clarity.  There may also be situations

 of which the Agency is unaware when one or another of these waste streams

 is is  not co-disposed, in which case the individual listing description

 prevents a  lapse in regulatory coverage.

 III.   Discussion of Basis for Listing

       A. Toxicity Hazard Posed by Wastewater Stripper Stream,  Acetonitrile
          Column Stream,  and  Acetonitrile Purification Column Bottoms

          These three waste  streams are commonly co-minged in a single

 settling pond,  where solids  are allowed to settle (see page 6),  and

 therefore are discussed together.   The wastes are certainly capable of

 creating a  substantial hazard if improperly  ponded.

          As  described above,  these waste streams contain acrylonitrile,

 a substance  identified by the Agency as  exhibiting substantial  evidence

 of being carcinogenic;  acrylamide,  which is  regulated  by OSHA as  a

 carcinogen; highly toxic  hydrocyanic acid; and  acetonitrile,  which is also

 toxic  (see page  13 below).  These  waste  constituents  are deemed  to be

 present  in sufficent  concentrations  to be of regulatory  concern.   Even in

 these highly  diluted  waste streams*,  acrylonitrile is  present in  concentra-

 tions up  to 500  ppm (Table 2,  p. 6).**   Hydrocyanic acid may  be present  in
 *Acetonitrile purification column bottoms  are  not  aqueous,  but probably are
  mixed with other aqueous waste streams, and so  are  included in the
  discussion in the text.

**The Agency policy is that carcinogens have no safe  level of exposure.
  See FR 15926, 15930 (March 1979).  Thus,  minute concentrations of carcinogens
  may well be of regulatory concern.  In  any case,  the Agency regards
  acrylonitrile concentrations in these wastes  to be  relatively substantial
  for purposes of making a hazardousness  determination.

-------
 concentrations of 7000 ppm.  Concentrations  of  these constituents in pond

 sediments are likely to be significantly higher,  since pond sediments are

 much more concentrated than aqueous waste  streams.

             These wastes are also generated  in very substantial  quantities

 Thus, the quantities of hydrocyanic acid,  acrylonitrile and acetonitrile

 discharged to a common holding pond annually, from  just one plant,  are

 very substantial.  '

                 Compound                  Amount/Year

              Hydrocyanic Acid         5 million 'pounds
              Acrylonitrile            300,000  pounds
              Acetonitrile             2 million  pounds

 Very large amounts of hazardous waste constituents  are thus potentially

 available for environmental release.  If mismanagement occurs,  large

 expanses of groundwater, surface water and soils may be contaminated.

 Contamination will probably be prolonged,  since large  amounts of

 pollutants are available for loading.  Site attenuative capacity  may

 be exhausted as well, again increasing the risk of  exposure.  All of

 these factors strongly support the listing.

             Waste constituents, moreover, have high migratory  potential.

 Acrylonitrile, acrylamide,  and acetonitrile are all highly  soluble

 (App. B).  (Acetonitrile, in fact, is miscible.(46))   in addition,

 acrylamide and acrylonitrile tend to volatilize (46) f  and so could  pose

 a hazard via an air inhalation pathway.   They may be highly mobile  as

well, particularly in areas with highly permeable soils,-or where soils

are low in organic content.(46)   Acrylamide has  in  fact been documented

to have moved  from a sewer  grouting operation through  the soil  to a

private water  will.d®)-  These  waste constituents also may persist

-------
 after migrating  from the waste site.   The major degradation




 mechanism for  acrylamide and acetonitrile is biodegradation^4"', which




 would not affect these  constituents  in the abiotic conditions of an




 aquifer.   Acetonitrile  also degrades  (although slowly) to highly toxic




 cyanide  W-6)^  increasing the opportunity for hazard if it is released.




 The major degradation mechanism for  acrylonitrile is photodetoxification'13,14)




 which again would not affect this  compound's persistence in groundwater.




             Hydrocyanic acid,  the other major waste constituent,  is




 also highly mobile  and  persistent.  Free cyanides,  which may migrate  from




 these wastes,  have  been shown to be extremely mobile in soil;  pH appears




 to influence the mobility with  greater mobility at  high pH. dU  Also,




 cyanide has been shown  to move  through soils into groundwater.d^;  £n




 surface waters,  cyanide often volatizes.   The hydrogen cyanide vapors




 pose a hazard  to workers  or  nearby populations  because of their




 extreme toxicity.




             An  actual  damage incident involving  wastes containing




 hydrocyanic acid confirm that cyanide  can migrate,  persist  and con-




 taminate  groundwater, public drinking  water,  and  soil.   A landfill  in




 Monroe County, Pennsylvania,  that accepts  plating process such as hydro-




 cyanic acid, has  created  a  groundwater pollution  problem in the  area. ^^^




             Thus,  these  wastes could  clearly create a substantial




 hazard via a   groundwater exposure pathway if improperly ponded,  or




 if concentrated  liquid  from  the holding  pond is improperly  well




 injected.  Improper ponding  also could result in  a  hazard via a  surface




water pathway.   If  flooding  occurs due to  heavy rainfall, these  hazard-




ous chemicals  could enter surface water  unless  adequate waste management

-------
methods  are utilized.   As most of the acrylonitrile plants are located

in Texas and Louisiana Gulf Coast area where average yearly rainfall is

heavy and the groundwater is close to the surface, the likelihood of

groundwater contamination is very high.

          The Agency therefore regards these three wastes as toxic.

      B.  Reactivity Hazard Posed by Wastewater Stripper Stream and
          Acetonitrile Column Stream

          Both of these waste streams contain hydrocyanic acid, which is

hydrogen cyanide gas in liquid form.  If these wastes ,are exposed to

relatively mild acidic conditions, hydrogen cyanide gas will be released.

The wastes thus meet the characteristic of reactivity contained in

Part 261.23(a)(b) and are listed accordingly.

      C.  Toxicity Hazard of Still Bottoms from Final Purification of
          Acrylonitrile

          The acrylonitrile final product purification column emits a

concentrated bottom waste containing large concentrations of acrolein,

acrylamide and acetonitrile.  These bottoms are typically disposed of by

incineration.   Mismanagement of this stream by improper incineration

(inadequate temperature or residence time) creates a high probability of

health risks resulting from exposure to uncontrolled contamination of

ambient  air with these waste constituents.  Also,  incineration is not an

assured  waste  management method,  so that the wastes could be improperly

land disposed  as well.   The waste is therefore deemed hazardous.

      B.    Health  and Ecological Effects
            1.  Acrylonitrile
                Health Effects  -  Industry-sponsored studies and other

-------
studies  of  data on exposed workers and animal tests strongly indicate that




acrylonitrile  is carcinogenic in humans.(20,24)  it has also been identified




by  the Agency  as a compound exhibiting substantial evidence of being a




carcinogen.  Evidence  has  also developed  from positive laboratory tests  in




several  organisms  that acrylonitrile  is a mutagen. (25,27; jt ^as




also been reported to  be teratogenic  and  toxic to mothers.(28,29;




Acrylonitrile  is an extremely toxic chemical  by inhalation,  ingestion, or




dermal routes  following exposure to small quantities (oral rat LD5Q=82mg/Kg.)




it  is rapidly  absorbed and distributed widely in the body, and acts  by




damaging respiratory processes (causing asphyxia) and many tissues  in a




manner similar to  cyanide  poisoning.(30,33;






             Ecological Effects  - The  fathead minnow has  an  observed 96-




hour LC-50  of  10-18  mg/1,  which  demonstrates  the toxicity of this substance




to  aquatic  biota(-^.   A bluegill in a 28-day study  bioconcentrated




acrylonitrile  48-fold(35>.




             Priority  Pollutant  - Acrylonitrile  is designated as  a priority




pollutant under  Section 307(a) of the  CWA.






             Regulations - Acrylonitrile  is regulated by  the Office  of




Water and Waste  Management under the Clean Water Act (304(a) and  311).  The




Office of Toxic  Substances has regulated  acrylonitrile under FIFRA and has




requested additional testing  under Section 4  of  the  Toxic Substances Control




Act.  The OSHA TWA is  2 ppm.




             Industrial Recognition -  Sax, Dangerous Properties of Indus-




trial Materials  designates acrylonitrile  as highly toxic  by  oral  and dermal




routes.   The Handbook  of Industrial Toxicology designates acrylonitrile  as
                                    -to-

-------
 extremely toxic via ingestion, inhalation,  and  percutaneous routes.   Addi-




 tional information on the adverse effects of  acrylonitrile can be found in




 Appendix A.






       2.    Acrylamide







             Health Effects - Acrylamide is regulated  by OSHA as  a carcinogen




 under OSHA Standard 1910.1000(g).  Acrylamide is  a highly toxic chemical  by




 inhalation, ingestion or dermal routes  (oral  rat  LD5Q=170 mg/Kg).  Acrylamide




 exposure produces a progressive neuropathy  in humans,  involving both  the




 central nervous system.  Reversal of symptoms is  seen  following removal




 from exposure.(36;  Fatal intoxication has been reported following industrial




 exposure.(37)







             The ability of acrylamide to alkylate tissue proteins and




 nucleic acids would suggest that investigations in these areas  are nec-




 essary. (36)




             Ecological Effects - Acrylamide has been  found  to  be  toxic




 to freshwater fish after acute exposures at concentrations ranging from




 89,000 to 1,000,000 micro-g/1.(36>






             Regulations -  Acrylaraide is regulated by OSHA  as  a  carcinogen




 under OSHA Standard 1910.1000(g).   The Office of Toxic Substances has




 requested additional information and testing under Section 4(e) of TSCA.




 The OSHA TWA  is  300 micro-g/m3  (skin).






             Industrial  Recognition of Hazard - Sax, Dangerous  Properties




of Industrial  Materials,  recognizes  acrylamide as a highly toxic hazard

-------
upon ingestion,  inhalation  and  skin absorption.







       3.    Acrolein






             Health Effects - Acrolein  is  suspected to be mutagenic and is




an extremely toxic chemical by  ingestion  (oral rat  LD5Q=46 mg/Kg).   Mutagen-




icity was evidenced in  several  test  systems  involving various  species. (38,39)




Toxicity was demonstrated in animals  chronically  exposed  to low levels of




acrolein in.air.




             Priority Pollutant - Acrolein is a priority  pollutant




under Section 307(a) of the CWA.






             Industrial Recognition  of  Hazard - Sax (Dangerous  Properties




of Industrial Materials) lists  the  toxic hazard rating of acrolein  as high




via oral routes  and moderate via dermal routes.   It  is considered a




priority pollutant by EPA.






             Regulations - OSHA has  set a  TWA of  0.1  ppm  and has regulated




it under OSHA Standard  1910.1000.  Acrolein  is regulated  by the Office of




Water and Waste Management under the Clean Water  Act  Sections 311 and 304(a)




and under the Safe Drinking Water Act.  The  Office  of Air,  Radiation and




Noise has regulated acrolein under the  Clean Air  Act.   The Office of Toxic




Substances has requested additional  testing  under Section 4 of  TSCA and




has regulated acrolein  under FIFRA.  Additional information in  the  adverse




effects of acrolein can be found in Appendix A.






       4.    Hydrocyanic Acid/Hydrogen  Cyanide (HCN)







             Health Effects - Hydrocyanic  acid in acrylonitrile produc-

-------
 tion wastes is extremely toxic to humans  and animals via ingest ion,  causing




 interference with respiration processes leading to  asphyxiation and  damage




 to several organs and. systems.  Toxic  effects have  been reported in  humans




 at the very low exposure level of less than  1 mg/kg. (40,41)  Human poisonings,




 including several involving deaths, have  been reported since the 1920's.




 HCN in gaseous state is extremely toxic (LC5Q = 544 ppm.)  to humans.   In




 addition the U.S. Public Health Service established a drinking  water  standard




 of 0.2 mg/1 as an acceptable level for:cyanide in water supplies.




             Priority Pollutant - Cyanide is  a priority pollutant  under




 Section 307(a) of the CWA.






                 Regulations - The OSHA permissible limit  for exposure to




 HCN is 10 ppm (skin) (11 rag/nH) as an eight hour time weighted  average.




 DOT requires a label stating that HCN is  a poisonous  and flammable gas.






                 Industrial Recognition of Hazard - Sax, Dangerous Properties




 of Industrial Materials lists HCN as highly toxic through  ingestion,  inhal-




 ation and skin absorption.  Additional information  on the  adverse effects




 of cyanide can be found in Appendix A.
             5.   Acetonitrile




                 Exposure to acetonitrile occurs primarily through vapor




inhalation and skin absorphion.  Exposure may cause liver and kidney




damage,  disorders of the central nervous system, cardiovascular system and




gastrointestginal system.   It is the release of the cyanide from




acetonitrile  that is believed to cause these effects.  Acute poisoning




and death  have occured in workers inhaling acetonitrile in industry

-------
Acetonitrile is a  component  of  cigarette  smoke  and  is  absorbed by the oral




tissues. (4-7,50) Nitriles and their metabolic  products  have been




detected in the urine., blood, and tissues. ^0)  jn a two  year study




with rats, carcinogenesis was not shown for the  chemical.(49;  Mutagenic




effects have not been demonstrated.  Teratogenic effects  in rats  include




fetal abnormalities in pregnant rats^9)  an(j  skeletal  abnormalities. (53)




From chronic exposure, rat developed liver and kidney  lesions,  and




monkeys showed poor coordination.^^  Until  recently, acetpnitrile




has been investigated by toxicologist chiefly because  of  its relationship




to thyroid metabolism.
                                   -X-

-------
IV.   References


 1.   Synthetic Organic  Chemicals.   United States  1977 Production and Sales.
     United States  International Trade Commission.  Washington, B.C.

 2.   1979 Directory of  Chemical Producers, SRI International, Menlo Park,
     California.

 3.   Blackford, Judith  L.   Chemical Conversion Factors and Yields.  Chemical
     Information  Services,  Stanford Research Institute.  Menlo Park,
     California,  1.977.

 4.   Lowenheim &  Mbran.   Faith, Keyes & Clark's Industrial Chemicals, 4th ed.
    .1975.

 5.   EPA-IMPQCE Series  02/78-03 February 1978.

 6.   Hobbs, F. D. and J.  A.  Key.   Emissions Control Options for the Synthetic
     Organic Chemicals  Manufacturing Industry.  Acrylonitrile Draft Product
     Report.  EPA Contract  68-02-2577.   Hydroscience.  August, 1978.

 7.   Hughes, T. W.  and  D. A.  Horn.   Source Assessment:  Acrylonitrile Manu-
     facture (Air Emissions).   EPA 600/2-77-107J.  September, 1977.

 8.   Lowenbach, W.  and  J. Schlesinger.   Acrylonitrile Manufacture:  Pollu-
     tant Prediction and Abatement.   Mitre Technical Report MTR-7752.
     February, 1978.

 9.   Bernstein and  Avital.   HCN poisoning in a tobacco warehouse,
     Harefuah £2:165-167, 1962  (Hebrew).

10.   1978 Registry  of Toxic  Effects  of  Chemical Subs lances.  U.S. Depart-
     ment of Health, Education,  and  Welfare.   National Institute of Occupa-
     tional Safety  and  Health.   Cincinnati,  Ohio.  January, 1979.

11.   Alesii, B.A. and W.A* Fuller.   1976.   The Mobility of Three Cyanide
     Forms in Soil.  pp. 213-223.   In Residual Management by Land Disposal.
     W.H. Fuller  (ed.), EnvironmentaT Protection Agency,  Cincinnati, OH.
     PB 256768 268.

12.   Cruz, M.,  et al.   1974.  Absorption and Transformation of HCN on
     the Surface of Copper and  Calcium  Montmorillonite.   Clay Minerals
     22:417-425.

-------
 13.   Water-Related Environmental Fate of 129 Priority Pollutants.   1979.
      EPA-440/4-79-029a.   U.S.  EPA, Washington, D.C.

 14.   The  Prevalence of Subsurface Migration of Hazardous Chemical
      Substances  at Selected Industrial Waste Land Disposal Sites.   1977.
      EPA/530/SW-634.   U.S.  EPA,  Washington, D.C.

 15.   Oil  and  Hazardous Materials Technical Assistance Data System.  EPA/
      NIH  (124) Water  Chemistry.

 16.   Preliminary Assessment of Suspected Carcinogens in Drinking Water.
      EPA-560/4-75-003a.   U.S.  EPA, Washington, D.C., June 1975.

 17.   Sheldon,  S.  Lande,,Stephen  J. Bbsch,  and Philip H.  Howard.  1979.
      Degradation and  Leaching  of Acrylamide in Soil.  J. Environ. Qual.
      8:133-137.

 18.   Igisu, Hideki, et al.   1975.   Acrylamide Encephaloneuropathy Due to
      Well Water  pollution.   J. of  Neurology,  Neurosurgery and Psychiatry.
      38:581-584.

 19.   Midwest  Research Institute,  1977.   Sampling and Analysis of Selected
      Toxic  Substances.   Section  V  Sampling and Analysis  Protocol for
      Acrylonitrile.   Progress  Report  10.  13.   Oct.  1-31, 1977.

 20.   O'Berg,  M.   Epidemiologic Studies  of  Workers exposed to  acrylonitrile:
      Preliminary Results.   E.I.  DuPont  de  Nemours,  1977.

 21.   Monson,  R.R.  Mortality and Cancer Mortality Among  BF Goodrich White
      Male Union  Members  who Ever Worked in Departments 5570 through 5579.
      Report to BF Goodrich  Company and  to  the United Rubber Workers.  FR
      43FR 45762,  1977.

 22.   Norris,  J.M.   Status report on 2-year study incorporating Acrylonitril
      in the drinking  water  of  rats.   Health Environ.  Res. Dow Chemical
      Company,  1977.
23.  Quast et al.  Toxicity of Drinking Water  Containing Acrylonitrile
     in Rats:  Results after  12 Months.   Toxicol.   Res,  Lab Health Environ
     Res., Dow Chemical,  1977.

24.  Maltoni et al.  Carcunogenicity Bioassays  on  Rats  of Acrylonitrile
     administered by inhalation and by ingestion.   La Medlcina del Lavoro
     68:401, 1977.

25.  Benes and Sram.  Mutagenic Activity  of  Some Pesticides in Drosophila
     melanogaster.  Ind. Med  Surg 38:442,  1969.                 "

-------
 26.  Milvy and Wolff.   Mutagenic Studies with  acrylonitrile.   Mut. Res.
     48:271,  1977.

 27.  Venitt et al.   Mutagenicity of Acrylonitrile  (cyanrethylene) in
     Escherichia cole.  Mut. Res. 45:283,  1977.

 28.  Murray et al.   Teratologic evaluation of  acrylonitrile monomer given
     to rats  by garbage.  Dow Chemical,  1976.

 29.  Murray et al.   Teratologic evaluation of  inhaled  acrylonitrile
     monomer  in rats.   Dow Chemical,  1978.

 30.  NIOSH.  A Recommended Standard for Occupational Exposure to
     Acrylonitrile.   NIOSH #78-166, 1928.

 31.  Plunkett.  Handbook of Environmental  Toxicology,. 19?  .

 32.  Babanov et al.   Adaptation of an Organism to  Acrylonitrile  at a
     low concentration factor in an industrial environment.   Toksikol.
     Gig. Prod. Neftekhim 45:58, 1972.

 33.  Sakarai  and Kusimoto.  Epidemiologic  Study of Health  Impairment
     Among AN Workers.  Rod. Kagaku 48:273,  1972.

 34.  Henderson et al.   The effect of some  organic  cyanides  (nitriles)
     in fish.  Eng.  Bull. Ext. Ser. Purdue  Univ. No. 106, 130,  1961.

 35.  U.S. EPA, 1979.   In-Depth Studies on  Health and Environmental
     Impacts  of Selected Water Pollutants.  U.S. EPA,  Contract 68-01-4646.

 36.  U.S. EPA.  1979.   Environmental Criteria  and  Assessment  Office.
     Acrylamide:  Hazard Profile. (Draft)

 37.  U.S. EPA.  1976.   Investigation of selected environmental contami-
     nants:  Acrylamides.

 38.  NIOSH.  1978.   Registry of Toxic Effects  of Chemical  Substances.
     OHEW Pub. No.  79-100, p. 51.

 39.  U.S.E.P.A.   Environmental Criteria and Assessment Office.   Hazard
     Profile  of Acrolein, December 1979.

 40.  NIOSH.  Criteria  for recommended standard occupational exposure to
     HCN and  cyanide salts,  #77-108, 1976.

41.  Henderson, et al.   1961.  The Effect of Some  Organic  Cyanides on
     Fish.  Eng.  Bull.  Ext.  Ser. Purdue University No. 106:130.

42.  Deguidt et al.  Mortality from poisoning  by acetonitrite.   Europ J
     Toxicol Environ Health  7:41-97, 1974.

-------
43.  Chemical Engineering News, Editors  Newsletter,  November 1979.

44.  U.S. Environmental Protection Agency.   1978.   Hazardous Waste Incidents,
     Office of Solid Waste, Hazardous Waste  Management Division.  Unpublished,
     open file data.

45.  Kirk-Othmer Encyclopedia of Chemical Technology.   2nd Edition.   John
     Wiley Interscience Publishers, New  York,  1963.

46.  Dawson, Petty, and English, 1980.   Physical Chemical  Properties  of
     Hazardous Waste Constituents.

47.  Dalhamn, T., et al. 1968.  Mouth absorption of  various compounds in
     cigarette smoke.  Arch. Environ* Health  16:   831.

48.  Dequidt, J., et al.  1974.  Intoxication  with acetonitrile  with  a
     report on a fatal case.  Eur. J. Toxicbl.  7:   91.

49.  Dorigan, et al.  1976.  Preliminary scoring of  selected  organic
     air pollutants.  Environ. Prot. Agency, Contract  No.  68-02-1495.

50.  McKee, H.C., et al.  1962.  Acetonitrile  in body  fluids  related
     to smoking.  Public Health Rep.  77:  553.

51.  Patty, Frank A., Editor, Industrial Hygiene and Toxicology, Vol. II,
     Interscience Publishers, New York, 1963.

52.  Pozzani, V.C., et al.   1959.   An investigation of the mammalian
     toxicity of acetonitrile.  J. Occup. Med.  1:   634.

53.  Schmidt, W., et al.  1976.  Formation of  skeletal abnormalities
     after treatment with aminoacetonitrile and cycylophosphamide
     during rat fetogenesis.  (Verh. Anat.   71:635-638 Ger.)
     Chem. Abst.  1515w.
                                 -p

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                        LISTING BACKGROUND DOCUMENT

                              BENZYL CHLORIDE



Still Bottoms from the Distillation of Benzyl Chloride  (T)



!•  Summary of Basis for Listing

    Production of benzyl chloride results in the generation of still bottoms

which contain hazardous aromatic compounds that include toxic organic sub-

stances* carcinogens and suspected carcinogens.  The waste constituents of

concern are benzyl chloride, toluene, chlorobenzene, and benzotrichloride.

    The Administrator has determined that the still bottoms from benzyl chlo-

ride production may pose a substantial present or potential hazard to human

health or the environment when improperly transported, treated, stored, dis-

posed of or otherwise manag.ed, and therefore should be subject to appropriate

management requirements under Subtitle C of RCRA.  This conclusion is based on

the  following considerations:

    1.  Still bottoms from the distillation of benzyl chloride contain benzyl
        chloride, benzotrichloride (when the dark chlorination, (i.e.,
        catalytic light process is used), toluene, and chlorobenzene isomers.
        Benzyl chloride has been identified as a carcinogen and a mutagen;
        the other compounds are toxic.

    2.  Total quantities of benzyl chloride and benzotrichloride generated
        per year in this waste equal approximately 90,000 pounds.

    3.  Disposal of waste in improperly designed or operated landfills could
        result in substantial hazard via groundwater or surface water exposure
        pathways.  Disposal by incineration,  if mismanaged, can also result
        in  serious air pollution through release of hazardous vapors, due
        to  incomplete combustion.  Storage of the wastes before incineration
        presents a potential for contamination of surface or groundwater.

    4.   The hazardous waste constituents such as chlorobenzene are likely
        to  persist in the environment and to  bioaccumulate in environmental
        receptors.

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II.   Sources  of  the Waste and Typical Disposal Practices




      A.  Profile of the Industry




      Benzyl chloride (Cg^CI^Cl) is used as a raw material for Pharmaceuticals




and  as an  intermediate in the preparation of p-benzylphenol and benzyl alco-




hol. (1)  The  major  use for the chemical, however, is in the production of butyl




benzyl phthalate, which is a plasticizer used in the manufacture of vinyl




products.(2)




      Significant production of benzyl chloride is reported ,by two plants  re-




sponding to the  Clean Water Act Section 308 BAT questionnaire of 1979.  These




plants reported  only one process route:   toluene chlorination.  Total reported




production was 223,000 Ib/day (100,000  kg/day),  which is  equivalent to  73.6




million Ib/yr (33.4 million kg/yr).(5)   Both plants  that  reported production




of benzyl  chloride  also provided data on average production per day.   Indi-




vidual plant  production ranges  from 25,000  to 198,000 Ib/day (11,400  to 89,900




kg/day), and  averages 112,000 Ib/day (50,600 kg/day).(5)




      B.  Manufacturing Process  (1»2)




      Benzyl chloride is produced from the chlorination of toluene.   Chlorina-




tion  may either  be  by UV  light  (photochlorination) or by  the catalytic  process.




Catalytic  chlorination requires more severe reaction conditions.   There are




certain differences  in waste  composition depending on which type of chlorina-




tion  is used.  These differences are described more  fully below.   The overall




process, however, may be  generally  described.




      Chlorine is fed  to  a heated  reactor containing  boiling toluene (see  Figure




1).   For production  of benzyl chloride,  the reaction is allowed to  continue




until there is a 37.5%  increase in  weight;  at this point, a mild alkali is




added to neutralize  the acid  formed.  The by-product hydrogen chloride vapors

-------
                To Hydrochloric Acid P^ant
CHLORINE
 TOLUENE
             REACTOR
               1
                                 VENT
VENT
^S
COLUMN
	 X
Be
i *
*
*
Crude
nzyl Chlor
v

.de

^
PRODUCT FRACTIONATION
COLUMN
X_^
f/
BENZYL CHLORIDE
i ll

                                                       Bottom WASTE







                  figure 1. BENZYL CHLORIDE BY THE CHLORINATION OF TOLUENE



                              -Modified from (1,?.)

-------
from the reactor may be  passed  to  a  hydrochloric  acid  plant or recovered as

compressed gas.

     The following equation  shows  the main  reactions:
C6H5CH3
Toluene
   C12
Chlorine
    C6H5CH2C1
Benzyl Chloride
                                                                        HC1
                                                                      Hydrogen
                                                                      Chloride
     One side reaction is as  follows:
     C6H5CHCl2
       Benzyl
     Bichloride
                      C12
                   Chlorine
                         C6H5CC13
                     Benzotrichloride
                          HC1
                        Hydrogen
                        Chloride
     Reactor products are passed to a toluene-removal vacuum distillation

column, where unreacted toluene is removed overhead and recycled  to the re-

actor.  Crude benzyl chloride from the bottom of the toluene column is then

purified under vacuum in the product-fractionation column.  Here, benzyl

chloride product is drawn off as a sidestream and the listed waste stream,

the still bottom stream, is._generated.

     C.  Waste Composition, Generation and Management

         1.  Waste Composition and Generation

     The still bottoms waste consists predominantly of chlorinated benzene

molecules.  If the photochlorination process is used, waste constituents will

be benzal chloride (not a waste constituent of concern), and smaller concen-

trations of benzyl chloride (the product), a range of chlorinated benzenes

(from toluene feed stock impurities), and some residual feedstock toluene

The chlorinated benzenes in the still bottoms will probably be chiefly the

heavier chlorinated benzenes (tri, tetra, penta, and hexa) since lighter

chlorobenzenes will go overhead with the product.

     It is estimated that benzal chloride will be present in concentrations

of .02 kg/kg product, and additional constituents will be present in concen

trations of .005 kg/kg product.  (Modified from 2, 23)

                                    X-

-------
     If  the liquid  phase catalytic chlorination process is used, these  same




 waste constituents  will  be  present.(2)  In addition, benzotrichloride will be




 formed due to the severer reaction conditions.(2)  (The reaction pathway for




 benzo trichloride is indicated on p. 3 above.)  Benzotrichloride and benzal




 chloride are  expected  to be present in the still bottoms in the amount  of




 0.01 kg/kg and  0.1  kg/kg respectively.  (Modified from 2, 23)




     Waste quantities  are expected to be significant.  To gain a rough  idea of




 waste loading,  one  can assume that half the industry uses the photochlorination




 process  while the other  half uses the catalytic process.  Therefore, based




 on total industry annual production of 33.4 million kg (p.2), waste loads




 from the catalytic  process  will be over 2 million kg annually (assuming




 benzal chloride is  not recovered) with hazardous waste constituent loading




 exceeding 200,000 kg a year.  Wastes from the catalytic process would be




 generated in  quantities  of  approximately 3.3 million kg annually (assuming




 benzal chloride is  not recovered), with hazardous waste loadings of approx-




 imately  80,000  kg annually.




     2.   Waste  Management




     Two operating  benzyl chloride plants reported that incineration of the




 waste was their usual  practice.(24)  ^ third company is temporarily using




 landfills until incineration equipment can be obtained.(24)   Because of the




 high chlorine content  of the waste, an incinerator with alkali scrubbing of




 off-gases is necessary for  proper environmental control.




     During incineration, supplemental fuel is usually necessary because of




the small heat  content of the waste.  Flame-out and consequent release of un-




burned toxic chlorinated hydrocarbons is not uncommon in such situations.

-------
III.  Discussion of Basis for Listing

     A. Hazards Posed by the Waste

     As noted above, the principal waste components  are  benzyl  chloride and

benzotrichloride.  Toluene and chlorobenzene are also reported  to  be  present,

since they are present as feedstock materials.  Benzyl chloride has been

identified as a carcinogen and benzotrichloride is structurally similar to

other demonstrated carcinogens.  (See pp. 9-11 following.)  Chlorobenzene

and toluene are toxic chemicals.

     1.  Exposure Pathways

     As noted, the typical disposal method for these wastes is  discharge to a

holding pond or other temporary storage area prior to incineration.   One com-

pany currently landfills these toxic wastes.

     The waste constituents of concern may migrate from  improperly designed or

managed holding ponds or la'ndfills and contaminate ground and surface waters.

First of all, the waste constituents are soluble in significant  concentrations,

Benzyl chloride is extremely soluble in water (solubility 330,000 mg/1), while

toluene and chlorobenzene are also very soluble (470 mg/1 and 488 mg/1 respec-

tively) .  (Appendix B.)  Toluene would also tend to promote solubilizing of

other waste constituents, since it is a widely-used commercial  solvent.

Thus, these waste constituents could leach into groundwater if  holding

ponds or landfills are inadequately designed and constructed,  or  lack

adequate leachate collection systems.* Siting of waste management  facilities

in areas with highly permeable soils could likewise facilitate  leachate

migration.  Disposal or storage in improperly designed or managed  ponds
*Some of these waste constituents' mobility are effected  by certain soil
 attenuation mechanisms. (App. B)  Pollutant mobility could be  high,  however,
 where soil attenuation would be slight; for example, where soil  is low in
 organic content, highly permeable, or where attenuative  capacity is  exhausted.

-------
could  similarly promote leachate  formation and migration (indeed, the large

quantity of percolating liquid  available could facilitate environmental

release by acting as a hydraulic  head) .

    There is also a danger  of  migration into and contamination of surface

water  if holding ponds are improperly designed or managed.   Inadequate

flood  control measures .could result  in washout or overflow of ponded wastes.

    The migratory potential .of Chlorobenzenes and toluene  is confirmed by

the fact that chlorobenzenes (mono,  di,  tri,  tetra,  and penta) and toluene

have been detected migrating from the Love Canal site into  surrounding resi-

dential basements and solid  surfaces, demonstrating  ability to migrate through

and persist in soils.  ("Love Canal  Public Health Bomb",  A  Special Report to

the Governor and Legislature","""New York State  Department of  Health (1978)).

Benzyl chloride, although subject to hydrolyzation (App.  B),  has  also been

identified as leaching from  the Hyde Park Site.   (OSW Hazardous Waste Divi-

sion,  Hazardous Waste Incidents,  Open File, 1978.)

    Once these three contaminants migrate from  the  matrix  of the waste,  they

are likely to persist in groundwater (see App. B).   Chlorobenzene, toluene,

and benzyl chloride have in  fact  been shown to persist in soil and ground-

water, as demonstrated by the above-described  damage incidents.*
 *The above discussion does not consider benzotrichloride,  another waste constit-
  uent of concern.   This waste constituent is relatively  insoluble, not very vo-
  latile, and tends to degrade in water.  It is, however, relatively bioaccumula-
  tive (App.  B).   Thus, this waste constituent shows a  lesser  propensity to migrate
  and reach environmental receptors, but could accumulate in harmful concentrations
  if it reached a receptor.  Furthermore, benzotrichloride  has been identified as
  migrating from the Love Canal site (OSW Hazardous Waste Division, Hazardous Waste
  Incidents,  supra), demonstrating some ability to migrate  and persist if im-
  properly managed.

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     There  also may be a danger of migration and exposure via an air inhalation




pathway if  disposal sites lack adequate cover.   Toluene is relatively volatile




(App.  B), and  is mobile and  persistent in air,  having been found in school and




basement air at Love Canal ("Love  Canal Public  Health Bomb", supra).  Chloro-




benzenes and benzyl chloride,  while less volatile (App. B),  are also mobile and




persistent  in  air.   Chlorobenzene  (mono through penta)  have  been identified




in  school and  basement air at  Love Canal ("Love Canal Public Health Bomb,"




supra), while  benzyl chloride  has  been shown  to persist in the  atmosphere  in




the New Jersey area for considerable periods  of time.(6)   Thus,  these hazard-




ous constituents could migrate from uncovered landfills or holding  ponds




and persisit for long periods  in the environment.




     Disposal  by incineration,  if  mismanaged, also can  result in serious air




pollution through  the release  of toxic fumes.   This may occur when  incinera-




tion facilities are operated"in such a way that  combustion is incomplete (i.e.,




inadequate  conditions of  temperature,  mixing, and  residence  time) resulting in




airborne dispersion of hazardous vapors  containing undestroyed waste  constit-




uents.  This could  present a significant opportunity  for  exposure of  humans,




wildlife and vegetation in the vicinity of these operations  to hazardous




constituents through direct contact  and  also  through  pollution of surface




waters.




     The waste constituents in the  still bottoms from benzyl chloride produc-




tion are of the highest regulatory concern.   For example,  there  is  no known




safe level  of  exposure for carcinogens  (see 44  Fed. Reg.   15926,  15940,




(March 15,  1979).).   The Administrator would  require assurance that these




waste constituents  could not migrate and  persist to justify  a determination




not to list this waste  stream.  These waste constituents,  to the contrary,

-------
 have migrated  and  persisted to cause substantial hazard in actual instances.

 The waste is therefore deemed hazardous.*

     B.  Health and Ecological Effects

         1.  Benzyl Chloride

            Health Effects - Benzyl chloride has been identified as a

 carcinogen^), and is  also mutagenicW.  Additional information and specific

 references on  the  adverse effects of benzyl chloride can be found in Appendix A.

            Regulatory Recognition of Hazard - The OSHA TWA for.benzyl chloride

 is 1 ppm.  DOT requires la.bej.ing as a corrosive.  The Office of Water and Waste

 Management, EPA, has regulated benzyl chloride under Section 311 of the Clean

 Water Act- Preregulatory assessment has been completed by the Office of Air,

 Radiation and  Noise under the Clean Air Act.  The Office of Toxic Substances

 has requested  additional testing under Section 4 of the Toxic Substances Con-

 trol Act.


            Industrial Recognition of Hazard - Benzyl chloride is listed in

 Sax's Dangerous Properties of Industrial Materials as highly toxic via inhala-

 tion and  moderate  via  the oral route.

         2.  Chlorobenzene

            Health Effects - Chlorobenzene is a toxic chemical absorbed into

 the body  by inhalation,  ingestion,  and through the skin.   Doses of chloroben-

 zene have been reported  to cause liver damage in animals,  abnormal dumping of

 porphyoin pigments  from  the liver,  weakness and stupor.  Additional information
*Furthermore, the waste constituents  are generated in large annual quantities,
 thus increasing the possibility  of exposure  if the wastes are managed
 improperly.  These large quantities  of  hazardous constituents potentially
 available for release further justify a hazardous listing.

-------
and specific  references  on  the  adverse  effects  of  chlorobenzene can be found




in Appendix A.




              Environmental Effects - Chlorobenzenes  are  toxic  to lower order




organisms and aquatic  toxicity  of chlorobenzene is indicated from studies




with saltwater shrimp  species.  Chlorobenzene has  been shown to  bioaccumulate




in fishC1*).




             Regulations - The  OSHA TWA in air  is 75 ppm.  Chlorobenzene is




designated as a priority pollutant under Section 307(a) of the CWA.   (10, H,




12, 13, 14)




              Industrial Recognition of Hazard - Chlorobenzene is  listed in




Sax1s Dangerous Properties of Industrial Materials as a dangerous chlorine




compound.




         3-   Toluene




             Health Effects - Toluene is a toxic chemical absorbed into the




body by inhalation, ingestion, and through the skin.   The acute toxic ef-




fect of toluene in humans is primarily depression of the central nervous




system(16).  Chronic occupational exposure in shoe workers was  reported to




lead to the development of neuro-muscular disorders,  such as abnormal ten-




don reflexes and decreased grasping strength(17).   In animal studies, pre-




liminary evidence of bone marrow chromosomal abnormalities was  report-



edttS,  19).




             Since toluene is metabolized in the body by a protective enzyme




system which is also involved in the elimination of other toxins, it appears




that overloading the metabolic pathways  with toluene will greatly reduce the




clearance of other, more toxic chemicals.   Additionally,  the high affinity of




toluene for fatty tissue can assist in the absorption of other  toxic chemi-

-------
cals into the body.  Thus,  synergistic effects of toluene on the toxici-




ties of other contaminants  may render the waste stream more hazardous.  Be-




yond these considerations,  toluene,  by virtue of its solvent properties, can




facilitate mobility and  dispersion of other toxic substances, assisting




their movement toward ground  or surface waters.  Toluene is designated as




a priority pollutant under  Section 307(a) of the CWA.  Additional informa-




tion and  specific  references  on the adverse effects of toluene can be found




in:Appendix A.




            Ecological  Effects'-  Toluene has been shown to be acutely toxic




to freshwater fish and to marine fish.  Chronic toxicity is also reported




for marine fish(20) .  The USEPA recommended criterion levels to protect




aquatic life are:  freshwater,  2.3  mg/1, and marine, 100 mg/l^O).




            Regulations -  Toluene has an OSEA standard for air (TWA) of 200




ppm.  The Department of  Transportation requires a "flammable liquid" label.






            Industrial  Recognition of Hazard - Toluene is listed as having a




moderate  toxic hazard rating  via oral and inhalation routes (Sax, Dangerous




Properties of Industrial Materials).




         4.  Benzotrichloride




            Health Effects -  Benzotrichloride is toxic with vapors that are




highly irritating  to the skin  and  mucous membranes.  In addition, large doses




have caused central nervous system depression in experimental animals^1'.  In-




halation  of 125 ppm for  4 hours  was  lethal to rats(22).  Benzotrichloride has




been designated as a priority  pollutant under Section 307(a) of the CWA.




Additional information and  specific  references on the adverse effects of benzo-




trichloride can be found in Appendix  A.

-------
             Industrial Recognition of Hazard - Benzotrichloride has a high




toxicity rating via inhalation (Sax, Dangerous Properties of Industrial Ma-



terials).

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IV.  References




 1.  Kirk-Othmer.  Encyclopedia  of  Chemical Technology. _5.  John Wiley and




     Sons, Inc., New York, 1964.




 2.  Lowenheim, F. A. and Moran, M. K.  Faith,  Keyes and Clark's Industrial




     Chemistry.  Fourth Ed.  John Wiley and Sons,  New York,  1975.




 3.  Preliminary Assessment of Suspected Carcinogens in Drinking Water.




     EPA-560/4-75-003.  USEPA, Washington,  D.C., pp. 70-71.




 4.  Lu, P. and R. Metcalf, 1975.   Environmental Fate and Biodegradability




     of Benzene Derivatives as Studied  in a Model  Aquatic Ecosystem.   En-




     viron.  Health Perspect.  10:269-284.




 5.  Individual Plants1 Responses to EPA's  308 questionnaire.




 6.  Altshuller, A. P., Lifetimes of Organic Chemicals in the  Atmosphere,




     Environmental Scientific Technology,  1980, in press.




 7.  U.S. EPA, 1979.  Chlorinated Benzenes:  Ambient Water Quality  Criteria




     (Draft).




 8.  Druckrey, H., H. Druse, R.  Pruessmann,  S.  Ivankovic, C. Landschutz.




     [Carcinogenic alkylating substances 	 III.   Alkyl-Halogenides,  -sul-




     fates, -sulfonates and strained heterocyclic  compounds.]   Z.  Krbsforsch




     74:241-70, 1970 (Ger).




 9.  McCann, J., E. Choi, E. Yamasaki,  B. N. Ames:  Detection of carcinogens




     as Mutagens in the Salmon el la/micro some Test  — Assay of  300  chemicals.




     Proc. National Academy of Sciences VSA 72:5135-39,  1975.




10.  U.S. EPA,  1977.  Investigation of  selected potential environmental




     contaminants:  Halogenated benzenes.  EPA-560/1-77-004.

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11.  Lr, A. Y. H., et al, 1974.  Liver microsomal electron  transport  systems.




     III.  Involvement of cytochrome 85 in the HADE-supported cytochrome




     p5-450 dependent hydroxylation of chlorobenzene.  Biochem.  Biphys,




     Res. Comm. 61:1348.




12.  Brodie, B. B. et al, 1971.  Possible mechanism of liver necrosis caused




     by aromatic organic compounds.  Proc. Natl. Acad. Sci. 68:160.




13.  Knapp, W. R., Jr., et al, 1971.  Subacute oral toxicity of monochloro-




     benzene in dogs and rats.  Toxicol. Appl. Pharmacol. 19:393-




14.  Irish, D- D., 1963.  Halogenated hydrocarbons: II.  Cyclic.  In Indus-




     trial Hygiene and Toxicology,  Vol. II, 2nd Ed., (ed. F. A. Patty),




     Interscience, New York.  P. 1333.




15.  Lu, P. and Metcalf,  1975.  Environmental Fate and Biodegradability of




     Benzene Derivatives as Studied in a Model Aquatic Ecosystem.  Environ.




     Health Perspect.  10:269-285.




16.  U.S. EPA, 1979.  Toluene ambient water quality criteria (Draft).




17.  Matsushita, T., et al,  1975.  Hematological and neuro-muscular re-




     sponse of workers exposed to low concentration of toluene vapor.




     Ind. Health 13:115.




18.  Dobrokhotov, V. B., and M. I.  Enikeev, 1977.  Mutagenic effect of ben-




     zene, toluene, and a mixture of these hydrocarbons in a chronic experi-




     ment.  Gig. Sanit. 1:32.




19.  Lyapkalo, A. A., 1973.   Genetic activity of benzene and toluene.  Gig.




     Tr. prof. Zabol.




20.  U.S. EPA, 1979.   Toluene: Hazard Profile.  Environmental Criteria




     and Assessment Office,  U.S.  EPA,  Cincinnati, Ohio.

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21.  Merck Index.




22.  Sax, I.   Dangerous Properties of Industrial  Materials.




23.  Groggins,  Unit Processes on Organic  Synthesis,  2nd  ed.,  1938.




24.  U.S. Department of Health, Education, and Welfare.   Criteria for a Recom-




    mended Standard — Occupational Exposure to  Benzyl  chloride.   Washington,



    B.C., 1978.

-------
                       LISTING BACKGROUND DOCUMENT
                     CARBON TETRACHLORIDE PRODUCTION
Heavy ends or distillation residues from the production of
carbon tetrachloride (T)

I.    Summary of Basis for Listing
      Heavy ends or distillation residues from carbon tetrachloride produc-

tion contain carcinogenic and toxic organic substances.  These include

carbon tetrachloride, hexachlorobutadiene, hexachlorobenzene,

perchloroethylene and hexachloroethane.


      The Administrator has determined that the solid waste from carbon

tetrachloride production may pose a substantial present or potential hazard to

human health or the environment when improperly transported, treated,

stored, disposed of or otherwise managed, and therefore should be subject

to appropriate management requirements under Subtitle C of RCRA.  This

conclusion is based on the following considerations:

      1.  The heavy ends or distillation residues from the various carbon
          tetrachloride production processes contain some or all of the
          following constituents:  perchloroethylene, carbon tetrachloride,
          hexachlorobutadiene,  hexachlorobenzene, and hexachloroethane.
          All of these substances except hexachloroethane have been
          identified by the Agency as compounds which have exhibited
          substantial evidence  of being carcinogenic; hexachloroethane is
          a suspect carcinogen.   Hexachlorobenzene is also a teratogen. All
          of these compounds are very toxic as well.

      2.  Approximately 8.6 million pounds/year of waste containing these
          hazardous compounds are generated in the United States by six
          manufacturers at 10 plants.

      3.  Disposal of these wastes in drums in improperly designed or
          operated landfills represents a potential hazard due to the
          probable corrosion of drums and the resulting leaching into
          groundwater of these  hazardous compounds.

-------
      4.  Mismanagement  of  incineration operations and volatilization from
         landfills could result in the release of hazardous vapors to
         the  atmosphere, and  present a significant opportunity for
         exposure of humans,  wildlife and vegetation in the vicinity of
         these  operations  to  potentially harmful substances.

      5.  The  components of concern are persistent in the environment,
         thus increasing the  chance for exposure.

      6.  The  components of concern have been implicated in actual
         damage incidents.

II.   Sources  of the Waste  and Typical Disposal Practices

      A.  Profile of the Industry

         There  are six  major  corporations involved in the production of

carbon tetrachloride.  The  locations and annual capacity for each  plant

are listed  in  Table 1.

      The current principle use of  carbon tetrachloride is in the

manufacture of chlorofluoromethanes used in refrigeration and aerosols.

Other uses  include grain fumigation and a variety of solvent and chemical-

manufacturing  applications.(2)

      B.  Manufacturing  Process

         Carbon tetrachloride is produced principally via four processes:

direct chlorination of methane,  pyrolysis or chlorinolysis of hexachloro-

ethane with simultaneous chlorination of perchloroethylene,  direct

chlorination of  propane  (in which perchloroethylene is produced as a

co-product), and direct  chlorination of carbon disulfide.  These processes,

and the listed waste streams generated thereby,  are discussed below.*(4,2,31)
* These processes generally involve  production of  a  range  of  chlorinated
  organic products as well as carbon tetrachloride

-------
                                 TABLE 1

          Plant Sites for Carbon Tetrachloride Production^3)
                      I
      Company
   Location
  Annual Capacity
(Millions of Pounds)
Allied Chemical Corp.|
  Specialty ChemicalsI
  Division
Moundsville, WV
         8
Dow Chemical, U.S.A.
Freeport, TX
Pittsburg, CA
Plaquemine, LA
       135
        80
       125
E.I. duPont de
  Nemours & Co., Inc.
  Petrochems Dept.
    Freon® Prod. Div.
Corpus Christi, TX
       500
Stauffer Chemical Co.
  Ind. Chems. Div.
Le Mogne, AL
Louisville, KY
        200
         70
Vulcan Material Co.
  Chemical Div.
Geismar, LA
Wichita, KA
         90
         60
FMC Corporation
S. Charleston, WV
        300
                                  Total
                             1,568

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          1.   Direct Chlorination of Methane (31)




              The  sequence of reactions for production of carbon




 tetrachloride from the direct chlorination of methane is:




              CH4+C12    	>     CH3CH-HC1




            CH3C1+C12    	>     CH2C12+HC1




           CH2C124C12    	>     CHC13+HC1




            CHC13+C12    	>     CC14+HC1






 The reaction is  conducted adiabatically at temperatures ranging from




 350° - 370°C and at approximately atmospheric pressure.  In this process,




 methyl chloride, methylene chloride and chloroform are usually




 co-produced with carbon tetrachloride.  The ratio of formation of




 these reaction products may be controlled to favor production of higher




 chlorinated products (e.g., carbon tetrachloride) by recycle of less




 chlorinated products (e.g., methyl chloride).   Typical yields range from




 85% to 95% based on methane.






      Figure 1 represents a simplified process for production of carbon




 tetrachloride via  direct chlorination of methane.  Methane is mixed with




 chlorine,  preheated and fed to a reactor fitted with mercury arc lamps




 to enhance disassociation of chlorine.  Chlorine is the limiting




 reactant and  about 65% of the methane reacts.   A typical range of




 products leaving the reactor is:   methyl chloride - 58.5%;  methylene




 chloride - 29.3%;  chloroform - 9.7%;  and carbon tetrachloride - 2.3%.




 The effluent  gases  from the reactor also contain unreacted methane




and hydrogen  chloride which are separated by scrubbing the reacted




gases  with a mixture of liquid chloromethanes,  usually a refrigerated

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     MtlHANt

     METHYL CHLORIDE

     MOHYLENE CHLORIDE
                                 CARBON TETRACHLORIDE
      RECYCLED
      METHANE
METHANE-

CHLORINE-
 SPENT
 CAUSTIC
                           NaOH
REACTOR
                 a:
                 UJ
                 ca
                 ce
                 O
                 v*
                 CO
                                                   HOT
                                                  WATER
                                                             HCI
                                                          ABSORBER
            u:
              o


                           o:
                           O
                           £
                           u
/ ^
ABSORBER

cT



f v

-;*-
f \
STRIPPER
V

-
J
V

^~
                                                                       OS
                                                                       UJ
                     a:
                     »->
                     s
                                                                           NaOH
                                                                      Y
                                                                                   o
                                                                      SPENT
                                                                     CAUSTIC
                                                                      O

                                                                        T
                                                                      SPENT
                                                                      ACID
                                   HCI
                             RECYCLE
           *-* **• t

           2
REACTOR
                                  Ul
                                              ca
                        i i I    UJ


                       /""\  PC
           i
           o
                          FTk
                                                        o
                                                        fc
                                                        3

                                                     REACTOR
                                                   -H	J
  METHYL CHLORIDE

   Figure  1.
       METHYLENE CHLORIDE
CHLOROFORM
                                  CARBON
                                TETRACHLORIDE
                                  COLUMN
                                                                                  ->-HEAVY ENDS
                                         CARBON TETRACHLORIDE
     Methyl chloride,  methylene  chloride,  chloroform and carbon
     tetrachloride by the direct chlorination of  methane.
                 (Modified from  31)

-------
 mixture of chloroform and carbon tetrachloride.  Methane and hydrogen

 chloride are not  absorbed and go overhead.  Hydrogen chloride is

 removed by scrubbing with water and methane is recycled.  The enriched

 chloromethane solvent absorber effluent is stripped of methyl chloride

 and some methylene dichloride.  The stripped solvent bottoms are

 recycled to the absorber.  The overhead product is condensed and

 purified successively by a hot water wash (to remove residual hydrogen

 chloride), an alkali wash, and a strong sulfuric acid wash (to dry the

 chlorinated organic stream).  The stripped methyl chloride, methylene

 chloride and any  heavy ends are separated by fractional distillation.

      A portion of the bottoms from the stripping column together with

 some or all of the recovered methyl chloride and methylene chloride

 is then fed to a  secondary reactor where chlorination is again carried out

 photochemically,  but this time in the liquid phase.   Hydrogen chloride is

 vented from the reactor.  The reaction products are purified and separated

 by a sequence similar to that used for methyl chloride and methylene

 chloride, except  that any product less chlorinated than chloroform may

 be recycled.   Desired quantities of chloroform are removed by distillation,

 and the remaining material is chlorinated in a third reactor to produce

 carbon tetrachloride.   The effluent from the third reactor is distilled

 to recover carbon tetrachloride.  The heavy bottoms  from this tower is

 the process  waste.

    Waste constituents predicted to be present in heavy ends from this

 process  in substantial  concentrations are hexachloroethane, hexachlorobuta-

diene, perchloroethylene (tetrachloroethylene),  and  carbon tetrachloride.*
*As presented in Table 2, little  or no carbon tetrachloride was recorded
 found in the air, aqueous and  solid emissions.   However, based on industry
 process, this constituent is predicted to be present in the waste.  Further,
 the presence of even very small  concentrations  of this very potent carcinogen
 are of concern to the Agency.

-------
Hexachloroethane would  result  from  chlorination of  G£  molecules,  which

could be formed from methyl radicals.  The same general  type  of reaction

would also  result in formation of hexachlorobutadienes,  except  that  C^

molecules (rather than  G£ molecules) would be chlorinated.  Perchloro-

ethylene is expected to result from the dechlorination of hexachloroethane.


     A literature source estimating emissions from  direct chlorination

of methane  is  set forth in Table 2.


     2.  Chlorinolysis of Hydrocarbon Feedstocks


         Chlorinolysis* processes, in fact, make up the  bulk of carbon

tetrachloride  (perchloroethylene is a co-product) capacity in the United

States.  Feedstocks for this process include aliphatic hydrocarbons

(e.g., propane), chlorinated aliphatic hydrocarbons, and chlorinated

aromatic hydrocarbons.  Use of chlorinated feedstocks is particularly

valuable for control of residues from other chlorination processes,

which otherwise would pose a difficult disposal problem.

     The conditions necessary for Chlorinolysis of hydrocarbon feedstocks

are somewhat more severe than those of direct chlorination of methane;

both higher temperatures and higher molar ratios of chlorine to hydrocarbon

are used.   The product distribution is quite dependent on the feedstock used

and varies  from over 90% carbon tetrachloride (propane)  to over 90%

perchloroethylene (propene).
*Chlorinolysis reactions refer to those chlorination reactions which
  result in extensive rupture of carbon-carbon bonds.

-------
                                 TABLE 2 ESTIMATED EMISSIONS FROM THERMAL CHLORINATION OF METHANE
      Species
                                                            EMISSIONS kg/Mg  of  product1
 Air
Aqueous
Solid
      Methane
      Methyl chloride
      Carbon tetrachloride
      Perchloroethylene
      Hexachloroethane
      Sodium chloride
      Sodium hydroxide
 28

trace

  0.3
   39
                               16
                                0.6
                                                        17

                                                        16
                                                                                                   33
Source:  Wasselle, "Chlorinated Hydrocarbons", Process Economics Program Report No. 126,  Stanford Research Institute,
 Menlo Park, CA, August, 1978.

^Based on hydrogen chloride product.  To convert from hydrogen chloride product to a specific chlolorinated
 hydrocarbon product, the following factors are used:  0.72 Ibs HCl/lb ClvjCl

                                                        0.86 Ibs HCl/lb CH3C12

                                                        0.92 Ibs HCl/lb CH2C13

                                                        0.95 Ibs HCl/lb CC14

-------
carbon bonds  (at  severe  reaction  conditions),  followed by rechlorination




of the fractured  portions.  Waste residues result  from incomplete chlorina-




tion of the cracked hydrocarbons.  Hydrocarbon chlorinolysis  reactions




thus tend to  produce similarly-composed residual wastes.   Waste  con-




stituents predicted to be generally present are hexachlorobenzene,




hexachioroethane, perchloroethylene, hexachlorobutadiene,  and carbon




tetrachloride.  Two principal chlorinolysis processes  for  the




production of carbon tetrachloride are described more  fully below.




                a.  Chlorinolysis of Propane (31)




     The basic chemical  equation  representing  the direct chlorination of




propane to produce carbon tetrachloride and perchloroethylene is:




                C3H8 +8C12       	>   C2C14+C12




                C2C14+C14        	>   C2C16




                2C2C14           	>   C4Cl6-K:i2




Figure 2 is a simple block flow diagram for the production of carbon tetra-




chloride and perchloroethylene by the direct chlorination of propane.




Feedstock chorine, together with recycled chlorine, and propane are introduced




into a vaporizer where they are mixed with recycled chlorocarbons.  Chlorine




is used in approximately 10% to 25% excess.  The mixed gases react adiabati-




cally at atmospheric pressure in a refractory-lined reactor at temperatures




ranging from 550°C and 700°C (controlled by the diluent action of




recycled streams).  The recycle ratio also affects the product distribution.




Effluent from the rector (mainly carbon tetrachloride, perchlorethylne,




hydrogen chloride, chlorine, and unreacted hydrocarbon) is quenched with




perchloroethylene to minimize formation of by-products.




     Carbon tetrachloride, separated by fractionation, is condensed and

-------
                                      CC1
C£
o

o


UJ
C£
                                                    e
                                                  o n
                                       ac
                                       0
                                       =D o
                                       CD-I—
                                       UJ
                                       CO


                                     <3 CD
                                     oc to
                                         O
                                                     RECYCLE

                                                       TANK
                                                                                      I
                                                                                      o
             FIGURE
                     I-
                    *Mocliflcd  from 31

CARBON TETRACHLORIDE AND PERCHlOROETHYLENE MANUFACTURE VIA* Chlorlnolysis of Propane
r
!!IOi!IMIifliliIllH

-------
withdrawn.  Hydrogen  chloride and  chlorine are separated and scrubbed with

water in a hydrogen chloride  absorber  to  remove HC1  as  hydrochloric acid

by-product.  The carbon  tetrachloride  column  returns bottom liquid that is

rich in perchloroethene  to  the heavy ends column.  Light ends  from this

column are recycled to the  reactor.  In the heavy  ends  column,  the

perchloroethylne-rich stream  is distilled to  remove  the  heavy  ends that

are returned for recycle.   Overhead from  the  heavy ends  column  is

fractionated in the perchloroethylene  column where  the  desired

quantity of perchlorethylene  is removed as  bottoms and  the  overhead,

containing largely carbon tetrachloride,  is sent to  recycle.  The  final

product mix is contgrolled  by the amounts of  product recycled to the

reactor.  Estimated emissions  from this process are  shown in Table 3.*

      The reaction pathways for these waste constituents are as follows:

Hexachloroethane results from the chlorination of  product perchloroethylene.

Free radical reactions will result in the formation  of hexachlorobutadiene

(see p. 8 where the reaction  chemistry is described).  Hexachlorobutadiene

could also be formed by chlorination of ethylene radicals under chlorinolysis

conditions.  Hexachlorobenzene would result from the cyclization and

chlorination of G£ molecules  under the high temperature reaction conditions

via a Diels-Alder reaction, whereby a cyclic  compound is formed from

double bond systems.
*As presented in Table 3, little or no carbon tetrachloride was recorded
 found in the air, aqueous and solid emissions.  However, based on
 industry process, this constituent is predicted to be present in the
 waste.  Further, the presence of even very small concentrations of
 this very potent carcinogen are of concern to the Agency.

-------
                                               TABLE 3

           ESTIMATED  EMISSIONS FROM CARBON TETRACHLORIDE MANUFACTURE:  Chlorinolysis of Propane
Species
                                                          EMISSIONS kg/Mg
                                      Air
                                                                Aqueous
Solid
Carbon tetrachloride
Hexachloroethane
Hexachlorobutadiene
Hexachlorobenzene
Tars
Sodium hydroxide
                                                                  trace
                                                                   1.1
 trace

  3.3

  3.3

  3.0



 10
Source:  Elkin,  "Chlorinated  Solvents,"  Process Economics Program Report No. 48, Stanford Research
         Institute,  Menlo Park,  CA,  1969

-------
                  b.  Chlorinolysis of hexachloroethane with  simultaneous
                      chlorination of perchloroethylene  (4,2)


          Expected waste constituents of concern from this process  (Figure 4)

    are hexachlorobenzene, hexachlorobutadiene, hexachloroethane, and carbon

    tetrachloride.*  Some carbon tetrachloride is expected to be present in

    distillation bottoms since it is the product and would not be completely

    removed from the bottoms.  Hexachloroethane is a feedstock and thus is

    also expected to be found in the waste.  Hexachlorobenzene will result

    from the cyclization and chlorination of C2 molecules under high tempera-

    ture pyrolysis conditions.

          The final production process considered is the production of carbon

    tetrachloride by chloronation of carbon disulfide.

              3.  Carbon Tetrachloride by Chlorination  of Carbon Disulfide (3)

                  Direct chlorination of carbon disulfide to  carbon tetra-

    chloride is a long-established process which,  until  challenged  by

    chlorination of methane and chlorinolysis of hydrocarbons, was  the sole

    source of carbon tetrachloride.  Chlorination of carbon disulfide does

    have certain advantages:   hydrocarbon co-products or by-products and

    hydrogen chloride are not formed.   Because sulfur must  be  recovered  and

    recycled however, this process is  presumed to  be integrated  with a carbon

    disulfide production facility.

        The overall chemistry of this  process is represented  by  the following

    equations:
                    2CS2+6C12   	>   2CC14+2S2C12
     *Additional  heavy chlorinated  hydrocarbons  will  probably also  be
present, but their  existence  is  more  speculative since  they  would probably
"crack" into lower  molecular  weight compounds  under chlorinolysis conditions
                                     13

-------
CHLORINE
                         t
PURGE ON RECYCLED CHLORINE (GAS)
                 CARBON
               TETRACHLORIDE
                                    1 ........
                                  r\
                                                                PERCHLOROETHYLENE
                                                                         PERCHLOROETHYLENE
                                                                             RECYCLE
                •  HEAVIE!
J
1 ,
I
rioN
N
H
ORI

ER


                 (iEAWENDs
               Figure^. CARBON TETRACHLORIDE BY THE PYROLYSIS OF
                     "  HEXACHLOROETHANE & PERCHLOROETHYLENE
                           (Modified  from A, 2)

-------
The sulfur monochloride formed reacts with a fresh feed  of  carbon disulfide




to form additional carbon tetrachloride:
This reaction, in contrast to the first reaction, goes only to  about 75%




completion.  The sulfur formed is recyled to carbon disulfide production.




Reaction yield is about 95% based on carbon disulfide.




     Carbon disulfide, a recycle stream of carbon disulf ide/carbon tetra-




chloride/sulfide monochloride from dechlorination, and chlorine (approx.




1% wt over the stoichiometric requirement) . react in the ehlorinator at




an approximate temperature and pressure of 100°C and 1 atm., respectively.




The reaction goes to near completion and the crude product consists




principally of carbon tetrachloride and sulfur monochloride, and a small




amount of carbon disulfide (>0.1% wt ).  Sulfur dichloride formation is




minimized by the presence of the carbon disulfide.




     The crude product is fractionated into  an overhead stream of carbon




tetrachloride and a bottom stream of sulfur  monochloride and carbon




tetrachloride.  Chlorine is added to the bottom stream to form small




amounts of sulfur dichloride which catalyzes the subsequent dechlorination




reaction.  The dechlorination reactor operates under reflux conditions




using the bottom stream as a feedstock.  After dechlorination, the reaction




product is separated:   the overhead stream (CC14/CS2/S2C12) is recycled




to the chlorination reactor;  the bottom stream, which is largely sulfur,




is purified and recycled to carbon disulfide production.  Crude carbon




tetrachloride, separated as an overhead stream from the distillation of




the chlorination mixture,  is washed with either a dilute solution of




sodium hydroxide or a  suspension of calcium  hydroxide to decompose sulfur
                                   *•«.  ,
                                   -S "7V-

-------
 monochloride and  dichloride.  This stream is distilled and water, carbon




 tetrachloride,  and  carbon disulfide are removed as an overhead stream.




 Water is decanted,  and the organic layer distilled.  The bottom stream




 from this column  is sent to carbon tetrachloride storage.




     When properly  conducted, this process would probably be waste free.




 However, if conducted inefficiently, heavy ends could be generated consist-




 ing of sulfur monochloride and carbon tetrachloride, probably in equal




 concentrations.   Obviously, the Agency is only listing this process when




 waste heavy ends  are actually generated.




          C. Waste Generation and Management




             The distillation residue waste from the direct chlorination




 or chorinolysis of  hydrocarbons thus consist of heavy chlorinated hydro-




 carbons, such as  hexachlorobenzene, perchloroethylene, hexachlorobutadiene,




 carbon tetrachloride, and hexachloroethane.   These wastes are generated




 in large quantities.  Based on U.S.I.T.C 1978 production figures of




 334,000 metric  tons of carbon tetrachloride^^) and the waste emission




 factors set forth above, an estimated 3200 metric tons of waste is




 generated each  year.  This estimate may be conservative,  since waste




 emission factors  were not calculated for wastes from carbon tetrachloride




 production by pyrolysis of hexachloroethane.  In any case, this is a




 significant annual  quantity of waste generated, and it must further be




 remembered  that this waste will accumulate in greater quantities over




 time.




    Heavy  ends from carbon tetrachloride production have typically




been disposed of  in drums in land  disposal facilities, or have been




incinerated.

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III.  Discussion  of Basis  for  Listing


      A.  Hazards Posed by the Waste

          The waste constituents of concern, which  as  shown  above are

present in these  wastes in substantial concentrations, are:

          o  Hexachlorobenzene
          o  Hexachlorobutadiene
          o  Carbon Tetrachloride
          o  Hexachloroethane
          o  Perchloroethylene

      All of these substances  except hexachloroethane have been  identified

by the Agency as  being carcinogenic and they are all very toxic.

Hexachlorobenzene is also  a teratogen.  Generation  and accumulation of

large quantities  (over 3000 MT annually, see p. 16) of wastes containing

these constituents is itself a reason for imposition of hazardous status.

The large quantities of these contaminants pose the danger of polluting

large areas of ground or surface waters.  Contamination could also

occur for long periods of  time, since large amounts of pollutants are

available for environmental loading.  Attenuative capacity of the environment

surrounding the disposal facility could also be reduced or used up due

to the large quantities of pollutant available.  All of these considerations

increase the possibility of exposure to the harmful constituents in the

wastes, and in the Agency's view, support a hazardous listing.


      In light of the extreme danger posed by these waste constituents,

and the large quantities of waste generated, a decision not to list

these waste would be justified, if at all, only if waste'constituents

were demonstrably unable to migrate and persist.  This is not the

case,  however,  since most of these waste constituents have migrated

and persisted in actual damage incidents, via both groundwater and air

                                   TT

-------
exposure pathways.






      Carbon tetrachloride,  for example, has been identified as present




in school and basement air at Love Canal, as has hexachlorbutadiene and




perchloroethlyene .   (Source:  "Love Canal, Public Health Bomb", a Special




Report to the Governor and Legislature, New York State Department of




Health,  1978.)   Carbon tetrachloride has also been implicated in two




groundwater contamination incidents in Plainfield, Connecticut, where




drinking water sources were adversely affected (Table 1, Reference 31).






      Heaxchlorobutadiene, hexachlorbenzene and hexachlorethane also have




been shown to migrate from waste disposal sites to groundwater.  EPA




conducted groundwater monitoring in the vicinity of an (unnamed) chemical




waste disposal site  in an effort to quantify migrating organic waste




constituents.  These waste constituents were all found to have migrated




(Table 7.2,  Reference 31).




      Another incident illustrates even more dramatically the migraory




potential of these waste  constituents.   Chemical wastes from Hooker




Chemical's disposal  sites at Montague,  Michigan have migrated from




landfills and underground injection wells,  moved through and contaminated




groundwater supplies,  and contaminated  a recreational lake.  The contaminated




plume is 2,000  ft. wide and  extends for over 1 mile.   Among waste




constituents present in the  plume are hexachlorobutadiene, hexachlorbenzene




and carbon tetrachloride.  (31)




      Hexachlorobenzene may  also pose a hazard through volatilization.




A case history  of environmental damage  in which air,  soil, and vege-

-------
tation  over  an  area  of  100  square miles  was  contaminated  by hexachloro-




benzene (HCB) occurred  in 1972.(7)  There was volatilization of  HCB




from  landfilled wastes  and  subsequent bioaccumulation  in  cattle  grazing




in the  eventually contaminated  areas.  Accumulation in  tissues of  cattle




occurred, so that the potential risk to  humans from eating  contaminated




meat  and other  foodstuffs is significant.






      These waste constituents  thus have proven capable of  migration,




mobility and persistence, and are, demonstratably capable of causing




substantial hazard via  groundwater, surface water and air exposure




routes, if improperly managed.  Disposal by incineration is  another type




of management which  could lead  to substantial hazard.  Improper  incinera-




tion  can result in serious air  pollution by the release of  toxic fumes




occuring when incineration facilities are operated in such  a way that




combustion is incomplete.  In the incineration of wastes containing




carbon  tetrachloride, phosgene  (a highly toxic gas) is likely




to be emitted under  incomplete combusion conditions.(32,33,34)




These conditions can, therefore, result in a signifcant opportun-




ity for exposure of  humans,  wildlife and vegetation,  in the vicinity




of these operations, to potentially harmful substances.




      B.  Health and Ecological Effects






          1.  Hexachlorobenzene






              Health Effects - Hexachlorobenzene has  been found to be




carcinogenic in animals.(8»9)  It has  also been identified by the Agency




as a compound which exhibits substantial evidence of  being  carcinogenic.

-------
 This chemical is reportedly teratogenic, known to pass through placental



 barriers, producing toxic  and  lethal effects in the fetus.(10)  Chronic



 exposure to HCB in rats has been shown to result in damage to the liver



 and spleen.(^/  It has been lethal in humans when ingested at one-twentieth


                                  (12}
 the known oral LD^Q ^ose f°r rats.^  }  It has also been demonstrated



 that at doses far below those  which are lethal, HCB enhances the body's



 capability to toxify rather than detoxify other foreign organic compounds



 present in the body through'its  metabolism.^ 3) Hexachlorobenzene is
       >                                          -


 designated a priority  pollutant  under Section 307(a) of the CWA.



 Additional information and specific references on the adverse effects of



 hexachlorobenzene can  be found in Appendix A.





             Ecological Effects - Hexachlorobenzene is likely to contaminate



 accumulated bottom sediments within surface water systems and bioaccumulate



 in fish and other aquatic  organisms.(6)



             Regulations  - Hexachlorobenzene is a chemical evaluated by



 GAG as  having substantial  evidence of carcinogenicity.   Ocean dumping of



 of hexachlorobenzene is prohibited.  An  interim food contamination toler-



 ance of 0.5 ppm has been established  by  FDA.





             Industrial Recognition  of  Hazard - According to Sax, Danger-



 ous Properties of Industrial Chemicals,  HCB is a fire hazard and,  when



 heated, emits toxic fumes.



         2.  Hexachlorobutadiene (HCBD)





             Health Effects - Hexachlorobutadiene (HCBD) has been found



to  be carcinogenic in animalsC1^).  It has  also been identified by the

-------
Agency as a compound which exhibits  substantial  evidence of being




carcinogenic.  It is an extremely  toxic  chemical  [LD5Q  (rat)"  90  mS/kg]




via ingestion.  Upon chronic exposure of animals  in  tests conducted  by




the Dow Chemical Company and others, the kidney appears  to be  the organ




most sensitive to HCBD^**15*16).  Effluents from industrial




plants have been found to have HCBD  concentrations as high as  240 g/l,(19)




more than 200 times the recommended  criterion level.  HCBD is  considered




a priority pollutant under Section 307(a) of the  CWA.  Additional in-




formation and specific references on the adverse  effects  of  hexachloro-




butadiene can be found in Appendix A.






              Ecological Effects - HCBD is likely to contaminate  accumu-




lated bottom sediments within surface water systems and is  likely to




bioaccumulate in fish and other aquatic organisms(°).




              The USEPA (1979) has estimated the BCF at 870  for the edible




portion of fish and shellfish consumed by Americans.  Hexachlorobutadiene




is persistent in the environment(^8).






              Industrial Recognition of Hazard - Hexachlorobutadiene is con-






sidered to have a high toxic hazard rating via both oral  and inhalation




routes (Sax, Dangerous Properties of Industrial Materials).




          3.  Carbon Tetrachloride






              Health Effects - Carbon tetrachloride is a  very  potent carcin-



ogen (19) an(j has been identified by the Agency as a compound which exhibits




substantial evidence of being carcinogenic.  It has also  been  shown to




be teratogenic in rats when inhaled at low concentrations.(20)






                                   X

-------
 Chronic effects  of  this chemical in the human central nervous  system




 have occurred following inhalation of extremely low concentrations  [20




 ppm](21) with death at 1000 ppm.(22) Adverse effects of carbon




 tetrachloride on liver and kidney functions(23) an£j on respiratory




 and gastrointestinal tracts(23>24) have also been reported.  Death  has




 been caused in humans through small doses.(25) The toxic effects of




 carbon tetrachloride are amplified by both the habitual and occasional




 ingestion of alcohol.(26)   Especially sensitive to the toxic effects




 of carbon tetrachloride are obese individuals because the compound




 accumulates in body fat*(^6)  it aiso causes harmful effects in




 undernourished humans, those suffering from pulmonary diseases, gastric




 ulcers, liver or kidney diseases, diabetes, or glandular disturbances.(27)




 Carbon tetrachloride is a  priority pollutant under Section 307(a) of the




 CWA.  Additional information and specific references on the adverse




 effects of carbon tetrachloride  can be found in Appendix A.




     Ecological   Effects - In measurements made during the National




 Organics Monitoring Survey of 113 public water systems sampled, 11 of




 these systems had carbon tetrachloride at levels at or exceeding the




 recommended safe limit.(28)




              Regulations  -  OSHA has set a TWA for carbon tetrachloride




 at 10 ppm.   Carbon  tetrachloride has been banned under the Hazardous Sub-




 stances Act by the  Consumer  Product Safety Commission.






              Industrial Recognition of  Hazard - According to Sax, Danger-




ous Properties of Industrial Materials,  carbon tetrachloride is considered




a high  systemic  poison  through ingestion and  inhalation.

-------
          4.  Hexachloroethane






              Health Effects - Hexachloroethane  has  been  reported to  be




carcinogenic to animals, meaning that humans may be  similarly affected\25)t




Humans exposed to vapors at low concentrations for long periods have  had




liver, kidney and heart degeneration and central nervous  system damage(26)t




Hexachloroethane is slightly toxic via ingestion.  It is  a  priority




pollutant under Section 307(a) of the CWA.  Additional information and




specific references on the adverse effects of hexachloroethane can be




found in Appendix A.






              Regulations - OSHA has set a TWA for hexachloroethane at 1




ppm (skin).




              Industrial Recognition of Hazard - According  to Sax, Danger-




ous Properties of Industrial Materials, hexachloroethane has  a moderate




toxic hazard rating.




          5.  Perchloroethylene  (Tetrachloroethylene)






              Health Effects - Perchloroethylene (PCE) was reported




carcinogenic to mice (36).  It has also been identified by  the Agency




as a compound which exhibits substantial evidence of being carcinogenic.




PCE is chronically toxic to rats and mice, causing kidney and liver damage




(36,37,38), and to humans, causing impaired liver function  (39).




Subjective central nervous system complaints were noted in workers occupa-




tionally exposed to PCE (40).   PCE is also reported acutely toxic  in




varyin degrees to several fresh and salt water organisms, and chronically




toxic to salt water organisms  (41,42).

-------
 IV.   References


 2.   Kirk Othmer, Encyclopedia  of  Chemical Technology,  Second Edition,  1968

 3.   1979 Directory of  Chemical Products of the US.,  SRI.

 4.   Source Assessment:   Chlorinated  Hydrocarbons.,  Z.S. Kahn and  T.W.
      Hughes.  EPA-600/2-79-019g.   August 1979.

 5.   Report No. 48 Chlorinated  Solvents by Lloyd M.  Elkin.   February 1961.
      Process Economics  Program  SRI.

 6.   Technical Support  Document for Aquatic Fate and Transport Estimates
      for Hazardous Chemical Exposure  Assessments.  1980. , U.S. EPA,
      Environmental Research Lab.,  Athens,  GAi

 7.   U.S. EPA.  Hazardous Waste Disposal Reports,  No. 3, EPA/530/SW  151.3,
      1976.

 8.   Cabral, J. R. P.,  et al.   Carcinogenic activity of Hexachlorobenzene
      in hamsters.  Tox. Appl. Pharmacol.  bl_:l55 (1977).

 9.   Cabral, J. R. P.,  et al.   1978.   Carcinogenesis  study in mice with
      hexachlorobenzene.  Toxicol.  Appl.  Pharmacol.  45:323.

 10.   Grant, D. L. et al•  1977.  Effect  of hexachlorobenzene on reproduc-
      tion in the rat.   Arch. Environ.  Contam. Toxicol.  Jx207.

 11.   Koss, G., et al.   1978.  Studies  on the toxicology of hexachloroben-
      zene.  III.  Observations  in  a long-term experiment.  Arch. Toxicol.
      40:285.

 12.   Clinical Toxicol.  of Commercial Products -  Acute Poisoning.   Gleason,
      M. N. et al (1969) 3rd Ed., p. 76.

 13.   Carlson, G. P., 1978.  Induction  of cytochrome P-450 by halogenated
      benzenes.  Biochem. Pharmacol. 27:361.

 14.   Kociba et al.  Toxicologic Study  of Female  Rats Administered  Hex-
      achlorobutadiene or Hexachlorobenzene for 30 Days.  Dow Chemical
      Company, 1971.

15.   Kociba, R.J., Results of a Two-year Chronic Toxicity Study with
      Hexachlorobutadiene in Rats.  Amer. Ind. Hyg. Assoc. 38:  589, 1977.

16.   SchwetZj et. al., Results  of  a Reproduction Study in Rats Fed Diets
      Containing Hexachlorobutadiene.   Toxicol. Appl. Pharmacol. 42:387,
      1977.

-------
17.    Li, et. al.,  Sampling  and Analysis  of  Selected  Toxic Substances.
       Task  IB - Hexachlorobutadiene.EPA-56076-76-015^USEPA,  1976.

18.    U.S.  EPA, 1979.  Water-Related Environmental  Fate  of 129 Priority
       Pollutants.   EPA-440/4-79-029b.

19.    National Cancer  Institute.  Carcinogens Bioassay of  Carbon Tetra-
       chloride, 1976.

20.    Schwetz, B. A.,  B. K.  J. Leong and  P. H. Gehring,  "Embryo- and
       Fetotoxicity  of  Inhaled Gabon Tetrachloride,  1,1-Dichloroethane
       and Methyl Ethyl Ketone in Rats," Toxicolgy and Applied Pharma-
       cology, Vol.  28, No. 3, June 1974,  p. 452-464.

21.    Elkins, Hervey B.  The Chemistry of Industrial Toxicology.  1959.
       2nd Ed.  John Wiley &  Sons: , New York, p. 136.

22.    Association of American Pesticide Control Officials,  Inc.   1966 Ed.
       Pesticide Chemical Official Compendium, p. 198.

23.    Texas Medical Association, Texas Medicine, Vol. 69, p. 86,   1973.

24.    Davis, Paul A.   "Carbon Tetrachloride as an Industrial Hazard," The
       Journal of the American Medical Association.  Vol. 103, July-Dec.
       1934, p. 962-966.

25.    Dreisbach, Robert H.   1974.  Handbook of Poisoning:  Diagnosis and
       Treatment, 8th Ed.   Lange Medical Publications,  Los Altos,  CA,
       p. 128.

26.    U.S. EPA.  Carbon Tetrachloride:   Ambient Water Quality Criteria
       Document, 1979.

27.    Von Oettingen, W.F., The Halogenated Hydrocarbons of Industrial and
       Toxicological Importance.   In:   Elsevier monographs on Toxic Agents,
       E. Browning, Ed., 1964.

28.    U.S. EPA.  Determination of Sources of Selected Chemicals in Waters
       and Amounts from these Sources,  1977.

29-    National Cancer Institute.  Bioassay of Hexachloroethane for
      Possible Carcinogenicity.   No.  78-1318, 1978.

30.    U.S. EPA.  Chlorinated Ethanes:   Ambient Water Quality Criteria,
      1979.

31.   Acurex Corp.,  1980,  "Chlorinated  Hydrocarbon Manufacture:  An
      Overview",  pp. 44-59.

-------
32.  "Combustion Formation and Emission of  Trace Species",  John B.
     Edwards, Ann Arbor Science,  1977.

33.  NIOSH Criteria for Recommended  Standard:   Occupational Exposure
     to Phosgene, HEW, PHS, COC,  HIOSH,  1976.

34.  Chemical and Process Technology Encyclopedia,  McGraw Hill, 1974.

35.  U.S. International Trade Commission, Synthetic Organic Chemical,
     1979.

36.  National Cancer Institute 1977.  Bio Assay of  Tetrachloroethylene
     For Possible Carcinogenicity.   CAS  No.  177-18-4,  Nc  I-C6-TR-13,
     DHEW Publication No. (NIH) 77-813.

37.  Rowe, v.k; et al 1952.  Vapor Toxicity Of  Tetrachloroethylene  For
     Laboratory Animal and Human  Subjects.   AMA Arch.  Ind.   Hyq. occup.
     med. 5: 566.

38.  Klaasen, c.d., and g.c. place 1967.  Relative  Effects  Of  Chlorinated
     Hydrocarbons On Liver and Kidney Function  In Dogs.   Toxicol.
     Appl. Pharmocol.

39.  Coler, H. R., ano H. R. Rossmiller* 1953
     Tetrachloroethylene Exposure In a  Small Industry.  Ind.  hyg, med.
     8:227

40.  Medek, V. and J. Kavarik. 1973.  The Effects of Perchloroethylene on
     the Health of Workers.  Pracovni Lekarstvi. 25:339

41.  U. S. EPA 1978.  In-depth Studies  on Health and Environmental  Impacts
     of Selected Water Pollutants.   Contract No. 68-01-4646.

42.  U. S. EPA 1979-  Tetrachloroethylene Ambient Water Quality criteria
     (Draft).
                                   X

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                           LISTING BACKGROUND DOCUMENT

                            EPICHLOROHYDRIN PRODUCTION


Heavy ends (still bottoms) from the purification column in the production of
epichlorohydrin. (T)


I.   Summary of Basis for Listing


     Heavy ends from the fractionator column for the production of epichlorohydrin

contain carcinogens, mutagens, and toxic organic substances.  These include

epichlorohydrin, trichloropropane and dichloropropanol, and the chloroethers,

as pollutants of concern.


    The Administrator has determined that the solid waste from epichlorohydrin

production may pose a substantial present or potential hazard to human health

or the environment when improperly transported, treated, stored, disposed of

or otherwise managed, and therefore should be subject to appropriate management

requirements under Subtitle C of RCRA.   This conclusion is based on the

following considerations :


         1.   The heavy ends from the production of epichlorohydrin
              contain epichlorohydrin and chloroethers which have been
              identified by EPA's Cancer Assessment Group as substances
              exhibiting substantial evidence of carcinogenicity.
              These compounds have also been reported in the literature
              to show mutagenic potential.   The waste also contains
              trichloropropane and dichloropropanols which are very
              toxic.

         2.   Approximately 12,500 tons of the heavy bottoms were
              generated in 1978 by two manufacturers at three .
              locations along the Gulf Coast.

         3.   The heavy wastes are stored in holding ponds prior to
              incineration; during storage there is the potential for
              ground and surface water contamination by leaching.
              Epichlorohydrin in the waste also would tend to volatilize
              and could present an air pollution hazard.  If incineration

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             »is incomplete,  airborne dispersion of hazardous vapors presents a
              potential of human  risk.

         4.   Incidents of epichlorohydrin contamination of water supplies
              have occurred.
    XI.    Sources of Wastes  and Typical Disposal Practices


          A.   Industry Profile


     Epichlorohydrin is manufactured  by Dow,  U.S.A. at.Freeport,

Tex. and  by Shell Chemical  Co.  at  Deer Park, Tex,, and Norco, La. (25)

The capacities of these plants  range  from 55  to 275 million pounds per

year.  About 470 million pounds of epichlorohydrin were produced in

1978. (26, 27)


    Epichlorohydrin is used  mainly as an intermediate for the manufacture

of glycerin and epoxy resins. (25)   it  is also  used in the manufacture

of plasticizers, surfactants, stabilizers,  and ion exchange resins. (25)

Growth is  expected at 6 to  7% per  year. (25)


       B.  Manufacturing Process


    Epichlorohydrin is produced by the  following reaction sequence:

 Step 1:
        +     H20  ---------- >  HOC1    +     HC1
 (Chlorine)     (Water)        (Hypochlorous  (Hydrochloric
                                  Acid)          Acid)


 Step 2:

 CH2  - CH-CH2C1    + HOC1   ---- >      CH2OHCHC1CH2C1 (65-70%) + CH2C1CHOHCH2C1( 30-55%
 (allyl chloride)    HC1                1,2-dichloropropanol-l)  (1,3-dichloropropanol-:
                    hypochlorous acid
                    and hydrochloric
                    acid

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Step 3:

CH2OHCHC1CH2C1           + CH2C1CHOHCH2C1          +NaOH	•	>
(1,2-dichloropropanol-l)   (l,3-dichloropropanol-2)              (Epichlorohydrinj
           By-products produced in small quantities are 1,2,3-trichloro-

      propane (CH2C1 CHC1CH2C1) and chloro-ethers such as:


           (CH2C1-CHC1~CH2)2 - 0 •              [(CH2C1)2 - CH]2 - 0

        bis-2,3-dichloropropyl ether      bis-1,3-dichloropropyl ether


           A process flow diagram is shown in Figure 1 attached.


           The mixture of hypochlorous acid and hydrochloric acid react-

ants is produced by absorbing chlorine in water.   This acid mixture

plus allyl chloride are then fed to the reactor.   After chlorination,

the reaction mixture (containing the dichloropropanols, some feed

materials and reaction by products) is sent to the separator.  The top

aqueous layer containing hydrochloric and hypochlorous acids is then

recycled to the absorber;  the bottom organic layer is sent to the

dehydrochlorinator where the dichloropropanols are dehydochlorinated

using sodium hydroxide.

           The reactant mixture from the dehydrochlorinator is steam

stripped.   An azeotropic mixture is formed consisting of water and

crude epichlorohydrin.   This mixture is taken overhead, condensed, and

sent to a liquid/liquid separator.
                                  -V

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o
 f
v»
2.
                                                WATER
                        HYPGCHLOROUS ACID RECYCLE
                             AQUEOUS PHASE
                CHLORINE
                ADSORBER
                     HYPOCIILOROUS ACID FEED
            REACTOR
            CHLORINE
               ALIYI
             CHLORIDE
  I
01ILORINATION
  REACTOR

         I
                                CRUDE CHLOROHYDRIN
                                            1
                                         SEPARATOR
                                                                                   Y    1 AQUEOUS PHASE
                                                         UL
                                                     SEPARATOR
                                        STEA
                                      STRIPPER
      I
ORGANIC PHASE
                               AQUEOUS
                                 PHASE
                               STRIPPER
                                                                          STEAM
                                                                                                              STEAM
                                                                      WASTEWATER
                                  CRUDE
                             EPICHLOROHYDRIN
                             h CALCIUM CHLORIDE
        ORGANIC PHASE I 2

^ WATER    STRIPPER
 (TO AQUEOUS
  PHASE  	_^
 STRIPPER)?	**
                                             | ORGANIC PHASE
                                      SODIUM
                                    HYDROXIDE'

                                                                           •e
                                                                    PURIFICATION
                                                                      COLUMN
                                                                    '--.»
                                              DEHYDROCHLORINATION
                                                    REACTOR
                                                                                                 It
                                     WASTEWATER
                              EPICHLOROHYDRIN

                              (09% PRODUCT)
                                                                                     HAZARDOUS
                                                                                    WASTE STREAM
                                                                                  (TRICHLOROPROPANE)
                              Figure 1: EPICHLOROHYDRIN FROM ALLYL CHLORIDE VIA DEHYDROCHLORINATION
                                     OF DICHLOROHYDRINS

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     The waste water from the bottom of  the  steam stripper'1'  is  stripped




in the aqueous phase stripper where small amounts of epichlorohydrin




are recovered overhead and recycled to the steam-stripper condenser;




the bottom stream is discharged as water waste.*






           The bottom organic phase from the liquid/liquid separator is fed




to the organic phase stripper where residual water is removed  overhead.(2)




The bottom stream of crude epichlorohydrin is fed to the purification column




where it is purified by fractionationC3)  Purified epichlorohydrin is




distilled overhead.  The bottom stream from the purification column




is the waste stream of concern in this document.
      C.   Waste Generation and Management






           The waste stream from this process is the heavy organic




bottoms (stream 3) from the product purification column.  Three plants




(two in Texas, one in Louisiana) generated 12,500 tons of heavy ends (still




bottoms) in the production of 469.6 million Ibs. of epichlorohydrin




in 1978(26,27).  ^e primary disposal technique (1979) was reported to be




incineration.  It is assumed, based on usual waste management practice, that




the heavy ends are stored in holding ponds or other temporary storage




facilities prior to incineration.






Ill.  Discussion of Basis for listing






      A.   Hazards Posed by the Waste






     Epichlorohydrin purification column bottoms typically contain the following




contaminants in the indicated concentrations:(27)
*This water stream is not presently listed as hazardous
                                 -3OO-

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                                                   Percent






                    Epichlorohydrin                    2




                    Chioroethers                      14




                    Trichloropropane                  70




                    Dichloropropanol                  10




                    Chlorinated aliphatics         	4_




                                                     100
     The waste constituents of concern are epichlorohydrin, the chloroethers,




 trichlorpropanel and dichloropropanol.  Epichlorhydrin has been identified




 as a substance exhibiting substantial evidence of carcinogenicity by




 EPA's Carcinogen Assessment Group.  It is also an animal mutagen and




 is very toxic.  The chloroethers are likewise recognized by the




 Agency as known animal and likely human carcinogens.  Their toxicity




 is likewise high.  (See pp. 9-13 following.)  Trichloropropane and




 dichloropropanol are very toxic.  Large quantities are therefore available




 for environmental release in high concentrations.






      These waste constituents are present in very substantial




 concentrations and are generated in large quantities (12,500 tons in



 1978).   There is thus a strong likelihood that the waste constituents




will reach environmental receptors and cause substantial Hazard if




waste constituents are mismanaged.

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      Waste mismanagment may certainly occur.  As  noted  above,  the




 primary disposal for this waste is by incineration prior  to  which




 the waste may be stored in holding ponds or other temporary  storage




containers.  Disposal by incineration, if mismanaged, could result in




serious air pollution through release of toxic fumes.  This may occur




when incineration facilities are operated in such  a way  that  combustion




is incomplete (i.e. inadequate conditions of temperature mixing and




residence time) resulting in airborne dispersion of hazardous vapors




containing waste constituents of concern, as well  as other newly formed




harmful organic substances.  Phosgene is an example of a partially




combusted chlorinated organic which is produced by the decomposition



of chlorinated organics by heat.(^2,33,34)  This could present  a significant




opportunity for exposure of humans, wildlife and vegetation in  the




vicinity of these operations to risk' through direct contact and also




through pollution of surface waters.








     Temporary storage, if not properly managed, may also lead  to  the



release of harmful constituents.  Thus, if holding ponds lack proper




flood control design features,  there is a danger that the organics,




during periods of heavy precipitation could be emitted due to flooding




of the ponds.  Should flooding occur,  epichlorohydrin is stable enough




to be transported to surface waters.  (Appendix B)  This eventually




could result in drinking water contamination.   Actual contamination of
                                 -302."

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a public water  supply by epichlorohydrin occured on January 23, 1978,

when a tank car derailed,  spilling 197,000 pounds of epichlorohydrin in

West Virginia.*  Nearby wells at a depth of 25 feet were heavily contaminated,

demonstrating ability to be mobil in soils.   A similar hazard could result

if epichlorohydrin-containing wastes were disposed in an uncontrolled

pond or lagoon.


           The  chloroethers are also capable of significant migration via

surface water pathways. '^'  They have been found in surface and groundwaters

at concentrations exceeding the USEPA recommended maximum allowable concen-

tration levels  in drinking water of 0.42mg/l, demonstrating a propensity

to migrate and  persist.(6)**



      Waste constituents might also escape from the holding pond via

a groundwater pathway if storage is improper (for instance using ponds in

locations  with  permeable soils). Epichlorhydrin is highly soluble (66,000

ppm), and  is thus capable of migration.   It absorbs to organic constituents

in soil, and so mobility would be high where organic content is low.(28)

The chloroethers are also highly soluble (Appendix B) and, although tending

to absorb  to soils,  have been shown to be mobile and persistent enough to

be found in groundwater at concentrations exceeding the proposed human

health water quality criteria, as noted above.**
 * OSW Hazardous Waste  Division,  Hazardous Waste Incidents, unpublished,
   open file, 1978.

 * The Agency is not  using  these  standards as quantitative benchmarks, but
   is citing them  to  give  some indication that very low concentrations of
   these contaminants may  give rise to substantial hazard.
                                   -305-

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      From the holding ponds or in surface water, most  of  the  chlorin-




ated propanols would undergo hydrolysis and biodegradation.  The  dissolved




portion, however, could move with a water front through the soil  profile.




Under some conditions, the chlorinated propanols could  reach a ground




water aquifer (Appendix B).  Degradation of chlorinated propanols in




groundwaters would be much slower as evidenced by the observance of




many related chlorinated ethanes, ethylenes, in Love Canal leachate,




methanol, ehanol and isopropyl alcohol some 30 years after disposal.



(29,30,31)









     Data show that chemical analogs, dichloroethane( ' and




dibromochloropropane,'°' have permeated the soil mantle to contaminate




ground water, again suggesting a similar behavior for propanols.  In




addition the chioropropanels tend to bioaccunulate in aquatic




organisms,^' thus increasing potential exposure to higher levels  of




the food chain,  including man.








      Epichlorohydrin could also pose a threat via an inhalation exposure




pathway due to its relatively high volatility. (28)  Thus, lack of adequate




cover could result in air pollution to surrounding areas.


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     B.    Health and Ecological Effects






           1.    Epichlorohydrin






                Health Effects - Epichlorohydrin has been demonstrated to




be carcinogenic in animals(*/ upon inhalation of vapors.  This compound




has also been recognized by the Agency as a chemical compound which has




exhibited substantial evidence of carcinogenicity.  (^5) Epichlorohydrin




is very toxic [oral rat LD5Q=90mg/Kg].  Both respiratory cancers and




leukemia are in excess among some exposed worker populations.(l®>11)




Epichlorohydrin vapor also has been demonstrated to induce aberrations in




humans and animal chromosomes'^, 13) ancj has induced birth defects in




animal studies conducted by the Dow Chemical Company.   It is a known mutagen




to non-mammalian species.(''  Several investigators have found that epichloro-




hydrin possesses anti-fertility properties'^'.  Altered reproductive




function has been reported for workers occupationally exposed to epichloro-




hydrin.  Dow Chemical Company researchers have observed degenerative changes




in nasal tissue; severe kidney and liver damage has also been found in




animals exposed to vapors of epichlorohydrin.^°>*'' Additional




information and specific references on the adverse effects of epichlorohydrin




can be found in Appendix A.









           Regulatory Recognition of Hazards - The OSHA time weighted




average for skin contact with epichlorohydrin in air is 5'ppm.  DOT




requires a label warning that this chemical is a poison and a flammable




liquid.

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           Industrial Recognition of Hazards - Epichlorohydrin is intensely

irritating and moderately toxic by the oral, percutaneous  and  subcutaneous

routes as well as by inhalation of the vapors (Fassett  and Irish,  Industrial

Hygiene and Toxicology).  Plunkett considers it highly  toxic in his

Handbook of Industrial Toxicology*
      2.   Chloroethers - bis (chloromethyl) ether and bis  (2-chloroethyl)
                          ethers
           Health Effects Both bis (chloromethyl) ether and  bis  (2-

chloroethyl) ethers are identified as carcinogens in animals'*°»*"'

under laboratory conditions.  These chemicals have also been recognized

by the Agency as demonstrating substantial evidence of carcinogenicity.

Bis (chloromethyl) ether is very toxic  [oral rat LD5Q=210 mg/Kg; inhalation

rat LD5Q=7ppm/7h].  Bis (2chloroethyl) ether is also very toxic  (oral

rat LD5Q=75mg/Kg].  Epidemiological studies of workers in the United

States, Germany and Japan who were occupationally exposed to both ethers

indicate that they are human carcinogens. (™)  They have also been

shown to be mutagens in bacterial screening systems.(20)  Additional

information and specific references on the adverse effects of chloroethers

can be found in Appendix A.



           Regulatory Recognition of Hazard - Chloroethers are designated

as priority pollutants under Section 307(a) of the CWA.  Bis (chloroethyl)

ether has a designated OSHA ceiling of 15 ppm.  Bis (chloromethyl) ether

is designated by OSHA as a carcinogen.  Chlormethyl ether is designated

by OSHA as a carcinogen and is required by DOT to carry labels that

say "flammable liquid" and "poison".

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           Industrial Recognition of Hazard - Sax (Dangerous Properties




 of Industrial Materials) states that bis (chloromethyl) ether has an




 unknown systemic toxic hazard rating but it is a carcinogen.  Bis 2




 (chloroethyl) ether is highly toxic via ingest ion, inhalation and skin




 absorption.   Both chemicals are listed as priority pollutants by the EPA.




      3.    Trichloropropane






           Health Effects - 1,2,3-Trichloropropane is a strong irritant




 and can be toxic by oral ingestion, inhalation,  or dermal application.^1, 22)




 Trichloropropane is very toxic [oral rat LD^Q=320 mg/Kg].   Tsulaya et al^   '




 observed significant changes in central nervous system function, as well as




 enzyme changes in blood, liver, and lungs.   Additional information and specific




 references on the adverse effect of trichloropropane can be found in Appendix A.






           Regulations - The OSHA TWA for trichloropropane in air is 50 ppm.






           Industrial Recognition of Hazard - Trichloropropane is designated




 in Sax, Dangerous Properties of Industrial Materials, as a highly toxic




 skin irritant, moderately toxic systemic poison via oral,  inhalation and




 skin absorption routes and as a cumulative toxin.






      4.   Dichloropropanols






          Health Effects - Both industrially occurring isomers, 1,3-dichloro-




 propanol-2 [oral rat LD5o=90 mg/Kg] and l,2-dichloropropanol-3 [oral rat




 490 mg/Kg] are very toxic to laboratory animals, causing systemic as well




as local  toxic effects.   The toxic symptoms caused by the 1,3 isomer have
                                   -301-

-------
been compared to that of the liver toxin carbon tetrachloride which causes




acute and often irreversible hepatic failure.  Both compounds are potent




skin and lung irritants, absorbed by all routes of exposure and tend to accum-




ulate in the organism.'^4)  Additional information and specific references




on the adverse effects of dichloropropanols can be found in Appendix A.








                Industrial Recognition of Hazard  - Dichloropropanol is desig-




nated in Sax, Dangerous Properties of Industrial Materials as moderately



toxic via inhalation and highly toxic via ingestion(2*0.
                                 -308-

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IV.   References


 1.   Nelson,  N.  Communication to the regulatory agencies  of  preliminary
      findings of a carcinogenic effect in the nasal cavity of rats exposed
      to epichlorohydrin.  New York University Medical  Center,  letter  dated
      28 March 1977.

 2.   Nelson,  N.  Updated communication to the regulatory agencies of  pre-
      liminary findings of a carcinogenic effect in the nasal  cavity of rats
      exposed to epichlorohydrin.  New York University  Medical Center, letter
      dated 23 June 1978.

 3.   Peterson, EPA, OAQPS, 1979.

 4.   Zoeteman, B. C. J., K. Harmsen, J. B. H. J. Linders,  C.  F. H.
      Morra and W. Sloof.  Persistent Organic Pollutants in River Water
      and Ground Water of the Netherlands.  L979.  Paper presented at
      3rd Int'l Symposium on Aquatic Pollutants. Jekyll Island, GA,.

 5.   Subsurface Transport and Fate of WS-12 Epichlorohydrin,  Ada Oklahoma
      Lab, 1980.

 6.   U.S.E.P.A.  Preliminary Assessment of Suspected Carcinogens in Drinking
      Water.   Report to Congress.  USEPA, 1975.


 7.   De Walle, F. P., and E.S. K. Chian.  1979.  Detection of Trace
      organics in well Water Near a Solid Waste Landfill.   Environ. Sci.
      Technol.  (In Press).

 8.   Weisser, P.  Aug. 23, 1979.  News Release, Department of  Health

      Services, Sacramento, CA.

 9.   Clement  Associates, Inc. Dossier on Chloropropanes (Draft),
      Contract No. EA8AC013, prepared for TSCA Interagency  Testing
      Committee, Washington, D.C.   August, 1978.

10.   Enterline, P.  E. "Mortality experience of workers exposed to epichloro-
      hydrin."  In press:  Jour.  Occup. Medicine, 1979.

11.   Enterline, P.  E. and V. L.  Henderson.  Communication  to  Medical  Direc-
      tor of  the Shell Oil Company:  Preliminary finding of the updated
      mortality study among workers exposed to epichlorohydrin.  Letter dated
      31 July  1978.   Distributed to Document Control Office, Office of Toxic
      Substances (WH-557),  USEPA.

12.   Syracuse Research Corporation.   Review and evaluation of  recent  scien-
      tific literature relevant to an occupational standard for epichloro-
      hydrin.   Report prepared by Syracuse Research Corporation for NIOSH,
      1979.

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IV.   References  (Continued)

13.   Santodonato et al.   "Investigation of  selected potential environmental
      contaminants:  Epichlorohydrin  and epibromohydrin."  Syracuse Research
      Corporation.  Prepared for  the  Office  of Toxic Substances, USEPA, 1979.

14.   Halen, J. D.  "Post-testicular  and anti-fertility effects of epichloro-
      hydrin and  2,3-epoxypropanol."   Nature 226:87, 1970.

15.   Cooper et al.  "Effects of  alpha-chlorohydrin and related compounds on
      the reproduction and fertility  of  the  male rat."  J.  Reprod. Fert.
      38:329, 1974.

16.   Quast, J. F. et al.  "Epichlorohydrin  - subchronic studies I.  A 90-day
      inhalation  study in  laboratory  rodents."  January 12,  1979.   Unpublished
      report from Dow Chemical Company,  Freeport,  Texas.

17.   Quast, J. F. et al.  "Epichlorohydrin  - subchronic studies II.   A 12-day
      study in laboartory  rodents."   January 12,  1979.   Unpublished report
      from Dow Chemical Company,  Freeport, Texas.

18.   Innes et al.  "Bioassay of  pesticides  and industrial  chemicals  for
      tumorigenicity in mice, A preliminary  note."  J.  Nat'l.  Cancer  Inst.
      42:1101, 1969.

19.   Juschner et al.  "Inhalation  carcinogenicity of alpha haloethers III.
      Lifetime and limited period inhalation studies with bis(chloromethyl)
      ether at 0.1 ppm."   Archives  of Environmental Health  30_:739  1975.

20.   U. S.E.P. A.   Chloroaklyl Ethers:  Ambient Water Quality Criteria,  1979.

21.   Hawley, G.   G., 1977.  Condensed Chemical Dictionary,  9th Edition.
      Van Nostrand Reinhold Co.

22.   NIOSH 1978.  Registry of Toxic  Effects of Chemical Substances.

23.   Tsulaya, V. R. et al, 1977.   Toxicology Features of Certain Chlorine
      Derivatives of Hydrocarbons.  Gig.  Sanit.  _8:50-53.

24.   Sax, I. , Dangerous Properties of industrial Materials.

25.  Kirk-Othmer  Encyclopdia of Chemical Technology.  2nd Ed.  Vol. 1.
     John Wiley and Sons,  New York, 1970.

26.  Peterson, C. A., "Emissions  Control Options for the Synthetic Organic
     Chemicals Manufacturing Industry:   Glycerin and It's Intermediates."
     Hydroscience, Inc.  (Draft report prepared for EPA/OAQPS, March 1979.
                                 -•310-

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27.   Gruber, G. I.,  "Assessment of Industrial Hazardous Waste Practices,
     Organic Chemicals,  Pesticides and Explosives Industries."   TRW, Inc.
     USEPA, SW Il8c,  January,  1976,  p. 5-20.

28.   Dawson, English and Petty, 1980.   Physical Chemical Properties
     of hazardous Waste  Constituents.

29.   Earth, E. F., and Cohen,  J.M., "Evaluation of Treatability of Industrial
     Landfill Leachate,  unpublished report,  U.S. EPA, Cincinatti.
     (Nov., 1978).

30.   O'Brien, R.P.,  City of Niagra Falls,  N.Y., Love Canal Project,
     Unpublished Report,  Calgon Corp., Calgon Environmental Systems
     Division, Pittsburgh,  Pa.

31.   Rcera Research,  Inc.,  P:riority Pollutant Analyses prepared for Nuco
     Chemical Waste  Systems,  Inc., unpublished report, Tonawanda, N.Y.,
     1979.

32.   "Combustion Formation and Emission of Trace Spcies", John B. Edwards,
     Ann  Arbor Science,  1977.

33.   NIOSH Criteria  for  Recommended Standard:  Occupational Exposure
     to Phosgene,  HEW, PHS, COC, HIOSH, 1976.

34.   Chemical and  process Technology Encyclopedia, McGraw Hill, 1974.

35.   Carcinogen Assessment Group's List of Carcinogens, April 22, 1980.

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                         LISTING BACKGROUND DOCUMENTS

                          ETHYL CHLORIDE PRODUCTION


       Heavy Ends  from the  Fractionation Column in Ethyl Chloride Production (T)


  I.    SUMMARY  OF  BASIS FOR LISTING

       The heavy ends  or bottoms  from the fractionation column used in

  the  production of ethyl chloride contains 1,2-dichloroethanene trichlor-

  ethylene and many other heavy chlorinated organics.   The Administrator

  has  determined that these  sludges are solid  wastes which may pose a

  present or potential  hazard to human health  and the environment when

  improperly transported,  treated,  stored,  disposed of or otherwise managed

  and  therefore  should  be subject  to  appropriate management requirements

  under Subtitle C  of RCRA.   This  conclusion is  based  on the following

  considerations :

       (1)  The fractionation column bottom or  heavy  end sludges contain
            3%  ethyl chloride*, 22%  dichloroethanes,  32% trichloroethylene,
            and 43% heavy chlorinated organics.   1 ,2-Dichloroethane is  a
            suspected  carcinogen  and trichloroethylene and many of the
            heavy  chlorinated organics  in the wastes  have been identified
            by  the Agency as  exhibiting substantial evidence of being
            carcinogenic.

       (2)  The wastes  traditionally have  been  managed by land disposal.
            Information obtained  from telephone contacts with manufacturers**
            indicates  that  some of the  wastes are  also incinerated in
            thermal destruction facilities.  The substances  in the wastes,
            if  not managed  properly,  could be emitted to the air if the
            wastes are  inadequately  incinerated or  improperly land disposed,
            or  could leach  from improperly managed  or designed landfills
            and injection wells to reach humans  and other environmental
            receptors.   Hexachlorobenzene  (a typical  heavy chlorinated
            organic in  column bottoms)  has  been shown to bioaccumulate  in
            animal and  human  tissues  through inhalation following mismanagement
 *The Agency is aware that ethyl chloride is highly  ignitable, with  a  flash
  point of -58 °F.  Generators are, of course, responsible  for determining
  if these wastes are ignitable, even though listed  for  toxicity only.

**Those manufacturers requested to remain anonymous.

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           during transportation and  improper disposal.   Trichloroethylene
           (another waste component)  has  shown to have  leached into well
           water from waste disposal  sites.

      (3)  A large quantity (a combined total of about  35,000  metric
           tons per year) of these wastes  is  generated  annually.


 II.   INDUSTRY PROFILE

      In 1979, there were reported to be  six  plants  in  the U.S. with capacity

 to produce about 330,000 metric tons/year  of  ethyl chloride. ^'  Two of the

 plants are located in Texas, two in Louisiana,  one in New Jersey and one in

 California.  The average plant produces about 64,000 metric  tons/year.  The

 range for individual plants is about  35,000 to  100,000 metric  tons/year.

 Since most of the ethyl chloride produced  is  used for the manufacturing of

 tetraethyl lead, production is on the decline.


 III.  MANUFACTURING PROCESS DESCRIPTION

      Most of the ethyl chloride produced  is  manufactured by catalytic

 hydrochlorination of ethylene.^D  A  process  flow diagram is given  in

 Figure 1.  Ethylene and anhydrous hydrogen chloride  gases  are mixed  and

 reacted at 35-40*C in the presence of an aluminum chloride catalyst.  The

 reaction is exothermic.  The vaporized products are  fed into a column or

 "flash drum" where crude ethyl chloride is separated from heavier

 polymers.   The polymer bottoms are a  salable  by-product.   Finally,  the

 crude ethyl chloride is refined by fractionation.  The fractionation waste

 (on figure 1),  or heavy ends,  is composed  of  3% ethyl chloride, 22%  dichloro-

 ethanes,  32Z trichloroethylene, and 43% heavy chlorinated  organics.^2' This

 is the waste stream listed in this document.

IV.    WASTE GENERATION AND MANAGEMENT

      The heavy ends  from the  fractionating column are generated at  a rate

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t  I
                  BASIS:   1 KG ETHYL CHLORIDE
        ETHYLENE  0.488
        HYDROGEN  0.625
        CHLORIDt
MIXER
                                                 ALUMINUM CHLORIDE  (
-------
 of about .093 tons per ton of ethyl  chloride  produced/2)   The total




 quantity of waste produced is, therefore,  approximately 35,000 metric




 tons per year (based on the 1979 production figures).




      The wastes from ethyl chloride manufacture  are usually combined for




 disposal with chlorinated hydrocarbon wastes  of similar composition




 generated in the manufacture of chlorinated solvents  (chloromethanes) at




 the same plant site.  In 1973, it was reported  that the combined wastes




 were sent to land disposal. ^2'  More recent information indicates  that




 some wastes are being incinerated in thermal  destruction facilities




 (see p. 1, above).






 VI.   DISCUSSION OF BASIS FOR LISTING




      A.   HAZARDOUS POSED BY THE WASTE




           As indicated earlier, the heavy ends from fractionation in




 ethyl chloride production contain 22% dichloroethanes,  32%  trichloro-




 ethylene, and 43% heavy chlorinated  organics  (such as hexachlorobutadiene,




 and hexachlorobenzene'2)) many of which have  been identified by the Agency




 as  substances which exhibit substantial evidence of carcinogenicity.




 Further, all of the chlorinated organic constituents in the waste




 demonstrate acute aquatic toxicity,  generally showing increasing




 toxicity with increasing chlorination.  Should these compounds reach




 environmental recepters, the potential for resulting adverse effects




 would  be extremely high.




      These waste constituents are capable of migration.  The  solubility




 in water of these chlorinated  compounds is quite high:   dichloroethane -




8700 ppm^),  trichloroethylene - 1000 ppm^) f  and hexachlorobenzene -




500 ppm^).   The  high  solubilities of these constituents indicate  a

-------
strong propensity  to migrate from inadequate land disposal facilities.




Thus, improperly constructed or  mangaged landfills (for example, landfills




located  in  areas with  permeable  soils,  or with inadequate leachate control




practices)  could easily  fail to  impede  leachate formation and migration.




      Once  released from the matrix  of  the waste,  these constitutents




could migrate  through  the  soil to ground and surface  waters  utilized as




drinking water sources.  A number of actual  damage incidents documenting




the  leaching of constituents from waste sites  and  subsequent to ground-




water contamination (see Damage  Incidents  pp.  7-8)  have occurred.   These




damage incidents also  confirm that many of these  chlorinated compounds




are  environmentally persistent,  since they obviously  persist in the




environment long enough  to reach  environment receptors.




      Another  problem  which  could result  from  improper  landfilling  of




these wastes is the potential for contaminants  to  volatilize into the




surrounding atmosphere.  Volatilized waste constituents, hexachlorobenzene




in particular,  have caused actual damage  (see Damage  Incidents,  1-3, pp.




6-7).  1,2-Dichloroethane  (60 mm  Hg  at  20°C)^ is  also highly  volatile,




and  therefore,  could volatilize and  thus present an air pollution problem




if improperly managed  (for example,  if  landfilled without  adequate  cover).




      More recent information indicates that some wastes are being




incinerated in  thermal destruction facilities.  Inadequate incineration




conditions  (temperature  plus residence  time) can result in incomplete




combustion and  air emission  of the harmful chemical substances  contained




in the wastes as well as degradation products.




      The large quantities (a combined  total of about 35,000 metric tons




per year) of this waste disposed of annually is another area of concern




to the Agency.   As  previously indicated, there  are  substantial  concentrations

-------
 of these toxic constituents (22% dichloroethanes,  32%  trichloroethylene,




 43% heavy chlorinated organics) in the waste  stream.  The  large  quantities




 of these contaminants pose the danger of polluting  large areas of




 ground and surface waters.   Contamination could  also occur  for  long




 periods of time, since large amounts of pollutants  are  available




 for environmental loading.  All of these considerations increase the




 possibility of exposure to the harmful constituents in  the wastes.




      B.   DAMAGE INCIDENTS




           The constituents found in the ethyl chloride fractionation column




 wastes have been implicated in a number of past damage  incidents.




           There have been three damage incidents caused by  one  of the



 substances present in the heavy ends, hexachlorobenzene^):




           (1)  In Louisiana, hexachlorbenzene (HCB), a toxic industrial




 by-product, was dumped in a rural landfill where  it sublimated.  Cattle




 absorbed HCB in their tissues and 20,000 animals were quarantined by the




 State Department of Agriculture (Lazar, 1975).  This incident illustrates




 the ability of HCB to bioaccumulate.




           (2)  In Southern Louisiana, industrial wastes containing




 hexachlorobenzene (HCB),  a relatively volatile material, were transported




 over a period of time to  municipal landfills  in uncovered trucks.  High




 levels of HCB have since  been reported in the blood plasma of individuals




 along the route of transport.   In a sampling  of 29 households along the




 truck route,  the average  plasma level of HCB  was 3.6 ppb with a high of




 23 ppb.   The  average plasmal level of HCB in  a control group was 0.5 ppb




with  a high of 1.8 ppb (Farmer et al., 1976).  This incident illustrates




the ability of HCB to get into the blood stream from inhalation.
                                   -^/^7-

-------
            (3)   Hexachlorobenzene wastes were disposed in landfill sites




 in  southern Louisiana.   Some of the waste was covered following disposal,




 and some was not.   Soil  and plant samples taken near the landfill area




 showed  a decreasing HCB  content as distance from the landfill increased.




 The HCB levels  in  the plasma of landfill workers was reported to range




 from 2  to  345 ppb;  the average  level in a control group was 0.5 ppb with




 a high  of  1.8 ppb.   A study of  the land disposal of the hexachlorobenzene




 wastes  indicated that uncovered wastes  released 317 kilograms per hectare




 per year  (kg/ha/yr) .  This  incident further illustrates the ability of




 HCB to  present  a hazard  due to  improper landfil management  and inhalation.




            There have also  been three damage incidents resulting from  the




 mismanagement of trichloroethylene,  another waste constituent.




            (1)   In  one incident in Michigan,  an automotive  parts manu-




 facturing  plant  routinely dumped spent  degreasing solutions  on the open




 ground  at  a rate of about 1000  gallons  per  year from 1968 to 1972.




 Trichloroethylene was one of the degreasing solvents  present in the  spent




 solutions^   Beginning in 1973,  trichloroethylene in nearby  residential




 wells was  detected  at levels up to 20 mg/1.   The dump site  was  the only




 apparent source  of  possible contamination ^'.   This  illustrates the




 migratory  potential and  persistence  of  improperly disposed  trichloro-




 ethylene.




            (2)   In  a  second incident, also  in Michigan,  an  underground




 storage tank  leaked trichloroethylene which was  detected in local ground-




water up to  four miles away from the  land'?) .   This also illustrates the




migratory  potential of trichloroethylene.




            (3)  In  April of 1974,  a private water well in Bay City Michigan




became contaminated by trichloroethylene.   The  only nearby  source of this
                                    -JIS-

-------
 chemical was the Thomas Company (which replaced  the well with  a  new  one).


 The company claimed that, although it had discharged  trichloroethylene


 into the ground in the past, it had not done so  since 1968.  Nevertheless,


 in May, 1975, two more wells were reported to be contaminated  with tri-


 chloroethylene at concentrations of 20 mg/1 and  3 mg/1, respectively ^8^.


 This further illustrates the migratory potential and  persistence of  this


 compound.


      C.   Health and Ecological Effects Associated With The Constituents


           1.  1,2-Dichloroethane


               Health Effects - 1,2-Dichloroethane is a carcinogen.'^) in


 addition, this compound and several of its metabolites are highly mutagenic


 (10, 11).  1,2-Dichloroethane crosses the placental barrier and  is embryo-


 toxic and teratogenic ^^ ~ ^ > and has been shown to concentrate in the


 milk of nursing mothers. d?)  Exposure to this compound can cause a  variety


 of adverse health effects including damage of the liver, kidneys and other


 organs, internal hemorrhaging and blood clots d°'.   1,2-Dichloroethane


 is a designated priority pollutant under Section 307(a) of the CWA.


 Additional information and specific references on adverse health effects


 of 1,2-dichloroethane can be found in Appendix A.


               Ecological Effects - Values for a 96-hour static LC5Q for


 bluegills ranged from 236 to 300 mg/1 making it moderately toxic. (19)


               Regulations - OSHA has set the TWA at  50 ppm.  DOT requires


 the containers for this chemical to carry a warning that it is a flammable
                                                          >

 liquid.

               The Office of Air, Radiation and Noise has completed  pre-


regulatory assessment of 1,2-dichloroethane under Sections 111 and 112


of the  Clean Air Act.  Pre-regulatory assessments are also being conducted

-------
by EPA's  Office of Water and Waste Management under the Safe Drinking




Water  Act and by the Office of Toxic Substances under the Toxic Substances




Control Act.




                Industrial Recognition of Hazard - Sax, in Dangerous Properties




of Industrial Materials,  rates 1,2-dichloroethane as highly toxic upon




ingestion and inhalation.




            2.   Trichloroethylene




                Priority  Pollutant  - Trichloroethylene is  listed as a




priority  pollutant in accordance with §307(a)  of the Clean Water Act of



1977.(20)




                Health Effects  - Trichloroethylene is identified as a




carcinogen.(39)   Trichloroethylene has been  shown,  both through acute




and  chronic exposure,  to  produce disturbances  of the central  nervous




system and  other  neurological  effects(22,23,24)t   Trichloroethylene




has  been  found  to cause heptacellcer  cancinoma in mice.




           3.   Hexachlorobenzene (HCB)




                Priority Pollutant  - HCB  is listed as a priority pollu-




tant under Section 307(a)  of the Clean Water Act.




                Health Effects  - Hexachlorobenzene (HCB) has produced cancers



in animal species(25,26) an
-------
 foreign organic compounds present  in the body through its metabolism.




           The recommended ambient criterion^)  level for RGB in wastes




 is  1.25 nanograms per liter.  Actual measurements,  on the other hand,  of




 finished drinking water in certain geographic areas have been measured




 at  levels up to six times the recommended criterion designed to protect




 human health, demonstrating the mobility and  persistence of the material. (38)




               Ecological Effects  - Hexachlorobenzene is very persistent.(32)




 It  has been reported to move through the soil into  the groundwater. (2D




 Movement of hexachlorobenzene within surface  water  systems  is projected



 to  be widespread.(30)  Movement to this  degree will likely  result  in




 exposure to aquatic life forms in  rivers,  ponds,  and reservoirs.




 Similarly, potential exposure to humans  is likely where water supplies




 are drawn from surface waters.




           Hexachlorobenzene is likely to  contaminate accumulated  bottom




 sediments within surface water systems and bioaccumule in fish  and other



 aquatic organisms.(30)




                Regulatory Regulation of Hazard - Ocean dumping of hexa-




 chlorobenzene is prohibited.   An interim food contamination tolerance  of




 0.5 ppm has been established by FDA.




           Additional information  on the adverse  effects  of hexachlorobenzene




 can be found in Appendix A.




           4.   Hexaclorobutadiene(HCBD)




               Priority Pollutant - Hexachlorobutadiene is  considered  a  priority




pollutant  under Section 307 (a)  of the CWA.




               Routes  of Exposure - oral-very  toxic




               Health  Effects  - Hexachlorobutadiene  (HCBD)  has  been found




to be  carcinogenic  in  animals.(23,39; jjpon chronic  exposure of  animals

-------
by the DOW Chemical Company and others,  the kidney appears  to be the




organ most sensititve to HCBD.(34^35,36,37)




           The proposed human health criterion  level  for  this compound




in water is  .77 ppb.




           Ecological Effects - Movement of HCBD within surface water




systems is projected to be widespread.(30)




           HCBD is likely to contaminate accumulated bottom sediments




within surface water systems and is likely to bioaccumulate in fish  and




other aquatic organisms.(30)




           The USEPA (1979) has estimated that  the BCF  is 870 for the




edible portion of fish and shellfish consumed by Americans.




           Hexachlorobutadiene is persistent in the environment.(32)  it




has been reported to move through soil into groundwater.




           Industrial Recognition of Hazard - Hexchlorobutadiene is  considered




to have a high toxic hazard rating via both oral and inhalation routes (Sax,




Dangerous Properities of Industrial Material).




           Additional information on the adverse effects of hexachlorabutadiene




can be found in Appendix A.

-------
                                     IENCES


  1.   1979 Directory of Chemical Producers, Stanford Research Insititute.

  2.    Assessment of Industrial Hazardous Waste Practices:  Organic Chemicals
       Pesticides and Explosive Industries," TWR report to U.S. Environmental
       Protection Agency.

  3.   OSW - Hazardous Waste Management Division, "Hazardous Waste Incidents":
      Incidents":  Unpublished Cpen File Data, 1978

  4.   Dawson, Siglish, Petty, 1980, "Physical Chemical Properties of Hazardous
      Waste Constitutents11.

  5.   Patty, Franle A., Editor, Industrial Hyginene and Toxicology.  Volume II,
      Interscience Publishers, New York, 1963.

  6.   Michigan Department of National Resources - Geological Survey Divison.
      Case History #48.

  7.   Schellenbarger, P. 1979, "new Charge Hits Air Force."  Ihe Detroit
      News, May 17, 1979.

  8.   Mitre Corporation, 1979. Draft Report in Support of Subsection C.
      Prepared for U.S. Environmental Protection Agency.

  9.   National Cancer Institute.  Bioassay of 1,2-Dichloroethane for Possible
      Carcinogenicity.  U.S. Department of Health, Education and Welfare,
      Public Health Service, National Institutes of Health, National Cancer
      Institute,  Carcinogenesis Testing Program, DEEW Publication No. (NIH)
      78-1305, January 10, 1978.

10.   McCann, J., E. Choi, E. Yamasaki, and B. Anes.  Detection of Carcino-
      gens a Mutagenic in the Salmonella/Microsome Test:  Assay of 300
      Chemicals.   Proc. Nat. 2cad. Sci. USA 72^(2):5135-5139, 1975a.

11.   McCann, J., V. Simmon, D. Streitwieser, and B. Ames.  Mutagenicity
      of Chlorocetaldehyde, a Possible Metabolic Product of 1,2-Dichloro-
      ethane (ethylene dichloride), Chloroethanol (ethylene cholorhydrin),
      Vinyl chloride, and cyclcphosphamide. Proc. Nat. Acad. Sci. 72
      (8)"3190-3193.

12.   tozovaya, M., Changes in the Esterous Cycle of White Rats Chronically
      Exposed to  the Combined Action of Gasoline and Dichloroethane Vapors .
      Akush. Genecol.  (kiev) 47 (12): 65-66, 1971.

13.   Vozovaya, M., Developnent of Offspring of two Generations Obtained
      fron Females Sujected to the Action of Dichloroethane.  Gig. Sanit.
      7:25-28,  1974

-------
14.   Vozovaya, M., The Effect of Lew Concentrations of Gasoline,
      chloroethane and Their Combination on the Generative Function
      of Animals and on the Development of Progeny.  Gig. Tr.  Prof.
      Zabo.  7^:20-23, 1975.

15.   ^zoakya, M., Effect of Low Cbncentrations of Gasoline,  Dichloro-
      ethane and Their Gscribination on the Reproduction Function  of
      Animals.  Gig. Sanit. 6:100-102, 1976.

16.   Vozovaya, M.A., The Effect of Dichloroethane on the Sexual Cycle
      and Embryogenesis of Experimental Animals.  Akush. Genecol.
      (Moscow) 2^:57-59 , 1977.

17.   Urusova, T.P  (About a possibility of dichloroethane absorption
      into milk of nursing vjomen vhen contacted under industrial
      conditions.)

18.   Parker, J.C., et al. 1979.  Chloroethanes:  A Review of  Toxicity.
      Amer. Indus. Hyg. Assoc. J., 40;  A 46-60, March 1979.

19.   U.S. EPA, 1979. Chlorinated Ethanes:  Atrnbient Water Quality
      Criteria (Draft).

20.   U.S. EPA States Regulation Files? January 1980.

21.   Mansville Chemical Products.  1976.  Chemical Products Synopsis -
      Tr ichloroethylene.

22.   tfcmiyama, K. and H. Nomiyama.  1971.  Metabolism of Trichloroethylene
      in Human Sex Differences in Urinary Excretion of Trichloroacetic
      Acid and Trichloroethanol.  Int, Arch. Arbeitsmed.  28:37.

23.   Bardodej, A., and J. Vyskocil.  1956.  The Problem of Trichloroethylene
      in Occupational Medicine.  AMA Arch. Ind. Health.  13:581.

24.   MsBirn'ey,  B.S., 1954.  Trichloroethylene and Dichloroethylene
      Poisoning.  AMA. Ind. Hyg.  10:130.

25.   Cabral, J. R. P- et al.  Carcinogenic Activity of Hexachlorobenzene
      in Hamster.  Tox. Appl. Pharmacol.  41:155 (1977).

26.   Cabral, J.  R. P., et al.  1978.  Carcinogensis Study in  Mice  with
      Hexachlorobenzene.  Tox. Appl. Paramacol.  45:323.

27.   Grant, D. L. et al.  1977.  Effect of Hexachlorobenzene  on Reproduction
      in the Rat. Arch, Environ. Contam. Toxic.  5_:207.

28.   Koss, G. et al.  1978.  Studies on the Toxicology of Hexachlorobenzene.
      III.  Observation in a long-term experiment Arch. Tbxicol. 40:285.
                                   -32.V-

-------
29.   Carlson, G. P., 1978.   Induction of Cytochrone P-450 fcy Haulcgenated
     Benzenes.  Brochem. Eharmacol.   27:361.

30.   Technical Support Document for Aquatic Fate and Transport Estimates
     for Hazardous Chemical  Exposure  Assessments.   Estimates for Hazardous
     Chemical Exposure Assessments.   1980.  USEPA,  Environmental Research
     lab., Athens, Georgia.

31.   U.S. EPA.  Chlorinated  Benzenes:   Ambient Water Quality Criteria,  1979.

32.   U.S. EPA.  1979.  Water-Related  Environmental  Fate of 129 Priority
     Pollutants.  EPA-^40/4-79-029b.

33.   Itociba, R. J., Results  of  a Two-year Chronic Ibxicity Study vdth
     Hexachlorobutadiene in  Rats.  Amer.  Ind.  Hyg.  Assoc.   38:589,  1977.

34.   Kbciba et. al.  Toxicologic Study of Female Rats Administered
     Hexachlorabutadiene or  Hexachlorobenzene  for 30 Days.  DOW Chemical
     Company, 1971.

35.   Schwetz, et al., Results of a Reproduction  Study in Rats Fed Diets
     Containing Hexachlorobutadiene.   Toxicol.  Appl. Pharmacol.
     42:387, 1977.

36.   Schroit, et. al., Kidney Lesions Under Experimental Hexachlorobutadiene
     Poisoning.  Aktual, Vpo. Gig. Epidemiol.  73"!   CA:81:73128F (translation),
     1972.

37.   "Emission Control Optional for the Synthesis Organic Chemicals
     tfenufacturing Industry: Carbon  Tetrachloride  and  Perchloroethylene,"
     EPA, Office of Air Quality Planning and Standards.   Contract Number
     68-02-2257.

38.   U.S. EPA.  1975.  "Preliminary Assessment of Suspected Carcinogens
     in Drinking Water", Report to Congress.   EPA 560/4-75-003,
     Environmental Protection Agency,  Washington, D.C.

39.   CAG List of Carcinogens, April 22,  1980

-------
                        LISTING BACKGROUND DOCUMENT

        ETHYLENE DICHLORIDE  AND VINYL CHLORIDE MONOMER PRODUCTION
          Heavy ends  from  the distillation  of  ethylene dichloride in
          ethylene dichloride production.  (T)
          Heavy ends  from  the distillation  of  vinyl  chloride in vinyl
          chloride monomer production.   (T)
I.        Summary of Basis  for Listing


          The heavy ends  from the distillation  of  ethylene dichloride in

ethylene dichloride (EDC) production, and  the distillation of  vinyl chloride

in production of vinyl chloride monomer  (VCM) contain  toxic chemicals

and chemicals that are carcinogenic, mutagenic, or  teratogenic.  The

waste constituents of concern are ethylene dichloride,  trichloroethanes

(1,1,1/1,1,2), tetrachloroethanes (1,1,2,2/1,1,1,2), vinyl chloride,

vinylidene chloride, chloroform, and carbon tetrachloride.


          The Administrator has determined that the heavy  ends generated

during the purification (distillation) of crude EDC and VCM is a solid

waste stream which may pose a substantial present or potential hazard to

human health or the environment when improperly transported, treated,

stored,  disposed of, or otherwise managed, and therefore should be subject

to appropriate management requirements under Subtitle C of RCRA.  This

conclusion is based on the following considerations:
                                -32.6*-

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          1.  Of the compounds present  in the  ethylene dichloride
              and vinyl chloride monomer wastes, many are known or
              suspected carcinogens, and several are mutagenic and/or
              teratogenic.

          2.  Disposal of these wastes  is accomplished partially by use
              of landfills, which, if improperly designed or operated,
              could result in leaching  of hazardous substances into
              ground or surface water and subsequent risk of human
              exposure to the dangerous components of the waste.

          3.  Hydrocarbons, such as those predominating in this waste,
              are highly mobile and persistent in the soil profile
              and saturated subsurface, and have been responsible for
              many reported cases of ground water pollution.  Enhancing
              this potential for ground and surface water pollution is
              the fact that most of this waste is produced and disposed
              of in Gulf coastal areas where water tables and rainfall
              are generally high.

          4.  The total combined waste  generation for the balanced EDC/VCM
              process is estimated to be 170-370 million Ib./yr.  Such a
              large volume of waste containing dangerous constituents
              justifies imposition of strict controls.

II.       Source of the Wastes and Typical Disposal Practices


          A.  Profile of the Industry (1,2)

              Ethylene dichloride (EDC) and vinyl chloride monomer (VCM)

are produced at 20 plants within the United States.  Table 1 presents a

list of EDC and VCM producers.   EDC is produced by both the direct

chlorination of ethylene and the oxychlorination of ethylene.  VCM is

produced by the thermal cracking (dehydrochlorination) of EDC.   The waste

streams listed in this document thus arise in many cases out of a common

production process.   Figure 1 presents a summary of the chemical reactions

involved in producing EDC and VCM.

              Production in 1978 was 6.346 million metric tons  for EDC

and 3.776 million metric tons for VCM (Table 1).


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TABLE 1.  PRODUCERS AND 1978 PRODUCTION CAPACITIES OF
          ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER
               (metric tons/yr) (1, 2)

Company
Allied
Borden
Conoco
Diamond Shamrock

Dow


Ethyl

Goodrich
PPG

Monochem
Shell

Stauffer
Union Carbide

Vulcan
Plant location
Baton Rouge, Louisiana
Geismer, Louisiana
Lake Charles, Louisiana
Deer Park, Texas
LaPorte, Texas
Freeport, Texas
Oyster Creek, Texas
Plaquemine, Louisiana
Baton Rouge, Louisiana
Pasadena, Texas
Calvert City, Kentucky
Lake Charles, Louisiana
Guayanilla, Puerto Rico
Geismar, Louisiana
Deer Park, Texas
Norco, Louisiana
Long Beach, California
Taft, Louisiana
Texas City, Texas
Geismar, Louisiana
Ethylene
dichloride
272,000
—
544,000
145,000
-
726,000
499,000
590,000
318,000
113,000
454,000
585,000
485,000
-
635,000
544,000
141,000
68,000
68,000
159,000
Vinyl chloride
monomer
136,000
136,000
318,000
-
454,000
91,000
318,000
363,000
136,000
-
454,000
181,000
277,000
136,000
381,000
318,000
77,000
-
-
-
                       TOTALS
6,346,000
3,776,000

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     ETHYLENE BICHLORIDE VIA DIRECT CHLORINATION OF ETHYLENE
                    CH2=CH2 + C12 -> CH2C1CH2C1
       ETHYLENE BICHLORIDE VIA OXYCHLORINATION OF ETHYLENE
            CH2=CH2 + 1/202 + 2HC1 -> CH2C1CH2C1 + H20                (2)
VINYL CHLORIDE MONOMER VIA THERMAL CRACKING OF ETHYLENE DICHLORIDE
                   CH2C1CH2C1 -> CH2=CHC1 + HC1                       (3)
          ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER
                     VIA THE BALANCED PROCESS
                  2CH2=CH2 + 2C12 -> 2CH2C1CH2C1                       (4)
                              -> 4CH2-CHC1 + 4HC1                      (5)
                       t        ....__	I
2CH2«CH2 + 02 + 4HC1 -> 2CH2C1CH2C1 •«• 2H20
       Figure 1.   Alternative methods of producing ethylene
                  dichloride and vinyl chloride monomer.
                                                                       (6)

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B.  Manufacturing Process,  Waste Composition and Waste Management  (1, 65, 66)




               As  noted above,  ethylene dichloride (EDO) is produced by two




processes:   the direct chlorination of ethylene and the oxychlorination of




ethylene.  Vinyl  chloride monomer (VCM) is produced by the thermal cracking




of EDC yielding hydrogen chloride (HCL) as a by-product.  In the "balanced




process", ethylene is  converted  to EDC in two equally sized production




units utilizing direct chlorination and oxychlorination of ethylene.   The




HCL by-product  produced by  the thermal cracking of EDC to form VCM and by




direct ethylene chlorination is  used as feed for the oxychlorination




unit.  The flow diagram for the  balanced process is given in Figure 2.




For those VCM  plants that purchase EDC,  the by-product HCL is recovered




and sold or  used  in other hydrochlorination processes.




          1.   EDC Production by  Direct Chlorination of Ethylene




               The chemical  reaction for the direct chlorination of ethylene




to produce ethylene dichloride is  equation (1)  in Figure 1.   Ethylene  is




chlorinated  catalytically in a vapor-  or liquid-phase  reaction, in the




presence of  ethylene dibromide to  prevent  polychlorination,  at  temperatures




ranging between 50°C and  150°C and at  10 to 20  psig pressure.   The catalysts




used are metallic chlorides; e.g.,  ferric,  aluminum,  copper,  or antimony.




Commercially,  ferric chloride is employed  as  a  catalyst in the  liquid-phase




system.  Yields are reported at  approximately 90%  based on ethylene. (3)




          Chlorine  is mixed with ethylene  and fed  to  a reactor  where the




reaction takes  place in the liquid  phase with an excess- of EDC.  The




reaction is exothermic  (217.6 MJ/mole  or 52 kcal/mole), and heat is




removed by jacketed walls,  internal  cooling coils,  or  external  heat
                                 -330-

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VENE
                                CHLORINE   ETHYLENE
               DILUTE
               NaOH
                1
           CHLORINATION
             REACTOR
VENT SCRUBBER
i
>
. /
* (
6 TO 8%
NaOH
              AQUEOUS
               WASTE
                                                                   I
                                             AIR
  OXYCHLORINATION
      REACTOR
                                   CAUSTIC WASH
           EDC DISTILLATION
               HEAVY
               ENDS
                          TO
                        SHIPPING
    VCM DISTILLATION
         HEAVY
         ENDS
 HEAVY
WASTES
                                                 AQUEOUS
                                              ALKALINE WASTE
                                   LIGHT ENDS AND
                                    WATER COL
                                       I
                                                LIGHT ENDS TO
                                                 RECYCLE
                                     WASTE
                                     WATER
          2ND. DISTILLATION
              COLUMN
                  PURIFIED EDC
                                       VCM
                                     CRACKING
                                     FURNACE
                                    HCI REMOVAL
               VCM
            DISTILLATION
VCM
                                                                            RECYCLE HCI
                      Figure 2. PRODUCTION OF EDC & VCM

                     Modified from references  1,  65, 66
                                    -331-

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exchange.  A liquid and a vapor  stream  are  obtained  from the reactor.

          The overhead vapor effluent from  the  reactor  is condensed  in a

water-cooled or refrigerated heat exchanger to  condense any ethylene

dichloride present in the vapor  stream.  Noncondensables  are sent  through

a scrubber fed with diluted sodium hydroxide to remove  small amounts of

hydrogen chloride and chlorine gas before venting to  the  atmosphere.

          Liquid effluent from the reactor, consisting  mainly of crude

ethylene dichloride, is cooled,  then washed with a 6% to  82  caustic  solution,

Water is removed either by coalescing and phase separation,  or by  phase

separation and light ends distillation.  Ethylene dichloride  is obtained

as overhead in a heavy ends distillation column.  Based on common  practice

in the chlorinated hydrocarbon industry, these  distillation bottoms, consist-

ing of heavy ends, are sent to disposal; this is the  first waste stream of

concern in this document.

          A list of the pollutants found in the distillation  column heavy

ends in the direct chlorination process are presented in  Table 2,  along

with their amounts.


          Table 2.  HEAVY ENDS FROM DIRECT CHLORINATION [1]
      Ethylene dichloride - 3.3 Ib/ton of ethylene dichloride
      1,1,2 Trichloroethane - 5.39 Ib/ton of ethylene dichloride
      Tetrachloroethane - 5.39 Ib/ton of ethylend dichloride
      Tars - trace
                                 -331.-

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          2.  EDO Production by Oxychlorination of Ethylene




          The chemical reaction for  the  oxychlorination of ethylene  to  pro-




 duce ethylene dichloride follows  is  presented as equation (2)  in Figure 1.




          Air and hydrogen chloride  react  with ethylene in a fluidized-




 or fixed-bed catalytic process to produce  ethylene dichloride.   The




 catalyst used is a mixture of copper chloride and other chlorides.




 Reactor temperature varies between 180°C and  280*C,  and pressure ranges




 from 340 to 680 kPa gauge (50 to  100 psig).   Yields  are over 902 based




 on ethylene, depending on the presence of  excess ethylene or hydrogen




 chloride.  Excess hydrogen chloride  favors  the reaction.




          Stoichiometric amounts  of  ethylene,  anhydrous hydrogen chloride,




 and air are fed to a catalytic reactor.  The  air is  compressed  and preheated




 prior to entering the reactor as  a means of initiating  the reaction.  Con-




 version of ethylene is virtually  complete  in  one pass through  the reactor.




 The reaction is highly exothermic, and heat is recovered as  steam, with




 internal cooling, using coils or  fixed-bed  multitube reactors which  resemble




 a heat exchanger, with the catalyst  contained  inside the tubes,  while




 coolant flows through the shell.(3)




          Effluent from the reactor  is cooled  by either direct  water quench




 or indirect heat exchange.  Condensed effluent is  sent  to a  phase separator.




Noncondensable gases consisting mainly of nitrogen are  contacted in  an




 absorber with either water or aromatic solvent for removal of HC1 and




recovery of ethylene dichloride before venting to  the atmosphere.  The




organic liquid product obtained in the phase  separator  joins the stream




of the product from direct chlorination  and is contacted with  aqueous
                                 -333"

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 caustic soda to neutralize any remaining hydrogen chloride.

           Effluent from the neutralizer is distilled for removal  of  light

 ends  consisting of water and light chlorinated hydrocarbon impurities.  The

 light ends are recovered as overhead and sent to waste disposal.  Bottoms

 from the distillation column, which consist mainly (96% to 98%) of ethylene

 dichloride,  are sent to the final products purification or distillation

 column.  Pure ethylene dichloride is obtained as overhead and sent to storage,

 The heavy ends from the EDC purification (or distillation) column are the

 waste stream at issue here.  Table 3 indicates pollutants contained in the

 EDC heavy ends from the oxychlorination process.


           Table 3.   HEAVY ENDS FROM OXYCHLORINATION [2]
        Ethylene dichloride - 4.6 Ib/ton of ethylene dichloride
        Trichloroethane - 4.6 Ib/ton of ethylene dichloride
        Heavy chlorinated compounds  - 5.8 Ib/ton of ethylene dichloride
      Disposal  of these wastes  is  expected to be by incineration or landfilling,

based on common practice in the chlorinated hydrocarbon industry.

           3.   VCM Production

           Vinyl chloride is produced  from purified EDC.  The purified

EDC is  thermally cracked to yield crude  VCM and hydrochloric acid (HCl).

The HCl  is recovered  and used  as  feed to the oxychlorination reactor.
jV This waste stream  is not  presently  listed as hazardous.

-------
Crude VCM is  distilled to yield pure VCM.  Heavy ends from VCM distillation

are disposed  of as waste or are recycled for additional thermal cracking

and/or further chlorination to form other chlorinated organic products.

          It  should be noted that the balanced process generates both EDC

heavy ends and VCM heavy ends.  In an integrated plant some heavy ends

from the VCM  plant are cycled to the ethylene dichloride still.  In a

non-integrated plant,  they are stripped of the ethylene dichloride,

which is to be recycled to the VCM unit.  In either case, the ultimate

residue is expected to be disposed of by incineration or landfill,

based on common practice in this industry (i.e., the chlorinated hydro-

carbon industry).

          The bottoms  from the ethylene dichloride plant are partially

cycled to a downstream chlorination unit where the residual heavy ends

are partially retained and partially sent to disposal.  Based on common

industry practice, disposal is expected to be by incineration or land-

fill.

          The heavy ends waste discharge (for both EDC heavy ends and VCM

heavy ends) for a  plant producing ethylene dichloride and vinyl chloride

monomer by the balanced process is estimated to consist principally of

the components listed  in Table 4 below:

          Table 4   Estimated Heavy Ends Waste Discharge for EDC
                   and VCM Production by the Balanced Process


          Ethylene Dichloride                    3-5 Ib/ton of EDC

          Trichloroethane                        4-5 Ib/ton of EDC

          Tetrachloroethane                      2-5 Ib/ton of EDC

          Heavy Chlorinated Compounds (Tars)     3-6 Ib/ton of EDC


                                   -•he
                                   -33S--

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           This  estimate assumes that the major constituents  of EDC heavy




 ends  and  VCM heavy ends will be the same - a reasonable  supposition since




 not  all the carbon bonds in the EDC feedstock will be cracked  by




 dehydrochlorination,  so that these waste constituents will remain  to be




 separated as heavy ends in the VCM distillation step.






           The quantities shown in Table 4 are averages derived  from the heavy




 end  composition data  shown in Tables 2 and 3.  Relative concentrations of




 major waste constituents may be determined from the amounts of constituents




 shown in  Tables 2-4.




           In addition to the major components listed in Table 4, the combined




 ethylene  dichloride - vinyl chloride monomer heavy ends waste discharge also




 is expected to  contain lesser quantities of the following compounds:




           Vinyl Chloride




           Vinylidene  Chloride




           Trichloroethylene




           Tetrachloroethylene




           Chloroform




           Carbon Tetrachloride






           The postulated reaction  pathways  for  these constituents  (briefly




 stated) are  as  follows.   Vinyl  chloride is  likely to be present since  it




 is the product  and  would not  be removed completely in the distillation step,




Vinylidene  chloride would result from the  dehydrochlorination of trichloro-




ethylene  (a major constituent of EDC heavy  ends)  trichloroethylene would




result from the  dehydrochlorination  of  tetrachloroethane (another major
                                  -33G -

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constituent of EDC heavy ends).  Trichloroethylene could in turn be




chlorinated to form tetrachloroethylene.  Chloroform could result from




the dehydrochlorination of feedstock EDC, and could in turn be chlorinated




to form carbon tetrachloride.




III.      Discussion of Basis for Listing






          A.  Hazards Posed by the Waste




                  1.  Quantities of Wastes Generated




          Based on annual production capacities of approximately 14




billion pounds (6.35 million metric tons) for ethylene dichloride inter-




mediate and 8.3 billion pounds (3.78 metric tons) for vinyl chloride




monomer end product, as much as 30 million pounds of ethylene dichloride




and 30 million pounds each of trichloroethane and tetrachloroethane may




be present in the heavy ends waste generated from the production of these




substances each year.  Very large quantities of other waste constituents




will also be generated.  Thus, extremely large quantities of waste consti-




tuents are available for environmental release.  Additionally, ethylene




dichloride, 1 ,1,2-trichloroethane, and 1,1 ,2,2-tetrachloroethane — also




present in high concentrations — are known carcinogens, while 1,1,1-tri-




chloroethane and 1 ,1 ,1,2-tetrachloroethane, also present in high concen-




trations, are suspected carcinogens.  In addition, the waste also contains




lesser quantities or vinyl chloride, vinylidene chloride, tetrachloroethylene,




trichloroethylene, and chloroform, all of which are known carcinogens.  A




number of the compounds found in this waste also exhibit mutagenic or




tetraogenic effects, including 1,1,1, -trichloroethane, 1 ,1,2-trichloroethane,




and the tetrachloroethanes.  Should release occur, large-scale contamination




of the environment is likely.  Moreover, contamination will be prolonged,
                                 -331-

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 since  large  amounts of the pollutants are available for environmental loading




 Attenuative  capacity of individual disposal sites also could be exhausted




 due  to the  large  quantities of pollutants available.  These considerations




 themselves  justify hazardous waste listing status.




          Further,  as shown below, the waste constituents are capable of




 migration, mobility,  and persistence if improperly managed.  Indeed,  numer-




 ous  damage  incidents  involving these waste constituents have actually




 occurred.




          2.   Exposure Pathways  of Concern




          Based on common industry practice,  current methods for disposal




 of this waste  are by  incineration  or landfilling.   Improper management




 of either method  can  result in substantial hazard.  Improper incineration




 could  result in serious air pollution through release of toxic  fumes.




 This may occur when incineration facilities  are  operated in such a way




 that combustion is  incomplete  (i.e.,  inadequate  conditions of temperature




 mixing and residence  time)  resulting in airborne dispersion of  hazardous




 vapors containing partially combusted organics,  newly formed organic




 compounds, and hydrogen chloride.   Phosgene  is an  example  of a  partially




 chlorinated organic which  is produced by the  decomposition or combustion




 of chlorinated organics  by heat. ( 61 >  62)   Phosgene has been used as a




 chemical warfare  agent,  and  is extremely toxic.   Improper  incineration




 thus could present  a  significant opportunity  for exposure  of humans,




wildlife and vegetation  in  the vicinity of these operations to  risk




 through direct contact.




          Improper disposal  in landfills  can  also  lead to  substantial




environmental hazard.  Migration to and subsequent contamination of ground
                                 -33?-

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 and  surface waters  is  a  particular danger.   All of the waste constituents




 of concern tend to  be  highly soluble in water (with the exception of




 vinyl chloride, which  is a  gas),  with solubilities ranging from 800 mg/1




 (carbon tetrachloride) to 8700  mg/1 (ethylene dichloride (Appendix B).




 Thus, these waste constituents  will tend to migrate in high concentrations




 under even relatively  mild  environmental conditions.   Improperly sited




 landfills (for example,  in  areas  with highly permeable soils,  or in areas




 where soil is low in attenuative  capacity)  or improperly managed (for




 instance, landfills with inadequate leachate collection or minotoring




 systems) could easily  prove inadequate to prevent  waste migration.




          Once these waste  constituents migrate from  the waste,  they are




 likely to persist in groundwater  for long periods  of  time (App.  B).




 Thus, improperly designed landfills could well lead to human  and




 environmental exposure,  and attendant substantial  hazard in light  of the




 hazardous nature of the  waste constituents.




          An air inhalation pathway is  an additional  exposure  route  of




 concern.  Of the waste constituents,  ethylene dichloride,  the  trichloro-




 ethanes, the tetrachloroethanes,  chloroform,  and carbon tetrachloride all




 tend to be relatively  to  highly volatile, with vapor  pressures ranging




 from 5mm Hg.  (tetrachloroethanes)  to  116  mm Hg.  (chloroform) (App. B.).




Vinyl chloride is already a  gas,  so it  also  poses  a substantial  air  pollu-




tion hazard.   Inadequate  site cover could therefore lead to escape of




volatile waste constituents  and resulting contamination of  air in  the




vicinity surrounding the  site.




          There  is,  therefore, a  strong potential  that landfilling of




these wastes  will ultimately result  in  pollution of nearby  groundwater

-------
by ethylene  dichloride,  the trichloroethanes, the tetrachloroethanes,




and  other  similar  waste  components.   This  is enhanced by the fact that




most  of  this waste is  produced  and,  presumably,  disposed of in Gulf




coast  areas  (see Table 1)  where water tables are generally shallow and




rainfall is  relatively high.




           There is also  the possibility that components of this waste




could  enter  surface waters,  either by mishandling of the waste prior  to




disposal or  by migration of individual compounds through groundwater  to




points of  discharge to surface  waters.




           In surface waters,  the chlorinated ethanes and ethylenes  will




tend  to  volatize due to  their high vapor pressures.   However,  traces  will




probably remain for extended  periods  of time.  Chloroform,  one of the




waste  components,  in fact,  has  been  shown  to persist almost indefinitely




in surface water.  (App.  B)




           3.  Actual Damage  Incidents




              Actual damage  incidents  confirm these  waste constituents'




ability  to migrate and persist  and cause substantial hazard if improperly




managed.   The chlorinated  ethanes and  ethylenes-such as those  which




predominate  in this waste-are the classes  of organic pollutants  being




identified far more often  than  any other pollutant types in current




groundwater  pollution  incidents.  For  example, ethylene dichloride,




(1,2-dichloroethane) has been found  in groundwater from public water




supply wells at Bedford, Massachusetts,  where  the source is believed  to




be industrial operations upstream.(4)




          At the Llangollen landfill  in Delaware, dichloroethane (ethylene

-------
 dichloride and/or 1,1-dichloroethane)  has  been found migrating from the




 landfill through nearby ground water.(5)    In New Jersey,  seepage from




 landfilled wastes near the CPS chemical  company resulted  in contamination




 of nearby ground water by trichloroethane  and tetrachloroethane.(6)




 1,1,1-Trichloroethane was detected  in  ground  water at Acton, Massachusetts,




 where the source is believed  to be  a settling lagoon at a  nearby  manufacturing




 plant. (4)  Extensive contamination  of  ground  water by trichloroethylene




 has also been reported in southeast Pennsylvania.(7)   Trichloroethylene




 has also been found in school and basement air,  and in residential




 basements in Love Canal.(64)




          Field reports such  as these  clearly indicate that the release of




 low molecular weight chlorinated hydrocarbons into the soil will  result




 in pollution of groundwater with the potential risk of substantial  adverse




 health effects.  This is further substantiated by  recent  laboratory  studies




 in which 1,1,2-trichloroethane, chloroform, and similar compounds were




 observed to move through a four foot profile  of sandy soil  with little




 retardation relative to water and no apparent degradation.(8)  Also,




 field studies in the Netherlands and California have  shown  that low




 molecular weight chlorinated hydrocarbons,  such  as those occurring




 in this waste, are highly mobile and persistent  in the saturated  ground




 water environment.(9, 10)




    In light of the highly dangerous character of  the constituents  of




 concern in the waste, some of which are likely to  be  present in high




 concentrations,  the Agency would require strong  assurance  that these




 constituents will not migrate and persist  if  improperly landfilled  or




 incinerated.  Data in fact indicate that these constituents may well




migrate  and  persist via a number of exposure  pathways.  Thus,  these




                                    -X-

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 wastes  clearly should be listed as hazardous.




           B.   Health and Ecological Effects




               1.   Sthylene Dichloride




                   Health Effects - Ethylene dichloride (1,2-dichloroethane)




 has  been shown to cause cancer in laboratory animals.(11)  Ethylene




 dichloride is  extremely toxic (oral rat LD5Q « 12 mg/Kg).  In addition,




 this compound  and several of its metabolites are highly mutagenic.(12)




 1,2-Dichloroethane crosses the placental barrier and is embryotoxic and




 teratogenic.(13-17)   It has also been shown to concentrate in milk.(18)




 Exposure to this  compound can cause a variety of adverse health effects




 including damage  to  the liver,  kidneys and other organs.   It can also




 cause internal hemorrhaging and blood clots.(19)  Ethylene dichloride




 (1,2-dichloroethane)  is designated as a priority pollutant under section




 307(a)  of the  CWA.   Additional  information and specific references on




 adverse effects of ethylene dichloride can be found in Appendix A.




                   Ecological Effects  - Values for a 96 hour static LC5Q




 for  bluegills  range  from 256 to 300 mg/1 making it moderately toxic.(20)




                   Regulatory Recognition of Hazard  - OSHA has set the




 TWA  at  50  ppm.  DOT  requires the containers for this chemical to carry a




 warning that it is a  flammable  liquid.   The Office of Air Pollution and




 Noise has  completed  the preregulatory assessment of 1,2-dichloroethane




 under sections  111 and  112  of the  Clear Air Act.   Preregulatory assessments




 are  also being  conducted  by EPA's  Office of Water and Waste Management




 under the  Safe  Drinking Water Act  and by the Office of Toxic Substances




 under the  Toxic Substances  Control Act.   Ethylene dichloride is currently




being studied by  the Consumer Product Safety Commission under the Consumer




Product Safety Act.

-------
          Industrial Recognition of Hazard - Sax in Dangerous Properties
of Industrial Materials rates 1,2-dichloroethane as highly toxic upon
ingestion and inhalation.
              2.   1,1, l~Tridiloroethane (Methylchlorof orm )
                  Health Effects - 1,1,1-Trichloroethane is a suspected
carcinogen and when tested for carcinogencity by NCI was found to induce
a variety of malignant tuners in two species of rodents.  (21)  Experiments
involving rat embryo cell cultures indicated that 1,1,1-txichloroethane
transforms cells in vitro.  Transplantation of these premalignant trans-
formed cells into an intact animal produced cancers in all of the animals
injected. (22)
          1,1,1-Trichloroethane was found to be mutagenic in the Ames Sal-
monella essay (23) and was shown to cause fetal development abnormalities. (24)
          Acute and chronic intoxication of humans have caused severe
central nervous systsn impairment, such as lengthened reaction and per-
ception time, decreased manual dexterity,  equilibrium disturbance (3).
Animal studies have shown that methylchloroform causes organ damage to
heart, lungs, liver and kidneys. (25)  1,1,1-Trichloroethane is designated
as a priority pollutant under section 307(a) of CWA.  Additional informa-
tion and specific references on the adverse effects of 1,1,-trichloroethane
can be found in j^ppendix A.
                  Ecological Effects -  1,1,1-Trichloroethane is very toxic
to aquatic life.   Lethal concentrations (96 hour) of 37-38 mg/1 were
registered for bluegills, 52 mg/1 for fathead minnows and 26 mg/1 for
shrimp. (26)  lfae gcp factor is set by USEPA at 21. (2°)
                  Regulations - OSHA has set the TWA at 350 ppn.
                                  -J43-

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                   Industrial Recognition of Hazard - Sax Dangerous Property
                                                                       ^^^^*^^»

of Industrial Matrials  lists 1,1,1-trichloroethane as carcinogenic and



moderately toxic.


              3.   1,1,2-Trichloroethane


                   Health Effects -  1,1,2-Trichloroethane has also been


shovvn to cause cancer in mice. '^7)   it. has  also been identified by the


Agency as a compound exhibiting substantial evidence of carcinogenicity.


(67) There is evidence  that 1,1,2-trichloroethane  is mutagenic and


may be sribryo toxic or  cause teratogenic effects.'13-17,28-30)



1,1,2-Trichloroethane is considered toxic [oral rat 11)50 = 1140 rag/Kg].


                   LiKe  the other compounds  of this type,  the trichloro-


ethanes are narcotics,  produce central  nervous  system effects, and can


damage the liver,  kidney and other  organs. (19)  1,1,2-Trichloroethane is


designated as a priority pollutant  under Section 307(a)  of the Q&.


Additional information  and specific references  on  the adverse effects of


1,1,2-trichloroethane can be found  in Appendix  A.


                   Ecological Effects - Aquatic  toxicity data are Limited


with only three acute studies  in freshwater fish and invertebrates with


doses ranging frcm 10,700 to 22,000 mg/l.(20)


                   Regulations  - OSHA has set the TWA at 10 ppn (skin).


                   Industrial Recognition of Hazard - Sax,  Dangerous


Properties of Industrial Materials,  lists 1,1,2-trichloroethane as being


moderately toxic ty inhalation, ingestion and skin absorption.


              4.   Tetrachloroethanes

-------
                  Health Effects -  1,1,2,2-TetracMoroethane has been



 shewn to produce liver cancer in laboratory mice. (31)   It has also been



 identified by the Agency as a compound  etfiibiting substantial evidence of



 being carcinogenic.  (67)   It is also shown to be very  toxic [oral rat



 1X50 = 20° rag/Kg].   In addition, passage of 1,1,1, 2-tetrachloroethane



 across the placenta! barrier has been reported. (29)  In  Ames  Salmonella



 bicassay 1,1, 2, 2-tetrachloroethane  was  shown to be mutagenic.(32)



 Occupational exposure of workers to 1,1, 2, 2-tetrachloroethane produced



 neurological damage, liver and kidney ailments, edema,  and fatty degeneration



 of the heart muscle. <33)  Both 1,1,1, 2-tetrachloroethane and 1,1,2,2-



 tetrachloroethane are designated as priority pollutants under Section



 307 (a) of the CWA.   Additional information and specific references on



 the adverse effects  of tetrachloroethanes can  be  found  in Aperdix A.



                  Ecological Effects  -  Freshwater invertebrates are



 sensitive to 1,1, 2, 2-tetrachloroethane  with a  lethal concentration of



 7-8 mg/1 being reported. (2°)  USEPA estimates  the BCF to be  18.



                  Regulations - OSHA. has set the 1WA at 5 ppn (skin) for



 1,1,2, 2-tetrachoroethane .



                  Industrial Recognition of Hazard - Sax, Dangerous



 Properties of Industrial Materials, lists 1,1, 2, 2-tetrachloroethane as



 being highly toxic via ingestion, inhalation and skin absorption.



              5.   Trichloroethylene



                  Health Effects - Trichloroethylene has been demonstrated
to induce liver cancer in mice. (34)  It has also been identified by the



Agency as a ccmpound exhbiting substantial evidence of carcinogenic ity.(67)
                                  -2V

-------
This compound nay be absorbed into the bocty by inhalation, by  ingestion,



or ty absorption through the skin.(34)



                  An excess of lung/ cervical, and skin cancers and a



slight excess of leukemias and liver cancers were observed in a study of



330 deceased laundry and dry-cleaning workers who had been exposed to



carbon tetrachloride, trichloroethylene, and tetrachloroethylene.(35)



                  Trichloroethylene is mutagenic in bacteria and yeast



and in spot tests for somatic nutations in mice. (36)



              Numerous fatalities resulting from anesthesia with tri-



chloroethylene and fron industrial intoxications have been reported. (34)



Acute and chronic inhalation of trichloroethylene effects the central



nervous system.  Toxic effects on the liver and other organs can occur



from exposure by any route, and there is an indication that the hepa-



totoxic effect of trichloroethylene is enhanced by concomitant exposure



to ethanol or isopropyl alcohol. '34,36)  Additional information and



sepcific references on the adverse effects of trichloroethylene can be



found in Appendix A.



                  Ecological Effects - Freshwater fish (bluegill) are



poisoned by trichloroethylene during a 96 hour exposure to 40-60 mg/1



concentration range.(37)



                  Regulations - OSHA has set a TWA at 100 ppn.



                  Industrial Recognition of Hazard - Sax, Dangerous



Properties of Industrial Materials, lists trichloroethylene as a high



systemic toxicant via inhalation and moderate via ingestion.

-------
              6.  Tetradhloipethylene
                  Health Effects - Tetrachloroethylene is a carcinogen
 in laboratory mice. (38)  It has also been identified by the Agency as a
 compound exhibiting substantial evidence of carcinogenicity.(67) The
 conpound can be absorbed into the body via inhalation, by ingest ion,
 and through the skin to increase its toxic effects. (39)
                  It has also been reported to be inutagenic and to cause
 trans formation of mamnalian eel Is. (39)  ^ excess of lung, cervical and
 skin cancers and a slight excess of leukemias and liver cancers ware observed
 in a study of 330 deceased laundry and dry-cleaning vorkers Who had been ex-
 posed to carbon tetrachloride, trichloroethylene, and tetrachloroethylene.
                  There is sone evidence that tetrachloroethylene may be
 teratogenic.  Repeated exposures to tetrachloroethylene vapors produced a
 variety of pathological change in the liver ranging from fatty degeneration
 to neurosis in rats, rabbits and guinea pigs.  Exposure to this compound
 may also effect the kidneys and other organs.  It also causes central
 nervous system effects and gastrointestinal symptoms.(39)
                  A case of "obstructive jaundice" in a six veek old
 infant has been attributed to tetrachloroethylene in breast milk.(40)
 Additional information and specific references on the adverse effects of
 tetrachloroethylene can be found in Appendix A.
              7.  Vinyl Chloride (VCM)
                  Health Effects - Vinyl Chloride has been shown to be
a carcinogen in laboratory studies. (41,42)  it has also been identified
ty the Agency as a compound exhibiting substantial evidence of carcino-
genicity.(67)  ihis finding has subsequently been supported ty epidemological

                                  -x-

-------
findings.^43'44^  Vinyl  chloride is very toxic [oral rat



= 500 mg/Kg].  Acute exposure to vinyl  chloride results in anaesthetic



effects as veil as uncoordinated muscular activities of the extremeties,



cardiac arrythmas^4^ and sensitization of the myocardium. '46)  in severe



poisoning, the lungs are congested  and  liver and kidney damage occur. (47)



A decrease in \foite blood cells  and an  increase in red blood cells vas



also observed and a decrease in  blood clotting ability. (48)  Vinyl chloride



is designated as a priority pollutant under Section 307(a)  of the CWk,



Additional information and specific references on the adverse effects of



vinyl chloride can be  found in Appendix A.



                  Industrial Recognition of Hazard - Sax, Dangerous



Properties of Industrial Materials, lists vinyl chloride as having a



moderate toxic hazard  rating via inhalation.



              8.  Vinylidene Chloride



                  Health Effects - Vinylidene  chloride has  been shown to



cause cancer in laboratory animals. (49, 50)  it has  also been  identified



by the Agency as a compound exhibiting  substantial  evidence of (sarcinogencity.



'67^ It is very toxic  [oral rat  LDgQ  =  200 mg/Kg]^49^.   Chronic exposure



to vinylidene chloride can cause damage to the liver and other vital



organs as well as causing central nervous system effects.   Mditional



information and specific references on  the adverse  effects  of vinylidene



chloride can be found  in Appendix A.



                  Regulations -  OSHV has set the 1WA at 10  ppn.



                  Industrial Recognition of Hazard - DOT requires containers



to be labeled "flammable liquid".



                  The toxic hazard  of vinylidene chloride  is suspected of

-------
being similar to vinyl chloride which is moderately toxic via inhalation,



Sax, Dangerous Properties of Industrial Materials.



              9.  Chloroform




                  Health Effects - Chloroform has been shown to be carcinogenic



in animals and is recognized as a suspect hunan carcinogen. (51)  it has also



been identified ty the Agency as a compound eriiibiting substantial evidence



of carcincgenicity(67).  Tangential evidence links human cancer epidemiology



with chloroform contamination of drinking water. (52,53)  Chloroform has



also been shown to induce fetal toxicity and skeletal malformation in



rat anbryos.(54,55)  chronic exposure causes liver and kidney danage and



neurological disorders. (52)  Additional information and specific references



on the adverse effects of chloroform can be found in ^pperrlix A.



                  Ecological Effects - USEPA has estimated that chloroform



accumulates fourteenfold in the edible portion of fish and shellfish. (52)



The USEPA has recommended that contamination by chloroform not exceed



500 mg/1 in freshwater and 620 mg/1 in marine environment. (52)



                  Regulations - OSHA has set the TWA at 2 ppn.  FDA pro-



hibits use of chloroform in drugs, cosmetics, and food contact materials.



The Office of Water and Waste ffenagement has proposed regulation of



chloroform under Clean Water Act 311 and is in the process of developing



regulations under dean Water Act 304(a).  The Office of Air, Radiation,



and Noise is conducting preregulatory assessment of chloroform under the



Clean Air Act.   The Office of Toxic Substances has requested additional



testing of chloroform under Section 4 of conducting preregulatory assess-



nent under the Federal Insecticide,  Fungicide and Rodenticide Act.

-------
                   Industrial Recognition of Hazard -  Chloroform has been




 given a moderate toxic hazard rating for oral and inhalation  exposures,




 Sax, Dangerous Properties of Industrial Materials.




              10.  Carbon Tetrachloride




                   Health Effects - Carbon tetrachloride is estimated to




 occur in this waste stream in low concentrations, but is a very potent




 carcinogen. ^"'  It has been identified by the Agency as a compound




 exhibiting substantial evidence of carcinogenicity. (67)  -j^e toxic effects




 [oral rat LD5Q = 2800 mg/Kg]  of carbon tetrachloride are amplified by




 both the habitual and occasional ingestion of alcohol.(57)




                   Obese individuals are especially sensitive to the




 toxic effects of carbon tetrachloride  because the compound accumulates




 in  body fat.'58)  xt also causes harmful effects in  humans as  the




 undernourished, those suffering from pulmonary diseases,  gastric ulcers,




 liver and kidney diseases,  diabetes, or glandular disturbances.(59)




                   The recommended criterion  level in water designed to




 protect humans  from the toxic effects  of carbon  tetrachloride  is 2.6




 mg/l.'57)  jn measurements made  during  the National  Organics Monitoring




 Survey  of 113 public water  systems  sampled,  11 of these systems  had carbon




 tetrachloride at levels  at or exceeding the  recommended safe limit. (6°)




 Carbon  tetrachloride is  a priority  pollutant  under Section 307(a)  of the




 C¥A.  Additional information and  specific references  on the adverse




 effects  of carbon  tetrachloride  can be  found  in  Appendix A.




                  Ecological Effects -  Movement  of carbon  tetrachloride




within  surface water  systems is  projected to  be  widespread,  (see App.  B)
                                  - 3.T6 -

-------
Movement to this degree will  likely  result  in  exposure  to  aquatic  life


forms  in rivers, ponds and reservoirs.


                 Carbon tetrachloride  is likely  to  be  released  to the


atmosphere from surface water systems.  In  the atmosphere, carbon  tetra-


chloride is slowly decomposed to phosgene,  a highly  toxic  gas.   In the


incineration of carbon tetrachloride-containing wastes, phosgene is


likely to be emitted under incomplete combustion  conditions.


                 Regulations  - OSHA has set a TWA for  carbon tetrachloride


at 10  ppm.  Carbon tetrachloride has been banned  by  the Consumer Product


Safety Commission under the Hazardous Substances  Act.


                 Industrial  Recognition of Hazard - According to  Sax,


Dangerous Properties of Industrial Materials,  the oral  toxicity  rating is


high.
                                 -k-
                                -3S1-

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IV.   References
 1.   Industrial Process Profiles  for Environmental Use:   Chapter 6,
      The Industrial Organic Chemicals  Industry.   Reimond Liepins, Forest
      Mixon, Charles Hudak, and Terry Parsons,  February 1977,  EPA-600/
      2-77-023f.

 2.   Engineering and Cost Study of Air Pollution  Control for  Petrochemical
      Industry-Vol. 3.  Ethylene dichloride manufacture by oxychlorination,
      November 1974, EPA-450/3-73-006-C.

 3.   Source Assessment:  Chlorinated Hydrocarbons Manufacture,  EPA-600/
      2-79-019g, August 1979.

 4.   Water Quality Issues in Massachusetts, Chemical  Contamination,
      Special legislative Commission on Water Supply.   September 1979.

 5.   DeWalle, Foppe B. and Edward S. Chian.  Detection of  Trace Organics
      in Well Water Near a Solid Waste Landfill.   Environ.  Sci.  Technol.
      (In Press).

 6.   Memo from Roy Albert to E.G. Beck, Administrator  EPA  Region II,
      Drinking Water Contamination of New Jersey Well Water, March 31, 1978.

 7.   Buller, R.D.  1979.  Trichloroethylene Contamination  of  Ground Water
      Case History and Mitigative Technology.   Presented  at American
      Geophysical Union Fall Meeting, December  3-7,  San Francisco,  CA.

 8.   Wilson, J.T. and C.G. Enfield, 1979.  Transport of  Organic Pollutants
      Through Unsaturated Soil.  Presented American  Geophysical  Union Fall
      Meeting, December 3-7, San Francisco, CA.

 9.   Zoetman, G.C.J., K. Harmsen, J.B.H.J. Linders, C.F.H. Morra, W. Sloop,
      1979, Persistent Oranic Pollutants in River  Water and Ground Water
      of the Netherlands.  Presented at the 3rd International  Symposium
      on Aquatic Pollutants, October 15-17, Jekyll  Island,  GA.

10.   Roberts, P.V., P.L. McCarty, Mr.  Reinhard, and J. Schriener,  1978.
      Organic Contaminant Behavism During Ground Water  Recharge.   Presented
      at the 51st Annual Conference of the Water Pollution  Control  Feder-
      ation.   October 1-6, Anaheim, CA.

11.   National Cancer Institute.   Bioassay of 1,2-Dichloroethane for
      Possible Carcinogenicity.  U.S. Department of  Health, Education and
      Welfare, Public Health Service, National  Institutes of Health,
      National Cancer Institute,  DHEW Publication  No.  (NIH) 78-827,  1978.

-------
 IV.   References  (Continued)


 I2a.  McCann,  J.,  E.  Choi, E. Yamasaki, and B. Ames.  Detection of Carcin-
      ogens  as Mutagenic in the Salmonella/Micro some Test:  Assay of 300
      Chemicals.   Proc.  Nat. Acad. Sci.  USA _72(2):  5135-5139, 1975a.

 12b.  McCann,  J.,  V.  Simmon, D. Streitwieser, and B. Ames.  Mutagenicity
      of chloroacetaldehyde, a possible metabolic product of  1,2-dichloro-
      ethane (ethylene dichloride), chloroethanol (ethylene chlorohydrin),
      vinyl  chloride, and cyclophosphamide.  Proc. Nat. Acad. Sci. 72(8):
      3190-3193,  1975.

 13.   Vozovaya, M.  Changes in the Esterous Cycle of White Rats Chronically
      Exposed to  the  Combined Action of Gasoline and Dichloroethane Vapors.
      Akush. Geneko.  (Kiev) £7_(12):  65-66, 1971.

 14.   Vozovaya, M.  Development of Offspring of Two Generations Obtained
      from Females Subjected to the Action of Dichloroethane.  Gig. Sanit.
      £  25-28,  1974.

 15.   Vozovaya, M.  The Effect of Low Concentrations of Gasoline, Dichloro-
      ethane and  Their Combination on the Generative Function of Animals.
      Gig. Sanit.  _6:  100-102, 1976.

 16.   Vozovaya, M.  Effect of Low Concentrations of Gasoline, Dichloro-
      ethane and  their Combination on the Reproductive Function of
      Animals. Gig.  Sanit. 6_: 100-102, 1976.

 17.   Vozovaya, M.A.   The Effect of Dichloroethane on the Sexual Cycle
      and Embryogenesis of Experimental Animals.  Akusk. Ginekol.
      (Moscow) 2:  57-59, 1977.

 18.   Urusova, T.P.   (About a possibility of dichloroethane absorption
      into milk of nursing women when contacted under industrial conditions.)
      Gig. Sanit.  _18(3):  36-37, 1953 (Rus).

 19.   Parker,  J.C.,  et al.  1979.  Chloroethanes:  A review of Toxicity.
      Amer.  Ind.  Hyg. Assoc. J., 40;  46-60, March 1979.

 20.   U.S. EPA 1979.   Chlorinated Ethanes:  Ambient Water Quality Criteria
      (Draft)

 21.   NCI 1977.   Bioassay of 1,1,1-trichloroethane for possible carcinogen-
      icity.   Carcinog.  Tech. Rep. Ser. NCI-CG-TR-3.

22.   Price,  P.J.  et  al.  1978.  Transforming activities of trichloroethane
      and proposed industrial alternatives.

23.   U.S. EPA Report 1980 in Vitro 14:290.  In Vitro microbiological muta-
      genicity of  81  compounds.

-------
IV.   References  (Continued)
24.   Schwetz, B.A. et al.   1974.   Embryo  and  fetal toxicity of inhaled
      carbon tetrachloride,  1,1-dichloroethane and methylchloroform in
      rats.  Toxicol. Appl.  Pharmacol.  28:  452.

25.   Walter, P. Chlorinated hydrocarbon toxicity a monograph  PB-257185
      Natl. Tech. Inf. Serv.   Springfield,  Virginia.

26.   U.S. EPA,  1979.  In-depth studies on  health and environmental impact
      of selected water pollutants.  Contract  No.  68-01-4646.

27.   National Cancer Institute.  Bioassay  of  1,1,2-trichloroethane for
      Possible Carcinogenicity.  U.S. Department  of Health,  Education, and
      Welfare, Public Health Service, National Institutes  of Health,
      National Cancer Institute, DHEW Publication No.  (NIH)  78-1324,  1978.

28.   Elovaara, E., et al.   Effects of CH2C12,  CH3C13,  TCE,  Perc and
      Toluene in the development of Chick Embryos,  Toxicology 12;  111-119,
      1979.

29.   Truhaut, R., Lich, N.P., Dutertre-Catella,  H. ,  Molas,  G.,  Huyen,
      V.N.:  Toxicological Study of 1,1,1,2-tetrachloroethane.   Archives
      des Maladies Professionnelles, de Medicine  du Travail  et  de  Securite
      35(6): 593608, 1974.

30.   Parker, J.C., I.W.F. Davidson, and M.M.  Greenberg.   EPA Health
      Assessment Report of 1,2-Dichloroethane  (Ethylene Diehloride (Ethylene
      Dichloride) In Preparation.

31.   National Cancer Institute.  Bioassay  of  1,1,2,2-Tetrachloroethane
      for Possible Carcinogenicity.  U.S. Department  of Health,  Education,
      and Welfare, Public Health Service, National  Institutes of Health,
      National Cancer Institute, DHEW Publication No.  (NIH)  78-827,  1978.

32.   Brem H., et al.  1974.   The Mutagenicity and  DNA-modifying effect
      of Haloalkanes.  Cancer. Res. 34:  2576.

33.   National Institute for Occupational Safety  and  Health.  Criteria
      for a Recommended Standard ... Occupational  Exposure to  1,1,2,2-
      Tetrachloroethane.  U.S. Department Public  Health Service, Center
      for Disease Control, National Institute  for  Occupational  Safety and
      Health, DHEW (NIOSH) Publication No.  77-121,  December  1976.

34.   Page, Norbert P., and  Jack L. Arthur  Trichloroethylene.   Special
      Occupational Hazard Review with Control  Recommendations   DHEW
      Publication No. (NIOSH) 78-130.   January,  1978.

35.   Blair, et al.   1979.   Causes of death among  laundry  and dry cleaning
      workers.   Am.  J.  Publ.  Health 69:  508-511.
                                       - 3S4 '

-------
 IV.   References  (Continued)


 36.   IARC Monographs,  Volume 20:  545-572.

 37.   U.S. EPA,  1979.   Trichloroethylene.  Ambient Water Quality Criteria.

 38.   National  Cancer  Institute (1977) Bioassay of Tetrachloroethylene
      for Possible  Carcinogenicity, DHEW Publication No. (NIH) 77-813.

 39.   C.  Parker,  EPA,   ECHO/ICTP.

 40.   Bignell,  P.C.  &  Ellenberger, H.A. (1977).  Obstructive jaundice
      due to  a  chlorinated hydrocarbon in breast milk.  Con. Med. Assoc.
      £., 117,  1047-1048.

 41.   Viola,  P.L.,  et  al.   Oncogenic response of cat skin, lungs, and
      liver  to  vinyl chloride.   Cancer Res. 31: 516. 1971.

 42.   Maltoni,  C. and  G. Lefemine, Carcinogenicity bioassays of vinyl
      chloride.   Am. N.Y.  Acad. Sci.  246: 195., (1975).

 43.   Creech  &  Johnson. Angiosarcoma of the liver in the manufacture
      of  polyvinyl  chloride.  J. Occup. Med. 161:  150, 1974.

 44.   Tabershaw,  I.R.,  and Gaffey, W.R.  Mortality study of workers
      in  the  manufacture of vinyl chloride and its polymers.  J. Occup.
      Med.  16:  509  (1974).

 45.   Oster,  R.H. et al.   Anesthesia XXVII Narcosis with Vinyl Chloride.
      Anesthesiology 3: 359, 1947.

 46.   Cair, J.  et al.   Anesthesia XXIV.  Chemical constitution of
      hydrocarbons  and cardiac automaticity.  J. Pharmaceut. 97: 1 (1949).

 47.   Torkerson,  T.R.,  et  al.  The toxicology of Vinyl Chloride
      by  repeated experience of laboratory animals.  Amer. Ind.
      Hyg. Assoc. J.  22;  304.   1961.

 48.   Lester  D.,  et  al. Effects of single and repeated exposures of
      humans  and  rats  to vinyl chloride.   Amer. Ind. Hyg. Assoc. J.
      _24: 265.  1963.

 49.   Environmental  Health Perspectives,  1977.   Vol. 21, 333 pp.

 50.   USEPA,  1979 Vinylidene Chloride Hazard Profile, USEPA/ECAO
      Cincinnati, Ohio  45268 1979.

51.   National Cancer  Institute, 1976.  Report on Carcinogenesis Bioassay
      of  Chloroform.   National  Technical  Inf. Serv.  PB-264018.  Spring-
      field,  VA.

-------
IV.   References  (Continued)
52.   USEPA,  1979.   Trichloromethane  (chloroform) Hazard Profile, USEPA/
      ECAO Cincinnati,  Ohio   45268.   1979.

53.   McCabe, L.J.,  1975.  Association between Trihalomethanes in Drinking
      Water  (NORS  data) and Mortality.   Draft report.   U.S. Environmental
      Protection Agency.

54.   Thompson, D.J., et al.   1974.   Teratology Studies on Orally Admin-
      istered Chloroform in the Rat and Rabbit.   Toxicol.  Appl.  Pharmacol.
      29: 348.

55.   Schwetz, B.A., et al.   1974.  Embryo  and Fetotoxicity of Inhaled
      Chloroform in  Rats.  Toxicol. Appl. Pharmacol.  28:  442.

56.   National Cancer Institute.  Carcinogens  Bioassay of  Carbon Tetra-
      choride, 1976.

57.   U.S. EPA.  Carbon Tetrachloride:   Ambient  Water  Quality  Criteria
      Document, 1979.

58.   U.S. EPA, 1979.  Water-Related  Environmental  Fate of 129 Priority
      Pollutants.  EPA-440/4-79-029b.

59.   Von Oettingen, W.F., The Halogenated  Hydrocarbons of Industrial
      and Toxicological Importance.   In: Elsevier monographs on  Toxic
      Agents, E. Browning, Ed., 1964.

60.   U.S. EPA.  Determination of Sources of  Selected  Chemicals  in
      Waters and Amounts from these Sources,  1977.

61.   "Combustion  Formation and Emission of Trace Species",
       John B. Edwards, Ann Arbor Science,  1977.  .

62.   NIOSH Criteria for Recommended  Standard:   Occupational Exposure
      to Phosgene, HEW, PHS, COL, HIOSH, 1976.

63.   Chemical and Process Technology Encyclopedia, McGraw Hill,  1974.

64.   "Love Canal Public Health Bomb."  A Special Report to  the  Governor
       and Legislature, New York State  Dept.  of  Health (1978).

65.   Lowenheim and Moran.  Faith, Keyes, and  Clark's  Industrial  Chemicals,
      4th ed., John Wiley and Sons, Inc.  1975»

66.   Kirk-Othmer.  Encyclopedia of Chemical  Technology -  3rd  ed., John Wiley
      and Sons, Inc.  1979.

67.   Cancer Assessment's Group List  of Carcinogens, April 22, 1980.

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                       LISTING BACKGROUND DOCUMENT

                         FLUOROCARBON PRODUCTION


     Aqueous  spent antimony catalyst waste from fluoromethanes
     production.  (T)

 I.   Summary  of  Basis for Listing

     The production of chlorofluoromethanes via the liquid phase

 fluorination  process  results in the generation of an aqueous

 spent antimony catalyst waste which contains both toxic organic

 and inorganic substances, two of which are carcinogenic.  The

 waste constituents of concern are antimony compounds, chloro-

 form and/or carbon tetrachloride.

     The Administrator has determined that the wastewater from

 the production of chlorofluoromethanes via the liquid phase

 fluorination  process  is a solid waste which may pose a sub-

 stantial present  or potential hazard to human health or the

 environment when  improperly transported, treated, stored, dis-

 posed of or otherwise managed, and therefore should be subject

 to appropriate management requirements under Subtitle C of

RCRA.   This conclusion is based on the following considerations:

 (1)  The waste stream contains significant quantities of antimony
     compounds,  chloroform and/or carbon tetrachloride.*
     *Depending  on  the  type of fluorocarbon being, produced, either
chloroform or  carbon  tetrachloride will be used as a raw material
and  appear in  the waste stream as an excess reactant (see dis-
cussion,  "Industry  Profile  and Process Description," below).

-------
(2)  Chloroform, carbon  tetrachloride,  and antimony compounds are
     highly toxic.   Chloroform  and  carbon tetrachloride has been
     evaluated by EPA  as  substances exhibiting substantial evidence
     of carcinogenicity.   Carbon  tetrachloride has been shown to be
     teratogenic.

(3)  Chloroform  and  carbon tetrachloride are resistant to water
     treatment methods and are  therefore likely to appear in drink-
     ing water if allowed  to  migrate from the waste into drinking
     water sources.  These two  constituents are also volatile and
     may pose a  threat to  human health  via an air exposure pathway
     if not properly managed.   Antimony compounds will persist in
     the environment (in  some form)  vitually indefinitely;  therefore
     if allowed  to migrate from the waste may contaminate drinking
     water sources for long periods of  time.

(4)  It is estimated that  approximately 30,000 to 60,000 Ibs.  of
     spent catalyst  is generated  annually by the two plants using
     liquid phase fluorination  and  will be in the aqueous waste
     stream.  The substantial quantity  of waste generated increases
     the possibility of  exposure  should mismanagement occur.

(5)  Damage incidents  involving the contamination of groundwater
     by antimony compounds, chloroform  and carbon tetrachloride
     confirm the ability of these waste constituents to be  mobile,
     persist, and cause  substantial  harm.*

II.  Industry Profile  and  Process Description (29,30)

     Chlorofluoromethanes  are manufactured by the fluorination of

chlorocarbons.   Two  different fluorination processes may be used:

liquid phase or  vapor  phase.  This  document is concerned solely with

the aqueous spent catalyst waste  from the manufacture of the
     *Although no data on  the  corrosivity  of  spent antimony
catalyst is currently available,  the  Agency believes that
this waste stream may have a pH greater  than  12.5 and may
therefore be corrosive.  Under §§261.22  and 262.11,  generators
of this waste stream are responsible  for testing their wastes
in order to determine whether  their waste  is  corrosive.

-------
chlorofluoromethanes  that are produced via liquid phase

fluorination.*   The commercial products produced by this

segment  of  the  fluorocarbon industry include chlorotrifluoro-

methane  (CC1F3),  dichlorodifluoromethane (CCl2F2), trichloro-

fluoromethane  (CC13F) ,  and chlorodifluoromethane (CHC1F2).  Of

the five (5) companies  that manufacture these products, it is

believed that  two have  plants that use the liquid phase fluorina-

tion process and generate the waste stream of concern:
 (1)
 (2)
 (3)
(4)
(5)
                                                    Plant Size - Million
Company
DuPont
Allied Chemical
Kaiser Aluminum
& Chemical
Pennwalt
Racon, Inc.
Location Pounds Per Year
Antioch, CA
Deepwater, NJ
East Chicago, IN
** Louisville, KY
Matague, MI 500
Baton Rouge, LA
Danville, IL
Elizabeth, NJ
El Segundo, CA 190
Gramercey, LA 80
Calvert City, KY
Throughfare, NJ 60
** Wichita, KS 50
                                                       Total:  880
         (Source:  reference 31)
     *In  the vapor  phase fluorination process, a proprietary,
largely insoluble,  metallic catalyst is used in place of the
antimony  catalyst.   The vapor phase catalyst will tend to last
longer and have  lower  concentrations of the constituents of con-
cern than the  antimony catalyst used in liquid phase fluorination

    **These two  plants use liquid phase fluorination and generate
spent antimony chloride catalyst waste.
                                  -359-

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     The  chlorofluoromethanes in the product  family of concern are




manufactured  by fluorinating either carbon  tetrachloride (CCl^) or




chloroform  (CHC13)  using hydrogen fluoride  (HF)  and antimony penta-




chloride  (SbC^)  as a catalyst (see Figure  1) .   Carbon tetrachlorid*




is used as  a  starting material when trichlorofluoromethane  (CC13F),




dichlorodifluoromethane (CC12F2), and chlorotrifluoromethane (CClF3)



are the desired products.   (Tetrafluoromethane (CF4>  is  also  formed




as a co-product waste.)  Chloroform is used as feedstock when




chlorodifluoromethane (CHC1F2) and dichlorofluoromethane (CHC^F)




are the desired products.   (A small amount  of trichlorotrifluoroethi




(C2C13F3) and  trifluoromethane (CHF3> are formed as co-product wasti




In both processes,  the chlorine (Cl)  in the starting  materials is




successively  replaced with fluorine (F) .   For example, starting witl;




carbon tetrachloride  (CC14),  and  hydrogen fluoride, the  reactionist




carried out continuously to  produce the product mix desired, usually




a 50/50 blend  of  trichlorof luoromethane (CC^F) and dichlorodifluori




methane (CCl^F^)  as illustrated by the following equations:




          (1)  CC14 + HF	—> C13C-F + HC1




          (2)  C13C-F  + HF	> CC12F2 + HC1




     The main  features of  the process are shown in  Figure 1.




During the process, the antimony  pentachloride catalyst




(SbCl5) is reduced  to  antimony trichloride (SbCl^).   A slip
                                 K

-------
 I
IAJ
HEAT
         LIQUID PHASE
         FLUORINATION,
                                     CF4.CHF3. CCiFa

                                           VENT
                                                    *~ (TO OTHER PLANT USES)
                             HF SOL'N.
                           HEAT
                                                              HEAT
                                         ~l
                                                                                COOLING
  CRUDE
 PRODUCT
  + HCI
 ,RECYCLEV
CHLORO AND
  Cl ILORO-
  FLUORO
  ARBONS; ,
             CHLORO-
             CARDONS
  STILLATION FROM
LIQUID PHASE
FLUORINATION 2]
                                         CO
                              10- U-
                              1O /
                              ^klt•?/
                                         SEP.. NEUT.,
                                         OF PRODS. FROM
                                         LIQ.PH. FLUORIN.3
DECANT
 SPENT
CATALYST
                                                                           DISTILLATE
                                                                            CRUDE
                                                                           PRODUCT
                                                                                         CALCIUM
                                                                                         FLUORIDE
                                                  SILICA
                                                   GEL
                                                 WORN-OUT
                                                 MOLECULAF
                                                 1  SIEVE
                                                                                       *- TO LANDFILL
                                                                          TO HF PLANT
              Figure 1. FLOWSHEET FOR PRODUCTION OF FLUOROCARBONS
                      BY LIQUID PHASE FLUORINATION   (Baged on lnformatlon ln Refere'nce§ 29 and

-------
s
 cream is taken from  (F)  (see  Figure  1.)  to  remove an aliquot

portion of the spent  catalyst.  After washing,  the aqueous

spent catalyst wastes  (G) are  sent  to pits  (H)  where they are

either disposed of or  stored until  further  treatment.   (The

bulk of the antimony  trichloride  is recovered by  the catalyst

filter and dried and  reactivated  by chlorination  to  form  antimony

antimony pentachloride, which  is  recycled to the  fluorinator.)

Ill. Waste Composition, Generation  and Management

     Based on knowledge of process  chemistry and  best  engineering

judgment, the spent catalyst wastewater from liquid  phase

fluorination is expected  to contain significant concentrations

of the following constituents:

     (1)  Spent antimony  chloride catalyst not  recovered  by the

catalyst filter.  This spent catalyst wastewater will  contain

antimony trichloride  as a metallic ion and other antimony

compounds.

     (2)  Organic residues from feedstock materials.   These

will include either carbon tetrachloride or chloroform,

depending on which fluorocarbons are  being produced.

     Based on an estimated production of 100 million Ib/yr

(at the Dupont, Louisville,  and Racon plants),  it  is estimated
                               a
                             -362-

-------
that  30-60 thousand  Ibs.  of spent catalyst are generated annually

and will be contained  in  the spent catalyst wastewater.*  The

wastewater will  also  contain dissolved chloroform and carbon

tetrachloride in maximum  concentrations of about 0.8 gms/100 gms

of wastewater (based  on  these constituents water solubilities).

Undissolved chloroform and carbon tetrachloride will also be

entrained  in the wastewater unless the organic layer of the

aqueous wastestream  has  been separated prior to disposal.

These wastes are typically discharged to clay-lined pits

(26)  either for  disposal  or storage until further treatment.

IV.  Discussion  of Basis  for Listing

          A.  Hazards  Posed by Waste

          As noted above,  the waste components of concern are

antimony compounds,  carbon tetrachloride and/or chloroform.

Antimony compounds,  chloroform and carbon tetrachloride are

highly toxic.  Chloroform is a suspected carcinogen.  Carbon

tetrachloride is a very  potent carcinogen and has also been

shown to be teratogenic.
     *This  estimate  is  also based on data in "Fluorocarbon
Hydrogen Fluoride  Industry",  EPA-600/2-77-023 February 1977.
This  quantity is believed  significant, since large quantities
of hazardous waste constituents are available for environmental
release, increasing  the risk of exposure should mismanagement
occur.

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           B.   Exposure pathways  and migratory potential




           The  waste  constituents of concern may migrate from




improperly designed  or managed  disposal or storage sites and




contaminate ground and surface  waters.   Antimony trichloride




is extremely soluble (601.6  gm/100  gm H20 @ 0°C), chloroform




is highly  soluble  (2200 mg/1 @  25°C),  and carbon tetrachloride




is quite soluble (800  mg/1 @ 20°C).   Chloroform and carbon




tetrachloride  are  also highly volatile:  160 mm Hg @ 20°C and




91 mm Hg @ 20°C, respectively (water  has a volatility of about




17.5 mm Hg 
-------
are allowed  to  reach too high a level in the  pits,  the  pits




may overflow during  periods of heavy rain, releasing  their




contents  which  may  find their way into and contaminate




surface water.




     There  is also  a danger of migration into  the atmosphere




if the disposal sites are inadequately designed or  managed.




Since chloroform and carbon tetrachloride are  highly  volatile,




they may  escape into the air and present a hazard to  human




health via  an air inhalation pathway.  Thus,  these  hazardous




constituents could  migrate from disposal sites with inadequate




cover •




     Actual  damage  incidents confirm that these waste




constituents are mobile, persist and cause substantial  hazard



if improperly managed.  The migratory potential of  antimony




compounds is confirmed by the fact that groundwater contamina-




tion from disposed  antimony sludges has been  observed in an




Iowa incident (2).




     The  migratory  potential via an air pathway of  chloroform




and carbon  tetrachloride is confirmed by the  fact that  both




constituents have been identified as air contaminants in both




schools and  basements of homes located at Love Canal,




New York  ("Love Canal Public Health Bomb", A  Special  Report




to the Governor and  Legislature, New York State Department




of Health, 1978).   Chloroform has also migrated from  the

-------
Love Canal  site  into  surrounding  basement sumps, demonstrating




ability  to  migrate  through  soils.  (Id. )  Other incidents of




groundwater contamination due  to  improper storage and burial




of chloroform-containing wastes further  confirm chloroform's




ability  to  migrate  through  soils  and  contaminate groundwater.




In one incident, chloroform  was detected in  a well at




Dartmouth,  MA.   In  a  similar  incident at Woburn, MA., chloro-




form migrated  from  an underground  burial site to contaminate




a municipal well in the vicinity  (4).



     Antimony, since  it is an  elemental  metal,  will persist




indefinitely in  some  form in  the  environment.  Antimony




trichloride also reacts vigorously  with  moisture,  generating




heat and highly  irritating hydrogen chloride  gas.   The  antimony




component which  results from this  reaction can  also cause




systemic effects (27).




     The carbon  te trachloride  and  chloroform  in the waste  are




volatile and if  stored in an open  clay pit will tend to  slowly




evaporate.   Should  the chloroform  or  carbon  tetrachloride  reach




ground or surface water prior  to  evaporation, as both have been




known to do (see above and p.  12),  they  could travel significant




distances due  to their resistance  to  microbial  degradation




(3).  In addition,  carbon tetrachloride  and  chloroform  are




resistant to water  treatment and,  if  they are present in




drinking water sources, are likely  to appear  in drinking




water . ( ^ > ^8 )  The  incidents of the migration of these  harm-




ful constituents previously mentioned (see p, 9) demonstrate
                            -364-

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 that they may  persist long enough to reach and  cause  harm  to




 a receptor,  via  either a water (ground or surface) or  air




 pathway.



     C.   Health and Ecological Effects




         1.  Chloroform




              Health Effects - Chloroform has been recognized




 and regulated  as a  suspected carcinogen (32).   It is  also  con-




 sidered  toxic  [oral rat LD5o=800 mg/kg] and has been  evaluated




 by CAG as having substantial evidence of carcinogenicity.




 Tangential  evidence links human cancer epidemiology with chloro-




 form contamination  (6) of drinking water.  In laboratory studies,




 chloroform  induces  liver cancers in mice and causes kidney tumors




 in experimental  rats (7).  Chloroform was shown to induce  fetal




 toxicity  and skeletal malformation in rat embryos (8,9).   Chloro-




 form is  a priority  pollutant under Section 307(a) fo  the CWA.




 Additionaly  information on the adverse health effexts  of chloro-




 form can  be  found in Appendix A.



         Ecological Effects - The U.S. EPA has determined




 that chloroform  accumulates fourteen-fold in the edible




 portion of  fish  and shellfish (10).



         Regualtions - OSHA has set the time weighted average




at  50 ppm.




         Industrial Recognition of Hazard - Chlorofrom has




been given a toxic  hazard rating via oral routes by Sax in




Dangerous Properties of Industrial Materials.

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     2.   Carbon Tetrachlorlde




          Health Effects - Carbon  tetrachloride  is  a  very




potent carcinogen  (11) and has also  been  shown  t,o  be  teratogenic




in rats when inhaled at low concentrations  (12).   It  has  also




been evaluated by  GAG as having substantial  evidence  of carcino-




genicity.  Chronic effects of this chemical  on  the  human  central




nervous system have occurred following  inhalation  of  extremely




low concentrations (20 ppm), with  death at  1000  ppm (13).




Adverse effects of carbon tetrachloride on  liver and  kidney




function  (acute and often irreversible  hepatic  failure),  and on




respiratory and gastrointestinal tracts (14,15)  have also been




reported.  The toxic effects of carbon  tetrachloride  are  ampli-




fied by both the habitual and occasional  ingestion  of alcohol




(16).  Especially  sensitive to the toxic  effects of carbon




tetrachloride are  obese individuals  because  the  compound




accumulates in body fat (17).  It  also  causes harmful effects




in undernourished  humans, those suffering from pulmonary




diseases, gastric  ulcers, liver or kidney diseases, diabetes,




or glandular disturbances (18).   Carbon tetrachloride is  a




priority pollutant under Section 307(a) of  the CWA.   Additional




information and specific references  on  the  adverse  effects of




carbon tetrachloride can be found  in Appendix A.




          Ecological Effects - In  measurements made during the




National Organics Monitoring Survey  of  113  public  water systems




sampled, 11 of these systems had carbon tetrachloride at  levels




at or exceeding the recommended safe limit  (19).

-------
         Regulations -  OSHA  has  set a TWA for carbon




tetrachloride as 10 ppm.   Carbon  tetrachloride has been banned




under  the Hazardous Substances  Act by the Consumer Product




Safety Commission.




         Industrial Recognition  of Hazard - According to Sax,




Dangerous Properties of  Industrial Materials, carbon




tetrachloride is considered a high systemic poison through




ingestion and inhalation.




     3.   Antimony Compounds




         Health Effects  - Chronic antimony exposure has been




most  commonly associated  with pulmonary,  cardiovascular, (20)




dermal, and certain effects on  reproduction, (21) development,




(22)  and longevity (23,24).   Antimony trichloride [oral rat




LD5Q=525 mg/kg] and antimony  pentachloride [oral rat 1050=!,115




mg/kg] are considered toxic.  Adverse effects can be expected




from  the tri- and pentachlorides  based on acute toxicities of




the compounds to rats.   Additional information on the adverse




health effects of antimony compounds can  be found in Appendix A,




         Regulations -  OSHA  has  set the  TWA at 0.5 mg/rn3.




         Industrial Recognition  of Hazard - Sax, Dangerous




Properties of Industrial  Materials, lists antimony as highly




toxic via oral and inhalation routes.

-------
IV.  References
 1.  Jennings, A.F. and M.C. Schroeder, 1968.  Laboratory
     Evaluation of Selected Radioisotopes as Groundwater
     Tracers.  Water Resources Res. 4:829-838.

 2.  Iowa Department of Environmental Quality, South  Charles
     City, IA, 1977.

 3.  Zoetlman, B.C.J., et al. 1979.  Persistent Organic
     Pollutants in River Water and Ground Water of  the
     Netherlands. Presented at 3rd International Symposium
     on Aquatic Pollutants, Oct. 15-17, Jekyll Island, Ga.

 4.  Water Quality Issues in Massachusetts, Chemical
     Contamination, Special Legislative Commission  on Water
     Supply, Sept. 1979.
 5.  Naitonal Cancer Institute, 1976.  Report on Carcinogenesis
     Bioassay of Chloroform. National Technical Inf.  Serv. PB-
     264018.  Springfield, Virginia.

 6.  McCabe, L.J. 1975.  Association between trihalomethanes
     in drinking water (NORS data) and mortality.   Draft
     report.  U.S. Environmental Protection Agency.

 7.  U.S. EPA, 1979.  Trichloromethane (Chloroform), Hazard
     Profile, USEPA/ECAO, Cincinnati, Ohio, 1979.

 8.  Schwetz, B.A., et al. 1974.  Embroy and Tetotoxicity of
     Inhaled Chloroform in Rats.  Toxicol.  Appl. Pharmacol.
     28:442.

 9.  Thompson, D.J., et al. 1974.  Teratology Studies on
     Orally Administered Chloroform in the Rat and  Rabbit.
     Toxicol. Appl. Pharmacol.  29:348

10.  National Academy of Sciences.  1978a.  Non-fluorinated
     Halomethanes in the Environment, Environmental Studies
     Board, National Res. Council, Washington, D.C.

11.  National Cancer Institute, 1976.  Carcinogen Bioassay of
     Carbon Tetrachloride.

12.  Schwetz, B.A., B.K.K. Leong and P.J.  Gehring,  "Embroy-
     and Fetotoxicity of Inhaled Carbon Tetrachloride, 1,1-
     Dichloroethane and Methyl  Ethyl Ketone in Rats,"
     Toxicology and Applied Pharamacology, Vol. 28, No. 3,
     June 1974,  p. 452-464.
                              IX

-------
13.   Association of American* Pesticide Control Officials,
     Inc.   1966 ed., Pesticide  Chemical Official Compendium
     p. 198.

14.   Texas Medical Association,  Texas  Medicine,  Vol.  69,
     p.  86, 1973.

15.   Davis, Paul A. "Carbon  Tetrachloride as an  Industrial
     Hazard," The Journal  of  the American Medical Association.
     Vol. 103, July-Dec. 1934,  p.  962-966.

16.   U.S. EPA.  Carbon Tetrachloride:   Ambient Water  Quality
     Criteria Document,  1979.

17.   U.S. EPA. Water-related  Environmental  Fate  of 129 Priority
     Pollutants.  EPA-440/4-79-0296,  1979.

18.   Von Oettingen, W.F.,  the  Halogenated Hydrocarbons of
     Industrial and Toxicological  Importance.   In:  Elsevier
     Monographs on Toxic Agents, E. Browning,  Ed., 1964.

19.   U.S. EPA.  Determination  of Sources of Selected  Chemicals
     in Waters and Amounts from  These  Sources, 1977.

20.   Brieger, H. , et al. 1954.   Industrial  Antimony Poisoning.
     Ind. Med. Surg. 23:521.

21.   Belyaeva, A.P.  1967.   The  Effect of Antimony on
     Reproduction.  Gig. Truda.  Prof.  Zabel 11:32.

22.   Gross, Hal, 1955.   Toxicological  Study of Calcium
     Halophosphate Phosphors  and Antimony Trioxide in Acute
     and Chronic Toxicity  and  Some Pharmacological Aspects.
     Arch.  Indust. Health 11:473.

23.   Schroeder, H.A., 1970,  A  Sensible Look at Air Pollution
     by Metals.  Arch. Environ.  Health,  21:798.

24.   Schroeder, H.A., and  L.A.  Kraemer.   1974.  Cardiovascular
     Mortality, Municipal  Water, and  Corrosion.   Arch. Environ.
     Health.  28:303.

25.   Casarett and Doull, Toxicology,  p.  627, MacMillan, New York.

26.   Personal Communication, Richard  Deutsch,  E.I. Dupont de
     Nemours and Company, Louisville,  KY, December 1979.

27.   Sax, N. Irving, Dangerous  Properties of Industrial Materials.
     ^th Edition,  Litton Education Publishing, Inc.,  1975.

-------
28.  Dawson, English, and Petty, 1980.  Physical Chemical
     Properties of Hazardous Waste Constituents.

29.  Kirk-Othemer.  Encyclopedia of Chemical Technology. j[.
     John Wiley and Sons,Inc.,New York,1964.

30.  Lowenheim, F.A. and Moran,  M.K. Faith,  Keyes and Clark's
     Industrial Chemistry.  Fourth EdTJohn Wiley and Sons,~
     New York, 1975.

31.  SRI International, Directory of Chemical Producers -
     United States, Menlo Park,  California,  1979.

32.  CAG List of Carcinogens, April 22,  1980.

-------
                     LISTING BACKGROUND DOCUMENT

                      PHENOL/ACETONE PRODUCTION

             Distillation Bottom Tars from the Production of Phenol/
             Acetone from Cumene, (T)*

 I.   Summary of Basis for Listing

     Distillation bottom tars from the production of phenol/acetone from

 cumene contain toxic and potentially carcinogenic organic substances.

 These include phenol and polycyclic aromatic hydrocarbons (PAH) as

 the pollutants of concern.

     The Administrator has determined that the solid waste from phenol/

 acetone production may pose a substantial present or potential hazard

 to human health or the environment when improperly transported, treated,

 stored, disposed of or otherwise managed, and therefore should be sub-

 ject to appropriate management requirements under Subtitle C of RCRA.

 This conclusion is based on the following considerations:

     1.  Approximately 100-220 million pounds of these wastes containing
         phenol and polycyclic aromatic hydrocarbons from tars are
         generated per year at 11 plants in the United States.

     2.  Tars containing polycyclic aromatic hydrocarbons are demon-
         strated carcinogens and mutagens, as well as being toxic.
         Phenol is a suspect carcinogen and is toxic.

     3.  There is potential for mismanagement of the waste by leakage
         during transport or storage, by improper disposal allowing
         leaching, or by incomplete incinerator combustion.
*T&e Agency believes  that the listing description "distillation
 bottom tars"  is  more accurate than the originally proposed descrip-
 tion "heavy tars".   The stream listed in this document -does not, how-
 ever,  differ  from the one initially proposed.
                                  -373-

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      4.  The waste tars persist in the environment, and  phenol can spread
          rapidly in ground or surface water, posing a risk  of  exposure
          to these hazardous compounds to humans•

 II.   Sources of Waste and Typical Disposal Practices

      A.  Profile of the Industry

          Phenol/acetone is produced from cumene in eleven manufacturing

 plants scattered throughout nine states.   Production data from  1978

 have been reported to be 1,915 MM* Ib phenol and 1,171 MM Ib acetone^.

      B.  Manufacturing Process(13,14)

          There are two steps in the manufacturing process: (1) oxida-

 tion of cumene to cumene hydroperoxide, and (2) cleavage of the hydro-

 peroxide to form phenol and acetone.   (A  process flow chart is contained

 as Figure I below.)  Cumene hydroperoxide is  the first main reaction

 product when cumene is oxidized with air  at 130°C in an aqueous sodium

 carbonate medium.   The reaction mix is circulated to a vacuum column

 where unreacted cumene is  separated from  the  mix and a cumene hydrpper-

 oxide concentration of about 80% is obtained  in the  bottoms  product.

 Recovered cumene is recycled to  the reactor.  Any alpha methyl  styrene

 contained in the recovered  cumene  is  separated  by distillation  and

 sold  or incinerated.   However, not  all of  the alpha  methyl styrene

may be  separated at this point.  The  80%  cumene hydroperoxide cumene

mixture is  then reacted with 10-25% sulfuric  acid at 60°C and co-mixed

with  an inert  solvent  (such as benzene) to  extract organic material

from  the  aqueous acid.  The mixture is allowed  to settle.  The  acid

phase is  separated  out  and  recycled to the  process.  The  organic

layer remaining  is  neutralized with dilute  sodium hydroxide.   The
*MM - one million

-------
 resultant aqueous waste stream containing sodium sulfate,  sodium

 phenate, phenol, acetone, and sodium  stearate is separated and sent

 to wastewater treatment.   The crude,  neutralized organic  layer is

 then sent to a series of distillation columns where acetone,  cumene,

 phenol and acetophenone and the solvent are  recovered.   The first

 column separates a crude acetone product  overhead that  is  further

 purified by distillation.  The bottoms from  the  acetone distillation

 column pass through a water scrubber  to remove residual acetone and

 inorganic salts.  They then pass to a  series  of  columns where  the

 lower boiling hydrocarbons, solvents,  cumene,  and alphamethyl  styrene

 are successively removed, recovered and sold,  or recycled  or disposed.

 The bottoms from the last of the series of columns  is crude phenol.

 It goes to a crude phenol surge where  any remaining water  is settled

 out.  The crude phenol is refined in  the  next  distillation column

 from which the purified phenol is removed overhead.

     The bottoms from the phenol still contain phenol,  acetophenone,

 cumyl phenol, phenyl di-methyl carbinol,  higher  boiling phenolic

 compounds, and polymers.  This mixture may be  further distilled to

 recover the acetophenone.  The still bottoms  remaining  at  the  comple-

 tion of distillation are the waste streams of  concern in this  document.

     C.  Waste Generation and Management

         The distillation bottoms are  a tarry  solid in  physical
*The Agency is  not listing this wastewater stream at the present time,
 but solicits  data regarding waste composition and quantity, waste con-
 stituent  concentrations, and waste management practices.
                                  -375"-

-------
                             CUMENE
         RECYCLE
                            RECYCLE
                          Na2CO3
                 SODIUM STEARATE
         CUMENE
                           HYDROPEROXIDATION
                                REACTOR
                            AIR
   J
                                                       ACE1GNE
                                                    (TO PURIFICATION)
                                                  DILUTE
                                             SODIUM HYDROXIDE
                  Zh:
                                                  ofe
                                                    o
                                                      80%
 I
U)
N/
e^
 i
                 CUMENE HYDRO-
                   PEROXIDE
                      20%
                    CUMENE
         O

                                                                          SEPARATOR
                                                                       RECYCLE
                                                                                            cc
                                                            DC

                                                            UJ
                                                            z
                                                                         ACID
                                                                                               SEPARATOR
                                                                                                                ujO
                                                         OH
                                                           <2
                                                           O
                          WATER
                        cc
                            I
                           mO
                           r
oc
UJ
N

O
UJ
O
CC
O
   RECOVERED
    CUMENE
  (TO a -METHYL
STYRENE REMOVAL
   & RECYCLE)
                                        PHENOL
                                          UjQ
                                                       CRUDE
/PHENOL
 SURGE
                                                        to
                           cc
                           ui
                           H
                               I
    LIGHT ENDS
   (TO ACETONE
   PURIFICATION
  OR INCINERATION)
                                                                                                             ACETOPHENONE
D.CC
  D
  CL
                                                                                          PURIFIED
                                                                                          PHENOL
                                                                         BOTTOMS
                                                                         PHENOL. ACETOPHENONE. TARS

                                    Figure 1. FLOW DIAGRAM— PHENOL/ACETONE FROM CUMENE
                                            (MODIFIED FROM REFERENCE 13)
                                                                                                                      TARS

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                                  -X-
 form.  An EPA study  (Monsanto  Research Study Vol.  6) states that




 these wastes (i.e,   the  tars generated at  the bottom of the aceto-




 phenone distillation column) amount  to 50  - 110 g  tar/Kg (100-220




 lb tar/ton of phenol) of phenol  product.   The reported analysis and




 quantification breakdown of this residue is:




         Acetophenone            1.9  g/Kg (3.8 Ib/ton) phenol




         Phenol                  0.75  g/Kg  (1.5 Ib/ton) phenol




         Cumyl phenol            0.85  g/Kg  (1.7 Ib/ton) phenol




         Total tars              50 -  110 g/Kg (100-220 Ib/ton)  phenol




 The relative concentrations of the various waste constituents can




 thus be calculated from  these  production figures.




         As is shown above, the  waste tars are expected to  contain




 large concentrations of  polycyclic aromatic hydrocarbons for the




 following reasons.   Cumene (the  essential  feedstock  material) is




 itself an aromatic.  In  the successive steps  of hydroperoxidation




 and acid cleavage, the aromatic  ring  can open,  and polyaromatic ring




 structures formed.   These are  high-boiling substances and will  be




 found in the distillation bottom tars.




     The subject bottom  tar residue is  generally incinerated in combined




 organic wastes incinerators within plant limits.'2'   Plants  which do




 not have incinerators hire contract waste  haulers/landfillers.'2'




 III. Discussion of Basis for Listing




     A.   Hazards posed by the Wastes




         Based on 1977 product production  levels (p.  2),  the U.S.  prod-




uction of phenol/acetone from  cumene  generates  an estimated  100-220




million  Ibs  of the subject waste  annually.  The principal waste

-------
 components  of concern are phenol and tars.'-*)  Phenol is a suspect

 carcinogen  and is  toxic.   The tars are also suspect carcinogens due

 to  the  presence of polycyclic aromatic hydrocarbons (PAH).  These

 waste constituents are capable of migration from the waste to ground-

 water.   Phenol is  extremely soluble (67,000 ppm in water) (App B).

 PAH's contained in tars  are less subject  to migration,  but are highly

 persistent.   (See  p.  8 below.)  Actual damage incidents and field

 measurements  confirm  predictions that  waste constituents are capable

 of  migration,  mobility,  and persistence.   Phenol has been found in

 ppb and ppm concentrations  in leachate from sites such  as Love Canal,

 Story Chemical and La Bounty in  Charles City,  lowa.d^)   Levels some

 eight times above  the proposed water quality criteria were found in

 runoff  1.5 miles from a disposal site  near Byron,  Illinois.(13)*

 Residuals and  ppb  levels  of PAH's  have been found in leachate samples

 from the Wade  Site (Chester,  PA),  Reilly Tar and Chemical Co.  (St.

 Louis Park, MN), and  Kin-Buc Landfill  (Middlesex,  NJ)(13>.

         The primary  means  of disposal of  residue are landfilling or in-

 cineration,^'  prior  to which the  wastes are held temporarily in stor-

 age  containers.  Mismanagement by  leakage  during transport or storage,

 improper disposal  allowing  leaching, or incomplete incinerator com-

bustion may all realistically occur, with  resulting high potential to

cause serious human health  effects  and exposure  of animals in the area

through direct contact and  through  pollution of  surface'and  groundwater.


*The reference to  the  proposed water quality criteria in the text is
 not meant to use  the  proposed standard as  a regulatory  benchmark,
 but to indicate qualitatively that  phenol  may cause a  potential
 hazard if it migrates from the  waste  in small concentrations.

-------
 Thus, disposal in a landfill,  even if plastic-lined drums are used,




 represents a potential hazard  due to the leaching of toxic compounds




 if the landfill is improperly  designed or operated (i.e., drums




 corrode in the presence  of  even small amounts of water).  Landfills




 may, for example, be sited  in  areas with highly permeable soils,




 allowing leachate to migrate to groundwater.   Proper leachate control




 and monitoring may not be in current use, again facilitating leach-




 ate migration to groundwater,  and resulting migration to environmental




 receptors.  Storage prior to incineration or  off-site disposal could




 lead to similar hazards  as  improper landfilling, since improperly




 stored wastes are capable of leaking and contaminating soil and ground-




 water.




         Transport to off-site disposal sites by contract haulers also




 could result in mismanagement  and environmental insult.   Not only




 could these wastes be mishandled in transit,  but (absent of proper




 regulatory control) there is no assurance that these wastes will




 arrive at their intended destination.   As a result,  they may become




 available to do harm elsewhere.



         Mismanagement of incineration operations resulting from




 improper combustion conditions  related to temperature,  residence  time




 and mixing, could lead to the  release  into the atmosphere of vapors




 containing hazardous products  of  incomplete combustion,  including




 the waste constituents of concern.




     Should waste constituents  be released from the  management envi-




 ronment,  they are likely to persist  and reach environmental receptors,




as shown  by the data presented  on p. 6 above.  Degradative processes

-------
 do not  appear  to  appreciably reduce dangers of exposure.  Phenol

 biodegrades  at a  moderate rate in surface water and soil, but moves

 readily (App.  B.).  Even with persistence of only a few days, the

 rapid spreading of  phenol (due to its  very high solubility) could

 cause widespread  damage  of the ecosystem and contamination of potable

 water supplies.   A  phenol spill accident in Wisconsin resulted in the

 movement  of  phenol  into  groundwater and  contamination of well water

 for more  than  1000  ft. from the spill.   Phenol poisoning symptoms in

 humans  developed  from consumption of the well  water. (5)   Phenols

 were also implicated in  one of the  damage incidents mentioned in

 the principal  Congressional report  on  RCRA,  again indicating  their

 likelihood to  migrate and persist  if mismanaged.   (See H.  Rep. No.

 94-1491,  94th  Cong., 2nd  Sess.,  21.) High  local concentrations from

 indiscriminate dumping could  easily exceed  the  limit.  If  phenol

 were to migrate to  its limit  of  solubility,  concentration  levels

 would be  over  10,000  times  the  proposed human health water quality
criteria, indicating a potential chronic toxicity hazard

         Tar substances of the subject type generally contain polycyclic

aromatic hydrocarbons (PAH) which are classified as priority pollutants.

The PAH's are limited in movement, but persistent in the environment.
*The reference to the proposed water quality criteria in the text is
 not meant to use the proposed standard as a regulatory benchmark, but
 to indicate qualitativly that phenol may cause a substantial hazard
 if it migrates from the waste in small concentrations.

-------
 PAH's are tightly absorbed by fine  particles,  and so  are most likely

 associated with stream, river, and  lake  sediments.(15)   Aquatic animal

 and plant species living in these media  could  suffer  serious  adverse

 effects.  Furthermore, substantial  hazard  is associated  with  exposure

 to extremely small PAH concentrations  (concentrations of PAH  estimated

 to result in additional lifetime cancer  risks  of  1  in 100,000 one  9.7

 ng/l(15)) so that only minute concentrations need migrate to  create

 substantial harm.(15)*

     B.  Health and Ecological Effects

         1.  Tars

             Health Effects - Tars  containing  polycyclic aromatic  hydro-

 carbons (PAH) are suspected carcinogens  and mutagens, as well as being

 toxic.(15>

             Tars, in an oily waste containing petroleum lubricants,

 are very toxic chemicals.  They are absorbed into the body by inhala-

 tion, ingestion, and through the skin.   The oral  LD5Q in animals (dog,

 rabbit) is 600 mg/kgW.  Long term dermal exposure (1-43 years) to

 coal tar has been reported to cause malignant  tumors  on  hands,  face,

 and neck of briquette factory workers(7).  The U.S.E.P.A.  Cancer As-

 sessment Group has recommended 9.7  ng/1  total  PAH limit  for water  cri-

 teria.   The limit was based on animal test data and designed  to mini-

mize lifetime cancer risk at a rate below  1 in 100,000 (8).  The limit

might reasonably be expected to be  exceeded in cases  of -inadequate
     reference to the proposed water quality criteria  in  the  text
 is  not meant  to use the proposed standard as a regulatory  benchmark,
 but to indicate qualitatively that PAH's may cause a  potential hazard
 if  it migrates from the waste in small concentrations.

-------
 industrial  waste  disposal.   Polycyclic aromatic hydrocarbons are desig-




 nated  as  priority pollutants (acenaphthylene, anthracene, benzo(a)




 anthrocene,  benzo(a)  pyrene, benzofluoranthene, benzo perylene, chry-




 sene,  dibenzo(a,  h) anthracene,  fluorene,  indenopyrene, phenathrene,




 pyrene) under  section 307(a) of  the CWA.   Additional information and




 specific  references on the  adverse effects of PAH tars can be found in




 Appendix  A.




             Ecological Effects  - When small amounts of coal tar were




 mixed  with  food and fed to  ducks,  the  toxicologic effect was anemia




 and extensive  liver damage.(^)




             Regulations -  The NIOSH recommended standard for occupa-



 tional exposure to tar products  shall  be controlled so employees are




 not exposed  to substances at a concentration greater than 0.1 mg/m^ for




 a ten-hour work shift.   PAH's are  regulated  by  the Office of Water  and



 Waste  Management  of EPA under the  Clean Water Act.




             Industrial Recognition of Hazard - According to handbook




 used by industry  Sax,  Dangerous  Properties of Industrial Chemicals,



 petroleum tar is  a recognized carcinogen.




          2.  Phenol




             Health Effects  - NIOSH lists  phenol as a suspected carcin-



 ogen.  Prolonged  exposure to phenol vapors has  resulted in human diges-




 tive disturbances and  skin eruptions(10).  Damage  to liver and kidneys




from this exposure can  lead  to death.(10)  Exposure to phenol can re-




sult in chronic and acute poisoning.   It can be absorbed into the body




by inhalation, ingestion, or through the skin.   Phenol is very toxic




 [oral LD5Q in rats is  414 mg/kg]/11'   Additional  information and spe-

-------
                                 -X-
cific references on the  adverse effects of phenol can be found in Ap-




pendix A.



            Ecological  Effects - Concentrations of phenol as low as 79




mg/l have been  reported  to be toxic to freshwater minnows(12),




            Regulatory  Recognition of Hazard - OSHA has set a TLV for




phenol at 5  ppm.



            Industrial  Recognition of Hazard - Phenol is listed as a




dangerous disaster hazard, according to the handbook, Dangerous Proper-




ties  of  Industrial Chemicals(10).

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IV.  References




  1.  Synthetic Organic  Chemicals,  United States Production and Sales,




     1978.  U.S.  Trade  Commission,  Washington, DC




  2.  U.S. EPA, Survey Reports  on Atmospheric Emissions from the Petro-




     chemical Industry,  Volume III.   EPA 450/337/005C.  Research Tri-




     angle Park,  NC April  1974.



  3.  Stuewe, C. Emission Control Options for the Synthetic Organic Chem-




     icals Manufacturing Industry,  Trip  Report - Allied Chemical Cor-




     poration, Frankford,  PA,  EPA  Contract  No. 68-02-2577, March 1977.



  4.  U.S. EPA, 1979 Phenol: Ambient Water Quality Criteria (Draft)




  5.  Baker, E.L.  et al.  1978.  Phenol Poisoning Due to Contaminated




     Drinking Water.  Archives Env. Health,  Mar/Apr pp.  89-94.




  6.  NIOSH Registry of Toxic Effects of  Chemical Substances.   U.S.




     Dept. of health, Educatin,  and Welfare.   January 1979 p.  370.




  7.  Pierre, F.,  J. Robillard, and A. Mouchel:  Skin tumors in  workers



     exposed to coal tar.  Arch. Mai. Prof.  Med. Trav.  Secure.  Soc.




     26:475-82, 1965.




 8.  U.S. EPA, Cancer Assessment Group,  Derivation of the Water Quality



     Criterion for Polycyclic Aromatic Hydrocarbone,  July 1979.




 9.  Carlton, W. W. Experimental Coal Tar Poisoning in the White  Peking




     Duck.  Avian Dis 10:484-502,  1966.




10.  Sax, N. Dangerous Properties of Industrial Materials, 1975.   4th




     Ed. Van Nostrand Reinhold Co., New  York,  p. 1008.




11.  EPA Multimedia Environmental Goals  for  Environmental Assessment.




     Volume II.   Nov.  1977.  EPA-600/7-77-1366.

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                                 -X-
12.  National Academy  of  Sciences,  National Academy of Engineering,




    Water Quality  Criteria  1972.   A Report, National Academy of Sci-




    ences, Washington, DC EPA-R3-73-033 (1973).




13.  Lowenheim and  Koran,  Faith, Reyes, and Clarks's Industrial



    Chemicals,  4th ed.,  John Wiley and Sons, Inc., 1975




14.  Industrial  Process Profiles for Environmental Use: Chapter 6,




    The  Industrial Organic  Chemicals Industry.   Ralmond Liepins,  Forest



    Mixon, Charles Hudak, and Terry Parsons, Beb. 1977, EPA - 600/2-




    77-023f.




15.  Section 304(a)(l) Draft Water Quality Criteria Document, Poly-



    nuclear Aromatic  Hydrocarbons.




16.  Dawson, English and  Patty.  1980.   Physical Chemical Properties




    of Hazardous Waste Constituents.
                               -3*5--

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              HAZARDOUS  WASTE  BACKGROUND DOCUMENT
                 PHTHALIC  ANHYDRIDE PRODUCTION
     Distillation  light  ends  from the production of phthalic
     anhydride  from  naphthalene  (T).

     Distillation  bottoms  from  the production of phthalic
     anhydride  from  napthalene  (T)

     Distillation  light  ends  from the production of phthalic
     anhydride  from  ortho-xylene  (T).

     Distillation  bottoms  from  the production of phthalic
     anhydride  from  ortho-xylene  (T)
I.    Summary  of Basis  for  Listing

           The  production of  phthalic  anhydride  via vapor

phase  oxidation of  napthalene  or ortho-xylene results  in the

generation of  distillation residues which  contain carcinogens,

suspected  carcinogens  and  toxic organic  compounds.  The

residues of concern are the  light  ends and  bottoms which

result from the distillation step  in  which  crude  phthalic

anhydride  is  purified.  The  waste  constituents  of concern are

phthalic anhydride, maleic anhydride, napthoquinones,  quinones,

and miscellaneous organic compounds composed primarily of

polynuclear tarlike materials.

          The  Administrator  has determined  that these  distill-

ation residues are  solid wastes which may  pose  a  substantial

present or potential hazard  to human  health or  the environment
                     <
when improperly transported, treated, stored, disposed of or

otherwise managed, and therefore should  be  subject to  appro-

priate management requirements under  Subtitle C of RCRA.

This conclusion is based on  the following  considerations:

-------
 (1)  The  light  ends  from both processes contain phthalic
     anhydride  and maleic anhydride while the heavy ends from both
     processes  will  contain phthalic anhydride and miscellaneous
     organic  compounds composed principally of polynuclear tar-
     like materials.   The heavy bottoms from the napthalene-based
     process  will  contain napthoquinones and the heavy bottoms
     from the ortho-xylene-based process will contain quinones.

 (2)  Phthalic anhydride, maleic anhydride, napthoquinone,
     quinones and  the tars containing miscellaneous organic com-
     pounds  are organic toxicants.  Napthoquinone and maleic
     anhydride are  animal carcinogens and quinones are suspected
     carcinogens.   The tar-like waste constituents may also
     contain fused  ring components that are potential carcinogens.

 (3)  More than 16  million pounds of the constituents of
     concern will  be generated annually and require disposal as
     a result of phthalic anhydride production (assuming plants
     are  operating  at production capacity).

 (4)  Disposal of these wastes in improperly designed or
     operated landfills could result in substantial hazard via
     groundwater or  surface water exposure pathways.  Disposal by
     incineration,  if mismanaged, can result in serious air pollu-
     tion through  release of hazardous vapors, due to incomplete
     combustion.  Transportation of wastes off-site by contract
     haulers  increases the possibility of mismanagement.*

 II.  Sources  of Waste and Typical Disposal Practices

          A.   Industry Profile

              The  major use of phthalic anhydride is in the

 manufacture  of  plastics, plasticizers, paints and synthetic

 resins (3).   Producers of phthalic anhydride from ortho-xylene

 or napthalene and  the production capacities of these plants

 are listed in Table  1.  About 70% of industry capacity is

 ortho-xylene-based.
     *Although  no  data on the corrosivity of these waste
streams  are  currently available, the Agency believes that
phthalic  anhydride,  maleic anhydride and napthoquinone are
highly corrosive materials,  and that these waste streams may
therefore be  corrosive.   Under §§261.22 and 262.11, generators
of these  waste  streams are responsible for testing their
wastes in order to determine whether they are corrosive.
                            -SS7-

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          Table 1.  Producers of phthalic anhydride
Producer

Allied Chem. Corp.
  Specialty Chems. Div.
BASF Wyandotta Corp.
  Colors and Intermediate Group
    Intermediates Div.
Exxon Corp.
  Exxon Chem. Co., div.
    Exxon Chem. Co. U.S.A.

Koppers Co., Inc.
  Organic Materials Group
Monsanto Co.
  Monsanto Chem. Intermediates Co.
Location
El Segundo, Calif.
Kearny, N.J
Baton Rouge, La
Bridgeville, Pa

Cicero, 111.
  Annual  Capacity
(Millions of  Pounds)
         36


        150


        130


         90

        235
   Raw Material
Bridgeport, N.J,
Texas City, Tex.
         85
        150
o-xylene
o-xylene
o-xylene
Desulfurized coal-tar
naphthalene
o-xylene or
naphthalene
Petroleum naphthalene
o-xylene
Occidental Petroleum Corp.
  Hooker Chem. Corp., subsid.
    Hooker Chems. and Plastics Corp.
      subsid.
     Puerto Rico Chem. Co., subsid.
Standard Oil Co. of California
  Chevron Chem. Co., subsid.
    Petrochem. Div.
Stepan Chem. Co.
  Surfactant Dept.
United States Steel Corp.
  USS Chems., div.
Arecibo, P.R.
Richmond, Calif.

Millsdale, 111.

Neville Island, Pa
                                                          TOTAL
         87


         50

        100

        205


       1318
o-xylene
o-xylene

o-xylene

Desulfurized  coal  tar
naphthalene
 Source:   Reference  1

-------
 Manufacturing  Process




     phthalic  anhydride is manufactured by the vapor phase



 oxidation of ortho-xylene or napthalene (see Figures 1 and



 2 for flow diagrams).  The primary napthalene-based processes



 use fluidized  bed reactors.  All xylene-based processes incor-



 porate tubular fixed bed reactors.  Except for the reactors



 and catalyst handling and recovery facilities required for



 the fluid unit,  these vapor phase processes are similar (3).



 The two basic  reactions are as follows:
 Napthalene-based
                           ^--_TIL i
                           VzOs
    /\
    i
                                              0  -r 2HrO + 2CO2
    NAPHTHALENE
Ortho-xylene  based
PHTHALIC ANHYDRIDE
                            V2°5
                   +   3 0.
              0-xylene  Oxygen
                      3 H20
     Phthalic

     Anhydride (PAN)    Watei
     In  the  napthalene-based process,  napthalene is introduced



into a fluidized  bed  reactor near the  catalyst bed.  In the



xylene-based  process,  o-xylene is mixed with air and introduced



into a fixed  bed  tubular  reactor (in which the catalyst is con-



tained in  the  tubes).   Both  processes  typically use a vanadium




pentoxide  catalyst  (3).
                            -3<3tt-

-------
 i
V
                     NAPTHALENE.



                             AIR
                   DISTILLATION
                      COLUMN
                                                 FILTER
                                                     CATALYST
                                                     RECYCLE
                                                                    MULTIPLE
                                                                    SWITCH
                                                                  CONDENSERS
   1
 CRUDE
STORAGE
                                     FLUIDIZED
                                   BED REACTOR
                                            -ALIGHT ENDS
                                               PURIFIED
                                               PHTHALIC
                                              ANHYDRIDE
                                     BOTTOMS
             STORAGE
PRETREATMENT
TANK
                          Figure 1. PHTHALIC ANHYDRIDE PRODUCTION FROM NAPHTHALENE
                                  Source: Reference 3

-------
                                  H gure 2.    pntna i ic nnnyari
                                                                                 i~lV*fl  I I wilt v* • **i »w
AltZ.
                        S.TE-AU
                                                                                                          (Source:   reference 3)
                                                               MULTIPLE-
                                                                                                          MOT A.VJO COOU
                                                                                                                        O«U
                                                                          &4.1.T COOLfcrR
                                                                                                                11II
                                                         TO
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                                                                     VfrUT
                                                            Cg.UOEr
                                                           pe.ooucT
                                                                                                                                        (OOLTErU)
                                                                                        HEM EXCHANGER
                                                                                                                                                            -o

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    ~2
    J)
    2

    4
    0)
    tJ
    ^-

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    a
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                                                                                                       i. UUMtfetfeO btet^M^ A.OLC:
                                                                                                                         fHEr
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                                                                                                                                                       A

-------
       The  reactor  effluent  from  both processes will contain

phthalic anhydride, maleic anhydride*,  and  miscellaneous organ-

ics  (including  fused-ring  compounds).   The  ortho-xylene-based

process will generate  quinones  as  part  of  its  waste stream.  The

napthalene-based  process will generate  napthoquinones.(3)

     Crude  phthalic anhydride is  condensed  by  passing through

a  series of switch  condensers.  (The  condenser effluent gases

are  normally water  scrubbed  and/or  sent  to  an  incinerator

before being released  to the atmosphere.)   As  part  of the  puri-

fication process, the  crude  product is  first distilled  to

remove light ends.  The stripped  crude  phthalic anhydride  is

then distilled  in a second column  where  heavy  bottoms will

remain once the pure product is removed.(3)  These  distillation

residues are the  waste streams  of  concern.

II.  Waste Generation  and Management

     Some actual  plant data  describing  light ends and bottoms

generation are  available.  One  napthalene-based plant,  with a

published production capacity of  125 million pounds/year

phthalic anhydride, reported to dispose  of  58,000 pounds/month

light ends and 400,000 pounds/month bottoms.   This  plant had

these wastes hauled off-site by a  contractor O), probably for

disposal by landfill.

     A second napthalene-based  plant, with  nominal  capacity

of 90 million pounds/year, reported a combined total  waste
     *Process chemistry indicates that maleic  anhydride  will
be present in lower concentrations in the  effluent  generated
from ortho-xylene-based phthalic anhydride  production.

-------
  load of 45,000 pounds/month.  This  plant  utilized  an on-site

  landfill f°r solid waste disposal. (3)

      One plant using ortho-xylene  as a  raw  material  reported

  a light and heavy ends generation  rate  of 0.02  tons/ton of

  phthalic anhydride produced.  Another ortho-xylene plant

  reported that it generated 0.002 tons of  distillation bottoms

  per ton of phthalic anhydride produced.   Both  plants reported

  that these wastes are sent off-site  for disposal(3).

      Based on typical material balance  data(3)*, it  can fce

  estimated that the following amounts of the constituents of

  concern will be contained in the distillation  residues

  generated as a result of total phthalic anhydride  production

  (assuming all plants are operating  at production capacity):
Constituent
phthalic
anhydride
maleic
anhydride
Amount from xylene-based production
(million Ibs./yr.)
light ends heavy bottoms
>4.9 X).9
**
Amount from Napthalene-based
(million Ibs./yr.)
light ends heavy bottoms
>0.2 >2.5
>1.9
quinones                          ***

napthoquinone

misc. Org. (as tars)                >1.1
 *Estimates based on typical material  balance  data  for  average plants
 producing 130  million Ibs./yr of phthalic  anhydride  from  ortho-xylene
 and from napthalene.  Source: reference  3.
 **Process chemistry indicates that maleic  anhydride  will  be  present
 in lower concentrations in the light  ends  generated  from  phthalic
 anhydride production from ortho-xylene than from napthalene,  due to
 the nature of  the basic chemical reactions.
 ***Although no data are currently available on  the concentrations  of
 quinones in the bottoms from ortho-xylene-based production of phthalic
 anhydride,  process chemistry indicates that quinones will be  present
 in this  waste  stream, due to the oxidation of para-hydrogens  on the
 xylene molecules.

-------
           Disposal  practices for distillation residues will

vary.   Light  ends,  either  in a vapor or liquid state, are

usually incinerated.   However, as noted above, one plant

reported  having  this  waste,  along with the heavy ends, hauled

off-site  by a  contractorO) , probably to a landfill disposal site.

Distillation  bottoms  may also be incinerated,  but are typically

disposed  of in landfills either on or off-site.(3)

III. Discussion  of  Basis for Listing

           A»  Hazards  Posed  by the Waste

           As  noted  above,  distillation residues  (light ends

and heavy bottoms)  from phthalic anhydride production contain

the following  components as  they are discharged  from  the

plant distillation  units:

           Phthalic  anhydride
           Maleic  anhydride *>
           Quinones
           Napthoquinones
           Miscellaneous polynuclear  organic  compounds in
           distillation tars

     All  of the  above waste  constituents  are toxic.   Napthoquinone

and maleic anhydride  are demonstrated  carcinogens,  and quinones

are suspected  carcinogens.   The  miscellaneous  organic component

of this waste  has not been chemically  characterized but is composed

principally of tar-like materials  probably including  fused-ring

compounds  that are  potential  carcinogens.
     *Maleic anhydride, while an animal carcinogen,  hydrolizes
and photolyses rapidly to non-toxic maleic acid  and  thus  is not
expected to pose a hazard via a water or air  exposure  pathway.
It may, however, prove hazardous during waste  transport  to
off-site disposal.
                               -y-
                              -VH-

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     These  waste constituents appear capable  of migration,




 mobility  and  persistence if mismanaged, creating  the  potential




 for substantial  hazard in light of the dangers associated with




 contact with  the waste constituents.  As  previously noted,  dis-




 posal of  these wastes may be by incineration, on-site  landfilling




 or off-site disposal (probably a landfill).   Improper  design and




 management  of land disposal facilities could  lead  to  the release




 of hazardous  constituents and pose a hazard via a  groundwater




 exposure  pathway.  Some of the waste constituents  have  in fact




 proved capable of migration, mobility and persistence  via this




 pathway.   Various quinones have been identified in rivers,  wells,




 groundwater,  effluent from landfill leachate, and  in  finished




 drinking  water.   Phthalic anhydride has been  identified in




 finished  drinking water.(14)




     Napthaquinones and quinones are relatively soluble




 (about 200  mg/1), and thus may also migrate from  the matrix




 of the waste.




     Disposal by incineration, if mismanaged, can  present a




 health hazard via an air inhalation pathway.  Incomplete




 combustion  of the distillation residues from  phthalic  anhydride




 production  can result in the formation of various  phthalate




 esters which  will be released from the incinerator into the




air.  (These esters would be formed from the reaction  of




phthalic  acid with alcohols.) Certain phthalates  have  shown




mutagenic effects.  Phthalates have also been shown to  produce




teratogenic effects in rats.  Chronic toxicity includes toxic
                             -ViS-

-------
polyneuritis  in  workers exposed primarily to dibutyl^phthalate




(see Appendix A).   Further information on incinerator  emission




content  is  solicited  by the Agency.




     Contract hauling,  in  particular, presents an additional




potential for mismanagement in the transportation and  handling




operations.   Transportation of these wastes off-site,  if not




properly managed,  increases the likelihood of their causing harm




to human health  and the environment.   The mismanagement of wastes




during transportation thus may result in hazard to human health




and wildlife  through  direct exposure to the harmful constituents




listed above  (either  by direct contact with the waste or through




wind-carried  particulate matter and vapors).   Furthermore, absent




proper management  safeguards,  the  wastes might not reach the




designated  destination  at  all,  thus making them available to do




harm elsewhere.  It should be  noted that maleic anhydride, which




is not otherwise a constituent  of  concern due to  its lack of




persistence,  could prove hazardous during transport and handling,




since the possibility of Immediate exposure exists.




     The large quantity of waste generated and requiring disposal




is another  factor which increases  the likelihood  of exposure to




the harmful constituents in the waste via the various exposure




pathways.   Should the large amounts of waste  constituents exposed




to leaching activity  be released as a result  of mismanagement,




large areas of ground and  surface  waters may  be a'ffected.  Contam-




ination could also occur for long  periods of  time, since large




amounts of  pollutants are  available for  environmental loading.

-------
 Attenuative  capacity of the environment  surrounding  the  disposal




 facility could  also be reduced or used up  due  to  the  large  quan-




 tities of pollutants available over long periods  of  time.   All




 of these considerations, in the Agency's view,  strongly  support



 a hazardous  waste listing.




     B.   Health and Ecological Effects




          1.   Maleic Anhydride




               Health Effects - Maleic anhydride  can  produce



 cancers following subcutaneous injections  in rats.(5)  Maleic




 anhydride is also highly toxic [ORAL rat LD50  = 481 mg/Kg]  and




 is known to  cause acute irritation of the  eyes, skin  and upper




 respiratory  tract.   There is also evidence that this  compound may




 cause reproductive  impairment in male rats (4).   Additional infor-




 mation and specific references on the adverse  health  effects of



 maleic anhydride can be found in Appendix  A.




          Regulations - OSHA has set a standard for air  of




 TWA=0.25 ppm for an 8-hour day.




          Industrial Recognition of Hazard - In Sax,  Dangerous




 Properties of Industrial Materials, Maleic anhydride  is  desig-




 nated as highly toxic by ingestion, and also as an irritant.




 Fassett and  Irish in Industrial Hygiene and Toxicology state




 that  maleic  anhydride can produce severe eye and  skin burns.




 Plunkett,  in  his Handbook of Industrial Toxicology designates




maleic  anhydride as a causal agent of severe eye  and  skin




burns.
                             -yt-

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     2.   Phthalic Anhydride




          Health Effects  -  There  is  evidence  that  phthalic




anhydride may  act as  a  teratogen  in  chick embryos'6'.   It is




a potent irritant of  the  skin,  eyes,  and  upper  respiratory




tract.  Exposure has  been reported to  produce progressive




respiratory damage, including fibroses  of the lungs'°>9).




In addition, degeneration of liver,  kidney and  myocardium




occured^6).  There is also  evidence  that  this compound  may




cause  reproductive impairment in  male  rats'^'.   Additional




information and specific  references  on  the adverse  effects of




phthalic anhydride can  be found in Appendix A.




          Regulations - OSHA has  set a  TWA for  an  8-hour




exposure at 2  ppm.




          Industrial  Recognition  of  Hazard - Sax (Dangerous




Properties of  Industrial Materials)  lists  phthalic  anhydride




as having a moderate  toxic  hazard rating  via oral  routes.




     3.   Napthoquinone




          Health Effects -  Napthoquinone  has been  demonstrated



to be  a carcinogen when applied to the  skin of  test  animals^).




This chemical  is extremely  irritating  to  the skin,  mucous  mem-




branes and respiratory  tract.   It can  cause skin and pulmonary




sensitization  resulting in  asthmatic and  allergic  responses.




Changes in the blood  that reduce  its oxygen carrying capacity




have also been demonstrated following naphthoquinone exposure




which may develop into hemolytic  anemia.   Naphtoquinone is also




suspected of causing adverse reproductive  effects.   Additional

-------
 information  and  specific references on the adverse effects




 of napthoquinone can be found in Appendix A.




          Ecological Effects - Napthoquinone, at a concentration




 of 1.0 mg/1  will cause death within 3 hours for bluegill and



 trout, and 14  hours  for larval lamprey (10).




          Industrial Recognition of Hazard - Naphthoquinone




 is designated  in Saxfs Dangerous Properties of Industrial Materials



 as a moderately  toxic irritant to skin, eyes, and the upper




 respiratory  tract.




     4.    Quinone -  (p-Bezoquinone; 1,4-Benzoquinone)




          Health Effects - Quinones are highly toxic  [Oral rat




 LD50=120 mg/Kg].  Quinone has been reported to produce neo-




 plasms but upon  review by the International Agency for Research




 on Cancer it was determined that there was insufficient data to




 conclude that  it was a carcinogen.(H/  Upon exposure local




 changes  in humans may include discoloration, severe irritation,




 erythemia, swelling, and the formation of papules and vesicles.




 Prolonged contact may lead to necrosis. (12) Vapors condensing




 upon the eyes  are capable of inducing serious disturbances of




 vision.   Ulceration  of the cornea has resulted from one brief




 exposure to  a  high concentration of the vapor of quinone, as




 well as  from repeated exposures to moderately high concentra-




 tions . (12)




          Regulations - Threshold limit values have been




 established  in air for quinone in the United States at a




concentration  of  0.1 ppm,  and the U.S.S.R. at a concentration




of  0.01  ppm.(13)

-------
          Industrial Recognition  of  Hazard  -  Quinone is
designated in Sax's Dangerous Properties  of Industrial
Materials as highly toxic via oral and  inhalation  routes.
     5.   Tars
          Health Effects - Tar-like  material  containing quinones
and asphalt materials must be considered  suspect carcinogens
based on the data available on chemical tars.   (NIOSH  Criteria
for Recommended Standard for Occupational Exposure  to  Coal Tar
Products.)  Considering the highly reactive nature  of  maleic
anhydride, various toxic effects such as  skin and respiratory
tract irritation and sensitization would  also be expected from
tars containing this material.
          Industrial Recognition of Hazard - Sax's  Dangerous
Properties of Industrial Materials designates dehydrated and
liquid tars as highly toxic skin and respiratory irritants
when exposure is of long duration.  Tar dusts are designated
as moderate skin and eye irritants upon acute exposure.
                             -yS-
                            -WOO-

-------
 IV.  References


 1.  SRI  International,  Directory of Chemical Producers -
     United States, Menlo  Park,  California, 1979.

 2.  U.S. Environmental  Protection Agency, Source Assessment:
     Phthalic Anhydride  (Air Emissions), EPA-600/2076-032d ,
     Washington,  B.C., December,  1976.

 3.  U.S. Environmental  Protection Agency, Office of Air
     Quality Planning  and  Standards, Engineering and Cost
     Study of Air Pollution Control for the Petrochemical
     Industry, Volume  7;   Phthalic Anhydride Manufacture from
     Ortho-Xylene,  EPA-450/3-73-006g,  Research Triangle Park,
     North Carolina, July,  1975.   PB 245 277

 4.  Protsenko,  E.I.,  1970.  Gonadotropic Action of Phthalic
     'Anhydride.   Gig.  Sanit. 35;105.

 5.  NIOSH, Registry of  Toxic Effects  of Chemical Substances,
     1979. GPO.

 6.  Preliminary Environmental Hazard  Assessment of Chlorinated
     Naphthalenes,  Silicones, Flourocarbons, Benzenephlycarboxylates
     and  Chloraphearls,  Syracuse  University Research Corporation,
     EPA  Report  PB-238-074, 1973.

 7.  American Conference  of Governmental Industrial Hygienists,
     1971.  Documentation  of Threshold  Limit Values for
     Substances  in  Workroom Air.   3rd  Edition, pg.  263.

 8.  Markman and Savinkina, 1964.  The  Condition of the Lungs
     of Workers  in  Phthalic Anhydride  Production (an X-ray study).
     Kemerovo 35.

 9.  Plunkett, E.R., Handbook of  Industrial Toxicology, pg.  338.

10.  Applegate,  V.C.,  J.H.  Howell, and  A.E. Hall, Jr.  1957.
     Toxicity of  4,346 chemicals  to larval lampreys and
     fishes.  Department  of Interior,  Special Scientific
     Report Number  207.

11.  IARC Monographs on  the Evaluation  of Carcinogenic Risk
     of Chemicals  to Man,  Vol. 15. World Health Organization.
     (1977).

12.  Patty, F.A.  (editor).   Industrial  Hygien and Toxicology.
     Second Revised Edition.   Interscience Publishers.  New York
     1967.

-------
13.   Verschueren, Karel.  Handbook of Environmental Data on
     Organic Chemicals.  Van Nostrond Reinhild Co., New York.
     1977.

14.   Shackelford and Keith,  Frequency of Organic Compounds
     Identified in Water, EPA-600/4-76-062,  Environmental
     Research Laboratory, Athens, Ga.,  Dec.  '76.
                             -yf-

-------
                     LISTING BACKGROUND DOCUMENT

                       NITROBENZENE PRODUCTION

             Distillation  bottoms  from the production of nitrobenzene
             by  the nitration of benzene (T)

 I.    Summary of  Basis  for  Listing

      Distillation bottoms  from the production of purified nitrobenzene by

 the  nitration of benzene contain carcinogenic,  mutagenic,  and  toxic organic

 substances.  These include meta-dinitrobenzene and  2,4-dinitrotoluene as

 the  pollutants of concern.

      The Administrator has determined  that the distillation bottoms

 from nitrobenzene production by the nitration of benzene may pose a

 substantial present or potential hazard to human health  or the environ-

 ment when improperly transported,  treated, stored,  disposed of or

 otherwise mismanaged,  and  therefore should be subject  to appropriate

 management requirements under Subtitle C of RCRA..  This  conclusion

 is based on the  following  considerations:

      1)  The waste contains  meta-dinitrobenzene which  is extremely
         toxic and 2,4-dinitrotoluene,  a carcinogen and  mutagen.

      2)  The distillation  bottoms  from the distillation  of nitro-
         benzene are currently disposed of in drums in private land-
         fills.  However,  these drums  have a  limited  life-time and
         eventual rupture  is likely.   When this occurs,  the potential
         for ground water  contamination is high if  the landfill is
         not properly  designed or  operated.   Such nitrobenzene accidents
         have actually occurred.

     3)  The wastes in this  stream biodegrade very  slowly, thereby in-
         creasing the  chances  for  exposure and  posing  a  risk to humans.

 II.  Sources of Waste  and Typical  Disposal Practices

     A.  Profile of the Industry

         The major use of nitrobenzene  (^1^02)  (about  97%)

is as an intermediate  in the manufacture of aniline dyes.^

The balance  is  purified for  use  chiefly as a  solvent or  in the manufac-

-------
 ture  of Pharmaceuticals.   Nitrobenzene is manufactured in seven

 plants,  all  located in the eastern and southern regions of the

 U.S.   Table  1  lists these plants and their production capacities.
      TABLE  1.   Nitrobenzene  Producer Locations and Production Capacities^)
         Company
American Cyanamid  Co.
  Organic Chems Div.
E.I. DuPont  deNemours
 & Co., Inc.
  Chems. Dyes  and
  Pigments Dept.
  Indust. Chems. Dept.

First Mississippi  Corp,
 First Chem. Corp.,
 Subsid.
Mobay Chem.  Corp.
  Polyurethane Div.

Rubicon Chems., Inc.
  Facility
Bound Brook, NJ

Willow Island, WV

Beaumont, TX

Gibbstown, NJ
Pascagoula, MS
New Martinsville, WV

Geismar, LA
  1978
Production
 Capacity
   (Gg)*

    48

    33

   140

    90


   151


    61

    34
                                                      TOTAL
                               557**
*Gg = billion grams or 1000 metric tons  (mt).
 mt * 2,200 pounds.

**The 1978 U.S. production of nitrobenzene by  the  nitration of benzene
  was 260 (103) mt.<2'

-------
         The production of nitrobenzene has been fairly stable and can




 be  expected to  grow in relation to the growth in demand for aniline




 production that requires nitrobenzene as a feedstock.




     Based on a total  nitrobenzene production of 260 Gg/yr (286,000




 tons), the amount  of nitrobenzene subject to purification by distillation




 is  3% of production, or 7.8 Gg/yr (8580 tons).^22)




     B.  Manufacturing Process  (2D




         Nitrobenzene  is made by the direct nitration of benzene  using




 a sulfuric-nitric  acid mixture  (Fig. 1).   Commercial specification for




 the benzene raw material is:




             Benzene                       99.8%




             Toluene                        0.1% Maximum




             Saturated hydrocarbons          0.1% Maximum




             Thiophene                      1 ppm




         Benzene is  added to a  slight excess of the sulfuric-nitric




 acid mixture (53-60% sulfuric acid;  32-39% nitric acid;  8% water;




 a stochiometric  excess of nitric acid is  used)  slowly with agitation




 and heat removal.  The reaction residence time  is 2-4 hours.   At




 the end of this  time,  the mixture  is allowed to settle and the crude




 nitrobenzene is withdrawn;  the  separated,  mixed acids (mostly  sulfuric)




 are then sent to acid  recovery  and reused.   The small amount of




 organic material contained  in this stream is recovered from the acid




 concentration plant and  recycled.  The  crude nitrobenzene is first




washed with dilute sodium carbonate  solution to neutralize acids,




then distilled.   The nitrobenzene is  recovered  as an overhead  product.




Distillation  bottoms,  the  listed waste  stream,  are  then disposed  of




as waste.

-------
MIXED SULFURIC
NITRIC ACID
BENZENE

s~
C
~x
D
V

:
TO'ANILINE'
MANUFACTURE

.. •* HFC A MTFR < . '

i
SPENT MIXED
ACIDS TO
NazCOs
H2O NITROBENZENE
< -
WASHING
*" DECANTER
WASTE
WATER
C

1
ISTILLATIO
1
ORGANIC
WASTES
M
I

o

-------
       C.   Waste Generation and Management

           The  distillation bottoms are deemed to consist primarily of

  nitrobenzene,  meta-dinitrobenzene, and 2,4-dinitrotoluene.  Meta-

  dinitrobenzene and 2,4-dinitrotoluene are the waste constituents of

  concern.

           2,4-Dinitrotoluene is predicted to be present from the nitra-

  tion of  impurities in feedstock benzene, chiefly toluene (0.1%) and

  paraffinic hydrocarbons of the C$ to CQ range (0.1%).  (See p.  3,

  above).

           Meta-dinitrobenzene is predicted to result from the dinitra-

  tion of  benzene feedstock.  Based upon reaction and equilibrium chemis-

  try, it  is estimated that approximately 2-3% of the benzene feedstock

  will produce  dinitrobenzene.

           The  potential amounts of carcinogenic and/or toxic chemicals

  that will be  in the waste from the distillation of 7.8 Gg/yr of crude

  nitrobenzene  (p.  3) are estimated to be:

               meta-dinitrobenzene           156-195 mt/yr

               2,4-dinitrotoluene            	10 mt/yr

                        Total                166-205 mt/yr*

     The usual  disposal method of the subject distillation bottoms that

cannot be  recovered or used directly as a chemical intermediate is

disposal in drums in private landfills.^)
  *These estimates  assume  that  all contaminants will be separated from
   the product by distillation,  and consequently will all be present in
   the waste.

-------
III. Discussion of Basis for Listing

     A.  Hazards Posed by Waste

           As stated above, the constituents of  concern in this waste are

  meta-dinitrobenzene, an acutely toxic compound, and  2-4-dinitroben-

  zene, a carcinogen and mutagen.  Both of these constituents  are esti-

  mated to be present in substantial concentrations, and  to be  generated

  in large quantities annually.  This information itself  is sufficient

  to warrant hazardous waste listing, in light of the danger posed by

  the waste constituents*,  unless it can be demonstrated  that the waste

  constituents will not migrate and come in contact with  environmental

  receptors.

           No such assurance appears possible,  as both waste constituents

  are projected to have migratory potential and to be mobile and persistent

  in ground and surface water (App.  B),  so that they can  create a

  substantial hazard if disposal  landfills are  not properly designed

  and operated.   Thus,  meta-dinitrobenzene,  which is highly water

  soluble  (3000  ppm),  can migrate without  degradation through unsaturated

  sandy soils,  and resist degradation in ground and  surface waters

  (App.  B).** 2,4-Dinitrotoluene  is  also  highly  soluble  (2000 ppm in

 water),  and has  been  demonstrated  to migrate  through  unsaturated

 sandy  soil, and  to be  persistent in  the  environment.   (App  B).
 *For example, it is Agency policy  that  there is no safe exposure  level
 for carcinogens, i.e., a single dose  in any concentration being suffi-
 cient to cause cancer in some part of the  exposed population.

 **For example, meta-dinitrobenzene has  been demonstrated to be only
 slowly biodegradable in a synthetically prepared sewage effluent. ^>5) '
                                -WO*-

-------
         If the wastes are landfilled, even  in  plastic-lined drums, they

create a potential hazard.  All drums have a limited life  span,  for the

exterior metal corrodes in the presence of even small amounts of moisture

When this occurs the potential for groundwater  contamination is  high if

the landfill is not properly designed or operated.  It  should be noted

that all of the subject production facilities are located  in regions of

significant rainfall (Gulf Coast, NJ, WV), so that ample percolating

liquid is available for leachate formation.  (In any case, there is no

reason to believe that wastes will be containerized at  all, since,

absent Subtitle C regulation, wastes could be landfilled in a

variety of improper ways.)

         Nitrobenzenes have in fact migrated from landfills, persisted

in and contaminated groundwater in actual waste management practice.

Nitrobenzenes and other wastes from a Monsanto  Chemical dump migrated

into and caused contamination of groundwater in E. St.  Louis, Illinois.*

At the La Bounty dump along the Cedar River  in  Charles  City, Iowa,

130,000 kg of nitrobenzenes were disposed of along with several

other chemicals.  Groundwater collected between the La  Bounty dump

and the Cedar River contained considerable concentrations  of the

chemicals including nitrobenzenes.*

         These waste constituents, therefore, are capable  of migrating

from improperly designed and operated landfills, and reaching environ-

mental receptors.  Drumming of these wastes, as occurs  in  actual prac-
*OSW Hazardous Waste Division, Hazardous Waste Incidents, Unpublished,
Open File,  1978.

-------
 tice,  is  not  an  adequate precaution as demonstrated by the Love




 Canal  incident,  among  others.




     These wastes may  also  create a substantial hazard via a sur-




 face water exposure  pathway.   Should the disposal site be flooded and




 the wastes come  into contact with the surface water, the nitrobenzenes




 and nitrotoluenes will resist  evaporation due to their weight relative




 to air and their low vapor  pressure.   As they are also soluble and




 only slowly degradable (App. B),  they have the potential for wide-




 spread exposure  should surface waters become  contaminated.




     B.   Health  and  Ecological Effects




          1.   Meta-dinitrobenzene




              Health  Effects -  Meta-dinitrobenzene is extremely toxic




 [LD5Q  rat 30mg/Kg.]  acting  as  a potent methemoglobin-forming agent,




 i.e.,  an  agent that  reduces the oxygen-carrying capacity of  the blood,




 a condition that can rapidly lead to  death.(?)   Meta-dinitrobenzene




 can also  cause liver damage, serious  visual disturbances, and severe




 anemia, as well  as a variety of central  nervous system and gastrointes-




 tinal  symptoms.(?)(8)  Meta-dinitrobenzene can  be stored in  body fat.




Exposure  to sunlight or  ingestion of  alcohol  may potentiate  or  in-




 crease  the adverse effects of  poisoning.(?)   Meta-dinitrobenzene




 is designated as a priority pollutant  under Section  307(a) of the




CWA.  Additional information on the adverse effects  of meta-dinitro-




benzene can be found in Appendix  A.




             Ecological Effects -  Concentrations of from 2  to  12 mg/1




of unspecified isomers of dinitrobenzene  have been reported  lethal to




fish.^9'^-10'   Meta-dinitrobenzene has  been shown to  inhibt photosyn-



thesis  in algae.  (ID







                                  ft

-------
             Regulatory Recognition of Hazard - OSHA has set the TWA




for dinitrobenzene at 0.15 ppm.  Dinitrobenzene is regulated by the




Office of Water and Waste Management of EPA under the Clean Water Act,




Section 311.   Technical assistance has been requested to obtain data




on environmental effects, high-volume production, and spill reports.




             Industrial Recognition of Hazard - According to handbooks




used by industry such as, Sax, Dangerous Properties of Industrial




Chemicals, (12) the oral toxic hazard rating is high for dinitro-




benzene.  When heated, it is dangerous, decomposing to emit toxic




fumes; it is  also an explosion hazard.  According to Plunkett,




Handbook of Industrial Toxicology, (8)  M-dinitrobenzene is extremely




toxic by oral, inhalation, and percutaneous routes.  According to




Patty, Industrial Toxicology, '^) m-dinitrobenzene is highly toxic.




     2.  2,4-Dinitrotoluene




         Health Effects This compound has been shown to be a



carcinogen^) (15) an
-------
         Ecological Effects - An aquatic toxicity for 2,4-dinitrotoluene




of 10-100 ppm has been established^20).




         Regulatory Recognition of Hazard OSHA has set the TWA for




2,4-dinitrotoluene in air at 1500 micro-g/m? (skin).




         Industrial Recognition of Hazard - According to handbooks  used




by industry, such as Sax, Dangerous Properties of Industrial teterials(12)




the oral toxic hazard rating for 2,4-dinitrotoluene is very high.

-------
IV.  References




 1.  Gruber, G.I. Assessment of  Industrial  Hazardous  Waste  Practices,




    Organic Chemicals, Pesticides,  and  Explosive  Industries.  EPA/530/




    SW-118C TRW Systems  Group,  Redondo  Beach,  California,  January, 1976.




 2.  Directory of Chemical  Producers,  1979.   Stanford Research Institute.




 3.  Recommended tethods  of Reduction, Neutralization, Recovery, or Dis-




    posal of Hazardous Wastes,  Volume XI:  Industrial and Mmicipal Dis-




    posal Candidate Waste  Stream  Constituent Profile Reports, Organic




    Compounds (continued)  EPA 670/2-73-053-k,  TRW Systems  Group, August



    1973.




 4.  Bernhard, E.L. and G.R.  Campbell, "The Effects of Chlorination on




    Selected Organic Chemicals,"  U.S. Environmental  Protection Agency,




    PB-211-160, NTIS, Springfield, Virginia, 1972.




 5.  G. Bringmann and R. Kuehn,  "Biological Decomposition of Nitroto-



    luenes and Nitrobenzenes by Azotobacter agilis," Gesundh. Ing.




    92(9):273-276 1971.




 6.  L.A. Allen, "the Effect of Nitro-Compounds and Some Other Sub-




    stances on Production of Hydrogen Sulphide by Sulphate-Reducing




    Bacteria in Sewage," Proc. Soc. Appl. Bact. (2):26-38,  1949.




 7.  U.S. EPA,  1976, Investigation of Selected Potential Environmental




    Contaminants:  Nitroaromatics.




8.  Plunkett,  E.R., Handbook of Industrial Toxicology.




9.  JfcKee and  Wolf..  1963.   Water Quality Criteria.  The Resource Agen-




    cy of California State  Water Quality Control Board Publication




    No. 3-4.

-------
10.   teinck,  et  al.  1956.   Industrial Waste Water,  2nd Edition, Gustay




      fisher Verlag Stugart,  p.  536.




11.   Howard,  et  al •  1976.   Investigation of Selected Potential Environ-




      mental Contaminants;  Nitroaromatics,  Syracuse  Research Corporation,




      TR  76-573.




12.   Sax, N.  Irving, Dangerous  Properties  of Industrial teterials, Fourth




      Edition,  New York, Van  Nostrant  Reinhold Company,  1975.




13.   Patty, Frank A. Industrial Hygiene  and Toxicology.  G.D.  Clayton and




      F.E. Clayton, (Eds.)  Third Revision.  NY,  Wiley  Publications, 1978.




14.   Purchase, I.F.H., et  al.   An Evaluation of 6 Short-Term Tests for




      Detecting Organic Chemical Carcinogens.   Br. J.  Cancer  37;873-958




      (1978).




15.   National Cancer Institute. Bioassay  of  2,4-dinitrotoluene for




      Possible Carcinogenicity.  U.S.  Department of Health, Education




      and Welfare, Public Health Service, National Institute  of Health,




      1978.




16.   Won, W.D., et al.  Mitagenicity  Studies  on 2,4-dinitrotoluene.



      Mitation Research 3jh387 (1976).




17.   Hodgson, J.R., et al.   Mitagenicity Studies on 2,4-dinitrotoluene.




      Mitation Research ^:387 (1976).




18.   Friedlander, A. 1900.  On  the clinical picture of  poisoning with




      benzene and toluene derivatives with  special reference  to the so-




      called anilinism.  Neurol. Centrlbl.  19; 155.




19.   teGee, L.C., et al.  1942.  tetabolic disturbances'in workers ex-




     posed to dinitrotoluene.   Am. Jour. Dig. Pis. 9; 329.




20.  NIOSH, Registry of Toxic Effects of Chemical Substances, 1976 Edition.

-------
21.  Lowenheim and fcbran, Faith, Keyes and Clark*s Industrial




    Chemicals, 4th ed., New York, 1975.




22.  Synthetic Organic Chemicals U.S. Production and Sale, U.S




    International Tariff Commission, 1978.

-------
                  LISTING BACKGROUND DOCUMENT

               METHYL  ETHYL PYRIDINE PRODUCTION
       Stripping  Still  Tails from the Production of Methyl
       Ethyl Pyridine   (T)
I.  SUMMARY OF BASIS  FOR  LISTING

     This waste  consists  of the stripping still  tails generated

in the production  of  methyl ethyl pyridine.  The  waste is

expected to contain  toxic organic materials — paraldehyde,

pyridine(s), and picoline(s)  -- based on a review of  the

process involved.  The  Administrator has determined  that

this is a solid  waste which may pose a substantial  present  or

potential hazard to  human health or the environment  when impro-

perly transported, treated, stored, disposed of or  otherwise

managed, and therefore  should be subject to management controls

under Subtitle C of RCRA.   This conclusion is based  on the

following considerations:

     1)  The waste is expected to contain the following
         toxic organic  chemicals:   paraldehyde, pyridines,
         and picolines.   Paraldehyde is included  on  the
         NIOSH list  of  suspected carcinogens.  The  constit-
         uents also  exhibit human and aquatic toxicity.

     2)  The constituents  in  the waste could migrate  to
         groundwater  by leaching from improperly  managed
         lagoons or  landfills, due to their high  solubilities.
         Release to  the atmosphere is also probable  due  to  the
         high volatility  of these compounds;  volatization
         poses the risk of direct inhalation of these toxic
         organic chemicals.

     3)  An appreciable amount of the waste is produced
         (calculated  to be 720 metric tons in 1973).   Approxi-
         mately  75%  of  the total generated is paraldehyde.

-------
II.  INDUSTRY  AND PROCESS DESCRIPTION
    A.  Profile of the Industry
         Methyl ethyl pyridine  (MEP)  is  a cyclic intermediate
    produced  commercially by  synthesis.   Only limited infor-
    mation is available from  which  to  draw an industry
    profile.   A 1976 study^1) indicated  that  the 1973
    U.S. production capacity  was  about 18,000 metric tons
    (40 million pounds).  A more  recent  statistical review
    of the cyclic intermediates  industry^)  does not include
    methyl ethyl pyridine among  the cyclic intermediates
    for which production and  sales  data  are available.
The TRW study
                            identified  Union Carbide
    as a major producer of  2-me thyl-5-e t hyl pyridine
    (Diagram I, p. 3).  This  appears  to be the isomer of
    major commercial  impo r tanc e . ( -*- » •* )   Koppers Company,
    Inc., Nepara Chemical  Company,  Inc.,  and Reilly Tar  and
    Chemical were cited as  other  producers.  Chem Sources-USA,
    1980 edition(^) lists RIT-Chem  Company, Inc.  as a
    producer of 4-methyl-3 - ethyl  pryridine.
                                          '   (II )j
        No  important commercial  end  uses  of  MEP have been
    identified.(3,5)  2-Methyl-5-ethyl  pyridine is a raw
    material  used for the industrial  production of
    nicotinic acid (3-pyridien-3-carboxylic  acid)  by

                            -X-
                           -MH-

-------
     nitric  acid  oxidation and decarboxylation.^'   It is

     also a  precursor  for 2-methyl-5-vinyl pyridine (MVP),

     which is  used  in  acrylic fiber manufacture  and in some

     styrene/butadine  polymer formulations.  Producers

     of MEP  end products  identified in Chem Sources-USA^)

     are Vitamins,  Inc.  (nicotinic acid) and Philips  Chemical

     Company  (methyl vinyl pyridine).
     B .  Manufacturing  Process

          Methyl  ethyl  pyridine is among the pyridine  bases

     that are  produced  commercially by synthesis  (1,3,5),

     rather  than  by  isolation from coal tar.

          Figure  1 is  the  process diagram for MEP  production.

     In the  initial  steps  of  MEP  production, paraldehyde  is

     usually generated  at  the plant site by reacting acetalde-

     hyde with  sulfuric  acid  to produce crude paraldehyde.

     A portion  of the  crude  paraldehyde is used in the

     production of MEP,  while the remaining portion is used

     for the production  of refined paraldehyde.   The batch

     still tails  from  paraldehyde production are  sent  to  a

     wastewater treatment  sytem.*
*This waste stream is  sent,  along  with the listed'waste  stream
 to a lagoon.  At this  time,  data  is  not available on the
 constituents in this  waste  stream.   However, since  the  waste
 stream is mixed with  the  listed  waste stream, the resulting
 mixture is defined by  the Agency  as  being a hazardous waste,
 unless generators demonstrate  otherwise.
                             -HIS--

-------
      BASIS:   1  KG METHYL-ETHYL PYRIDINE
1.94
I.ULIII UC.
«»-•
1C ACIO~*~
REACTOR
t

1
Ajft0.rjJA
BKD'itRTf

»
AMMONIA
.«»j 	 ,

REFRIGERATION


• >

RECYCLt 1.94

AWOJ11A
SlBimNG
STILL
,


BATCH STILL


REFINED PARALHIHYOE
[ - i. pM
»
	 ;—*- ^ STILL TAILS -*-
\ f
CRUDE PARALDEHY\T_
-01 	


\
REAfTnn

'
s
V
.. J
\ \
•* '' PREHEATER

} AMMONIA 0.3]
ACETIC AC 10
                                                                                                               Aqueous
                                              WASTE HATER
                                              TREATMENT
                                                                                                               SLUDGE
               BATCH STILL
          REFINED *
         HEP  1.0
                METRES I PUSS TO
                       Sl  O.O1
IITEH).«J
/




WATER LAYER
STRIPPING
sim

v
LIGHTS
PROCE!
WATER
                                                                                 FOR Fur,; HER .
                                              RECOVERED BENZENE
                          .STILL TAILS  0.4^
BENZENE
                                                             BATCH STILL5
                                                             PICOLINES  0.044
                        —~-LIGHTS TO
                         STORAGE  0.3-1

                              AMMONIA
                             PYRIOINI.5
                          .   PICOLINIS
       PHENOL  0.0000003
 SULFUR1C ACID  0.003
    CHLORIDES  0.00015
SOLUBLE ABIDES  0.000004

     ACETATES  0.0025
   PARALDEHYOE  0.03
    PICOLINES  0,0025
                                                                                                                         VATER

                                                                                                                        LWIO DISPOSAL'
        Source:   Reference  1.
                                                                                               WASTE WATER TREATMENT

                                                                                            SLUCC-t |     |  AQUT013
                                              I    l
                                                                                            . U/IO
                                                                                           DISPOSAL
                                                  WATER
        Figure   1:      Pyridines  (2-Methy1»  5-Ethyl  Pyridine  and  ot-Picoline) Manufacture,

-------
           After  the production of  the  crude paraldehyde,

     2-methyl-5-ethyl pyridine is  synthesized  in high yield

     from  the  liquid phase reaction  of  paraldehyde and

     ammonia acetate, aluminum ozide,  ammonium fluoride

     or  cobalt  chloride cayalyst.(3)    This process which takes

     place  in  the  reactor is shown by  equation (!)•'


                                       Odz CV\j
                                                             CO.)
          As  shown  in the equation, an  identified  by-product

     in  the reaction is 2-methyl pyridine  ( <=C -picoline).

     The resulting  process  fluid is then transferred  to  an

     ammonia  stripping  still for ammonia recovery.   The

     remaining  fraction goes to a cleaner  (decanter).   The

     cleaned  MEP  fraction residue is further  refined  by  a

     batch still.*   The residue from the cleaner is  processed

     by a water layer stripping still.  The  stripping  still

     tails from this  process are labelled  (1)  in Figure  1.
III.  WASTE GENERATION  AND  MANAGEMENT

     The stripping  still  tails are generated at  a  rate  of

approximately 0.04  Kg/Kg  of refined MFP.C1) This  amounts
*The process effluent  stream indicated as "MEP  residues"  from
 the batch still is  not  included in the waste  listing  because
 data is not yet available  on the constitut ents  in  this  waste
 s tr earn .

                              -sf-

                             - <-\2O-

-------
 to 720  metric  tons of waste  in  1973.


     The  TRW  StudyC1) identifies  the  following as the major


 contaminants  in  the listed waste  stream:






          paraldehyde                 0.03 Kg/Kg MSP


          sulfuric acid               0.003 Kg/Kg MEP


          pryidines and picolines     0.0025 Kg/Kg MEP


          soluble acetates            0.0025 Kg/Kg MEP


          phenol                      0.0000003 Kg/Kg MEP*
This data  indicates that approximately  75 percent of the


total waste  accounted for is paraldehyde.


     According  to  the 1976 study,  industry practice is to


manage the process effluent waste  stream by sending it to


wastewater treatment.  As part of  the  wastewater treatment


system,  the  waste  is most likely stored/treated in lagoons.
               «

IV.  HAZARDOUS  PROPERTIES OF THE WASTE


     The waste  is  considered to pose  a  potential hazard to


human health or the environment because of the presence of



toxic organics .


     All of  these  waste constituents  are acutely or chroni-


cally toxic,  and  paraldehyde is included in the NIOSH list



of suspect carcinogens (see pp. 11-16  for further health
*Phenol, while  a  hazardous waste  constituent,  is not deemed

 to be present  in  sufficient concentration  to  be of regulatory

 concern.
                            -Mai-

-------
effects).   The  waste constituents are  present  in the wastes


in high concentrations  (see p. 5), and are  also  generated in


fairly substantial  quantities annually, so  that  there is a


greater possibility of  the hazardous constituents  reaching


environmental  receptors should improper management  occur.


Exposure should  also take place over longer  periods  of  time,


since substantial  quantities of pollutants  are available for


environmental  loading.   Thus, the Agency would require  some


assurance  that  waste components will not migrate and  persist

to warrant  a decision not to list this waste stream.  No


such assurance  appears  possible.

     Each  of the  identified waste constituents has  extremely


high water  solubility (indeed, pyridene and 2-picoline  are

infinitely  water-soluble).   (See  Table 1.)


     As a  result  of  this  high constituent  solubility, this

waste are  likely  to  leach harmful constituents even under

relatively  mild  environmental conditions,  and to be highly


mobile in  ground  and surface waters* (App. B).   If  these

wastes are  exposed  to more  acidic environments,  such  as

environments subject to  acidic rainfall,  the potential  for


waste migration  increases.   (See  Table 1.)


     Current waste  management practices involve  waste water

treatment  in lagoons.   The  potential for  environmental
^Mobility through  soil  is  expected to be high in light of
 these waste constituents'  high  solubilities.  Further,
 disposal could occur in areas  with permeable soils,  so
 that mobility of  waste constituents would not be
 substantially affected.

                              -y-

-------
                           Table  1

    Physical/Chemical  Properties of  Organics Identified
                  in  Stripping  Still  Tailsa
Compound:

Structure :
paraldehyde
      CH3
pyridine
2-picoli,neb
                                                          II c
                                                              rf,j
                                                             xk N ,
Formula :
NW:
3 • P • j  « •

Vp> mm,  25°C :

Sat'd. vapor<*
conc'n,  25°C,  g/m3

Water  solubility6:

Octanol/wa ter*
partition  co-
efficient :
Acid  dissociation
cons tant &:
C6H1203
132
128
10
71
V
2 .8(est .)
C5H5M
79
115
22
93
inf .
4 .5
                                     C6H7N

                                     93

                                     129(143)

                                     10

                                     50


                                     v (inf,)

                                     13
                    5.2
                 5.9
                 (5.7;  6.0)
a Except as noted,  data are from  Weast, Ref. 6

b Most data are  available for 2-picoline.   This is  also  the
  identified  by-product of MEP  production and therefore  the-
  isomer most  likely present in the  waste.  Values  in  paren-
  theses are  for 3- and 4-picoline  which have the  same  B.P.
  solubility

c Calculated  from data in Weast(6)  pD-123.
                                              yp     MW
  Calculated  from vapor pressure  data:  g/m3  760 x  RT

-------
                     Table 1 (Continued)

e v = very soluble (probably > 1 % )
  inf = infinitely soluble
  s = soluble (probably > 0.1%)

f Source, Reference 7.

& For pyridine and picoline, value indicated is pka of  the
  conjugate acid.  Source, References 8,9.
                             -x-

-------
contamination exists from improper lagooning, or  through

subsequent  improper disposal  of  wastewater treatment  sludges.

Thus,  improperly designed or  managed lagoons -  for  example,

those  located in areas with permeable soils, or those  lacking

leachate control features --  could fail to prevent  leachate

migration into the environment  in light of the  solubility  of

the waste constituents, and the  large amounts of  available

percolating liquid in the lagoon.  Exposure via a surface

water  pathway is also possible  if lagoons are constructed

without  proper flood control  or  wash out measures

     If  waste sludges are improperly landfilled they  present

a similar potential hazard.   Lack of leachate control  or improper

siting thus could lead to waste  migration.

     Another pathway of_concern  is through airborne exposure

to these volatile organics  present in the stripping still

tails.  Some physical/ ch emical  properties of the  organic
                                              *
species  that are relevant to  their potential for  adverse

environmental impact are indicated in Table 1.  Each  of  the

organic  species listed is highly volatile, with vapor  pressures

corresponding to saturation concentrations in the range  of

grams  per cubic meter at 25°C  (1 ppm (v/v) corresponds  to

about  1  milligram per cubic meter).   Pyridine and 2-picoline

are particularly volatile.  Substantial fractions of  contam-

inants present in the waste could thus volatilize to  the

atmosphere  from lagoons and landfills that are  not  properly

designed  and operated, increasing the risk of inhalation of

waste  contaminants.
                             -I-12.M-

-------
     Once released  from the matrix of the waste  these constituents




can persist and  reach  environmental receptors.   Available dat-a




(21) indicates  that  biodegradation is the chief  degradation




mechanism with  respect  of  paraldehyde and pyridine.   Thus,




these constituents  could persist in the abiotic  conditions  of




an aquifer similarly,  persistence in air may occur.
V.  HEALTH AND ENVIRONMENTAL EFFECTS




     There is substantial  evidence concerning the  toxic




effects of the organic  species of concern. Table 2  summarizes




some data from the Registry  of Toxic Effects of Chemical




Subs tances.C11) Paraldehyde  is included in the NIOSH  List




of Suspected  Carcinogens.'-^)
     1.  Parald ehyde




          Paraldehyde  exhibits  moderate toxicity when  injested




     and low toxicity  when  applied  to the skin.(13)  Signs and




     symptoms of paraldehyde  poisoning are uncoordination and




     drowsiness, followed  by  sleep.    With larger doses, the




     pupils will dilate  and reflexes  will be lost; comotosis




     will follow.  The  systems  of  chronic intoxication  from




     this material are  disturbances  of digestion, continued




     thirst, general emaciation, muscular weakness and  mental




     fatigue.(13) Sax  also  warns that paraldehyde is dangerous




     and should be kept  away  from  heat and open flames,




     because when heated, it  emits  toxic flames.(13)

-------
                Table 2
Summary of Data on Toxlcity of Organics
Identified in Stripping -Still Tails
                          Compound
   Paraldehyde      Pyridine      2-Picoline

       14              500
     1530   —    "     891            790
                  100-1000
                  -u'-

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    2.   Pyr ines




         Pyrines exhibit moderate  toxicity when introduced




    to  the  human through oral, dermal  and  inhalation routes. (13)




    Liver and  kidney damage have been  produced in animals and




    in  man,  after oral administration.^^'   In smaller doses,




    conjunctivitis,  dizziness, vomiting,  diarrhea and jaundice




    may appear ;(-*-->)  also tremors and atoxia (deffective control




    of  muscles), irritation of the  respiratory tract with




    asthemic breathing, parlysis of eye muscles,  paralysis




    of  vocal chords  and paralysis of bladder  have been




    reported.(^5)  Threshold limit  values  (TLV)  have been




    established by a number of countries  for  the  protection




    of  employees.  These values should not  be  exceeded for




    an  8-hour  shift  of..a 40-hour week:
                  USSR:    1.5 ppm =  5 mg/cum




                   USA:    5   ppm = 15 mg/cum




                  BRD*:    5   ppm = 15 mg/cum




                Sweden:    5   ppra = 15 mg/cum
        In drinking  water pyridene produces a  faint  odor  at




   0.0037 ppm  and  is a  taste and odor problem  at  0.8 ppni.^   '




   Adverse taste in  fish (carp, rudd) is reported at 5 ppm.'  '




   Pyridine causes inhibition of cell multiplication algae
Federal Republic  of  Germany
                            -yf-

-------
(Michrocystis aeruginosa)  and bacteria  (Pseudomas




putida) at 28 and  340  ppm, respectively.   SaxC1^)




reports a number of  other  hazards assoiated  with pyridines:




(1) fire hazard, that  is dangerous when  it is  exposed




to heat, flame or  oxidizer;  (2) explosive  hazard,  that  is




severe when it is  in the form of a vapor and  is  exposed  to




flame or spark; and  (3)  disaster hazard, that  is dangerous




when heated to decomposition, the pyridine emits highly




toxic fumes of  cyanides.




     An EPA report(20) suggests that, based  on health




criteria, the ambient  level of pyridines in  water  should




not exceed 207 mg/L.   On an ecological basis,  it should  not




exceed 5000 mg/L.
3 .  Picolines




     Picolines  as  a  class exhibit high toxicity  via




dermal route and moderate toxicity via oral  and  inhalation




routes.(13) ^ -picolines, °L -picolines andQ -picolines




are dangerous when heated to decomposition  because




of the emission of toxic fumes of NOX.  The  USSR  has




established a threshold limit value at 5 mg/m3  for




mixed i s oiner s . ( 1" '




     An EPA report(2°)  suggests that, based  on  a  health




criteria, the ambient  levels of picolines in water  should





not exceed 316 mg/1.

-------
                           REFERENCES
  lt  G.  I. Gruber, et_ aj_. ,  (TRW)  "Assessment  of Industrial
     Hazardous Waste Practices:   Organic  Chemical,  Pesticides
     and  Explosives Industries,"   U.S.  EPA,  SW-118C,  January
     1976, pp. 5-26 to 5-28.

  2.  United States International  Trade  Commission,  Synthetic
     organic Chemicals:   United  States  Production  and Sales,
     1978.  USITC Publication  1001,  1979.   pp.  33-80.

  3.  R.  A. Abramovitch,  "Pyridine  and  Pyridine  Derivatives,"
     in  E.. P. Dukes, C.  Coleman,  P.  Hirsch,  G.  Joyce,
     P.  Van Reyen and G.  C. Wronker,  eds.,  Kirk-Othmer
     Encyclopedia of Chemical  Technology,  2nd  Edition, Vol. 16,
     John Wiley and Sons,  N.Y.,  1968.   pp.  780-803.

  4.  M.  J. Baker, B. D.  Bradley,  C.  L.  Gandenberger,  E.  M.
     Giordano, J. B. Mertz, L. E.  Nash  and  M.  S.  Nash, eds.,
     Chem-Sources-USA, 1980 edition,  Directories  Publishing
     Co., Ormond Beach,  FLorida,  1980.   pp.  296.

  5.  M.  J. Astle, Industrial Organic  Nitrogen  Compounds,  ACS
     Monograph Series, ReAnhold  Publishing  Corporations  N.Y.,
     1961. pp. 134-145.

  6.  R.  C. West, Ed. in  Chief, Handbook  of  Chemistry  and
     Physics, 47th Editon,  Chemical  Rubber  Company, Cleveland,
     Ohio, 1966.

  7.  C.  Hansch and A, J,  Leo,  Substituent  Constants or Correlation
     Analysis in Chemistry  and Biology,  John  Wiley  and Sons,
     N.Y., 1979.  Paraldehyde  value  is  for  oil/water  rather than
     octanol/water.

 8.  D. D. Perrin, Dissociation  Constants  of  Organic  Bases  in
     Aqueous Solution, Butterworts,  London,  1965.

 9.  G. Kortum, W. Vogel  and K.  Andrussow,  Dissociation  of
     Organic Acids in Aqueous  Solution,  Butterworths, London,
     1961 .

10.   Federal  Register, Vol  4_3, No. 243,  59025-27,  "B i oaccumul at i on
     Potential  Test."

H-   R. J. Lewis, Sr;, and  R.  L. Tatked, eds.,  NIOSH, Registry
     of Toxic  Effects of  Chemical  Substances,  U.S.  Department
     of Health, Education  and  Welfare,  1978.

-------
12.
13.
14.
15.
16.
18.
19.
20.
21 .
U.S. EPA, An Ordering of the NIOSH Suspected Carcinogens
List, NITS Report No. PB 251 851  (EPA No. 660/1-76-003);
March, 1976.

Sax, N. Irving, Dangerous Properties of  Industrial Material,
fifth edition,  VAn Nostrand Reinhold Company, 1979.

Deichmann, W. R., Toxicology of Drugs and Chemicals.
Academic Press, Inc.  Ill Fifth Avenue,  New York, New York
10003.  1969

Toxic and Hazardous Industial Chemical  Safety Manual
for Handling and Disposal with Toxicity  and Hazard Data.
The International  Technical  Information  Institute.
Toranomon-Tachikawa Bldg.,  6-5, 1  Chome, Nishi-Shimbashi ,
Minato-ku, Tokyo, Japan.  1976.

Verchuerer, Karek, Handbook  of Environmental  Data on
Organic Chemicals.  VanNostrandReinhold Company.
1977.
Merli ss ,  R. R
14:55.   1972.
Phenol  moras.   Mus.  Jour.   Occup.  Med.
Gosselin, R.  E.,  H.  C.  Hodge,  R.  P.  Smith and M.  N.
Gleason, Clinical  Toxicology of Commercial  Products,
Acute Poisoning.Fourth edition.The Wi11iams and
Wi1ki ns Co.,  Baltimore ,  Md.  1976.

J. G. Cleveland  and  G.  L.  Kingsbury, "Multimedia
Environmental  Goals  for  Environmental  Assessment,"
Vol.  2.  EPA  Report  No.  600/7-77-1365, November,  1977.

Dawson, English  and  Petty,  1980.   Physical  Cheminal
Properties of  Hazardous  Waste  Constituents.

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                       LISTING  BACKCS.ODND DOCUMENT
                     TOLUENE DIISOCYANATE PRODUCTION
 Centrifuge residues from  toluene diisocyanate production (R,T)


 I.    Summary of Basis  for Listing


      The centrifuge residues  from  the production of  toluene diisocyanate

 (TDI)* contain toxic organic substances,  mutagenic substances, and

 substances that are probably carcinogenic.   The wastes  are also highly

 reactive upon contact with water.   These  wastes result  from the produc-

 tion  of toluene diisocyanate through  the  coupling of  toluene diamines

 and phosgene.


      The Administrator has determined that  toluene diisocyanate wastes

 may pose a substantial	present or potential  hazard to human health or the

 environment when improperly transported,  treated,  stored, disposed of or

 otherwise managed, and  therefore  should be subject to appropriate manage-

 ment  requirements under Subtitle  C  of  RCRA.   This  conclusion Is based on

 the following considerations:
          I)  The TDI centrifuge and  vacuum distillation wastes consist of
              toluene diisocyanates,  toluene diamines, and polymeric tars,
              all of which are suspected  carcinogens.

          2)  More than 6000 metric tons  of TDI production wastes are
              produced per year.

          3)  Storage in drums in a landfill, a known management method
              for this waste, poses a risk because toluene diisocyanate
              (TDI) is a highly reactive, pressure-generating compound
              which has caused explosion  of drums.  Several such damage
*This compound is also referred to as tolylene diisocyanate or tolyl
diisocyanate.

-------
               incidents have occurred demonstrating the potential for
               improper  disposal  of diisocyanate wastes.

           4)   In  addition to the reactivity hazard, this waste could leach
               toxic  toluene  diamine into groundwater, if improperly managed
               posing  a  human health risk.
II.    Sources  of  the Waste  and  Typical  Disposal Practices


       A.   Profile of the Industry


           Toluene diisocyanate  (TDI)  production in the United States

in 1973^ ) was 330,000 metric tons  (661 million pounds).   The major

producers  of mixed  toluene  diisocyanate isomers^'  in  1979 were

Allied Chemical Corporation (Specialty Chemicals Division),  BASF

Wyandotte  Corporation, E. I. duPont de Nemours  and  Company,  Inc., Dow

Chemical,  U.S.A., Mobay Chemical Company, Olin  Corporation,  Pvubicon

Chemicals  Inc., and Union Carbide Corporation.   Toluene diisocyanate

is the major intermediate for the production of  polyurethanes.  A

typical TDI continuous process  plant  capacity is 27,500 metric tons

(60 million pounds  per year).   The process is illustrated  in Figure 1.


      B.  Manufacturing Process (9,10)


          The starting raw materials  for a continuous  process  plant are

a solution of toluene-2,4-dianiine, 2,6-toluene-diamine, or an 80:20

mixture of the two, an inert solvent  (o-dichlorobenzene)  and gaseous

phosgene.   These compounds are  fed to two jacketed, agitator-equipped

reactor kettles,  in series,  along with recycled solvent where  the

-------
TOLUENEDIAMINE-
     PHOSGENE—i
           TWO
         REACTORS
          (SERIES)
                      RECYCLE
                     PHOSGENE
                         1	
                    WASTE GAS
                    SCRUBBER
    TO
WASTE WATER
                  ©
                                                                       STEAM EJECTOR
                                            DEGASSER
                                                      VENT KETTLE


NnOH , 	
rQ
rv
1
TO
i
ST
A^
EVAPO

                                                                        TO WASTE WATER
                                            t
                    PHOSGENE &
                       HCI
                     RECOVERY
                                                  WASTE
                                                  WATER
                                               .SOLVENT RECOVERY .
VENT COMPRESSOR
                                           RECYCLE
                                           VENT GAS
                                                                                            REFINED TOLUENE
                                                                                            DHSOCYANATE 1.0
EVAPORATOR
  RESIDUE
PROCESSING
CENTRIFUGE
    OR
VAC. DISTILL.
                                               1
                                                                                                       VENT
                                                                                                       TOAiR
                                                                                               •WATER
                                                TO
                                              WASTE
                                              WATER
                                 BYPRODUCT 37.5%
                                HYDROCHLORIC ACID
                                                                               CENTRIFUGE OR DISTILLATION
                                                                                        RESIDUE
                                                                                        STEAM EJECTOR
        WASTE GAS SCRUBBER (WATER)
                  HCI
                   I
               WASTEWATER
                                      CENTRIFUGE/DISTILLATION RESIDUE (LIQUID & SOLID)
                                      POLYMERS AND TARRY MATTER
                                      FERRIC CHLORIDE
                                      WASTE ISOCYANATES
                                                          LAND
                                     Figure 1. TOLUENE DIISOCYANATE MANUFACTURE
                                             (MODIFIED FROM REFERENCE 9)

-------
following  reactions  shown in Figure 2 and 3 take place.   An  excess of




is used  in  this  process  step.   The unreacted phosgene and hydrogen chloride




formed by  the  reaction constitute the major components of the gas stream




exiting  the  second reactor.   The reactor exit gas goes to a  phosgene




recovery/by-product  hydrochloric acid recovery system.  All  equipment




is vented  to scrubbers.   The phosgene and hydrogen chloride  are recovered




in the scrubbers.







          The  recovered  phosgene is recycled as a solution in the recovered




solvent  to  the first reactor.   The by-product hydrochloric acid (2.32 Kg




of 37.5  percent  HCl/Kg TDI product) is recovered from the gas stream




after removal  of the phosgene  and is  stored or sold-   The waste gas




scrubber effluent, containing  residual hydrogen chloride (0.025 Kg/Kg




TDI product) dissolved__jLn water,  is neutralized and then sent to the




plant industrial outfall.







          The  dehydrochlorination to  form TDI takes place after the reactor




liquid (from Reactor 2)  has  been  fed  to the degasser.   The reaction




products from  the second  reactor  are  dehydrochlorinated by blowing an




inert gas such as natural gas  through the solution  to  remove  HC1.  The




degasser gas is  sent to  the  phosgene  and HC1 recovery system, where the  HC1




and phosgene are recovered as  noted above and the inert gas  is  recyled-







          The crude TDI  solution  from the degassers is fed to the stills




and evaporators  to recover o—dichlorobenzene solvent  and purify the TDI.




The purified TDI is sent  to  storage.   The recovered solvent  is  recycled




for use in recovery of phosgene and as a solvent for  the toluenediamine
                                  -M3M-.

-------
                       CH-
                           NH2
                                                   CH3
                                + COCI,
                                        25-3CPC
                                                             HC!
2,4 TOLUENE DIAMiNE
NH2
                               PHOSGENE
                           NHCCC!
                                               (REACTOR 1)
       'CH3
                  CH3
               -  HCI
                    + COC!2
      NHCOC!
   2,6 TOLUENE DIAMINE
                             180-190°C
                NHCOCi
                    O
                    II
                CI —C
                                           COCI2
                          CH3
                    H
                               NH2-HCI
                                         COCI2
                                                        2HC1
                                               (REACTOR 2)
                                                              CH3
                                                                   NHz-HCI
                                                                         C-CI
                    Figure 2.  REACTIONS OF 2,4 AND 2,6-TOLUENEDiA.ViINE  ( 9 )
                             CH3
                                  NHCOCI
                                         95-11Cr-C
                           NHCOC!
                                                      CH3
                  INERT GAS    fl
                                    NCO
                                                              -2HCl|
                                                      NCO
                    iqure 3, 'DEHYDROCHLORINATICN REACTION TO FORM TDl(9 )
                                     - <-/ S if-

-------
feed.  The liquid  evaporator  residue containing some TDI and waste products

is then further  processed  by  either centrifugation or vacuum distillation

to recover additional TDI  product.   The remaining centrifugation or vacuum

distillation residue is  the waste  stream listed in this document.


      C.  Waste  Generation and Management


          Approximately  0.021 Kg of waste are generated per Kg of TDI pro-

duced, C11) Based on 1973 production,  this results  in an excess of

6000 metric tons of centrifuge and  distillation residues requiring  disposal,

The material contains 90 percent polymers and tarlike matter,  6 percent

ferric chloride  (largely from process impurities)  and 3 percent waste

isocyanates.C11)

          The wastes are known to be  disposed of  in  both on- and off-site

landfills, and on occasion to be containerized  in  drums prior  to landfilling

(See pp. 5-6 following.)


Ill.  Discussion of Basis  for Listing


      A.  jiazards Posed by the Waste


          As shown above,  the 6000  metric tons  of  TDI production wastes

that are generated annually are expected  to contain  the following comp-

onents :
          o   Polymers and tarlike materials    -  90%
          o   Ferric chloride                   -   6%
          o   Waste isocyanates (including TDI) -   3%

-------
              The waste isocyanates  and  polymer  and  tar-like material are




 toxic and the free isocyanates are potentially highly reactive with other




 materials, including water.







          1.  Reactivity Hazard







              Toluene diisocyanate,  and  other free isocyanates present in




 TDI waste, are known to react violently  upon contact with water.  The




 reaction of free isocyanate groups with  water usually occurs very rapidly,




 is exothermic, and results in the violent  formation  of aromatic diamines




 and carbon dioxide gas.  The disposal  of these residues is potentially




 hazardous to the people handling them, since, should water come in




 contact with the waste, there could  be explosive release of toxic and




 potentially carcinogenic aromatic chemicals over a wide area.  A similiar




 danger exists even if the wastes are drummed, since  if water enters,




 dangerously high pressures can result  in rupture of  the drum, followed




 by explosive release of the contaminants.  For this  reason, long-term




 storage of these wastes in steel drums at  waste disposal sites is




 considered extremely hazardous if containment is breached and water




 infiltrates the drum.




              There have been several  damage incidents associated with-




 improper disposal of toluene diisocyanate  wastes, which confirm that this




waste stream is reactive.  In California in 1978, a drum containing TDI




waste was picked up by a scavenger waste hauler and  placed in an unprotected




storage area.   After having been exposed to rain, the drum was then removed

-------
to a  Class  I  landfill where it exploded, requiring the hospitalization of

several  people.*   In  Detroit in May of 1978, a tank truck waiting to

dispose  of  a  quantity of  TDI waste experienced a boil-over.  As a result

nine  people exposed  to the  toxic fumes were hospitalized.*


          These damage incidents illustrate the hazards created by impro-

per treatment, storage or disposal of  TDI production waste.  In view of

the above information, it is apparent  that the waste meets the standard

for reactivity set in §26'1.23(a)  (2) and (4).


      2.  Toxicity Hazard Via Ground and Surface Water Exposure Pathways


          These wastes also  pose  a hazard via  ground  and  surface water

pathways due  to their toxicity and potential for genetic  harm.   The

principal component of...concern for this  route  of exposures  is  toluene-2,4-

diamine, which is produced  by the reaction of  diisocyanates with water,

and is a suspect carcinogen.**  (See pp.  8-10  following.)   TDI  tars are

also  suspect  carcinogens, and  are toxic  as well (Id.)

          These materials are  capable  of migrating  from improperly designed

and managed waste disposal  sites.   Toluene-2,4-diamine, produced by the react

of the diisocyantes with water  (12) j_s very soluble  (13).

          Thus, if waste disposal  sites  are designed  improperly or are

improperly managed—for example  sited  in areas with highly  permeable
*OSW Hazardous Waste Division, Hazardous Waste  Incidents,  unpublished,
 open file, 1978.
**Toluene diisocyanate, while toxic and a  suspect  carcinogen,  is  too
  reactive to persist in water, and so probably would  not  pose a
  toxicity hazard via water.  It may, however,  pose  a  toxicity hazard
  in direct handling of the waste.
                                -43S-

-------
soils, or constructed without natural or  artificial liners—there is a




possibility of escape of waste constituents  to groundwater.  A further




possibility of substantial hazard arises  during  transport of these wastes




to off-site disposal facilities.  This increases the likelihood of their




being mismanaged, and may result either in their not being properly




handled during transport or in their not  reaching their destination at




all, thus making them available to do harm elsewhere.  A transport mani-




fest system combined with designated standards for the management of




these wastes will thus greatly reduce their  availability to do harm to




human beings and the environment.  The damage incidents described above




in fact demonstrate hazards which may arise  during off-site transpor-




tation and management.






          The Agency presently lacks reliable data as to the environmental




persistence of the waste constituents of  concern (although polymeric tars




are generally persistent due to their physical character).  It is assumed




that waste constituents are persistent enough to remain in the environment




long enough to cause substantial hazard,  a conclusion supported by the




actual damage incidents involving these wastes.  Further information as




to the waste's and waste constituents' persistence is, however, solicited.






          A final reason for listing these wastes as hazardous is the




quantity of wastes generated.  The wastes are generated in fairly sub-




stantial quantity—6,000 MT annually.  Thus, large quantities of hazardous




constituents are available for environmental release, increasing the




likelihood of exposure if the wastes are mismanaged.  Large expanses

-------
of groundwater could similarly be polluted.   Contaminant migration

also may occur for long  periods of time,  since large amounts of pollutants

are available for environmental loading.   All of these considerations

increase the possibility of  exposure,  and support a hazardous waste

listing.

B.    Health and Ecological Effects

      1.  Toluene Diisocyanate

          Health Effects -  TDI is a suspect  carcinogen under bioassay

study by National Cancer Institute.  TDI  is toxic [inhalation rat LD5Q

=600ppm/6hr.] and is an  irritating material,  both in its liquid  and

airborne forms, because  of its  high reactivity.   It can produce  skin and

respiratory tract irritation,  and  can  cause sensitization so  that sen-

sitized individuals are  subject  to asthmatic  attacks upon re-exposure to

extremely low concentrations of TDI.   Additional  information  and specific

references on the adverse effects  of TDI  can  be  found  in Appendix A.

          Regulations - The OSHA standard  for  toluene  diisocyanate is 5

ppb, with a ceiling of 20 ppb  in 10 minutes.

          Industrial Recognition of Hazard ~  Sax's  Dangerous  Properties of

Industrial Materials^) designates toluene diisocyanate as an emitter of

highly toxic fumes containing hydrogen cyanide when heated to decomposition.

          2.  Toluene-2,4-diamine
                                   -vs-
                                   -MWO-

-------
              Health Effects - Toluene-2,4-diamine is a suspect carcino-




gen^).   Although it did not cause cancer in animals upon skin painting,




it increased the incidence of lung cancer in the test animals.  Toluene




diamine was also shown to induce liver tuniors(^) in rats,(6) morphological




aberrations in mammalian cells('), and causes bacterial mutation in the




Ames test.W  Additional information and specific references on the ad-




verse effects of toluene 2,4-diamine can be found in Appendix A.






              Industrial Recognition of Hazard - Toluene-2,4-diamine is




designated in Dangerous Properties of Industrial Materials (Sax)^2) as




moderately toxic when inhaled.






          3.  Tar from TDI Manufacturing






              Health Effects - Tarllke material from TDI manufacturing con-




tains benzidimidazapone and must be considered suspect carcinogen based on




the data available on coal tar and other chemical tars.  (NIOSH Criteria




for recommended standard for occupational exposure to Coal Tar Products.)




Considering the highly reactive nature of isocyanates and their polymers,




various toxic effects such as skin and respiratory tract irritation and




sensitization also would be expected.  Sensitized individuals are subject




to asthmatic attacks upon re-exposure to extremely low concentrations




of this material.  Additional information on the adverse effects of




tarlike materials can be found in Appendix A.






              Industrial Recognition of Hazard - Sax's Dangerous Properties




of Industrial Materials(2> designates dehydrated and liquid tars as highly
                                   -MMS-

-------
toxic skin and respiratory irritants when  exposure  is  of  long  duration.




Tar dusts are designated as moderate skin  and  eye irritants  upon acute




exposure.

-------
 IV.   References


 1.   U.S. Tariff Commission (U.S.  International Trade Commission) Synthetic
      Organic Chemicals, United States Production and Sales.  1974 Prelim-
      inary Reports.  Washington, U.S. Government Printing Office.

 2.   Sax, N. Irving.  Dangerous Properties of Industrial Materials. Fourth
      Edition, Van Nostrand Reinhold  Co., New York, 1975.~~'

 3.   USEPA.  Report 1980 Contract  #  68-02-2773.  Potential Atmospheric
      Carcinogens.  Phase I - Identification and Classification, pp. 204.

 4.   Giles, A.L., et al.  Dermal Carcinogenicity Study by Mouse-Skin
      Painting with 2,4-Toluenediamine Alone or in Representative Hair
      Dye Formulations.  J. Toxicol,  Environ. Health, 1(3):433-440,  1976.

 5.   Bridges, B.A. , and M.H. Green.  Carcinogenicity of Hair Dyes by
      Skin Painting in Mice (letter to editor).  J. Toxicol. Environ.
      Health, 2(1):251-252, 1976.

 6.   Shah, M.J., et al.  Comparative Studies of Bacterial Mutation
      and Hamster Cell Transformation Induced by 2,4-Toluenediamine
      (Meeting Abstract).  Proc. Am.  Assoc. Cancer Res., 18:22, 1977.

 7.   Cancer Research_,_29:1137, 1969.

 8.   Pienta, R.J., et al.  Correlation of Bacterial Mutagenicity and
      Hamster Cell Transformations  with Tumorigenicity Induced by 2,4-
      Toluenediamine.  Cancer Lett. (Amsterdam), 3(1/2): 45-52, 1977.

 9.   Lowenheim and Moran.  Faith, Keyes, and Clark's Industrial Chemicals,
      4th ed., John Wiley and Sons, 1975.

 10.   Kirk-Othmer.  Encyclopedia of Chemical Technology. 3rd ed.,
      John Wiley and Sons, Inc., New  York, 1979.

11.   Industrial Process Profiles for Environmental Use:  Chapter 6,  The
      Industrial Organic Chemicals  Industry.  Reimond Liepins, Forest Mixon,
      Charles Hudals, and Terry Parsons,  February 1977, EPA-600/2-77-023f.

12.   "Criteria for a Recommended Standard Occupational Exposure to TDI,"
      U.S. Dept. of HEW,  Public Health Service and National Institute of
      Occupational Safety and Health, HSM 73-110-22 (1973).

13.   Handbook of Chemistry and Physics,  56th ed.,  Cleveland, CRC Press
      (1975).

-------
                     LISTING BACKGROUND  DOCUMENT
                      TRICHLOROETHANE PRODUCTION
        0 Waste from the product  steam  stripper  in the  production of
          1,1,1-trichloroethane (T)

        0 Spent catalyst from the hydrochlorinator reactor  in the pro-
          duction of 1,1,1-trichloroethane via the vinyl  chloride
          process (T)

        0 Distillation bottoms from the production of 1,1,1-trichloro-
          ethane (T)

        0 Heavy ends from the production of 1,1,1-trichloroethane (T)

I.   Summary of Basis for Listing

     Waste from the heavy ends column, distillation column, and

product steam stripper, and spent catalyst from  the hydrochlorinator

reactor in the production" of 1,1,1-trichloroethane  contain  carcinogenic,

mutagenic, teratogenic or toxic organic substances.  The waste stream

constituents of concern are 1,2-dichloroethane,  1,1,1-trichloroethane,

1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane,  and 1,1,2 ,2-tetra-

chloroethane, vinyl chloride, vinylidene chloride,  and  (possibly)

chloroform.

     The Administrator has determined that these solid wastes  from 1,1,1"

trichloroethane production may pose a substantial hazard to human health

or the environment when improperly transported,  treated, stored,  dis-

posed of or otherwise managed,  and therefore should be  subject to ap-

propriate management requirements under Subtitle C  of RCRA.   This con-

clusion is based on the following considerations:

     1)   These wastes are listed as hazardous because  they are  likely to
                                  - HHM-

-------
          contain  1,2-dichloroethane;  1,1,1-trichloroethane;  1,1 2-tri-
          chloroethane;  1,1,1,2-tetrachloroethane;  1,1,2,2-tetrachloroethane-
          vinylidene chloride; vinyl  chloride  and  chloroform.  Of these
          substances, 1,2-dichloroethane,  1,1,2-trichloroethane, vinyl-
          idene chloride, vinyl  chloride  and  chloroform are recognized
          carcinogens and 1,1,1-trichloroethane  is  a  suspected car-
          cinogen;  also  a number of these  chemicals have been found to
          be mutagenic  in laboratory  studies;  the  chlorinated ethanes
          also pass the  placental barrier  and  several have been docu-
          mented to produce  teratogenic effects.

     2)   Significant quantities  of wastes  containing these hazardous
          compounds may  be generated  each  year,  increasing the possi-
          bility of exposure  should mismanagement  occur.

     3)   Mismanagement  of incineration operations  could result in
          the release of hazardous vapors  to  the atmosphere and
          present  a significant  opportunity  for  exposure of humans,
          wildlife  and vegetation in  the vicinity  of  these' operations
          to potentially harmful  substances through direct contact
          and also  through pollution  of surface waters.  Disposal of
          these wastes  in improperly  designed  or operated landfills
          could create  a substantial  hazard due  to  the potential of
          waste constituents  to  migrate and persist in aqueous
          environments,

     4)   Damage incidents illustrating the mobility and persistence of
          chloroethanes  have  occurred which resulted in surface and
          groundwater contamination.

 II.  Sources of the Waste and Typical Disposal Practices

     A.  Profile of the  Industry

         Currently, there are three producers  of 1,1,1-trichloroethane

 in the United States.   Table  1 lists  the producers, sites,  and esti-

 mated capacities of each plant.   Actual production of this  compound  in

 1978 was 644,475,000 pounds^3).

         The production  of 1,1,1-trichloroethane has shown a steady  in-

 crease in production as  shown in  Table 2.  It  is mainly used (92%)  for

metal degreasing and for electrical, electronic and instrument cleaning.

Growth  in the use of 1,1,1-trichloroethane is being accelerated because

of the  potentially greater health hazard exhibited by trichloroethylene.
                                - 4HS-

-------
                               TABLE 1
1,1,1-Trichloroethane Producers, Sites, Capacities  and Processes  (1»2)
      Company
    Location
  Annual Capacity
(Millions of Pounds)
Process
  Dow Chemical
    U.S.A.
Freemport, TX
Plaquemine, LA
       450
       300
Via Vinyl
Chloride
  PPG Indus-
  tries
Lake Charles,  I
  LA           !
       350
Via Vinyl
Chloride
  Vulcan
  Materials
Geismar, LA
        65
 Via  Chloro-
 nation of
 ethane
  TOTAL
               I       1,165
                                -HHC.-

-------
              TABLE 2
U.S. International Trade Commission
1,1,1-Trichloroethane Production (3)
Year !
i
1968
1969
1970
1971
1972
1973""
1974
1975
(Millions of Pounds)
299.4
324.3
366.3
374.6
440,7
548.4
i
590.8
|
i
i
i
1976 1 631.2
!
1977
634.8
                 -MM1-
                  -X-

-------
 Other  solvent  uses  are in formulating a variety of products including

 adhesives,  spot  cleaners  and printing inks.

     B.   Manufacturing and Waste Generation  Process*

          The bulk of  1,1,1-trichloroethane production in the United  States

 is based  upon  the vinyl  chloride process; minor amounts (— 10%)  are

 made by the ethane  process.   In  the  vinyl chloride process,  vinyl

 chloride  reacts  with  hydrogen chloride to form  1,1-dichloroethane,

 which  is  then  thermally chlorinated  to produce  1,1,1-trichloroethane.

 The yields  based  on vinyl  chloride are approximately 95%.

          1,1,1-Trichloroethane is also produced by the  noncatalytic

 chlorination of  ethane.  Ethyl chloride, vinyl  chloride,  vinylidene

 chloride, and  1,1-dichloroethane are  produced as co-products.  When

 1,1,1-trichloroethane  is the  only desired product,  vinyl  chloride and

 vinylidene  chloride are hydrochlorinated to  1,1-dichloroethane and

 1,1,1-trichloroethane  respectively; ethyl chloride  and  1,1-dichloroe-

 thane  are recycled  to the chlorination  step  (Kahn  and Hughes, Monsanto

Research Corp., Source Assessment:  Chlorinated Hydrocarbons Manufac-

ture, EPA 600/2-78-004, 1978).

Vinyl Chloride Process

     The chemical reaction for the hydrochlorination of vinyl chloride is:

                           Fed 3
            H2C-CHCl-i-HCl  	>  CH3HC12

                           35-40°C
*Based on the process description in Key, J.A. and Standifer, R.L.,
 Emissions Control Options for the Synthetic Organic Chemicals
 Manufacturing Industry," U.S. Environmental Protection Agency,
 SPA 68-02-2577,  July 1979

-------
  Chlorination of 1,1-dichloroethane is represented  as:


             CH3-CHCl2-K:i2  	>  CH3CC13+HC1


  Figure 1 represents a simplified process  for  production of 1,1,1-tri-

  chloroethane via the vinyl chloride process.  Vinyl chloride and hy-

  drogen chloride* (and the recycled overhead stream from the light ends

  column) react at 35-40°C in the presence  of ferric chloride.  The re-

  actor effluent is neutralized with ammonia.   The resulting solid com-

  plex (residual ammonium chloride and ferric chloride, and ammonia) is

  removed by the spent catalyst filter as a semisolid waste stream

  (Stream G, Fig. 1).  The filtered hydrocarbon stream is then distilled

  in the heavy ends column and high-boiling chlorinated hydrocarbons

  (tars) are removed as a waste stream (Stream  H, Fig. 1)-**   The

  overhead from this column is further fractionated in the light

  ends column into two streams: 1,1-dichloroethane and the lighter

  components (primarily unreacted vinyl chloride).  The lighter components

  are recycled to the hydrochlorination reactor.  The 1,1-dichloroethane

  product is removed as the bottom stream and is then reacted with

  chlorine in the chlorination reactor at a temperature of about 400°C.

  The products from this reaction are distilled, and hydrogen chloride
 *The hydrogen chloride (HC1) used for vinyl chloride hydrochlorination
  is often  a  by-product from the chlorination of 1,2 dichloroethane
  or from other processes in the plant complex.  If by-product HC1 is
  used,  it  can contain  as much as 3.5% of 1,2-trichloroethane which
  will carry  forward to the product stream stripper waste streams.

**The Agency  requests further information on the existence and compo-
  sition of this Identified waste stream.  It is anticipated that
  most heavy  waste  constituents will be found in the residue of the
  final  distillation column.

-------
o
I
                  HCI


(

__-^

TC2A(=-



T



'•



d
1

>
LO
, X.


AD,
)
                                                                                                       M i *^-C £
                                                                                    WJCq
                      Figure 1.    Flow  Diagram for 1,1,1-Trichloroethane  from Vinvl Chloride

-------
and low boiling organic  hydrocarbons are taken overhead in the HC1




column.   (This stream may be recycled to supply the hydrogen chloride




required  in the hydrochlorination step, or used for other chlorinated




organic processes directly (e.g., oxy-chlorination processes)). The




bottom stream from the hydrogen chloride column is further fractionated




to recover  1,1,1-trichloroethane as the overhead product, which,




after the addition of a  stabilizer, is stored.  The bottom stream




from the  1,1,1-trichloroethane column is comprised largely of 1,1,2-




tric hi oro ethane, tetrachloroethanes, and pentachloroethanes (stream




14, Fig.  1).  (These bottoms may be used as a feedstock for produc-




tion of other chlorinated hydrocarbons (e.g., perchloroethylene-tri-




chloroethylene, vinylidene chloride), in which case they will not be




discarded.) Estimated emissions from this process are shown in Table




3.  The listed waste streams are shown in  Figure 1 as follows:




spent catalyst wastes are noted as stream G, heavy ends




as stream H, and distillation bottoms as stream 14.




     Certain 1,1,1-trichloroethane production processes use a steam




stripper  prior to final  distillation and recovery of 1,1,1 trichloro-




ethane, in which case a  separate waste stream is generated.  The




attached  Figure 2 shows  a process where a steam stripper is used.






Chlorination of Ethane



     The main sequence of reactions occurring during the free radical




chlorination of ethane is:



         +  ci2	> CH3CH2C1 + CH3CHC12 + CH3CC13 +  HC1




         +  C12	> CH2HC1 + CH2CC12 + HC1
                                   t

-------
                                                   TABLE  3

              ESTIMATED EMISSIONS FRCM   1,1,1-TRICHLORDETHANE MANUFACTURE:  Vinyl Chloride  Process
                  Species
Mr
EMISSIONS kg/Mg
   Aqueous
Solid
Hydrogen chloride

Ethane

Ethene

NH4-FeCl3~3 Complex

1,1-Dichloroetihane

1,1-Dichloroethene

1,2-Dichloroethane

1,1,1-Trichloroethane

1,1,2-TGr ichloroethane

1,1,1,2-Tetxachloroethane

1,1,2,2-Tetrachloroethane

Pent-achloroethane

Sodium hydroxide

Sodium chloride
1.6

1.6
2.2

9.9
3.5

2.6
                       33.7

                      449.
                                                2.2
                                0.8

                                0.8

                                3.9

                               51.2

                               35.3

                               40.8

                                1.8
 Sources  EUcin, L.M.  "Chlorinated Solvents," Process Economic Program Report No. 48,
          Stanford ReseaarcVi Institute, Menlo Park:, Califiornia,  February, 1969.

-------
 Small amounts of 1,2-dichloroethane  and  1,1,2-trichloroethane  are also

 formed in minor amounts.  The  product mix,  however,  can  be  varied some-

 what by operating conditions.  Furthermore,  to  maximize  1,1,1-trichloro

 ethane production, ethyl chloride  and 1 ,1-dichloroethane are recycled

 to the chlorination reactor; vinyl chloride  and vinylidene  chloride

 are catalytically hydrochlorinated to 1 ,1-dichloroethane and 1,1,1-

 trichloroethane respectively:

                            FeCl3

            H2C=CHCr «• HC1  _ .
                            FeCl3
            CH2=CCl2 + HC1  _   CH3CC13


 Figure 3 represents a simplified process  for production of 1 ,1 , 1-trichloro-

 ethane via direct chlorination of ethane.  Chlorine and ethane react in

 an adiabatic reactor at" 'an approximate temperature of 400°C  and a pres-

 sure of 6 atmospheres with a residence time of approximately 15 seconds.

 The reactor effluent (containing  unreacted ethane, ethylene together

 with vinyl chloride, ethyl chloride, vinylidene chloride, 1 ,1-dichloro-

 ethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1 ,1 ,1-trichloroethane,

 a small amount of higher chlorinated hydrocarbons, and hydrogen chloride)

 is quenched and cooled.   The bottom stream from the quench column, consisting

 primarily of tetrachloroethane and hexachloroe thane, is removed.  The

 overhead product from the quench column is fractionated into a chlorin-

 ated  hydrocarbon stream  and light products — ethane,  ethylene, and

hydrogen chloride.   A portion of the crude hydrogen chloride stream

is used in subsequent hydrochlorination reactions; excess hydrogen

chloride is  purified for  reuse or resale.   The bottom stream from
                              -W53-

-------
HYDROGEN
CHLORIDE •

  VINYL
CHLORIDE
                        HYDROGEN CHLORIDE +
                  TRICHLOROETHANE + DICHLOROETHANE
                                   r
              TO ATMOSPHERE
                                        •NaOH +H2O
                                                  B
                                          SCRUBBER
                                         WASTEWATER
               A
-(CONDENSER)  'DICHLOROETHANE
-(DECANTER)
          HYDROCHLORINATOR
               REACTOR
           PURIFICATION
             COLUMN
            REACTOR SPENT
              CATALYST
               WASTE
                                                           STEAM STRIPPER
                                                            GAS EFFLUENTS
                                                        CHLORINE
                                J
                                       STEAM
                                      STRIPPER
                               STEAM-
                                                CHLORINATOR
                                                  REACTOR
                                          DECANTER
                                                         1,1,1-TRICHLOROETHANE
                                                       DISTILLATION
                                                         COLUMN
                                                         HEAVY ENDS
                                                               STEAM STRIPPER WASTE
                  Figure 2. 1,1,1-TRICHLOROETHANE BY THE HYDROCHLORINATION AND DIRECT
                          CHLORINATION OF VINYL CHLORIDE. (53)

-------
                                            TO  MCI
PV.AMT
           FR.CM
          COUUMM
FCCM
                                     HCI
                                    COL.UMKJ
                       CCK.UMM
                            HEAVY

                            OCCUMIJ
                                                     ^>
                                                                             J
l,l,l-TRt-
CHLOEOETHMJC
COuUMM
                                                                                                                     TO
                                                                                                                     C»^»-^
                       Figure 3.    Flow Diagram  fpr 1,1,1-Trichloroethane from Ethane

-------
the hydrogen  chloride  column is  further separated by distillation




into various  products.   The lower boiling hydrocarbons are removed




as an  overhead  product  in the first column.   The bottoms contain




substantially all  the heavy waste materials  (tetrachlorinated ethanes




and higher).    The bottoms  may be disposed of as waste or used as




feedstock  for as a bottom stream and are  suitable as feedstock for




other  chlorinated  hydrocarbon processes.   These bottoms are the




waste  stream  of concern from the ethane chlorination process.   (The




remaining  process  description is provided  for informational purposes.)]




     The overhead  product  (principally  1,1,1-tricholroethane,  vinyl




chloride,  vinylidene chloride, ethyl chloride,  and 1,1-dichloroethane)




is fractionated and 1,1,1-trichloroethane  removed as a bottom  product.




The overhead  stream from the  1,1,1-trichloroethane column is  fed  to




the 1,1-dichloroethane  column, where 1,1-dichloroethane is  separated




as the bottoms  stream and is  recycled as a feedstock to the chlorination




reactor.   Vinyl chloride, vinylidene chloride,  and ethyl  chloride




(the overhead stream) are fed  to  the hydrochlorination reactor,




where vinyl chloride and vinylidene  chloride  react with hydrogen




chloride to form 1,1-dichloroethane  and 1,1,1-trichloroethane




respectively.   Approximate hydrochlorination  reaction  conditions




are at a temperature of 65°C  and 4 atm.




     The reactor effluent stream  from the hydrochlorination reactor




is neutralized with ammonia.  The resulting complex (ammonium  chloride-




ferric chloride - ammonia) is removed by the  spent  catalyst filter




as a semisolid waste.   (This  is  the  analogous  stream to the spent




catalyst waste in the vinyl chloride process  (see Fig.  1),  but is not

-------
 listed as hazardous when arising  in the ethane chlorination process




 since it consists principally  of  iron chloride and hydrogen chloride




 (see Table 4)).  The filtered  hydrocarbon stream is fractionated




 further: the bottom fraction (primarily 1,1,1-trichloroethane)  is




 recycled to the trichloroethane column.   The overhead stream (primarily




 ethyl chloride and 1,1-dichloroethane)  is recycled to the  chlorination




 reactor.  Table 4 summarizes the  estimated emissions  from  this  process.




 As  shown, predicted waste constituents  are 1,2-dichloroethane,  1,1,1-




 trichloroethane and higher boiling  ethanes which are  expected to




 comprise the major percentage  of  the waste.




         Table 5 summarizes waste consituents and estimated waste




 constituent amounts in waste streams generated by each process.




     C.  Waste Management Practices




         The Agency presently  lacks  reliable information as to  the  manage




 ment practices for these wastes,  but based on typical waste management




 practices in the chlorinated organic manufacturing industry it  is




 likely that distillation bottoms  and heavy ends  are landfilled




 (perhaps in drums).   Aqueous wastes  are  probably stored on  site  in




 pits that equalize surges in the  waste  flow  to  landfill operations.




 Some wastes also may be incinerated.






 III. Discussion of Basis for Listing




     A.   Hazards Posed by the Waste




         The various waste streams from  the  production of 1,1,1-




 trichloroethane are  likely to be  generated in  large quantities,  as




 indicated by a comparison of the waste emission  factors contained in




Tables 3, 4,  and 5  and the production data in Table 2.  Such substantial

-------
                                                   TABLE A


               ESTIMATED EMISSIONS FROM 1,1,1-TRICHLOROETHANE MANUFACTURE:   Chlorlnation of Ethane
               Species
Air
EMISSIONS kg/Mg
   Aqueous	
Solid
Ethene
2.4
1,1-Dlchloroethane


1,2-Dlchloroethane


1,1,1-Trichloroethane


1,1,2-Trlchloroethane
Tetrachloroethanes
Hexachloroethanes
                                               trace


                                               30.7


                                               39.0


                                               49.7
                                            Oo
                                            \n
                                            T
                                             I
                                               51.4
Iron (III) chloride


Hydrogen Chloride
                                                 2.8
                                                                                                173.6
Source:  Elkln, 1969

-------
                                TABLE 5
                       Via Vinyl Chloride Process
   Stream
 :illation bottoms  and
 rj ends
          Compound

  1,1,2-trichloroethane
1,1,1,2-tetrachloroethane
1,1,2,2-tetrachloroethane
Pentachloroethane
      kg/Mg of
1,1,1-Trichloroethane

         51.2
         35.3
         40.8
          1.8
 > from product - stream
 )per*
     1,2-dichloroethane
   1,1,1-trichloroethane *
          0.8
          3.9*
  catalyst
         **
NH4Cl-FeCl3-NH3  complex
          2.2
                                                                          **
                           Via Chlorination of Ethane
 :e Stream
 rj ends
         Compound

     1,1-dichloroethane
     1,2-dichloroethane
   1,1,1-trichloroethane
   1,1,2-trichloroethane

   tetrachloroethanes)
   hexachloroethanes  )
      kg/Mg of
1,1,1-trichloroethane

       trace
         30.7
         49.7
         49.7

         51.4
 * spent  steam stripper waste  is  also expected to contain small concentrations
 rtnyl chloride, vinylidene chloride  and chloroform.  Vinyl chloride is expected
 >e present since it is a feedstock constituent.  Vinylidene chloride is a"
 Jroduct  from the dehydrochlorination of 1,1,2-trichloroethane.  Chloroform
 mother  predicted reaction by-product,  and is expected to be formed from
 splitting off of vinyl chloride monomer and ethane into single carbons,
 * are subsequently chlorinated.

 1 spent  catalyst waste is also expected to contain small concentrations of
 ^chloride feedstock, 1,1,1-trichloroethane product and some polymeric
 trials.  The Agency solicits information as to the presence of these or
 ler compounds in this waste, and notes  that hazardous constituent concen-
lt*ons in this waste stream may  be too  minute to be of regulatory significance.

-------
 waste  quantities  are  themselves  of regulatory concern in light of

 the hazardous  constituents  present.   Thus,  waste mismanagement

 poses  the  threat  of contaminating  large expanses of groundwater,

 surface water  and air,  and  of  reaching large numbers of environmental

 receptors.

      Of the  chemicals potentially  present  in the wastes,  1,2-dichloro-

 ethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, vinylidene

 chloride,  vinyl chloride  and chloroform are on the GAG carcinogen

 list;  1,1,1-trichloroethane is a suspected  carcinogen and 1,1,1-

 tetrachloroethane is  toxic.*   Some  of these  chemicals are  also

 suspected  mutagens and  teratogens.  Should  these compounds  reach

 human  receptors,  the  potential for  resulting adverse health  effects

 would  be extremely high.  These constituents are capable of  migration.

 For example, 1,2  dichloroethane, the  trichloroethanes,  and  the

 tetrachloroethanes all  are  relatively  soluble  in water (solubility

 ranging from 200  ppm -  8700 ppm) (App.  B),  and  thus,  these  compounds

 are capable  of causing  chronic toxicity via a water  exposure pathway.

 Indeed, if they solubilize  these compounds  could pose  a substantial

 hazard at  a  level many  orders of magnitude  less  than their  solubility

 limits.  In  addition,  1,2-dichloroethane and 1,1,2-trichloroethane

 are fairly volatile as well (vapor pressure 60 mm Hg.)**; thus, 1,1,2-

 trichloroethane and the tetrachloroethanes  may  pose  a  chronic toxicity
 *Pentachloroethane poses some threat of chronic exposure via  an
  inhalation pathway, but is not presently considered  to pose
  sufficient danger to be listed as a waste constituent of  concern.

**!,!,! trichloroethane is also volatile, but is expected to photolyse
  rapidly so probably would not pose a substantial hazard via  air  in-
  halation beyond the immediate disposal site (App. B.).

                                   VI

                                  -VfcO-

-------
problem via inhalation as well.





     These waste constituents are capable  of mobility  and  persistence




as well, as shown by numerous damage  incidents  involving these waste




constituents.  Chlorinated ethane and ethylene  contamination  of




groundwater in areas adjacent to disposal  sites  in  fact is  not uncommon.




For example, 1,1,1-trichloroethane has been detected in groundwater




in Acton, MA, where residents believe the  source is a  disposal site




at a nearby manufacturing facility.(4)   £n jqew  Jersey,, seepage




from, landfilled wastes near the CPS Chemical Company also  resulted




in well contamination by trichloroethylene, tetrachloroethane, and




methylene chloride'*'.  1,2-dichloroethane has  also been detected




in groundwater supplies in Bedford, MA,  where the source of contam-




ination has not been positively identified but  is believed  to be due




to industrial uses upstream. ^'  Dichloroethanes  are among  the waste




constituents which have migrated from Hooker Chemical's facility at




Montague, Mich., contaminating large  expanses of  ground and surface




water.(48)  Trichloroethane has also  migraged and contaminated




private drinking wells in Canton, Connecticut.(48)




     Thus, these wastes are capable of causing  substantial  hazard un-




less properly managed, and the possibility of mismanagement and en-




vironmental release of contaminants is certainly  plausible.  Some




portion of these wastes are expected  to  be landfilled, while other




residue is expected to be incinerated.   Improper  landfilling —




siting  in areas with permeable soils, inadequate  leachate  control or




monitoring,  lack of landfill cover, and  the like  — could  allow




waste constituents to leach into groundwater, or  escape via volatilization,

-------
 Even if plastic lined drums are used for disposal, they represent a




 potential hazard if the landfill is improperly designed or operated




 (i.e.,  drums  corrode in the presence of even small amounts of water).




 The  current  disposal sites (the Gulf Coast) receive considerable




 rainfall and  have a high ground water table creating a potential for




 drum corrosion.




      Given the presence of the chlorinated ethanes and ethylenes and




 the  potential for drum degradation, it  is  likely that these wastes,




 if improperly landfilled (i.e. ,  improperly designed or operated




 landfill), would come into contact  with ground water.   This is  par-




 ticularly true of deeper deposits or those in cooler climates where




 vapor losses  will be mimimized.  In these  two cases,  the waste  con-




 stituents will readily move with the groundwater,  just as  they  have




 have been observed to do""at sites such  s Love Canal,  the Kin-Buc




 Landfill,  and Story Chemical  in  Michigan County, Michigan.™^»50,51,52)




 The  above damage incidents  support  laboratory findings that any




 released 1,1,2-trichloroethane  and  1,2-dichloroethane  will  pass




 through  sandy soils  with less  than  a 50 percent  loss  due to volati-




 lization^.




      In  addition to  landfilling, the 1,1,1-trichloroethane  steam strip-




 per  bottoms waste stream that  is recycled  or  incinerated is often




 stored temporarily at  the  production site.  Should leaks occur,  simi-




 lar  problems  to  those  from  landfills could  be expected.




     Mismanagement  of  incinerating  operations could result  in the re-




 lease of hazardous vapors,  containing among other  substances  the




waste constituents of  concern, to the atmosphere and  present  a  signifi-







                                  V*

-------
 cant opportunity for exposure of  humans,  wildlife and vegetation in




 the vicinity of these operations  to  potentially harmful substances




 through direct contact and  also through pollution of surface waters.




     Finally, should these  waste  constituents migrate into the environ-




 ment they can be expected to  persist,  thus  increasing the likelihood




 of reaching environmental receptors  and causing substantial harm.




 The damage incidents above  demonstrate environmental persistence of the




 released constituents.  All of ttiese waste  constituents  are expected,




 on the basis of literature  degradation values,  to persist in groundwater




 (1,1,2-Trichloroethane is subject  to hydrolysis,  but has  a hydrolysis




 half-life of 6 months.  1,1,2-Trichloroethane may also  persist  in  air as




 well (App. B)).  Again, the persistence of  these  constituents is




 evidenced by the measurable concentrations  of these  chemicals in Love



 Canal leachate some thirty years after  disposal.(49.50.51)    in any




 case, in light of the hazardous character of  these waste  constituents,




 the Agency could not justify a decision not to  list  these  wastes




 absent assurance that waste constituents are  incapable of  migration




 and persistence.  As demonstrated above, such assurance is not possible.




     B.  Health and Ecological Effects




         1-   1,2-Dichloroethane




             Health Effects - 1,2-Dichloroethane  is  a carcinogen; (7)




 it has  also  been identified by the Agency as demonstrating substantial




 evidence  of  carcinogenicity.C^A)    in addition, this compound and




 several of its metabolites are highly mutagenic (8>9).  1,2-Dichloro-




 ethane crosses  the  placental barrier and is embryotoxic and terato-




genic(10~14) ,  and has been shown  to concentrate in the milk  of

-------
nursing mothers.      Exposure  to  this  compound can cause a




variety of adverse health  effects  including  damage  to the liver,




kidneys and other organs,  internal hemorrhaging and blood clots




1,2-Dichloroethane is designated a priority  pollutant under Section




307(a) of the CWA.  Additional  information and  specific  references




on adverse health effects  of  1,2-dichloroethane can be found in




Appendix A.




            •Ecological Effects -  Values  for  a  96-hour static  
-------
 genie in the Ames  Salmonella assay(2°) and was shown to cause fetal de-



 velopment abnormalities.(21)





             Acute and chronic intoxication of humans have caused severe




 central nervous  system impairment.(22^  Animal studies have shown that




 1,1,1-trichloroethane  causes organ damage to heart, lungs, liver and




 kidneys, t23-'  Additional  information and specific references on the




 adverse effects  of 1,1,1-trichloroethane can be found in Appendix A.




             Ecological Effects -.1.1.1-Trichloroe'thane is very toxic




 to aquatic life.   Lethal  concentrations (96 hour) of- 37-58 mg/1  were




 registered for bluegills,  52 mg/1  for fathead minnows and 26 mg/1 for




 shrimp.(2^'




             Regulations  - 1,1,1-Trichloroethane  is designated  as a




 priority pollutant  under  Section 307 (a) of the CWA.  OSHA has set the




 TWA at 350 ppm.  EPA has"'re commended an ambient water quality criterion




 at 15.7 mg/1.




             Industrial Recognition  of Hazard - Sax (Dangerous Properties




 of Industrial Materials)  listsvl,1,1-trichloroethane as  moderately  toxic




 via inhalation.




         3.   1,1,2-Trichloroethane




             Health Effects  -  1,1,2-Trichloroethane has  been shown  to




 cause cancer in mice;(2^)  it has also  been identified by the Agency




 as demonstrating substantial evidence  of  carcinogenicity. ^'  There




 is evidence  that 1,1,2-trichloroethane  is  mutagenic and  may be embryo-




 toxic  or  cause  teratogenic effects.'26*27^




    Like  the other compounds  of this  type, the trichloroethanes  are




narcotics  that  produce central nervous  system effects, and  can damage




the liver, kidney and other organs

-------
              1,1,2-Trichloroethane is designated as a priority pollu-




 tant  under  Section 307(a)  of the CWA.  Additional information and




 specific  references on  the adverse effects of 1,1,2-trichloroethane




 can be  found  in Appendix A.




              Ecological Effects  - Aquatic toxicity data are limited




 with  only three acute studies  in freshwater fish and invertebrates,




 with  doses  ranging from 10,700 to 22,000  ug/.l.^17^




              Regulations - OSHA  has  set the TWA at  10  ppm (skin).




          4.   Vinylidene Chloride




              Health Effects  -  Vinylidene  chloride has  been shown  to




 cause cancer  in laboratory animals  '28,29;  ancj  to ^e mutagenic. ^8)




 It has  also been identified  by the Agency as  demonstrating substan-




 tial  evidence of carcinogenicity.    '  It is  very toxic  [1^50




 (rat) = 200 mg/kg]  and-chronic exposure can cause damage  to  the




 liver and other vital organs as  well  as causing central nervous




 system  effects.   Additional  information and specific references on




 the adverse effects  of  vinylidene chloride  can  be found in Appendix




 A.




         Regulations -  DOT requires containers  to be labeled "flam-




mable liquid."   OSHA has set the TWA  at 10  ppm.




         Industrial Recognition  of Hazard - The toxic hazard of vinyli-




dene  chloride is  suspected of being similar to  vinyl chloride which is




moderately toxic via inhalation  (Sax, Dangerous  Properties of Industrial




Materials)(3°).




         5.   Vinyl Chloride




             Health Effects -. Vinyl chloride  has  been  shown  to be a

-------
 carcinogen in laboratory studies;<31,32,33) it hag algo been identi_




 fied by the Agency  as  demonstrating substantial evidence of carcino-



 genicity.(54)  This  finding has subsequently been supported by



 epidemiological findings.(33-37)




             Vinyl  chloride is  very toxic [LD50 (rat) = 500 rag/kg] and



 acute exposure results  in anaesthetic effects as well as uncoordinated



 muscular  activities  of  the extremities,  cardiac arrythmias(38)  atl(j



 sensitization of the myocardium. (39)  in severe poisoning,  the  lungs



 are congested and liver and kidney damage also occur.(40)   A decrease
                                                     «*


 in white  blood cells and an increase in  red blood cells was also



 observed, as well as a  decrease in blood clotting ability.(41)



 Vinyl chloride is designated as a  priority pollutant under  Section



 307(A) of the CWA.   Additional  information and specific references



 on the adverse effects-o-f  vinyl chloride can be found in Appendix A.



             Regulations - OSHA has set  the TWA at  1  ppm with a 5 ppm



 ceiling over 15 minutes.   DOT requires this to be labeled "flammable



 gas."



             Industrial  Recognition of Hazard  - A vinyl chloride has  a



 moderate  toxic hazard rating via inhalation (Sax, Dangerous  Properties



 of Industrial Materials).



         6.   Chloroform



             Health Effects  - Chloroform has been shown to  be carcino-



 genic (42,54)  and tangential  evidence  links  human  cancer epidemiology



with  chloroform contamination of drinking water.(43,44)  Chloroform



has also been shown to induce fetal  toxicity and  skeletal malforma-



tion  in  rat  embryos.(45»4°)  Chronic  exposure  causes  liver  and  kidney



damage and neurological disorders.^3)   Additional  information  and

-------
specific references  on  the  adverse  effects  of chloroform can be found




in Appendix A.




             Ecological Effects - The U.S.  EPA has estimated that




chloroform accumulates  fourteen-fold in  the edible portion of fish




and shell fish.^3^  The U.S. EPA has also  recommended  that




contamination by chloroform not exceed 500  ug/1 in freshwater and




620 ug/1 in marine environments. *^3'




             Regulations -  Chloroform has been designated  as a priority




pollutant under Section 307(a) of the CWA.   OSHA has  set the TWA at




2 ppm.  FDA prohibits use of chloroform  in  drugs,  cosmetics and food




contact material.  The Office of Water and  Waste Management has pro-




posed regulation of  chloroform under Clean  Water Act  Section 311 and is




in the process of developing regulations under Clean  Water Act  304(a).




The Office of Air, Radiation and Noise is conducting  preregulatory




assessment of chloroform under the Clean Air Act.   The  Office  of Toxic




Substances has requested additional testing of chloroform  under Section




4 of the Toxic Substances Control Act and is conducting pre-regulatory




assessment under the Federal Insecticide, Fungicide and Rodenticide Act.




             Industrial Recognition of Hazard  -  Chloroform has  been




given a moderate toxic hazard rating for oral  and  inhalation exposures




(Sax, Dangerous Properties of Industrial Materials).^3Q'




         7.  Tetrachloroethanes




             Health Effects - 1,1,2,2-Tetrachloroethane has been




shown to produce liver cancer in laboratory mice; (31.) £t ^as aiso




been identified by the Agency as demonstrating substantial evidence




of carcinogenicity.(54)  xt is also shown to be very  toxic [oral rat

-------
LD5Q  s  20° mg/Kg-K   In addition, passage of 1,1,1,2-tetrachloroethane


across  the placental barrier has been reported.^29)  In Ames Salmonella
bioassay  1,1,2,2-tetrachloroethane was shown to be mutagenic.



Occupational  exposure of workers to 1,1,2,2-tetrachloroethane produced


neurological  damage,  liver and kidney ailments, edema, and fatty de-



generation  of the hear muscle.^3)  Both 1,1,1,2-tetrachloroethane


and l,l,2,2^tetrachloroethane are designated as priority pollutants
               i


under Section 307(a)  of the CWA.  Additional information and specific


references  on the adverse effects of tetrachlorbethanes can be found


in Appendix A.



             Ecological Effects - Freshwater invertebrates are


sensitive to  1,1,2,2-tetrachloroethane with a lethal concentration of


7-8 mg/1  being reported.(2°)  USEPA estimates the BCF to be 18.


             Regulations^'- OSHA has set the TWA at 5 ppm (skin)  for


1,1,2,2-tetrachloroethane.


             Industrial Recognition of Hazard - Sax, Dangerous


Properties  of Industrial  Materials, lists 1,1,2,2-tetrachloro-


ethane  as being highly toxic via ingestion, inhalation and skin


absorption.

-------
IV.  References




 1.  1979 Directory of Chemical Producers  United States.




 2.  Chemical Economics Handbook, Menlo  Park,  California.   December




     1978.  (May be purchased from SRI.)




 3.  Synthetic Organic Chemicals, U.S. Production and Sales,  U.S.  Inter-




     national Trade Commission.




 4.  Water Quality Issues in Massachusetts, Chemical  Contamination,




     Special Legislative Commission on Water Supply,  Sept.  1979




 5.  Memo from Roy Albert to E.G. Beck, Administrator,  EPA  Region  II,




     Drinking Water Contamination of New Jersey  Well  Water, March  31, 1978.




 6.  Wilson, J.T., and C.G. Enfield, 1979, Transport  of Organic Pollu-




     tants Through Unsaturated Soil.  Presented  American Geophysical




     Union.  December 3-7, San Francisco, CA.




 7.  National Cancer Insti-tute.   Bioassay of 1,2-Dichloroethane for




     Possible Carcinogenicity.  U.S. Department  of Health, Education and




     Welfare, Public Health Service, National Institutes of Health,




     National Cancer Institute,  Carcinogenesis Testing Program, DHEW




     Publication No.  (NIH) 78-1305,  January 10,  1978.




 8.  McCann, J., E. Choi,  E. Yamasaki,  and B. Ames.   Detection of Carcino-




     gens as Mutagenic in the Salmonella/Microsome Test: Assay of 300




     Chemicals.   Proc. Nat.  Acad.  Sci.  USA 72(2):5135-5139, 1975a.




 9.  McCann, J., V. Simmon,  D. Streitwieser, and B. Ames.  Mutagenicity




     of  Chloracetaldehyde,  a Possible Metabolic  Product of  1,2-Dichloro-




     ethane (ethylene  dichloride),  Chloroethanol  (ethylene chlorohydrin),




     Vinyl chloride, and  Cyclophosphamide.   Proc. Nat. Acad.  Sci. T2.




     (8):3190-3193.

-------
 10.  Vozovaya,  M., Changes in the Esterous  Cycle of White Rats Chronically




     Exposed to the Combined Action of  Gasoline and Dichloroethane Va-




     pors.   Akush. Genecol. (Kiev) 47  (12):  65-66,  1971.




 11.  Vozovaya,  M., Development of Offspring of Two  Generations Obtained




     from Females Subjected to the Action of Dichloroethane.   Gig. Sanit.



     7^:25-28, 1974.




 12.  Vozovaya,  M., The Effect of Low Concentrations of Gasoline,  Di-




     chloroethane and Their Combination on.the Generative Function of




     Animals and on the Development of'Progeny.   Gig.  Tr.  Prof.  Zabol.




     7_: 20-23, 1975.




 13.  Vozovaya,  M., Effect of Low Concentrations  of  Gasoline,  Dichloro-




     ethane and Their Combination on the Reproductive  Function of Animals.




     Gig. Sanit. 6:100-102, 1976.




 14.  Vozovaya,  M.A., The.^Effect of Dichloroethane on the  Sexual  Cycle




     and Embryogenesis of Experimental  Animals.  Akush. Genecol.   (Mos-




     cow) _2:57-59, 1977.




 15.  Urusova, T.P. (About a possibility of dichloroethane  absorption into




     milk of nursing women when contacted under  industrial conditions.)




 16.  Parker, J.C., et al. 1979.  Chloroethanes:  A Reveiw of Toxicity.




     Amer.  Indus. Hyg. Assoc.  J., 40: A 46-60, March 1979.




 17.  U.S. EPA,  1979.  Chlorinated Ethanes: Ambient Water Quality Cri-




     teria  (Draft).



 18.  NCI, 1977.   Bioassay of 1,1,1-Trichloroethane  for Possible




     Carcinogenicity.   Carcing. Tech.  Rep. Ser.  NCI-CG-TR-3.




 19.  Price,  P.J.,  et  al.  1978.   Transforming Activities of Trichloro-




     ethane  and  Proposed Industrial Alternatives.




20.  U.S. EPA Report,  1980,  In  Vitro,  14:290.  In Vitro Microbiological




    Mutagenicity  of  81  Compounds.
                                 -Mil-

-------
 21.   Schwetz,  B.A.,  et al.   1974.  Embryo and Fetal Toxicity  of  In-




      haled  Carbon Tetrachloride, 1,1-Dichloroethane and Methyl Chloro-




      form in Rats.   Toxicol.  Appl.  Pharmacol. 28:452.




 22.   Stahl,  C.J.,  et al.   1969.   Trichloroethane Poisoning.   Observa-




      tions  on  the Pathology and  Toxicology of Six Fatal Cases.  Jour.




      Forensic  Sci.,  14:393.




 23.   Walter  P.,  Chlorinated Hydrocarbon Toxicity, a Monograph.  PB-257185




      National  Technical Information Service,  Springfield, Virginia.




 24.   U.S. EPA,  1979.   In-Depth Studies on Health and Environmental Impact




      of  Selected Water Pollutants.   Contract  No. 68-01-4646.




 25.   Chlorinated Solvents,  Lloyd Elkin.   February 1969.  (May be purchased




      from SRI.)




 26.   Elovaara, E., et  al.   Effects  of  CH2C12,  CH3C13,  TCE,  Perc and Tol-




      uene in the Development  of  Chick  Embryos,  Toxicology 12:  111-119,  1979.




 27.   Parker, J.C., I.W.F. Davidson  and M.M. Greenberg, EPA Health Assess-




      ment Report of  1,2-Dichloroethane (Ethylene Dichloride).   In prepara-



      tion.




 28.   Environmental Health Perspectives,  1977, Vol.  21, 333  pp.




 29.   Van Duuren, B.L.,  et al.  1979.  Carcinogenicity of Halogenated




      Olefinic and Aliphatic Hydrocarbons  in Mice.   J.  Nat.  Cancer Inst.




     _63(6):   1433-1439.




 30.   Sax, N.I.,  Dangerous Properties of  Industrial  Materials.




 31.  Viola,  P.L., et al., Oncogenic Response of  Rat Skin, Lungs,  and




     Bones to Vinyl Chloride.  Cancer  Res. 31:  516, 1971.




32.  Maltoni, C., and G. Lefemine, Carcinogenicity  Bioassays of Vinyl




     Chloride.   Am. NY Acad. Sci. 246:195 (1975).

-------
33.  Lee, F.I.,  and Harry, D.S., Angiosarcoma  of  the  Liver in a Vinyl




     Chloride Worker.   Lancet 1: 1316 (1974).




34.  Creech  & Johnson,  Angiosarcoma of the Liver  in the Manufacture




     of  Polyvinyl  Chloride.  Jour. Occup. Med.  16:150,  1974.




35.  Falk, H.,  et  al.   Hepatic disease among workers  at a  Vinyl




     Chloride Polymerization Plant.  Jour. Amer.  Med. Assoc.  230:59




     (1974).




36.  Makk, L.,  et  al.   Liver Damage and Liver  Angiosarcoma in Vinyl




     Chloride Workers.   Jour. Amer. Med. Assoc. 230:64  (1974).




37.  Tabershaw,  I.R.,  and Gaffey, W.R., Mortality Study of Workers in




     the Manufacture of Vinyl Chloride and its  Polymers. Jour.  Occup.




     Med.  16:509 (1974).




38.  Oster,  R.H.,  et al.  Anesthesis, XXVII, Narcosis with Vinyl




     Chloride Anesthesiology 8: 359, 1947.




39.  Carr, J.,  et  al.   Anesthesis XXIV.  Chemical Constitution of




     Hydrocarbons  and  Cardiac Automaticity.  J. Pharmacol.  97:1  (1949).




40.  Torkerson,  T.R.,  et al.  The Toxicity of  Vinyl Chloride  by Re-




     peated  Exposure of Laboratory Animals - Amer. Ind. Hyg.  Assoc.




     Jour. ^:354  1961.




41.  Lester, D., et al.  Effects of Single and  Repeated Exposures of




     Humans  and  Rats to Vinyl Chloride.  Amer.  Ind. Hyg. Assoc. Jour.




     2.4^:265, 1963.



A2.  National Cancer Institute,  1976.  Report on  Carcinogenesis Bio-




     assay of Chloroform.   National Technical  Information  Service,




     PB-264018.  Springfield,  Virginia.



A3.   U.S. EPA,  1979.  Trichloromethane (Chloroform) Hazard Profile,




     USEPA/ECAO, Cincinatti,  Ohio 45268.   1979.

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44.  McCabe,  L.J.,  1975.   Association Between Trihalomethanes in




     Drinking Water (NORS Data) and Mortality.  Draft Report.  U.S.




     EPA.




45.  Schwetz,  B.A., et  al.   1974.   Embryo and Fetotoxicity of Inhaled




     Chloroform in  Rats.   Toxicol.  Appl.  Pharmacol. 28:442.




46.  Thompson,  D.J.,  et al.1974.   Teratology Studies on Orally Admin-




     istered  Chloroform in the  Rat  and Rabbit.  Toxicol. Appl. Pharmacol.




     29:348.




47.  Dawson,  English, and Petty,  1980.   "Physical Chemical Properties of




     Hazardous  Waste  Constituents",  Table 1.




48.  EPA, Hazardous Waste Division,  Technology and Management Assessment




     Branch,  "Annual  Study  of Personal  Injury, Economic Damage or




     Fatalities  from  Hazardous  Waste",  1978.




49.  Barth, E.  F.,  Cohen, J. M., "Evaluation  of Treatability of  Industrial




     Landfill Leachate",  unpublished report,  U.S.  EPA,  Cincinnati,  November




     30, 1978.




50.  O'Brien, R.  P.,  City of Niagra  Falls,  New York,  Love Canal  Project,




     unpublished  report.  Calgon Corp., Calgon Environmental Systems




     Division, Pittsburgh,  Pennsylvania.




51.  Rcera Research,  Inc.   Priority  Pollutant Analyses  prepared  for Nuco




     Chemical Waste Systems, Inc., unpublished report,  Tonawanda, New




     York, April, 1979.




52.  Sturino, E., Analytical Results:   Samples From Story Chemicals,  Data




     Set Others 336", unpublished data, U.S.  EPA Region 5,  Central  Regional




     Laboratories, Chicago, Illinois, May,  1978.




53.  Source Assessment Chlorinated Hydrocarbons Manufacture.   EPA-600/2-



     78-004.
                                   -SIS-

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                LISTING BACKGROUND DOCUMENT


     TRICHLOROETHYLENE AND PERCHLOROETHY.LENE  PRODUCTION


Column bottoms or heavy ends from the combined
production of trichloroethylene and perchloroethylene  (T)


Summary of    **
    The column bottoms or heavy ends from  the  combined  pro-

duction of trichloroethylene and perchloroethylene are generated

when recycling streams from the chlorination and oxychlorination

processes become contaminated and must be removed and disposed.

The Administrator has determined that these heavy ends are

solid wastes which may pose a present or potential hazard to

human health and the environment when improperly transported,

treated, stored, disposed of or otherwise managed and therefore

should be subject to appropriate management requirements

under Subtitle C of RCRA.  This conclusion  is based on the

following consideration:

    (1)  The column bottoms or heavy ends  from combined
         trichloroethylene and perchloroethylene production
         contain significant concentrations of 1 , 1 , 2 , 2-tetra-
         chloroethane , hexachlorobutadiene , and hexachloro-
         benzene,  each of which are carcinogenic.  Also,
         1,1, 2, 2-tetrachloroethane is a known mutagen.  All
         of these  substances are also toxic to aquatic  lif.e
         and bioaccumulate in living tissues.   In addition,
         the waste contains smaller amounts of ethylene di-
         chloride, hexachloroethane and 1,1,1,2 tetrachloro-
         ethane,  all substances with carcinogenic and/or
         mutagenic properties.

    (2)   A  large  quantity (a combined estimated total of at
         least  15,000 metric tons) of these wastes is generated
         annually.
                             -M7S"-

-------
      (3)   The  wastes  are  disposed of primarily through
           incineration  or landfilling.   Smaller amounts are
           deep well  injected into limestone formations.  If
           not  managed properly,  these hazardous contaminants
           could be emitted to the air from inadequate incinera-
           tion or  improper land  disposal or leach from landfills
           and  injection wells to expose humans and other life.
           The  chlorinated organics  1 , 1 , 2 , 2-tetrachloroethane,
           hexachlorobutadiene , and  hexachlorobenzene , as well
           as ethylene dichloride,  are water soluble and there-
           fore could  migrate from the wastes to contaminate
           groundwater in  concentrations sufficient to cause
           substantial hazard.
 Industry  Profile ^>2» 3> *)

      Perchloroethylene  and  trichloroethylene  are  produced  in

 a  combined  process  by seven companies  at  ten  manufacturing

 locations primarily situated  in  the  Texas  and Louisiana  Gulf

 area.   The  location of  the  facilities,  their  annual  production

 capacity, and  es t imated~'±'979  production are shown in Table 1

 and Figure  1.  As shown in  Table  1,  the estimated 1979 production

 for perchloroethylene and trichloroethylene are 367,500  and

 125,300 MT, respectively.   The annual  production  levels  for

 each  individual plant are variable and  range  from 12,600 to

 63,700 MT for  perchloroethylene  producers  and  14,000 - 63,700

 MT for manufacturers of trichloroethylene.  Average  annual

 per plant production figures  are  36,750 MT for perchloroethylene

 and 41,400 MT  for trichloroethylene.

     There currently is excess capacity within this  industry

 for both the production of  perchloroethylene  and  trichloroethylene

 Increased regulatory pressures from  both the  Environmental

Protection Agency (EPA)  and the Occupational  Safety  and  Health

-------
                                         ESTIMATED CAPACITY AND PRODUCTION

                                      PERCHLOROETHYLENE AND TRICHLOROETHYLENE
COMPANY
                       LOCATION
                                                1979 CAPACITY  (MT/YR)B                1979 PRODUCTION  (MT/YR)
                                        PERCHLOROETHYLENE    TRICHLOROETHYLENE  PERCHLOROETHYLENE  TRICHLOROETHYLENE
Diamond Shamrock
Dow


Deer Park, TX
Freeport, TX
Pittsburg, CA
Plaquemine, LA
75,000 A
68,000 68,000
18,000
54,000
52,500
47,600
12,600
37,800

47,600


Dupont
                       Corpus Christ!, TX     73,000
                                                                                      51,100
Ethyl
                       Baton Rouge, LA
                                               23,000
20,000
16, 100
14,000
PPG
                       Lake Charles, LA
                                              91,000
91,000
63,700
63,700
Stauffer
                        Louisville, KY
                                               32,000
                    22,400
Vulcan
                        Geismar,  LA

                        Wichita,  KS
                                               68,000

                                               23,000
                                     TOTAL    525,000
                                                                 179,000
                    47,600

                    16,100

                   367,500
                                                                                                         125,300
A23,000-MT/yr.  capacity  unit  placed on  standby in early 1978
BMT  =  Metric  tons
SOURCE:  References  1,  2,  3, 4

-------
                                   FIGURE 1

                      LOCATIONS OF PLANTS MANUFACTURING
                  PERCHLOROETHYLENE  AND TRICHLOROETHYLENE
\ V.-.
 >  \ !•
                                                                        .
                                                                      .-'  \
                                                                    ,./..    \
                                                                   —"'    \
6)
7)
8)
9)
     1)  Diamond Shamrock Corp., Deer Park,
     2)  Dow Chemical Co., Freeport, IX
     3)  Dow Chemical Co., Pittsburg, CA
     4)  Dow Chemical Co., Plaquemine, LA
     5}  DuPont, Corpus Christi, IX
         Ethyl Corp., Baton Rouge, LA
         PPG Industries, Inc., Lake Charles, LA
         Stauffer Chemical Co., Louisville, KY
         Vulcan Materials Co., Geismar, LA
     10) Vulcan Materials Co., Wichita, KS
     A = perchloroethylene, B = trichloroethylene
     SOURCE:  Reference 9
Chemicals Produced
         A
        A,B
         A
         A
         A
        A,B
        A,B
         A
         A
         A
                                       -*-

-------
 Administration  (OSHA)  are serving to  inhibit  future growth in


 demand  for  these  chemicals.  It is anticipated  that short-


 and long-term growth will average 1-2%  and  that  the industry


 output  can  be represented by a flat growth  curve.




 Manufacturing Process (3)
 •••••>—>—>im m' ** *""" *" '*" ^*•••   •

     Perchloroethylene and trichloroethylene  are  produced


 either  separately or as co-products by  either the .chlorination


 or oxychlorination  of  ethylene dichloride or  other  €£-


 chlorinated hydrocarbons.   The ratio  of raw material  feed


 determines  the  relative yields of perchloroethylene and


 trichloroethylene.   Perchloroethylene is also produced by  the


 chlorlnolysis of  light hydrocarbons with by-product production


 of carbon tetrachloride.


     This listing document covers wastes generated  by the


 co-production process.




     °  Direct Chiorinationo^ Ethylene Pichloride (See Figure 2)




    Perchloroethylene and trichloroethylene are produced  by


 a single-stage  oxychlorination process from ethylene dichloride


 and  chlorine.    Ethylene dichloride,  chlorine, oxygen, and


 recycled chlorinated organics are fed  to a fluid bed reactor.


An inexpensive  oxychlorination catalyst (e.g., copper chloride)


is used and  the  reactor is  maintained  under pressure and at


about 425°C.  Feed adjustments  may be  employed to vary product

-------
                                                                           NI
                        FIGURE 2
       DIRECT  CIILORINATION OF ET1IYLENE BICHLORIDE
Ethylene

dichloride-H

Chlorine	

Oxygen	

Steam	
Reactor
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0)
x>
,0
3
M
O
                            4-J
                            d
                            
fd
(U

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c
<
1
(
r-
J
(
*r
>
t


H
H
_i
n
D
M
H
3
J
H
-i
H









V
^


J
> f

K
a
ts
*r"
i —
tt
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4-
t-
CL
^

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>

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t


»







»-
Q
*r
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c

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4
)
H
-l
5



*T*v 4 »-.
i ric
V




§
M
PI
^C
W
«J
iH
PH
0
„ v

Perchlor Still
                                                                       Flash

                                                                       Drum
                                                                                               Trichloroethylene
                                                                       

a;
J3
Q)
•H
M
                                                                                  Perchloroethylene
                                                                                                Waste
             Reaction
             2CJ1,C1.
               7HC1
                                     1.750
                           1.5C12'+ 1.7502
                                                                  5HC1
                           - C2HC15

                           2HC1  + (
                  3.5H20 + 3.5C12 (Deacon)

                         + CCl   + 3.5H0
                                       85 to 90% yield
      SOURCE:   Reference 3.

-------
 ratios, depending upon  producer requirements.




     The condensed crude  and weak acid are then phase-separated




 with the crude, being dried by azeotropic distillation.   In




 the perchlor-trichlor column, the crude is split into two streams,




 one trichlor-rich and the other perchlor-rich.  The perchlor-




 rich stream, containing midboilers and heavies, is fed to the




 heavies column where high boilers (1,1,2,2- and 1,1,1,2-




 tetrachloroethane, pentachloroethane,  hexachloroethane, dimers,




 tar and carbon) are removed as bottoms and flashed to remove




 tars and carbon.  Midboilers are concentrated in the overheads




 and recycled.  Perchlor recovered from the bottoms of the




 still is neutralized with ammonia, washed, and dried.




     The crude trichlor stream is fed  to the trichlor product




 still, where low boilers,  such as dichloroethylenes,  are




 removed overhead and recycled to the reactor.  Trichlor is




 removed from the bottom,  neutralized with ammonia, washed,




 and dried.




     This process description is an example of one of several




 processes for the manufacture of perchloroethylene and tri-




 chloroethylene from ethylene dichloride.   Similar waste con-




 stituents (i.e., a range  of chlorinated organic hydrocarbons,




 including 1,1,2,2-tetrachloroethane, hexachlorobutadiene,




and hexachlorobenzene), are expected regardless of the




process.
                            -M9I-

-------
Waste Generation and Management




     1.   Waste Generation




     The column bottoms  or heavy  ends  from  the  combined  pro-




duction of perchloroethylene and  trichloroethylene  can contain




a wide variety of chlorinated hydrocarbons.   A  typical chemical




composition for the waste stream,  often  referred  as  hex  waste,




is shown in Table 2 with composition presented  in terms  of




weight and mole percent.(2»9) This information  indicates




that the primary constituents of  the waste.stream are 1,1,2,2-




tetrachloroethane, hexachlorobutadiene,  and hexachlorobenzene.




(Table 2 also includes solubilities of the waste  stream



constituents.)(2,9,20)




     The information presented in  Table  2 was employed to cal-




culate the expected quairtities of  each hazardous  component which




is generated on an annual basis.   Personal communications(5,6, 7)




with selected chemical manufacturers and a review of the




available literature indicate that the quantity of still




bottoms which becomes contaminated and must be disposed can




approach 3-5 percent of production.  Assuming that these wastes




are generated at a rate of 3% of production, the  estimated




quantity of each component is presented  in Table  3.  The




estimated annual generation rates are shown to range from




88-4996 metric tons  for the individual waste components.



     2.    Waste  Management (5,6,7)




     Additional  information was  collected to assess  the current




practices employed for handling  these waste streams  on an

-------
                              TABLE  2
TYPICAL

	 —
rlene Bichloride
rTrichloroethane
ihloroethylene
1 2-Tetrachloroethane
,2 2-Tetrachloroethane
tachloroethane
achlorobutadiene
achlorobenzene
ichloroethane
TOTAL
ICE: References 2,9
Dnverted to PPM, Value -
SOLUBILITY OF P
IN
plene Bichloride
a-Trichloroethane
COMPOSITION OF HEX-WASTES

MOLE % WEIGHT % SOLUBILITY g/lOOg
distilled water
1.4 0.6 .80
7.2 4.5 .50
5.7 4.5 .01
7 .9 ,6.3 .01
2.9.1 23.0 .29
2.7 3.3 <.05
27.5 33.8 .0000005
14.9 20.0 <.05
3.6 4.0
100.0 100.0

g/lOOg x 104
ARTICULAR HEX WASTE CONSTITUENTS
PPM (DISTILLED WATER)
8,690
4,500

in
PPM*
8,000
5,000
100
100
2,900
<500
0.005
<500
Very low




:hloroethylene            150 -  200




,2,2-Tetrachloroethane       2,900
achlorobutadiene




.achlorobenzene




achloroethane
  :   Reference 20
                       0.006  -  0.020
                                50

-------
                           Table 3

   PROJECTED QUANTITIES OF INDIVIDUAL HEX-WASTE  COMPONENTS
MOLE %
Hexachlor
1,
He
1,
He
Et
Pe
be
Pe

1,2,2-T
xachlor
1,1, 2-T
xachlor
hylene
rchloro
ta-Tric
ntachlo

ob
et
ob
u
r
e
etr
oe
Di
et
hi
ro

t
c
t
a
n
a
adiene
chloroe thane
zene
chloroethane
hane
hlor ide
hylene
0
e

r
t

oe thane
hane
TOTAL
27
29
14
7
3
1
5
7
2
100
.5
.1
.9
.9
.6
.4
.7
.2
.7
.0
WEIGHT % ANNUAL PRODUCTION
33
23
20
6
4
0
4
4
3
100
.8
.0
.0
.3
.0
.6
.5
.5
.3
.0
4,9
96
3,400
2,956
931
5

91
88
665
6
65
448
14,7
80
SOURCE:  Estimate based on Table 2 and waste generation
        rate of 3% of production.  (Waste streams are,
        however, subject to variation in terms of both
        composition and rate of generation.)
                             -vf-
                             -S34-

-------
individual basis.  The  available information indicates  that




these wastes are either being incinerated or disposed  of




through landfill or  deep well injection into limestone  for-




mations.  Table 4 identifies the estimated quantities  of




waste being generated at each production facility and  the




current procedures for  disposing of these wastes.  As  shown




in Table 4, approximately 70% of the wastes are incinerated,




with 22% going to landfill and 7% to deep well injection.




D.  Hazards -Posed by Waste
    •m mf *m • • »• •• m\\ mi'umi •§•§!• \m n> in m MI HI • m



    As noted above, most of these hex wastes are incinerated.




Inadequate incineration conditions -- i.e., temperature and




residence times—can result in the airborne disposal of uncom-




busted chlorinated organics, partially combusted organics




and newly formed organic compounds.  Phosgene is an example




of a partially combusted chlorinated organic which is produced




by the decomposition or combustion of chlorinated organics




by heat.(1Q»11i12)  Phosgene has been used as a chemical




warfare agent and is recognized as extremely toxic.




    The landfilling of  column bottoms or heavy ends in an




unsecure land disposal  facility may result in groundwater




contamination caused by  migration of the toxic chlorinated




organics from the waste  into the surrounding environment.




The most carcinogenic wastestream pollutant,  1,1,2,2-tetra-




chloroethane,  is  highly  soluble in water,  as shown in Table 2.




Ethylene dichloride,  another carcinogen found in the waste-




stream,  is  even more  soluble and thus would also tend to migrate

-------
                                                         TABLE 4
                                      WASTE GENERATION RATES AND MANAGEMENT PROCEDURES
         Company

         Diamond Shamrock Corporation
                                    Location
                                    Deer Park, TX
                     Waste Production
                     	MT	

                          1,570
                 Current Disposal
                     Practice	

                        LF
         Dow Chemical U.S.A.
                                    Freeport, TX

                                    Pittsburg, CA

                                    Plaquemine, LA
                         2,850

                          370

                         1,130
                        I

                        I

                        I
 I
£
oO
^
 I
         E.I. DuPpnt de Nemours
           Company, Inc.
Ethyl Corporation
         PPG Industries
                                    Corpus Christi, TX
Baton Rouge,  LA
                                    Lake  Charles, LA
                         1,530
940
                          3,820
DWI
         Stauffer Chemical Company
                                    Louisville, KY
                           670
                         LF
  Vulcan Material Company
  I  -  Incineration
  DWI  - Deep Well Injection
      - L,andfill
   SOURCE:  References 5,  6,  7
                                    Geismar,  LA

                                    Wichita, KS
                          1,420
                                                                              480
                                                                 TOTAL    14,780

-------
 from the waste.   The  remaining chlorinated organics  in  the waste




 stream  are also water soluble to some extent  (see  Table  2).




 These compounds also  have demonstrated potential for mobility




 through soils  and persistence in groundwater.(1?)   (See




 also information  summarized at pp. 15-20 below.)   Thus,  it




 appears likely that hazardous constituents may escape from




 this waste stream and contaminate groundwater.  There clearly




 is insufficient' justification to warrant , finding that waste




 constituents will not migrate into groundwater if  improperly




 managed.  It should be noted that many facilities  generating




 these wastes are  located in the Texas and Louisiana Gulf




 area (see Figure  1) where rainfall precipitation is heavy,




 so that the wastes are exposed regularly to solubilizing media.




     Another problem  wi'fh" the landfilling of  these wastes is




 the potential  for these contaminants, particularly hexachloro-




 benzene, to volatilize into the surrounding atmosphere.  An




 actual  damage  incident confirms this risk.   In the Louisiana




 area in the early 1970Ts, hex wastes containing hexachlorobenzene




 (HCB),  a relatively volatile material, were transported  over




 a period of time  to municipal landfills in uncovered trucks.




 High levels of HCB have since been reported in the blood




 plasma  of individuals  along the route of transport'8'.




 Jn a sampling of  29 households along the truck route, the




average plasma level  of HCB was 3.6 ppb with a high of 23 ppb,




while the average plasma  level of HCB in a  control group was




°«5  ppb with a high of  1.8  ppb (Farmer et.  al., 1976).

-------
Additionally,  cattle  in  the  surrounding area absorbed HCB in




their  tissue  and  20,000  animals  were quarantined by the State




Department  of  Agriculture  (Lazar 1975)(8).




     The  deep  well  injection  of  these wastes in permeable




limestone formations  is  also  practiced by the industry and




could  result  in the migration of the hazardous  constituents




from the  waste and  present the same  type  of  problems  presented




when these  wastes are  insecurely landfilled.




     An additional  reason.for listing these  wastes, as  hazardous




are the large  volumes  generated  annually.  The  estimated




quantities  of  hex wastes disposed  of by each producer  range




from 370  to 3,820 metric tons per  year (Table 4).   This is a




significant quantity  of waste disposal by individual  generators




in the same area.   It  i"s~"~expected  that producers will  use  the




same disposal  facility for long  periods of time, causing  more




exposure  over  longer  time  periods  to populations in the same




disposal  facility areas if wastes  are  improperly managed.




Also, more  exposure would  be  expected  along  prevalent  migration




and transport routes.




     Additional health and environmental  fate information  on




the listed  constituents of concern is  presented  in  the following




section of  this document.  In  general,  this  information indicates




qualitatively that these constituents  are sufficiently mobile and




persistent  to reach environmental  receptors.  In light of  the ex-




treme dangers to human health  and  the  environment posed by these




constituents,  there is insufficient  indication  of environmental




degredation to justify a failure to  list  this waste as hazardous.

-------
      and EcologicalEf f ects
 1.   Hexachlorobenzene  (HCB)




     Priority_Pollutant  - HCB is currently listed as a pri-




 ority pollutant under  Section 307(a) of the Clean Water Act.




               ££? ~   Hexachlorobenzene (HCB) has produced
 cancers in animal species.(13, 14)  Other animal studies have




 shown  that HCB crosses  the  placental barrier to produce toxic




 effects and fetal mortality.(15)   Hexachlorobenzene is stored




 for long periods in body  fat*  Chronic - exposure to HCB has




 been shown to result  in damage  to the liver and spleen.(16)




 It has also been demonstrated that at doses far below those




 which  are lethal, HCB enhances  the body's capability to




 toxify, rather than detoxify, other foreign organic compounds




 present in the body.'*7)




    Virtually all hexachlorobenzene emitted from an uncontrolled




 landfill is expected  to persist  in groundwater or reach




 surface waters via groundwater  movement.(*°/   Such behavior




 is likely to result in exposure  to humans using potable




 water supplies within the exposed adjacent areas.




    The recommended ambient  criterion(*^^ level for HCB in




 water is 1.25 nanograms per liter.   Actual measurements,  on the




 other hand,  of finished drinking  water in certain geographic




 areas have  been measured at levels  six times the recommended




 criterion  designed to protect human health,  demonstrating the




nobility and  persistence of the material  (See Appendix A.)

-------
     Ecological  Effects  -  Hexachlorobenzene is very persistent.




It has  been  reported  to  move  through  the soil into the ground-




water.^^   Movement  of  hexachlorobenzene within surface




water systems  is  projected  to  be  widespread.(1°)  Movement to




this degree  will  likely  result  in exposure to aquatic  life




forms in  rivers,  ponds,  and reservoirs.   Similarly,  potential




exposure  to  humans  is  likely where  water supplies  are  drawn




from surface waters.




     Hexachlorobenzene is likely  to contaminate  accumulated




bottom  sediments  within  surface water  systems  and  bioaccumulate




in fish and  other aquatic organisms.(18)




     Regulatory Recognition of Hazard  -  As  indicated in  Appendix




A, hexachlorobenzene  is  a chemical  evaluated  by  GAG as having




substantial  evidence  of  carcinogenicity.   Ocean  dumping  of




hexachlorobenzene is  prohibited.  An interim  food  contamination




tolerance of 0.5  ppm  has been established  by  FDA.




     Additional information on the  adverse  effects of




hexachlorobenzene can be found in Appendix  A.




2.   Hexachlorobutadiene (HCBD)




     Priority^Pollutant  - Hexachlorobutadiene  is a priority




pollutant under Section  307(a) of the  FWPCA.




     Health^Effects - Hexachlorobutadiene  (HCBD) has been  found




to be carcinogenic in animals.(22)  Upon  chronic exposure  to




animals  by the DOW Chemical Company and  others,  the kidney




appears  to be the organ most sensitive to HCBD.(22,23,24,25)




The recommended human health -criterion level  for this  compound

-------
in water, is  .77 ppb.   (See 44 Fed. Reg. 15926, 15954  (March

15, 1979).)

    Virtually all  HCBD emitted from the waste management

scenario described  previously is expected to persist in

groundwater or reach  surface waters via groundwater movement.C18)

Such behavior is likely to result in exposure "to humans

using  such groundwater,sources as drinking water supplies

within adjacent areas...

    Ecological Effects - Movement of HCBD within surface water

systems  is projected  to be widespread. (18)

    HCBD is  likely to  contaminate accumulated bottom  sediments

within surface water  systems and is likely to bioaccumulate in

fish and other aquatic  organi sms . ( ^ )

    The USEPA (1979) has estimated that the BCF is at 870 for

the edible portion  of fish and shellfish consumed by Americans.

    Hexachlorobutadiene  is persistent in the environment.^^)

It has been reported  to move through soil into groundwater

from Hooker Chemical's  Hyde Park waste disposal site,* and

thus is mobile enough to  migrate from improperly managed

landfills into the  environment.

    Industrial Recognition of Hazard - Hexachlorobutadiene is

considered to have  a high toxic hazard rating via both oral

and inhalation routes (Sax, Dangerous Properties of Industrial

Materials).

    Additional information on the adverse effects of  hexa-
*°SW Hazardous Waste Division,  Hazardous Waste Incidents,
 Published,  Open File, 1978.
Un-
                             -vf-

-------
chlor obutadiene can  be  found  In  Appendix A.



3 .   Hexachloroethane



     Priority Pollutant  -  Hexachloroethane  is  a  priority



pollutant under Section  307(a) of  the  FWPCA.



     Health Effects  - Hexachloroethane  has  been  reported to  be



carcinogenic to animals, meaning that  humans may be  similarly



affected. (27)  Humans exposed to vapors  at  low concentrations



for short periods have had liver,  kidney, and heart degeneration


                                   / O Q A
and centra:! nervous  system damage, \*-'° '


     Virtually all hexachloroethane  emitted from a landfill



is expected to persist in  groundwater  or  reach surface waters


via groundwater movement. (18)  Such  behavior is  likely to



result in exposure to humans using  such  groundwater  sources as



drinking water supplies -within adjacent  areas,



     Ecological Effects  - Movement  of hexachloroethane within


surface water systems is projected  to be widespread . (1 8)



Movement to this degree  will likely  result in  exposure to



aquatic life forms in rivers, ponds, and reservoirs.


     Hexachloroethane is likely to  be released to the atmosphere


from surface water systems. (18)



                Reognition of Hazard -  OSHA has  set a TWA for
hexachloroethane at 1 ppm (skin).  Measurements of this


compound in finished drinking water have shown that hexachloro-


ethane occurs at least at the recommended water criterion


level, (28) confirming that this compound may persist in

-------
 dangerous  concentrations.




     Additional  information on the  adverse  effects of hexa-




 chloroethane  can be found in Appendix  A.




 4.   Tetrachloro ethanes
     «•«••'• ^*^r^r-^r*^^mr*^**r*r*mr***^**r



     Priority Pollutant - Both 1 , 1 , 1 , 2-tetrachloroethane and




 1,1,2,2-tetraehloroethane are designated  as  priority pollutants




 under Section 307(a) of the FWPCA.




   ,  Hgaitj^Ej^g^s ~ 1,1, 2, 2-Tetrachloroetharie  has  been shown



 to produce liver cancer in laboratory  mice. (29)   in  addition,




 passage  of 1 , 1 , 1 , 2-tetrachloroethane across  the  placental




 barrier  has  been reported. (30)   jn  an  Ames  Salmonella bioassay,




 1,1,2,2-tetrachloroethane was shown to be mutagenic. ( 31)




 Occupational  exposure o.f_. workers to 1,1,2,2-tetrachloroethane




 produced neurological damage, liver and kidney ailments, lung




 edema and  fatty  degeneration of the heart muscle. (32)




     Ecological  Effects - Freshwater invertabrat es are  sensitive




 to 1,1,2,2-tetrachloroethane with a lethal concentration of  7-



 8 mg/1 being  reported. ( 33)  USEPA estimates  the  BCF  to  be 18. (33)




     Regulations  -  OSHA has set the TWA at 5  ppm  (skin)  for




 1,1,2,2-tetrachloroethane.




     Additional  information on the adverse effects of tetra-




 chloroethanes can be  found in Appendix A.





 6'
    Priority Pollutants  -  Ethylene dichloride  (1 , 2-dichloroethane)




is designated as a priority pollutant under Section  307(a)  of

-------
the FWPCA.




     Health Effects - Ethylene dichloride has  been  shown  to




cause cancer in laboratory animals.(34)  jn addition,  this




compound and several of its metabolites are highly  mutagenic.(35)




Ethylene dichloride crosses the placental barrier and  is




embryotoxic and teratogenic.(36»37»38>39»40^   It has also




been shown to concentrate in milk.(4D  Exposure to this




compound can cause a variety of adverse health effects




including damage to the liver, kidneys and other organs.  It




can also cause internal hemorrhaging and blood clots. (42)




     Regulatory Recognition of Hazard -  OSHA has set  the




TWA at 50 ppm.  The Office of Air, Pollution and Noise has




completed a preregulatory assessment for ethylene dichloride




under Sections 111 and 112 of the Clean Air Act.  Preregulatory




assessments are also being conducted by EPA's Office of




Water and Waste Management under the Safe Drinking Water Act




and by the Office of Toxic Substances under the Toxic  Sub-




stances Control Act.




     Indus trial Recognition of Hazard - Sax in Dangerous




Properties of Industrial Materials rates ethylene dichloride




as highly toxic upon ingestion and inhalation.




     Additional information on the adverse effects of  ethylene




dichloride can be found in Appendix A.
                             -vf-

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                          References

1.   Chemical Profiles,  Schnell Publishing Company, Inc.,
     New York,New York.

2.   "Emission Control Options for the Synthetic Organic
     Chemicals Manufacturing  Industy:  Carbon Tetrachloride
     and Perchloroethylene,"  EPA,  Office of Air Quality
     Planning and Standards.   Contract Number 68-02-2257.

3.   Lowenhein, F. A., and Moran,  M. K., Faith, Keyes, and
     Clark's Industrial  Chemicals,  4th Ed., Wile.y Inter-
     science, 1975.

4.   TRW, "Assessment of  Industrial Hazardous Waste Practice:
     Organic Chemicals,  Pesticides, and Explosives," USEPA,
     SW-118c, January 1976.

5,   Personal communication with Dr. H. Farber, Dow Chemical
     Company, Midland, Michigan, February 1980.

6.   Personal communication with Mr. Perry Norling, DuPont Co.,
     Wilmington, Delaware,  February 1980.

7.   Personal communication with Dr. Frederick C.  Dehn, PPG
     Industries, Pittsburgh,  Pennsylvania, February 1980.

8.   OSW - Hazardous Waste Management  Division - "Hazardous Waste
     Incidents": Unpublished  Open  File Data,  1978.

9.   Emmission Control Options for  the Synthetic Organic Chemical
     Manufacturing Industry:  1,1,1-trichloroethane  Product Re-
     port," EPA, Office  of Air Quality Planning and Standards,
     July 1979, Contract  Number 68-02-2577.

10.   Combustion Formation and  Emission of Traces Species", John
     B. Edwards, Ann Arbor Science, 1977.

11.   NIOSH Criteria for  a Recommended  Standard: Occupational
     Exposure to Phosgene,  HEW,  PHS,  CDC, HIOSH, 1976.

12.   Cabral, J. R. P., et al.   Carcinogenic activity of Hexa-
     chlorobenzene in hamsters.  Tox.  Appl. Pharmacol.   41:155
     (1977).

13.   Cabral, J. R. P., et al.  1978.  Carcinogenesis study in
     mice with hexachlorobenzene.   Toxicol. Appl.  Pharmacol.
     45:323.

14-   Grant,  D.  L.  et al.   1977.  Effect of hexachlorobenzene on
     reproduction  in the  rat.   Arch. Environ.  Contam.  Toxicol.
     5:207.

-------
15.  Grant, et. al.,  1977.

16.  Koss, G., et  al.,  1978.   Studies on the toxicology of
     hexachlorobenzene .   III.   Observations in a long-term
     experiment.   Arch.  Toxicol.   40:285.

17.  Carlson, G. P.,  1978.   Induction of cytochrome P-450 by
     halogenated benzenes.   Biochem.  Pharmacol.  27:361.

18.  Technical Support  Document  for  Aquatic Fate and Transport
     Estimates for Hazardous  Chemical Exposure Assessments.
     1980.  USEPA, Environmental  Research  Lab., Athens, Georgia.

19.  U.S. EPA.  Chlorinated  Benzenes:  Ambient Water Quality
     Criteria, 1979.

20.  U.S. EPA.  1979.   Water-Related  Environmental Fate of
     129 Priority  Pollutants.   EPA-440 /4-7 9-02 9b .

21.  Zoeteman, B., et.  al.,  1979.  Persistent Organic Pollutants
     in River Water and  Ground  Water  of  the Netherlands.
     Presented at  3rd  International  Symposium on Aquatic
     Pollutants, October  15-17,  1979.   Jekyll Island, Georgia.

22.  Kociba, R. J., Results  of  a  Two-year  Chronic  Toxicity Study
     vith Hexachlorobutadiene  in  Rats.   Amer .  Ind .  Hyg . Assoc.
     38: 589, 1977.

23.  Kociba et. al.   Toxicologic  Study  of  Female Rats Administered
     Hexachlorobutadiene  or Hexachlorobenzene for  30 Days.   DOW
     Chemical Company,  1971.

24.  Schwetz, et.  al.,  Results  of  a Reproduction Study in  Rats
     Fed Diets Containing Hexachlorobutadiene.   Toxicol. Appl.
     Pharmacol. 4_2_:387,  1977.

25.  Schroit, et.  al.,  Kidney Lesions Under Experimental Eexa-
     chlorobutadiene Poisoning.   Aktual, Vpo.  Gig.  Epidemiol.
     73. CA:81:73128F  (translation),  1972.

26.  Li, et. al.,  Sampling and Analysis  of  Selected Toxic
     Substances .   Task  IB- Hexachlorobutadiene.  EPA-560/
     6-76-015.  USEPA,  1976.

27.  National Cancer Institute.   Bioassay  of  Hexachloroethane for
     Possible Carcinogenicity .  No. 78-1318,  1978.

28.  U.S. EPA.  Chlorinated Ethanes:  Ambient  Water Quality Criteria,
     1979.

29.  National Cancer Institute.   Bioassay  of  1 , 1 , 2 , 2-Tetrachloro-
     ethane for Possible  Carcinogenicity.   U.S. Department of
     Health,  Education  and Welfare, Public  Health Service,
                             -HU-

-------
     National Institutes  of Health, National Cancer Institute
     DREW Publication  No.  (NIH) 78-827, 1978.

 30.  Truhaut, R. , Lich, N.P.,  Dutertre-Catella, H. T. Molas, G.
     Huyen, V.N.: lexicological Study of 1,1,1,2-tetrachloro-   '
     ethane.  Archives  des  Maladies Professionnelles, de Medecine
     du Travail  et  de  Securite 3_5_( 6):  593608,  1974.

 31.  Brem, H., et al.   1974.   The Mutagenicity and NDA-Modifying
     Effect of Haloalkanes.  Cancer Res. 34:2576.

 32.  National Institute for Occupational Safety and Health.
     Criteria for a Recommended Standard...Occupational
     Exposure to  1,1,2,2-Tetrachloroethane .   U.S. Department
     of Public Health  Service, Center for Disease Control,
     National Institute for Occupational, Safety and Health,
     DHEW (NIOSH) Publication  No. 77-121, December, 1976.

 33.  U.S. EPA, 1979.   Chlorinated Ethanes: Ambient Water Quality
     Criteria (Draft).

 34.  National Cancer  Institute.  Bioasay of  1,2-Dichloroethane
     for Possible Carcinogenicity.  U.S. Department of Health,
     Education and  Welfare, Public Health Service, National
     Institutes  of  Health,  National Cancer Institute,  Carcino-
     genesis Testing  Program,  DHEW Publication No. (NIH) 78-1305,
     January 10,  1978.	

 35a.  McCann, J.,  E.  Choi,  E.  Yamasaki,  and B. Ames.  Detection
     of Carcinogens  as  Mutagenic in the Salmonella/Micro some
     Test:  Assay of  300  Chemicals.  Proc. Nat. Acad.  Sci.
     USA ^2_(2):  5135-5139,  1975a.

 35b.  McCann, J.,  V.  Simmon, D. Streitwieser, And B. Ames.
     Mutagenicity of  chloroacetaldehyde, a possible metabolic
     product of  1,2-dichloroethane (ethylene dichloride),
     chloroethano1  (ethylene  chlorohydrin),  vinyl chloride,
     and cyclophosphamide.   Proc. Nat.  Acad. Sci. 72(8):
     3190-3193,  1975.

 36.  Vozovaya, M.   Changes  in  the Esterous Cycle of White Rats
     Chronically Exposed  to the Combined Action of Gasoline
     and Dichloroethane Vapors.  Akush.  Genekol.  (Kiev)
     47(12): 65-66,  1971.
37.
Vozovaya,  M. Development of Offspring  of  Two  Generations
Obtained from Females Subjected  to  the  Action of  Dichloro-
ethane.   Gig. Sanit. 7: 25-28, 1974.
38.  Vozovaya, M.  The Effect  of  Low Concentrations of Gasoline,
    Dichloroethane and Their  Combination on the Generative
    Function of Animals and on  the Development of Progeny.
    Gig. Tr. Prof. Zabol.  7:  20-23, 1975.

-------
39.  Vozovaya, M-  The Effect  of  Low Concentrations of
     Gasoline, Dichloroethane  and  Their  Combination on the
     Reproductive Function  of  Animals.   Gig.  Sanit. 6:
     100-102, 1976.

40.  Vozovaya, M. A.  The Effect  of  Dichloroethane on the
     Sexual Cycle and Embryogenesis  of Experimental Animals.
     Akusk.  Ginekol.  (Moscow) 2_: 57-59,  1977.

41.  Urosova, T. P. (About  a possibility  of  dichloroethane
     absorption into milk of nursing  women when  contacted
     under industrial conditions.)   Gig.  Sanit.  18(3);
     36-37, 1953 (Rus).
                         ;,'
42.  Parker, J.C., et al. 1979.   Chloroethanes:  A Review  of
     Toxicity.  Amer. Ind.  Hyg. Assoc. J., 40: A46-60,  March, 1979.

43.  U.S. EPA 1979.  Chlorinated Ethanes:  Ambient Water  Quality
     Criteria (Draft).

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Pesticides

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                       LISTING BACKGROUND DOCUMENT:

                      MSMA AND CACODYLIC ACID PRODUCTION


By-product Salts Generated in the Production of MSMA and Cacodylic Acid. (T)


I.     Summary of Basis for Listing

       The hazardous waste generated in the production of MSMA (monosodium

oiethanear senate) and cacodylic acid is an arsenic-contaminated salt byproduct

The Administrator has determined that the solid waste from MSMA and cacodylic

acid production may pose a substantial present or potential hazard to human

health or the environment when improperly transported, treated, stored,

disposed of or otherwise managed, and therefore should be subject to appro-

priate management requirements under Subtitle C of RCRA.  This conclusion is

based on the following considerations:

       1.  These wastes contain very substantial concentrations of
           arsenic,  which is  an extremely toxic heavy metal.   Arsenic
           has also  been shown to be carcinogenic, mutagenic, and
           teratogenic.  The  waste generated at one plant was con-
           taminated with arsenic at a concentration of 6300  mg/1.

       2.  Large quantities of arsenic-contaminated wastes  are generated
           annually  in the production of MSMA and cacodylic acid.  Further-
           more, large quantities are often disposed of at  individual sites.
           Approximately 190,000,000 Ibs of arsenic-contaminated salt
           have been stored in an open,  uncovered pile in Wisconsin.

       3.  In mildly reducing environments,  prevailing in most shallow
           groundwaters, arsenic is most likely to be present as the
           very toxic arsenite,  to be relatively mobile, and  to persist
           virtually indefinitely.

       4.  Several  incidents  of environmental contamination have occurred
           due to the leaching of MSMA/cacodylic acid wastes  disposed of
           in landfills,  resulting in adverse human health effects.
                                  -soo-

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 II•    Sources of the Waste


       A.  Profile of the Industry - MSMA is  used  primarily as a

 herbicide, and is also an intermediate  in the production of cacodylic  acid

 MSMA is produced in the U.S. by Diamond Shamrock (Green Bayou, Texas);

 Crystal Chemical (Houston, Texas); and  Vineland  Chemical (Vineland, New

 Jersey).  Estimated production of MSMA  in 1974 was 35  million pounds. C1)

 Both Crystal Chemical and Vineland .Chemical also manufacture cacodylic

 acid which results in a similar arsenic-contaminated salt  by-product.

 Combination of the salt by-products from  both the  manufacture of MSMA and

 cacodylic acid probably occurs at most  manufacturing sites,  a supposition

 could not be confirmed for all sites.*

       B.  Manufacturing Process and Waste Composition - The manufacture

 of MSMA involves the reaction of arsenic  trioxide  and  liquid caustic

 soda to form sodium arsenite.  This solution  of  arsenite is  then reacted

 with methyl chloride to form a disodium methylarsenate (DSMA)  slurry.

 This slurry is concentrated, cooled and centrifuged with the DSMA cake

 going to acidifying tanks and the liquid  going to  storage  for  reuse.

 The DSMA cake is then acidified to form monosodium methylarsenate (MSMA).

 This slurry is concentrated, cooled and centrifuged, with  the monosodium

 methylarsenate in the liquid phase being  transferred to a  formulating

 tank,  and the resulting salt cake being collected  for  disposal.  The

 final  MSMA product is formulated to various strengths  and  is shipped in

 either bulk form or containers.   Arsenic  is persent in the  salt byproduct
^Crystal  Chemical  evidently combines its two waste streams, since its
 state  disposal  permit  provides' for disposal of the combined waste
 streams.
                                   -SOI-

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in  substantial  concentrations,  since it is a prevalent feedstock con-

stituent.   The  production  scheme  for MSMA is depicted in Figure 1.

       The  manufacture  of  cacodylic  acid involves the reduction of MSMA

using  sulfur  dioxide.   This reduced  MSMA is neutralized with caustic soda

and  then  reacted with methyl  chloride to form cacodylic acid.  The cacodylic

acid is concentrated, cooled'and  centrifuged.   The cacodylic acid in the

liquid phase  goes  to a  formulating tank and the salt cake is collected  for

disposal.   Again,  it is reasonable to  expect  that arsenic is heavily

concentrated  in the waste  because it is a dominant feedstock constituent.

            The  presence of arsenic in  the waste in high concentrations is

confirmed by  an analysis of MSMA  salt  cake  waste generated  by Crystal

Chemical  and  provided to the  Texas Department  of Water  Resources.  This

analysis  indicates that the waste contains  arsenic concentrations  of 6,300

mg/1 (6).   The  National Inferim Primary  Drinking Water  Standard  for

arsenic, a  standard regulatory benchmark for measuring  arsenic contamination

in drinking water, is .05 mg/1, demonstrating  the  significant concentration

level  or arsenic in the waste stream.*

           The  Agency does not presently possess waste  concentration data

for cacodylic acid waste, but arsenic concentrations are  similarly believed

to be  high, in  light of arsenic presence as an  essential  feedstock material.

Further, it is  believed that the MSMA and cacodylic  acid  wastes  are often

combined for  disposal (see page 2),  again suggesting that the waste'streams

will contain substantial concentrations  of arsenic.
*With regard to the comparison of waste concentrations and  the Drinking
 Water Standards,  which assume environmental release, although not all
 the arsenic contained in the waste is likely to be released from the
 waste into the environment, arsenic in these wastes may well be released
 in concentrations well above .05 mg/1.  (see p. 2 following).
                                    -£"02-

-------
o
u)
i
              CH3CI.
               H2SO4,
                           SODIUM
                          ARSENITE
                            UNIT
     25%
   Na3AsO3
   STORAGE
                                                    1
METHYLARSONIC
   ACID UNIT
                                                    T
                                                  CRUDE
                                                   DSMA
                                                    Y
    MSMA
   REACTOR
                                                                      PURIFICATION
-*>-
EVAPORATOR
                                                              STRIPPER
                                   I
                           ^AQUEOUS
                              CH3OH
                                                               CHjOH

                                                                 I
                                                             RECOVERED
                                            DSMA SALES
CENTRIFUGE
50% MSMA

                                        BY-PRODUCT SALTS
                     WASHER
                               Na2SO4
                                NaCI
                                         LIQUID
                                                       TO
                                                   APPROVED
                                                    LANDFILL
                                      Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR MSMA.

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       C.  Waste Generation  and Management  Practices and Quantites of Wastes

           Managed


           There are a number of waste management  practices in current


industry use, which are discussed below.  In  addition to these described


practices, however, there  is a history of waste mismanagement  resulting

                                             i
in environmental harm.  Descriptions of damage incidents resulting from


mismanagement of these wastes are set forth at p.  6-7  following.


           Vineland Chemical has disposed of  its solid waste in several


landfills in Pennsylvania.   In May, 1979, Vineland received a  permit,


from the State of Pennsylvania to dispose of  3,000 tons  of  arsenic  con-


taminated waste.(^'


       Diamond Shamrock has a permit from the Texas  Department of Water


Resources to dispose a monthly average of 481 tons of  solid waste  from


the production of various_._c.ompounds.
                                        * (2)
           Crystal Chemical has a state permit for deepwell injection of


MSMA-cacodylic acid solid wastes which are slurried with liquid wastes


and rainwater and are injected 3500 to 4500 feet below the surface in


the Frio Formation (Attachment I).  Prior to obtaining this permit, the


company utilized unlined earthen holding ponds for waste management'in


combination with an off-site disposal program in commercial facilities.



III.   Discussion of Basis for Listing


       A.  Hazards Posed by the Waste


           The Agency has a number of reasons for listing these wastes
*The underlined daa are those obtained from proprietary reports and data
 files

-------
as hazardous.  First, these  waste streams have been implicated in a number




of actual damage incidents,  demonstrating the potential for substantial




hazard  if these wastes  are improperly managed.




          Second, the  concentrations of arsenic contained in these wastes




are very significant, so  that if even a small percentage of the arsenic




escapes from the waste, it will enter the environment in high enough




concentrations to cause substantial harm.  Further, arsenic is likely to




be mobile., and will be  highly persistent upon- escaping from the waste,




thus increasing the likelihood of it reaching receptors in concentrations




sufficient to cause a substantial hazard.  Certainly, there is insufficient




evidence to indicate  that arsenic will not migrate from the waste,  and




in light of the known dangers of this contaminant and its high concentra-




tions in the waste, such .assurance is necessary to justify not listing




these wastes.




          Finally, these wastes contain large quantities of arsenic




(as well as high concentrations) , and wastes containing large quantities




of arsenic are often disposed of at individual sites, thus increasing




the likelihood of a major damage incident.




          1.  Incidents  Involving Mismanagement of These Wastes.




          A history of mismanagement of solid waste from the manufacture




of MSMA and cacodylic acid has been documented.  It has been reported




that Ansul Company, a former manufacturer of MSMA and other arsenical




compounds, has stored 95,000 tons of arsenic-contaminated salt on




company property in Marinette,  Wisconsin.  Until recently, this stockpile
                                   -SOS"-

-------
was left  open  to  the  weather with no containment of runoff.  The State



of Wisconsin Department  of  Natural Resources has ordered Ansul to cover



the pile  as an interim measure and to truck the waste to a landfill in



Illinois.(28)



           A report from the files of the  Texas Department of Water
                                                             i


Resources  (Attachment I)  indicates that  a  landfill  containing these waste



streams was subject to overflow conditions during high rainfall periods,



causing waste  washout, so.il  contamination,  and  potential leaching hazard.



The report indicates  that elevated levels  of arsenic  were detected  to



"depths of several feet"  in  soil  surrounding the landfill.   This  could



result in  the  leaching of arsenic  into ground water and  potable water



supplies.



           2.   Hazards Based  on Arsenic  Concentrations in These Wastes

                and Likely^Environmental  Fate of  Released  Wastes



           As  noted above, arsenic  is present in these waste  streams in



very high concentrations.  Thus,  improper management  of  these wastes, for



example in unlined landfills, could  easily result in  a substantial hazard



to human health and the environment, in  light of the  health hazards



posed by arsenic (see  pp. 8-10  following).



           Two likely  exposure  pathways  for  the  leaching  of arsenic are



into groundwater and  surface water.  The potential for this to  occur from



a waste/soil matrix depends on  the concentration of arsenic in  the soil,



soil type (clay, sand, loam, etc.), the  soil  pH, as well  as the concen-



trations of cadmium,  magnesium, iron, and aluminum in the  soil.  Arsenic



is not  easily leached in fine-textured  soils (clay materials)  but may



be leached downward in sandy or loam soils.(30)

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          Once arsenic 'escapes from these wastes and migrates to groundwater,

it can be expected  to bi> both mobile and persistent.  Thus, in mildly reducing

environments present in most  shallow groundwaters, arsenic is most likely to

be present in the form of  arsenite, a mobile and highly toxic compound/7)

As an elemental heavy metal,  arsenic will persist in some form virtually

indefinitely.

          The propensity  for Arsenic to migrate through soil and groundwater

and to persist is illustrated by an arsenic poisoning incident occurring in
                            1             t
Minnesota in 1972. (8)  in  this case, eleven persons became seriously ill

by drinking water from a well 31 feet deep.  Water from this well was found

to contain up to 21,000 mg/1  of arsenic.  The source of the arsenic was

established to be some 50  pounds of arsenic-containing grasshopper bait

buried in a seven foot trench near the well about 40 years previously.

          Significant pollution of groundwater by arsenic moving from  the

La Bounty landfill  in Iowa has also been noted recently^), and the potential

for movement of this element  through the soil profile has been illustrated by

its appearance in increased concentration in ground water at a land treatment

site for municipal  wastewater.v^-0)

          A second exposure  pathway of concern is surface water.  These

wastes, unless properly managed to prevent washout or runoff,  could easily

contaminate surface waters.   Indeed, two of the incidents described above

illustrate potential surface  water contamination as a result of improper

management of these wastes  (Attachments I and II).

          3.   Quantities  of  the Waste Generated

          MSMA and cacodylic acid by-product salts are generated in large
                                  -S07-

-------
 concentrations,  and also  are disposed of in large quantites at individual

 sites.   The  above described damage incident from Marinette, Wise,, indicates

 that  95,000  tons of these wastes were stored (improperly) at a single site.

 Similarly, Vineyard disposes of  3,000 tons of these wastes each year.(4)

 Obviously, such  large  quantities of this hazardous constituent has the pro-

 pensity  for  large-scale environmental harm—for instance, there is a greater

 chance of  exposure, and environmental leaching will continue for longer periods

 The large  quantities of waste generated  is thus a further reason for listing

 these wastes.

       B.  Health and  Ecological Effects

           1.  Arsenic

               Health  Effects -  Arsenic  is extremely toxic in  animals  and

 humans(H).  Death in  humans  has occurred  following ingestion  of very

 small amounts  (5mg/Kg)  of  this chemical(12).   Several  epidemiological

 studies  have associated cancers  with  occupational exposure to  arsenic(13-15) j

 including those  of the lung,  lymphatics  and  blood(16,17).   Certain

 cases involving  a  high prevalence of  skin  cancer  have  been associated

 with  arsenic in  drinking water(18), while  liver cancer has developed  in

 several  cases  following ingestion of  arsenic(19).  Results from  the

 administration of  arsenic  to  animals  in  drinking  water or by injection

 supports the carcinogenic  potential of arsenic.

               Occupational  exposure  to  arsenic has  resulted in  chromosomal

 damage(™), while  several  different arsenic  compounds  have demonstrated

 positive mutagenic  effects  in laboratory studies(21~23).

               The  teratogenicity of  arsenic and  arsenic  compounds is

well established  (24-26) and  inciudes defects  of  the skull,  brain, kidneys,


                                    -X-
                                   -50S-

-------
gonads, eyes, ribs and genito-urinary system.




              The effects  of  chronic a-senic exposure include skin diseases



progressing to gangrene,  liver damage, neurological disturbances^7)



and cardiovascular disease(13).




              Arsenic is designated as a priority pollutant under Section



307(a)  of the CWA.  Additional information and specific references on



adverse effects of arsenic  can be found in Appendix A.






              Ecological Effects - The data base for the toxicity of



arsenic to aquatic organisms  is more complete for freshwater organisms,



where concentrations as low as 128 ng/1 have been acutely toxic to freshwater



fish.  A single marine species produced an acute value in excess of 8,000



ng/1.  Based on one chronic life cycle test using Daphnia magna, a chronic



value for arsenic was estimated  at 853 ng/1.(28)



              Bioaccumulation factors can reach 13,000 in oysters,  8,600



in lobsters, and 23,000 in  mussels.(28)



              Regulations  - OSHA has set a standard air TWA of 500 mg/M3



for arsenic.  DOT requires  a  "poison" warning label.



              The Office of Toxic Substances under FIFRA has issued a
                  t


pre-RPAR.  The Carcinogen Assessment Group has identified arsenic as a com-



pound which exhibits substantial evidence of carcinogenicity.  The Office  of



Drinking Water has regulated arsenic under the Safe Drinking Water Act due to



its toxicity and the Office of Air Quality Planning and Standards has begun  a



preregulatory assessment  of arsenic based on its suspected carcinogenic



effects.  The Office of Water  Planning and Standards under Section 304(a)



of  the Clean Water Act has  begun development of a regulation based on
                                    -SCft-

-------
health effects other than on carcinogenicity and environmental effects.

Finally, the Office of Toxic Substances has completed Phase 1 assessment

of arsenic under TSCA.

           In addition, the states of Pennsylvania, Texas, and Wisconsin

obviously deem this waste to require careful management to prevent

substantial environmental harm (see attachment I and II).

               Industrial Recognition of Hazard - Arsenic is rated as

highly toxic through intra-muscular and subcutaneous routes in Sax,

Dangerous Properties of industrial Materials.(29)  Arsenic is  also rated

as highly toxic through ingestion, inhalation,  and  percutaneous routes

in Patty, Industrial Hygiene and Toxicology.
                                   -X-
                                  -SJO-

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 V.    References


 !.    Kelso, G,, R. Wilkinson, J. Malon,  Jr.,  and  T.  Ferguson.  Develop-
       ment of Information on Pesticides Manufacturing for Source Assessment
       EPA-600/2-78-100.  Environmental Protection  Agency, Research
       Triangle Park, NC, 1978.

 2.    Proprietary information submitted to EPA by  Diamond Shamrock in
       response to a "308" letter.

 3.    Sittig, M., Pesticides Process Encyclopedia  Noyes Data Corporation
       Park Ridge, New Jersey, 1977.                                     '

 4.    Personal Communication, Kirti Shah, Pennsylvania Department of
       Environmental Resources (717-787-7381), ,1/31/80.  See Appendix D.

 5,    Personal Communication, David Barker, Texas Department of Water
       Resources. (512-475-5633),  12/18/79.  See Appendix D.

 6.    Personal communication, David Jeffrey, Texas Department of Water
       Resources (512-475-7097),  12/31/79.   See Appendix D.

 7.    NIOSH, 1978.   Registry of Toxic Effects of Chemical Substances.

 8.    Thornhill,  J.,  198.0,...  USEPA-ORD,  Ground Water Research Branch,
       Ada,  OK  Personal Communication.

 9.     Koerner,  E. L.  and D.  A.  Haus,  1979.  Long-Term Effects of Land
       Application of  Domestic Wastewater.   EPA-600/2-79-072.  USEPA,
       Washington, D.C.

 10.    Hounslow,  A.  W.   1980  Ground Water Geochemistry: Arsenic  in  Land-
       fills.   Ground Water Journal (in  press).

 11.    Gleason,  M. N., et al.  Clinical  Toxicology of Commercial Products.
       Acute  Poisoning.   (1969) 3rd ed.,  p. 76.

 12.    Lee, A. M.  and Fraumeni, J.  F., Jr.   Arsenic  and respiratory cancer
       in man:  An occupational study.  Jour.  Natl.  Cancer Inst.  42:1045
       (1969)

 13.    Pinto, S. S. and  Bennett, B. M. Effect  of arsenic trioxide exposure
       on mortality.  Arch. Environmen. Health 7:5883  (1963).

14.    Kwratune, M., et  al.   Occupational lung  cancer  among copper  swelters.
       Int. Jor. Cancer 13:552 (1974).

15-    OH,  M. G., et al.  Respiratory cancer and occupational exposure  to
       arsenicals.  Arch. Environ. Health 29:250 (1974).
                                   -SM-

-------
16.    Baetjer, A.  M.,  et  al.   Cancer and occupational exposure to inorganic
       arsenic.  18th Int.  Cong.  Occup.  Health.   Brighton,  England,  p. 393
       jLn Abstracts, September  14-19  (1975)

17.    Tseng, W. P., et  al.  Prevalence  of skin  cancer in an endmeic  area
       of chronic arsenicism in Taiwan.   Jour. Natl.  Cancer Inst.   40:453
       (1968).

18.    ECAO Hazard  Profile;  Arsenic.  (1980) SRC,  Syracuse,  NY

19.    Nordenson, I., et al.  Occupational and environmental  risks  in and
       around a swelter  in  northern Sweden.  II.   Chromosomal aberrations
       in workers exposed  to arsenic.  Hereditas   88:47  (1978).

20.    Petres, J.,  et al.   Zum  Einfluss  a  norgan  ischen  Arsens  auf  die
       DNS-Synthese menschlicher  Lymphocyten in vitro.   Arch. Derm  forsch,
       242:343 (1972).                                               .

21.    Paton, G. R- and Allison,  A. C. Chromosome  damage in human cell
       cultures induced by metal  salts.  Mutat. Res.   16:332  (1972).
                                                            i
22.    Moutsheen, J. and Degraeve, N.  Influence of thiol-inhibiting
       substances on the effects  of ethyl  methyl sulphonate on chromosomes.
       Experientia  21:200  (1965)

23.    Hood, R. D.  and Bi,shpp,  S. L. Teratogenic effects  of sodium
       arsenate in  mice.  Arch. Environ. Health  24:62 (1972).

24.    Beandoin, A. R.  Teratogenicity of sodium arsenate  in rats.
       Teratology   10:153 (1974).

25.    Ferm, V. H., et al.  The teratogenic profile of sodium arsenate in
       the golden hamster.  Arch. Environ. Health  22:557 (1971).

26.    U.S. EPA.  1979.   Arsenic: Ambient Water Quality Criteria.  Environ.
       Protection Agency, Washington,  D.C.

27.    WHO.  1979.  Environmental Health Criteria: Arsenic.  World Health
       Organization.  Geneva.

28.    Sperling, L.  Wisconsin's Hazardous Waste Line, Wisconsin Natural
       Resources.   Vol  4 (1): 14-16, 1980.

29.    Sax, N.  Irving,  1975.  Dangerous Properties of Industrial Materials.
       Fourth Edition,  Van Nostrand Reinhold, New York.

30.    National Research Council,  Arsenic, National Academy of Sciences,
       Washington,  D.  C.  1977

-------
                               ATTACHMENT I



       Plant located in West Harris  County,   Crystal manufactures arsenic-

 based pesticide chemicals for sale.   The proposed well will be used  to

 dispose of water which has been contaminated  as  a result  of these

 manufacturing processes.  To the present time,  the Company has utilized

 only unlined earthen holding ponds for wastewater management,  in  combination

 with a program of off-site disposal  in commercial waste facilities.

 Efforts to minimize the volume of contaminated waste water in  the Company's

 ponds by evaporation, are thwarted by the heavy  rainfalls  which occur in

 the Houston area.  Site inspection after such rainfall typically  reveals

 that water, tinged an orange-brown color,  covers  much of  the site, and in

 some instances, slowly drains off-site.   Analyses of soil  samples  from

 the plant indicate elevated levels of arsenic compounds in the soil  to

 depths of several feet.  To prevent  further soil  and water pollution, the

 Company has undertaken the waste disposal  well project as  the  most

 environmentally safe method of plant waste disposal.   Along with  the

 implementation of the proposed injection operations,  it will be necessary
                                                 t
 to correct the existing pollution by closing the  ponds, and diking and

 paving the plant area.   Effective control  of rainfall runoff will prevent

 off-site  discharge of arsenic-contaminated waters.   Evaluation of the

 disposal  well  project plans  follow.


            CHARACTERISTICS  AND COMPOSITION OF THE WASTE WATER


Manufacturing  Process - Listed below is  a  summary of operations at Crystal's

Rogerdale  Road  facility.
                                   -SJ3-

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       MSMA - Arsenic  trioxide and liquid caustic soda are reacted to




 form  sodium arsenite.   This  solution of sodium arsenite is then reacted




 with  methyl chloride  to form a DSMA (disodiun methylarsenate) slurry.




 This  slurry is  concentrated, cooled and centrifuged with the DSMA cake




 going to  acidizing  tanks and the  liquid going to storage for reuse.   The




 DSMA  cake is acidized  to form monosodium uethylarsenate.  This slurry is




 concentrated, cooled and centrifuged with the monosodium methylarsenate




 in  the liquid phase being transferred to a formulating tank,  and the




 resulting salt  cake being collected for disposal.   The final  MSMA product




 is  formulated to various strengths  and is shipped  in either bulk form or




 containers.






       Dinitro  General  - Dinoseb  (2-Sec-Butyl-4, 6-Dinitrophenol)  is




 dissolved in a  solvent,  an-emulsifier is added,  and  the  product  is shipped




 in  either bulk  or containers.






       Dinitro  3 -  Dinoseb is  reacted with triethanolamine  to form the




 triethanolamine salt of  Dinoseb.  A surfactant is  added  and the  material




 is  shipped in bulk  or containers.






       Naptalam - Alphanaphthyl amine and  phthalic anhydride  are reacted




 in  a  closed system  to form sodium naphthylphthalamate.   This  material is




 one of the ingredients  of a  product  produced  under the  trade  name  NAPTRO.






       Naptro - Naptalam, caustic soda,  and Dinoseb  are  mixed to form




NAPTRO.  This material  is solid in  5  gallon and  in 30 gallon  containers.

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      Dimethoate 267 - Technical dimethoate is dissolved  in  a  solvent

and enulsifiers are added.   The product is then either drummed  at  the

plant or shipped in bulk  form to a packager.


      Cacodylic Acid - MSMA is reduced using sulfur dioxide.   This

reduced HSMA is neutralized with caustic soda and then reacted  with methyl

chloride to form cacodylic  acid.  The cacodylic acid is concentrated,

cooled and centri'fuged with the cacodylic acid in the liquid  phase going

to a  formulating tank and the salt cake collected for disposal.


      Chemical Analysis  -  Samples from the Company's existing  waste
water holding  ponds  have yielded the following analysis.
pH
Total Residue  (105°C)

Alkalinity, as CaC03
  Hydroxyl
  Bicarbonate
  Carbonate

Chloride

Nitrate N

Sulfate

Total Organic  Carbon

Metals
  Arsenic
  Barium
  Boron
  Cadmium
  Calcium
  Chromium
                         MSMA
                       Salt Cake
Wastewater
  (Pond)
Wastewater
  (Sump)
-_7. 9
30%
0 mg/1
1,800
3,920
78,000
0.60
103,000
2,400
6,300
<0.5
<0.02
4.6
116
26
9.8
7.7%
3,000 mg/1
0
8,000
20,800
0.26
11,600
2,000
6,900
<0.5
0.08
0.13
85
5
9.4
5,100 mg/1
0 mg/1
220
1,080
850
0.16
564
180
1,500
<0.5
0.08
<0.01
24
0.6
                                    -SV6--

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Treatability  Studies  -  Various alternative methods of disposal and treat-




ment  of  the waste  streams  have been investigated.  While some of these




various  methods  could be marginally successful in eliminating the waste,




each  produces  contaminated sludge or residue.   Therefore, deep well




injection  is  judged to  be  the most practical and economic solution for




disposal of this waste  stream.






       The following  methods  were investigated as an alternative  to




injection:






       1.  Solar evaporation  -  The efficiency  of solar evaporation  is




related  to temperature, humidity  and rainfall  rate,  among other factors.




The annual rainfall rate at the plant site  is  in excess  of 50" per  year




while  the  evaporation rate is  approximately 43"  per  year.   Evaporation




would  also produce a  concentrated,  contaminated  precipitate which would




pose additional disposal problems.
       2.  Stream stripping - Little,  if  any,  of  the  contaminants would




be removed and an extremely high level of energy  consumption  would be




required.






       3.  Spray evaporation - Spray evaporation, while more  effective




than solar ponds, will also be inefficient because of  the humid climatic




conditions.  Spray evaporation has a potential  for air pollution and will




produce a contaminated sludge.  Large  surface  areas would be  required for




this type of system and these areas are not available  at the  plant site.

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       *•   Biological treatment - The nature  of  this waste does not enable




 it to support  sustained biological growth.  Any  sludge  produced by this method




 would be highly contaminated and would pose additional  disposal problems.






       5.   Neutralization - Neutralization is not a viable method of dis-




 posal in this  instance because highly toxic precipitates would be produced.






       6.   Incineration - Since the principal contaminant in this waste




 stream is arsenic,  incineration is not an acceptable method of-disposal.




 Arsenic trioxide sublimes at a temperature of 192 degrees C. and results




 in highly toxic conditions with the potential for serious air pollution.






 Compatibility  - Compatibility studies will be conducted after cores are




 taken from the injection interval and a sample of formation water is obtained.






 Pretreatment Facilities - Existing settling ponds will  be closed at the




 company's  plant site.  Crystal proposes to transfer waste from the process




 area to two welded  steel storage/settling tanks  comprising a total capacity




 of 420,000 gallons.   A portion of the waste stream will be diverted to




 slurry the salt cake by-product of the MSMA process.  This slurry will




 then be transferred  to the settling tanks.  From the settling tanks, fil-




 tration will be accomplished by two 60 GPM units installed in parallel.




 From these filters,  the waste stream will enter  a 2,000 gallon surge tank,




 and pass through a  cartridge-type guard filter on the way to the injection




 pumps and  the  wellhead.






       Solids  accumulating in the settling tanks will be removed periodically




and  transported to an approved off-site disposal facility.  Crystal currently

-------
operates  under Registration No.  30781,  Class I,  and No. 30722, Class I




and Class II covering  off-site disposal of  solid waste.






Emergency Storage - In the  event  of  an  extended  well shut down,  normal




waste output plus any  contaminated runoff will be stored in steel tanks




and will  be transported  off-site  to  a commercial deep well facility.






              DRILLING AND  COMPLETION OF THE DISPOSAL WELLS






       A  14-3/4" hole  will  be drilled to 2,200 feet.   Surface  casing




(10-3/4") will be set  to this depth  and cemented in  place.   From  2,200




feet, a 9-7/8" hold will be advanced to the  total  depth of  4,500  feet,




whereupon longstring casing (7") will be set to  TD and  cemented in place.




Only the primary injection zone from a  subsurface  interval  of  4,350 + to




4,500 + will be initially^completed.   Injection  into  this zone will be




accomplished through 3-1/2" steel tubing.  A 4"  wire-wrapped stainless




steel screen will be utilized throughout the injection  zone.   Isolation




of the injection zone  from the tubing longstring casing annulus will be




maintained by a packer.  Gravel packing will be  employed  to control sand




influx to the wellbore in the injection zone.
                                   -svs-

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ATTACHMENT II
  PHONE LOG
    -sn-

-------
                        MEMORANDUM OF ORAL ADVICE


Bureau of Solid Waste Management           Date;     January 31, 1980
Division of Hazardous Waste Management
State of Pennsylvania
Department of Environmental Resources

Name:  Kurti Shah, 717-787-7381

Re:    Vineland Chemical Solid Waste       Telephone JXX| Conference
       (MSMA & Cacodylic Acid)	
Facts and Query:
  Quantity, Composition and Present and Past Disposal Practices for

  Disposal of MSMA and Cacodylic Acid Waste in Pennsylvania.	



  Is this information Public Record?  Yes.
Answer;  Disposed of in past at Grove Sanitary Landfill (used a process

  developed by Stobatrol Corporation to encapsulate waste.   Monitoring

  wells in area show high sulfates  and chlorides.   No arsenic yet.	

  State may order recovery of waste) and at  Lyncott Landfill (uses	

  terra-tite system).	
                                           By;   E.G. Monnig
Comments:   Waste is said to be    60%  NaCl,   40%~Na9S04 and less than 1%

  arsenic  (according to VineJand).  Vineiand permitted to dispose of

  1,000 tons (850 yd3)'in'August,  1977. "May'1979  - permit" to dump 2,000-

  3,000 pounds of solid waste from'MSMA  and Cacodylie Acid production.
                                   -520-

-------
                        MEMORANDUM OF ORAL ADVICE
                                           Date:  December 18, 1979
Name:   David Barker,  TDWR 512-475-5633




Re;    HSMA Waste - Diamond Shamrock       Telephone  |xx| Conference  |"~






Facts  and  Query:   Quantity, Composition and Disposal practices ,of MSMA




  solid waste — Diamond Shamrock.
Answer;  Waste contains  NaCl-Na?SO,4 and arsenic.  Relative concentration




  unknown.  Diamond  Shamrock permitted to dispose on-site and off-site.




  Off-site permit allows 481 tons on a monthly average.	
                                           By;  E.G. Monnig




Comments:                                        	

-------
                        MEMORANDUM OF  ORAL  ADVICE
                                           Date;  December 31,  1979
Name:  David Jeffrey TDWQ
Re;    Cacodylic Acid and MSMA Waste       Telephone  |XX|  Conference




Facts and Query:  1)  Is the Crystal Chemical Solid waste  report a matter


  of public .record?  Yes*	•	
                                                 j

	2)  Does MSMA salt also contain Cacodylic Acid by-	


  products?  Probably*	
Answer:
                                           By:  E.G. Monnig


Comments:

-------
                  LISTING BACKGROUND DOCUMENT

                       CHLORDANE PRODUCTION
Wastewater and Scrub  Water from the Ch lor inat ion  of
Cyclopentadiene in  the  Production of Chlordane  (T)

Wastewater Treatment  Sludges from the Production  of  Chlordane  (T)

Filter Solids from  the  Filtration of Hexachlorocyc lopent adiene
in the Production of  Chlordane (T)

Vacuum stripper discharges from chlordene chlorinator  in
the production of chlordane (T)

I.   SUMMARY OF BASIS FOR LISTING

    'The hazardous  waste  streams generated from chlordane

production include  process wastewater and scrubwater, waste-

water treatment sludge,  filter solids,  and vacuum stripper

discharges.  These  waste  streams contain hexachlorocyc lopent a-

diene, chlordane, heptachlor,  and other chlorinated organics.

     The Administrator  has determined that the solid waste

from  chlordane production may  pose a substantial present or

potential hazard to human health or the environment when

improperly transported, treated,  stored,  disposed of or

otherwise managed,  and  therefore should be subject to appro-

priate management requirements  under Subtitle C of RCRA.

This conclusion is  based  on  the following considerations:

    1.    Wastewater and  scrubwater from the chlorination of
         Cyclopentadiene, wastewater treatment sludge and
         filter solids from hexach lorocyc lopent adiene
         filtration contain hexach lorocyc lopent adiene .
         Hexachlorocyclopent adiene is  very  toxic.

    2.    The  vacuum stripper  discharges  from chlordene
         chlorinator waste  is  expected  to  contain chlordane,
         heptachlor, and  other  chlorinated  organics.
         Chlordane  and heptachlor  have  been reported to
         be carcinogenic  and/or  mutagenic.
                               -5-23-

-------
      3.
      4.    If the wastes are mismanaged,  the  toxic  constituents
           in the waste could migrate from  the  waste  and
           contaminate groundwater.  Certain  constituents
           of the waste (e.g., chlordane  and  heptachlor)  are
           proiected to be persistant in  groundwater.

 II.    SOURCES OF THE WASTE AND TYPICAL DISPOSAL  PRACTICES

       A.    Profile of the Industry

            According to SRI Directory of Chemical  Producers^)

 and  two  other sources'^ , 3)^ chlordane is produced  by

 only  one  company,  Velsicol Chemical Company  (a subsidiary of

 Northwest  Industries) at  a plant in Marshall,  Illinois.  The

 chlordane  industry production capacity is estimated at 13,600

 metric tons/yr  (15,000 tons/yr).^3)  	
                                                       (4)
      Chlordane  is  a  versatile,  broad-spectrum insecticide

which has  been  in  commercial use for more than 20 years.'^)

It is used  to protect  a  large variety of food crops, lawns,

turf, ornamental and shade  trees,  and the like from parasitic

insect  life.  In 1972, nonagricu1tural uses of chlordane

accounted  for an estimated  80 percent of total U.S. consumption

of chlordane in that year.(3)

     B.   Manufacturing  Process

          Figure 1 presents  a generalized production and waste

schematic for chlordane.  As shown in Figure 1,  the first

production  step involves  chlorination of eyelopentadiene to
* All underlined  information  is  from properietary reports
  and data files.

-------


3RUBE
I
iA
JO
r-



t
CYCrOPeNTAD16Rl~ VENT
•f CHLORINE p '
I Wj _


1 il i
5ER WATER WASTE WATER
r
_r
SOLIDS
/ENT

DECA

WASTE
MTCD
IM 1 tn

WATER"
f
POND
>

FILTER"

t
"DEEP
WELL

m—m—m^ ^11 TfTH M.

i T s
( III
1 FILtER CAKE
TO CLAY PIT
OR LANDFILL
< II
WASTE WATER
•TREATMENT
SLUDGE
I
fO OFF-SITE
LANDFILL


CYCLOPENTADIENE
1_
	 ._ lfci oriMnr
I
KBfDIELS"
"" * ALDER
I
CHLORDENE
02C12 f

,(C) VI

I
.CHLORDANE


. 	 „,_„„,,_ \/i^MT \iAr*t 11 iim
'NSCri VCNTr VACUUM
.nouii — *- STRIPPtH
J...
STRIPPER
^"WATER TO
' HOLDING PON!
..- ^ __ ^n 	 __ „
ENT ^ / VACUUM

1
~~~i\r
'STRIPPER
, WATER
! TO
HOLDING
POND
PROCESS AND WASTE SCHEMA1TC~(MO^

-------
   to obtain hexachlorocyclopentadiene.   The hexachlorocyclopen-

   tadiene is then condensed with  cyclopentadiene to form chlor-

   dene via the Diels Alder reaction.   The chlordene is chlori-

   nated to form chlordane.  The main  process reactions are as

   follows:(3)
(A)
+ Cl,
     CYCLOPENTADIENE
(B)
 KEXACHLOROCYCLOPEN lADIENE
(C)
           +  C\z or
             S02CL2
    C!
            C!
        CHLORDENE
                           HEXACHLOROCYCLOPENTADIENE

                                      Cl
                                          DIELS
                                          ALDER
                      CONDENSATION
                                 Cl
                               CHLORDENE
                                      Cl
                                                                      Cl
                              CHLORDANE
                                       Cl
                                                                  Cl

                                                         HEPTACHLOR

                                                       + OTHER ISOMERS
                                -X-

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     These process  reactions indicate  the  sources  of the




 hazardous constituents in the wastes.   They  are  marked A,




 B and C  in Figure  1 to illustrate  precisely  where  the




 reactions take  place in the process.




 C.   Waste Generation and Management




     1.   Waste  Streams




         The  four  waste streams from  the  production of chlor-




 dane which are  listed as hazardous are:




         Wastewater and scrub water from  the  chloric-nation




         of eyelopentadiene




         Wastewater treatment sludges




         Filter  solids from the filtration  of hexachlorocvclo-




         pent ad iene




         Vacuum  stripper discharges from  chlordene  chlorinator




         in the  production of chlordane




     Hexachlorocyclopentadiene is  the  constituent  of concern




 in the first three  listed wastes;  chlordane, heptachlor, and




 other chlorinated organics  are the constituents  in the last




 listed waste.




     Each of the wastes—wastewater and scrubwater,  wastewater




 sludges, filter solids and  vacuum  stripper discharges--are




marked I, II, III and  IV respectively,   in Figure 1.




     Wastewater and  scrubwater (I)  are  generated during the




chlorination of eyelopentadiene and subsequent separation




steps.	
                             -x-

-------
                              (4).   The  eyelopentadiene contai
ns
 numerous  cyclic compounds, which  when  chlorinated result in




 a  multiplicity of toxic chlorinated  cyclic  compounds, among




 which  hexach lorocyc lopent adiene predominates,  since it is the




 principal  reaction product.  Wastewater  from reactor cleanup,




 decanting  and vent scrubbing thus  contain  significant amounts




 of  these  components.   As shown in  Figure  1,  this  waste is




 sent  to  a  settling pond.




      The  second listed waste (II)  is a result  of  the treatment




 of  the wastewater which contains hexach lor ocyc lopent adiene  and




 other  toxic  chlorinated organics.  Since, hexach lor ocyc lopent-




 adiene is  relatively  insoluable (25mg/l)  (29)  and  is amenable




 to  b iode gr adat ion due to its physical chemical  form, the  Agency




 expects  this  toxic organic to be present in  the  sludge.




 Furthermore,  concentrations of hexach lor ocyc lopent ad i ene  in




 the sludge would  be  expected to be significantly higher  than




 in  wastewaters due to the undiluted composition  of  this  waste.









                              '4")   Wastewater treatment  sludge is
sent to an off-site  landfill for disposal. '^)




     The third  waste,  namely filter solids from  the  filtration




of hexachlorocyc lopent adiene (III) results when  the  crude




hexach lorocyc lopent adiene  is filtered before it  is reacted  to




form chlordene  (before reaction B).  The filtration  process  is




intended to remove organic impurities, including hexachloro-




cyc lo pen t ad iene .   It  is  thus expected that this  constituent

-------
will be present  in  this  waste,  probably in significant concen-


trations.  This  solid  waste is  sent to a commercial landfill


for disposal.  (3)


     Vacuum stripper wastewater (IV) from the chlordene
                    *

chlorinator vent vacuum  scrubber contains chlordane (which


would not be  completely  stripped)  and heptachlor (the


principal reaction  product) in  dissolved or suspended states.


This waste goes  'to  a holding pond prior to treatment. (3)


     While the precise concentration of waste constituents


in these waste streams are not  presently available, even


very small concentrations  are of concern due to these compounds'


extreme toxicity and capacity for genetic harm, as well as the


history of waste mismanagement  associated with the sole


producer of chlorodane (see pp.  12-13 below).  In any case,


concentrations of these  waste constituents are probably


quite substantial,  since the identified waste constituents


are either principal reaction by products (hexachloro-


cyclopentadiene, heptachlor), or the end product (chlordane).



III.  DISCUSSION  OF  BASIS FOR LISTING


     A*   Hazards Posed  by the  Wastes


         As previously  mentioned,  the listed wastes contain


one or more of the  hazardous constituents hexachlorocyclopenta-


diene, chlordane and heptachlor.


     Chlordane and  heptachlor have  been well documented as


having lethal effects  in humans  when ingested in small amounts,


   hexachloropentadiene has been documented to alter kidney

-------
functions,  and  cause  eye  and throat irritation and headache




in humans.   (For  further  information,  see Health and Ecological



Effect of Constituents  pp.  14-17.)





      1.   Risks in Waste  Management



          As  previously indicated,  (Figure 1),  the wastewaters



from  chlordane manufacture  are  discharged to  a  holding pond and



filtered prior  to disposal.(3)   sludges  from  this holding  pond



and filter  solids from  hexachlorocyclopentadiene filtration



are taken off-site for  disposal*(3)  Disposal of the  latter in



landfills,  even if plastic-lined drums are  used,  represents a



potential hazard  if the landfill is improperly  designed or



operated (i.e., drums corrode in the presence of even small



amounts of  water) .  ThJLs  can result, in the  leaching of hazardous



compounds and the subsequent  contamination  of groundwater.  The



holding pond presents a comparable  risk  if  not  properly managed.



      Further, damage incidents  indicate  (see Damage Incidents,



pp. 10-14)  that hexachlorocyclopentadiene and heptachlor



contaminated wastes have been disposed of in  improperly



designed and managed disposal facilities, which resulted in the



contamination of  the air and drinking water in  the area.   The



possibility of improper management  of these wastes and the



resulting associated hazard, is thus highly realistic.



     A further consideration  is the actual  transportation  of



these wastes to off-site disposal facilities.   This increases



the likelihood of their being mismanaged, and may result
                             -S3O-

-------
 either in their not being properly handled during transport


 or in their not reaching  their destination at all (thus


 making them available  for harm elsewhere) .  A transport


 manifest system combined  with designated standards for the


 management of these wastes will greatly reduce their availability


 to do harm to human beings and the environment.  in reference

                                                    /
 tp this particular consideration,  there was a damage incident


 in'Memphis/.Tennessee,  .(discussed in detail on p. 12), due to


 similar, unmanifested  waste being illegally transported and


 disposed.


    2.   Fate of Constituents in Waste Stream


         The waste constituents, appear to be fully able to


 migrate, pass through  soils,  and persist in the environment


 to an extent which could  cause substantial harm to human


 health and the environment.   Although heptachlor and chlordane


 are relatively insoluble,  their ability to migrate has been


 demonstrated by documented damage incidents (see pp. 10-14).


 Based upon estimates by EPA,(6) the constituents chlordane


 and heptachlor in these waste streams are projected to be


 persistent in ground water,  and exposure to humans using


 drinking water drawn from ground water in areas adjacent to


 disposal sites is likely.   Movement of all the constituents


 identified in the waste stream is  projected to be widespread


within surface water systems,  resulting in likely exposure


to aquatic life forms  in  rivers,  ponds, and reservoirs.


Concentrations up to 0.8  mg/1 and 0.04 mg/1 of chlordane and
                            -X-
                            -5-31-

-------
heptachlor respectively,  have been observed in surface waters,



confirming these  compounds'  mobility and persistence.'(?,8)



      Chlordane  is  a persistent chlorinated hydrocarbon



insecticide.   It  persists in the  soil for more than one year,



sometimes  for many years.   Its overall  rate of degradation



is  low.(29)



      Further damage incidents (see Damage Incidents, below)



illustrate that hexachlorbcyclopentadiene and  heptachlor have



posed a hazard  via air  exposure to workers in  contaminated



areas; they have  also migrated from disposal sites  to  surface



and ground waters  resulting  in the contamination of drinking



water sources in the vicinity.



      3.    Damage  Incidents



           The most serious wastewater and solid waste  disposal



problems from the  manufacture  of chlordane  result from the



synthesis  of the hexachlorocyclopentadiene intermediate.



The  wastes  from this process  step  contain highly toxic hexa-



chlorocyclopentadiene reaction product.   The link between



disposal and management of heptachlorocyclopentadiene  contam-



inated wastes and  the hazardous implications of the leaching



of the toxic organic into drinking  water  and/or air is well



documented  by the  damage  incident  described below.   Further,



the  vacuum  stripper discharges  from the chlordene chlorinator



are  of particular  concern to  the Agency because there  also



have been documented damage incidents which show the mis-
                             -vf-

-------
management, mobility and  persistence of heptachlor contaminated



waste streams (also described below).




    Sometime during March,  1977,  an unknown toxic substance



began entering the Morris Forman waste treatment plant in



Louisville Kentucky.  As  a result,  employees on sight suffered



from eye, nose, throat, lung, and skin irritation.  It was



found that mar;/ wastewaters  from this plant contained con-



stituents that are toxic.  One of the predominant contaminants



identified was hexachlorocyclopentadiene.  Upon an investiga-



tion to determine the point  of entry of these contaminants



into the sewer system,  it was found that a local waste handler



had storage facilities  for industrial wastes in the Louisville



area.  An  investigation of five sights suspected to be used



by the local disposal company confirmed the existence of



hexachlorocyclopentadiene at one or more of the locations.



Drums out in the open,  buried drums and barrel storage were



some of the implemented storage facilities and thus the points



of release of these contaminants.   As a result, towns whose



water comes directly from the Ohio River had been alerted to



the flow or raw sewage  containing the contaminant hexachloro-



cyclopentadiene into the  river at Louisville.  Many of these



toxic constituents were thus available for release due to



improper management and disposal practices and even in minimal



concentrations, many cause a potential health or environmental



hazard via air exposure or contamination of drinking water



sources.
                             -5-33-

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     Further, the same type of waste  as  the  toxic heptachlor

reaction by-products from chlordane production was generated

by Velsicol in Memphis, Tennessee in  the production of hepta-

chlor.  This waste material from the  Memphis plant was one

of the industrial wastes which was illegally dumped into the

Louisville, Kentucky sewer by a contract waste disposal

company.  Again, the specific results were the killing of

all sewage treatment plant biota and a resulting  water con-

tamination problem.  The cost of decontamination  was in

excess of one million dollars and many workers were exposed

to this toxic material.*

     Velsicol1s Memphis plant has also created groundwater

contamination problems resulting in several wells becoming

contaminated following disposal of highly toxic heptachlor

containing waste.*  Disposal of this waste in either deep

wells or#even in clay-lined pits can,  and has, resulted in

contamination problems.

     In another serious instance of waste mismanagement

involving both hexachlorocyclopentadiene containing wastes

and Velisicol.  Velsicol buried chlorinated pesticide waste

containing hexachlorocyclopentadiene in drums at  a Hardenman

County site beginning in 1964.  A U.S.G.S. Study  (1966-1967)

revealed that the wastes had migrated vertically  to a depth

of 90 feet and laterally to a distance of 25 feet.  Hexachloro-

cyclopentadiene and other chlorinated hydrocarbons were also


*OSW Hazardous Waste Division,  Hazardous Waste  Damage
   Incidents,  unpublished,  open file 1978.

-------
detected in  surface runoff.  Samples of adjacent  water  wells

taken  in April-May  of 1978 showed contamination by  the  wastes.

The contamination was sufficient to advise  the well owners

not to drink the water.   At the time of the  report  a  line

was being  laid  to connect these owners with  the Town  County

Water  Supply.   The  cost  of cleaning u,p the  damage was $741,000

plus an outlay  of $120,000 to supply water  for the  residents.

(Source:   United State Geological Survey  (1966-1967); OSW

Hazardous  Waste Division, Hazardous Waste incidents,  unpublished,

open file,  1978).   This  damage incident again illustrates the

hazardousness of the waste, since upon mismanagement, waste con-

stituents  (including hexachlorocyclopentadiene) proved  capable

of migrating, persisting, and causing substantial hazard.

     Past  waste management practices of waste containing the

constituents of concern  have presented special problems.  (For

a more detailed discussion, see the report on Hazardous Waste

Disposal,  Subcommittee on Oversight and Interstate  and  Foreign

Commerce,  96th  Congress  1st sess.  4,10,17).  As  stated there,

16.5 million gallons of  waste contaminated with heptachlor,

endrin, benzene, and aldrin was dumped at a  Hardenman County

dump site.   The dump site was ordered closed by the State of

Tennessee  in 1972,  but local drinking is contaminated and

unusable.  This further  indication of waste  mismanagement by
                          ' •»
the sole producer of chlordane production wastes  confirms

the need for hazardous waste designation of  these wastes.

    Thus, these damage  incidents illustrates the potential
                             -535--

-------
 environmental  and health hazard resulting from leaching



 contaminants from these  improperly disposed and managed



 wastes.





      B.    Health  and  Ecological Effects  of Constituents



           1.    Chlordane



           Health  Effects -  Chlordane  is  a very toxic chemical



 [oral rat  LD5Q  =  283  mg/Kg] with  lethal  effects in humans



 when  ingested  in  small amounts.(9)  Chlordane_administered



 orally in  mice  is  carcinogenic  causing liver cancers  in both



 sexes.(10)  Chlordane has also  been evaluated  by CAG  as having



 substantial evidence  of  carcinogenicity.   Chlordane has been



 mutagenic  in certain  human  cell assays. (H)  Repeated doses



 of chlordane have  altered blood protein, blood  glucose and



 certain  enzymes in gerbils.d^)



     Chlordane  is  designated as a  priority pollutant  under



 Section  307(a) of  the CWA.  Additional information and



 specific references on adverse  effects of  chlordane can be



 found in Appendix  A.



     Ecological Effects  - Chlordane is acutely  toxic  to most



 aquatic animal life.  Lethal concentrations to  freshwater



 fish are in the microgram/liter range.   Invertebrates appear



to be more sensitive  to chlordane.(13)   Similarly, salt



water fish and invertebrates have been shown to be very



sensitive to chlordane.(14)   Chronic aquatic toxicity of




this compound is even more severe  across all freshwater and

-------
 marine animal life.in particular, fish  embroyos  appear

 to suffer devastating  damage from as little as  a  tenth of  a

 microgram of chlordane.(14)   The acquatic damage  is amplified

 by the bioaccumulation factor of chlordane, i.e.,  scuds

 bioaccumulate chlordane  7,400 fold, freshwater  algae bioaccumulate

 133,000 fold.  Chlordane  is slightly toxic to birds, moderately

 toxic to wild mammals,  highly toxic to soil insects, and
                                        ' K
 moderately tpxic to  some  soil bacteria and to earthworms.

    Regulations - The OSHA standard for amounts of chloraane

 in air is a TWA of 600 n/m3 (skin), based on  the "one  hit"

 model of chemical carc.inogenesis.  The USEPA  has estimated

 levels of chlordane  in ambient water which will result in a

 risk of 10""" cancer  incidence of 0.12 nanograms/liter.

 Presently, a limit of  S^nanograms/liter for chlordane  has

 been suggested under the  Interim Primary Drinking Water

 Standard.  The Canadian Drinking Water Standard is also 3

 nanograms/liter.  To protect freshwater life,  the 24-hour

 average is 0.24 micrograms/liter and may not  exceed 0.36

 micrograms/liter.  For  saltwater species,  the  draft criterion

 is 0.0091 micrograms/liter  for a 24-hour average, not  to exceed

 0.18 micrograms/liter,(15)*



    *The Agency is not using the proposed water quality cri-
teria as  a regulatory  benchmark,  but is referring to them here
to illustrate a potential substantial hazard  if it migrates from
the waste at  small concentrations.

-------
      Industrial  Recognition  of  Hazard - Sax, Dangerous Proper"



ties  of  Industrial  Materials)  designates chlordane as highly



toxic systematically  via  oral,  skin absorption and inhalation



routes of exposure.



      2.   Heptachlor



          Health Effects  -   Heptachlor  is  extremely toxic in



animals  [oral  rat LD5Q  =  40  mg/Kg],  also causing deaths  in



humans following ingestion of very  small amounts..(16)



Heptachlor  is  carcinogenic,  causing liver  cancer in, mice.(l^)
     ^


Heptachlor  has also been  evaluated  by GAG  as having substantial



evidence of carcinogenic!ty,



      This chemical  is mutagenic  and  teratogenic  in animals,



causing  resorbtion  of fetuses^"),  chromosomal abnormalities



in bone  marrow cells  in*-adults,  and' cataracts  in of f spring. (^)



Heptachlor  has caused a marked decrease  in  litter  size and



lifespan in newborn rats.(^O)  It also  causes  abnormal



DNA synthesis in human  cell  cultures.(32)



     Heptachlor  is a  convulsant(21)  and  also interferes with



glucose metabolism when administered  in  chronic  studies.(22)



Additional  information  and specific  references on  adverse



effects of heptachlor can be found  in Appendix A.



     Regulations - The  OSHA  standard  for heptachlor is TWA



(air) 500mg/m3.



     Industrial Recognition  of Hazard -  Sax,  Dangerous Proper-



ties  of Industrial Materials, designates heptachlor as highly



toxic via oral and dermal routes.

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    3.   1,2,3,4,5,5-Hexachloro-l,3-cyclopentadiene  (HCCP)



         Health Effects  -  1,2,3,4,5,5-Hexachloro-l,3-cyclo-



pentadiene (HCCP) is very toxic  to animals [oral rat  LD50 *



113 mg/kg].  Adverse effects  have  been reported when  plant



workers were exposed to  this  chemical  as a volatile component



of municipal sewage.(2^)  These  included alterations  in kidney



functions, elevation of  liver  enzyme,  eye and throat  irritation
                                                      •• i


and headache*



    While the hexachlorocyclopentadiene is not metabolicly



activated to a mutagenic  form  in vitro,  it may form a number



of halogenated hydrocarbon  residues  [which have been  demonstrated



to be mutagenic (^->) ] when exposed  in the ecosystem.   Hexachloro-



cyclopentadiene has been  designated  as a priority pollutant



under Section 307(a) of^the  CWA.   Additional information



and specific references  on  adverse effects of hexachlorocyclo-



pentadiene can be found  in  Appendix  A.



    Ecological Effects  - HCCP is  extremely toxic to  minnows



with an LC$Q of 7 micrograms/liter following 96 hours of ex-



posure. (27)  Bioaccumulation  of  HCCP in  these fish is evident



from the recovery of 89%  of  this contaminant (on a wet-weight



basis) and, moreover,  the extremely  low  chronic lethal concen-



tration of 6.7 micrograms/liter  over a 30-day period.



    Regulations  - Hexachlorocylopentadiene is regulated by



the  Office of Water and Waste Management of EPA under the



Clean Water Act,  Section  311.  Technical assistance data has



been requested to obtain  data on environmental effects,  high-
                            -yf-

-------
^olume production and spill reports.   Under  Judicial  Order of




December 15, 1978 pursuant to the case  of  NRDC  VS.  Costle,




preregulatory assessment of suspect carcinogenicity/mutagenicity



and establishment of Safe Drinking Water Act and  Clean  Water




Act, Section 304(a), criteria was initiated  in  February  1979.




In addition, in April 1979, under the  Clean  Air Act,  hexa-




chlorocyclopentadiene was proposed, Section  112,  as a hazardous




pollutant and as a potential airborne,  carcinoger*.  Under the;




Toxic Substances Control Act,  preregulatory  assessment is




underway pursuant to possible  Section  6 control actions.

-------
     References
 lt   1977 Directory  of  Chemical Producers, Stanford Research
     Institute, Menlo  Park,  California.

 2.   Farms  Chemical  Handbook,  1977, Master Publishing Company,
     Willoughby,  Ohio.

 3.   von Rumker et al.   Production, Distribution, Use and
     Environmental Impact"Potential of Selected Pesticides,
     USEPA  Office of Pesticide Programs, EPA 540/1-74-001
     1975.

 4.   Proprietary  information submitted to EPA by Velsicol
    .Chemical  Company  through  1978 response to "308" letter.

 5.   Clement Associates,  Inc.   Dossier on Hexachlorocyclo-
     pentadiene,  Contract No.  EA8AC013, prepared for TSCA
     Interagency  Testing  Committee, Washington, D.C.
     August 1978.

 6.   Aquatic Fate and  Transport Estimates for Hazardous
     Chemical  Exposure  Assessments, U.S. Environmental
     Protection Agency..,__Environmental Research Laboratory,
     Athens, Georgia,  February 1980.

 7.   Pesticide Monitoring Journal, 8,33 (1974).

 8.   Pesticide Monitoring Journal, 3,124 (1969).

 9.   Clinical Memoranda on Economic Poisons,  (1956).  U.S.
     Department of HEW, PHS, CDC,  Atlanta, GA.

 10,   National Cancer Institute,  (1977).  Bioassay of chlordane
     for possible carcinogenicity.  NCI-CG-TR-8.

 11.   Ahmed, F. E., et  al.  Pesticide-Induced  DNA damage and
     its repair in cultured  human  cells.   Mutat.  Res.  42:161
     (1977).
12.   Karel, A. K. and  Sapena,  S.  C. Chronic chlordane  toxi'city:
     effect on blood biochemistry  of  meriones  hurrianae.

13.   Chlordane Hazard Profile,  USEPA,  1979 (draft).

14.   Kats,  M.,  1961.   Acute  toxicity  of some  organic insecticide
     to three species of  salmonids and to the  threespine
     stickleback.   Trans. Am.  Fish. Soc.  90:264.

-------
 15.   U.S.E.P.A.,  1979.   Chlordane:  Ambient Water Quality
      Criteria  (draft).

 16.   Clinical  Toxicology of  Commercial Products.  Acute
      Poisoning.   Gleason,  et.  al..,  3rd Ed., Baltimore,
      Williams  and  Wilkins  (1969).

 17.   U.S.  EPA  1977.   Risk  Assessment  of chlordane and hepta-
      chlor.  Carcinogen  assessment  group.   U.S. Environmental
      Protection Agency,  Washington,  D.C.

 18.   Cerey,  K., et  al.   Effect  of heptachlor on dominant
      lethality and  bone  marrow  in rats.  Mutat. Res.  21:26
      (1973).

 19.   Mestitzova, M.   On  reproduction  studies on the  occurrence
      of  cataracts  in  rats  after  long—term  feeding of  the
      insecticide heptachlor.  frxperientia   23:42 (1967).

 20.   Ahmed,  F. E.,  et al.  Pesticide-induced DNA damage and
      its repair in  cultured  human cells.   Mutat. Res.  42:161
      (1977).

 21.   St. Omer, V.   Investigations into  mechanisms responsible
      for seizures induced  by chlorinated hydrocarbon  insecti-
      cides:  The role  of  braim ammonia  and  glutamine  in  con-
      vulsions in the  rat., and cockeral.  Jour.  Neuroceue.
      18:365  (1971).

 22.   Kacew,  S. and  Singhal,  R. L.  The  Influence of p.p^-DDT,
      and Chlordane, Heptachlor and Endrin  on  Hepatic  and
      Renal Carbohydrate Metabolism and  Cyclic  AMP-adenyl
      Cyclase system.  Life Sci.  13:1363 (1973).

 23.   NIOSH:  Registry of Toxic Effects  of  Chemical Substances
      (1978).

 24.  Morse, D.  H.  et al., Occupation Exposure  to Hexachloro-
      cyclopentadiene: How Safe is Sewage?  JAMA.  241-2177-2179
      (1979).                               	

25.  Goggelman, W. et al., Mutagenicity of Chlorinated  Cyclo-
     pentadiene Due to Metabolic Activation.   Biochem.  Pha'rmacol^
     27:2927-2930.                                             ~~

26.  Winteringham, P.  Chemical Residues and  Pollution  Program
     of the Joint  Division of the International  Atomotic
     Energy Agency and the Food and Agriculture  Organization
     of the United Nations.  Ecotoxicol. Environ. Safety.
     1:407-25.  (1977)	
                             -ssa-

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27.  Spechar,  R.  L.  et al, Toxicity and Bio-accumulation of
    Hexachlorocyclopentadiene, Hexachloronorbornadiene,
    and  Heptachlorobornene in Larval and Early Juveniles
    Fathead  Minnows.   Hull. Environ. Contam. Toxicol.
    21:576-83.

28.  Control  of  Hazardous Material Spills; Proceedings of
    the  1978 National Conference on Control  of Hazardous
    Material Spills,  Miami Beach, Florida, April 11-13, 1978.

29.  Dawson,  English,  Petty, 1980.  "Physical Chemical
    Properties  of Hazardous Waste Constituents"
M
 •
                             -yf-

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                  LISTING  BACKGROUND DOCUMENT

                      CREOSOTE PRODUCTION
          Wastewater  Treatment  Sludges Generated in the
          Production  of  Creosote (T)

          Process  Wastewater  from Creosote Production (T)
I.   Summary  of  Basis  for  Listing


     The process Wastewater  and  was t ewa t er . tr,ea tment sludges

generated  in  the production  of  creosote have been found to

contain the toxic  substance,  creosote  and the constituents of

creosote,  benz(a)anthracene,  benzo(b)fluoroanthene and

benzo(a)pyrene.  Creosote  is  contained in the GAG list of

chemicals  having substantial  evidence  of carcinogenicity, as

are its three constituents,  benz(a)anthracene,  benzo(b)

fluoranthene.

     The Administrator has determined  that solid  wastes from

creosote production may  pose  a  substantial present or potential

hazard to  human health or  the  environment when  improperly

transported,  treated, stored,  disposed of or otherwise managed,

and therefore should be  subject  to  appropriate  managment

requirements  under Subtitle  C  of  RCRA.   This conclusion is

based on the  following considerations:

     1.    The hazardous substances  likely to be present in
           the wastes include  creosote  and its constituents,
                               -5MH-

-------
         benz(a)anthracene,  benzo(b)fluoroanthene, and
         benzo(a)pyrene ,  all  of  which are carcinogens.
         Several reported  cases  of  cancer in humans have
         been attributed  to  creosote  exposure.

     2.   If the lagooning/landfilling of these wastes is
         improperly conducted,  the  contamination of soil,
         land, ground, and  surface  water is likely to result.
         Since creosote is  highly  mobile and persistent,
         there is increased  likelihood of hazardous waste
         constituents reaching  environmental receptors.
         There is a reported  incident of surface and ground-
         water contamination  due to improper disposal of
         creosote contaminated  wastes, demonstrating that
         creosote is capable  of  migration,  mobility and
         persistence and  of  causing substantial hazard if
         improperly managed.

     3.   It is estimated  that 60-115  million Ib/yr of creosote
         is contained in  the  listed wastewater treatment
         sludge.  Thus, substantial amounts of waste con-
         stituents are potentially  available for environmental
         release.

 II.  Sources of the Waste  and  Typical  Disposal Practices

     A.   Profile of the Industry

         In 1972, creosote  was  produced  by  six companies at

 25 locations; the estimated  1972  production  was 521,000 metric

 tons  (575,000 tons).(^)  A complete  list  of  producers,  pro-

 duction plants and the estimated  1972  production at each  site

 is presented in Table 1.  Creosote is  a wood preservative,

 characterized by a high toxicity  to  wood-destroying organisms

 and a very low evaporation rate. (2)  Nearly  all creosote

 produced is  used for wood preservation.   However,  creosote

has other uses, including as a preservative,  insecticide,

herbicide, fungicide,  disinfectant and  tree  dressing.

    B.    Manufacturing Process

         Creosote is  produced by the  distillation of coal


                            -x-

                            -SHS-

-------
         Table  1.   CREOSOTE PRODUCTION  PIANTS  IN  THE
                                      Estimated
                                   Plant  Capacity
                                   (million Ib/year)
ALLIED CHEMICALS CORPORATION

   Detroit, Michigan
   Ensely, Alabama
   Ironton, Ohio

KOPPERS COMPANY, INC.

   Cicero  (Chicago), Illinois
   Follansbee, West Virginia
   Fontana, California
   Houston, Texas
   Portland, Oregon
   Kearney (Seaboard), New Jersey
   St. Paul, Minnesota
   Swedeland, Pennsylvania
   Woodward, Alabama
   Youngstown, Ohio

REILLY TAR AND CHEMICAL CORPORATION
   Cleveland, Ohio
   Granite City, Illinois
   Ironton (Provo), Utah
   Lone Star, Texas
   Chattanooga, Tennessee
USS CHEMICALS

   Clairton, Pennsylvania
   Fairfield, Alabama
   Gary, Indiana

THE WESTERN TAR PRODUCTS' CORPORATION

   Memphis, Tennessee
   Terre Haute, Indiana

WITCO CHEMICAL CORPORATION

   Point Comfort, Texas
100-200
100-200
100-200
100-200
100-200
200-300
 10-20
 10-20
 10-20
 10-20
 10-20
100-200
100-200
 10-20
 10-20
 10-20
 10-20
 10-20
100-300
100-200
100-200
 10-20
 10-20
                    Estimated
                 Annual  Production
                   (million Ib)

                     250-350
                     350-450
                      50-100
                     250-350
                      20-40
                      10-20
 10-20
TOTAL ANNUAL PRODUCTION (1972)
                  930-1,310

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tar which is produced by the  high temperature carbonization

Of bituminous coal.  A generalized production and waste

schematic for creosote is  presented in Figure 1.

    C.   Waste Generation  and  Management

         The two waste streams generated in the production

of creosote are (1) the process wastewater and (2) the sludge

resulting from the wastewater  treatment plant.

         During the distillation process, an appreciable

quantity of the water contained in the coal tar (1-2 percent

of the total volume) (1) is boiled off and disposed of along

with other process waters.  This aqueous waste from the

distillation step in the process is the source of hazardous

constituents of both listed waste streams.

    Creosote wastewater is either discharged to publicly owned

treatment works (at smaller facilities)* or treated on-site in

holding ponds (at larger plants).   Where on-site treatment is

utilized, ponds are dredged periodically, giving rise to the

second listed waste stream.  Based on  the prevalent waste

disposal practice in the chemical  industry, these wastewater

treatment sludges are transferred  to a landfill for final

disposal .(!)

    Discussion of Basis for Listing

    A.   Hazards Posed by  the  Wastes

         1.   Creosote Wastewater
     listing  does not include any  wastewater which is dis-
 charged  to  a  POTW and which is mixed  with domestic sewage
 and that  passes  through a sewer  system  before it reaches a
 POTW.

                            -X-

                            -5H7-

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                                COAL           LIGHT
                                GAS   AMMONIA  OIL
                      CARBOLIC OIL
                                                                       BIOLOGICAL TREATMENT IN  HOLDING PONDS
                            COAL
COKE OVEN
1650-2150°F
                                         I
                                                         NAPHTHALENE OIL
                                                         (OTHER PRODUCTS)
COAL TAR
                                                               t
                         T
                         1
                                         WATER
                                                                 DISTILLATION
                                                                 (B.P. 106-395°C)
                                    CREOSOTE
                                       COKE
                                PITCH
                                Rgure 1. PRODUCTION AND WASTE SCHEMATIC FOR CREOSOTE'"
00
 i

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         The  raw  wastewater from  the  production of creosote

 is expected  to  contain varying amounts  of  creosote, the

 creosote constituents  benz(a)anthracene, benz(b)fluoranthrene

 and benzo(a)pyrene,  all of which are polycylic  aromatic hydro-

 carbons, and other distillation intermediates.   The actual

 composition  of  the constituents in the  wastewater from creosote

 production depends on  the source of the coal  used to  produce

 the tar, the design  and attendant  operating conditions (temper-

 ature,  coking  time,  gas collection systems) of  the  coke

 ovens,  and the  design  and operating parameters  of the  still

 (e.g.,  the feed rate,  temperature, and  the blending of various

 tar distillation fractions).  As a result  of  these  factors

 the fractional  distillation is ordinarily  incomplete  so that

 a certain amount of  creosote residue is present  in  the raw

 wastewa ter .

     Based on  the  estimated annual production of  1,150 million

 Ib/yr of creosote,*  and a generation of 1  Ib  creosote  per  12

 Ibs coal tar(6), and a 1-2% volume water content  in coal  tar

 which is boiled off  in the distillation process  and disposed

 of as wastewater,  it is estimated that  60-115 million  Ibs  of

 creosote per year  are  present in the raw process  wastewater

 sent  to treatment.   Obviously,  such large  quantities of this

 waste have the  propensity for large-scale  environmental harm.

 There is a greater chance that  exposure (since  larger  expanses


*Hls figure was calculated by  rounding off the mean total
 annual production estimated' for 1972 shown in  Table 1.

-------
of groundwater may be  contaminated)  and environmental loading

will occur for longer  period  in  light  of contaminant availa-

bility.
     The components of  this waste  stream are also of con-

siderable concern as potential health  hazards.   As previously
mentioned, these wastes  contain  benz(a)anthracene, benzo(b)
fluoranthene, and benzo(a)pyrene and creosote which are

known carcinogens.
     As will be demonstrated  below,  these waste  components
could be released from  holding ponds into the environment,
unless proper waste management is  assured.   Creosote and
the other waste constituents may be  both mobile  and highly
persistent, increasing  the likelihood  of its reaching  receptors
in concentrations sufficient to cause  a  substantial hazard
should migration occur,  the migratory  potential  via ground
and surface water, as well as the  persistence of creosote has
been demonstrated by the damage incident described below  (see
damage incident,  p. 10).  Further, the  sheer quantity  of
creosote and its constituents in the waste  could overload the
sorptive capacity of the sediments.  Accordingly,  those con-
stitutents of creosote not adsorbed  to  sediments are mobile.
The following section elaborates on  these  points.

(a)  Wastewater's Constituents' Potential  to Migrate and
     Cause Substantial Hazard

     The two  most likely exposure  pathways  for this waste


                             -x-
                            -S"S"O-

-------
 are groundwater  and  surface water via  migration from holding




 ponds «




     As  to  the migratory potential  of  creosote that is present




 in the waste, creosote has proven,  in  spite  of its relatively




 low solubility (3°)  in water (5 ppm) ,  to  have  sufficient




 migratory  potential  and persistence  to  cause long-term con-




 tamination  following improper waste  disposal.   Creosote can




 be expected  to be  highly persistent  in  groundwater,  since




 the chief  degradation mechanism is  oiod egr ada t ion , (30 )




 which would  not  be expected to be a  factor in  the  abiotic




 conditions  of an aquifer.  Exposure  also  may occur via a




 surface  water exposure pathway should  precipitation  result




 in flooding  of holding ponds.




     The waste constituents of creosote:   benz ( a) anthracene ,




 benzo(b) f luoranthene and benzo( a) pyr ene ,  are also  capable




 of migrating and persisting if these wastes  are  managed




 improperly.  While these constituents  tend to  adsorb  to




 organic  matter, (30)  management could occur on  sites  with




 soils low  in organic content or with highly  permeable  soil




 so that  mobility would not be deterred.




     The polycyclic  aromatic hydrocarbons are  persistent in




 nature,  especially soils^10) with half lives,  for  benzo(a)-




 anthracene and benzo( a) pyr ene,  reported to be  7,000  and 21,000




 hours, respectively^11)   The Agency possesses no  evidence




 that  benzo(a)anthracene,  b enzo( a) pyr ene or benzo( b) f luorathene




do not persist.   Furthermore,  benzo(a)pyrene is  bioaccumula-
                            -55)-

-------
tive,(30)  ancj  benz( a) anthracene is extremely bio accumula-




tive (octanol/water  partition coefficient of 426,579 (30)),




so that  these constituents  could accumulate in harmful concen-




trations  if  they  reach  a  receptor.




     If  this waste is  improperly managed, these constituents




of creosote  may be released  and  reach  environmental receptors




and cause substantial hazard.   Improper  management iss certainly




reasonably plausible or possible; holding ponds may be sited




in areas  with highly permeable  soils,  or they may lack adequate




leaching  control  features.   Further, there may be inadequate




cover to  impede migration of  the waste constituents or




inadequate flood  control measures to impede waste washout in




the event of heavy rainfall.  Thus, mismanagement could




realistically occur, resulting  in substantial hazard.




     For  both the creosote and  its  related constituents,  the




Agency presently  does not possess information indicating  that




these compounds would no t migrate and  persist in the environmen




and cause a  substantial health  hazard.   Therefore,  the Agency




would be  unjustified in not  listing this  waste (the treatment




sludges)  on  the basis of these  contaminants until such




contradictory information is  readily available.




     Additionally, there has  been a documented incident of




surface and groundwater contamination  due to  improper  disposal




of creosote containing wastes.   In  the 1950's, waste chemicals




including creosote and other  types  of  wood-preserving  oils

-------
 were Injected  into  wells in Delaware  County,  Pennsylvania.




 The injected wastes migrated into groundwater,  infiltrated a




 storm drain sewer,  and  discharged into  a  small  stream,  causing




 odor and biological damage.  Although injection of  the  wastes




 into the wells  ceased  in the 1950's,  contamination  was  first




 observed in 1961.'*)  Thus, the waste constituents  proved




 capable of migration via both ground  and  surface waters, and




 were able to persist and cause damage for  long  periods  of




 time.




     2.   Creosote  Wastewater Treatment Sludge




     The wastewater treatment sludges that  remain after




 biological treatment are also hazardous.   The carcinogenic




 constituents of  creosote,  namely benz( a) anthracene ,  benzo(b)-




 fluoranthene and  benzo ( a) pyr ene , are  especially likely  to  be




 present in the  treatment sludge since these constituents




 adsorb to sediments at  very high levels (App. B) .   Where




 treatment is incomplete, creosote (which is, however, somewhat




 amenable to biodegradation (App. B)), is projected  to be




 present in the  sludge as well.   If these sludges  are placed




 in a leaking landfill,  an  unlined holding  pond  or an improperly




 sited facility  (i.e., as in an  area with permeable  soil) the




 waste constituents  may  be  released.




     As demonstrated above, the waste constituents  of concern




 are  capable of migrating and persisting and reaching environ-




mental receptors if  managed improperly.   Since  the  waste




constituents  include benz( a) anthracene ,  benzo( b) f luoranthene ,
                            -55S-

-------
benzo(a)pyrene  and,  creosote,  which are known carcinogens

should  substantial  environmental harm can result from exposure

even to  minute  concentrations* if mismanagement should occur.


     B.   Health  and  Ecological Effects

          1.    Creosote

     Health Effects -  Creosote is carcinogenic in animals(25)

and has  been associated  with  several  occupational cases  of

skin cancer over  a  fifty year  period.(26)   Creosote has  also

been identified by  the Agency  as a compound which exhibits

substantial (31)  evidence of  carcinogenicity.   This chemical

is mutagenic in a variety of  bioassay  test systems,(25)

and reportedly  affects fetal  development.^/)

     Creosote is  toxic in rats  (oral  LD5Q  = 275  mg/Kg],

while death in  humans has  resulted from ingestion of much

smaller  doses.(24)

     Additional information and  specific references on adverse

effects  of creosote can  be found in Appendix A.

     Ecological Effects  -  Creosote is  a mixture  of  chemical

compounds, and while there was  an  abundance of data on its

various  components, data  were  somewhat  limited on creosote

itself.  Ellis'^' found  fish  kills occurring  at concentrations
*See 44 Fed. Reg. 15926, 15930  (March  15,  1979)  (no  zero
 exposure level for carcinogens).

-------
 as low as 6.0 mg/1  in  less than 10 hours.   Applegate,  et  al.,(13)


 in a large battery  of  tests with a limited  number  of  animals,


 including rainbow trout  Salmo gainneri and  lamprey larvae


         marinus,  found that concentrations of  5.0 mg/1
 induces mortality.


     It has been  reported that PAH's from a contaminated


 lagoon were accumulated  to  a greater degree of biota species


 near the  top of the  food chain . C12 ), One PAH, benzo( a) pyr ene ,
     1                                    '          '   i
            •(       '            '    ' i      • • >        'i

 has been  reported  to  accumulate  in mussels taken from PAH-


 treated pilings. (3)


     Regulatory Recognition of Hazards - The Office of Toxic


 Substances has issued  an RPAR on creosote and is continuing


 preregulatory assessment under Section 6 of the Federal


 Insecticide, Fungicide and  Rodenticide Act.


     Industrial Recognition of Hazard - Sax, Dangerous


 Properties of Industrial Materials,  designates creosote as


 moderately toxic via  oral,  inhalation, and dermal  routes.


         2 .   Benz(a) anthracene ,  B enzo ( b) f luoranthene and


              Benzo(a)pyrene.


     Health Effects - Benz ( a) anthracene and Benzo ( b) f luoran-


 thene are carcinogenic in animals .( 28 > 29)  Benzo( a)pyrene


 has  been tested extensively  for  carcinogenic! ty and found to


 exert positive results by all  routes tested. (22)   The Agency


 has  also  identified these compounds  as carcinogenic'3 '.


     Additional information  and  specific references on the ad-


verse effects  of  benz( a) anthracene ,  benzo( a) pyr ene  and benzo(b)-
                           -sss-

-------
f luor an thene can be  found  in  Appendix  A.




     Ecological Effects -  Eighty-seven percent  of freshwater




fish exposed to 1,000 ug/1  benz ( a) ant hr acene for six months
     Regulations - Benz( a) anthracene  and  benzo ( b) f luoranthene




are undergoing pr e-r egula to ry assessment  by  the  Office of




Water and Waste Management under  the  Safe  Drinking Water Act




for health effects other than oncogenici ty .   The  Office of




Water and Waste Management under  the  Safe  Drinking Water Act




is also conducting a pr e-r egula tory assessment of  benzo(a)-




pyrene based on its car cinogenici ty and other health  effects.
                             -sst,-

-------
                         References
 lt   von Rumker et al, Production,  Distribution,  Use and
     Environmental Impact Potential of  Selected Pesticides
     EPA 540/1-74-001, 1975.

 2,   Farm Chemicals Handbook,  1977, Meister Publishing  Company
     Willoughby, Ohio.                                         '

 3.   American Wood Preservers'  Association (1976).   A.V.P.A.
     Book of Standards, Washington, D.C.

 4.  .NIOSH Registry of Toxic Effects  of.Chemical  Substances,
     U.S. .Department of Health,  Education  and  Welfare.

 5.   Damage incident, u.b. environmental Frotection  Agency,
     open file, unpublished data.

 6.   Telephone communication to:  Mr. J. Burroughs,  Manager,
     Allied Chemical Corporation, Detroit,  Michigan,  12
     February 1980. (S. Quinbran, TRW.)

 7.   (1978) Wood Preservative  Pesticides - Notice  of  Rebuttable
     Presumption.  Fedejcal Register - Vol.  43:48154-48295.

 8.   I. S. Schipper (1961).  The Toxicity  of Wood  Preserva-
     tives for swine.  Am. J.  Vet.  Res.  22:401-405.

 9.   (1978) NIOSH.  Registry of  Toxic Effects  of  Chemical
     Substances.

 10.   National Academy of Science. 1972.  Particulate  Polycyclic
     Organic Matter.   Committee  on  Biological  Effects on
     Atmospheric Pollutants, Div. of Med.  Sci., Natl. Res.
     Council, Natl. Acad. Sci., Washington, D.C.  361  pp.

 11.   Herbes, S. and L. Schwall.  1978. Microbial  Transfor-
     mation of Polycyclic Aromatic  Hydrocarbons in Pristine
     and Petroleum Contaminated  Sediments.  Appl.  Environ.
     Microbial. 35(2): 306-316.

 !2.   Naiussat,  P.  and C.  Auger  1970. Distribution  of  benzo-
     (a)pyrene and Perylene in various organisms  of  the
     Cliperton Lagon  Ecosystem.  C.R. Acad. Siv.,  Ser. D.
     270(22):  2702-2705.

13»   Applegate,  V.C.,  J.H.  Howall,   and A.E. hall,  Jr. 1957.
     Toxicity of 4346 chemicals to  larval  lampreys and
     fishes,   Dept. of Interior, Special Sci.  Rept.  No.
     207.
                            -X-
                            -5S-7-

-------
14.   Ellis, M.M.  1943.   Stream  pollution studies in the State
      of Mississippi.   U.S.  Dept.  of  Interior,  Special Sci.
      Kept. No. 3

15.   Gleason, et  al  1969.   Clinical  toxicology of commercial
      products.  Acute  poisoning.  3rd ed.  Baltimore,  Williams
      and Wilkins, p.42.

16.   NIOSH, 1978.  Registry  of  Toxic Effects  of Chemical
      Substances.  DHEW Publication No.  79-100,  p. 370.
      (crossed out in notes)

17.   Patty, F.A.  1963, Industrial Hygiene and  Toxicology,
      Vol. 2, 2nd  ed. New York,  Interscience.

18.   U.S. EPA. 1979.   Environmental  Criteria  and Assessment
      Office.  Benz(a)anthracene:  Hazard  Profile, (draft)

19.   U.S. EPA. 1979.   Environmental  Criteria  and Assessment
      Office.  Benz(b)fluoranthene:   Hazard  Profile  (draft)

20.   U.S. EPA. 1979.   Investigation  of  selected environmental
      contaminants:  Acrylamides.

21.   U.S. EPA. 1979. Environmental Criteria and Assessment
      Office.  Acrylami^de:  Hazard Profile (draft)

22.   U.S. EPA. 1979. Environmental Criteria and Assessment
      Office.  Benzo(a)pyrene:   Hazard Profile  (draft)

23.   Toxicol. Appl.  Pharmacol.  6:378 (1964).

24.   Gleason, et  al.,  (1969) Clinical Toxicology of  Commercial
      Products.  Acute  poisioning,  3rd  ed.  Baltimore, Wiliams
      and Wilkins, p.42.

25.   Wood Preservation Pesticides -  Notice  of  Rebuttle  Resumptin.
      Fed. Reg. 43:48154-48295 (1978).

26.   Farm Chemicals  Handbook.   (1977) Meister  Publishing
      Company, Willoughby, Ohio.

27.   Schipper, I.S.   The Toxicity of Wood Preservatives  for
      Swine.   Am.  J.   Vet. Res.  22:401-405  (1961).

28.   U.S. EPA.  (1979) Environmental Critera  and Assessment
      Office.   Benz(a)  anthracene:  Hazard Profile (draft).

29.   U.S. EPA.  (1979)  Environmental Criteria  and  Assessment
      Office.   Benz(b)  fluoranthene:  Hazard Profile  (draft).

-------
30.   Dawson,  English,  and Petty, 1980,  "Physical  Chemical
     Properties  of Hazardous Waste Constituents.


31.   Cancer  Assessment Groups List of Carcinogenic  Compounds,
     April  22,  1980.

-------
                            LISTING BACKGROUND DOCUMENT

                               DISULFOTON PRODUCTION
     Wastewater Treatment Sludges from the Production of Disulfoton (T)

     Still Bottoms from Toluene Reclamation Distillation in the Production
     of Disulfoton (T)
     I.     SUMMARY OF BASIS FOR LISTING


           The organic waste streams from disulfoton production contain a

     variety of intermediate products  which are toxic  (i.e.,  toluene and

     o,o,o-triethvl ester of phosphorodithioic acid).


           The Administrator has  determined that  the solid  waste  from disulfoton

     production may pose a substantial present or potential hazard  to human

     health or the environment  when  improperly transported,  treated,  stored,

     disposed  of or otherwise managed,  and  therefore should be  subject to

     appropriate management  requirements  under Subtitle  C of RCRA.  This

     conclusion is based on  the following considerations:
           1.   It  is estimated  that disulfoton production  is  responsible for
               generating approximately 300 Ibs/day of wastewater  treatment
               sludges.  The sludge is expected to contain the  toxic constituents
               toluene and 0,0,0 triethyl ester of phosphorodithioate.

           2.   It  is estimated  that 120 metric tons/yr of  still bottoms con-
               taining o,o,o-triesters of phosphorodithioic acid and toluene
               are generated from the production of disulfoton.*
*The Agency is aware that these wastes also contain the toxic organic, disulfo-
 ton.   However, due to the propensity of disulfoton to rapidly hydrolize, it
 will not persist in the waste for extended periods of time.  Based  on this
 fact,  the Agency will not presently regulate these wastes on the basis of
 disulfoton contamination.

-------
     3.    Disposal of these^wastes, even  in  drums,  in improperly designed
          or  operated landfills represents a potential hazard  due to  the
          migratory potential of these hazardous  compounds.

II.   SOURCES  OF THE WASTE AND TYPICAL DISPOSAL  PRACTICES


     A.    Profile of the Industry


          Disulfoton is produced in this  country  by only  one manufac-

turer, Mobay Chemical Corporation, at its  Chemagro Agricultural Division

in Kansas City, Missouri. V'  Production for  1974  was estimated at 10  mil-
:       '
lion pounds.
          Disulfoton is a systemic insecticide,  primarily  used  to  control

sucking insects, especially aphids and plant-feeding mites.   It  was de-

veloped in the 1950*s and has been in commercial  use for  about  15 years.

Agricultural uses accounted for almost all  of  the estimated U.S. consump-

tion in 1972.  Small quantities are used  on ornamentals  in  the home and

garden market in the form of dry granules of very low  active  ingredient

content. ^'


     B.   Manufacturing Process


          Disulfoton is produced according to the following  three-step

scheme^);

                               Toluene
(A)   P2S5  + 4C2H5OH + 2NaOH	>  2(C2H50)2P(S)SNa  +  H2S +  2H20
                               Solvent
            Ethanol                      "Diethyl Salt"  (DES)
 * The underlined  data are those obtained  from  proprietary reports and
  data files.

-------
 (B)    PCL3  +  3HOC2H4-S-C2H5	>  3C1C2H4-S-C2H5 + H3P03

              "Thio-Alcohol"                "Chloro Thio Alcohol" (CTA)
 (C)    (C2H50)2P(S)SNa +  C1C2H4-S-C2H5 —> (C2H50)2P(S)-S-C2H4-S-C2H5 + NaCl

            DES               CTA           Disulfoton


       A  process  flow diagram and  waste schematic is shown in Figure 1.

 The  reaction  between P2S5  and ethanol in toluene solvent occurs and

 produces  the  diethyl phosphorodithioic acid.   The major side product of

 the  reaction  is  the  o,o,o-triethylester  of'the phosphorodithioic acid*.

 The  dithioic  acid  is next  converted  on the diethyl salt (DES)  with caustic

 soda.  These  two substeps  are summarized in reaction (A) (see  equation

 on page  2 and corresponding  (A) in Figure 1).

       The DES is separated in the toluene recovery unit while  the  remaining

 mixture  of  toluene,  triester,  and other  organic residues is  sent to a

 toluene  recovery unit.   The  toluene  is recycled to the  salt  production  process

 and  the  still bottoms  (Waste Stream  II  in Figure 1)  containing o,o,o-triethyl

 ester  of phosphorodithioic acid go to  disposal.       	  	
     PC13 and thio alcohol are then reacted  to  form  the  chloroethyl

thioethyl ester ("chloroethyl thioethyl alcohol,  CTA") and  phosphorous

acid (Reaction B, above, and corresponding (B)  in Figure 1).

      The third step of the production process, reaction C  above,  involves

the reaction between the diethyl salt (DES)  and chlorothio-alcohol

(CTA) to form disulfoton and sodium chloride.   This  is shown  in Figure 1

as the disyston unit, and marked (C).
*Also referred to in this document as o,o,o-triester.

-------
 MAKEUP
.TOLUENE
!SOLVENT
 ETHANOL
                                                 PC13
                   RECOVERED TOLUENE
               DES
             UNIT (A)
CRUDE
 DES
 TOLUENE
RECOVERY
  UNIT
DES
                                              WASTE
                                              SOLIDS
                                    (II) 0.0.0 TRIES TER ,
                                       TO BURIAL
                                     WASTE WATER
                                         'THIO-ALCOHOL
                                 CTA
                                UNIT (B)
                                                          CTA
                                  I
DISYSTON
  UNIT
   (C)
                                                        •\ f
                                DISYSTON
                                SOLVENT
                                RECOVERY
                                  UNIT
                                                         WASTE
                                                         WATER
                                                       TREATMENT
                                                      (I) WASTE WATER
                                                     TREATMENT SLUDGE
DISULFOTON
 PRODUCT
                                                WASTE
                                                WATER
        Figure 1. PRODUCTION AND WASTE SCHEMATIC FOR DISULFOTON
                  [ADAPTED FROM CHEMAGRO DRAWING (3)]

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      Treatment  of  waste water from the manufacturing process results

 in  a  sludge  (Waste  Stream I  in Figure 1).

      C.   Waste Generation  and Management

           As  indicated  in Figure  1,  the diethyl salt from the DES unit  is

 separated  for  further  processing and  the toluene,  triester and other

 waste solids are sent  to a toluene recovery  unit.   The recovered toluene is

 recycled back  to the production process;  the waste stream from this process

 (Stream II, Figure  1)  is composed  of the unrecovered  toluene,  o,o,o-triester

 of  phosphorodithioic acid  and  associated organic residues.   This waste

 is  combined with waste solids  from the  downstream disyston recovery unit

 and sent for burial in landfills.^  '
      The disyston unit process water,  along with  wastewater from the

toluene recovery unit, is sent to the disyston  solvent  recovery  unit where

some disulfoton is recovered and recycled  to the disyston unit.
The sludge from wastewater treatment  (Waste Stream  I  in Figure  1)  is

disposed of by landfill; 	
                                                                (11)
*/ The waste stream from the disyston recovery  unit  is  not  specificically
listed as hazardous, but the combined waste stream is deemed hazardous
under the 'mixing' provision of §261.3.

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 HI.  DISCUSSION  OF  BASIS FOR LISTING

      A.   Hazards Posed by the Wastes

          There are  two solid waste streams which are considered in

 this document.  As-previously mentioned, both waste streams contain

 toxic constituents which pose a potential hazard if improperly managed

 and disposed.

     The  still bottoms  from the toluene recovery unit (Waste Stream II)
                                                              \
 are expected  to contain triesters and unreacted toluene.  There is

 little information on the toxicity of the triesters; however, the

 compound  is structurally similar to 0,0,s-triethylester, a member of

 a family  of compound which is very toxic (LD5Q = 80 rag/kg after 8

 days) (22)t  Toluene  is  a toxic chemical with such acute toxic effects

 in humans  exposed to low concentrations (200 ppm) as excessive depression

 of the nervous system. d°)

      The wastewater treatment sludges (Waste Stream I) also contain

 toluene solvent and  o,o,o-triethylester of phosphorodithioic acid,

 which is a process intermediary.    (For information on the toxic effects


 of these compounds,  see  Section ill B.)


      1.  Exposure Pathways

         As noted above,  the typical  disposal method for both of these

wastes is  in landfills.   Disposal  of these wastes in landfills,  even if
                                  -sw-

-------
 plastic lined drums are used, represents  a potential hazard  if the  landfill




 is improperly designed or operated  (the drums  corrode  in  the presence of




 even small amounts of water).  This can result  in leaching of hazardous




 compounds and subsequent contamination of ground water.




       As a result, the waste constituents of concern may migrate from




 improperly designed and managed landfills and contaminate ground and




 surface waters.   Toluene is highly soluble (470 ppm)^4) an<£ by




 virtue of'its solvent  properties,  can facilitate mobility and




 dispersion of other toxic constitutents assisting their movement toward




 ground and surface waters.   The migratory potential  of toluene is confirmed




 by the fact  that toluene has been  detected migrating from the Love  Canal




 site  into surrounding  residential  basements  and solid surfaces, demon-




 strating ability to migrate  through  soils  ("Love Canal  Public Helath




 Bomb",  A Special Report  to  the  Government  and Legislature,  New York




 State Department of Health  (1978)).   Thus,  once toluene migrates from




 the matrix of the waste,  it  is  likely  to  persist in  soil and  groundwater.




 There also may be a danger of toluene  migration and  exposure  via an




 air inhalation pathway if disposal sites  lack adequate  cover.  Toluene




 is relatively volatile (28.4 mm Hg (24)) and  is mobile  and persistent




 in air, having been found in school  and basement air at Love  Canal




 ("Love Canal  Public Health Bomb", supra).




      Although very little information is  available  on  the  characteristics




of o,o,o-triethylesters, the  Agency  is  aware  of the  hazardous characteristics




of the same family  of compounds as this particular triester.   The Agency

-------
 would require some assurance that the waste components will not migrate




 and persist to warrant a decision not to  list  the vaste.  No cuch assurance




 appears readily available.




      Thus, these waste constituents could  leach into groundwater if




 landfills are unlined, or have inadequate leachate collection systems.




 Waste management facilities located in  areas with highly permeable




 soils would likewise facilitate leachate migration.




     There also* may be a danger of toluene  migration  and exposure via an




 air inhalation pathway if disposal sites 'lack  adequate cover.   Toluene




 is relatively volatile (28.4 mm Hg (24)) and is  mobile and  persistent




 in air, having been found in school and basement air  at Love  Canal




 ("Love Canal Public Health Bomb," supra).




      B.    Health and Ecological Effects




           1.   Toluene






               Health Effects  - Toluene is  a toxic chemical  absorbed into




 the body  by inhalation,  ingestion,  and through the skin.  The acute toxic




 effect in humans  is excessive  depression of the  central nervous  system,^15'
 and this occurs  at  low concentrations [200 ppm] .  -   Chronic occupational




 exposure to toluene has led  to the development  of neuro-musnular disorders.




              Since  toluene is metabolized in  the body by a protective




 enzyme system which is  also  involved in the elimination of other toxins,




 it appears that over-loading the matabolic pathways with toluene will greatly




reduce the clearance  of other,  more toxic chemicals.  Additionally, the high




affinity of toluene for fatty tissue can assist in the absorption of other

-------
 toxic chemicals into the body.  Thus, synergistic  effects  of toluene  on the




 toxicities of other contaminants may render the wastes  more  hazardous.




 Toluene is designated as a priority pollutant under  Section  307(a) of the




 CWA.  Additional information and specific references on the  adverse




 effects of toluene can be found in Appendix A.




                Ecological Effects - Toluene has been shovn to be acutely




 toxic to freshwater fish ^and to marine fish.   Chronic toxicity is also




 reported for marine fish.'•A***'




                Regulations - Toluene has an OSHA standard ,for air TWA of




 200 ppra.  The Department of Transportation requires a "flaamable liquid"




 label.




                Industrial Recognition of Hazard - Toluene is listed as




 having  a moderate  toxic  hazard  rating via oral and inhalation routes  (Sax,




 Dangerous  Properties  of  Industrial  Materials).







            2.   Phosphorodithioic  and  Phosphorothioic  Acid Esters  (Triesters)






                Health Effects - The -s,s-methylene o,o,o,o-tetraethyl




 ester is extremely  toxic  by various  routes  of  administration to  animals




 [oral rat LD^Q  = 13 mg/kg]/19'   Toxic effects in  the blood of humans  have




 been observed at minute  doses [100  micrograns/kg],(20)  v^^e human  death




 from ingestion  of this chemical has  also  occurred  at  low doses [50  mg/kg].^ '




 The phosphorothioic acid  -o,o,o-triethylester  is  a member of a family  of




 compounds, which, when given orally to rats is very toxic [LD5Q  = 80




rag/kg after 8 daysj.^22'  The -0,0,s-trimethyl ester  is  extremely toxic




to rats  [LD5Q = 15 mg/kg],'23'  Additional  information and  specific




references on adverse effects of phosphorodithioic  and  phosphorcihioic

-------
acid esters can be found in Appendix A.




              Industrial Recognition  of  Hazard - Sax (Dangerous  Proper-




ties of Industrial Materials),  lists triethyl phosphorothioate  (phosphoro-




thioic acid, o,o,o-triethyl ester)  as  being highly toxic via ingestion




and inhalation.

-------
 IV.   References
 1.     1977 Directory of Chemical Producers, Stanford Research Institute,
       Menlo Park, California.

 2.     Kelso, G. L, R. Wilkenson, T. L. Ferguson, and J. R. Maloney,
       Development of Information on Pesticides Manufacturing for Source
       Assessment, Final Report, Midwest Research Institute, EPA Contract
       No.  68-02-1324, July 30,  1976.

 3.     von  Rumker et al, Production, Distribution, Use and Environmental
       Impact Potential of Selected Pesticides, USEPA Office of Pesticide
       Programs, EPA 540/1-74-001,  1975.

 4.     Lawless,  E. W., R.  von Rumker, T. L.  Ferguson, The Pollution Poten-
       tial in Pesticide Manufacturing, TS-00-72-04,  June 1972.

 5.     Cotton,  F.  A. and G.  Wilkinson,  Advanced Inorganic Chemistry,  New
       York,  Interscience Publishers, 1972.

 6.     Bailer,  J.  C.,  Comprehensive Inorganic  Chemistry,  Volume  2,  New York,
       Pergamon Press, 1973.

 7.     Fezt,  C., and K.  J.  Schmidt,  The Chemistry of  Organophosphorous Pest-
       icides,  New York,  Springer-Verlag,  1973.

 8.     Parsons,  T.,  Editor,  Industrial  Process  Profiles  for Environmental
       Use: Chapter  8, Pesticide  Industry, EPA-600/77-023h,  Technology
       Series, EPA PB-266  225.

 9.     Marcus, M.,  J.  Spigarelli  and  H.  Miller,  Organic  Compounds in Organo-
      phosphorous Pesticide Manufacturing Vastewaters, Midwest Research
      Institute, Kansas City, Missouri, Contract No. 68-03-2343,  1977.

10.   Office of Water Programs, Applied Technology Division, The  Pollution
      Potential in Pesticide Manufacturing, TS-00-72-04.

11.   Proprietary information submitted to EPA by Mobay Chemical  Corporation
      through 1978 response to "308" letter.

12.   Office of Water and Hazardous Materials, Effluent Guidelines Division,
      Development Document for Interim Final Effluent Limitations Guide-
      lines for the Pesticide Chemicals Manufacturing Point Source Category,
      Washington, 1976.

13.   NIOSH (1978) Registry of Toxic Effects of Chemical  Substances.
      Pyridene.

-------
IV.   References (Continued)
14.   Gleason, H.N., et al.  Clinical  Toxicology of Commercial Products.
     Acute Poisoning.  (1969) 3rd Ed.,  p.  61.            ~~      ~"	"'

15.   U.S. EPA (1979) Toluene Ambient  Water Quality Criteria.

16.   NIOSH (1978) Registry of Toxic Effects  of  Chemical  Substances.
     Toluene.

17.   U.S. EPA.  1979.  Toluene Ambient  Water Quality  Criteria.   (Draft).
             i
18.   U.S. EPA.  1979.  Toluene:  Hazard Profile.   Environmental  Criteria
     and Assessment Office, U.S. EPA, Cincinnati,  Ohio.

19.   Pharmaceutical Journal  185:361  (1960).

20.   Toxicol. Appl. Pharmacol.  22:286  (1972).

21.   Clinical Toxicology of Commercial  Products.   Acute  Poisoning.
     Gleason, M.N. , et al.  (1969) 3rd  Ed.,  p.  65.

22.   Mallipute et al.  J. Agric. Food Chen.  27:463-466  (1979).

23.   Fukukto et al.  Quarterly Progress Reports  to EPA,  August 1978 -
     November, 1979.  EPA Grant No. R804345-04.

24.   U.S. EPA.  1980.  Physical Chemical Properties of Hazardous
     Waste Constituents"(Prepared by Southeast Environmental Research
     laboratory;  Jim Felco, Project Officer.

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                       LISTING BACKGROUND DOCUMENT

                            PRORATE PRODUCTION
Wastewater Treatment Sludges from the Production of Phorate  (T)

Filter Cake from the Filtration of Diethylphosphorodithioic  Acid
in the Production of Phorate (T)

Wastewater from the Washing and Stripping of Phorate Production (T)
I.    Summary of Basis for Listing


      The hazardous wastes from phorate production are:  (i; wastewater

treatment sludges from the production of phorate, (2) filter cake from the

filtration of diethylphosphorodithioic acid, and (3) wastewater from the

washing and stripping of phorate product.


      The Administrator has determined that these solid wastes from phorate

production may pose a substantial present or potential hazard to human

health or the environment when improperly transported, treated, stored,

disposed of or otherwise managed, and therefore should be subject to appro-

priate management requirements under Subtitle C of RCRA.  This conclusion

is based on the following considerations:
      1)   Wastes from the production of phorate may contain phorate,  for-
           maldehyde, esters of phosphorodithioic acid and phosphorothioic
           acid.

      2)   Phorate is extremely toxic and formaldehyde has been evaluated
           by the Agency as exhibiting substantial evidence of carcinogen-
           icity.  The other constituents expected to be present in the
           waste are also toxic.

      3)   Disposal of these wastes in improperly designed or operated
           landfills presents a potential hazard due to the risk of
           these hazardous compounds leaching into groundwater.  As

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          these hazardous  compounds are likely to persist in ground-
          water, drinking  water  supplies derived from these sources
          are likely  to  be contaminated.

     5)   Mismanagement  of incineration operations could result  in the
          release of  hazardous vapors to the atmosphere and present a
          significant opportunity for exposure of humans, wildlife and
          vegetation  in  the vicinity of these operations to potentially
          harmful substances.
II.   Sources of the Wastes  and Typical Disposal Practices


      A.   Profile of  the  Industry


          The principal use of phorate is as a soil and systemic  insect-

icide used to control  a wide range of insects on a variety of  crops:

alfalfa, barley, beans, corn,  cotton, hops,  lettuce, peanuts,  potatoes,

rice, sorghum, sugar,  beets, sugar cane, tomatoes and wheat(3).


          Phorate is  produced in  this country by two manufacturers, Amer-

ican Cyanamid at Hannibal, M0(l>6)  ancj Mo bay Chemical in Kansas City, MO.*
     B.   Manufacturing Process


          A generalized production and waste schematic  for  phorate is

shown in Figure 1.  Phorate is made by the  reaction of o,o-diethyl hydro-

gen phosphorodithioate with formaldehyde, followed  by the  addition of

ethyl mercaptan (ethanethiol).  The o,o-diethyl  hydrogen phosphorodi-

thioate is condensed with  formaldehyde and  ethyl mercaptan.   The reaction

chemistry is as follows (*):
"__               OT   The Agency has  been  informed,  however, that
 American Cyanamid no longer produces phorate.

 All underlined information is  from  proprietary reports  and  data.
                                 -S7H

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         P2S5         +      C2H5OH	-> 2 (C2H50)2PSH + H2S
     phosphorous             ethanol           o,o-diethyl
     pentasulfide                              hydrogen
                                               phosphorodithioate
     (C2H50)2PSH      +      H2C=0 ~	> (C2H50)2PS-CH2OH
     0,0-diethyl             formaldehyde      dithiophosphate
     hydrogen
     phosphoro-
     dithioate
     (C5H50)2P-S-CH2OH + C2H5SH	—	> (C2H50)2P-SCH2SEt + H20
                         ethyl
                        mercaptan                       Phorate
      These reactions indicate the source of the waste constituents of concern,


      C.   Waste Generation and Management


           Based on the generalized flow diagram shown in Figure 1,

three hazardous waste streams from the production of phorate are expected

to be generated. (See figure 1.) These are:

           (a)  Process wastewater:  The wastewater is likely to con-
                tain significant concentrations of phorate, and lesser
                concentrations of other process waste constituents inclu-
                ding formaldehyde, phosphorodithioc and phosphorothioc acid
                esters, and other main reaction byproducts.	

                                        CD
                -_	_	m

-------
Figure 1 is Confidential
             -576-

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            (b)   Filter Cake:  The filter cake is expected  to  contain
                 high concentrations of esters of phosphorodithioic
                 acid and esters of phosphorothioic acid.   These  esters
                 are  formed immediately prior to filtration in the dithio
                 acid unit, and filtration is intended to remove  the esters
                 from the process stream.

            (c)   Wastewater Treatment Sludges:  Wastewater  treatment sludges
                 result from the treatment of process waters.  The sludges
                 are  expected to contain high concentrations of phorate because
                 of its relative insolubility in water (about 50 ppm).(7)
                 Lesser concentrations of other process constituents are also
                 expected to be found in the sludge.
III.  Discussion  of  Basis  for  Listing
      A.    Hazards Posed  by  the  Waste



            These waste  streams contain  phorate,  which is extremely toxic, and

formaldehyde, a GAG carcinogen,  and 0,0,o-triethyl  esters of both phosphoro-

thioic acid and phosphorodithioic  acid  (as  well  as  other triethyl esters

which may be present),  which are toxic.   The  presence of phorate and  formalde-

hyde in particular, even  in  small  concentrations, is  of  considerable  regulatory

concern, and the Administrator would  require  strong assurance that these waste

constituents are incapable of migration,  mobility,  and persistence if improperly

managed, before determining not  to list these wastes  as  hazardous.



           Such assurance is not forthcoming.  Of the constituents likely to

be found in the waste stream, phorate, 0,0,o-triethyl esters of both  phosphoro-

thioic acid, and formaldehyde are able  to reach  environmental receptors upon

release, and can persist.  Phorate is moderately soluble (50 ppm), could be

transported through permeable soil, and, although subject to some hydrol-
                                     -577-

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 yzation and  biodegradation, will persist  for weeks in both surface waters

 and ground water (38).  o,o,o,-Triethyl  esters of  phosphorothioic  acid

 are soluble  and persist in both surface water and  groundwaters.C38)

 Formaldahyde is quite soluble and has  great  migratory potential. (38)  If

 disposed of  in areas with inorganic or permeable soils,  it could become

 highly mobile.  Formaldahyde also persists in surface and  groundwatersC38) .

 Based upon estimates of EPA, (?) exposure  to  these  compounds is likely via
                                                            i
 drinking water supplies derived from groundwater sources within  areas adjacent

 to mismanaged land disposal sites.  The projected  widespread movement of

 these compounds when discharged to surface waters  will also probably result

 in exposure  of aquatic life forms in rivers,  ponds, and  lakes.  Another

 waste constituent, o,o-diethyl ester of phosphorodithioic  acid, is less

 persistent than the prevously discussed compounds, but sufficiently soluble

 and resistant to degradation to result in widespread movement^' ' .  Thus,

 if improperly managed, these constituents are fully capable of migration,

 mobility,  and persistence in substantial concentrations.


          As the subject waste streams contain  extremely  hazardous

 constituents which may be mobile and persistent  upon release,  disposal of

 these wastes landfills can create a potential hazard if  landfills are im-

 properly designed or operated.  Disposal of  these wastes in lagoons or

 treatment  of wastes in holding ponds prior to final disposal,  also presents

 substantial  potential hazards as well.  Unless lagoons are properly designed

and operated (e.g.,  by lining the site with appropriate  liners and employing

leachate collection systems),  a strong potential exists  for contamination of

soil and groundwaters via leachate  percolation.  Heavy precipitation
                                   -57S-

-------
may result in flooding of the lagoon, thus, surface waters  can  become




contaminated-




           In light of the hazards associated with these waste  constituents,




and their potential for mobility and persistence in substantial concentra-




tions if mismanaged, the wastes are deemed to be hazardous.






      B.   Health and Ecological Effects






           1.  Phorate






               Health Effects - Phorate is extremely toxic in animals by




all routes of administration [oral rate LD5Q = 1.1 mg/kg].(9~11'  Death




in humans has been reported as a result of ingestion of extremely small




doses. (12)  Inhalation of phorate by mice caused adverse effects on




reproductive performance at very low concentrations (3.0 ppm),  (13)  while




the lethal dose by inhalation in rats is also very low [11 mg/kg].(14)




Minute oral dosages of this chemical (in the range of 0.05-1.24  mg/kg)




caused significant depression of a neurotransmitter (cholinesterase) and




mortality. (15)  phorate metablites are at least twice as toxic  as




phorate.(16,17) Additional information and specific references  on




adverse effects of phorate can be found in Appendix A.






           Industrial Recognition of Hazard - Sax (Dangerous Properties




of Industrial Materials)  lists the toxic hazard rating of phorate as very




high via oral and dermal  routes.






      2.    Formaldehyde






           Health Effects -  Formaldehyde is reportedly carcinogenic^)  with







                                   -X-

-------
nasal cavity  tumors  detected in two studies.  It has also been mutagenic in




several  bacterial  and human cell culture assays. (19-22)  Formaldehyde is very




toxic to animals by  all routes of administration (23-27) } causing death in




humans in small amounts (36 mg/kg).(28)  Additional information and specific




references on adverse effects of formaldehyde can be found in Appendix A.









          Ecological Effects - Formalin, an aqueous solution of formaldehyde




can cause- toxic effects to exposed aquatic life.(29)  It is lethal to Daphnia
          Regulatory Recognition of Hazard - Formaldehyde is a chemical




 evaluated  by GAG  as  having substantial evidence of carcinogenicity.(39)




 OSHA has set a  standard  air TWA limit of 3ppm for formaldehyde.






          Industrial Recognition of Hazard - Sax, Dangerous  Properties




 of Industrial Materials  ,  lists formaldehyde as highly toxic  to skin,




 eyes,  and  mucous  membranes.






      3.   Phosphorodithioic and Phosphorothioic Acid Esters






          Health Effects  - The phosphorodithioic acid s ,s!-methylene-




 0,0,0' ,o'-tetraethyl  ester is extremely toxic by various  routes of  admini-




 stration to animals  [oral  rat LD5Q = 13 mg/kg].(33)   Toxic effects




 in the blood of humans have been observed at minute  doses (100  ug/kg)(34),




 while human death from ingestion of this chemical has also occurred at




low doses  [50 mg/kg].(35>






          The phosphorothioic  acid o,o,o-triethyl ester  is similar to  the
                                 -sso-

-------
o,o,s-triethyl ester, which is very toxic when given orally to rats [LDcn =




80 mg/kgj.^ '  The o,o,s-triethyl ester is  extremely toxic to rats [LDsn *




15 mg/kg].(37)  Additional information and specific  references on  adverse




effects of phosphorodithioic and phosphorothioic acid  esters  can be found in




Appendix A.






           Industial Recognition of Hazards - Sax, Dangerous Properties of




Industrial Materials, lists triethyl phosphorothioate  (phosphorothioic acid




0,0,0-triethyl ester) as being highly toxic via ingestion,  inhalation and




skin absorption.
                                  -x-

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 IV.   References


 1.   1977 Directory of Chemical Producers,  Stanford Research  Institute
      Menlo Park, California.                                          *

 2.   Proprietary information  submitted  to EPA  by American Cyanamid through
      1978 response to "308" letter.

 3.   Farm Chemicals Handbook,  1977; Meister Publishing  Company, Willoughby,
      Ohio.

 4.   Lawless, E. W. et al.  The Pollution Potential in  Pesticide Manufac-
      turing USEPA, Office of  Water Programs, Technical  Studies Report TS-
      00-72-04, 1972.

 5.   NIOSH Registry of Toxic  Effects  of Chemical Substances,  U.S. Depart-
      ment of Health, Education, and Welfare, 1978.

 6.   Personal Communication,  S. R. Hathaway, American Cyanamid to D. K.
      Oestreich, 11 February 1980.

 7.   Aquatic Fate and Transport Estimates for  Hazardous Chemical Exposure
      Assessments.  U.S. EPA,  Environmental  Research Laboratory, Athens,  GA.
      February, 1980.

 8.   Martin, H.,  Pesticide Manual, 4th Edition.

 9.   Tox. Appl. Pharmacol.

10.   American Cyanamide.  Cited in USEPA Initial Scientific and Minieconomic
      Review of Phorate. 1974.

11.   Drinking Water and Health. (1977)  National  Academy of Sciences,
      Washington, D.C.

12.   Clinical Toxicology of Commercial  Products. Acute Poisoning.  Gleason,
      M.N., et al., 1969,3rd ed., p. 142.

13.   Hazard Profile on Phorate.  Greenberg,  M. ECAO/RTP NC, 1980, p. 2.

14.   National Technical Information Service #PB  277-077.

15.   Tusing, T.W.  1956 Unpublished report  of  American  Cyanamid.  Cited
      in USEPA Initial Scientific and  Minieconomic Review of Phorate, 1974.

16.   Rombunski, et al. (1958)  as cited  in Drinking Water and  Health. (1977)
      National Academy of Sciences, Washington, D.C.

-------
17.    Curry,  et  al.    J.  Agric.  Food Chem.   9:469-477 (1961).

18.   U.S. EPA. (1979)  The carcinogenic assessments group's  Preliminary
      Risk Assessment on Formaldehyde.  Type I - Air Progrsms.   Office of
      Research and  Development.

19.   Auerbach, C., Moutschen-Dahen,  M., and Mouytschen,  J.   Genetic and
      Cytogenetic Effects  of  Formaldehyde and Related Compounds.  Mutat.
      Res.   39:317-361  (1977).

20.   U.S. EPA. (1976)  Investigation  of Selected Potential Environmental
      Contaminants:  Formaldehyde.  EPA-560/2-76-009-

21.   Wilkins, R.J. and MacLeod,  H.D.   Formaldehyde-Induced  DNA Protein
      Crosslinks  in E_.  Coll..  Mutat. Res.  36:110-16 (1976).

22.   Obe, G.  and Beck,  B.  Mu.tagenic  activity of Aldehydes.  Drug Alcohol
      Depend.  4:91-4 (1979).                                 ~

23.   Union  Carbinde Data  Sheet.   Industrial Medicine and Toxicology Dept.,
      Union  Carbide Corp.,  270 Park Ave.,  New York,  N.Y. April, 1967.

24.   J. Ind.  Hyg.  Toxicol.   23:259 (1941).

25.   ACTA Pharmalogica et  Toxicologica 6:299  (1950)

26.   J. Ind.  Hyg. Toxicol.   31:343 (1949).

27.   Journal  of the National Cancer Institute.  (U.S.  Governemnt Printing
      Office,  Supt. of  DOC.,  Washington, D.C.)   30:31 (1963).

28.   Practical Toxicology  of Plastics.  (1968)  Lefaux, R. Cleveland, Ohio
      Chemical Rubber Company, p.  328.

29.   Chemical Industry Institute  of Toxicology.  1979.  Statement concerning
      research findings.

30.   Dowden,  B.F. and  M.J. Barrett.   1965.   Toxicity of Selected Chemicals to
      Certain  Animals. Jour. Water Pollut. Control  Fed.  3:1308.

31.   Fairchild, E.J. and Stokinger, H.E.  Toxicologic Studies on Organic
      Sulfur Compounds.  1. Acute Toxicity  of  Some Aliphatic  and Aromatic Thiols
      (Mercaptans).  Am. Ind. Hyg. Assoc.  J.    19:171-189 (1958).

32.   ACGIH  (American Conference of Governmental  Industrial  Hygienists)  (1971),
      Documentation of Threshold Limit  Values  for Substances in Workroom Air—
      Ethyl-Mercaptan.   Cinicnnati, Ohio,  p.  107.

33.   Pharmaceutical Journal  185:361 (1960)

34.   Toxicol. Appl. Pharmacol.  22:286  (1972).


                                   -Vf-

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35.   Clinical Toxicology of Commercial Products.   Acute Poisoning.
     Gleason, M. N., et al.(1969) 3rd ed., p. 65.

36.   Mallipute et al.  J. Agric. Food Chem.  27:463-466 (1979).

37.   Fukuto et al.  Quarterly Progress Reports to EPA, August 1978—
     Nov., 1979.  EPA Grant No. R804345-04.

38.   Dawaon, English, Petty, 1980, "Physical Chemical Properties of
     Hazardous Waste Constituents."

39.  GAG List of Carcinogens, April 24, 1980.
                                  -S'S'-J-

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                       LISTING BACKGROUND  DOCUMENT

                           TOXAPHENE  PRODUCTION


      Wastewater Treatment Sludge  from  the Production  of  Toxaphene  (T)

      Untreated Process Wastewater  from the Production of Toxaphene (T)


I.    Summary of Basis for Listing

           The production of toxaphene, a  chlorinated  hydrocarbon pesticide

results in the generation of process  wastewater containing heavily  diluted
                                         r
concentrations of toxaphene, and wastewater treatment  sludges that  contain

approximately one percent of toxaphene  by  weight.


     The Administrator has determined that process wastewater and waste-

water treatment sludge from toxaphene production may pose a substantial

present or potential hazard to human  health or the environment when

improperly transported, treated, stored, disposed of or otherwise managed,

and therefore should be subject to appropriate management requirements

under Subtitle C of RCRA.  This conclusion is based on the following

considerations:
      1)   Toxaphene is present in each of these waste streams; in the
           case of the wastewater treatment sludge, if it is found in
           very high concentrations.  Toxaphene has been reported to
           cause cancer in laboratory animals and is extremely toxic.
           Toxaphene has also been recognized by the Agency as exhibi-
           ting substantial evidence of being carcinogenic.  It is also
           a potent teratogen and has been shown to be mutagenic.

      2)   Approximately 7 tons of wastewater treatment sludge containing
           about 140 Ibs. of toxaphene are generated per production day.
           About 19,000 tons of sludge are already disposed of in a land-
           fill in Georgia.  (5)

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     3)    Disposal or treatment of these wastes in improperly designed
          or  operated landfills or unlined lagoons could result in
          substantial hazard if toxaphene migrates via groundwater or
          surface water exposure pathways.

     4)    Toxaphene is highly persistent in the environment and
          bioaccumulates greatly in environmental receptors.
II-   Sources of the Waste and Typical Disposal Practices


     A.   Profile of the Industry


          Toxaphene is produced in this country by two manufacturers

Hercules, Inc. at its Brunswick, Georgia  plant, and Vertac Chemical

Company at its Vicksburg, Mississippi plant.(1)  	
                      .(2,3)
          Toxaphene is a complex mixture of polychlorinated camphenes

containing 67 to 69 percent chlorine and has the approximate composition

of CiQH]_QClg.  it has been used exclusively as a non-systemic and persistent

contact and ingestion insecticide.  Toxaphene is marketed as a 90 percent

toxaphene-10 percent solvent solution using mixed or modified xylene

as the solvent.  This solution is then formulated by various companies

into emulsifiable concentrates, either alone or with other insecticides.

Little or no toxaphene is currently being used in dust, wettable powder,

or granule formulations.
*A11 underlined  data  are obtained from proprietary reports and data

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      B.   Manufacturing Process


      Toxaphene  is  produced  in essentially the same manner by both domestic


manufacturers.   The reaction chemistry is as follows:
                Ob
                   CATALYST.
                                         JVORCAT.
                                  CHa
                           •CAMPHENE
TOXAPH&NE
      C.   Waste Generation  and  Management*



           At the Hercules plant,  wastewater  is  generated  from the  toxaphene


production process (leaks, spills  and  washdowns) ,  as  well  as  from the scrubbing


of vent gases in the HC1  absorption  and  recovery step (see Figure 1).
                  _ (2)


                  (3)
                                                  The  treated  wastewater
is directly discharged to a navigable waterway.
           In Hercules' toxaphene wastewater  treatment  system,  an  average


of 7 tons/day of wastewater treatment  sludge  (settled solids) is


generated . (4»5)*  ^he sludge results  from  the addition  of diatomaceous earths
  Variations in wastewater treatment  systems  or  in wastewater sources at
 the two plants may result in different concentrations  of  toxaphene  in the
 wastewater treatment sludges.
                                   -y-
                                  -587-

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       SOUTMCniSI
        E STUMPS
      "| =S 1


REACTOR



WASTES
MAIN
WASTE
|

                      CAMPHENE
        CHLORINE

        SOLVENT -
    H,O



   LIME

  NaOH
  LIME-
  STONE'
SURFACE
WATERS '
                 t
          I
CHLORINATOR-
                r
        HCI GAS
 ABSORBER
    I
 SCRUBBERS
    (2)
                I
NEUTRALIZER
                I
  PRIMARY
   WASTE.
 TREATMENT
   PLANT
                T
           DISCHARGE TO
            TIDAL CREEK
                          TOXAPHENE-
                           SOLUTION
  SPILLS
  LEAKS
WASHDOWNS
                RECOVERED
                MURIAMC ACID
                                                                           MIXED
                                                                          XYLENES
                                                                             L
                            STRIPPER-*- TOXAPHENE-
                                  j
90% TOXAPHENE
SOLUTION
                   TO SOLID
                    WASTE
                                     DUST
                                  FORMULATION
                                                     BAGHOUSE DUST
                                                      COLLECTOR
                                                                  ATMOSPHERE
                                                                           SHIPMENTS
                      i
                      Oo
                      Co
                      VO
                      I
             Figure 1. HERCULES' PRODUCTION AND WASTE SCHEMATIC FOR TOXAPHENE
                                                                               (A)

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and lime  to  the wastewater as sorption agents for the removal of toxaphene


from the  wastewater.(5)  The solids  are allowed to settle in holding
                                                         11

ponds and may remain there for months at a time.(^)  After the basin


is filled with solids  it is taken off line and the sludge  is  allowed to


dry to approximately 50% solids.(5)   Analyses of  the  sludge performed


by Hercules  indicate that the sludge  contains approximately one percent


toxaphene by weight, or  10,000  mg toxaphene/kg of sludge.(5)   Some


140 Ib/day of toxaphene  are generated and will be contained in this waste


stream.(^ • »?)


           The ultimate  destination of the toxaphene  wastewater treatment


sludge generated at  the  Hercules plant is a state-approved  landfill.(6)


The landfill is known  as  the "009" landfill and is a  privately owned


site operating under Georgia permit.  It  is used exclusively for the


disposal  of the toxaphene  wastewater  treatment  sludge generated at the


Hercules  Plant,(6)   The  "009"  landfill used for disposal of the


Hercules  toxaphene wastewater  treatment  sludge has a  bentonite  clay


liner, and has 6 monitoring  wells which  are monitored 4  times  per year.


To date, no toxaphene  has  been  detected  in the wells.
                                                                    (3).
                    (5)

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                                 (3,5)
                                      (3)
       *  This pond, or lagoon, is  .unlined.'     The  treated waste-


water is discharged to the Mississippi River.



Ill,  Discussion of Basis for Listing



     A.   Hazards Posed by the Waste



          As noted above-,--in the Hercules  toxaphene  wastewater treatment


system, an average of 7 tons/day of waste sludge  are  generated.(4,5)


The toxaphene content in the waste sludge is approximately at  one percent


by weight or 10,000 mg/Kg sludge.  High concentrations  of  toxaphene


are undoubtedly present in process wastewater  to  account  for such high


concentrations in the sludge.


          Toxaphene is an exceptionally dangerous  waste  consitutent.  It


is extremely toxic, highly bioaccumulative, and has been  reported to  cause


cancer in laboratory animals.  It is also a potent  teratogen and has  been


shown to be miitagenic.  Toxaphene is regulated as a toxic  pollutant


under §307(a) of the Clean Water Act.  After an adjudiciative
*No data is currently available on the amount of  wastewater treatment
 sludges (settled solids) generated at the Vertac plant.   Nor is any data
 available on the concentrations of toxaphene in  these  sludges.

                                  -v-

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proceeding, a  discharge concentration limitation of 1.5 ppb has been




established for  toxaphene  discharges  into  navigable waters, and this




discharge  limitation was judicially upheld in Hercules, Inc.  v. EPA,




598 F.  2d  91  (D.C.  Cir  1978).   (The administrative  and  judicial records




are incorporated  by reference  into  this  listing  background  document.)




The Agency has also established a national interim  primary  drinking




water  standard of .005  mg/1  for toxaphene.  (That administrative record




is likewise incorporated by  reference.)




       The  wastes  are listed  as toxic  based on the potential for waste




mismanagement  and resulting  environmental  harm.  Toxaphene  is both mobile




and persistent, having  frequently been found  in  clarified and treated




municipal  drinking  water.(18)  Existing  waste management methods could




lead to  release of  waste toxaphene.   Wastewaters are presently  treated




in holding ponds.   Waste treatment  sludge, if generated, is now disposed




in landfills and  unlined lagoons.   Disposal in landfills represents




a potential hazard  if the  landfill  is improperly designed or operated.




This can result in  leaching  of hazardous compounds and  subsequent




contamination  of  ground water.  Disposal in unlined lagoons also represents




a potential hazard  since the wastes may  leach directly  into the ground,




resulting  in possible groundwater contamination.  Care must be  taken to




ensure that the lagoons and  landfills used for storage  or disposal of




the toxaphene  product wastes are properly  designed and  operated (e.g.,




lined with an  appropriate  thickness of impervious materials or  provided




with leachate collection/  treatment systems)  to prevent contamination




of groundwater or surface water.

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          Prior to disposal  in  the  "009" landfill, the Hercules plant

treats these wastes in holding ponds  which,  if not properly designed and

operated, may result in groundwater  or surface water contamination.  The

high water table and the sandy composition of the soil at the location

of the Hercules plant in Brunswick,  Ga.,  make careful managment of these

wastes particularly important. (13)*

     Wastewater treatment sludge  could also create a hazard if improperly

managed.  Although the sludges appear to  be managed properly at the present

time (suggesting that industry regards these wastes as hazardous), proper

management of an otherwise hazardous  waste does not make the waste non-

hazardous .

    One  final reason for regulatory  concern is noteworthy.   Since

toxaphene bioaccumulates in environmental receptors by factors of as

much as 300,000^), if only a small  amount leaches into the  environment,

a serious health hazard would be created.  In the soil, toxaphene may

persist from several months to more than  10  years (soil half-life is 11

years, Appendix B) .  It has also been shown  to persist for up to 9 years

in lakes and ponds.^)  Thus, the  potential  for human exposure is con-

siderable.  The potential for substantial hazard is,  therefore, very high.

     The need for the most careful management of toxaphene-containing

substances is thus well-establilshed.   In light of the documented health

and environmental hazards associated  with toxaphene,  and the fact that

substantial hazard is caused by  ingestion of extremely small (ppb) toxa-

phene concentrations, the Agency believes it is justified in listing

this waste.


*It should be noted that Hercules' past effluent management  practices have
 not always been adequate, as Hercules has conceded that its past effluent
 discharge "'had an adverse effect upon the  ecology1  of local waters."  (18)

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B.    Health and Ecological Effects




      1.   Toxaphene




           Health Effects - Toxaphene  is  extremely toxic  [oral  rat  LD^Q




= 40 mg/kg].(8)  Death in humans  from  ingestion of this dosage  has  also




been reported. (9)  Toxaphene  is  also  lethal  to animals by  inhalation and




skin absorption at dosages of  1 g/kg or less. (10)




           This chemical is teratogenic in mice when administered orally




at a relatively small dose (350 mg/kg) .(H)   Toxaphene is carcinogenic in




rats and mice, causing a significant .increase in the, incidence  of thyroid




and liver cancers when administered in the diet. (12)  A significant in-




crease in liver cancer has been reported  in mice at dietary levels of 50
           Toxaphene and its subfractions have been found mutagenic in the




standard bacterial assay (S_. typhimuriumm, strain TA100). (16)




           Ecological Effects - Toxaphene is extremely toxic to fish, and




toxic to lower aquatic organisms, birds, and wild animals.  The 11)50




(96-hour) of toxaphene in static bioassays is 3.5, 5.1 and 14 ng/1 for




bluegills, fathead minnows, and goldfish, respectively. (7)  Toxaphene




is also capable of producing deleterious effects in fish at levels as




low as 0.39 ng/1, and bio accumulates by factors of as much as 300, 000. (?)




           Regulations - Toxaphene has an OSHA standard for air, TWA =




500 mg/m3 (Skin, SCP-F) .  Toxaphene is listed as a priority pollutant in




accordance with §307(a) of the Clean Water Act of 1977.  A 0.005 mg/1 EPA




National Interim Primary Drinking Water Standard has been established




for toxaphene.

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          Industrial Recognition of Hazard - Toxaphene has been rated by




   j Dangerous Properties of Industrial Materials(15) to be highly toxic




through ingestion, inhalation, and skin absorption.






          Additional information and specific references on adverse




effects of toxaphene can be found in Appendix A.

-------
 IV.   References
 1.    1977 Directory of  Chemical  Producers.  Stanford Research Institute.
       Menlo Park, California.

 2.    Proprietary information  submitted  by Hercules, Inc.  to the U.S.
       Environmental Protection Agency  in 1978  response  to  "308"  letter.

 3.    Proprietary information  submitted  by Vicksburg Chemical Company to
       the U.S. Environmental Protection  Agency in  1978  response  to  "308"
       letter.

 4.    Meiners, A. F., C.E. Mamma, T. L.  Ferguson,  and G. L.  Kelso.
       Westwater Treatment Technology Documentation for  Toxaphene Manu-
       facture.  Report prepared by  the Midwest Research Institute for the
       U.S. Environmental Protection Agency.  EPA-400/9-76-013.  . ;February
       1976.

 5.    Telephone communication  to:  Ms. Jennifer Kaduck, State of Georgia,
       Land Protection Division, Department of  Natural Resources, Atlanta,
       Georgia (404-656-2833),  February 28, 1980 (Edward Monnig, TRW).

 6.    Telephone communication  to:  Ms. Jennifer Kaduck, State of Georgia,
       Land Protection Branch,  Environmental Protection  Division, Depart-
       ment of Natural REsources, Atlanta,  Georgia,  12 February 1980- (S.
       Quinlivan, TRW).

 7.    Criteria Document for Toxaphene.   U.S. Environmental Protection
       Agency.  EPS-440/9-76-Okl4.  June  1976.

 8.    Special Publication of Entomoligcal  Society  of America.  College
       Park, MD, Vol. 74:1 (1974).

 9.    Clinical Memorandum on Economic Poisons.  U.S. Dept. HEW, PHS.
       COG, Atlanta, GA.  p.l,  1956.

10-    Council on Pharmacy and  Chemistry.  Pharmacologic Properties of
       Toxaphene, a chlorinated Hydrocarbon insecticide.  JAMA 149:1135-
       1137, July 19, 1952.

11.    Chernaff, N.  and Carber, B.D.  Fetal toxicity of toxaphene in rats
       and mice.  Bull.  Environ. Contarn. Toxicol.   15:660-664, June, 1976.

12.    National Cancer Institute.  (1977) Guidelines for Carcinogensis Bio-
       assays in Small Rodents.   Tec. Rep. No. 1 Publ. No.  017-042-00118-8.
       U.S. Govn. Print. Office, Washington, D.C.

-------
IV.   References (Continued)


13.   Telephone Communications to:  Ms. Jennifer Kadinck, et  al.,  State
     of Georgia, Land Protection Division, Department of Natural  Resources,
     Atlanta, Georgia, 8 April 1980.  (Robert Karmen, EPA)

14.   Telephone Communication:  John King  (EPA) to Edward Monmig  (TRW),
     8 April 1980.

15.   Litton Bionetics, Inc.  Carcinogenic  evaluation in mice.  Toxaphene
     Final Report.  LBI Project No. 20602.  Kensington, MD.  Submitted  to
     Hercules, Inc., Wilmington, Del., Nov. 1978.

16.   Hill, R*N. (1977)  Mutagenicity Testing of Toxaphene Memo dated Dec. 15,
     1977, to Fred Hageman.  Off. Spec.;Pestic. Rev. U.S. Environmental Pro-
     tection Agency, Washington,'D.C.

17.   Sax, N. Irving, 1975.  Dangerous Properties of Industrial Materials.
     Fourth Edition, Van Nostrand Reinhold, New York.

18.   Hercules, Inc. v. EPA, 598 F. 2d 91,  99 (D.C. Cir. 1978).

19.   Lawless, E.W. Pesticide Study Series  -5- "The Pollution Potential in
     Pesticide Manufacturing,"  Technical  Studies Report; TS-00-72-04.
     Washington, U.S. GPOV> 1972.

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                      LISTING BACKGROUND DOCUMENT

                           2,4,5-T  PRODUCTION

          0   Heavy Ends or Distillation Residues from the  Distillation of
             Tetrachlorobenzene  in the  Production of  2,4,5-T(T)

I.   Summary of Basis  for Listing

     The  hazardous waste from 2,4,5-Trichlorophenoxyacetic  acid (2,4,5-j)

production consists of the heavy ends or distillation residues from the

distillation of tetrachlorobenzene  in the first  step  of 2,4,5-T

manufacture.

     The Administrator has determined that the tetrachlorobenzene dis-

tillation heavy ends in 2,4,5-T  production may pose a  substantial pres-

ent or potential hazard to human health  or the environment when im-

properly transportedy-treated, stored, disposed of or  otherwise man-

aged, and therefore should be subject to appropriate management re-

quirements under Subtitle C of RCRA.  This conclusion is based on

the following considerations:

     1.  The heavy ends from distillation of tetrachlorobenzene con-
         tain several  chlorinated benzenes including hexachloroben-
         zene and  ortho-dichlorobenzene.

     2.  Hexachlorobenzene  is a reported carcinogen.  Ortho-dichloroben-
         zene is chronically toxic.

     3.  Disposal  of  these  wastes in improperly designed or operated
         landfills  could  create a substantial hazard due to the
         migratory  potential  and  environmental persistence of these
         hazardous  compounds.  Both groundwater and surface water
         are exposure  pathways of concern.

     4.   Volatilization of  the waste constituents from landfills, as has
         been documented, could result in the release of hazardous
         vapors  to  the  atmosphere and present a significant opportunity
         for  exposure  of  humans,  wildlife,  and vegetation in the
         vicinity of these  operations to potentially harmful substances.

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II.   Sources of  the Waste and Typical Disposal Practices

     A.  Profile of the Industry
                                                     *(l,5,6)f
         The  2,4,:5-trichlorophenol (TCP) salts.and esters, including

2,4,5-T,  are  selective herbicides used to control woody plants, es-

pecially  on range  land and rights-of-way, where 2,4-D is not effective.

The properties  and actions of these compounds are similar to 2,4-D for-

mulations.  These  compounds are used extensively in forest conifer

control and for weed  control, and for rice crops.^°'

     B.   Manufacturing Process

         Figure 1  is  the process flow diagram of the manufacture of

2,4,5-T (2,4,5-trichlorophenoxyacetic Acid).^7^  The first step in

2,4,5-T manufacture is the reaction of chlorobenzene with chlorine

to form tetrachlorobenzene (TCB).  Distillation is then used to sep-

arate the TCB from other chlorobenzenes.  The waste of concern is gen-

erated at this  point  in the process,  and consists of the distilla-

tion  residues.  Following this, the distilled TCB is hydrolyzed to

form  TCP  and  then  esterified to form 2,4,5-T.
*The underlined data  are  those obtained from proprietary reports and
data files.

TSome of the companies  listed  above may no longer produce 2,4,5-T

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                                                                                          •*- TETRACHLOROBENZENE
                MONOCHLOROBENZENE-
-J?
                          CHLORINE
                                            REACTOR
                                                       TETRACHLOROBENZENE
DISTILLATION
  COLUMN
                                                                            HEAVY ENDS
                                                                        (DISTILLATION RESIDUE)
                                                                            TO LANDFILL
                               Figure 1. GENERATION OF HEAVY ENDS (DISTILLATION BOTTOMS) FROM
                                       TETRACHLOROBENZENE MANUFACTURE IN THE 2, 4, 5-T PROCESS (7)

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      C.   Waste Generation and Management

          The heavy ends or distillation residues generated in separating

 TC3 from other chlorobenzene make up the hazardous  waste  stream

 of concern.   These residues are likely to contain all  of  the  benzene

 chlorination by-products including those higher  than chlorobenzene,

 such as  ortho-dichlorobenzene and hexachlorobenzene.   Further,  since

 the waste consists largely of heavy chlorinated  organic by-products,

 concentrations of  these constituents will probably  be  high.

      Based on current  industry practice  involving similar  wastes,

 the distillation residues  are probably managed by landfilling.

 Disposal may involve surface  placement,  uncontained burial, or  burial

 in barrels in a landfill.

 Ill.  Discussion of Basis  for  Listing

      A.   Hazards Posed  by  the Waste
improperly managed or disposed.  Among the compounds expected to be
         The heavy ends discussed above contain hazardous compounds

which can be expected to pose a serious threat to the environment if

ini]

present are hexachlorobenzene and ortho-dichlorobenzene.

         Hexachlorobenzene is believed to be carcinogenic and terato-

genic, while o—dichlorobenzene may pose a chronic toxicity hazard via

a water exposure pathway-*  To warrant a decision not to list this

waste, therefore, the Administrator would require assurance that the

waste constituents are incapable of migration and mobility even if

improperly managed, and that these constituents will not persist if

they are released into the environment.
* It is projected that o-dichlorobenzene could create a chronic tox-
  icity hazard if it migrated at several orders of magnitude less than
  its solubility limit in water.(38)

-------
         Indications  are  that  these  waste constituents  are  capable

 of migration, mobility  and  persistence  to cause  substantial hazards.

 The groundwater  exposure  pathway  is  of  principal concern.   Hexachloro-

 benzene, while relatively insoluble,  has  been  detected  to have

 migrated via a groundwater  pathway from Hooker Chemical Corpora-

 tion's S area, Hyde Park, and  102d St.  landfills in Niagra, New York.O7)

 Orthodichlorobenzene  is relatively soluble (App.  B), and thus may be

 available for environmental  release.

         Present waste  disposal practices may  be inadequate to prevent

 waste migration.  Certainly, improper management may result in re-

 lease of harmful constituents.  Thus, uncontained landfill burial

 would not impede leachate migration  in  areas with relatively or high-

 ly permeable soils, or where the  water  table is  so high that ground-

 water acts as a leaching  medium.*  Containerization in landfilled

 drums could still result  in contaminant release,  since all drums have

 a limited life span as the  exterior metal corrodes in the presence

 of even small amounts of  moisture.  When  this  occurs, the potential

 for groundwater contamination  is  high if  the landfill is not properly

 designed and operated.  Improper  disposal techniques in surface

 containment sites may also present the  possibility of surface runoff

 contamination.  A break in a pond dike  or rainwater flowing over an

 improperly covered landfill containing  the  process wastes may allow

migration to surface  soils and surface  water.
^Laboratory studies of the behavior of chlorinated benzenes in soil
that is high in sand and low in organic content indicate that hexa-
chlorobenzene would be likely to exhibit slow but measureable mobility
in these soils again indicating that soil attenuation will not
prevent environmental release of migrating contaminants A

-------
      Hexachlorobenzene may also pose a substantial hazard  via an air

 inhalation pathway if landfills are not adequately convered, as shown

 by a number of actual damage incidents.  In May, 1976, hexachloroben-

 zene-containing wastes from a Vulcan plant in Louisiana volatilized

 and resulted in the death of cattle gra_zing in contaminated areas.(39)

 A similar case history of environmental damage in which air, soil,

 and vegetation over an area of 100 square miles were contaminated by

 hexachlorobenzene (HCB)  occurred in 1972.(39)  There was volatiliza-

 tion of HCB from landfilled wastes and  subsequent bioaccumulation in

 cattle grazing in the eventually contaminated areas.   Accumulation  in

 tissues of cattle occurred, so  the potential risk to  humans from eat-

 ing contaminated meat and other foodstuffs  is significant.

      The waste constituents of  concern  also can  be  expected to persist

 should they migrate-from  the matrix of  the  waste.  Hexachlorobenzene

 is  very persistent.*   (App.  B)   0-dichlorobenzzene  is subject to cer-

 tain degredative processes,  but would be  likely  to  persist  in ground-

 water.   (App.  B.)   Hexachlorobenzene, in  addition to  being  persistent,

 is  very bioaccumulative,  increasing its likelihood  to cause harm

 should  it  migrate.  (App.  B)

      B.   Health  and Ecological  Effects

          1 .  Hexachlorobenzene

             Health Effects - Hexachlorobenzene  has been  shown to be
carcinogenic in animals (^, 20) an^  |1£s 'oeen  identified by  the Agency

to be carcinogenic.  This  chemical  is reportedly  teratogenic, known


^Evidence of mobility and  resistance to  degradation has  been shown
 by identification of chlorobenzene isomers  in ground water in Florida.
 Chlorinated benzenes are  likely to persist  in the  environment and to
 bioaccumulate.(^')

-------
 to pass through placental barriers, producing toxic and lethal effects



 in the fetus.(2I)  Chronic exposure to RGB in rats has been



 shown to result in damage to the liver and spleen.(22)  It has



 been lethal in humans when ingested at one-twentieth the known oral


                    (23}
 LD5Q dose for  rats.^  >  It has also been demonstrated that at doses.



 far below those which are lethal, HCB enhances the body's capability



 to toxify rather than detoxify other foreign organic compounds



 present in the body through its metabolism. C2^)   Additional informa-



 tion and specific references on the adverse  effects of hexachloroben-



 zene can be found in Appendix A.





             Ecological Effects - Hexachlorobenzene is likely to  con-



 taminate accumulated bottom sediments  within surface water  systems  and



 bio accumulate  in fish and other aquatic  organises . ^°)



             Regulatory Recognition of Hazard -  Hexachlorobenzene is a



 chemical evaluated  by CAG as having substantial  evidence  of carcinogen-



 icity.   Ocean  dumping of hexachlorobenzene is prohibited.   An interim



 food contamination  tolerance of 0.5 ppm  has  been established  by FDA.



             Industrial Recognition of Hazard -  According  to  Sax, Danger-



 ous  Properties  of Industrial Chemicals,  HCB  is a  fire  hazard  and, when



 heated,  emits  toxic  fumes.



         2.  Ortho-dichlorobenzene



             Health Effects  - Ortho-dichlorobenzene  is  very toxic in



rats [oral LD5Q = 500 mg/Kg].^25^   Human death has  also occurred at



this level.(26)  Chronic  occupational exposure to  this  chemical and. its



isomer has resulted in  toxicity  to  the liver,  central  nervous  system



and respiratory system.C27)  Chronic oral  feeding of ortho-dichloro-
                                -GOB-

-------
benzene  to  rats  in small doses has caused anemia as well as liver




damage and  central nervous  system depression.\2o)  Additional infor-




mation and  specific references on the adverse effects of ortho-dichloro-




benzene  can be found in Appendix A.




             Regulatory Recognition  of Hazard - Ortho-dichlorobenzene




has been designated as  a priority pollutant  under Section 307(a)  of




the CWA.  The OSHA standard  for 0-dichlorobenzene is  50  ppm for an




8 hour TWA.  It  has been selected by  NCI  for  Carcinogenesis Bioassay,




September,  1978.




             The Office of Water and  Waste Management  has completed




pre-regulatory assessment of 0-dichlorobenzene  under  the  Clean Water




Act and the  Safe Drinking Water  Act.   Under section 311  of  the Clean




Water Act3 regulation has been  proposed.  The Office of Research and




Development  has  begun;; pre-r egulatory  assessment  of 0-dichlorobenzene




under the Clean Air Act.




             Industrial Recognition of Hazard -  Sax, Dangerous Proper-




ties of Industrial  Materials,  lists the toxic hazard ratings for 0-di-




chlorobenzene as moderate via  inhalation  and  oral  routes.

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IV.   References




 1.   Proprietary information submitted to EPA by Thompson-Hayvard' Chemi-




     cal Co.,  Kansas city, Kansas in 1978 Response to "308" Letter.




 2.   U.S. Department of Health, Education and Welfare, National Institute




     for Occupational Safety and Health, Registry of Toxic Effects of




     Chemical Substances, Cincinnati, Ohio, January 1979 in Radian Cor-




     poration Hazardous Waste Background Document, 1979.




 3.   U.S. Department of Health, Education and Welfare, National Insti-




     tute for Occupational Safety and Health, Suspected Carcinogens,




     A Subfile of the NIQSH Toxic Substances List, Rockville,  Maryland,




     June 1975 in Radian Corporation Hazardous Waste Background Docu-




     ment, 1979.




 4•   Identification of Organic Compounds in Effluents from Industrial




     Sources,  PB-241641, Versar, Inc.,  Springfield,  VA,  April  1975 in




     Hazardous Waste Background Document, 1979-




 5.   .Proprietary Information submitted  to EPA by Dow Chemical  Corporation,




     Midland,  Michigan in 1978 response to "308" Letter.




 6.   Proprietary Information submitted  to EPA by Transvaal,  Inc.  (Ver-




     tac), Jacksonville, Arkansas in 1978 response to "308"  Letter.




 7.   Gilbert,  E.  E.  et al;  U.S. Patent  2,830,083.   April 8,  1958;  As-




     signed to Allied Chemical Corporation.  In  M. Sittig,  Pesticides




     Process  Encyclopedia,  Noyes Data Corporation, Park Ridge,  New




     Jersey,  1977.




 8.   Farm Chemicals  Handbook,  1977,  Meister Publishing Company, Willough-




     by,  Ohio.
                                  t

-------
  9.   Midwest Research Institute, The Pollution Potential in Pesticide




      Manufacturing,  Washington, B.C., EPA, June 1972, in Pesticide




      Process Encyclopedia,  Noyes Data Corporation, Park Ridge, New




      Jersey,  1977.




 10.   Assessment of Dioxin-Forming Chemical Processes.  Walk,  Haydel-




      and  Associates,  600 Carondolet,  New Orleans,  LA, for USEPA/IERL-




      Cincinnati,  EPA Contract  No. 68-03-2579,  179  pp.,  undated.




 11.   Dow  Chemical Company.   The Trace Chemistries  of File - A Source




      of and Routes for  the  Entry of Chlorinated Dioxins  into  the En-




      vironment.   The  Chlorinated Dioxin  Task Force,  the  Michigan Divi-




      sion, Dow  Chemical,  USA,  November 15,  1978.




 12.   Stehl, R.  H, and L.  L-  Lamparski.   Combustion of Several  2,4 ,5-T




      Compounds: Formation of 2,3,7,8-Tetrachlorodibenzo-p-dioxin. Sci-




      ence, 1^:1008-1009, September 1, 1977.




 13.   Rappe, C., S. Marklund, H.  R.  Buser,  and  H. P.  Bosshart.  Forma-




      tion of Polychlorinated Dibenzo-p—dioxins  (PCDDs) and Dibenzofurans




      (PCDEs) by Burning  or Heating  C'nlorophenates.   Chemo sphere,  7(3):26S




      281,  1978.




14.   Crosby, D. G.,  land  A. S.  Wong,  1977.  Environmental Degradation




      of 2,3,7,8-Tetrachlorodibenzo-p-dioxin.   Science, 195:1337.




15.   Crosby, D. B. et al, 1971.  Photodecomposition  of Chlorinated




     Dibenzo-p-dioxin.  Science, 173:748.




16.   International Agency for Research on  Cancer.  IARC Monographs  on




     the Evaluation  of Carcinogenic Risk of Chemicals to Han.  Some




     Fumlgants,  the  Herbicides  2,4-D  and 2,4,5-T,  Chlorinated Diben-




     zodioxins,  and  Miscellaneous Industrial Chemicals.  World Health




     Organization, Lyon, France.  Volume 15, August  1977.

-------
17.  IARC Monographs on the Evaluation  of  Carcinogenic Risk of Chemicals




     to Man (International Agency  for Research on Cencer, Lyon, France




     World Health Organization.




18.  Technical Support Document  for  Aquatic Fate and Transport Estimates




     for Hazardous Chemical Exposure Assessments.  1980.  U.S. EPA,




     Environmental Research Lab.,  Athens,  GA.




19-  Cabral, J. R. P. et al.  Carcinogenic activity of Hexachlorobenzene




     in hamsters.  Tox. Appl. Pharmacol. 41:155 (1977).




20.  Cabral, J. R. P. et al,  1978.  Carcinogenesis study in mice with




     hexachlorobenzene.  Toxicol.  Appl. Pharmacol. 45:323.




21.  Grant, D« L. et al.  1977.  Effect of hexachlorobenzene on repro-




     duction in the rat.  Arch. Environ, contain. Toxicol. 5:207.






22.  Koss, G. et al, 1978.  Studies on  the toxicology of hexachloroben-




     zene.  III.  Observations in  a long-term experiment.  Arch.  Toxicol.




     40:285.




23.  Clinical Toxicol. of Commercial Products - Acute Poisoning.   Gleason,




     M. N. et al (1969) 3rd Ed., p. 76.




24.  Carlson, G. P., 1978.  Induction of cytochrome P-450 by halogenated




     benzenes.   Biochem,  Pharmacol. 27:361.




25.  Clinical Toxicology of Commercial Products.  Gleason, M.  N.  et al.




     (1969),  3rd Ed.,  p.  49.




26.  U.S.  EPA (1979).   Dichlorobenzenes: Ambient Water Quality Criteria.




27.  Varshavsakaya,  S.  P.   Comparative  toxicological characteristics of




     chlorobenzene and dichlorobenzene  (ortho- and para-isorners)  in re-




     lation to  the sanitory protection of water bodies.   Gig.  Sanit.




     33:17  (1967).

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35
 28.   Ben-Dyke,  R.,  Sanderson, D. H. and Noakes, D. N.  Acute toxicity




      for  pesticides.   World Rev. Pest Control 9:119-127 (1970).




 29.   NCI  Carcinogenesis Bioassay, National Technical Information Serrlrp




      Rpt.  PB223-159,  Sept.  1978.




 30.   Clinical  Toxicology of Commercial Products.  Gleason et al,  3rd Ed,




      Baltimore,  Williams and Wilkins,  1969.




 31.   Fahrig, R.  et  al.   Genetic activity of  chlorophenols  land  chloro-




      phenol  imparities,  pp.  325-338.   In Pentachlorophenol;  Chenistry.




      Pharmacology and Environmental Technology.   K.  Rango  Rao,  Plenum




      Press,  New  York.




 32.   Weinback, E. C. and Garbus,  J.   The interaction of  uncoupling




      phenols with mitochondria  and  with raitochondrial protein.  Jour.




      Biol. Chem. 210:1811 (1965).




33.   Hitsuda, H., et-'al.  Effect  of  chlorophenol analogues on the osi-




      dative phorphorylation  in  rat  liver mitochondria.  Agric. Biol.




      Chem. 27:366 (1963).




34.   U.S. EPA, 1972.  The effect  of  chlorination on  selected organic




      chemicals.  Water Pollut.  Control  Res. Agr.  12020.
     U.S. EPA,  1978.   In-depth  studies  on health and environmental im-




     pacts on  selected water  pollutants.   Contract  No.  68-01-4646.




36.  Wilson, J. T., and  C.  F. Enfield,  1979.   Transport of Organic Pol-




     lutants Through Unsaturated  Soil.   Presented at American Geophysi-




     cal union  Fall Meeting,  December 3-7,  San Francisco,  California.




37.  Complaint  in Civil  Action  No.




38.  Dawson, English, and Petty,  I960 "Physical Chemical Properties of




     Hazardous Waste Constituents."
                                 VI

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39.   OSW  - Hazardous Waste Management Division - "Hazardous Waste




     Incidents",  Unpublished Open Fie Data, 1978.




40.   The  Carcinogen  Assessment Group's List of Carcinogens,




     April 22,  1980.

-------
                    LISTING BACKGROUND DOCUMENT

                        2,4-D  PRODUCTION

2,6-Dichlorophenol waste from  the  Production of  2,4-D  (T)

Untreated  Wastewater from the  Production of 2,4-D  (T)


I.      Summary  of Basis for Listing

       These  wastes from 2,4-D  production may contain a  number

of toxic  constituents, including 2,4-dichlorophenol, 2,6-

dichlorophenol,  2,4,6 -trichlorophenol  and chlorophenol

po1ymer s.

       The  Administrator has determined that the  subject  solid

wastes from  2,4-D production may pose  a substantial present or

potential  hazard to human health or  the environment when

improperly transported, treated, stored,  disposed of or

otherwise managed, and therefore should be subject  to appropri-

ate management  requirements under  Subtitle C of RCRA-  This

conclusion is  based on the following  considerations:

       1.  The  wastewater generated  from the production of
           2,4-D  contains 2,4-dichlorophenol, and 2,4,6-tri-
          chlorophenol.  2,6-Diehloropheno1 waste contains
           substantial concentrations  of 2,6-dichloropheno1,
          2,4,6 -trichlorophenol and  2,4-dichlorophenol.

       2.  2,4,6-Trichlorophenol has  been  identified by EPA's
          Carcinogen  Assessment Group  as  a substance which
          has  exhibited susbtantial  evidence of carcinogeni-
          city.   It has also been  sited in literature as
          being  mutagenic.   2,4-Dichloropheno1  is a reported
          animal carcinogen and 2,6-dichlorophenol  is toxic,

       3.  Management  of these wastes  in treatment lagoons  or
          landfills creates the potential for  soil  or ground-
          water  contamination via  leaching if  mi smanag eiaent
          o c cur s .

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II.  Sources of Wastes  and Typical Disposal Practices

     A.  Profile  of  the Industry

         2,4-D is  a  selective herbicide  registered for use on

grasses, barley, corn,  oats, sorghum,  wheat and non-crop areas

for  post-emergent  control of weeds. (?)
         1.

         2 .
         3.
     B .   Manufacturing Process

          In  the  2 , 4-D._jnanuf ac tur ing  process,  benzene is

chlorinated to  produce monochlorobenzene,  which is hydrated to

produce  phenol.(2a)   Chlorination  of  phenol  also leads to the

generation of  by-product 2,6-dichlorophenol  and other chloro-

phenols  (principally  2,4,6-trichlorophenol).(2a)  Figure 1

illustrates an  example of  this manufacturing  process.

     C •   Waste Generation

          1.   Generation of 2,6-dichlorophenol waste.

          Chlorination of  phenol  inevitably  leads to the genera-

tion of  by-product  2,6-dichlorophenol  and  other chlorophenols. ( 2a)
                                           (8,10)   AS shown in

                              i
                             
-------
                                               SOLVENT
                                                 OR
                                               CATALYST

                                                I   I


— PHENOL -*-
i - i
CIILORO
PHENOL
UNIT
15-40°

f



. • '• 	 •• fr

                           2,6-DICHLOROPHENOL •



                           2,4-OICHLOROPHENOL
                                                                NEUTRALIZER
                                 NEUTRALIZER
J_   SODIUM   —
  CHLOROACETATE
                                                                     1
                          CONDENSATION
                             REACTOR

                           LIQUID
                           WASTE
                           _J

ACID -.. — , >
NaCI ^ 	
-* M '- 	 • 	 	 	 • ' 	 - 	
2,4-D
RECOVERY
EXCESS
*" CeHjCljOH
••4 	 «
                         SCRUBBER
                              y
                          TRICKLING
                           FILTER
                                                                                                 \
                                                                                        TO PENTACHLOROPUCNOL
                                                                                        MANUFACTURE (DOW)
                                                                                                 i
                                                                                          TO WASTE DISPOSAL
                                                                                          (RHODIA AND TRANSVAAL)
                                              DUST
                                           COLLECTOR
                          BIOLOGICAL
                          TREATMEMT
n
                              f      DISCHARGH
                           TREATED     SLUDGE
                         WASTEWATER
Figure.1.  PRODUCTION AND WASTE SCHEMATIC FOR 2,4-D
          (MODIFIED FROM  REFERENCE 1)

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 figure  1,  2,6-dichlorophenol  is  taken off overhead from

 the chlorophenol unit as a by-product.   This 2,6-dichlorophenol

 by-product  is  used in the production of pentachlorophenols

 in one  plant,  and therefore is not  a waste;  in two other

 2,4-D plants,  the 2,6-dichlorophenol by-product is disposed

 of as a waste,*  and is included  in  this listing.   This waste

 is composed of 2,6-dichloropheno1,  2,4,6-trichlorophenol,

 2,4-dichlorophenol, and chlorophenol polymers (see page 5). (8,10)

          Various 2,6-Dichlorophenol generation rates have been

 reported.   	
                   (10)
                                                      (8)
          2.    Generation of wastewater.
*The  Transvaal  (Vertac) plant does  not  reuse 2,6-dichlorophenol
 as feekstock material, so it is  quite  likely that this plant
 generates  2,6-dichlorophenol waste.

-------
	(8)   Process wastewater  is removed




for treatment.   This  wastewater, prior  to  treatment,  is listed




as hazardous.   2,4-Dichlorophenol is the intermediate used in




the production  of  2,4-D;  some of this chemical  becomes entrained




in the wastewater.   It  is  expected that some quantities of




2,6-dichlorophenol  are  also carried forward  (see Fig. 1).




      D.   Waste  Management
                            (10)
          Wastewater  from Dow Chemical's 2,4-D unit  is  first




chemically treated,  then  passed through a trickling  filter  on




the way to a  central  biological waste treatment  plant.(2a)




Biological treatment  sludges  from the production  of  2,4-D at




the Dow plant  are  limestone treated and disposed  in  an  on-site




landfill.  At  the  Transvaal,  Inc. (Vertac) plant,  wastewater




goes to a neutralization  ditch.
                                         (9)
III.  Discussion  of  Basis  for  Listing
      A.  Hazards Posed  by  the Waste

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                                           (8,10)
         (The waste constituents of concern  are 2,4,6 trichloro-

phenol  and  2,4 dichlorophenol . )*	



                                               Dis posal in
landfills,  even if plastic  lined drums  are  used,  could create

a potential hazard if  the  landfill is improperly  designed or

operated  (i.e., drums  corrode in the presence of  even small

amounts  of  water).  This  can result in  leaching of hazardous

compounds  with resultant  contamination  of  surface and ground

waters .

     A  similar potential  hazard exists  when wastewaters from

2,4-D  production are impounded in treatment lagoons.   The
*0~tfher  waste constituents  are not deemed  present in sufficient
 concentrations to be regulatory significance.

-------
same hazardous  constituents are  present  in the solids that

will settle  to  the bottom of the lagoon.   The concentrations

of the  hazardous  constituents in the  settled  solids are expected

to be much higher than those found in  the  wastewater itself,

which obviously contains a much greater  volume of water*.

Hazardous constituents may leach from  the  lagoon bottom to

contaminate  groundwater.  In addition, possible incomplete

treatment in biological treatment lagoons  may allow these

hazardous constituents to reach the ultimate  disposal  site,

where the potential  for leachate exposure  exists.

      An  example  of  the consequences which may result  when

these wastes are  mismanaged occured at the Transvaal,  Inc.

plant,  which produces  2,4-D,  in Jacksonville,  Arkansas.

Sludge  from  2,4-D manufacture is sent  to a chemical landfill

adjacent  to  the plant.  Soil and groundwater  near the  chemical

landfill  have been found to be contaminated with  toxic  chloro-

phenols from 2,4-D manufacture.**

        As this incident illustrates,  waste constituents may wel!

prove mobile and  persistent.   As to mobility,  the chlorinated

phenols present in the waste may undergo bio-degradation in
 *This indicates  that  the  dredged sludges from  lagoons  are
  not expressly listed  here.   These sludges are  nevertheless
  reached by  this  listing;  Section 261.3 of the  Regulations
  provide that the  solid wastes discharged from  a' hazardous
  waste treatment  facility are not also considered hazardous
  unless the  generator  demonstrates otherwise.
**OSW Hazardous Waste  Division, Hazardous Waste  incidents, un-
  published open  file  1978.

-------
                                 s
 soil if present  in  low concentrations.(25)  It seems




 likely, however,  the  rates of degradation  of these compound




 in the soil profile would be low because  of repression of




 soil microbial activity by these and other  waste components.




 (Also, mismanagement  could occur in areas  where soil is low




 in organic content,  so mobility in soil would not be sub-




 stantially effected.)   All of these compounds also are quite




 soluble in water  and  do not exhibit a high  propensity to




 adsorb in soils.(25)   Hence, they would be  expected to




 move readily into groundwater.  The potential for movement




 of these compounds  into and through groundwater is illustrated




 by a case history in  California, where long-term pollution




 of groundwater by phenolic substances occurred  because of




 release into the  soil  of water containing 2,4-dichlorophenol




 from 2,4-D manufacture.(26 )  High waste loads such as




 landfill dumping would inhibit degradation  and  therefore




 increase the likelihood  of adverse environmental effects.




      B.   Health and  Ecological Effects






           1 .   2 ,4-Dichlorophenol/2 ,6-dichlorophenol




               Health  Effects -  2,A-Dichlorophenol is  very toxic




 in rats [oral  LD5Q  = 580 mg/kg].(12^  This  chemical is




 carcinogenic when applied to the skin of mice in small doses.(13




 It is  also reported to  adversely affect cell  metabolism,(1^>15 /




An isomer,  2,6-dichlorophenol ,  is also toxic  in  animals.(16)




Additional information  and specific references  on  adverse




effects  of 2,4-dichlorophenol and 2,6-dichlorophenol can be
-6/7-

-------
found  in  Appendix A.




                Ecological Effects  -  Small doses  of  2,4-dichloro-




phenol have  been lethal to  fresh water fish and  invertebrates . (17)




                Regulatory Recognition of Hazard  -




2,4-Dichlorophenol is designated as  a priority pollutant




under  Section  307(a) of the CWA.   The Office of  Water  and




Waste  Management has completed  a pre-regulatory  assessment




and proposed water quality  criteria  for 2,4-dichlorophenol




under  sections 304(a) and 311 of the Clean Water. Act.   The




Office of  Research and Development  is presently  conducting




a pre-regulatory assessment of  2,4-dichloropheno1 under the




Clean  Wa ter  Act.




     Indus trial Recognition of  Hazard - Sax,  Dangerous Properties




of Industrial  Materials, designates  a toxic hazard rating of




moderate  toxicity for 2,4-dichloropheno1 .  However, chlorinated




phenols are  designated as highly toxic local  and systemic




compo und s .




           2.   2,4,6-Trichlorophenol




               Health Effects -  2,4,6 -trichloropheno1 induced




cancer in  mice during long-term oral  feeding  studies.(18)




This compound  has also been identified by EPA's  Carcinogen




Assessment Group as  exhibiting  substantial evidence of car-




cinogen icity.(27)  jt has been  acutely lethal to humans




by ingestion at  60 percent of the  oral LD5Q dose in rats




[500 rag/Kg]. (19)  This chemical is reportedly mu t ag eni c (20)

-------
and adversely affects  cell metabolism . (21>22)   Additional




information and specific  references on  the  adverse effects of




2 4-trichlorophenol  can be found in Appendix  A.




              Ecological Effects - Very  small concentrations




of 2,4,6-trichlorophenol  have been  lethal  to  freshwater fish




[LC50 = 426 ng/lj.   This  chemical is  also  lethal to freshwater




invertebrates at  very  low c one en t r a t io ns . ( 2 4 )




              Regulatory Recognition  of  Hazard  - 2,4,6-Tri-




chlorophenol has  been  designated as a  Priority Pollutant




under Section 307(a)  of the CWA.




              Industrial Recognition  of  Hazard  - Sax, in




Dangerous Properties of Industrial  Materials,  lists 2,4,6-




trichlorophenol as  moderately toxic via  the  oral route.

-------
IV.    REFERENCES

1.    U.S.  Environmental Protection Agency, Office  of Water
      Programs,  The Pollution  Potential in Pesticide  Manufac-
      turing,  Contract 69-01-0142,  June, 1972.

2a.   U.S.  Environmental Protection Agency, Office  of Pesticide
      Programs Production, Distribution, Use and Environmental
      Impact  Potential of Selected  Pesticides,EPA540/1-74-001
      Washington, B.C., 1975.

2b.   Aly,  O.M.,  and S.D. Faust.   Studies on the Fate of  2,4-D
      and  Ester  Derivatives in  Natural  Surface Waters.  J.
      Agr.  Food  Chem. 12((6):  541-546,  1964.

3.    U.S.  Environmental Protection Agency, Industrial Process
      Profiles for Environmental  Use,  Chapter 8:   Pesticides^"
      EPA-600/77-023h,  Research Triangle Park, North  Carolina,
      January , 1977.

4.    U.S.  Department of Health,  Education and Welfare, National
      Institute  for Occupational  Safety and Health, Registry  of
      Toxic Effects of Chemical Substances, Cine inna ti, Ohio ,
      January,  1979.

5.    U.S.  Environmental Protection Agency, "Hazardous Waste
      Guidelines  and Regulations,"  Fed.  Reg.  43 (243):  58960,
      December 18,  1979 .

6.    Proprietary information  submitted  in 1978 to EPA in
      response to "308" letter by Thompson-Hayward Chemical
      Company.

7.    Farm  Chemicals Handbook, 1977, Meister Publishing Company,
      Willoughby,  Ohio.

8.    Proprietary information  submitted  to  EPA by Rhodia,  Inc.,
      Agri.  Division Portland, Oregon  in  1978  response to
      "308" letter.

9.    Proprietary information  submitted  to  EPA by Transvaal, Inc.,
      Jacksonville,  Arkansas  in 1978 in  response  to "308"  letter.

10.   Proprietary  information submitted  to EPA by Rhodia, Inc.,
      on March 7,  1977.

11.   Proprietary  information from  Draft  Contractor  Technical
      report  for  BAT Technology in  the  Pesticide Chemicals
      Industry by  Environmental Science  and  Engineering,
      Inc . , for  U.S.  EPA,  1979.

-------
j_2.   Deichmann, W.   The  toxicity of chlorophenols for rats.
     Fed. Proc.  (Fed. Am.  Soc. Exp.  Biol.)  2:76  (1943).

13.   Boutwell, R. K.  and Bosch, D. K.   The  tumo r- pr omo ting action
     of phenol and  related  compounds  for  mouse  skin*  Can  Res
     19:413-424 (1959).                                 	L

14.   Farquharson, M.  E.  et  al.  The biological  action of
     chlorophenols.   Br. Jour. Pharmacol. 13:20 (1958).

15.   Mitsuda, W. et  al.   Effect of chlorophenol analogues on
     the oxidative  phosphorylation in  rat liver mitochondria.
     Agric. Biol. Chem.   27:366 (1963).

16.   Marhold, J. V.  (1972).  Sbornik  Vysledku  Toxikologickeho
     Vysetreni Latek a  Pripravku, p.  79.

17.   U.S. EPA (1978).   In-depth studies on  health and environ-
     mental impacts  of  selected water  pollutants.  Contract
     No. 68-01-4646.   U.S.  Environ.   Prot.  Agency.

18.   NCI Carcinogenesis  Bioassay, National  Technical Information
     Service, Rpt.  PB223-159, Sept. 1978.~

19.   Clinical Toxicology of Commercial  Products.   Gleason et al.,
     3rd Ed., Baltimore, Williams and  Wilkins,  1969.

20.   Fahrig, R. et  al.   Genetic activitiy of  chlorophenols and
     chlorophenol  impurities.  Pp. 325-338.   In Pentachlorophenol;
     Chemistry, Pharmacology and Environmental  Technology.
     K. Rango Pvao ,  Plenum Press, New  York.

21.   Weinback, E.  C.  and Garbus, J.   The  interaction of  uncoup-
     ling phenols  with  mitochondria and with  mitochondrial
     protein.  Jour.  Biol.  Chem.  210:1811  (1965).

22,   Mitsuda, H. et  al.   Effect of chlorophenol analogues on
     the oxidative  phosphorylation in  rat liver mitochondria.
     Agric. Biol.  Chem.   27:366 (1963).

23.   U.S. SPA, 1972.   The effect of chlorination on selected
     organic chemicals.   Water Pollut_.  Control  Res. Agr.
     12020.

24.   U.S. EPA, 1978.   In-depth studies  on health and environmen-
     tal impacts on  selected water pollutants.   Contract
     No. 68-01-4646.

-------
25.   Kozak, V. P.,  G.  V.  Simmons, G.  Chesters,  D.  Stevsby,
      and J. Harkins.   1979.   Reviews of the  Environmental
      Effects of  Pollutants:  XI Chiorophenols.   EPA-600/I-79-01 2 .
      U.S. EPA, Washington,  D.C.   492 pp.

26.   Sinenson, H.  A.,  1972.   The ~'Mon t eb el lo  Incident.   P r o c .
      Assoc. Water  Treatment  and  Exam.   11:84-88.

27.  Carcinogen Assessment  Group's List of Carcinogens,  April
     22, 1980.

-------
                      LISTING BACKGROUND  DOCUMENT

                          METHOMYL  PRODUCTION


 Wastewater from the Production of Methomyl (T)

 I.     Summary of Basis for Listing


       The Administration has determined that  the  process  wastewater

 from methoniyl production may pose a  substantial  present  or potential

 hazard  to human health or the environment  when improperly  transported,

 treated, stored, disposed of or otherwise  managed,  and therefore  should

 be subject to appropriate management requirements  under  Subtitle  C of

 RCRA,   This conclusion is based on the  following considerations:

       (1)  The content of the process  wastewater  from each plant will
           vary but the toxic substances  which may be found in the
           wastewater include methomyl, methylene  chloride, and  pyridine.
           Methomyl is extremely toxic and a  mutagen and  methylene chloride
           has been shown to be carcinogenic  and  inutagenic.  Pyridine is
           toxic.

       (2)  Placement of these wastes in lagoons creates the potential for
           either groundwater or surface  water contamination via leaching
           or overflow.   Disposal by incineration, if mismanaged, could
           result in substantial hazard via an air exposure pathway through
           the release of toxic fumes  due to  incomplete combustion.

       (3)  Hazardous compounds in the waste are persistent and mobile and
           pose a risk of exposure  to  humans  and  the environment.

       (4)  The industry generates at least 100,000 Ibs./year (dry weight)
           of wastewater treatment sludges, indicating that substantial
           amounts of process wastewater are  generated annually, and
           that substantial amounts of hazardous constituents may be
           available for environmental release,


11'    Sources_of Waste and Typical Disposal Practices


      A.   Profile  of the Industry


          According  to the  SRI  Directory of Chemical Producers/

-------
me thorny 1 is produced by E.I.  duPont  Nemours  and Company at its Houston

plant (La Porte, Texas)*  and  by  Shell  Chemical Company at its Denver,

Colorado plant.
                           (2)
       Methomyl is an insecticide used for broad-spectrum  control  of insects

in many vegetables, field crops, certain fruit crops  and ornamentals,^)  Metho-

    was developed by duPont in 1969 and its commercial use  is  relatively new.
       B.  Manufacturing Process - Methomyl synthesis may  involve the

following steps: ^)

                                           ETHER
           1.   CH3 - C - N + CH3SH -f HC1 -------- > Methyl  Thiolacetimidate
                                           SOLVENT   (MTH)

                               PYRIDINE
           2.   MTH + HO NH2'HC1 -------- > Corresponding Hydroxamates
           3.   Fydroxamate + CH3 NCO	> CH3 - C = NOCNHCH3
                                     CH2C12                 I
                                                           0
                                                         Methomyl
    The  duPont  plant  also  produces  bromacil,  diuron and several other
    chemicals,
                                         (5)
    :he  underlined  data  are  obtained from proprietary reports and data files

-------
      Process-details  for  the commercial production of methorny1 are not



known beyond those  shown  in Figure l.(5)  The waste of concern is the



wastewater from the  pesticide  reactor.   No information is available on



the Shell or Vertac  production processes.





      C.  Waste Generation and Management - Process wastewater from



methomyl production  will  contain methomvl, and is also expected to contain
                                                              *


methylene chloride  (a process  solvent), and pyridene,  -a process reactant.



Nitrosomethomyl, a  reaction intermediate, may also be present.
                         (5)
                           (5)
The plant itself is located very close to
the Houston ship channel, near  Galveston Bay.
                                   (5)

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                       (6).
                        (2)
 III,   Discussion  of  Basis  for  Listing







       A.  Hazards Posed  by the Waste







       As stated above  (p.3), the raethomyl  production process waste  waters




 are expected to contain methorny1, and probably  its  reaction intermediate




 nitrosoraethomyl3 methylene  chloride  (a  process  solvent),  and pyridene




 (a process reactant)  as well.




           Methorayl is mutagenic and extremely  toxic  and  its potential




metabolite, nitrosomethomyl  is  extremely carcinogenic and mutagenic,




Methvlene chloride is very  toxic and has been shown to be mutagenic.




There is  also evidence that methylene chloride  is carcinogenic,   Pvridene




is toxic.  In fact, both methomyl and pvridene  can  pose an acute toxiciiiy




threat if they migrate at an order of magnitude  less  than their  solubility




limit, and thus can reach lethal levels in  water  at one-tenth their
  The underlined data are obtained from proprietary  reports and data files

-------
 limit of solubility.Methyl  chloride would exceed the proposed

 human health criteria for water quality if it solubilizes at less than.

 one  ten thousandth of its solubility limit.(34)*/

     Furthermore, large quantities  of  process wastewater containing

 these harmful constituents are generated annually  (see p.3),  posing an

 increased likelihood of large-scale contamination  should mismanagement

 occur, and making increased amounts of hazardous constituents available

 for  environmental release.  Therefore,  the Agency  would  be justified in

 not  listing these waste streams only if it were assured  that  hazardous

 waste1constituents would not migrate and persist.   Such  assurance does

 not  appear possible.

       All of these compounds are capable of  migration.   They are all

 extremely soluble (solubility ranging  from 20,000  pptn  (methylene  chloride)

 to 100% solubility for pyridene) . (-^)  Methylene chloride may  also migrate

 by volatilizing (vapor pressure 350  mm  Eg, quite volatile).(34)

       The waste constituents, once  released  from  the  waste matrix, are

 expected to be mobile and persistent.   Methonyl would  undergo soma  degrada-

 tion in the soil,  but it is substantially more  stable  than most carbanate

 insecticides.   The reported half life of  methomyl  is 50  days.W  This,

 coupled with the high solubility of  this  compound  in water(') (34) £n^ ^ts

 tendency to move readily through the soil  with  infiltrating waterC10),

 would likely result  in its entering groundvater with little attenuation

 in concentration.   Once in the groundwater environment,  it would  be
             Agency is not using the proposed Water Quality Criteria as .a
regulatory benchmark,  but  is referring to them here to illustrate^ethylene
chloride can  create a  potential hazard substantial hazard if immigrates
from the waste at  a rate  far less than its water solubility limit.

-------
expected  to  be  persistent  and  mobile (App.  B ).   Hence, it could move to

wells providing drinking water or  to points of discharge of groundwater

into surface water,  resulting  in exposure of humans and aquatic ecosystems

to this compound  (App. B).

       Methylene  is  also very  soluble in water vllK34;j ancj voui^ ^e ex_

pected to move  readily through the  soil  profile  into and through groundwater

based on  the demonstrated  mobility  of closely related halomethanes such

as chloroform in  subsurface environments,  v.12,13,14;  Methylene chloride

has been  found  in  groundwater  in Massachusetts,  probably as the result of

leakage of nearby  chemical waste lagoons,  strongly suggesting potential

mobility  and persistence. ^^  Methylene chloride  is also stable in air

(34), and so could persist after volatilizing.

       Pyridine sorbs to clay  soils,  but desorbs  in acidic pH conditions.^)

Mobility, thus  could be high in non-clay soils,  on where soils are acidic.

It also biodegrades moderately quickly (34),  but would be exptected to persist

in the abiotic  conditions  of most aquifers.

       The pyridine  in this waste might  also  enter groundwater under

these conditions as  indicated  by a  recorded  case of the movement of this

and related  compounds from a chemical waste  lagoon through an unsaturated

soil into groundwater and  thence to  nearby  domestic wells. ^-^
               Treatment ponds could be  improperly  designed  or managed
(i.e., located in areas with highly permeable  soils,  lacking proper

leachate control systems, and where site runoff  or  lagoon washout is not

controlled) ,*
"Methylene chloride may also volatilize  from  a  sludge,  so that uncovered
 disposal sites may create a hazard via  an air  exposure pathway.

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                                        (5)
       Disposal  by incineration, if mismanaged, can result in substantial




hazard  to human  health via an air inhalation pathway.  If incineration




facilities  are operated in such a way that combustion is incomplete (i.e.,




improper conditions  of temperature, mixing and/or residence time), the




release into  the air of hazardous vapors containing undestroyed waste




constituents  and/or  their toxic degradation products could present a




significant opportunity for exposure of humans to hazardous constituents,




      In any case,  it should be noted that in making a determination as




to  the hazardousness  of this  waste, the Agency is not limited to

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 consideration of existing waste management methods, since absent regulation




 there is  no guarantee a particular method will be adopted.  Thus, less




 satisfactory management of this waste could be adopted, resulting in even




 greater potential for constituent release.




       Thus,  waste constituents appear capable of migration, mobility and




 persistence.   Mismanagement of the wastes is also possible.   Under these




 circumstances,  and in light of the hazards associated with waste con-




 stituents,  the  Agency believes that substantial hazard could follow
waste  mismanagement,
        ^*   Health  and  Ecological  Effects







            1.  Methomy1







               Health  Effects  - Methonyl  is  an  inhibitor  of the  nerve  trans-




mitter  (cholinesterase),  and is extremely toxic in rats  [oral  LD5Q  ~




20 mg/kgj.(2-O   The acute inhalation  toxicity of  this  chemical is also ex-




tremely high  [rats L^Q = 0.30 -  0.45 mg/L), depending on formulation.




Methomyl  is mutagenic  v-^) and a  potential metabolite  nitrosomethomyl  is




extremely  mutagenic (*•' ' and carcinogenic.(^8)   jn  animals,  methorayl  reduced




growth  and hemoglobin  levels.(29)




           Additional  information and specific  references on adverse effects




of Methomy1 can  be found  in Appendix A.




           Regulations -  The Office of Water and Waste Management is in the




process of conducting  preregulatory assessment  of  methomyl'under the Safe




Drinking Water Act.  The  Office of Toxic  Substances  has promulgated  regula-




          methonyl under  Section  3 of the  Federal  Insecticide, Fungicide
t. __>-'- ip  _ ^ L.
    ?\.3denticiie Act
                                  -(o

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       2.   Hethylene Chloride







           Health Effects - Methylene chloride  (dichloromethane)  has been




 shown to be mutagenic. '16>17)  Inhalation of this  chemical  in  an  occupa-




 tional setting  has reportedley caused gynecologic  problems  in  women^18),




 and been toxic  to fetuses and embryos of rats and  mice. ^9, 20)  Methylene




 chloride is very toxic  [oral rat LD5Q = 167 eg/kg] ^2i^  with acute sublethal




 exposures resulting in  central nervous system disfunction and  reduced




 oxygen-binding  in red blood cells.(22)




           There is evidence in animal studies  that nethylene  chloride is




 carcinogenic. {*••*)   Additional information and  specific references




 on adverse effects of inethylene chloride can be found in Appendix A.






           EC olog i c al E f f e c ts - For nethylene chloride,  the criterion values




 for protection  of freshwater^aquatic life protection is  4 mg/1 and for salt




 water aquatic life is 1.9 nig /I. (24)   Sensitivity  of lover  aquatic life




 forms (e.g., algae was  less than that of animal life).^2 '






           Regulatory Recognition of Hazard. - Methylene chloride  is desig-




 nated  as  a priority pollutant under section 307(a) of the CWA.  OSHA




 regulations  designate a TWA of 500 ppm for an 8-hour period of exposure.







           Industrial Recognition of Hazard - 2a2l!_L2i£iiI°Hl_Z£°2££~




lies of Industrial  Materials lists nethylene chloride as being moderately




toxic via  oral  and  inhalation routes.







      3.  Pyridene






          Health Effects  -  Pyridene is  toxic in rats<30) and humans^31),

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causing central nervous system depression, skin  and  respiratory tract




irritation in snail doses.(-^)  Small doses administered  chronically to




animals also interfere with platelet production  and  cause damage  to the




bone narrow, liver and kidneys. (-*->)




           Additional information and specific references on adverse effects




of pyridene can be found in Appendix A.







           Regulatory Recognition of Hazard - Pyridine has an OSHA standard




air TWA of 5 ppm (SCL-P).   DOT requires a label warning that the chemical




is a flammable liquid.







           Industrial Recognition of Hazard - Sax, Dangerous Properties




of Industrial Materials,  lists pyridines as having a moderate toxic hazard




rating via oral,  dermal  and  inhalation routes.

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 IV.    References


 1.    1977 Directory  of  Chemical Producers, Stanford Research Institute
       Metilo Park,  California.                                           *

 2.    Proprietary  information submitted to EPA by duPont and Eagle River
       Chemical Corporation in response to "308" letters.

 3,    Farm Chemicals  Handbook,  1977,  Meister Publishing Company,
       Willoughby,  Ohio.

 4.    Sittig, Pesticides Process Encyclopedia Noyes Data Corporation.
       Park Ridge,  new Jersey,  U.S.A.,  1977.


 5.    Proprietary  plant  report;  E.I.  duPont de Nemours and Co., Houston,
       Texas, EPA Pesticide BAT  Review; IKS, EPA IERL-RTP,  1979.

 6,    Proprietary  information  submitted to EPA by Shell Chemical  Company,
       1978, in response  to "308" letter.

 7.    Warner et al.   Identification of Toxic Impurities in Technical
       Grades of Pesticides Designated  as  Substitute Chemicals, EPA-600/1-
       78-031, Hay  1978.

 8.    Gubler, K, ,  V.  Flu'eck, and H.  Brechbaehler.  1970.  In:   Insecticides
       Proceedings  of  the Second  International  IUPAC Congress  of Pesticides
       Chemistry, Vol.  1,  A, Tahari,  ed. Gordon and  Breach  Science  Publisher,
       New York,

 9.    Lawless,  E.W.,  T.L.  Ferguson,  and A.F. Meivers.   1975,   Guidelines
       for the Disposal of  Small  Quantities  of  Unused Pesticides.   SPA-670/
       2-75-057.   U.S. EPA,  Washington,  D.C.

 10.    Fung,  K,H.  and  G.L.  Briver.   1977,   Leaching  of  Methomyl from Some
       Australian Tobacco  Soils,   Tob.  Sci.  21:120-121,

 11.    Verschueren,  Karl.   1977.   Handbook  of Environmental  Data of Organic
       Chemicals,   Van Nostrand Reinholt Co., N.Y.

 12.    Water  Quality Issues  in Massachusetts:   Chemical  Contamination Special
       Legislative  Commission on Water  Supply.   September,  1979.

 13.    Wilson, J.T.  and C.G. Enfield.   1979,  Transport  of Organic
       Pollutants  Through Unsaturated Soil.  Presented  American Geophysical
       Union,  Fall  Meeting.  December 3-7.   San  Francisco, CA.

14.    Roberts, P.V.P.L, McCarty, M. Rinhardt, and J.  Schriner.  1978.
       Organic Contaminant Behavior During Ground Water  Recharge.   Presented
       at  51st Annual Conference of the Water Pollution  Control Federation.
       October 1-6,  Anaheim, CA.

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 15.     Burttschell,  R.H. , A,A. Rosen, and F.M.  Middleton.   1961.  Proceedings
        of 1961 Symposium on Ground Water Contamination.   Technical Report
        W61-5.   R.A.  Taft Sanitory Engineering  Ctr.   U.S.  DREW,

 16.     Simmon, V.  F. ,  et al.  Mutagenic Activity  of  Chemicals Identified, in
        Drinking Water.  (1977) (S. Scott, et al., eds)  In  Progress in  Genetir
        Toxicology.

 17.     Jongeiij W.  M. F,, et al. Hutagenic Effect  of  Dichloromethane on
        Salmonella  typhinmriuin.  Mutat. Res.  56:245  (1978).

 18.     Vozovaya (1974) as cited by ECAO Hazard  Profile  (1980).

 19.     Schwetz,  B.  A., et al.   The Effect of Maternally Inhaled  Trichloro-
        ethylene, Perchloroethylene,  Methyl Chloroform, and Methylene
        Chloride on Embryonic and Fetal Development in Mice and Rats.   Toxicol,

        Appl» Pharaacol.   23:84 (1975).

 20.     Kat'l.  Inst.  Occup.  Safety and Health.  (1976) Criteria for  A Recom-
        mended  Standard:   Occupational Exposure  to Hethylene Chloride.  HEW
        Pub. No.  76-138.  _IL S.  Dept.  HEW, Cincinnati, Ohio.

 21.     DOW Chemcial  U.S.A.  Material  Safety Data Sheet,  (Dow  Chemical U.S.A,,
        Midland, MI  48640).   Jan.,  1976,

 22.     Nat7! Acad,  Sci.   (1978)  Non-Fluorlnated Halomethanes in The Environ-
        ment.   Washington, D.C.

 23.     Theiss,  J.C., et  al.  Test  for Carci-ogencity of Organic Contaminants
        of United States  Drinking  Waters  by Pulmonary Tumor Response in Strain
        A ilice.  Cancer Res.  37:2717  (1977).

 24.     U.S. EPA.   1979.   Halomethanes.   Anbient Water Quality Criteria.
        PB 296797.  Criteria  and Standards  Division,  Office of Water
        Planning and  Standards,  Washington,  D.C.

 25.     Toxic Substances  List,  1974.

26.     Guerzoni, M., et  al.  Riv.  Sci.  Technol., Alimenti. Nutri.  Ib.  6:161
        (1976).                                        '~

27,    Lijinsky, W.  ar.d  Schmael, D.    Ecotoricol,  Environ. Saf. 2:413 (1978).

2S.    Lijinsky, W.  and  Slespury,  R.  K.   IAKC Scientific Pub. No.  14 (1976).

29.    Kaplan,  A. and  Sherman,  H.  Tox.  Appl. Pharmacol. 40:1  (1977).

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30.    BIFAX Industrial Bio-Test  Laboratories,  Inc.   Data Sheets.  (1810
      Frontage Rd., Northbrook,  111.),  1970.

31.    Gleason, M.N., et al.   Clinical  Toxicology of Commercial Products
      Acute Poisoning. (1969)  3rd  ed.,  p.  69.             ~~	~~	

32.    Merck Index.

33.    AGIGR (1976) TLV Documentation.

34.    Dawson,  English, Petty,  1980,  "Physical  Chemical  Properties of
      Hazardous Waste Constituents."

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Explos ives

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                  LISTING BACKGROUND DOCUMENT

                       EXPLOSIVE  INDUSTRY
 Wastewater  Treatment Sludges  from the Manufacture  and  Processing
 of Explosives  (R)

 Spent  Carbon  from  the Treatment  of Wastewater Containing
 Explosives  (R)

 Wastewater  Treatment Sludges  from the Manufacture, Formulation
 and Loading of  Lead-Based Initiating Compounds  (T)

 Pink/Red  Waste  from TNT Operations (R)
 I.   SUMMARY  OF  BASIS FOR LISTING

     Explosives  manufacturing  produces wastewaters which  are

 often sent  to treatment facilities;  the resulting wastewater,

 spent carbon,  and/or wastewater  treatment sludges resulting

 from the  production of explosives have been found to contain

 explosive  components which  can pose  an explosive hazard;  one

 of the  listed wastes contains  the toxic heavy metal lead,

 and therefore,  poses a toxicity  hazard.  The Administrator

 has determined  that the explosives  industry generates  solid

 wastes  which  may pose a substantial  present or potential

hazard  to human  health or the  environment when improperly

 transported,  treated, stored,  disposed of or otherwise managed.

Under Subtitle  C of RCRA.    This  conclusion is based on the

following considerations:

!•   Wastewater  treatment  sludges from the manufacturing  and^
     processing  of  explosives  contain significant concentrations
     of explosive  compounds which could pose an explosion hazard

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     If  improperly  managed,  this waste could  thus  present a
     substantial  hazard to human health and the  environment.
     Therefore,  this  waste meets the reactivity  characteris-
     tic  (§261.23).

2.   Spent  carbon columns from the treatment  of  wastewater
     containing  explosives are saturated with  explosive com-
     pounds  (i.e.,  RDX, TNT,  etc.).  This waste,  if  improperly
     managed,  could  pose a substantial health  and  environmental
     hazard  due  to  the  explosive potential of  the  constituents
     in  this waste.   Therefore, this waste meets  the  reactivity
     characteristic  (§261.23).

3.   Wastewater  treatment sludges from the manufacture,  formu-
     lation, and  loading of  lead based initiating  compounds
     contain substantial concentrations of the toxic  heavy metal
     lead.   The  lead  is in a  relatively soluble  form,  and could
     migrate from the  disposal site into groundwater.   Therefore,
     if  this waste  is  improperly managed and  disposed,  it could
     pose  a  substantial hazard to human health and the  environ-
     ment .

4.   Pink/red  water  from TNT  operations contains high  concen-
     trations  of  the  explosive compound TNT.   If improperly
     managed,  this  waste could thus present an explosive
     hazard, r esu 11 ing - -rn- a  substantial hazard to human health
     and  the environment.  Therefore,  this waste meets  the
     reactivity  characteristic (§261.23).
II.  OVERALL DESCRIPTION  OF  INDUSTRY

     The explosives  industry is  comprised of those  facilities

engaged in the manufacture  and  load, assemble, and  pack  (LAP)

of high explosives,  blasting agents, propellants, and  initiating

compounds.  High explosives  and  blasting agents  are  substances

which undergo violent,  rapid decomposition upon  detonation .by

heat, friction, impact  or shock.   Initiating compounds,  on the

other hand, are used  to  initiate  or detonate large  quantities

of less sensitive propellants  or  explosives.

     Explosives are  manufactured  in both the commercial  and

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military sectors.   Those companies  (approximately 40) that


commercially manufacture explosives  are situated geographically


in 104 facilities*  located in 30  states throughout the country.


The states with  the greatest number  of facilities are


California, Utah, Missouri, and Pennsylvania.   The military


sector of the  explosives industry  is  segregated into two


groups: Government  Owned and Contractor Operated (GOCO) plants


and Government Owned and Government  Operated plants (GOGO).


The number of  military plants in  these two segments is


estimated to be  between 23 and 35.   The states with major


GOCO installations  are Tennessee,  Wisconsin, Virginia, and

Illinois.

     Approximate production ranges of  individual explosives


products are grouped below:


                               Production (average daily production
Production                          Range   while operating in Ib/day)


Manufacture of Explosives                1,000  to over 40,000

Manufacture of Propellants                 200  to over 30,000


Manufacture of Initiating               under 1 to over 300
  Compounds

     According to the U.S. Bureau  of Mines-*, total consumption


of explosives  and blasting agents  in  1978 was  approximately


1.8  million metric  tons.  This figure  only represents domestic


sales by commercial producers.  Production of  explosives by
^The Bureau of Alcohol,  Tobacco and Firearms  lists 621 expl
 sive manufacturers,  including licensees  and  permittees for
 manufacture of explosives,  distributors,  users and mix and
 blend operators  (LAP).

                             -y-
                                                            O

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 the military  sector  is  not currently available.

      In  terras  of  growth,  total commercial consumption  of

 explosives  and  blasting agents has increased each  year over

 the 1973-1978  period.  Consumption has risen from approximately

 1.3 million metric  tons in 1973 to 1.8 million metric  tons in

 1978, representing  an  increase of 38 percent.

      Out of the  total  1978 consumption figure, consumption of

 "permis s ib les11*  and  "other high explosives" were approximately

 19,000 metric  tons  and  81,000 metric tons respectively.  Over

 the 1973-1978  period,  consumption of permissibles  has  fluctuated

 from year  to  year;  in  1978 consumption was approximately 7

 percent  less  than  in 1973.  However, consumption of permissibles

 is expected to  increase in the future due to increased  coal

 mining activity  to  satiTlry energy demands.   Over  the  same

 five year  period,  consumption of  "other high explosives" has

 declined each  year;  in  1978 consumption was approximately 32

 percent below  1973  levels.   This  downward trend is largely

 attributable  to  the  increase  use  of water gels (permissibles

 in a slurry form).

 A.    Manufacturing Process**

      For the  purpose of discussing specific manufacturing

 processes,  explosives can  be  subcategorized into the following

 three groups:   explosives manufacturing (for example, TNT and
 *High explosives approved  by  the  U.S.  Bureau of Mines for the
  Safety and Health Administration for  use in underground coal
  mine s .

**This document describes only a  few processes in the explosives
  industry.  For a more  detailed  description, see Reference 22.

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RDX), explosives processing (for example,  dynamite  and




Qitrocellulose-base  propellants) and initiating  compounds




(for example, lead azide).




Explosives Manufacturing




    Most explosive  compounds are manufactured in a  nitration




reaction.  The raw material varies, but always includes  a




nitrating acid, usually  nitric acid or a mixture of  nitric




and sulfuric acids or  nitric and acetic acids with various




organic compounds  (i.e., toluene, cellulose, glycerin,  etc.).




The major explosives  produced are nitroglycerine (NG),  nitro-




glycerine ethylene glycol dinitrate (NG/EGDN), pent aerythrito1




tetranitrate (PETN),  nitrocellulose (NC),  trinitrotoluene  (TNT),




cyclotrimethylene  trinilramine (RDX), and  cyclotetramethylene




tetranitramine (HMX)  (see Table 1).  Figures 1 and 2  represent




typical production diagrams for NG and RDX, respectively.




Explosives Processing  (Dynamite and Propellants)




    Two types of  explosive processes will be discussed  below




as examples;  dynamite  and nitrocellulose-base propellants.




    Dynamite - Dynamite formulations are  usually composed  of




    several  dry ingredients in varying proportions  and  nitro-




    glycerin (see Tables 2 and 3).  In the formulation  of




    dynamite,  all ingredients except for  nitroglycerin  and/or




    ethylene glycol are premixed in batch dry blenders  in




    buildings  called  "dope houses".   The  dope and the nitro-




    glycerine  and ethylene glycol are then batch blended  in




    the  mix  house.  The mix is transported to packaging

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      houses  where they are loaded  into  waxed cardboard boxes




      or  plastic tubes.16




      Nitrocellulose-Based Propellants




      Nitrocellulose-based propellants can  be divided into single




      double,  and multi-based propellants.   These propellants are




      made  by  colloiding and molding processes  not unlike those




      used  in  the plastics industry.  Single  base propellants are




      compositions consisting mostly of  nitrocellulose  with  minor




      amounts  of p1 asticizers,  stabilizers,  burning rate  catalysts




      etc.  Double base implies nitrocellulose  plus a liquid  nitrate




      ester, usually nitroglycerin,  with stabilizers,  catalysts,




      etc.; and  multi-base implies a combination  of several  nitrate




      materials  such as nitrocellulose.,   ni t r og ly c er in ,  ni t roguanidine




      trie thyleneglycol dinitrate, with  stabilizers and the  like.26




Initating  Compounds




      Initiating compounds are  manufactured by  nitrating  the




starting materials (see Table  4) and precipitating the




explosive.  The three general  steps are:   (1)  reacting the




starting ingredients and precipitating  the product in  a




kettle;  (2) filtration;  and (3)  washing the  product  to




remove impurities.   Typical initiating  compounds  include




tetracene, trinitroresorcino1  (TNR), lead  azide,  lead




styphnate, lead  monomitroresoreinate (LMR),  tetry  and  nitro-




raannite.  Figures  4  and  5  are  typical  flow diagrams  for  the




production of initiating compounds, illustrating  typical




lead azide and  lead  mononitrorescorcinate  production schema-




tics respectively.





                             -ff-

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B.   Waste Generation and General Description

     Five solid  wastes generated in the  explosives  industry have

been identified  and  are described below.   The  production and waste

treatment methods  which generate these wastes  are  not  usually found

in any  single  facility.

     Wastewater  Treatment Sludges from the Manufacturing

     and Processing  of Explosives*

     Sludges are generated when wash waters pass  through settling

or catch basins  or screens to remove particulate  explosive  residues

Some, but not  all  of the concentrated sludges  are  returned  to the

process.  For  clarity, explosive manufacturing  and  explosive pro-

cessing will be  discussed separately.

     Explosive Manufacturing

     As illustrated  in^Jligures 1 and 2,  during  the  manufacturing

     of explosive  compounds, wastewaters  are generated  during the

     filtration/washing and the cleaning  of the production  equip-

     ment and  facilities.  Such wastewaters consist of  particles

     of the  explosive compound suspended  in the wastewater  along

     with solvents and cleaning agents.   The particles  of  explo-

     sives are removed by gravity separation in catch  basins or

     settling  tanks.  The resulting sludges contain significant

     concentrations  of the explosive compound  (i.e., nitro-

     glycerine,  TNT, RDX/HMX, etc.)-  While some  of these  sludges

     may be  recycled back to the process,  they  are  generally too
*Catch basin materials in RDX/HMX production  was  proposed  as
 a  hazardous waste  on December 18, 1978  (43 FR  58959).   This
 waste stream  will  not be listed in  the  final regulations  since
 it is already incorporated in this  listed waste  stream.

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     contaminated  with extraneous material  to be reused.  These

     sludges  constitute the first listed  waste stream and are

     marked  I  in Figures 1 and 2.*

     Explosive  Processing (e.g., blasting  agents and ordinance)

     During  the processing of explosive compounds  into commercial

     and military  explosive agents and propellants,  wastewaters

     containing explosive compounds are produced during several

     operations.   Among these operations  are  the following:

           0  Cleaning of blending, packaging  and  handling equip-
             ment and storage facilities;

           e  Wet milling of propellant castings;

           0  Operation of air pollution control devices which
             employ wet scrubbers to control  emissions  and
             dust inside production buildings;

             Loading, as"~s"emb 1 ing and -packaging  of ordinance.

Treatment  of  these wastewaters also produces  a wastewater

treatment  sludge.^^"^

Spent Carbon  from  the  Treatment of Explosives  Containing

Wastewaters

     Because  of the  potential hazard that might  result from

the discharge  of wastewater contaminated with  explosives,

a number of  military installations employ carbon treatment
*The other waste which  is  generated (as shown  in  Figures  1  and 2)
 consists of  spent  acid  solutions resulting  from  the  nitration
 step.  Acidic wastes  are  usually recovered  for reuse following
 acid reconcentrat ion  or reprocessing.  Presently,  the Agency does
 not have any data  to  justify listing this waste.   However,  if thes
 spent acids  are hazardous  as defined in Subpart  C  of Part  261, the
 generator would be  responsible for managing  these  wastes under th*
 Subtitle C regulatory  control system.

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 Of these wastewaters,  which result  from  the loading, assembling,


 and packaging operations.   This treatment  is  designed to


 remove organic contaminants (including those  that are explosive)


 from the wastewater  after  the initial settling (see Wastewater


 Treatment Sludges  from the Manufacturing  and  Processing of


 Explosives ) .


     During carbon treatment, the aqueous  waste is  passed


 through chambers or  columns containing activated  carbon.   The


 explosives and other  organic contaminants  are  then  abosrbed


 into the carbon.   After the carbon  becomes  saturated,  it  is


 removed from the chamber or column;  fresh  carbon  is then


 added and the spent  absorbant discarded.   At  this point,


 the  carbon contains  high concentrations  of  explosive com-


 pounds .


 Wastewater Treatment  Sludges from the Manufacture,  Formulation


 and Loading of Lead-Based  Initiating Compounds


     During the various stages in the manufacture and


 formulation of lead-based  initiating compounds  and  their


 fabrication into finished  products, wastewater  contaminated


 with the initiating  compounds and their  feedstock is produced.


 These wastewaters  are  treated in a  catch basin  and  the  re-


 sulting sludges treated with either sodium  hydroxide or heat


 to  remove  any residual  explosive material.  However, while


 this process  removes  any possible reactivity hazard, the


sludge  still  contains  substantial quantities of leachable


lead.
                              -X-
                                -C.N5"-

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Pink/Red Water  from  TNT Operations

     During  the  production and formulation  of  TNT  and  TNT-

containing formulations and products, an alkaline,  red-colored

aqueous waste is  generated.  This waste stream is  composed of

TNT purification  filtrates, air pollution control  scrubber

effluents, washwater  from cleaning of equipment  and  facilities,

and washwater from product washdown operations  (e.g.,  cleaning

of loaded shells  prior  to packaging).  The  pink  or  red

coloration of the waste stream results from contamination  of

the water with  traces of  TNT (solubility of TNT  in  water is

1 mg/liter).  Red water is more concentrated,  and  thus more

contaminated than the pink water.

C.   Quantities  of Waste  Generation

     It is estimated  that the  total amount of  hazardous waste

generated by all  commercial and GOCO facilities  is  approximately

21,500 tons  (19,350 metric tons dry basis)  per day.5  Approxi-

mately eight percent  of the waste  is from commercial sources

and 92 percent  is from  military and GOCO sources (Table 5).

IV.  CURRENT DISPOSAL PRACTICES

     Current disposal practices for the five listed wastes may

be summarized as  follows:

            Wastewater  treatment  sludges from  the manufacturing
            and processing of  explosives.

            In  explosives manufacturing, the wastewater treat-

     ment sludges removed from the manufacturing of explosives

     are typically disposed of by  open burning.  Some plants,

     however, make use  of  percolation/evaporation  ponds for

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     final  disposal of compounds  like NG,  where the liquid

     leaches  into the ground.   Another technique employed by

     some plants is the discharge of  wastewater to earthen

     sumps  where, twice a year, the  sumps  are allowed to dry

     up and the sediments decontaminated for residual NG and

     DNG (dinitroglycerin);  decontamination usually involves

     placing  the explosives  on  the bottom  of the sump and

     detonating the explosives.

            Spent carbon from the treatment of wastewater con-
            taining explosives

          At  present, the spent carbon are typically disposed

     of through open burning or incineration.

          0 Wastewater treatment  sludges from the manufacture,
            formulation and  loading  of lead-based initiating
            compounds .„__.

          The wastewater treatment sludges are treated by

     boiling  and/or the addition  of  a caustic solution,

     usually  sodium hydroxide and aluminum, to decompose any

     residual explosive compounds.   After  treatment,  the

     sludges  are sent to a lagoon.   The sludges from the

     lagoons  are removed every  few years and disposed of in

     a landfill. (4)  In some cases,  however, the sludges

     from the sumps and storage tanks will be sent directly

     to a landfill after treatment.

          0    Pink/red water from TNT operations *


*The  Agency is  aware that under full  production, AAP ' s have
used  the rotary kiln to incinerate  pink and red water.
However,  presently the Agency does  not have adequate information
on  the  residual ash to warrant  a  listing.
                                -CW7-

-------
           Disposal practices that  have  been used include

     the  placing  of pink/red water  in evaporation ponds.*

V.   DISCUSSION  OF BASIS FOR LISTING

     A.    Hazardous Properties of  the Wastes

           Solid  waste materials generated  by  the explosives

industry  contain  a number of explosive  components which, if

improperly managed, could pose a substantial  hazard  to human

health or  the  environment.   Data presented  in  Tables  7-10

support the listing of these waste  streams.

     1.    Wastewaters generated from the manufacturing and

     processing  of explosives have  been found  to contain

     significant  concentrations of  explosive  compounds

     such  as nitroglycerine, nitrocellulose,  TNT,  RDX, HMX,

     and  other nitrated  compounds  (Table 7).   These  explo-

     sives  are highly sensitive to  impact,  heat,  and  friction

     Most  of these compounds are relatively insoluble  in

     water  (see Table 6);  thus  they are expected  to  settle-

     out  of  the wastewater  and  be present in  the  waste-

     water  treatment  sludges.  The  presence of  these  ex-

     plosives in  the  sludges pose a substantial  explosive
*The disposal of  pink/red  water in evaporation  ponds  generates
 a bottom sludge  which  is  typically removed and  open  burned.(22)
 These sludges are  included  in the first listed  waste stream
 (i.e., "Wastewater  Treatment Sludges from the  Manufacture  and
 Processing of Explosives."   The industry practice  of open  burn-
 ing these wastes is  employed because it is by  far  the safest
 method of handling  these  highly reactive wastes.   This  cautious
 disposal practice  by the  industry substantiates  further the
 hazards posed by these  wastes if they are not  properly  disposed
 o f and manag ed .

-------
hazard to human  health and the envrionment;  therefore,




this waste meets  the  reactivity characteristic (§261.23).




2.   The spent carbon, when wasted, are saturated with




high concentrations  of explosive compounds (i.e., TNT




and RDX) (Table  8).   These compounds are highly reactive/




explosive, and thus,  the presence of these explosives




in the spent  carbon  would thus pose a substantial hazard




to both human health  and the environment;  therefore, this




waste would meet the  reactivity characteristic (261.23).




3.   Wastewater  treatment sludges from the manufacture,




formulation,  and loading of lead based initiating com-




pounds have been shown to contain significant concentra-




tions of lead (Table  9).  This waste, if improperly




managed, could pose  a substantial hazard to  human health




and the environment.   Typical industry disposal of this




waste is in a landfill, which, if subjected  to an acidic




environment,  will certainly enhance the solubility of lead




and other heavy  metals, since their solubility is pH de-




pendent (i.e., solubility increases as the pH decreases) .(27 )




     The hazard  associated with the leaching of lead from




improperly designed  and operated landfills is the migra-




tion of this  contaminant into ground and surface waters.




Thus,  if solids  are  allowed to be disposed of in areas




with permeable soils, the solubilized lead could migrate




from the site to  an  aquifer.  Surface waters may also




become contaminated  if run-off from the landfill is not




controlled by appropriate diversion systems.

-------
           Compounding this problem,  and  an important considera-




      tion  for  the future, is the  fact  that should the lead




      escape  from the disposal site,  it will not degrade with




      the  passage of time, but will provide a potential source




      of long-term contamination.




      4.    Finally,  red and pink water  from TNT operations have




      been  shown  to  contain significant concentrations of TNT,




      which  is  an explosive (Table 10).   These compounds are




      also  highly reactive/explosive, and  thus, the presence




      of TNT  in the  pink/red water would  also pose a substantial




      hazard  to both human health  and the  environment;  therefore,




      this  waste  would meet the reactivity characteristic (§261.23)




B .    Health  and  Environmental Effects




      Lead  is a toxic compound that could  threaten the health




of both humans and  other organisms.  The  hazards  associated




with  lead  include neurological damage, renal damage and




adverse reproductive effects.  In addition,  lead  is carcino-




genic  to  laboratory animals,  and  relatively toxic to fresh-




water  organisms.   It also bioaccumulates  in many  species.




Additional  information on lead can be found in Appendix A.




      Hazards associated with exposure to  lead has been




recognized  by  other regulatory programs.   For example,  Congress




designated  lead  as  a priority pollutant  under §307(a) of the




Clean  Water Act  and an interim drinking  water standard  of




0.05  ppm has also been promulgated by EPA.    Under §6 of the




Occupational Safety and Health Act of 1970,  a final standard

-------
for occupational exposure to lead  has  been established.(23>2ZO




Also,  a national ambient air quality  standard  for lead has




teen announced by EPA pursuant  to  the  Clean Air Act.(2^)




In addition,  final or proposed  regulation of the states  of




California,  Maine, Maryland, Massachusetts, Minnesota,




Missouri, New Mexico, Oklahoma  and Oregon define lead con-




taining compounds as hazardous  wastes  or components thereof,(2^)

-------
GUCIUIM

tmiYLEM
GLYOOL
>
               IIUnATOH
   T
no SPUIT
TGHAV 1 1 Y
siPAiuuou
IT
uurit

                                                  IKi
                                  (TO
                                     SPtMl) AC1U
                                                            WAH.U
                                                 SOOHII1 CA1U10IIAIC
                                                     SOlUMOtl
                                                            TAIIK
TAMK
                                                                           5ETTLHIG PIT(S)
                                    iKcovcntu no
                     wutn
                                                                                                    FHIAl WASH
                                                                                I. WASfC SLUDGE
                                                                                  (TO TUtATHEHT/DISPOSAL)
                                                                                        punirn
                                                                                          111!
                             Figure  1. Schematic Flow Diagram for NG Production

-------

X
 A
                    AMMONIA
          MHRIO ACID
          Acme AGIO   	
          ACt HC ANIIYtmiOt
               MAUH
        AMD
rnti*AitAtion
AO.IIC
                                                 IHXAI1IIII/
                                                AUilk ACID
               MHIlAHOtl
                             cmion nnx
                              (SUIHIXY)
                                                                                rnuwnY rmiiAit
                                                                                (60X ACtllC ACID;
                                                                                       2-3%
                               ACtTIC AflllYnnilJt
                                   (10 Rr.ust)
               CYAPOnAIIOH
                                                  do ntust)
                             I •irASUUAUft
                            do nimi
                                IM lAGOOM)
                                                                                           MCUIRAUIATIOH
                                   "CRACK MIC'
                                                 '."K AUUC
                                                    ACM)
                                Aitoiiippic
                               DIM IUAT KHI
   6U I WO
  AiuiYimnus AIMHIIA
     (H) HUM)
                              dot ACt11C
                                 AC 111
                                                                       (101 AC 1.11C  AC III
HtUinAli/.AIlOU
   CAUSIIC  IIA1IOS
      AIVKIIIIA
      IU.COYUIY
 SICOMUART
IVAPOMAriOII
                   tYAPOHATION
 CYClOllt
StPARATIOM
                                                             iDLMMtlllUCl/
                                                                                     runiFito ROX
                                                                                     iron ust IH
                                                                                      CW.0SIYC
                                                                                      FORHUIA1IOH)
                                                                                                               (conTAiNims nox)
                                                                                                                    ROX
     ROX
ICRYSTAUIZATIOII
                      (son
              ron rtnTitiun)
                                                          •nccovcnco ROX
                                                       (TO riURAnOfl/IIASUtllG)
                                          Figure  %   Schematic Flew Diagram for HDX Produchion.

                                          Source  (5); Figure 5-32, pg.  5-123.

-------
Ill
CO
vi'i
-J
INC
       SOLVENTS
                              MIX
                                     DEMY
                                 ULOCK
          PNESS
          AND
          CUT
                     SOLVENT
                    RECOVERY
                     PROCESS
                       FINISHING
                        PROCESS
                      FINISHED
                     SINGteUASG
                                                                                                       PROPELLANV
 UJ
 CO
 •
 p
 -J
 2
 5
         NC
         NO
                   PREMIX
                   PROCESS
 SOLVENTS
        NITROr.UANtOINE
          TRIPLEOASE
                                        [TRIPLE UASE CHEMICALS j
                                     [ DOUOLE DASE CHEMICALS

                                                          I
                                                  OEHY PROCESS
MIX
BLOCK
PRESS
 AND
 CUT
                                                                                                       FINISHED
                                                                                                   OOUOLE& TRIPLI
                                                                                                   DASE PROPELlAf
SOLVENT
RECOVERY
 PRQCESS
FINISIUNQ
 PROCESS
  tc
  III
  z
  IU
  X'
  o
NC
[NO
1 	 • "
UP-
	 *».

\ SOLVENT
* '
1 Ml
PREMIX
IMIOCESS
i 	

n
ii

rnnmiANlDtNE 1
JH5GH ENERGY CHEMICALS |


.
.


1


I OUHY PROCliSS

MIX

>-
UtCNO
"" \ l~~V


ULOCK



PIVIISS
AND
CUT





FINSIHEO HIGH ENERGY PKOPE

SOLVENT
RECOVERY
PROCESS
	 1 1



FINISHING
PROCESS



                                                 I AMMONIUM PERCIjLORATE .]
                                                 I	I.P«lllll •«•« .1 ••'» ' mi • I • '••! •""• ••
                               Figure  3 •  Solvent Propellant Production Scheiratic
             Sources  (1)  Figaro XV-6r pg. 50.

-------
                              WATER
        NUN-
        LEAD
        AZ1DE
        PbNc


PRECJP





           NITRIC ACID
         NiN0
•%
           i
                           KILL TANK
                                 Pb
                           DISCHARGE
                                           WATER
                                            .PPT   LEAD CARBONATE
?icure 4.  SVpical lead Aside Prooucticn Schismatic,

Source:  (2); Figure 1V-8/ pg. 53.

-------
         NaOH
     MNR
      I
    LEAD NITRATE
      REACTOR TUB
     REACTOR TUB
     EXCESS WATER
•5 WATER WASH '

    2 ACETONE WASH
                                             1
                                    3 AMYLACETATE WASH
                                     WASH-FILTER
                                           •*— AMYLACETATE WASH
                                              CAUGHT AND BURNED
                                           WATER WASH WASTE
                            ACETONE WASH WASTE
SVoicai Lead
Source:  (2); Figure IV-10, pg. SI
                                         ^s'i^> Prccucticn Schematic

-------
VII.  TABLES
     -CS7-

-------
                 IN
                                                    OF
                Haw Material (s)
                      Nitratin? Add       Additives
                                     nitric *^'" and      ethyl acetate
 NG/ECSN
 glycerine
                         glycol
nitric »n^ and      ethyl acetate
sulfuric aci£
 PEIN
pentaerythritol      nitric acid
                      acetone
NC

                     nitric  prid          diiutyl phthalate
                     and sulfaric acid    phenylsmine
SDX/HMX
hexsmine
nitric acid and
acetic ?ci.d
acetic
annxDnium nitrate
cyclcihexanaris
acetone
TNT

                     nitric ?cid
                     and sulfuric acid
                     sodinn sulfite

-------
  Source:  (4) page 32-2,
                              Nitroglycerin
                                     sulf ate
                                       nitarate
                                       Chloride
                              Sodium nitrate
                              Sodium chloride
                              Calciuiir stearats
                              'Sulfur
                                          *
                              Nitrocellulose •
                              Phenolic resin or glass beads
                              Bagasse
                              Sawdust and wood flour
                              Coal
                              (Vyrri Tr-ve^l and com starch
                              Inorganic _salts
                             -Grain" and seed h"i.ie and flours
                            3.   TCPICAL OPPOSITION CF
                                                         t>
                    lium nitrate
               nitroglycerine *
               sodium nitrate                        ' 0-17
               t«zce jngrg^J-gnt'S                      10—35
Source:  (11) Table 7, pg.30,

-------
S 4.  KM? fcSSSHIALS FOR
                                                CDMPCONDS
CcTuouno.
Tetracene

Nitrcraarmite


XMR



Tetryl
                     Startling
                           sodixza nitrate
                                         f sulfuric scid.
              Besorcinol, sulfuric acidf nitric acid


              Sodium azics, lead nitrate or lead acetate
              nitric acid, sodium nitrate

                                    •
              TNR,  magnesium oxide, lead nitrate


              Mannitol, sulfuric acid, nitric acid
                                    sodium hydroxide,,
              lead nitrate
             Nitric acid,  sulfuric acid, di

-------
                                     TABLE 5; - EXPLOSIVES*1
                                     Industrial Hazardous Waite Quantities  by OlsposaT Helhod
fUeferenco 5
bPredomlnantly  onslte, >90 percent
Includes chemical detoxification and subsequent disposal!  usually landfill, deep well disposal, spray Irrigation,

dIncludes spent activated carbon from processing aqueous hazardous wastes (open burned), red water from THT
 purification (evaporated and sold),  organic solvents from  propollant manufacture, and wastewatort containing
 dissolved and  suspended RDX/HMX
*0ry Basis •  Met BasU

 Ooutrooi  (1)  Table 6-9,  page  35.
I Industry Segment . • 1
1 * 1
1 Private Explosives Industry! I

1 Government Owned. Contractor I
1 Operated (GOCO) 1
I Explosives Industry: I


1 Explosives Industry
1 Grand Totals
Waste Type
fined high explosive waste
Blasting agents
Subtotals
Explosive wastes
Explosive contaminated
Inert wastes
Other hazardous wastes
Subtotals
.•
Total Hazardous Waste
Tonnes/Year, 1977 (Dry Basis)
-460
-1,700
(J5,500-Wet Basts)
4.900 •
14,700
240
* 19. 000*
-21.500
(-25,400-Wet Basis)
	 	 - 	 	 	 	
Disposal Methods
Tonnes/Year, 1977 (Dry Basis)'
Open Burned
>430
>1,100
>1,500
4,000
•
13,700
90
10.690
20,100
UndMUed
Negligible
Negligible
Negligible
.--
1,000
140
1,140
1,140
Sold
<5
51?
140
».
/20
160
-100
Olherc
.<«
<100
—
mm

                                                                                                                                    I

-------
                                IS 6
                    .rry 3OORS FOR EXPIOSTCS;
Ccrrrxxirjd
NG
KDX
lead aside
Nitrccannite
Solution

water
vater
                    water
water
0.14 gAOOg
0.24 g/lOOg
                    water          0.68 g/lOOg
                    acetone        vs^y soluble
                    ethyl ether    very soluble
               insoluble
insoluble
     styphhate
water
0.04 g/lOOg
Temperature

25eC
-60°C

20eC
25CC
V^t^-T
water""
water .
ethsnol
ether
' 0.02 g/lOOg
— _ M^* ^
0.09 g/lOOg
insolubl e
2.9 g/100g
4 g/100g
18°C
70°C

13°C
9°C

-------
                           TABLE 7.

     Wastewater  treatment sludges from  the  manufacture
     and processing  of explosives (R)
 Proc_es_s_

 Nitration of  cellulose
 (Note:  nitrocellulose
 is used in a  number of
 industries)19

 Nitrocellulose
 (NC) Production^
Nitroglycerin  (NG)  production^

                        o
Nitroglycerin  production^.


TNT production^

Nitrocellulose production^'


Batch Nitroglycerin Production'7

Combined wastewater of Radford
AAP continuous NG Nitration and
Spent Acid7
Waste (Concentration)

Sludge (25% water and
75% nitrocellulose) at
60 ton/yr at one plant
NC fines lost in overflow
will be picked up in settle
basin or other waste water
sludge and is estimated at
1 metric ton (2200 Ibs) per
day per line or about 0.072%
of NC output.

NG lost to wastewater at
0.006 kg per Kg NG produced

NG discharges in wastewater:
as high as 1000 mg/1

100 mg/1 of TNT to wastewater

NC fines can produce levels of
solids from 1000 to 10,000 mg/1

Wastewater (315 to 12,700 ppm)

Nitroglycerin in wastewater
(800 to 1,800 ppm)
RDX/HMX production7
Catch basins remove  33
percent of RDX  and  62
percent of HMX  from
                             -yf-

-------
                            TABLE  8.

3.    Spent carbon from  the  treatment of wastewater containing
     explosives  (R)
Proces s

LAP Melt loading of
105mm Cartridge-*
LAP 40mm Cartridge5
Waste (Concentration)

Composition B* washings
to Carbon Columns at a
rate of 3.64 kg per 10,000
loaded rounds

Composition B to Carbon
Columns at a rate of 0.45
kg per 10,000 loaded rounds
     "^Composition  B — 60%  RDX.  39% TNT,  1% Wax
                               -GC.H-

-------
                          TABLE  9.

     Wastewater  treatment sludges  from  manufacture,  formu-
     lation  and  loading of lead  based  initiating compounds (T)
Process

Initiating  Compounds19
Initiating compounds
                   19
Initiating Compounds1^
Production of lead azide
and lead styphnate^
Waste (Concentration)

Aqueous waste containing
0.3% Pb @ at one plant
that produced 300 M gal
per year

Precipitate 100%.  Pb CO-,
one plant produced 1 ton
per year.

Aqueous Waste (Pb 1.2 ppm)
one plant producing 12.5 M
gal/yr

200 mg/1 in wastewater which
contributes approximately
2 Ibs a day of  Pb

-------
                           TABLE  10.
 5.   Pink/red water  from  TNT  operations (R)
Proces s

TNT Production5
(bat ch process )
TNT Production5
(continuous process)
LAP
TNT Production
Evaporator Condensate'
(A source of pink water)
Waste  (Concentration)

Red water solids are
produced at a  rate of
(0.2398 kg per Kg TNT
 produced)

Red water produced at
a rate of )0.50 kg per
kg TNT) produced which
contains 6% TNT isomers
and alpha- TNT

Pink water with about
4.5% TNT (2,4,6-TNT)
and by products (isomers)

Red water (0.34 kg per kg
produced TNT)

Pink water (as high as 150
mg/1 of TNT)
     Note:  Despite the relatively  low  TNT  concentration  of
evaporator condensate, the mass discharged  may  be  substantial.
For example, at full TNT production  the  condensate discharged
for Joliet AAP is projected at  325  gals  per minute.   A TNT
concentration of 4 mg/1, this represents  a  daily-discharged
of 15.6 pounds of TNT.1
                             -yf-

-------
 VI.  References


 1§   Van Noordwyk, H., L. Schalit,  W.  Wyss,  H.  Atkins.
     Quantification fo Municipal  Disposal Methods for
     Industrially Generated Hazardous  Wastes.   USEPA-
     600/2-79-135, Municipal  Environmental Research
     Laboratory, Cincinnati,  Ohio,  August 1979.

 2.   U.S. Environmental Protection  Agency.  Development
     Document for Interim Final Effluent  Limitations,
     Guidelines and Proposed  New  Source Performance Standards.
     Effluent Guidelines Division,  Office of Water and
     Hazardous Materials, USEPA 440/1-76-060,  Washington, D.C.,
     March 1976.

 3.   Bureau of Mines, U.S. Department  of  the Interioor.
     Mineral Industry Surveys.  Explosives Annual.  1978.

 4.   Patterson, James, Norman I.  Shapira, John  Brown,
     William Duckert, and Jack Poison.   State-of-the Art:
     Military Explosives and  Propellants  Production Industry.
     Volume II, Waste Characterization.   EPA-600/2-76-213b,
     August 1976.

 5.   TRW Systems Group.  Assessment  of  Industrial Hazardous
     Waste Practices, Organic Chemicals,  Pesticides, and
     Explosives Industries.   PB 251-307,  April  1975.

 6.   Hudak, Charles E., and Terry B. Parsons.   Industrial
     Process Profiles for Environmental Use.  Chapter 12,
     The Explosives Industry.  PB 291-641, February 1977.

 7.   Patterson, James, J. Brown,  W.  Duckert, J. Poison,
     and N.I. Shapira.  State-of-the-Art:   Military Explosives
     and Propellants Production Industry.  Volume III,
     Wastewater Treatment.  EPA-600/2-76-213c,  October 1976.

 8.   Process Research, Inc.   Alternatives for  Hazardous
     Waste Management in the  Organic Chemical,  Pesticides,
     and Explosives Industry.  EPA  Contract  No.  68-01-4127,
     September 2, 1977.

9.   U.S.  Department of Health, Education, and  Welfare.
     Registry of Toxic Effects of Chemical Substances,
     June  1975.

0.   U.S.  Environmental Protection  Agency.  Disposal of
     Hazardous Wastes.  Office of Solid Waste  Management
     Programs, 1974.

-------
11.   Patterson,  J.W.,  and R.A. Minear.   State-of-the-Art
      for  the  Inorganic Chemicals Industry  Commercial
      Explosives.   EPA-600/2-74-009b , March  1975.

12.   Ottinger,  R.S.  J.L.  Bluraentahl, D.F.  DalPorto,
      G.I. Gruber,  M.J. Santy, and C.C.  Shih.   Recommended
      Methods  of  Reduction, Neutralization,  Recovery,
      or Disposal  of  Hazardous Waste.  Volume  VIII.   EPA-
      670/2-73-053g,  U.S.  EPA, Washington,  D.C.   August 1973.

13.   Patterson,  James, Norman I. Shapira,  John  Brown,
      William  Duckert,  and Jack Poison.   State-of-the-Art:
      Military Explosives  and Propellant  Production  Industry.
      Volume I,  The Military Explosives  and  Propellants Industry.
      EPA-600/2-76-213a,  October 1976.

14.   Hydroscience, Inc.  Draft Development Document  for Proposed
      Effluent Limitations Guidelines, New  Source Performance
      Standards  and pretreatment Standards  for  the Explosives
      Manufacturing Point  Source Category, April  1979.

15.   Griffin, T.B.,  and  J.H. Knelson.  Environmental Quality
      and  Safety,  Supplement Volume II.   Academic Press,
      New  York,  1975.

16.   U.S. Environmental  Protection Agency.  The  Health and
      Environmental Impacts of Lead and an Assessment of  the
      Need for Limitations.  Office of Toxic Substances,
      EPA-560/2-79-001, 1979.

17.   Sax, Irving,  Dangerous Properties of Industrial Materials.
      Third Edition.  Van  Nostrand Reinhold  Company,  New  York,
      1968.

18.   U.S. Environmental  Protection Agency.  The  Prevalence of
      Subsurface Migration of Hazardous Chemical  Substances at
      Selected Industrial  Waste Land Disposal  Sites.  EPA-530
      SW-634,  October 1977.

19.   State of New  Jersey.  Unpublished Data, Waste  Ch ar ac t erizati
      Data from  the State  file of "Industrial Waste  Surveys" to
      Claire Welty  of OSW.  8/31/79 and 9/4/79.

20.   Sax, Irving.  Dangerous Properties  of  Industrial  Materials.
      Fifth Edition.  Van  Nostrand Reinhold  Company,  New  York.
      1979 .

21.   Searle,  C.E.  (editor) Chemical Carcinogens  ACS  Monograph
      173.  Washington, D.C.   1976.
                               -vi-

-------
22.  JRB Associates,  Inc.,  Evaluation of Treatment,  Storage
    and Disposal Techniques  for Ignitable, Volatile  and
    Reactive Wastes.   U.S.  EPA, OSW, Contract Number 68-
    01-5160.  Draft.   January 17, 1980.

23.  U.S. Department  of Interior, Bureau of Mines, Mineral
    Commodity Summaries,  1979.

24.  U.S. Department  of Health,  Education  and Welfare,
    National Institute for Occupational Safety  and  Health.
    Registry of Toxic  Effects of Chemical Substances.   1977.

25.  U.S. EPA States  Regulation Files, January,  1980.

26.  U.S. EPA, State-of-the-Art: Military  Explosives  and
    Propellants Production Industry, Volume  1 - The  Military
    Explosives and Propellants  Industry,  Industrial  Environ-
    mental Laboratory, PB 265-3885 c.l, October,  1976.

27.  Pourbaix, Marcel.   Atlas of Electrochemical Equilibria
    in Aqueous Solutions, London, Pergamon Press, 1966.
                             -yS-

-------
Petroleum Refining

-------
                 LISTING BACKGROUND DOCUMENT

                      PETROLEUM REFINING
    API Separator Sludge  (T)
                    j

    Dissolved  Air Flotation  (DAF)  Float  (T)

    Slop Oil Emulsion Solids  (T)

    Heat Exchanger Bundle  Cleaning Sludge  (T)

    Tank Botton  (Leaded)  (T)

Summary of Basis  for Listing

    .The listed wastes discussed  in this  document  are  sludges

which  arise  either from the treatment of  wastewater  generated

during petroleum  refining  operations (i.e., API  separator

sludge, dissolved air  flotation  (DAF) float and  slop oil

emulsion solids)  or from the  clean-up of  equipment / s to r-age

tanks  used in the refinery  (i.e.,  heat exchanger bundle

cleaning sludge and tank bottoms  (leaded)).  The Administrator

has  determined  that these  sludges  are solid wastes  which may

pose a substantial present  or  potential hazard to  human health

or  the environment when improperly  transported,  treated,

stored, disposed  of,  or otherwise  managed,  and therefore

should be subject to management  under Subtitle C of  RCRA.

This conclusion is based on the  following considerations:

    1.  These  wastes  contain  significant concentrations of
        the toxic heavy metals,  lead and chromium.
 *These-wastes  also  contain concentrations of certain  other  heavy
 metals  listed  in Appendix VIII  of  Part 261.  However,  in  the
 Administrator's view,  the concentrations of these  waste  con-
 stituents are  insufficient to warrant regulatory concern.
                                      I-

-------
     In some waste  streams  the concentrations of  lead  and
     chromium  exceed  1,000  mg/kg (dry weight).  In  addition
     to being  toxic,  lead  has been shown to be  potentially
     carcinogenic and  bioaccumulative .

     2. Large  quantities  (a combined total of approximately  66,610
     metric tens  (dry  weight)) of these wastes  are  generated
     annually.

     3.  Chromium and  lead  have been shown to leach  from the
     waste API separator  sludge and DAF float in  significant
     concentrations when  subjected to a water-washing  step
     which simulates  leaching activity.  Furthermore,  if the
     last three listed  wastes are disposed of in  an  acidic
     environment, the  solubility of the lead and  chromium
     waste constituents will certainly  be enhanced,  since
     these toxic  heavy  metals'  solubilities are pH  dependent
     (i.e., solubility  increases as the pH decreases).
     .Therefore, these  metals could potentially  migrate  from
     the waste into the environment. Additionally,  if  these
     wastes are incinerated without proper air  pollution
     control equipment, the possibility exists  that  lead
     will be released  into  the environment and  create  an air
     pollution problem.

     4. Current disposal methods such as landfilling,  land-
     farming,  lagooning and incineration, if not  properly
     designed  and operated, can lead to the contamination of
     surface water  and  groundwater either by the  overflowing
     of wastes or the  leaching of harmful constituents  from
     the disposal sites into the environment thereby constituting
     a potential  substantial hazard to  human health  and the
     environment.

Profile of the Industry

     Industry  Structure

     The petroleum  refining industry is perhaps one  of  the

most complex and  technically sophisticated in the United

States.  There are  some 250 to 300 refineries in  the United

States, ranging in  size from about 400,000 BPD* to  only a few

hundred BPD.   These refineries vary from a fully  Integrated,

high-complexity plant  capable of producing a complete  range
     *BPD = Barrels per  day
                              i

-------
of petroleum products  and  some petrochemicals,  to very simple

plants capable of producing only a very  small number of

products.  Some refineries are modern  and  of  recent construc-

tion, while others  contain at least  some operating process

units constructed 40  or more years ago.  The  crude slates

for refineries vary widely.  The product mixes,  and to

some extent the product properties,  also vary from refinery

to refinery.  Because  of this, each  refinery  is  characterized

by a unique capacity,  processing configuration,  and product

distribution.  A survey of operating refineries  in the United

States between 1962 and 1972 is presented  in  Table 1 and the

geographic distribution of these plants  are  shown in Figure 1.

    Based on the Bureau of Mines figures  for 1974, total

U.S. refining capacity for 1974 was  14,486,000  BPD.  As

presented in Figure 2,  District III* has by  far  the greatest

capacity (6,086,000 BPD).   The four  other  districts, arranged

in decreasing order of capacity, are District II (3,950,000

BPD), District V (2,289,000 BPD), District I  (1,643,000 BPD)

and Distric IV (518,000 BPD).  (Figure 2 indicates which

states are included in each region.) In  the  period between

I960 and 1974, Districts II, III, and  V  experienced the

greatest growth.

    A typical breakdown of refinery capacity is shown in

Table 2 and indicates  that a majority  (55%)  of  the

individual plants are  in the size range  of 10 -  100,000 BPD
* For purposes of collecting statistics  on  the refining
 industry, the U.S.  have  been divided .into  several refining
 regions called Petroleum Administration  for Defense (PAD)
 districts .
                             -4-73-

-------
                                              SURVEY  OF OPERATING REFINERIES  IN TIIE  UNITED STATES  -  1962-1972
~£
 I
                                                                     	n««.rB?_.5:.l!r'!?J! Y-_l!^!"/?>l>)
N
Ditte P
1/1/62
1/1/61
1/1/64
1/1/65
1/1/66
I/I/*,/
1/1/68
1/1/69
1/1/70
1/1/71
1/1/72
0|>er«ttnR Refining
, Capic U y '
lnnt« (MMft/
299 10.
291 9.
288 10.
275 10.
265 10.
:i.\ 10.
269 11.
263 11.
262 12.
253 12.
247 13.
C')J (MMn/SD) 01 »l 111 lit lor
01 10.59 1.67
92 10.46 J.'»H
18 10.72 3.75
25 10:76 3.76
25 10.75 1.76
'.-, 10.95 1.M-.
14 11.66 4.0ft
57 12.08 4.12
15 12.65 4.55
68 11.28 4.74
09 11.71 4.85
Cntalyt Ic
Cr/irktnn C.unlyttc Cutnlyllc C*t«lytlc
Thermal Frenh Cntulytlr. Hydro- Hydio- llydro-
i Ojiftrntlon Yr.vil Recycle Reforming crncking reflnlnR trent Ing
1.81 1.75 1.47 2.02 2.
1.75 l.l«'> 1.5^ l.'fl 2.
1.72 1.99 1.62 2.05 - - 2.
1.64 1.99 1.57 2.06 - - 2.
1 . <>'> 1 . 96 1 . 5 .1 7 . 09 - - 1 .
I.I.'. 1. 'I', | . *.', J . I'l - - •).
1.66 4.18 1.60 2.1ft 0.41 - 3.
1.60 /..25 1.55 2.54 0.50 0.55 3.
1.64 4.17 1.49 2.7R 0.60 0.54 1.
1.56 4.51 1.46 2.89 0.73 0.54 1.
1.5) 4.57 1.26 1.17 0.84 0.61 4.
37
54
75
93
10
r,
66
27
51
81
26
Production Cnpacltjr (MMH/SO)
Cntnlyt Ic
Alkyl«- Polymerlt*-
t Inn t li>i\* l.tibv Aiphnlt
0.
0.
0.
0.
0.
O.
0.
0.
0.
0.
0.
46
49
50
51
55
60
65
67
75
78
82
0.14 0.
0.11 0.
0.13 0.
0.11 0.
0.12 0.
o.ll 0.
0.10 0.
+0.25 0.
0.29 0.
0.11 0.
0.29 0.
21
20
20
21 •
21
71
21
20
21
22
22
0.49
0.49
0
0
0
O
0
0
0
0
0
.51
.54
.51
. U
.53
.17
.58
.60
.62
Cuke
^m/sn|
in. 90
19. 70
30.94
71.14
2). 01
7 '..OO
28.43
79.41
35.49
38.77
41.47
Incremental Change
1962-1972
Z Crude
3.
100.
08 1.12 1 . 1 fl
0 101.3 17.R
(0.2H) O.fl2 (0.211 1.15 0.43 0.08 1.
(9.0) 26.) (n.7) 16.9 13.8 2.6 60.
89
6
0.
11.
16
5
0.
0.
01
1
0
4
.13
.2
22.57
-
NjPC_ _Q< i e_it t 1 o.n n « t r it
^ Cxj>.u\tinn IUt« (MMH/rDJ^
1971-1978

1.
100.
fl - 0.50
0 - 2H.O
(0.1M) 0./.0 n.O 0.67 0.11 0.67 0.
(1.0) II. 0 0.0 17.0 6.0 37.0 55.
99
0
0.
7.
11
.0
0.14 0.
8.0 1.
IA
0
0
5
.09
.0
6.4

                     M))B - ml lllon bnrrels
                     CD - caleml.ir 
-------
                                   C:KOC:UAPIITO m STUI mrrtoN  01--
SOURCE:   Reference 5

-------
                                                            FIGURE  2




                                    PETROLEUM ADMINISTRATION  FOR DEFENSE (PAD) DISTRICTS
S
6^
i
             . I At A'.K A V '
           ,,ri


           AND HAWAII)
                                                          - _ _ _»	I
                           Reference 5

-------
                           TABLE  2
              SURVEY  OF U.S. REFINING INDUSTRY
              BY  CAPACITY AND NUMBER OF PLANTS
PT.ANT SIZE, BPD:
10,000
10-100,000
Over
100,000
No. of plants

Total Refining  Capacity,
  74
    141
    44
J. -v
I
I
1,000 BPD
of Plants
of Capacity
348
28
2.3
6,032
55
40.7
8,465
17
57 .0
Source:   The  Oil and Gas  Journal, Annual Refining Survey (1975).
                               /

                              -4,77-

-------
while a majority  of total capacity  (57%)  lies in those

facilities  which  are greater than 100,000  BPD.

     Future  Trends

     The number  of  refineries in the United  States has

decreased  in the  last few decades (see  Table 1), while the

average size of  a refinery has increased.  Few  new refineries

have been  built  in  the past five years; however, changes

have been  made  in existing refineries to reflect changing

technology  and  product demand, largely  through  expansion and

revamping  of units  of existing refineries.   Although there

are several  new  facilities in the planning stages,  many such

projects have been  either cancelled or  greatly  delayed primarily

because of  the  uncertainty caused by unresolved  energy and

environmental issues.

     Growth  in  petroleum demand within  the next  10  years  is

expected to  be  lower than historical growth  rates,  thus

reducing projected  waste generation rates  for the  industry.*

Processing  Operations

     A petroleum  refinery is a complex  combination  of

interdependent  operations engaged in the separation of crude

oil by molecular  cracking, molecular rebuilding  and solvent

refinishing,  to  produce  a varied list of intermediate and

finished products,  including light hydrocarbons, gasoline,
^Projected decrease  in  growth is due to a  number  of factors:
 (1) improved  fuel  economy for automotive  engines  (2)  the
 trend among consumers  to  purchase smaller  cars  (3) slow down
 in jet fuel (4)  rapid  increase in the construction costs of
 petroleum refineries  and  (5) scarcity of  capital  (Reference  5).

-------
 diesel and  jet fuels,  light distillate  fuel  as well as heavy




 residual  fuel oil.  During the processing  of the crude oil, a




 number of waste streams  are generated either from the clean-




 up of equipment/storage  tanks used in the  refining process or




 from the  treatment of  wastewater generated during petroleum




 refining  operations.   The  remainder of  this  document will




 discuss these particular waste streams  and provide reasons




 for identifying these  wastes as hazardous.   (A detailed




 description of the petroleum refining process  is not included




 in this document.  However, to assist the  reader in understand-




 ing some  of the basic  processing operations  carried out in a




 petroleum refinery, a  brief description  of some of the individual




 operations  is included as  Attachment I.)




 Waste Generation  and M an a"g e m e n t
 1.    Was t e S tre ams




     The  five waste  streams  listed as hazardous  are:




     o  API Separator  Sludge




     o  Dissolved Air  Flotation (DAF) Float




     o  Slop Oil Emulsion  Solids




     o  Heat Exchanger Bundle Cleaning  Sludge




     o  Tank Bottoms  (Leaded)




     Lead  and chromium are the constituents  of concern in




these waste streams.   Lead in the waste  streams  comes predomi-




nantly from the use  of tetraethyl lead  in  the  blending of




leaded products.   Chromium in the waste  stream comes  predominantly

-------
from cooling  tower blowdown that  uses  a  chromium base corrosion

inhibitor.*   Concentration ranges  for  lead  and chromium in

representative  samples of each waste  are  presented in Table 3.

API Separator Sludge - The API Separator  provides for primary

refinery wastewater treatment.  The separators are usually

connected  to  the  oily water plant  sewer.  As  a result, the

API separator bottoms contain a mixture of  all sewered waste,

including  tank  bottoms,  boiler blow-down, desalter wastes, and

also traces of  all chemical elements which  enter the  refinery

process.

     Oil that is  present in the sludge will most likely  be

present in the  form of heavy tars  since the surface oil  is

skimmed periodically from the API  separator.   Oil content  of

the sludge is approximately 23% by weight while  water and

solids  constitute  approximately 53% and 24%,  respectively.

Most of the solids content is silt and sand,  but a significant

amount  of  heavy metals are also present in  the sludge.

     This  waste stream is listed because  it contains  significant

concentrations  of  the two heavy metals, chromium and  lead.

(Table  3 lists  the concentration ranges of  the constituents

of concern in each waste stream.)
*The Agency recognizes  that refineries not  implementing  these
 systems will have  lower  concentrations levels  of  these  toxic
 metals.  The delisting  provisions of §261.39  are  available
 to generators with  fundamentally different waste  streams  to
 justify delisting  of  their wastes.

-------
          " Some refineries utilize dissolved  air flotation




 Allowing primary separation in the API  Separator to remove




 additional oil and  solids.   The process  brings  finely divided




 oil and solid particles  to  the surface where  they are skimmed




 for disposal.




     Water typically  constitutes 82% by  weight  of this waste




 stream, while oil and  solids constitute  approximately 12.5%




 and 5.5% respectively.   The solids are generally fine silts




 which did not have  sufficient residence  time  in primary




 separators to settle,  but the waste stream  also contains the




 heavy metals chromium  and lead, for which it  is listed.




 Slop Oil Emulsion Solids  -  The skimmings  from  the API separator




 generally consist of  a three-phase mixture  of  oil,  water and




 a third emulsified  layer.  The oil is returned  to crude




 storage, the water  discharged to the wastewater treatment system,




 while the emulsion  (oil,  water and solids)  becomes  a process




 waste stream.  A typical  combination of  the waste stream by




 weight is 40% water,  43%  oil and 12% solids.   Among the




 solids are the heavy  metals chromium and  lead,  for  which the




 waste is listed.




 Heat Exchanger Bundle  Cleaning Sludge -  Heat  exchanger bundles




 are  cleaned during  plant  shutdown to remove deposits of scale




 and  sludge.  Depending  upon the characteristics of  the




 deposits,  the outside  of  the tube bundles may  be washed,




brushed,  or sandblasted,  while the tube  insides can be wiped,




brushed,  or rodded  out.   Sludge resulting from  the  cleaning

-------
                                                       TABLE  3
                               RANGE* IN CONCENTRATION**  FOR  CONSTITUENTS OF CONCERN
Contaminant
No. of Samples
Chromium
Lead


API Sludge
12

.10-6,790
.25-1,290
O f*\ I TV? f^ TV
CJ \^ Ui V \j 1.4
DAF Slop Oil Bundle Sludge
5 9 , 2
r
28-260 1-1,750 310-311
2.3-1,250 .25-580
_ — S
X
Tank Bottoms
2

—
158-1,420
*Range values represent high and low concentrations for samples of  each waste  stream




**Concentration In mg/kg dry weight, Including Inert solids but excluding  oil
 SOURCE:  Reference 1

-------
process has  approximately  53%  water, 11%  oil  and 36% solids.




    These  solids are composed largely of  silt  precipitated




from the water.   The metals  present are mostly  corrosion




products or  scale deposits  from the exchange  bundle tubes.




Chromium is  present in the  waste in substantial  concentrations,




and the waste  is  listed due  to the presence  of  this constituent.




Tank Bottoms  (Leaded) - The  petroleum products  (or fractions)




after  being  separated in  the distillation  column have to be




cooled before  they are sent  out or used for  making other by-




products.   This  is done in  product storage  tanks.   As cooling




occurs, the  water separates  from the hydrocarbon phase and is




continually  drained from  the tank,s to the  refinery water




treatment  system.  Solids  formed as products  of  corrosion and




rust in the  tanks cont airr---1 oxi c heavy- metals,  and  are




periodically  removed.  This  waste is being  listed  because it




cont ains lead .




    In summary,  the contaminants in these  wastes  which




caused EPA  to  identify these wastes as hazardous are as




follows :




    API Separator Sludge  -  chromium and  lead




    DAF Float  -  chromium  and  lead




    Slop Oil  Emulsion Solids  - chromium  and  lead




    Heat Exchanger Bundle  Cleaning Sludge  -  chromium




    Tank Bottoms (leaded)  - lead




2.   Waste Generation Ratio  and Composition




    There are  a  wide variety.of factors  which  can affect the

-------
quantity  and quality of individual  waste streams.   Factors

that  affect  quality include  crude  oil characteristics,  compo-

sition  of process wastewater,  occurence of spills  and  leaks,

composition  of cooling water blowdown,  use of corrosion

inhibitors  and the use of tetraethyl  lead for specific  pro-

ducts and modifications.  Factors  that  affect both  the  quantity

and quality  of the individual  waste  stream include  the  refinery

size  and  age,  the segregation  of refinery oil drains, and

the actual  quantity of process wastewater (Reference 2).

      The  constituents of concern in  the individual waste

streams  are  shown in Table 3.  As  this  data illustrates, each

waste stream varies with regard to  lead and chromium

concentrations,  but lead and chromium are found generally in

very  high concent rations^with  some  levels exceeding 1000 mg/kg

dry weight.*

      The  estimated quantities  of individual waste streams

range from  600 - 33,000 metric tons per year (dry weight)

(including  inert solids but excluding oil).  The combined

total estimated  quantity is 66,610 metric tons  per year (dry
*The Agency  is  aware  that these wastes  generally contain very
 high concentrations  of zinc.  Zinc  is  one  of the secondary
 drinking water  standard parameters, with  an MCL of 5 tng/1.
 At this time,  however, the Agency does  not  believe that ex-
 posure to concentrations of zinc, which may leach from the
 waste, will  result  in a human health hazard, and therefore
 is not presently  designating zinc as a  constituent of concern
 in these waste.

-------
weight)(including  inert solids  but  excluding oil)  based  upon




capacity of 14,200,000 BPCD*.




    The relative  quantities  of waste for the individual




waste components  for each waste stream are shown  in  Table  4




and  indicate  that  the API separator,  Slop oil and  DAF  Float




are  the major  waste generating  streams in terms of quantity.




Additionally,  the  data indicates  that chromium and lead  are




present in  substantial quantities  in  these wastes.




    A second  source of data, the  American Petroleum Institute




(API), took an extensive survey at  the quantities  of each  waste




component present  in two of  the waste streams from the Petroleum




Process which  concern the Agency.




    As shown  in  Table 5, the API  data on the API  sludge




and  the^ DAF float  generally  supports  the data found  in Table




3.   (it is  important to recognize  that the API data  reflect




a much larger  sampling effort relative to that encompassed




in the EPA  survey.)




Current Disposal  Practice -  There  are currently 4  principal




methods for disposing of petroleum  refinery solid  wastes.
*BPD - Barrels  per  Calendar Day

-------
                                                              TABLE 4
                                              TOTAL QUANTITIES OF EACH WASTE COMPONENT

                                                      Metric  Tons/Yr (Dry Weight)*,**
                 API SLUDGE
DAF FLOAT
SLOP OIL
HEAT EXCHANGER SOLIDS
TANK BOTTOMS
TOTAL
Chromium
Lead
17.6
1.2
8.4
.5
17.7 .4
.06
44.2
1.1 2.9
 i   SOURCE:   Reference 1
oO
    *Excludes Inert solids and oil

   **Even though the quantity of heavy metals  from any  one waste generated at any particular petroleum refinery
     may be small,  these wastes are normally disposed of  together;  therefore, the total contribution and  Impact of
     these heavy metals at any individual refinery would  be  substantial.

-------
                                                              TABLE 5
                                                       RESULTS OF API SURVEY
                              TOTAL WEIGHT
                             METRIC TONS/YR
                         API                DAF
                                                           CONCENTRATION
                                                               Mg/Kg
                                                      API*               DAF**
Chromium
Lead
8.6
2.4
5.3
.23
0-10,800
0-6200
0-3000
0-540
 I
o
oO
vj
 *Sample size ranges from 63-68
**Sample size ranges from 13-15
       SOURCE:  Reference  3

-------
These processes  include land  treatment,  landfilling,  lagooning




and incineration,  and may be  conducted either on-site  or off--




site, depending  upon the particulars  of  a given operation.




     The  results from both the EPA  and API studies  are




presented  in  Table 6 to provide  comparisons regarding  the




disposal  methods currently employed  for  refinery wastes.




Land treatment  and landfilling appear  to be the most widely




employed  disposal  processes with  up  to 75  percent of the




refineries  relying upon these processes  for solid waste




disposal.




Hazards Posed by Waste




     As indicated  earlier (Table  3),  the five waste streams for




the petroleum refining industry  contain  significant concentrations




of the  toxic  heavy me t a-l-s- 1 ead and chromium,  with some levels




exceeding  1,000  mg/kg (dry weight).  Additionally,  information




submitted  by  the API for two of  the waste  streams (API separator




sludge  and  DAF  float) in which a  water-wash ing step was




conducted  to  simulate leaching (see Table  7),  indicates that




lead and  chromium  will leach from the  waste  in significant




concentrations  (between 10 and 100 x the National Interim




Primary Drinking Water Standard)   even  when these metals are




subjected  to  mild  environmental conditions.   In many cases,




off-site waste disposal is implemented and these sites may be




characterized by acidic environments  (for  instance, if they




contain domestic refuse or other  acidic  wastes)  in which case

-------
                           TABLE  6
           DISPOSAL  METHODS FOR  REFINERY WASTES*
        Method
Landfill
Lagoon

Incinerat ion

Land Treatment
                          EPA  Survey^
APISurveyc
On-Site
5
3
1
10
Off-Site
14
2
0
0
On-Site
47
15
3
27
Off-Site
36
4
0
3
aReported  in  terms of number of refineries.

^Nineteen  refineries reported.

cSeventy-five r e f ineri es--report ed .

^Percent  refineries using  land treatment  on-site plus
 off-site,  Jacobs 10 of  19  equal  53  percent, API 30  of
 75  equals  40 percent.


SOURCE:   Reference 3.

-------
                             TABLE 7

     MEAN WASTE  EXTRACT CONCENTRATIONS  (WATER EXTRACTNANT)
                                 API*                   DAF**
 Con t aminant                    S ludge                 Float

 Chromium  (total)                 1.9                    3.3

 Lead                             2.3                    2.1
 *Sample size:   60-63
**Sample size:   12-15

 SOURCE:  Reference  3

-------
even more of the hazardous constituents  would be released



   environmental migration.
    Although leaching data for  the  other three waste  streams




is not presently  available, the  Agency believes that the




contaminants found  in  the waste  would  also tend to migrate




from the waste based  on the solubility of the contaminants.




An additional factor  supporting  this  belief is the fact  that




chromium and lead have been shown  to  migrate in significant




concentrations from the API separator  sludge and DAF float,  and




since the three remaining waste  streams are of roughly  similar




composition and are generated as part  of the same production




process, migration  patterns of these  similar waste streams




can be readily anticipated.  Further,  lead oxide, the  form




in which lead appears  in— these wastes, is soluble in moderately




acidic environments (7).   The solubility of chromium oxide




is pH dependent and,  like lead oxide,  will increase as  the




pH decreases (8).   Thus,  disposal  of  these wastes in acidic




environments is reasonably likely  to  result in the solubili-




zation of dangerous concentrations  of  heavy metals.




    Once released  from the matrix  of  the waste, lead  and




chromium can migrate  from the disposal site to ground




and surface waters  utilized as drinking water sources.




Present practices associated with  lan.df i 1 ling , land treatment




°r impounding the waste may be inadequate to prevent such  an




°ccurrence.   While  the Agency is presently unaware of  all

-------
management  practices employed  for  these wastes,  since  there




are a great  number of generating  and  management  sites  and




because wastes  that are disposed  of  off-site out of  the




generator's  personal supervision  are  particularly susceptible




to mismanagement,  there is a strong  likelihood that  some of




these wastes  are not properly managed  in actual  practice.




One example  of  inadequate management  would be improper selection




of disposal  sites  in areas with permeable soils,  permitting




contaminant-bearing leachate from  the  waste to migrate to




groundwater.   This is especially  significant with respect to




lagoon-disposed wastes because a  large  quantity  of liquid is




available  to  percolate through the solids and soil beneath




the fill.




     An overflow pr ob le"rrf"mi gh t also be  encountered if the




liquid portion  of  the waste has been  allowed to  reach too




high a level  in a  lagoon.   Under  these  circumstances, a




heavy rainfall  could cause flooding which might  reach surface




waters in  the vicinity.




     In addition to difficulties caused  by improper site




selection, unsecure landfills are  likely to have  insufficient




leachate control practices.  There may  be no leachate collection




and treatment  system to  diminish leachate percolation through




the wastes and  soil underneath the site  to groundwater, and




there may be  no surface  run-off diversion system to prevent




contaminants  from  being  carried from  the disposal site to
                               vt

-------
                                                          .ce
 nearby ground  and surface waters,  thereby  increasing the

 likelihood of  drinking water  contamination.   Further, on.

 lead  and chromium have escaped  from the disposal  site, they

 will  persist  in  the environment  (in some form)  for virtually

 indefinite periods, since they  are elemental  metals.

     Additionally,  if these wastes are incinerated without

 proper air pollution control  equipment, the possibility exists

 that  lead  (a  volatile heavy metal*) will be released into the

 environment  and  create an air  pollution problem.

     A further possibility of  substantial  hazard  arises during

 transportation of these wastes  to  off-site disposal facilities.

 This  increases the  likelihood  of their being  mismanaged,  and

 may result either in their not  being properly handled during

 transport  or  in  their not--reaching their destination at all,

 thus  making  them available to  do harm elsewhere.   A transport

 manifest system  combined with  designated standards for the

 management of  these wastes will  thus greatly  reduce their

 availability  to  do  harm to human beings and the environment.

     The Agency  has determined  to  list these  wastes as

hazardous wastes  on the basis  of lead and  chromium constituents,

even  though  these 'constituents  are also measurable by the

characteristic of extraction  procedure toxicity.   Although,
*An incinerator  operating  to  destroy organic  materials operates
 in the range  of 1000° C -  1200°  C.   This would  cause lead to
 evaporate out  of the equipment  as fast as  water would evaporate
 at II8 C.  The  temperature  at  which vapor  pressure equals 10 mm
 Hg for water  is 11° C and  for  lead  is  1162°  C  (11).

-------
concentrations  of  these constituents  in  an EPA extract  from




waste streams  from individual sites might  be less than  100




times the National Interim Primary Drinking Water Standards,




the Agency,  nevertheless, believes that  there are factors in




addition to  metal  concentrations  in leachate which justify




the T listing.   Some of these factors  already have been




identified,  namely the significant concentrations of chromium




and lead in  the five waste streams, the  non-degradabi1ity of




these substances-,  and the possibility  of improper management




of the wastes  in actual practice.




     The quantity  of these wastes generated (a combined total




of approximately 66,610 metric tons dry  weight)  is an additional




supporting  factor.   As previously indicated,  the wastes from




petroleum refining industry contain significant  concentrat-




ions and quantities  of chromium and lead.   Large amounts of




these metals  from  the five waste  streams are  thus available




for potential  environmental release.   The  large  quantities




of these contaminants pose the danger  of polluting large




areas of ground or surface waters.  Contamination could also




occur for long  periods of time,  since  large amounts  of pollutants




are available  for  environmental  loading.   Attenuative capacity




of the environment  surrounding the disposal facility could




also be reduced or used up due to the  large quantities of




pollutant available.   All of these considerations increase




the possiblility of  exposure to  the harmful constituents in




the wastes,  and in the Agency's  view,   support a  T listing.

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     _ects of Waste Constituents  of  Concern







    Toxic properties  of chromium and  lead have been well




documented.  Chromium  is toxic to man  and lower forms of




aquatic life.  Lead  is also poisonous  in all forms.  It is




one of the most hazardous of the toxic metals because it




accumulates in many  organisms, and  its deleterous effects are




numerous and severe.   Lead may enter  the human system through




inhalation, ingestion  or skin contact.   Improper management




of these sludges may  lead to ingestion of contaminated drinking




water.  Additional information on adverse health effects of




chromium and lead can  be found in Appendix A.




    The hazards associated with exposure to lead and chromium




have been recognized  by other regulatory programs.  Lead and




chromium are listed  as priority pollutants in accordance with




§307 of the Clean Water Act of 1977.   Under Section 6 of the




Occupational Safety  and Health Act  of  1970, final standards




for Occupational Exposure have been established and promulgated




in 29 CFR 1910.1000  for lead and chromium.  Also, a national




ambient air quality  standard for lead  has been announced by




EPA pursuant to the  Clean Air Act (9).   In addition, final




or proposed regulations of the States  of California, Maine,




Massachusettes , Minnesota, Missouri,  New Mexico, Oklahoma




and Oregon define chromium and lead containing compounds as




hazardous wastes or  components thereof (10).

-------
                            Re ferences
 1.   Jacobs Engineering Company.  Assessment  of Hazardous
      Waste Practices  in the Petroleum Refining  Industry.
      Environmental  Protection Publication  PB-259-097.
      National  Technical Information Service.  June 1976.

 2.   Jacobs Engineering Company.  Alternatives  for Hazardous
      Waste Management  in the Petroleum Refining Industry.
      OSW Contract Number 68-01-4167 unpublished data.
      July  1977.

 3.   Engineering-Science Inc.  The 1976 API Refinery  Solid
      Waste Survey,  prepared for the American  Petroleum
      Institute.  April, 1978-- 4 parts.

 4.   Radian Corporation.   Environmental Problem Definition
      for Petroleum  Refineries, Synthetic Natural  Gas  Plants
      and Liquified  Natural Gas Plants.  EPA,  68-02-1319.
      November,  1975.

 5.   A.D.  Little, Inc.   Environmental Considerations  of
      Selected  Energy  Conserving Manufacturing Process
      Options.   Vol.  IV  Petroleum Refining  Industry.
      EPA 600/7-76/034-d.   IERL, December,  1976.

 6.   Development Document  for Effluent Limitations  Guidelines
      and Standards  for  the Petroleum Industry.   EPA 440/1-79/
      014-b.   December,  1979.

 7.   The Merck  Index.   8th Edition.   1968.

 8.   Pourbaix,  Marcel.   Atlas of Electrochemi c a 1  Equilibria
      in Aqueous  Solutions, London, Pergamon Press,  1966.

 9.   U.S.  Department  of Interior,  Bureau of Mines.  Mineral
      Commodity  Summaries,  1979.

10.   U.S.  EPA  State Regulations Files; January  1980.

11.   Handbook  of Chemistry and Physics, 56th  ed.   Cleveland:
      CRC Press,  1975.

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     Wastes  from Petroleum  Refining Process  -  Response

                          to  Comments

 j_4   A number of commenters  stated that the proposed  listing

 "SIC 2911  API separator  sludge  (T,0)" should  not  apply to

 all wastes  from API separators  but only to waste  generated

 from petroleum refineries*.   The commenters argued  that API

 separators  are used in numerous industries and  processes

 (i.e,  the  food industry,  soap and detergent industry,  etc.)

 which generate sludges of  widely differing characteristics.

 These separators, however, do not necessarily  generate a

 hazardous  waste (i.e., the term does not  automatically suggest

 that the  sludge from any  use of such a piece  of equipment

 would be  a  hazardous waste).   Therefore,  the  commenters want

 the listing to be e i the'F"'c 1 ar i f i ed to indicate  that  the API

 separator  sludge is meant  to be specific  to separators used

 in the petroleum refining  industry;  or otherwise, want the

 process deleted from the  hazardous waste  list  in  Section

 250.14.

     o  The Agency agrees  with  the commenters.  The  listing

       has therefore been clarified to indicate  that  the

       API separator sludge is meant to  be specific  to

       separators used  in the  petroleum  refining industry.
*A note appeared before the  listed waste in  §250.14  which
 specified  that  the SIC code  used in the listing  was  for
 ease of reference only.  Thus,  the SIC classification of
 the industry  generating the  waste would have no  effect on
 the listing of  that process  waste as hazardous.

-------
2.    One  cotnmenter suggested  that  additional wastes  from the




petroleum refining industry be  added to the hazardous  waste




list.   These  wastes included:   (1)   petroleum refining sulfur




removal,  (2)  petroleum refining  wastewater treatment  sludges,




(3) petroleum refining boiler  cleaning, (4) petroleum  refining




alkylation*  and (5) petroleum  re fining-coke from  asphalt




cracking.   Data was submitted  along with the suggested




list ings.




      o   After evaluating all  the available data on the




         additional listed wastes,  the  Agency has  decided




         not  to add these wastes  at  the present time due




         to  the lack of supporting  data.  However, the




         Agency will reccnrisider  these' listings at  some  later




         time  once sufficient  data  becomes  available.




3.    One  commenter objected to  the  proposed listing "SIC  2911




Petroleum refining lube .oil filtration clays" due to the  lack




of supporting data.




      o   The Agency, in re-evaluating the available data,  has




         decided to defer the  listing "SIC  2911 Petroleum




         refining lube oil filtration clays" until additional




         data  is collected by  the Agency on which  to make  a




         de c i s ion.
*This waste was  listed in the December  proposal (43 FR  58959).

-------
                          Attachment  I







 The refinery process  can be categorized into the  following




 individual operations  which are  displayed schematically  in




 Figure A-l.




     o  S eparat ion




     o  Treating




     o Conversion




          o   cracking




          o   comb inat i on




          o   rearrangement




     o  Blend ing




     o  Auxiliary Process




     o  Storage




 Separat ion




     The individual* process steps  and operation in this  area




 include:




     o  Topping Unit - This unit separates  the crude in  an




 atmospheric  stage.   The process  streams from this unit normally




 include fuel gas, naphtha, middle  distillates,  and distillated




 fuel  oil.   The naphtha may be split  into  light  and heavy




 fractions  and the fuel oil into  light,  middle,  and heavy




 distillate components.




     o   Vacuum Towers  - Vacuum towers  are  utilized for




separation of the heavier fractions  from  the entire crude




stream.   For a comparable crude  input,  these units are capable

-------
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-------
Of producing a broader  spectrum of  process streams  than a


topping  unit.   For  example,  these units  may either  recover

additional  gas oil  from the  reduced  crude while producing a


heavy  vacuum residual  or may separate  the reduced crude into

special  lube oil cuts  with an accompanying residual  stream.

One of two  stages may  be utilized,  depending upon the  individual

end-product requirement,

     o  Light  Ends  Recovery  - This  operation is sometimes

referred to as vapor  recovery and involves the separation of

refinery gases from the crude distillation unit and  other

units  into  individual  component streams.   The separation

phase  is accomplished  by absorption  and/or distillation,

depending upon the  desired purity of the  product stream.

Treat ing

     o  Gas Treating  -  The major component of the various
                                     «
species  separated in  the crude distillation unit or  produced

in the various processing units is  hydrogen sulfide.   Acid

gases,  such as J^S,  normally are removed  from the light ends

fraction by absorption  with  an aqueous  regenerative  solvent.

There  is a  variety  of  treating processes  available with the

most  common refinery  operations based  upon ainine-b as ed


solvents.

    o   Hydro treat ing  - Hydrotreating  involves the  catalytic

conversion  of  organic  nitrogen, sulfur,  and oxygen  compounds


into hydrocarbons and  the more readily  removable sulfides,

ammonia,  and water.   Various process  streams normally  are
                               -701-

-------
treated separately  because of various  fuel  specifications and




the wide range  of  catalysts and reactor  conditions required




to hydrotreat  the  various petroleum fractions.




Convers ion




     Conversion processes typically involve  cracking,




combination, and rearrangement.




     o  Cracking




        Thermal Cracking - This is a relatively  simplistic




process which  involves  the heating of  hydrocarbon  fractions




in the absence  of  catalysts.   A modification  to  this  traditional




process, known  as  vis-breaking, is used  to minimize  coke




formation.   The moderate heating to 880°F is  employed  to




reduce the  feed viscosity and, therefore, reduce the  quantity




of blending  stock  required to upgrade  the feed to  fuel  oil




specifications.  Delayed coking uses severe heating  conditions




(1800°F-2000°F)  to  crack feedstock to  coke gas,  distillates,




and coke.   Fluid coking is a  recent innovation which  converts




the feed stream to  higher valued products and produces  less




coke .




        Hydrocracking - This  process involves the  cracking




of feedstocks  in the  presence of a high  hydrogen partial




pressure.   This process normally is employed  on  a  high  sulfur,




straight-run gas or  on  a gas-oil effluent from another  cracking




pro cess.




        Catalytic  Cracking -  Catalytic cracking  involves the




application  of  catalytic reactions to  reduce  heavy oils maxi-
                                 -702-

-------
      production  of light C4  hydrocarbons and  C5  and  C6

 gasoline compounds.   This process  is primarily  employed to

 maximum gasoline  production.

    o  Combination  - These  processes involve the  combination

 of two light hydrocarbons through  polymerization or  alklation

 to produce a gasoline-range  hydrocarbon.  The polymerization

 process combines  two or more gaseous olefins into  a  liquid

 product, while  the alkylation  process joins an  isoparaffin

 and olefin.  The  feedstock origin  is either a catalytic or

 hydrocracker and  the catalysts  include phosphoric, sulfuric,

 or hydrofluoric  acid.

    o  Rearrangement - This process involves the  application

 of catalytic reforming and isomerization to rearrange  the

 molecular structure  of a^feedstock to produce a high quality

 stream for gasoline  blending.

    Catalytic  reformers create  high octane naphthas (rich in
                                                      4
 benzene, toluene,  and xylene)  from a desulfurized, straight-

 run, or cracked  naphtha.  Hydrogen also may be  produced as

 part of the reforming operation  and other end-products,

 including non-aroma t ic s .

    Isomerization units are used  to increase the  octane

ratings of pentane and hexane  fractions to produce a gasoline-

blending stock  having an octane  number of 80-85.   The  reaction

is  conducted at  elevated temperatures (> 300°F) and  pressure

(400 psig) over  a  chlorinated-platinum-aluminum-oxide  catalyst.
                                 -70S-

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Blending




     The  typical in-line blending  operations most  commonly




involve  the  final processing  of  gasoline prior to  storage.  A




variety  of  gasoline components,  such  as cracked gasoline,




reformate,  isomerate, alkylate,  and  butane, are combined with '




selective  additives in the necessary  proportions to meet




marketing  specifications.




Auxiliary  Operations




     o   Crude  Desalting - This process  involves the separation




of inorganic  salts  and brines  from an  incoming crude to




prevent  process  fouling, corrosion,  and catalyst poisoning.




The desalting  process can be  conducted  either electrically or




chemically  with  the former being the more  prevalent.  In the




electric  process, the raw crude  is heated,  emulsified with




water, and  routed through a high-voltage vessel where the




electric  field demulsifies the oil and  water.   In the chemical




version  of  this  process, coalescing  agents  are applied to




demulsify  the  two-phase aqueous-organic system.




     o  Hydrogen Generation - Large  quantities of hydrogen




are consumed  in  numerous refinery  operations,  including




hydro treat ing, hydrocracking, and  isomerization.   The proper




maintenance of a hydrogen balance  within the typical refinery




requires  that  the hydrogen available from  the catalytic




reformers be  supplemented by  either  stream-hydrocarbon




reforming or  partial oxidation.  The selection of either
                               -70
u ~

-------
process  depends upon  the characteristics of the raw  feedstock




material.





     o  Sulfur Recovery - This process  involves the  application




Of specific processes,  such as the  Glaus process, to  convert




the hydrogen sulfide  content of  acid  gas to elemental  sulfur.




In this  process,  the  hydrogen sulfide  is combusted in  an




oxygen-deficient  atmosphere to produce  sulfur, sulfur  dioxide,




and water.  Additional  sulfur recovery  is obtained in  a series




of catalytic reactors  through reaction  of hydrogen sulfide




and sulfur dioxide.   The tail gas  from  the Glaus unit  may be




treated  further through a variety  of  processes.




     o  Power Generation - The major  factor affecting  power




generation in refining  operations  is  the requirement  for




steam and the over a 1 1 -f-ac i 1 i ty steam  balance.   Facility




requirements can  range  from a simple  back-up boiler for




operations where  there  are significant  amounts of by-product




steam to other situations where  continuous steam generation




is necess ry.




Storage  Technologies




     o  No Storage -  Raw material  is  not stored, but  is pumped




directly from an  adjacent process  area  or petroleum refining




facility where it  is  produced.    This  procedure is employed




when  the production in  two process  areas in integrated to the




degree that simultaneous operations occur and  no intermediate




storage  is necessary.   Material  transfer would occur by

-------
pulping  through  steel or other piping  from one process area




directly  to  the  other.




     o   Tank Storage




         Fixed R oof - These cylindrical  steel tanks have




permanently  attached conical steel  roofs.   The rigid construction




of these  tanks necessitates that  the roof  be installed with




pressure-vacuum  valves set at a few inches of water to contain




minor vapor  volume expansion.  Greater  losses of vapor




resulting  from tank filling should be controlled with an




attached  vapor recovery unit.




         Float ing Roof - Unlike fixed roof  tanks,  these tanks




are equipped with a sliding roof  that floats on  the surface




of the  product and eliminates the vapor  space between product




and roof.  A sliding seal attached to the  roof  seals the




annular  space between the roof and vessel  wall  from evaporation.




         Internal Floating Cover - To remedy  the  problems of




snow and  rain accumulation encountered with  floating roofs,




this design  utilizes both a fixed outer  roof and  an internal




floating  cover.   Again, the floating cover is equipped with




sliding  seals to prevent annular  space  evaporation.




         Variable Vapor Space - These tanks may  appear in two




basic designs:   lifter roof and diaphragm.   The  lifter roof




type utilizes a  telescopic roof,  free to travel  up or down as




the vapor  space  expands or contracts.  The diaphragm design




has an  internal  flexible diaphragm to accomodate vapor volume
c n a n g e s

-------
       Pressure - These  tanks are especially  useful  for




storing highly volatile materials.  These  tanks  come  in a




vide variety of shapes  and are designed  to  eliminate  vapor




emissions by storing  the  product under pressure.   These tanks




may be designed for pressures up to 200  psi.




    It has been noted  that fixed roof,  floating  roof,  and




internal floating  cover  tanks are the most  common varieties




in use for storage of organic materials.   These  tanks may




range  in size from 20,000 to 500,000 bbl.  and  average 70,000




bbl.
                               -707-

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Leather Tanning and Finishing

-------
                     LISTING BACKGROUND DOCUMENT


                LEATHER TANNING AND FINISHING INDUSTRY

 I.   LISTING OF HAZARDOUS WASTE STREAMS

 1.   Chrome (blue) trimmings generated by the following subcategories
     of the leather tanning and finishing industry:  hair pulp/
     chrome tan/retan/wet finish;  hair save/chrome tan/retan/wet
     finish;  retan/wet finish;  no beamhouse;  through-the-blue;
     and shearlings. (T)

 2.   Chrome (blue) shavings generated by the following subcategories
     of the leather tanning and finishing industry:  hair pulp/
     chrome tan/retan/wet finish;  hair save/chrome tan/retan/wet
     finish; retan/wet finish;  no beamhouse;  through-the-blue;  and
     shearlings. (T)

 3.   Buffing dust generated by the following subcategories of the
     leather tanning and finishing industry:  hair pulp/chrome tan/
     retan/wet finish;  hair save/chrome tan/retan/wet finish;  retan/
     wet finish;  no beamhouse;  and through-the-blue. (T)

 4.   Sewer screenings generated by the following subcategories of the
     leather tanning and finishing industry:  hair pulp/chrome tan/retan/
     wet finish;  hair save/chrome tan/retan/wet finish;   retan/wet
     finish;  no beamhouse;  through-the-blue;  and shearlings. (T)

 5.   Wastewater treatment sludges generated by the following  subcategories
     of the leather tanning and finishing industry:  hair pulp/chrome
     tan/retan/wet finish;  hair save/chrome tan/retan/wet finish;
     retan/wet finish;  no beamhouse; through-the-blue; and shearlings.  (T)

 6.   Wastewater treatment sludges generated by the following
     subcategories of the leather tanning and finishing industry:
     hair pulp/chrome tan/retan/wet finish;  hair save/chrome tan/
     retan/wet finish;  and through-the-blue.  (T, R)*

 7.   Wastewater treatment sludges from the following subcategory of
     the leather tanning and finishing industry: hair save/non-chrome
     tan/retan/wet finish. (R)**

 II.  SUMMARY OF BASIS FOR LISTING

     The first three waste streams listed above (trimmings,  shavings and

dusts)  are a direct result of processing operations conducted within


* Reactive (R) listing results from the inclusion of tanneries that^
  unhair;  this process generates reactive solutions containing sulfides.
**Vegetable tanneries generate sludges which are considered reactive.
  Data  on  the metal content of these sludges is not available at this
  time.   Therefore, these sludges are listed only as reactive.

-------
tanneries.  The four remaining waste streams (screenings and sludges)

are a result of tannery wastewater treatment facility operations which

have to comply with proposed categorical wastewater pretreatment standards

for existing sources (PSES) which discharge to publicly-owned treat-

ment works (POTW's), or proposed effluent limitations based upon best

practicable technology (BPT) and best available technology (BAT) for

plants which discharge to surface waters (44 FR 38746, July 2, 1979).

     The Administrator has determined that the above listed wastes

are solid wastes which pose a substantial present or potential hazard

to human health or the environment when improperly transported,

treated, stored, disposed of or otherwise managed, and therefore

should be subject to appropriate management requirements under Sub-

title C of RCRA.  This conclusion is based on the following considera-

tions:

     1.  These first six waste streams contain elevated concentrations
         and quantities of the heavy metals chromium and lead;

     2.  Wastewater sludges (product of the last two listed wastes)
         from chrome tanneries which employ unhairing operations also
         contain high concentrations of sulfides and sulfates which
         can react to form dangerously toxic hydrogen sulfide gas
         when subjected to an acidic environment,  a condition
         typical to landfills;

     3.  Approximately 190 leather tanneries currently generate  38,500
         dry metric tons (dry weight) of hazardous wastes;

     4.  Approximately 90 percent of the hazardous wastes listed above
         are disposed in landfills.   If improperly managed, the
         potential exists for these  metals to migrate from the waste
         in a landfill environment and to contaminate surface and
         groundwater supplies; this  has been demonstrated when
         these wastes were subjected to the proposed extraction
         procedure and found to meet the final  extraction procedure
         toxicity characteristic.
                               -7/O-

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III. DISCUSSION




    A.  Industry Profile




        There are  approximately 190 leather tanneries which are




responsible  for  generating the wastes of concern.   Production at




these  facilities ranges from less than 300 to greater than 2,000




equivalent hides (1 equivalent hide = 40 ft^) per  day.  Approximately




93 percent of these plants utilize chrome or chrome-tanned hides or




skins  in  their operations.  The leather tanning and finishing plants




identified are located  in  34 states.  Approximately 30 percent of




the total are located  in two states: New York and  Massachusetts.  In




general,  the greatest  concentration of tanneries are found in the New




England area and the Middle Atlantic States with approximately 85




percent of all tanneries located east of the Mississippi RiverC^->2,3).




    B.   Manufacturing  Processes




         Cattlehides constitute 81 percent (by weight) of the raw material




utilized  by  tanneries  in the United States.  Sheepskins and pigskins comprise




15 percent of raw material, while goatskins, calfskins, and other hide  and




skin types represent the remaining 4 percent of the raw material (1,2,3).




The three primary processing operations involved in producing leather




from cattlehides are depicted in Figure 1 and described as follows:




         1.  Beamhouse  Operations.  Beamhouse operations typically begin




            by  trimming the perimeter areas of the hide.  The hides are




            then washed and soaked in water to clean the hides and  re-




            store  their moisture.  Attached hair  is removed by either  a
                                -7/1-

-------
                                                   rigtzre  1

                                  PRODUCT AKD SOLID VASTS  TICK TDK TOLL LT?g
                                     LZATHE& TANNING AKD FTJTISBTHC FLASTS
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                           Briae ind Acid

                                  Ag eat
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                               Eaailaifiers
                          fatliquor*, Water
                                                           i.
                                                 Slaichicg & Coloring
                           liquoringj
                       [Setting Out]
                                                        Trin
                                                                                       Unfinished  L»»ci«r
                                         |Hanging I
                           Drying
' Pasting^
             Tojeglins;
! ^«cu^ j
                                                                                              DuaC
                     Solvent b*«e finishes,
                     Uater b*«« finishes,
                     Pignects 	•—•—
                                                   fConditioning'
                                                        "-£
                                                 [Staking  i  Drr Xil
                        [Buffing)-
                      riaishins & Platiag
                                                    [MeasurTi
                 'Buffing Doit
                                                                                                Leather Trixm±&t»

-------
             chemical  dissolving process or a combination of  chemical




             and  mechanical  means in an alkaline medium.




         2.   lanyard Processes.   Tanyard processes involve the  chemical




             fixation' in an  acid medium of organic (primarily vegetable




             tanning)  or inorganic (primarily trivalent  chromium) ma-




             terials to  the  protein structure of the hide to  prevent its




             deterioration.   Chromium tanning is the more prevalent




             tanning method  because it results in a product which is




             preferred for the majority of leather uses  and it  requires




             less process time to generate a tanned product,




         3.   Retanning and Finishing.  Retanning imparts  specific char-




             acteristics to. the leather which it lacks following the




             initial tanning step.  The more commmon retanning  agents




             are  chromium, vegetable extracts, and syntans.   Additional




             wet  finishing steps include coloring by a variety  of dye-




             stuffs, and fatliquoring using primarily sulfonated oils




             to restore  lubrication to the leather fibers.  Finishing




             processes include a number of operations which dry, con-




             dition, smooth, and apply surface finishes  to the  leather




             according to its end use.   Various finishes  (primarily




             water-base, as  well as solvent-base) provide abrasion




             and  stain resistance, and color enhancement  to the final




             product.




         The  manufacture of  leather from sheepskin is similar to cattle-




hide  tanning  except beamhouse operations are typically absent.  In addi-




tion, sheepskins  require degreasing prior to tanning.
                               -"7J3-

-------
         Shearlings  (sheepskins with wool retained)  require  essentially




the same sequence of processing steps as sheepskins  but  differences in




individual steps are necessary.




         The sequence of pigskin processing steps is essentially the




same as that used for cattlehide tanning; while most skins undergo ex-




ternal removal of most of the hair at the slaughterhouse, additional




unhairing is necessary to remove hair stubble and follicles.  Degreas-




ing is also practiced prior to the tanning of pigskins.  Solvents and/or




detergents are employed ot degrease the untanned skins.




     C.  Waste Generation




         Approximately 38,500 metric tons (dry weight) of hazardous




waste is currently generated by the leather tanning and  finishing




industry.  Wastewater sludges represent the largest portion of the




total at 47 percent.  The breakdown of the remaining hazardous wastes




is as follows: chrome trimmings and shavings, 45 percent; sewer




screenings, 4.5 percent; and buffing dust,  3.5 percent.  The projected




hazardous waste quantities which will be generated when BPT, BAT,




and pretreatment technologies are fully implemented are  43,400 and




58,000 metric tons (dry weight), respectively.  The incremental




difference between BAT and BPT quantities is attributed  primarily to




the implementation of pretreatment technology by indirect dischargers




(1,2,3).




         Facilities which utilize unhairing processes, chrome tanning




processes, and subject chrome tanned hides  to further processing are




the primary generators of hazardous waste within the leather tanning




and finishing industry.







                                 -ff-





                                -7/H-

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        The seven hazardous wastes  listed above occur at various




points within either  the  tanning  process or wastewater treatment




facilities.  Figure 1 is  a  generic process flow diagram which relates




the input materials and the solid wastes generated by the subprocesses




of a complete ("full  line") leather  tanning and finishing plant.   The




first three listed wastes,  namely the  trimmings, shavings and




buffing dust, are a product of  the tanning processes as shown in




Figure 1.  Figure 2 shows the various  waste sources and streams




resulting from in-plant controls, preliminary wastewater treatment




and end-of-pipe  treatment.   The general  waste control and treatment




scheme depicted  in Figure 2 is  a  generic control technology diagram




of the wastewater treatment methods  that serve as the basis for




proposed pretreatment standards of PSES  and BAT effluent limitations^)




The listed waste streams  present  in  this system are screenings and




sludges.  It is  noteworthy  that all  of the production and waste




treatment methods which are responsible  for the waste streams are




not always used  by a  single facility.   Hazardous waste streams are




described below.




        1.  Chrome (Blue)  Trimmings.   Blue trimmings are generated




            prior to retanning and  finishing when chrome tanned hides




            are hand trimmed to  remove  irregular pieces of hide which




            could disrupt  the  process machinery and which are not de-




            sired in the final product.  Blue trimmings contain ele-




            vated concentrations of chromium (2,200 to 21,000 mg/kg -




            wet weight)^1) and are  approximately 60 percent water by




            weight.
                                 -7/5"-

-------
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                                                 Setetna
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                                                    I U««levnt«r
                                                    I Screening*      j Uantcwatar
                                                    |                 , SludR«
uiiiiHiiiiiiiiniiiiiiKUiiueiiiiiiiiiiitMiuttiiiiiiiiiiiiiiitiiuitsstHUiiuiiiuiigiiateitiiiiii
                    TANVAKD
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 tlirotne
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  fluune
                                                                                    Equal I cation
                                                                                        and
                                                                                    Co«|ulatlon-
                                                                                    S*Jl»«ntatSon
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                                                                                                                                          Treatment
                                                                                                                                          (Ch«pp«l)
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                                                                        BAT WASTE COHTHOI.S. AMD EHl>-Or-PIPE TRKATMrMT

                                                                          FOB A Fin.L LINK CltROMK CATTLEII1DE TAHNERY

-------
2.   Chrome (Blue) Shavings.  Shaving adjusts the thickness of




    a split tanned hide or skin to generate a uniform product.




    This operation is accomplished mechanically and generates




    very small fibrous pieces of tanned hide which contain




    elevated concentrations of chromium (4,000 mg/kg - wet




    weight)'!'.  Chrome shavings also contain approximately




    60 percent water by weight.




3.   Buffing Dust.  Buffing dust is generated by mechanically




    sanding the leather to smooth or correct irregularities in




    the grain surface.  Buffing dust is usually collected in




    a dry form utilizing cyclone collectors and baghouses, al-




    though some dust may enter the process wastewater stream.




    Buffing dust contains significant concentrations of chromium




    and lead (as high as 22,000 and 924 mg/kg - wet weight, re-




    spectively)^'.  Lead originates from lead-based pigments




    in the finishing operation and possibly as impurities in process




    chemicals.   Because of the fine particle size and large




    surface area of the dusts, these elements are more sus-




    ceptable to leaching.




4.   Sewer Screenings.  Coarse and fine screens remove hair particles,




    wool, fleshings, trimmings (raw, chrome, unfinished) and other




    large particulates.  The chemical content of this waste




    is a function of the screen(s) location at the specific




    tannery.   Significant levels of chromium and lead (as high




    as 14,000 and 110 mg/kg - wet weight, respectively)^1) have




    been found in this waste, which ranges from 10 to 50 percent




    solids.

-------
         5.  Wastewater Sludges.   Sludges generated  from the  treatment of

             process wastewaters are typically  slurries  of  from 2  to  3

             percent solids.  In some instances,  these sludges  are de-

             watered to achieve from 12  to 50 percent solids  prior to

             ultimate disposal.  The three principle types  of dewatering

             equipment are centrifuge, vacuum filter, and pressure filter

             such as plate and frame or  belt press.  Sludge drying beds

             are also used where on-site land is  available.   Heavy metals

             and/or sulfides have been found in these sludges.

         As described above, wastewater  sludges are classified as being

either toxic wastes, reactive wastes, or toxic and reactive wastes.  Sludges

generated by tanneries which utilize the chrome tanning  process and tanner-

ies which utilize only retan-wet finishing processes have been found

to be toxic (T) because of heavy metal (i.e., chromium and lead) content.

         Sludges generated by tanneries which utilize the chrome tanning

process and which also unhair using concentrated depilatory (sulfide

containing) solutions are considered toxic and reactive  because they

contain, in addition to toxic chromium and lead, sulfides which, under

acidic conditions, may react to release poisonous hydrogen sulfide

gas.  Vegetable tanneries which use depilatory solutions also generate

sludges which are also reactive.

         In general, cattlehides are received with the hair attached to

the hide.  Prior to tanning, the hair is removed.  Hair  removal is usual-

ly accomplished by dissolving the material using depilatory (unhairing)

chemicals.   Chemicals used are commonly lime and  sodium  sulfide or

sodium sulfhydrate.  Concentrated depilatory chemical solutions dis-
                                 -yf-
                                 -718-

-------
 solve the hair within a few hours.  The hair may be saved by using

 less concentrated chemical solutions followed by mechanical removal.

     D.  Waste Management

         Based on a study completed prior to the adoption of the Re-

 source Conservation and Recovery Act of 1976, approximately 25 percent

 of the hazardous waste generated by leather tanneries and finishers is

 disposed of in the open'1).  Waste dumped in the open may or may not

 be burned.  This type of facility is relatively uncontrolled, uncovered,

 and little if any attempt is made to protect the environment.  Approxi-

 mately 60 percent of the hazardous waste is disposed of in landfills^) >

 with  about 10 percent of the landfilled material being disposed in sani-

 tary landfills^1).

         Certified hazardous waste disposal facilities accept only 6

 percent of the hazardous waste generated by tanneries.*  Seven percent

 of the wastes are disposed in lagoons, trenches, pits, and ponds, and

 the remaining 2 percent is spread on the land as a soil conditioner or

 amendment(^).

         At least three POTWs, which receive a large portion of

 their wastewaters from tanneries, are known to utilize incineration

 or a similar high temperature and pressure oxidation process to

 manage alkaline chromium bearing wastewater treatment sludges.   It

 is known that the processes can either partially or completely oxidize

 chromium from the trivalent form to the hexavelent form^3'.   Recovery

 of hexavalant chromium from these oxidized residues is technically feasible.


*The  facilities defined in the report as "certified hazardous waste dis-
 posal facilities" do not necessarily meet the §3004 requirements
 such  that  they may or may not be permitted as hazardous waste disposal
 facilities without some modification.

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IV.  HAZARDS POSED BY THE WASTE

     A.  Concentrations and Quantities of Hazardous Constituents

         in the Waste Streams

         Samples of wastes which are listed as hazardous were digested

and analyzed to determine the total content of the two heavy metals

present in each sample^'.  The hazardous constituents found to

be present in the waste streams are listed below:
Waste Stream

Chrome (blue)
  trimmings

Chrome (blue)
  shavings

Buffing dust
Sewer screenings
Wastewater treatment
 residues (sludges)
No. of
Samples

  10
  12
  17
  27
 Hazardous
Constituents

    Cr
               Cr
    Cr
    Pb

    Cr
    Pb

    Cr
    Pb
      Mean
  Concentration
(Wet Weight  mg/kg)

       7,600
                        4,000
       5,700
         150

       2,200
          30

       3,700
          60
     Additionally, the results of analyses of 16 sludge samples

obtained from two tanneries and four POTWs (which have tanneries

as the major flow contributors) are listed below(4):
                                  -vt-
                                  -71O-

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   CONCENTRATIONS  OF  CHROMIUM AND LEAD IN WASTEWATER SLUDGE SAMPLES
           MEAN CONCENTRATION (mg/kg - DRY WEIGHT BASIS)

Element        T-l        T-2      POTW-1    POTW-2    PQTW-3   POTW-4

Chromium    13,800     5,200      2,750    5,650     6,050    9,350
Lead           160       110         70      100        46       51
     Estimates  of  the total quantities of these heavy metals generated

in tannery wastes  have been computed and are shown below:


             HAZARDOUS CONSTITUENT (METRIC TONS/YEAR) (1)


Year                        Chromium                      Lead

1977                             851                      10.1
1983                           1,106                      12.5

         Tanneries with unhairing operations also generate wastewater

treatment sludges  which are reactive due to their sulfide content.

The waste material (sludge) removed from this process wastewater by

treatment contains relatively high concentrations of sulfide and, if

subjected to  an acidic environment, may generate highly toxic concen-

trations  of hydrogen sulfide gas.  Concentrations of sulfide in the

raw wastewater  of  tanneries belonging to subcategories hair pulp/

chrome  tan/retan/wet finish;  hair save/chrome tan/retan/wet finish;

hair save/non-chrome tan/retan/wet finish;  and through-the-blue had

mean concentration of 64,  20, 68 and 118 mg/1, respectively.  Sulfide

concentrations  up  to 680 mg/1 have been reported for subcategory

through-the-blue(3).  This waste thus exhibits the criteria of

reactivity (see §261.33(a)>C1)>(v)).

-------
          Samples of wastewater treatment sludges were obtained from

 a  POTW,  with over 90 percent contribution from a tannery with unhair-

 ing  operations,  and analyzed to determine the constituents which can

 contribute  to the generation of hazardous gases under reactive conditions

 in a disposal site.  Analytical results are listed below:
                           Constituent (mg/1)  (12)
    Sample

 Combined sludge

 Secondary  sludge
Sulfide

  730

   47
Sulfate

  465

  995
Sulfite

   21

  trace
      B.  Propensity for  the  Constituents  to  Migrate  from  the Wastes

         Samples  of process  wastes  and wastewater  treatment sludges

were  collected  by EPA  during the  period of December,  1979 through

February,  1980  and,  using  the acetic  acid extraction procedure (EP),

the extracts were analyzed for the  toxic heavy metals chromium and

lead.  Analytical results  for sample  sets from five  plants are listed

below.
Waste
Stream
Chrome Trimmings
Chrome Shavings

Buffing Dust
Screenings
Wastewater Treatment
  Sludges
   Hazardous       Number of
   Constituent    Samples
              Range and  Mean of
              Concentrations Found
              in Extracts  (mg/1)
Cr
Pb
Cr
Cr
Pb
Cr
Cr
9
3
5
4
1
2
10
Range
3.6 - 190
0.53 - 1.17 '
2.15-152
2.96 - 28.7
3.7
14.8 - 23.0
1.15 - 1,740
Mean
46.3
0.78
36.8
12.1
18.9
190
                                 -72.J-

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     These  data indicate that highly elevated concentrations of




 chromium, as  well as elevated concentrations of lead, can be leached




 from these  wastes.  These constituents are orders of magnitude above




 the National  Interum Primary Drinking Water Standard, and thus




 strongly indicate a potential to migrate in harmful concentrations.




 In fact, in most cases, extract levels would fail the toxicity




 characteristic and require irrevocable inclusion in the Subtitle




 C management  system.




         The  Tanners' Council of America also conducted leaching tests




 of various  chromium containing solid wastes.  These tests which used




 distilled water as the leaching solution indicated that 200 to 400




 mg of trivalent chromium is released from 1 kg of trimmings and




 shavings in periods ranging from 24 to 72 hours(•*•'.  Other research




 has shown that chromium is ""relatively unaffected by most organic




 acids,  but  is solubilized slowly by acetic acid(->).  Acetic acid




 is a major  product of anaerobic digestion processes within refuse




 containing  landfills, comprising an estimated 30 to 60 percent of




 the total organic acid produced^^^.  These two studies suggest




 that chromium could be leached out of the waste material in harmful




 concentrations following realistically occur ing types of land disposal.




     C.   Possible Pathways of Exposure of Improperly Managed Waste




        As previously mentioned,  use of both distilled water and acetic




acid extraction test data indicates that lead and chromium may leach




from these  waste in harmful concentrations unless the wastes are properly




managed.  As  a result,  these wastes may leach harmful concentrations of




the  metal constituents  even under  relatively mild environmental
                                 -723-

-------
conditions  (i.e., monodisposal) .   If  these wastes  are  exposed  to

strongly acidic disposal environments,  for example  disposal  environ-

ments subject to acid rainfall,  these  acid concentrations  in  leachate

would be higher since these metals  are more soluble in  acid  than in

distilled water.  Strongly acidic conditions are also created if

these wastes are co-disposed with other concentrated acid  wastes

or slurries resulting from the process.

     Incineration or similar high temperature and  pressure heat

treatment and destructive oxidation technologies are known to

oxidize chromium from the trivalent form to the hexavalent form'^).

Uncontrolled disposal of these sludges  can lead to serious and

prolonged contamination of groundwater  and surface water.  An

alternate to disposal of these sludges is recovery of the hexavalent

chromium for subsequent^ eduction and  reuse in the tanning process.

Recovery and reuse is technically feasible and is under study within

the industry.

         The Agency thus believes that  these toxic metals may pose  a

threat of serious contamination to groundwater unless proper waste

management is assured.  These wastes do not appear to be properly

managed at the present time.   Present industry practice of

disposing of these wastes in the open  (25%) or in inadequate land-

fills (60%), lagoons, trenches, pits,  ponds,  or by landspreading is

not environmentally sound.  These disposal sites are relatively

uncontrolled and unsupervised.

         The Agency is also concerned  that the lagooned wastes could
                                 -vf-
                                -72.4-

-------
contaminate surface waters if not managed to prevent flooding or total
washout.
         Another pathway of concern is through airborne exposure to
lead and  chromium particles escaping from buffing dust.  These particles
could escape when the waste is piled in the open, or placed in insecure
landfills.
         As previously mentioned, when forms of sulfur such as
sulfide and sulfate are subjected to an acid environment, they may
generate  highly toxic concentrations of hydrogen sulfide gas.  Hydrogen
sulfide gas is an irritant to the eyes and lungs in lower concentra-
tions of  exposure, and is highly toxic with inhalation in higher
concentrations.
         Additionally, should lead and chromium escape from the disposal
site, they  will persist in.,, .the environment for virtually indefinite per-
iods, since they are elemental metals.
     D.   The Large Quantities of these Generated Wastes are a Further
         Factor Supporting a T Listing of These Wastes
         The Agency has determined to list six of the waste streams
from the  leather tanning and finishing industry as a T hazardous waste
on the basis of lead and chromium constituents, although these consti-
tuents are  also measurable by the E toxicity characteristic.   Moreover,
in some cases,  concentrations of these constituents in an EP extract
from waste  streams from individual sites might be less than 100 times
interim primary drinking water standards although the Agency's own
extraction  data suggests that extract concentrations may exceed the
lOOx benchmark for some generators.   Nevertheless, the Agency believes


                                 -yf-
                                -725"-

-------
that there are factors in addition to metal concentrations  in leachate

which justify the T listing.  Some of these factors already have

been identified, namely the high concentrations of lead and chromium

in actual waste streams, the non-degradability of these substances,

indications (including damage incidents described below) of lack of

proper management of the wastes in actual practice, and the reactivity

hazard for certain wastes.

         The quantity of these wastes generated is an additional

supporting factor=  As previously indicated, the leather tanning and

finishing industry waste streams are generated in very substantial

quantities, and contain high concentrations of lead and chromium.

(See pp. 13 and 14 above.)  Large amounts of each of these metals

are thus available for potential environmental release.  The large

quantities of these contaminants pose the danger of polluting large

areas of ground and surface wastes.   Contamination could also occur

for long periods of time, since large amounts of pollutants are

available for environmental loading.   Attenuative capacity of the

environment surrounding the disposal  facility could also be reduced

or used up due to the large quantities of pollutants available.  All

of these considerations increase the possibility of exposure to the

harmful constituents in the wastes,  and in the Agency's view, support

a T listing,

     E.  Damage Incidents

         Contamination of groundwater has been reported at two sites in

Maine as a result of the uncontrolled land disposal of tannery solid wastes.
                                 -yt-
                                 -726-

-------
 At one  site,  monitoring wells at two separate disposal locations were
 found to  contain elevated chromium concentrations.  A land disposal
 site located  adjacent  to a tannery had been used for several years for
 the disposal  of  beamhouse sludge, trimmings, shavings and spent
 tanning agent.   Chromium concentrations of 0.25 and 0.084 mg/1 were
 reported  in a well  approximately 700 ft from the disposal area.
 Wastewater treatment sludge,  also containing chromium, which was
 disposed  at a municipal landfill, has contaminated a monitoring well
 located 200 ft from the disposal site.   Concentrations of chromium
 as high as 0.83  mg/1 have been reported in this wellW.
          At a second open land disposal site in Maine, large quantities
 of sludge have been received  since 1973 from  a primary treatment  fa-
 cility  at a tannery.   Testing of adjacent  groundwater was done in  1974
 after complaints  from  nearby  property owners.   Results showed traces
 of chromium were  present  in the groundwater while  surface water of
 the adjacent  property  has  been contaminated to  an  unknown extent^).
         In the Johnstown-Gloversville  area of  New York,  plumes of
 contaminated  groundwater have been identified adjacent to  each of
 two  landfill  sites  receiving  wastes  from a  large number of tanneries
 in  the area.   While chromium  has  not  yet been found in the ground-
 water, the sites have been closed due to contamination of  city wells
 near one site and stream contamination  from runoff  at  the  other  site(°'.
 V.   HAZARD  ASSOCIATED WITH LEAD,  CHROMIUM,  AND HYDROGEN  SULFIDE
     A.   Hazards  Associated with Lead and Chromium
         The  lead and chromium  that may  migrate from  the wastes  to  the
environment as a  result of improper disposal practices are heavy metals

                                 -yS-
                                 -727-

-------
that persist in the environment in some form and,  therefore, may

contaminate drinking water sources for long periods of  time.

Chromium is toxic to man and lower forms of acquatic life.  Lead

is poisonous in all forms.  It is one of the most  hazardous of the

toxic heavy metals because it accumulates in many  organisms, and its

deleterious effects are numerous and severe.  Lead may  enter the human

system through inhalation, ingest ion or skin contact.   Improper man-

agement of these wastes may lead to ingestion of contaminated drink-

ing water.  Aquatic toxicity has been observed at  sub-ppb levels.

Additional information on the adverse health effects of chromium and

lead can be found in Appendix A.

         The hazards associated with lead and chromium have been

recognized by other regulatory programs.   Lead and chromium are listed

as priority pollutants in-accordance with §307 of  the Clean Water

Act of 1977.  National Interim Primary Drinking Water Standards have

been established for both parameters.   Under §6 of the Occupational

Safety and Health Act of 1970, a final standard for occupational ex-

posure to lead and chromium has been established and promulgated in

19 CFR 1910.1000(8>9).  Also, a national ambient air quality standard

for lead has been announced by EPA pursuant to the Clean Air Act^°'.

In addition, final or proposed regulations of the  states of California,

Maine, Massachusetts, Minnesota, Missouri, New Mexico, Oklahoma and

Oregon define chromium and lead containing compounds as hazardous

wastes or components thereof^).
                                 -yt-
                                 -72S-

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    B.  Hazards Associated with Hydrogen Sulfide Gas




        As a result  of  the presence of sulfide, two wastewater treat-




ment sludges are being listed as reactive.   When sulfide and sulfate




are subjected to an acid environment they can react and generate




hydrogen sulfide gas.  Thus, present industry disposal practice,




particularly in lagoons  and landfills,  are insufficient to prevent




such an occurence.  For  this reason, the hazards associated with




contacting hydrogen sulfide gas are presented below.




        Hydrogen  sulfide gas is extremely irritating to the eyes and




mucus  membranes and highly toxic via inhalation.  Low concentration




of hydrogen sulfide,  in  the range of 20-150 ppm, causes irritation  of




the eyes, while slightly higher concentrations may cause irritation




of the upper respiratory tract, and if  exposure is prolonged,  pulmonary




edema  may result.  With  higher concentration the action of the gas




on the nervous system becomes more prominent.  A thirty minute exposure




to 500 ppm results in headaches, dizziness, excitement, staggering,




gait,  diarrhea, and dysurta, followed sometimes by bronchitis  or




bronchopneumonia.  Hydrogen sulphide asphyxiant action is due  to




paralysis of respiratory center^




        Repeated  exposures to low concentrations will result  in




conjunctivitis, photophobia, corneal bulge, tearing, pain and




blurring vision.   Exposure to high concentrations results in immediate




death(10).
                                 -731-

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                             REFERENCES



1.  Assessment of Industrial Hazardous Waste Practices  - Leather


    Tanning and Finishing Industry.  U.S. EPA, Office of Solid Waste,


    SCS Engineers, Inc.  EPA Contract Number 68-01-3261, November 1976.


2.  Economic Impact Analysis of Proposed Effluent Limitations Guide-


    lines, New Source Performance Standards and Pretreatment Standards


    for the Leather Tanning and Finishing Industry, U.S. Environmental


    Protection Agency, Report No. 440/2-79-019, July 1979.


3.  Development Document for (Proposed) Effluent Limitations Guidelines


    and Standards for the Leather and Finishing Point Source Category,


    U.S. Environmental Protection Agency, Report No. 440/1-79/016,


    July 1979.


4.  Correspondence from Clarence L. Haile, Program Manager, Survey


    and Assessment, Midwest Research Institute, to Donald Anderson,


    Project Officer, Effluent Guidelines Division, U.S.  Environmental


    Protection Agency.  EPA Contract No. 68-01-3861, Task 7, MRI


    Project No. 4436-L^7), "Analytical Data for Tannery/POTW Samples".


    October 10, 1979.


5.  Chromium, National Academy of Sciences, Washington,  D.C. 1974.


6.  Telephone conversation between Arthur Day (Maine, Department of


    Environmental Protection) and Peter Maher (Edward C. Jordan Co.,


    Inc.,  Portland, Maine) on January 25, 1980.


7.  Unpublished data, open file, U.S. EPA, 1979.


8.  Telephone conversation between Bud Golden (New York State Dept.  of


    Environmental Conservation, Warrensburg, NY) and Donald F. Ander-


    son (EPA, Effluent Guidelines Div., Washington, D.C.) on March 5,  1980.
                                -vf-
                                -730-

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 9.  U.S. EPA Regulations Files, January, 1980.




10,  Sax, H. Irving.  Dangerous Properties of -Industrial Materials.




    Van Norstand Reinbold Co., New York, 1979.




11.  Background Document 261.24, Extraction Procedure Characteristic.




12.  Correspondence from David B. Erty, E. C. Jordan Co., to




    Donald F. Anderson, Effluent Guidelines Div., EPA,  "Hartland,




    Maine POTW Sludge  Analysis.  Leather Tanning and Finishing




     Industry," March 10,  1980.
                                 -73/-

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          Comments - Leather Tanning and Finishing Industry
A number of comnienters argued that the background document issued on

January 8, 1979 which was used by EPA to support the four waste

streams listed from the leather tanning and finishing industry was

based on inadequate data (i.e., the only data presented in the

background document was taken from a report prepared by SCS Engineers,

Inc. entitled, "Assessment of Industrial Hazardous Waste Practices:

Leather Tanning and Finishing Industry" to which the Tanner's Council

of America has previously objected).


Since the end of the comment period (March 16, 1979), the Agency has

collected additional data (i.e., extraction data, damage cases, etc.)

which support the listing and clarification of the waste streams

from the leather tanning and finishing industry; therefore, the

background document has been expanded to make a more compelling

case.  Comments will be accepted on this additional data.


Several commenters argued that the Interim Primary Drinking Water

Standard for chromium which is used in §250.13(d) of the proposed

regulation to identify "toxic wastes" should distinguish between

trivalent chromium and hexavalent chromium.*  These coramenters indicated

that in a study conducted by the Oak Ridge National Laboratory

(Reviews of the Environmental Effects of Pollutants III Chromium),

trivalent chromium was not found to be an environmental hazard.

Additionally, these comnienters indicated that when EPA promulgated
*Chromiuin was but one of fourteen constituents used in §250.13(d)
 (extraction procedure) in defining a toxic waste.

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 the Interim Standard for chromium in 1975, it responded as follows to




 comments  that  suggested that the Interim Standard should be applied




 only to hexavalent chromium:




     "The limit for chromium is based on the known toxicity of the




     hexavalent form.   Since this form is the one most likely to be




     found in  drinking water, and since the specified analytical




     detection method (atomic absorption spectrophotometry) does




     not  distinguish between the valence states, the MCL is for




     total chromium.  If part of the chromium present is in a lower




     valence state, the MCL provides the additional margin for




     safety."




 These same commenters pointed out that in Appendix II to §3004 of the




 proposed rules (43 FR 59019), hexavalent chromium was cited as the




 parameter used in the EPA Interim Primary Drinking Water Standards.




 Thus, these commenters suggested that the definition of toxic wastes




 in §250.l3(d)  should apply only to wastes which contain hexavalent




 chromium.






 The Agency does not disagree with the commenters with respect to the




 toxicity and environmental hazards posed by trivalent chromium.




 However,  the Agency has evidence which indicates that trivalent




 chromium will  oxidize to hexavalent chromium under certain conditions




 (such as  destructive oxidation of alkaline sludges noted .in the




 background document) which could then pose a serious hazard both to




human health or the environment (see the EP toxicity characteristic

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background document for a more detailed discussion).  With  respect




to Appendix II to the §3004 regulations, the Agency has corrected




this inconsistency in the final regulations.






A number of commenters argued that the chromium found in the waste




sludge was in such an insoluble form that it would not migrate out of




the waste to present an environmental problem.  Monitoring  data was




provided by several commenters to support their argument.






The Agency disagrees with the commenters contention.   The monitoring




data provided in the comment letters already indicates that groundwater




contamination has occured.  For example, at the segregated  landfill




in Michigan, which one commenter included as an example in his




comments, the concentration of total chromium found in the ground-




water at just 50 feet from the site was 0.10, 0.14, 0.17 and 0.20




mg/1, all above the drinking water standard and indicating groundwater




contamination (the drinking water standard for total  chromium is 0.05




mg/1).   At further distances from the site the level  of chromium was




lower «0.04 mg/1), however, the Agency's concern is  that the




chromium will move as a slug (i.e., no dilution) and  eventually




contaminate groundwater at greater distances from the landfill.




Additionally, as demonstrated in the background document, two




disposal sites in the Johnstown-Gloversville area in  New York, known




to have accepted large quantities of tannery wastes have been closed




due to  contamination of city wells near one site and  stream contamina-




tion from run-off at the other.   Therefore, the Agency believes that




there is sufficient probability that the contaminants in the tannery

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the Interim Standard for chromium in 1975, it responded as follows to




comments  that  suggested that the Interim Standard should be applied




only to hexavalent  chromium:




     "The limit for chromium is based on the known toxicity of the




     hexavalent form.   Since this form is the one most likely to be




     found in  drinking water, and since the specified analytical




     detection method (atomic absorption spectrophotoinetry) does




     not  distinguish between the valence states, the MCL is for




     total chromium.  If part of the chromium present is in a lower




     valence state, the MCL provides the additional margin for




     safety."




These same commenters pointed out that in Appendix II to §3004 of the




proposed  rules (43  FR 59019), hexavalent chromium was cited as the




parameter used in the EPA Interim Primary Drinking Water Standards.




Thus, these commenters suggested that the definition of toxic wastes




in §250.l3(d)  should apply only to wastes which contain hexavalent




chromium.






The Agency does not disagree with the commenters with respect to the




toxicity  and environmental hazards posed by trivalent chromium.




However,  the Agency has evidence which indicates that trivalent




chromium  will  oxidize to hexavalent chromium under certain conditions




(such as  destructive oxidation of alkaline sludges noted .in the




background document) which could then pose a serious hazard both to




human health or the environment (see the EP toxicity characteristic

-------
background document for a more detailed discussion).  With  respect




to Appendix II to the §3004 regulations, the Agency has corrected




this inconsistency in the final regulations.






A number of cominenters argued that the chromium found in the waste




sludge was in such an insoluble form that it would not migrate out of




the waste to present an environmental problem.  Monitoring  data was




provided by several commenters to support their argument.






The Agency disagrees with the commenters contention.  The monitoring




data provided in the comment letters already indicates that groundwater




contamination has occured.  For example, at the segregated landfill




in Michigan, which one commenter included as an example in his




comments, the concentration of total chromium found in the ground-




water at just 50 feet from the site was 0.10, 0.14, 0.17 and 0.20




mg/1, all above the drinking water standard and indicating groundwater




contamination (the drinking water standard for total chromium is 0.05




mg/1).   At further distances from the site the level of chromium was




lower «0.04 mg/1), however, the Agency's concern is that the




chromium will move as a slug (i.e., no dilution) and eventually




contaminate groundwater at greater distances from the landfill.




Additionally, as demonstrated in the background document, two




disposal sites in the Johnstown-Gloversville area in New York, known




to have accepted large quantities of tannery wastes have been closed




due to  contamination of city wells near one site and stream contamina-




tion from run-off at the other.   Therefore, the Agency believes that




there is sufficient probability that the contaminants in the tannery
                                         -

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waste, especially chromium, will migrate out and escape into the




environment  so  as to present a potential hazard to human health or




the environment.







Several  commenters objected to the Agency's listing of the four tannery




waste streams for lead.   These commenters argued that the background




document magnified the industries use of lead.  These commenters




pointed  out  that  tanneries do not use lead compounds in the wet work




processes including the  bearnhouse, the tanning department, and the




retan/color/lubrication processes; small quantities of insoluble




pigments containing lead are used in the finishing department of




certain  tanners.   The commenters went on to say that the use of lead




in the leather  tanning and finishing industry has declined in recent




years due to restrictions on the use of these pigments, due to leather




style changes and due to industry volume decline resulting from the




import/export situation  in the hide, leather and leather products




industry.






As presented in the Leather Tanning and Finishing Industry Listing




Background Document, lead has been found present in the buffing




dust, sewer  screenings,  and two listed wastewater treatment sludges




(sludges listed separately because some contain sulfides and are




therefore listed  as reactive).  The designated subcategories that




produce  these waste streams are as follows:  hair pulp/chrome tan/




retan/wet finish;   hair  save/chrome-tan/retan/wet finish;  retan/




wet finish;   no beamhouse;  through-the-blue;  and shearlings (only




sewer screenings  and wastewater sludges include this subcatagory).

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Clearly, the subcategory  "hair  save/  non-chrome  tan/  retan/wet




finish" is not included as  one  of  the processes  used  by an industry




that produces these  lead  contaminated wastes.  It  is  noteworthy,  in




response to a particular  claim  made in an  industry comment,  that




the subcategory  "no  beamhouse"  is  properly included because  facilities




using this process would  generate  lead-contaminated wastes.






From the data presenting  the concentrations of lead and  chromium




in the four wastestreams, the Agency  is aware that  lead  appears in




concentrations considerably less than that of chromiuim.   But, a




consideration of the data from  the acetic  extraction  procedure (EP)




performed by the Agency in December 1979 through April 1980, will




reveal the leachability of the  inorganic compounds  (namely,  lead and




chromium) found  in the wastestreams.   Lead, as well as chromium, was




found to leach from  the waste in noteworthy concentrations (i.e.,  75




times the NIPDWS for lead).  Therefore, harmful concentrations of




these heavy metals may leach from  the  waste unless  these wastes are




properly managed.  As a result, if these wastes are exposed  to more




acidic disposal  environments, for  example  disposal  sites where




other strongly acid  industrial wastes  are  disposed, or environments




subject to acid  rainfall, these metals' concentrations in  leachate




would be higher, since these metals are more soluble  in  acid than




distilled water.  The quantity of waste lead generated annually,




and the indications of actual waste mismanagement by  the industry

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further  support  listing on this basis.  Therefore, lead constitutes




a potential  health hazard as a constituent which is present in these




improperly managed wastes, and the Agency believes, should be managed




as such.

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Iron and Steel Industry

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                 LISTING BACKGROUND DOCUMENT
                    •


                            COKING


 Ammonia  Still  Lime  Sludge (T)


 I.   Summary of  Basis  for Listing

     Ammonia still  lime sludge is generated when by-products

 are recovered  from  coke oven gases.  The Administrator has

 determined  that  ammonia still lime sludge may pose a  present

 or potential hazard to human health or the environment when

 improperly  transported, treated, stored, disposed of  or

 otherwise managed,  and therefore should be subject to appropri-

 ate management requirements under Subtitle C of RCRA.  This

 conclusion  is  based on the following considerations:

 1.   These  sludges  contain the hazardous constituents cyanide,
     naphthalene, phenolic compounds, and arsenic which adhere
     to  the lime floes and solids in significant concentrations

 2.   Cyanide and phenol leached in significant concentrations
     from an ammonia  still lime sludge waste sample which was
     tested by a distilled water extraction procedure.
     Although  no leachate data is currently available for
     naphthalene and  arsenic, the Agency strongly believes
     that based  on  constituent solubilities, the high concen-
     tration of  these  constituents in the wastes, and the
     physical nature  of the waste, these two constituents
     are likely  to  leach from the wastes in harmful concentra-
     tions  when  the wastes are improperly managed.

 3.   It  is  estimated  that a very large quantity, 963,000
     tons (1), of ammonia still lime sludge (5% solids by
     weight) is  currently generated annually, and that this
     quantity will  gradually increase to 1.45 million tons (5%
     solids by weight) per year as the remaining coke plants
     add fixed am/nonia removal capability to comply with BPT
     limitations (1).   There is thus the likelihood of large-
     scale contamination of the environment if these  wastes
     are not managed  properly.

4.    Coke plant  operators generally dispose of these  sludges
     on-site in  unlined sludge lagoons or in unsecured land-
     fill operations.    These management methods may  be in-

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     adequate to impede  leachate  migration*.

  '  Industry Profile and Process  Description

     The stripping of ammonia  during  the  by-product cokemaking

process is currently practiced at  39  facilities,  distributed

across 17 different states, with  about  half  of  the operating

plants located in Pennslyvania, Ohio  and  Alabama  (1).   These

plants are currently producing 45,000,000 tons  of coke  per

year (1).  (Coke, the residue  from the  destructive distillation

of coal, serves both as  a fuel and as a reducing  agent  in  the

making of iron and steel.)  Of the 39 plants  which practice

ammonia recovery, 31 use lime, generating, in the process, an

ammonia still lime sludge.**

     During the recovery of chemical  by-products  from the

cokemaking process, excess ammonia liquor is  passed  through

stills to strip the NH3  from solution for recovery as ammonium

sulfate, phosphate or hydroxide.   About half  of the  ammonia

originally present (5,000 mg/1) strips  readily, but  the

remaining fraction can only be recovered  by elevating the pH
 *Although no data on the corrosivity of ammonia  still  lime
  sludge are currently available, the Agency believes that
  these sludges may have a pH greater than  12.5 and  may,  there-
  fore, be corrosive.  Under §§261.22 and 262.11,  generators of
  this waste stream are responsible  for testing their waste in
  order to determine whether their waste is corrosive.

**Eight plants currently use sodium  hydroxide  as  their  alkali
  and produce about 1/5 of the sludge volumes  common to  lime
  systems (1). These eight plants tend to be smaller in  capacity,
  with lesser volumes of process wastewater to  treat. The Agency
  believes that this sludge will be  similar in  composition  to the
  ammonia still lime sludge, and plans on collecting additional
  data to determine whether this waste should  also be listed.
                               -7VO-

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Of the waste  liquor to 10-12 through  the  addition of  lime,




and passing additional steam through  the  solution.  This




stripping  transfers some of the contaminants  to  the gas stream,




but enough remains behind for the lime  sludges  to contain  high




levels of  hazardous constituents (i.e., cyanide,  naphthalene,




phenol and arsenic; see page 6, following).



II,  Waste Generation and Management




     Ammonia  still lime sludge is generated in  the recovery




of ammonia, by the addition of lime,  from  coke  manufacturing




operations.   Currently it is estimated  that 963,000 tons of




ammonia  still lime sludges (5% solids by  weight)  are  generated




annually,  and this amount will gradually  increase to  about




1.45 million  tons per year as the remaining coke  plants add




fixed ammonia removal capabilities  to comply  with BPT




limitations (1).   Based on process  wastewater analytical




data at  9  coke-making plants, an estimated industry total




of 1,468 tons (dry weight) of cyanide,  naphthalene, phenolic




compounds, and arsenic result each  year from  ammonia  still




lime sludges  (1) .



     Cyanide, naphthalene, phenol and other organic constituents




are formed as a result of the destructive  distillation  of




coal and are  present in the ammonia liquor.   Arsenic, on the




other hand, is present along with other naturally.occuring




metallic contaminants in the coal and is  also present in the




ammonia  liquor.  (Although other metals are present in  the




waste, only arsenic is deemed present in  sufficient concen-







                             -X-

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trations to present  a  problem  (1).)

     Review of the chemical  mechanisms,  pH and operating tem-

peratures at which the  ammonia  stripping process is conducted

indicates that cyanide, naphthalene,  phenol and arsenic tend

to remain relatively chemically unreactive in the ammonia

still stripping process.  As a  result,  the presence of these

four pollutants in the  ammonia  still  lime sludge is predictable.

     Sludges are typically settled out  in sedimentation basins,

from which settled material  is  periodically removed for

disposal (1).  Figure  1 presents  a process schematic of the

ammonia still recovery  process.

Current Disposal Practices

     Of the 39 ammonia  recovery operations,  approximately 30

plants presently dispose of  the  ammonia  still lime  sludges in

on-site unlined sludge  ponds.(1)  Lined  lagoons or carefully

controlled landfills have not been routinely used by the

industry to dispose of  these sludges  (1).

Hazardous Properties of the  Waste

     Using data collected by EPA  at coking operations  from the

process wastewater samples taken  before  and  after the  addition

of lime(l), an accounting of the  differences in pollutant mass

before and after the lime addition reveals that 13,640 ppm of

cyanide,  4,770 ppm naphthalene,  680 ppm  of phenols-* , and 1,086
*The mass of phenolic compounds  present  in  the  sludge is
 estimated and has been adjusted  for  partial  volatilization
 of the phenol in the stripper.

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                Cooling
                Jacket
                             DEPHLEGMAJOR V*	Cooling Waler

                                SECTION    9-	^Cooling Water Return
          E*ce«»
          Ammonia Liquor
          from Storage-
          (See Fig. I)
                                               To Ammonia Absorber
 I
•sj
a:
IA>
 i
               Steam-
         Fixed  Leg-
               Steam-
-Free  Lag
  LIME

  MIXER
«l	Lime Slurry

         Steam
                             AMMONIA  STILL
                                                                                WASTE  LIQUOR SETTLING  BASIN
                                                                            *»Wook Ammonia Liquor to
                                                                              Further  Treatment.

                                                                              Lime Still Sludge*
                                                                              Periodically  Removed
                                                                              (or Disposal.
                                                                                    Hazardous Woslo Source
                                                                                    Requiring  Controlled Disposal
                                                                                                                      ENVIRONMENTAL  PROTECTION AGENCY
                                                                                                                             STEEL  INDUSTRY  STUDY
                                                                                                                      BY-PRODUCT COKEMAKING OPERATIONS
                                                                                                                           HAZARDOUS WASTE  SOURCE
                                                                                                                          AMMONIA STILL LIME  SLUDGES
                                                                                                                                               FIGUR6

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ppm of arsenic  are  present  in  the ammonia still lime sludge.*

     A separate  study  of  ammonia  still lime sludge indicated

phenol and cyanide  concentrations ranging from 670 ppm to

1910 ppm for phenol and 343  ppm  to 1940 ppm for cyanide (2).

     Leaching tests (distilled water)  were also performed on

this waste sample.  Results  of these  test revealed leachate

concentrations  of 198  ppm for  cyanide  and 20 ppm for phenol

(2).

     The concentration of cyanide in  the leachate is far  in

excess of concentrations  in  water considered harmful to

human health and the environment.  For example, the U.S.

Public Health Service's recommended standard for cyanide  in

drinking water  is 0.2  mg/1 .  The  proposed EPA Water Quality

Criteria limits  the level of cyanide at 0.2  mg/1 and phenol

at 1 ppm for domestic  water  supply.**

     Although no leachate data is currently  available for  naph-

thalene and arsenic, the  Agency strongly believes that  these

constituents will leach in harmful  concentrations from  these

wastes if not properly managed.   Some  compounds of arsenic are

quite soluble.  Arsenic trioxide  has a solubility of 12,000

mg/1 at 0°C, and arsenic  pentoxide  has a solubility of  2,300 g/1

at 20°C (Appendix A).   The solubility,  the  high concentrations
 *These concentration figures are not  contained  in reference
  1 but are calculated using data contained  in  that reference.
**The Agency is not using these  standards  as quantitative
  benchmarks, but is citing them to  give  some  indication  that very
  low concentrations of these contaminants may  give rise  to a
  substantial hazard.
                             -X-

                                 -7H4-

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 Of arsenic  in the ammonia  still  lime  sludge and arsenic's ex-




 treme toxicity make it likely  that  it  will leach from the wastes




 in harmful  concentrations  (i.e.,  a  small quantity of arsenic




 is sufficient to present a  problem  to  human health and the




 environment)  if the wastes  are not  properly managed.  Naphthalene




 is water  soluble, with solubility ranging from 30,OOOyUg/l




 to 40,OOOyU.g/l.  The solubility  of  naphthalene in water and




 its presence  in such high  concentrations in the waste make




 it likely that it will leach from the  wastes in harmful




 concentrations if the wastes are  not  properly managed.




     In addition, cyanide,  phenol,  naphthalene and arsenic




 tend to remain chemically  unreactive  in  the ammonia still




 lime sludge.   Since lime is a  relatively porous substance,




 constituents  in the lime sludge  will  themselves therefore




 tend to be  released when the waste  sludge is exposed to




 a leaching  medium.




     As previously  discussed,  a  very  large quantity of ammonia




 still lime  sludge is produced  annually,  and is thus available




 for large scale contamination  of  the  environment.  Such large




 quantities  of waste likewise present  the danger of continued




 migration of  and exposure  to waste  constituents.  These wastes




 consequently  present a serious hazard  to human beings if not




 properly  managed.




     Current  practices of disposing of  these wastes in fact




appear  inadequate.    Disposal  of  ammonia still lime sludge in




unlined sludge lagoons or unsecured landfills (see p. 4 above)
                                 -T-l S-

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makes it likely  that  the  hazardous constituents in the wastes

will leach out and  migrate  into  the environment, possibly

contaminating drinking  water  sources.

     An overflow  problem  might  also be encountered if the

liquid portion of  the waste has  been allowed to reach too

high a level in  the lagoon; a heavy rainfall could cause

flooding which might  result in  the contamination of surface

waters in the vicinity.   Given  the large quantities of this

waste produced,  other types of mismanagement are likely to

result and to cause damage  to the  environment.

     As demonstrated  above, the  waste  constituents appear

capable of migrating  from the waste in harmful  concentrations.

The waste constituents  are  also  persistent,  and thus  have an

increased likelihood  of reaching an environmental  receptor.

Arsenic, as an element  will persist indefinitely in some

form.  Cyanides  also  tend to persist after  migration  (see

background document "Spent  or Waste Cyanide  Solutions and

Sludges" for further  information supporting  this conclusion).

Cyanide and phenols have  been implicated in  actual damage

incidents as well,  again  confirming the  ability of these

waste constituents  to be  mobile, persist, and  cause substantial

harm.  For example,

     A firm in Houston, Texas, as  early  as  1968, was  made
aware that its practices  of discharging  such hazardous wastes
as cyanide, phenols,  sulfides, and ammonia  into the Houston
Ship Channel was creating a severe environmental hazard.   The
toxic wastes in  question  were derived  from  the  cleaning of
blast furnaces from coke  plants.   According  to  expert testimony,
levels as low as 0.05 mg/1  of cyanide  effluent  are lethal to
shrimp and small fish.  The court  ordered the  firm to cease
discharging these wastes  into the  ship channel.  (EPA open files)

-------
     In  1971  a. newly drilled  industrial  well in an artesian
 aquifer  in  Garfield, New Jersey,  contained  water with an
 unacceptably  high concentration  of  phenolic materials.  The
 pollutants  originated from nearby industrial waste lagoons.
 (Draft Environmental Impact Statement, January, 1979).

     Fifteen  thousand drums of toxic  and corrosive metal
 industrial  wastes were dumped on  farmland in Illinois in
 1972.  As  a result, large numbers of  cattle died from cyanide
 poisoning  and nearby surface  water  was contaminated by runoff.
 (House Report Number 94-1491, 94th  Congress,  2nd Session,  page 19).


 Health and  Ecological Effects
 Cyani.de

     Congress listed cyanide as  a  priority  pollutant under

 §307(a) of  the Clean Water Act.

     The toxicity of cyanide has been  well  documented.

 Cyanide in  its most toxic form can be  fatal to  humans in a

 few minutes at a concentration of  300  ppm.   Cyanide is also

 lethal to  freshwater fish at concentrations as  low as about

 50 mg/1 and has been shown to adversely  affect  invertebrates

 and fish at concentrations of about  10 mg/1.

     The hazards associated with exposure  to  cyanide have

 also been recognized by other regulatory programs.   The U.S.

 Public Health Service established  a  drinking  water standard

 of 0.2 mg/1 as an acceptable level for water  supplies.  The

 Occupational Safety and Health Administration (OSHA) has

 established a permissible exposure limit for  KCN and NaCN at

 5 mg/m^ as  an eight-hour time-weighted average.

     Finally, final or proposed  regulations of  the states of

California,  Maine,  Maryland,  Mas sacuse t t s ,  Minnesota, Missouri,
                               -747-

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New Mexico, Oklahoma,  and Oregon define cyanide  containing

compounds as hazardous  wastes or components thereof.   Additional

information and  specific  references on the adverse  health

effects of cyanide  can  be found in Appendix A.

Phenol

     Congress designated  phenol a priority pollutant under

§307(a) of the Clean Water  Act.  Phenol is readily  absorbed

by all routes.   It  is  rapidly distributed to mammalian  tissues.

This is illustrated by  the  fact that acutely toxic  doses of

phenol can produce  symptoms within minutes of administration

regardless of the route of  entry.   Repeated exposures  to

phenol at high concentrations have resulted in chronic  liver

damage in humans. (3)   Chronic poisoning,  following  prolonged

exposures to low concentrations of the vapor or mist,  results

in digestive disturbances (vomiting, difficulty in  swollowing,

excessive salivtion, diarrehea),  nervous  disorders  (headache,

fainting, dizziness, mental disturbances), and skin erupt ions . (^ '

Chronic poisoning may  terminate fatally in some cases  where there

has been extensive  damage to  the  kidneys  or liver.

     Phenol biodegrades at  a  moderate rate in surface water and

soil, but moves readily.   Even with persistence of  only a few

days, the rapid spreading of  phenol could cause widespread

damage of the ecosystem and contamination of potable water
                                                   >
supplies .

     OSHA has set a TLV for phenol at 5 ppm.

     Phenol is listed in  Sax's Dangerous  Properties of

Industrial Materials as a dangerous disaster hazard because
                                -7S'8-

-------
when heated it emits  toxic  fumes.  Additional  information  and




specific references on  the  adverse effects of  phenol  can be




found in Appendix A.




Arsenic




    Congress has designated  arsenic as a priority pollutant




under Section 307(a)  of  the Clean Water Act.




    Arsenic is extremely  toxic in humans and  animals.




Death, in humans has occurred  following ingestion ,of very




small amounts (5mg/kg)  of  ttiis chemical.  Several epidemiolog-




ical studies have associated  cancers with occupational expoure




to  arsenic, including those of the lung, lymphatics and




blood.   Certain cases involving a high prevalence of  skin




cancer have been associated with arsenic in drinking  water,




while liver cancer has  developed in several cases following




ingestion of arsenic.   Results from the administration of




arsenic in drinking water or  by injection in animals  supports




the carcinogenic potential  of arsenic.




    Occupational exposure  to arsenic has resulted in




chromosomal damage, while several different arsenic compounds




have demonstrated positive  mutagenic effects in laboratory




studies.




    The teratogenicity  of  arsenic and arsenic compounds is




well established and includes defects of the skull, brain,




gonads,  eyes,  ribs and genito-urinary system.




    The effects of chronic arsenic exposure include  skin




diseases progressing to  gangrene,  liver damage, neurological

-------
disturbances,  red  blood  cell production, and cardiovascular


disease .


     OSHA has  set  a  standard air TWA of 500 mg/rn^ for arsenic.


DOT requires a "poision"  warning label.


     The Office of Toxic  Substances under FIFRA has issued a


pre-RPAR for arsenic.  The  Carcinogen Assessment Group has


evaluated arsenic  and  has determined that it exhibits sub-


stantial evidence  of carcinogenici t y .  The Office of Drinking


Water has regulated  arsenic under the Safe Drinking Water


Act due to its  toxicity and the  Office of Air  Quality Planning


and Standards  has  begun a pr e-r egulatory assessment of arsenic


based on its suspected carcinogenic effects.   The Office of


Water Planning  and Standards under  Section 304(a) of the


Clean Water Act  has  begun development of a regulation based


on health effects  other than on  oncogenicity and environmental


effects.  Finally, the Office  of  Toxic Substances has completed


Phase I assessment of  arsenic  under TSCA.   Additional informa-


tion and specific references on  the adverse effects of arsenic


can be found in  Appendix  A.


Naphthalene


     Naphthalene is designated a  priority pollutant under


Section 307(a)  of the  CWA.


     Systemic  reaction to acute  exposure to naphthalene

                                                   >
includes nausea, headache,  diaphoresis,  hematuria,  fever,


anemia,  liver damage,  convulsions and coma. Industrial


exposure to naphthalene appears  to  cause increased  incidence


of cataracts.  Also, hemolytic anemia with associated
                              -750-

-------
jaundice and occassionally renal disease  from  precipitated




hemoglobin has been  described in newborn  infants,  children,




and adults after  exposure to naphthalene  by  ingestion,




inhalation, or possibly by skin contact.




    OSHA's standard for exposure to vapor  for a  time-weighted




industrial exposure  is  50 mg/m^.




    Sax(^) warns  that naphthalene is  an experimental  neo-




plastic sub.stance :Via the  subcutaneous route;  that  is,  it




causes  formation  of,  non-metas tasizing abnormal or  new growth(s)




Additional information  and specific references on  the adverse




effects of naphthalene  can be found in  Appendix A.
                              -751-

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                          References

1.   Draft Development Document for Proposed Effluent
     Limitations Guidelines and Standards  for  the  Iron
     and Steel Manufacturing Point Source  Category;  By-
     product Cokemaking Subcategory.  Volume II, October
     1979.

2.   Calspan Corporation.  Assessment of Industrial  Hazardous
     Waste Practices in the Metal Smelting and Refining Industry.
     Appendices.  April 1977.  Contract Number 68-01-2604,
     Volume III, pages 97-144.  App. 12, 37.

3.   Merliss, R.R. Phenol Moras., Mus. Jour., Occup. Med.,
     14:55. 1972.

4.   Sax, N. Irving, Dangerous Properties of Industrial Materials,
     Fifth edition, Van Nostrand'Reinhold Co.,  1979

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                 LISTING BACKGROUND DOCUMENT

             ELECTRIC FURNACE PRODUCTION OF STEEL
Emission  control dusts/sludges from the electric
furnace production of steel*(T)
Summary  of  Basis  for Listing

     Emission  control dusts/sludges from the production  of

steel in electric furnaces are generated when particulate

matter in the  gases  given off by, electric furnaces during the

production  process  is removed by air pollution control equip-

ment. Dry  collection methods generate a dust; wet collection

methods  generate  a  sludge.  The Administrator has determined

that  these  dusts/sludges are solid wastes which may pose a

present  or  potential hazard to human health and the environ-

ment  when improperly transported, treated, stored, disposed

of or otherwise managed and therefore should be subject  to

appropriate management requirements under Subtitle C of  RCRA.

This  conclusion is based on the following considerations:

     (1)  The  emission control dusts/s ludges contain signifi-
         cant concentrations of the toxic heavy metals
         chromium,  lead,  and cadmium.

     (2)  Lead, chromium and cadmium have been shown to  leach
         in harmful concentrations from waste samples subjected
         to both a  distilled water extraction procedure and
         the  extraction procedure described in §250.13(d)
         of the  proposed  Subtitle C regulations.
*The listing description  has  been changed in response to a
 comment submitted by  the American Iron and Steel Institute
 that the previous listing was  incorrect.  The electric
 furnace process is used  for  steelmaking only, not iron and
 steelmaking, as was previously listed.
                               -7SE-

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       (3)  A  large  quantity  of  these wastes (a combined total
           of  approximately  337,000  metric  tons)  is generated
           annually  and  is  available for disposal.   There is
           thus  a  likelihood  of  large scale contamination
           of  the  environment  if these wastes  are mismanaged.

       (4)  The wastes  typically  are  disposed of by  being dumped
           in  the  open,  either  on-site or off-site, thus
           posing  a  realistic  possibility of migration of
           lead, cadmium,  and  chromium to underground  drinking
           water sources.  These metals  persist virtually
           indefinitely,  presenting  the  serious threat of
           long-term contamination.

       (5)  Off-site  dispos.al  of  these wastes will increase
           the risk  of mismanagement  during transport.

 I.    Profile  of the Industry

       The electric  furnace  (arc)  process  is one of  the three

 principal methods of  producing  steel in  the United States.

 In 1974, the  iron and steel  industry had the  capacity to

 produce approximately 27,000,000 metric  tons/year  of  steel

 via the electric furnace process (1).

      Plants are located  in 31 different  states,  with  70% of

 the estimated capacity  located  in Ohio,  Pennsylvania,  Illinois,

 Texas, Michigan and Indiana  (1).  A  typical integrated  electric

 furnace steel plant has  an electric  furnace capacity  of

 about 500,000 metric tons/yr (1).  Capacities  at different

 plants range from about  50,000  to 2,000,000 metric tons/yr (2).

II.    Manufacturing Process

      The raw materials  for the  electric  arc steelmaking

 process include cold iron and steel  scrap  and  fluxes,  such

 as  limestone and/or fluorspar.  The  raw materials  are  charged

 into  a refractory-lined  cylindrical  furnace and  melted  by
                              -75-4-

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 passing an  electric current  (arcing)  through  the scrap steel




 by  means  of  three triangularly spaced  carbon  electrodes




 inserted  through the furnace roof.  As  the  process proceeds,




 the electrodes  are consumed  at a rate  of  about  5 to 8  kg/kkg




 of  steel, with  the emission  of CO  and  CC>2  gases.  The  hot




 gases  entrain finely divided particulate,  70%  of which




 (by weight)  is  below 5 microns in  size, the majority of




 this being  less than 0.5 microns.  The  particulate fume or




 dust consists primarily of iron oxides, silica  and lime,




 with significant concentrations of the  toxic metals lead,




 chromium  and cadmium (1).




III.    Waste  Generation




      The  particulate produced during  the  electric furnace




 steelmaking  process is removed from the furnace  off-gases by




 means  of  baghouse fi1ters, electrostatic  precipitat ors,  or




 high-energy  Venturi scrubbers.  The baghouse filters and




 electrostatic precipitators, which are  used by  93% of  electric




 arc steelmaking furnaces, produce  an  emission  control  (dry)  dust




 for disposal at a rate of 12.8 kg  of  dust per metric ton of  steel




 produced.   Scrubbers, used by the  remaining 7%  of the




 steelmaking  industry, produce slurries  or sludges for  disposal




 at  a rate of about 8.7 kg (dry solids basis) per metric ton




 of  steel  produced.




     'Based on an electric furnace  steelmaking  capacity of




 27,000,000 metric tons/yr (see p.  2 above), and  assuming




 that the  electric furnaces that use dry air pollution  control

-------
 equipment represent 93%  of  that  capacity,  the industry-wide

 estimated quantities of  emission  control  dusts and sludges

 produced at full operating  capacity  are  321,000 metric tons/yr,

 and 16,000 metric tons/yr (dry solids  basis), respectively.

      The Agency has information  indicating that these wastes

 are typically dumped in  the  open  at  on-site or off-site

 disposal facilities (1,2).   The  emission  control sludges,

 however, are also amenable  to other  forms  of disposal,  such

 as disposal in lagoons or surface  impoundments.   The  large

 quantities of these wastes  generated annually,  combined with

 the fact that other emission control dusts/sludges  generators

 handle their wastes in this  manner, make  this type  of management

 situation plausible.  (See,  for example,  Secondary  Lead

 Hazardous Waste Listing  Background Document).

IV.   Hazardous Properties of the Wastes

      1.   Migrating Potential of Waste  Constituents

      An analysis of the  electric furnace dust supplied  by

 U.S.  Steel Corporation is given in Table 1  (3).   As the data

 indicate, two of the toxic heavy metal of  concern,  lead and

 chromium, are present in significant concentrations.   Lead, for

 example,  which has a usual range of lead-in-soil  concentrations

 of 2  to  200 ppm (4), is  present in this waste sample  at a

 concentration of 1,400 ppm.*
 *The absence of cadmium from the waste sample  described  in
  Table 1 may be attributable to the fact  that  29%  of  the
  constituents (by weight) of the waste sample  are  not  accounted
  for,  or the fact that the composition of  electric  furnace
  dust  can vary considerably depending on  the  type  and  quantity
  of  cold scrap used to charge the furnace.  Cadmium is  a  demon-
  strated waste constituent as evidenced by  its  presence  in
  significant concentrations in the leachate tests  on  electric
  furnace dusts shown in Table 2 below.
                             -75-4-

-------
    Another  analysis of waste samples  from both electric




furnace  dusts  and sludges also shows  lead  and chromium to be




present  in  the wastes in significant  amounts.  The analysis




of the emission control dust waste  sample  revealed chromium




to be present  at 1380 ppm and lead  to be present at 24,220




ppm.  The analysis of the emission  control  sludge revealed




chromium to be present in the waste at  2,690  ppm and lead at




7,900 ppm  (-1).




     The presence of such high concentrations of lead and




chromium in this waste stream, in and of itself,  raises




regulatory  concerns.  Furthermore,  the  Agency has data (see




table 2, p. 8) from the proposed EPA Extraction  Procedures




(Samples 1-4)  and an industry-conducted water extraction




(Sample  5)  which show that lead, chromium  and cadmium may




leach from  electric furnace dusts in  significant concentrations




All of the  waste extracts--either by  the EPA  EP  which uses




acetic acid as its leaching solution, or by the  industry




test which  uses - disti lied water--contain contaminants in




concentrations which are either equal to or,  for the most




part, exceed  EPA's National Interim Primary Drinking Water




Standards,  in  some instances by several orders  of magnitude.




The distilled  water extraction shown in Sample  5  of Table 2




indicates that these wastes may leach harmful concentrations




of lead, cadmium,  and chromium even under  relatively mild




conditions .
                            -75-7-

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                            Table  1


           Composition  of  an  Electric  Furnace Dust*


     Parameter                          Weight %  (not  intended  to
                                                  total 100%)

     Fe  (total)                          35.34

     MnO                                 :8.29

     Si02                                 5.61

     A1203                                0.62

     CaO                                 12.01

     Cr203                                2.69

     CuO                                  0.12

     Ni                                   0.59

     Pb                                   0.14

     Zn                                   0.39

     F                                    5.09


                               Total     70.89


     Source: Reference  3
     *Although the data in Table  1  is  presented  for  the
electric furnace dusts collected  by baghouse  filters  or
electric precipitat ors and not  for  the  sludges produced
by Venturi scrubbers, the solids  composition  of  the  sludges
produced by scrubbers can be assumed  to be  virtually  the  same
as that of the electric furnace dusts  since both wet  and  dry
air pollution systems entrain the same  heavy  metal  particulate

-------
     This  conclusion is further  supported  by different




solubility tests done on electric  furnace  emission control




dust  waste samples, also using water  as  the  leaching medium




(1).   In  this  test, lead was again  found  to  leach at dangerous




concentrations like 150 ppm.  Another  water  solubility test




done  on  an electric furnace sludge  waste  sample  likewise




showed chromium and lead to leach  from the  sludge in signifi-




cant  concentrations of 94 ppm and  2.0  ppm,,  respectively (1).




     If  these  wastes are exposed to more  acidic  environments




Uandfills or  disposal environments subject  to acid  rainfall)




these metals'  concentrations in  leachate would likely be




higher,  since  lead, cadmium, and chromium  (and their oxides)




are more  soluble in acid than in distilled water  (5,6,7).




     Many  of the states in which the majority of  these wastes




are generated, including Ohio, Pennsylvania,  Illinois and




Indiana,  are known to experience acid  rainfall (8).




     A further indication of the migratory potential of the




waste constituents is the physical  form of the waste itself.




These waste  dusts/sludges are of a  fine particulate  composition,




thereby exposing a large surface area  to any  percolating




medium, and  increasing the probability  for leaching  of hazardous




constituents from the waste to groundwater.




2.    Substantial Hazard from Waste Mismanagement




     In light  of the demonstrated migratory  potential of




harmful concentrations  of the waste constituents,  im-




proper management  of these wastes could easily result in the

-------
                                            Table 2.
                                  Leach Test Results (mg/1) on Electric Furnace Emission Dui

                National Interim
                Primary
                Drinking Water     Sample     Sample     Sample    Sample     Sample   Sam],
Contaminant     Standard           1*         2*         3*        4*         5**      6***
    Cd           0.01              0.05       2.84,      3.85    4.8-13.4,        3.5

    Cr           0.05             <0.1        0.48        -           0.05    1,248.0   120

    Pb           0.05              0.5        0.06      36.7         <0.2         0.3
       *EP extraction data submitted by an American Iron and Steel Institute
        letter to John P. Lehman from Earle F. Young, Jr., dated May 15, 1979

      **Waste Characterization Data for the State of Pennsylvania,
        Department of Environmental Resources.  The data for Sample 5
        was supplied by Allegheny Ludlum Steel Corporation from a
        water extraction procedure.  The apparent discrepancy between
        the result obtained for chromium in Sample 5 and those obtained
        for chromium in Samples 1-4 may be attributable to the particu-
        lar type and quantity of scrap metal used in the steelmaking
        processes which produced these waste samples.

     ***Source:   Reference 3 water extraction.

-------
release  of  contaminants.  For  instance,  selection of disposal

sites  in areas with permeable  soils  can  permit contaminant-

bearing  leachate from the waste  to migrate to surface water

and/or groundwater. The possibility  of  groundwater contami-

nation is  especially significant  with  respect to disposal of

these  wastes  in surface impoundments,  since a large quantity

of liquid  is  .available to percolate  through the solids 'and
           i      ;
soil beneath  the fill.

    An overflow problem might  also be  encountered if these

wastes are  ponded and the liquid  portion  of the waste has

been allowed  to reach too high a  level  in the lagoon; a

heavy  rainfall could cause flooding  which might result in

the contamination of soils and surface waters in the vicinity.

     In  addition to difficulties  caused by improper site

selection,  unsecure landfills  in  which dusts  and dredged

solids could  be disposed of are  likely to have insufficient

leachate control practices.  There may be no  leachate collection

and treatment  system to diminish  leachate percolation through

the wastes  and soil underneath the site to groundwater and

there  may not  be a surface run-off diversion  system to prevent

contaminants  from being carried from the  disposal site to

nearby surface waters.

    In  addition to ground and surface water  contamination,

airborne exposure  to lead, chromium, or cadmium particulate

escaping from  mismanaged emission control dusts is  another

Pathway  of  concern.   These minute particles could be dispersed
                            -741-

-------
by wind  if  waste  dusts  are piled in the open, placed  in


insecure  landfills  or  improperly handled during transportation.


As a result,  the  health of persons who inhale the airborne


particulates  would  be  jeopardized.


     Transportation of  these wastes to off-site disposal


facilities  increases  the likelihood of their causing harm to


human beings  and  the  environment.   The mismanagement of these


wastes during transportation may thus  result in an additional


hazard.   Furthermore,  absent of proper management safeguards,


the wastes  might  not  reach the  designated  destination at


all, thus making  them  available to do  harm elsewhere.


     The  lead,  chromium and  cadmium that may migrate from


the waste to  the  environment as a  result  of such improper


disposal  practices  are  elemental heavy metals that persist


indefinitely  in the environment in some form.  Therefore,


contaminants  migrating  from  these  wastes may pollute the


environment for long periods of time.


3.   Justification  for  T Listing


     The Agency has  determined  to  list emission control


dusts/sludges  from  the  electric furnace production of steel


as a T hazardous waste  on  the basis  of lead, chromium and


cadmium constituents, although  these constituents  are also


measurable  by  the E toxicity characteristic.  Although concen-


trations of these constituents  in  an EP extract from waste


streams from  particular  sites may  not  always be greater than


100 times the National  Interim  Primary Drinking Water Standards,
                              v*
                             -7L2-

-------
the Agency believes that  there  are  factors in addition to




metal concentrations in leachate  which justify the T listing.




Some of these factors have  already  been identified, namely




the high concentrations of  cadmium,  chromium and lead in the




actual waste and in distilled water  leachate samples, the




non-degradability of these  substances, and the strong possi-




bility of the lack of proper management of the wastes in




actual practices.




     The quantity of these  wastes  generated is an additional




supporting factor.  As indicated  above, electric furnace




emission control dusts/sludges  are  generated in very substan-




tial quantities, and contain high  concentrations of the




heavy toxic metals lead,  chromium  and  cadmium.  Large amounts




of each of these metals are available  for  environmental




release.  The large quantities  of  these contaminants pose




the danger of polluting large areas  of ground or surface




waters.  Contamination could also  occur for long periods of




time, since large amounts of pollutants are available for




environmental loading.  Attenuative  capacity of the




environment surrounding the disposal  facility could also be




reduced or used up due to the large  quantities of pollutant




available.   All of these  considerations increase the possibility




of exposure to  the harmful  constituents in the wastes,  and




in the Agency's view,  support a T  listing.




V.   Hazards  Associated with Lead, Chromium,  and Cadmium






     Lead  is  poisonous in all forms.   It is one of the  most
                             -743-

-------
hazardous  of  the  toxic  metals because it accumulates  in  many




organisms,  and  its  deleterious effects are numerous and  severe.




Lead may  enter  the  human system through inhalation, ingestion




or  skin contact.   Chromium is toxic to man and lower  forms of




aquatic life.   Cadmium  is also a cumulative poison, essen-




tially irreversible in  effect.  Excessive intake leads to




kidney damage,  and  inhalation of dusts also damages the




lungs.  Additional  information on the adverse health  effects




of  lead,  chromium,  and  cadmium can be found in Appendix A..




     The hazards  associated  with exposure to lead,  chromium,




and cadmium have  been recognized by other regulatory  programs.




Lead, chromium  and  cadmium are listed as  priority pollutants




in  accordance with  §307(a)  of the Clean Water Act of  1977.




Under §6 of the Occupational  Safety and Health Act  of  1970,  a




final standard  for  occupational  exposure  to lead  has been




established and a draft  technical standard  for chromium has




been developed  (9,  10).   Also,  a national ambient air  quality




standard for  lead has been  announced  by EPA pursuant to the




Clean Air Act (9).   In  addition,  final or proposed  regulations




of  the State  of California, Maine,  Massachusetts, Minnesota,




Missouri,  New Mexico, Oklahoma and  Oregon define  chromium and




lead containing compounds  as  hazardous wastes  or  components




thereof (11).




     EPA has proposed regulations  that will limit the  amount




of cadmium in municipal  sludge which  can  be landspread on




cropland (12).  The  Occupational  Safety and Health  Administration




(OSHA)  has issued an advance  notice of proposed rulemaking

-------
for  cadmium  air  exposure based on a recommendation by  the




National Institute  for Occupational Safety (13).  EPA  has  also




prohibited the ocean dumping of cadmium and cadmium compounds




except when  present  as trace contaminants (14).  EPA has




also promulgated pretreatment standards for e lectroplaters




which specifically  limit discharges of cadmium to Public




Owned Treatment  Works  (15).

-------
                            References
 1.  Calspan  Report,  "Assessment of Industrial Hazardous Waste
     Practices  in  the Metal Smelting and Refining Industry,
     "Volume  III,  April  1977.

 2.  Development Document  for  Proposed Effluent Limitations
     Guidelines  and  Standards  for the Iron and Steel Manufacturing
     Point  Source  Category, Vol. V., EPA 440/1-79/024a, October
     1979.

 3.  Waste  Characterization Data form the State of Pennsylvania
     Department  of Environmental Resources; letter from
     P.Y. Masciantonio to  T. Orlando, dated September 8, 1975.

 4.  U.S. Environmental  Protection Agency, Quality Criteria for
     Water, Washington,  D.C.,  1976.

 5.  Handbook of Chemistry and Physics,  52nd Edition.  Cleveland,
     The Chemical  Rubber Company,  1971-72.

 6.  The Merck  Index.   8th Edition.   1968.

 7.  Pourbaix, Marcel.   Atlas  of Electrochemical Equlibria in
     Aqueous  Solutions,  London,  Pergamon Press, 1966.

 8.  MITRE  Corporation,  "An Integrated Five-Year Research Plan
     (FY 79-83)  for EPA's  Atmospheric Acid Deposition Program11.
     (Draft)

 9.  U.S. Department  of  Interior,  Bureau of Mines.   Mineral
     Commodity Summaries,  1979.

10.  U.S. Department  of  Health,  Education and Welfare,  National
     Institute for Occupational  Safety and Health.   Registry
     of Toxic Effects  of Chemical  Substances.   1977.

11.  U.S. EPA States  Regulations Files,  January 1980.

12  .  44 JJj.  53449

13  .  42 £R  5434

14.  38 FR,  28610

15.  Federal Register  Vol.  44  No.  175 Friday,  September 7,  1979
     (40 CFR Part  413).

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                 LISTING BACKGROUND DOCUMENT

                       Steel Finishing


Spent  Pickle  Liquor (C) (T)

Sludge from Lime Treatment of Spent Pickle  Liquor  (T)



I.   Summary of Basis for Listing;

     Spent pickle liquor and the sludge resulting  from ,lime

treatment  of, spent pickle liquor are generated,,  respectively,

in  the pickling of iron and. steel to remove surface  scale, and

in  the lime neutralization of spent pickling liquors.  The

Administrator has determined that both the  spent pickle liquor

and the sludge from the lime treatment of spent  pickle liquor

are solid  wastes which may pose a present or potential hazard to

human  health  and the environment when improperly transported,

treated,  stored, disposed of, or otherwise managed,  and, there-

fore,  should  be subject to appropriate management  requirements

under  Subtitle C of RCRA.  This conclusion  is based  on the

following  considerations:

     1.  Spent pickle liquor is corrosive (has been  shown to
         have pH less than 2),  and contains significant
         concentrations of the toxic heavy metals  lead and
         chromium.

     2.  The  toxic heavy metals in spent pickle  liquor
         are  present in highly mobile form, since  it is
         an acidic solution.  Therefore, these hazardous
         constituents are readily available to migrate
         from the waste in harmful concentrations, causing
        harm to the environment.

    3.   The  sludge resulting from the lime treatment of the
        spent  pickle liquors has been shown to  contain
        significant concentrations of the heavy toxic metals
        lead  and chromium.
                               -76,7-

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          These  toxic metals have been shown to leach  in
          significant concentrations from a sample of  the
          lime  treatment sludge subjected to an extraction
          procedure.   Thus, the possibility of groundwater
          contamination via leaching exists if these waste
          materials  are improperly disposed.

          Current  waste management practices, which consist
          primarily  of land disposal either in unlined land-
          fills  or unlined lagoons,  may well be inadequate
          to  prevent  the migration of lead and chromium to
          underground drinking sources.

          A very large quantity (approximately 1.4
          billion  gallons of spent pickle liquor or,  if all
          spent  pickle liquor is treated,  5 million metric
          tons of  lime treatment sludge (at 5% solids)) is
          generated  annually.  There thus is greater  likeli-
          hood of  large-scale contamination of the environment
          if  these wastes are not managed properly.
     7.   Damage  incidents  have been reported that are
          attributable  to  the  improper disposal of untreated
          spent pickle  liquor  and the sludges resulting from
          the  lime  treatment of the  spent  pickle liquors.
II.  Industry Profile  and  Process  Description

     Pickling operations are  very  widespread across the

United States.   Spent  pickle  liquor  is generated at 240 plants

located in 34 states.   Approximately 70%  of these plants are

situated in Pennsylvania,  Ohio,  Illinois,  Indiana and Michigan.

Pickling capacity within the  iron  and steel industry, according

to the type of acid used,  is  shown in Table 1 below.(^)

     The pickling operation involves the  immersion of oxidized

steel in a heated solution of  concentrated acid or acids (the

pickling agent)  to remove  surface  oxidation or to impart specific

surface characteristics.   At  integrated steel plants, acid pickle

liquors are used in cold rolling mills and galvanizing mills

-------
                           Table  1



                         Number of            Annual Capacity,
   Pickling Agent          Plants*            tons  of steel/yr

     HC1                    43                   30,000,000

     H2S°4                 149                   28,000,000

     Mixed acid
    (e.g. HF-HN03)         152                   6,000,000
Depending on the type of steel being  processed,  or  the  type

of surface quality desired, different  types  of  acids  may  be

used.  After a certain concentration  of  metallic  ions build

up in the pickling bath, the  solution  is considered  spent

or exhausted and must be replaced.
      Waste Generation and Management

     Approximately 1.4 billion gallons  of  spent  pickle  liquor

are generated annually:  500 million gallons  of  spent  sulfuric

acid,  800 million gallons of spent hydrochloric  acid,  and  74

million gallons of a combination  (mixed) of pickling acids.**

When treated with lime, spent pickle liquors  form a spent  pickle

liquor lime treatment sludge, the second waste of concern  in

this document •
 *If  the  same plant uses two or  three  pickling  agents,  it  is
  listed  once for each agent used.

**Estimates  based on waste generation  data  contained  in
  Reference  1.

                            -X-

-------
     Approximately  40% of the mills utilizing the sulfuric
             5



acid pickling  process  discharge these and other pickling

             >


wastes  after treatment to a receiving body of water.  Another




45% of  these mills  have the spent pickle liquor hauled off-




site by  private  contractors,  presumably for subsequent treat-




ment. The remaining  15% of the sulfuric acid pickling mills




either  utilize deep  well disposal,  engage in acid recovery,




or discharge the  treated waste to Publicly Owned Treatment




Works (POTWs)  along  with other pickling wastes which have




undergone varying degrees of  treatment.   Disposal practices




of combination acid  pickling  mills  and hydrochloric  acid




pickling mills are  known to be similar to those  used by




sulfuric acid  pickling  mills.(1)




     Lime treatment  neutralization  of spent  pickle liquors,




shown in diagram  1,  results in the  formation of  a mixed metal




hydroxide sludge.  On-site lime neutralization by mills




involves the addition  of lime,  either in the hydroxide or the




carbonate form, to the  pickling wastes (spent  pickle liquor,




wastewaters, etc.) in  a mixing tank followed by  sedimentation




or filtration.(1)




     The total quantity of wet sludge (5% solids)  generated




annually from  the treatment of spent  pickle  liquors  has been




estimated at approximately 5  million  metric  tons per year.*
*Estimates based on waste generation  data  contained in

 Reference 1.
                             --no-

-------
This  quantity includes sludges from combined  treatment of  all

spent pickle liquors together with other aqueous waste streams

from  the pickling operations.  This sludge is usually disposed

of in unlined land disposal f acili ties . ( *)  Outside  contract

disposal services generally neutralize  spent  pickle  liquors

in unlined lagoons. (2)


IV .  Hazardous Properties of the Wastes



     1.  Spent Pickle Liquor

          The pickling process requires highly acidic solutions;

     hence, spent pickle liquors are highly corrosive, with a

     pH of less than 2 (see Table 2).   Therefore, this waste would

     meet the corrosivity characteristic (§261.22) and is  thus

     defined as hazardous.  In addition, Agency data indicate that

     significant levels of the toxic heavy metals lead and chromium,

     in a highly mobile form, are found in the spent pickle liquor

     (see Table 2 below).

                           Table 2

        Typical Concentratons of Lead  and Chromium in

Parameter
PH
Cr
Pb
Spent Pickle Liquors (mg/1)
H^SO^Bath HCL Bath Mixed Acid Bath
1.0-2.0 1.0-4.5 1.3-1.5
26-269 2-37 3300-4250
ND*-2 2-1550 1-4
*ND = Nonde tec table

Source:   Reference 1
                             -*-
                             -771

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PICKLE
RINSE
WATER
•
3PEMT
•PICKLE
LIQUOR
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tt
ir»i
	 • -g*
RAW WASTEWATERS
FROM PICKLING
OPERATIONS
«H » ^ .„_ 	 _
T T
fy .1 	 .
V RECYCLE FUME HOOD FRESH WATER
	 	 	 •- - . ,, — .. -._- ..u-fs. -fll • ijAt/f-llf?
	 S> SCRU1IUFR MAKE UP


*
LIME POLYMER
• 1  	 | 	
SLUDGES RF-QUIRING CONTROLLED DISPOSAL
FILTER CAKE
  SOLIDS
                                                                             ENVIRONMENTAL  PROTECTION   AGENC'
       STEEL INDUSTRY STUDY
     HAZARDOUS WASTE SOURCE
PICKLING TREATMENT  SYSTEM SLUDGE
                                                                                  t

-------
         Based  on  the higher concentration levels listed in

    Table  2  for chromium and lead (4250 and 1550, respectively),

    if only  .12% of the chromium and .332 of the lead leach

    from the  spent  pickle liquor, this amount would exceed

    the permissible concentrations in the EP extract.*  Since

    the spent  pickle liquor is a highly acidic solution, these

    toxic  heavy metals are readily available to migrate into

    the environment, as they are more soluble in acidic environ-

    ments. (6)   Thus, disposal of this waste in landfills or

    lagoons,  if improperly managed,  is likely to lead to the

    migration  of harmful constituents into the environment and

    pose a substantial hazard via a  groundwater exposure pathway.


    2.   Sludge from Lime Treatment  of Spent Pickle Liquor

         Calculations based on data  collected by EPA at 45

    plants(^)  - taking into account  the difference in pollutant

    mass before and after treatment  of the spent pickle liquor

    -  estimate  that, on the average, 22,400 ppm of chromium and

    11,380  ppm  of  lead are present in the lime treatment sludge.**

    Furthermore, lead and chromium have been shown to leach

    from the  sludge resulting from lime treatment of spent pickle

    liquor  in  significant concentrations when subjected to an


 *The concentrations of lead and chromium in these wastes can vary,
  depending  upon the composition of the raw materials used to manu-
  facture the  steel  and the particular type of steel pickled.

**The sludge,  since  it is a more concentrated waste form
  (i.e., the  ratio  of liquid to solids in the sludge is less
  than  the  liquid/solid ratio in the  spent pickle liquor) will
  have  a higher  concentration of the  contaminants of concern
  than  the  spent pickle liquor.  The  above calculations are not
  contained  in  reference 1, but are based on data contained in
  reference  1.
                              -773-

-------
     extraction  procedure.(5)   Results of an analysis of the
                                        )
     leachate  (pH and  test  conditions unspecified) from a
                                        < i
     neutralized pickling  liquor  sludge are shown in Table 3

     below.  These data  clearly indicate  that lead and chromium

     may leach from the  waste  in  harmful  concentrations unless

     properly managed  since  they  are  many times greater than

     the National Interim  Primary Drinking  Water Standards  for

     these substances.
                           Table  3
           Analysis of Leachate from  a  Neutralized
                  Spent Pickle Liquor Sludge
     Metal                      Leachate  Concentration  (ppm)
     Cr                                    429.0
     Pb                                      8.2
Source:   Reference 5
     3.   Possible Types of Improper Management  and  Available
         Pathways of Exposure

          As shown above, disposal of  spent  pickling  liquors and

     the sludge resulting from lime treatment of  spent  pickling

     liquors on land creates the  potential  for  leaching  of  the

-------
toxic heavy metals  chromium and lead to groundwater, a




common source of  drinking  water.   In addition, improper




storage and/or  disposal  of spent  pickling liquor poses




potential hazards  stemming from the high acidity of the




wastes.  In particular,  if not segregated in a landfill,




spent pickle liquors  can extract  and solubilize toxic




contaminants (especially heavy metals)  from other wastes




disposed in the landfill.   If  not stored in special




containers, pickle  liquo.rs can, over time,  corrode the




containers, resulting  in leakage  and potential acid burns




to individuals  who  may come in contact  with the waste.




     Transportation of about 45%  of the spent  pickle




liquors generated  to  off-site  disposal  facilities before




neutralization  (see p.4,  above) increases the  likelihood




of their causing  harm  to  people and the environment.




Improper containment  of  these  wastes may result in




their doing harm  to individuals or  to the environment




during transportation  to  their designated destination.




Moreover, mismanagement  of these  wastes during trans-




portation may result  in  their  not reaching  their




designated destination at  all,  thus making  them available




to do harm elsewhere.



     Solubility of  lead  and chromium present in lime




treatment sludges is pH  dependent (e.g. solubility




increases as pH deer eases).(6)  Thus,  co-disposal of the
                        -775--

-------
sludges with waste acids,  for  instance,  is  likely to
                                                   )


result in increased  solubilization  of  these heavy metals.
                                                   . ,i

Disposal in a surface  impoundment or landfill  with an



acidic environment will  certainly enhance  the  solubility



of lead and chromium hydroxide.  The result  of  the



leachate test shown  in Table 3'*) strongly  suggests



that lead and chromium may  be  released from lime  treated



sludges as well.



     Once released from  the matrix  of,  the waste,  lead and



chromium can migrate from  the  disposal site  to  ground and



surface waters used as or  constituting potential  drinking



water sources.  Present  practices associated with  land-



filling or impounding the waste may be inadequate  to



prevent such an occurence.  For instance, selection of



disposal sites in areas  with permeable soils can  permit



contaminant-bearing leachate from the waste  to  migrate



to groundwater.



     An over-flow problem might also be encountered if



the liquid portion of the waste has been allowed  to



reach too high a level in the  lagoon.  Thus, a  heavy



rainfall could cause flooding  which might reach surface



waters in the vicinity.





     In addition to difficulties caused by  improper



site selection,  unsecure landfills  in which  wastes may



be disposed  of are likely to have insufficient  leachate
                          -774-

-------
    control practices.  Available information, in fact,
    indicates that liners are not presently used in the
    landfilling or lagooning of these wastes.^1) There
    may be no leachate collection and treatment system to
    diminish leachate percolation through the wastes and
    soil underneath the site to groundwater and there may
    be no surface run-off diversion system to prevent con-
    taminants from being carried fron the disposal .site to
    nearby surface waters.
         An additional regulatory concern is the huge quantities
    of these wastes generated annually.  Spent pickle liquor
    and the sludge resulting from line treatment of the spent
    pickle liquor are generated in very large quantities.   The
    large quantities of these wastes and the contaminants they
    contain pose a serious danger of polluting large areas of
    ground or surface waters.  Contamination could also occur
    for long periods of time since large amounts of pollutants
    are available for environmental loading.  Attenuative capa-
    city of the environment surrounding the disposal facility
    could also be reduced or used up due to the large quantities
    of pollutants available.

V.   Hazards Associated with Lead and Chromium
    The lead and chromium that may migrate from the wastes
to the envirnoment as a result of such improper disposal
                           -vi-
                             -777-

-------
practices are heavy metals  that  persist  in  the  environment in




some form and, therefore, may  contaminate drinking  water sources




for long periods of time.   Chromium  is  toxic  to  man and  lower




forms of acquatic life.  Lead  is  poisonous  in all  forms.   It  is




one of the most hazardous of the  toxic  heavy  metals because  it




accumulates in many organisms, and its  deleterous  effects  are




numerous and severe.  Lead  may enter  the human  system  through




inhalation, ingestion or skin  contact.   Improper management  of




these wastes may lead to Ingestion of contaminated  drinking




water.  Aquatic toxicity has been observed  at sub-ppb  levels.




Additional infromation on the  adverse health  effects of  chromium




and lead can be fround in Apprendix A.




     The hazards associated with  lead and chromium  have  been




recognized by other regulatory programs.  Lead and  chromium are




listed as priority pollutants  in  accordance with §307(a) of the




Clean Water Act of 1977.   National Interim  Primary  Drinking




Water Standards have been established for both parameters.




Under §6 of the Occupational Safety and Health Act  of  1970, a




final standard for occupational exposure to lead and chromium




has been established and promulgated  in 19  CFR 1910.1000.(8>9)




Also, a national ambient air quality  standard for lead has been




announced by EPA pursuant to the  Clean Air  Act.  '^)  In  addition,




final or proposed regulations of  the  states of California, Maine,




Massachusetts, Minnesota, Missouri, New Mexico, Oklahoma and




Oregon define chromium and  lead containing  compounds as  hazardous




wastes or components thereof.(10)
                               -778-

-------
VI.  Damage Incidents*

    These damage incidents are 'attributable  to  the  improper

disposal of spent pickle liquor and  sludges  from the  lime

treatment of spent pickle liquors.   They  are  just  a  few

examples of the damage which may  result  if  these wastes  are

mismanaged.
      In '1970, neutralized spent  pickling  liquors  dumped

      in an abandoned strip mine  by  a  waste  disposal

      firm leached into the surrounding  soil  and,

      eventually, into streams  in Monroe County, Ohio.

      Fish were killed as a result in  nearby  Wilson's Pond.

      In 1971, Wilson's Pond overflowed  into  Little Beaver

      Creek, causing a major kill of some  77,000 fish.

      The disposal firm was ordered  to construct facilities

      to contain and treat wastes which  were  being discharged

      into a nearby stream.  Extensive pollution of

      groundwater persists, however, and there  is  a threat to
              t
      the water supply of several homes  and  a school.



      In Washington County, Pennsylvania,  leachate from a

      landfill has entered the  groundwater and  has contaminated
*°raft Environmental Impact Statement for  Subtitle  C,
 Resource Conservation and Recovery Act  of  1976,  Appendices
                            -yf-
                            -771-

-------
a farmer's well and spring a half mile away.  The




landfill accepts sludges containing heavy metals and




poorly neutralized pickle liquor from steel mills.
In April, 1975. an employee in York County, Pennsylvania,




siphoned wastes from a company's settling pond into a




storm drain emptying into a fishing creek.  The acidity




of the drained wastes caused a fish kill;in the creek.




The waste and sludge in the ponds were spent pickle




liquors which had allegedly been neutralized.   The




sludge is to be hauled to a landfill and the lagoons




are to be lined.
                      -7SO-

-------
                         References
1.  Draft Development Document  for  the  Proposed Effluent




      Limitations Guidelines and Standards  for the  Iron




      And Steel Manufacturing  Point Source  Category;  Sulfuric




      Acid Pickling Subcategory, Hydrochloric Acid  Pickling




      Subcategory.  Volute VIII, November,  1979.








2.  Calspan Corporation, Assesment  of Industrial Hazardous




      Waste Practices in the Metal Smelting and Refining




      Industry.  Appendices.   April, 1977.  Contract




      Number  68-01-3604, Volume III,  pages 6-69.




      App. 12, 37.








3.  Waste Characterization Data, from the State of Illinois




      EPA, as selected from State  files by  US EPA/OSW on




      3/14/79 and 3/15/79.








4.  Waste Characterization from  the State of Pennsylvania




      Department of Environmental  Resources, Division of




      Solid Waste Management, March 20, 1978, as selected




      from State files by US EPA/OSW,  on 1/4/79 and




      1/5/79.
                             -731-

-------
 5.  Waste Characterization Data  from  the  State  of  Illinois




       EPA, as selected from State  files by  US EPA/PSW  on




       3/14/79 and 3/15/79.
 6.  Pourbaix, Marcel.  Atlas of Electrochemical Equilibria




       in Aqueous Solutions, London, Pergamon Press, 1966.
 7.  Appendix J--Hazardous Waste Incidents, Draft Environmental.




       Impact Statement for Subtitle C, RCRA, January 1979,




       as synopsized from Office of Solid Waste, Hazardous




       Waste Management Division; Hazardous Waste Incidents,




       unpublished open file data, 1978.
 8.  U.S. Department of the interior, Bureau of Mines.




       Mineral Commodity Summaries, 1979.








 9.  U.S. Department of Health, Education and Welfare,




       National Institute for Occupational Safety and




       Health.  Registry of Toxic Effect of Chemical




       Substances.  1977.
10.  U.S. EPA States Regulations Files, January, 1980.








11.  MITRE Corporation, "An Integrated Five-Year Research




       Plan (FY 79-80) for EPA's Atmospheric Acid Deposition



       Program".  (Draft)

-------
Non-Ferrous Smelting and  Refining  Industry
                   -7S3-

-------
              PRIMARY COPPER SMELTING AND REFINING
       Acid  plant  blowdown slurry/sludge resulting  from
       the  thickening of blowdown slurry (T)
 Summary  of  Basis  for Listing

     Acid plant  blowdown slurry/sludge,  resulting  from

 the'  thickening  of the blowdown slurry, is a waste  stream

 from the treatment  of the acid pl.ant blowdown slurry at

 facilities  where  primary copper is smelted in a reverberatory

 furnace.  The Administrator has determined that these

 sludges  are solid wastes wh ich pose a substantial  present or

 potential hazard  to  human health or the  environment when

 improperly  transported,  treated, stored,  disposed  of or

 otherwise managed and,  therefore,  should  be subject to

 appropriate management  requirements under Subtitle C of

 RCRA.  This conclusion  is based on the following considerations:

 1)   Acid plant blowdown slurry contains  high concentrations
     of  the toxic heavy  metals lead and  cadmium.*

 2)   A large quantity of these wastes  is  generated annually
     (approximately  286,000 MT (dry weight)  was produced in
     1977)  and this  quantity is expected  to increase to
     360,360 MT by 1983.

 3)   A solubility study  has shown  that lead and cadmium can
     be leached from these sludges  by  even a mild  (distilled
     water)  leaching media.   Therefore,  even under the mild
     conditions,  the possibility of groundwater contami-
*For concentrations of other  listed  toxic heavy metals that
 do not warrant waste  listing,  see Attachment 1.

-------
     nation .via leaching  will  exist if these waste materials
     are improperly  disposed.

4)   Current waste management  practices consist of storage or
     disposal in unlined  lagoons.   These waste management
     practices may not  be adequate to prevent a hazard
     to human health  and  the  environment.
Discus sion

A.   Profile for the  Industry

     A 1977 review  (1)  indicated  that  there were  15  primary

copper smelters in  the  United  States ''operated  by  eight

companies.  A more  recent  source  (2)  identifies  seventeen

primary smelters operated  by nine  companies.   Table  1  lists

the seventeen plants  and their  production  capacities.   Almost

all of the smelting capacity is  concentrated  in  the  south-

western United States,  primarily  Arizona  and New  Mexico.  An

average smelter can be  assumed  to  have  a  capacity of  100,000

metric tons per year  (1).  Total  national  production  of

copper is increasing, based on  a  comparison of total  capacities

cited by References 1 and  2.

B.   Manufacturing Process

     Processing of copper  includes mining,  concentrating of

ores,  smelting and refining.  The  smelting  process involves

two basic steps (3).  First, the  copper concentrate  is melted

in a reverberatory furnace to yield matte,  which  is  essentially

a  mixture of copper and iron sulfides.  The matte is  then

fed to  converters  in which air oxidation converts the  copper

sulfate  to impure  copper and the  iron sulfide  to  an  iron

-------
oxide/si1icate  slag  that  can be separated from the copper.




The product  resulting  from the  reverberatory furnace converter




smelting  is  blister  copper.   Depending on the intended final




use, the  blister  copper  is purified by fire refining and




electrolytic  refining.   A flow  diagram for the primary copper




smelting  process  is  shown in Figure 1.




     The  source of the listed waste stream is also indicated




in Figure  1.  (Note  that  the reverberatory furnace slag- is




not included  in the  listing  since  data submitted  during the




comment period  indicated  that the  contaminants  in the slag




tend not  to migrate  out  of the  waste.)    Lead and cadmium,




the metals that constitute the  basis  for  listing, are always




in the waste  since they  are  always  present in the basic raw




material,  namely  copper  ore.




C.    Waste Generation and  Management




     As indicated in Figure  1,  the  listed  waste  addressed  in




this document arises from  the acid  plant  which  constitutes




the principal controller  for removal  of sulfur  dioxide  from




furnace and converter off-gases  (3).   The  converter off-gases




typically  contain 5% or more of  sulfur  dioxide  (3).   According




to  the Calspan report (1), the  acid plant  for an  average




100,000 metric ton/year smelter  generates  a  blowdown  slurry




at  a rate of about 2,270 cubic meters/day.   After thickening,




the bulk  of the  solid content of slurry is  recycled to  the
                             -y-

-------
                            CWTtftJUlflDl
         DUST TO
         RWEft.
                                                                         VALUIS
                                                                 IW klLOCRAWMITWCTXSH
COffCRfflOOUCTl
LISTED WASTE
 (SLUDGE)
            Figure 1  PR.MARV COPPER SMELTING AND
   Source:   Reference  1

-------
reverberatory  furnace.*   The  overflow from the thickener -

about 2,200  cubic meters  per  day,  containing 0.77 metric tons

of suspended solids  and 40  metric  tons of dissolved solids -

is sent to a lagoon  for settling.   The suspended solid content

is eventually  recovered and recycled to the smelter.*  The 40

metric tons/day of dissolved  solids  remain in the aqueous la-
                               ,'j
goon effluent  which  is discharged  to the main tailings p.ond.

     Available documentation  (1)  indicates that this sludge

is allowed to  accumulate, along with the tailings waste,  in

the tailings pond.   There is  no evidence that this  sludge/

tailings mixture is  dredged out for  further treatment  or

disposal.  Available documentation  also indicates that

these tailings ponds are  unlined.  These unlined tailings

ponds are, therefore, the point of  disposal for the 40 MT/day

of material from the acid plant blowdown slurry that is

not recycled.  In comparison, 46 MT/day of thickener

underflow solids and 0.8 MT/day of  the overflow suspended
*At this time, applicable requirements  of  Parts  262  through
 265 apply insofar as the accumulation,  storage  and  transpor-
 tation of hazardous wastes that  are  used,  reused,  recycled,
 or reclaimed.  The Agency believes that  this  regulatory
 coverage is appropriate for the  subject  wastes.   The slurry/
 sludge is hazardous insofar as they  are  being accumulated
 and stored in surface impoundments and  insofar  as  they may
 be stored in piles prior to recycling.   This  waste  may not
 pose a substantial hazard during  the  recycling  and, even
 though listed as a hazardous waste,  this  aspect  of  their
 management is not now being regulated.
                             -y-

-------
                           Table 1
        GEOGRAPHICAL DISTRIBUTION AND CAPACITIES  OF
                  PRIMARY  COPPER SMELTERS
Company
Location
    Smelting
Capacity (MT*/yr)
Anac6nda

ASARCO
Cities Service
Copper Range

Hecla Mining

Inspiration
Kennecot t
Magma

Phelps Dodge
Anaconda,  MT

Hayden, AZ
El Paso, TX
Tacoma, WA

Copper Hill,  TN

White Pine, MI

Casa Grande,  AZ

Miami, AZ

Garfield,  Utah
Hurley, NM
Hayden, AZ
Me Gill, NV

San Manuel, AZ

Morenci, AZ
Hidalgo, NM
Douglas, AZ
Ajo, AZ
     198,000

     180,000
     115,000
     100,000

      22,000

      90,000

      31,000**

     150,000

     280,000
      80,000
      80,000
      50,000

     200,000

     177,000
     140,000
     127,000
      70,000
* MT - metric tons
** Smelting is done  by  a leach process,  but  the  plant  has an
  acid plant associated with the roaster.
                              -781-

-------
 solids  are  eventually recycled during treatment of  the  acid




 plant blowdown  slurry.




     Table  2  summarizes  the total quantities of acid plant




 blowdown  slurries  (and  miscellaneous other small volume




 slurries) that  are  generated.   A total of 286,000 metric
                   !



 tons (dry weight)  of  waste  sludge from primary copper




 smelters was  generated  in  1977.   It is estimated (1) that




.this quantity will  increase by about 26% to '3 60 , 360 me trie




 tons by 1983.   The  total quantity of waste sludge disposed




 of  (not recycled)  by  primary copper smelters in 1977 was




 128,400 metric  tons  (dry weight).




 D .   Hazards Posed  by the Waste




     1 .  Concentrations of  Lead  and Cadmium in the Waste Stream




          The listed  waste  has  been analyzed (1) and found




     to contain  toxic heavy metals.  The concentrations




     found  are  summarized in Table  3.




          Sludges  also have been  subjected to leaching  tests




     and have been  shown (1)  to  leach  lead and cadmium in




     significant concentrations.   The  leaching tests in  the




     Calspan Study  (1) was  performed on  one sample by




     agitating one  part waste  with  two parts  distilled  water




     (initial pH 5.5) for 72 hours.   The mixture was then




     filtered and analyzed.  Table  4 presents the concentrations




     found  in the leachate  from  the sludge sample.




     As  shown by the  test results  in Table 4, cadmium




     appears in concentrations  17,000  times the EPA




     National Interim Primary  Water Standard, and lead
                              -790-

-------
                           TABLE 2

  ESTIMATED TOTAL WASTE  SLUDGES FROM PRIMARY COPPER  SMELTERS
- — • IN 1977*
S_tate
Tennessee
Michigan
Texas
New Mexico
Montana
Utah
Arizona
Nevada
Washington
(METRIC TONS - DRY
Total Slowdown
Slurry
2,300
17 ,500
14,800 ,
24,800
28,500
34,300
143,600
6,100
14 ,100
WEIGHT)
Total
1
7
6
11
13
15
64
2
6
Disposed
,000
,900
,700
,200
,000
,000
,600
,700
,300
     Total                286,000                  128,400
*A number of copper  smelters which were in existence in 1974
 are no longer in operation, thus, the wastes produced by
 these smelters are  not  included in this table.
Source:   Reference 1,  Table 7d

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                            TABLE  3




           CONCENTRATIONS OF  HEAVY  METALS  IN WASTE




          SLUDGES FROM PRIMARY  COPPER  SMELTERS  (PPM)




                Metal                Sludges
               Cadmium                520




               Lead                  8000
Source: Reference 1

-------
appears  in  concentrations 150 times the National




Primary  Interim Standard.




     The  distilled water leaching procedure used in




the  Calspan tests (1) thus indicates that lead and




cadmium  will  leach from the waste even when subjected to




mild environmental conditions.  A more aggressive leaching




agent may  lead  to more substantial release of the toxic




metals.   Disposal/storage in a. surface impoundment or




landfill  with  an acidic environment will certainly




enhance  the solubility of lead and other heavy metals,




since their solubility is pH dependent (i.e., solubility




increases  as  the pH decreases (4)).




     The  information on the solubility of the compounds




coupled  with  the fact that solubilizat ion can occur more




readily  due to  the fine particulate composition of the




sludges  suggests that the heavy  metals present in the




listed waste may be released from the  acid plant  blowdown




under improper  storage/disposal  conditions.




     Once released from the matrix of  the waste,  toxic




heavy metals can migrate from the disposal/storage site




to ground and surface waters utilized  as  drinking water




sources.  Present practices  associated with  impounding




the waste may be inadequate to prevent such  an occurence.




For instance, selection of disposal sites in areas with




permeable soils  can permit contaminant-bearing leachate

-------
                          Table 4




    CONCENTRATIONS OF HEAVY  METALS  IN  FILTERED  DISTILLED




                    WATER LEACHATE,  PPM
                                 Sludges
            Cadmium                 8.4
            Lead                     7.8
Source:   Reference  1
                           -v-

-------
from the waste to migrate  to  groundwater.   This is


especially significant with respect  to  ponded  wastes


because a large quantity of liquid  is  available


to percolate through  the solids  and  soil beneath


the fill.
     i

     In addition to difficulties caused  by  improper


site selection, the lagoon/tailing  ponds are likely to


have insufficient leachate and 'surface  run-off  control


practices.  Therefore, there  may be  no  leachate collection


and treatment system  to diminish leachate percolation


through the wastes and soil underneath  the  site to


groundwater.  Further, there  may be  no  surface  run-off


diversion system to prevent contaminants from  being


carried from the disposal  site to nearby surface waters.


     An overflow problem would thus  be  encountered if


the liquid portion of the  waste  has  been allowed to


reach too high a level in  the lagoon/tailing pond; a


heavy rainfall could  cause flooding  which might reach


surface waters in the vicinity.


     Should lead and  cadmium  migrate from this  waste,


they would persist in the  environment (in some  form)


virtually indefinitely and, therefore, may  contaminate


drinking water sources for long  periods of  time.


Furthermore, cadmium Is bioaccumulated at all  tropic


levels.   Lead can be bioaccumulated  and passed  along

-------
the food chain, but  not  biomagnifled.   The liklihood




of human exposure Is  thus  increased.




     The large quantities  of  this  waste  stream generated




(a total of approximately  286,000  MT  (dry  weight)  in 1977)




is an additional factor  supporting a  listing  of this




solid waste as hazardous.  As  previously indicated,  the




waste from primary copper  smelting is  generated in




substantial quantities and contains significant concen-




trations (See Table  3) of  cadmium  and  lead.   Large




amounts of these metals  from  the waste  sludge  are  thus




available for potential  environmental  release.   The  large




quantities of these  contaminants pose  the  danger of




polluting large areas of ground or surface waters.




Contamination could  also occur for long  periods of time,




since large amounts  of pollutants  are  available for




environmental loading.  Attenuative capacity  of the




environment surrounding  the disposal  facility  could




also be reduced or used up due to  the  large




quantities of pollutants available.  All of these




considerations increase the possiblity or  exposure




to harmful constituents and,  in the Agency1s  view,




support a T listing.
2 .   Hazards Associated with Lead and Cadmium




     As presented below, The actual toxicity  of  these




harmful constituents is well documented.
                          -7
-------
         A  1977  review (6) summarizes much  of  the  available

    data  on the  toxicity of lead and cadmium.   Capsule

    descriptions of adverse health and  environmental  effects

    based on Reference 6 are summarized below;  more detail

    on the  adverse effects of lead, and cadmium can be
                       i
    found in Appendix A.

         Lead is poisonous in all forms.  It is one of the

    most  hazardous of the toxic metals  because  it  accumulates

    in many organisms, and it's deleterous effects  are numerous

    and severe.   Lead may enter the human system through

    inhalation,  ingestion or skin contact.  Lead is a cumulative

    poison  in humans, leading to damage in  kidneys, liver,

    gonads, nervous system and blood vessels.   Lead compounds

    also  have been reported to cause oncogenic  and teratogenic

    effects in animals.  Toxicity to aquatic organisms

    occurs  at ppb concentrations.

         Cadmium shows both acute and chronic  toxic effects

    in humans.   The LD50 (oral, rat) is 72  mg/kg of CdO.

    Cadmium and  its compounds have been reported to produce

    oncogenic and teratogenic effects.  Aquatic toxicity

    has been observed at sub-ppb levels.



    The hazards  associated with exposure to lead,  and

cadmium have been recognized by other regulatory programs.

Lead and cadmium  are listed as priority  pollutants  in

accordance with §307 of the Clean Water Act  of  1977.   Under
                             -717-

-------
§& of the Occupational Safety and Health Act of 1970, a final




standard for occupational exposure to lead has been established




(7,8).  Also, a national ambient air quality standard for




lead has been announced by EPA pursuant to the Clean Air Act




(8).  In addition, final or proposed regulation of the State




of California,  Maine,  Maryland,  Massachusetts, Minnesota,




Missouri, New Mexico,  Oklahoma and Oregon define cadmium or




lead containing compounds as hazardous  wastes or components




thereof (9).
                             -y-

-------
                         Attachment  1
These wastes  contain measurable concentrations  of certain
other constituents listed in Appendix  VIII  of Part 261,  in-
cluding  arsenic,  chromium, mercury  and  selenium.   The  concen-
trations  of  these constituents in both  the  waste  and  distilled
water leachate samples are, however, deemed insufficient  to
warrent  listing the wastes on basis  of  these additional
constituents,  as  demonstrated by the following  tables:
       CONCENTRATIONS OF HEAVY METALS  IN  WASTE  SLUDGES
              FROM PRIMARY COPPER  SMELTERS  (PPM)
                   Metals           Sludges

                  Chromium             50

                  Mercury               0 . 8

                  Selenium             30
Source:   Reference 1.
                              -71°!-

-------
                          REFERENCES
1.   Calspan Corporation, "Assessment  of  Industrial  Hazardous
     Waste Practices in the Metal Smelting  and  Refining
     Industry," Volume 2.  Calspan Report Number  ND-5520-M-1,
     April, 1977.

2.   U.S. Department of the Interior,  Bureau of Mines,  "Copper
     Mineral Commodity Profiles" September, 1979.

3.   P. D. Dougall, "Copper" in M. Grayson  and  D. Eckoth, eds.
     Kirk-Othmer Encyclopedia of Chemical Technology.  3rd. ed.
     Volume 6, John Wiley and Sons, New York, 1979.

4.   Pourbaix, Marcel.   Atlas of Electrochemical  Equilibria in
     Aqueous Solutions, London, Pergamon Press, 1966.

5.   The Merck Index.   8th Edition.  1978.

6.   Cleland & Kingsbury.  "Multimedia Environmental Goals
     Volume 2."  EPA Report Number 600/7-77-136B, November,
     1977.

7.   U.S. Department of Interior, Bureau of Mines,  Mineral
     Commodity Summaries, 1979.

8.   U.S. Department of Health, Education and Welfare, National
     Institute for Occupational Safety and Health.  Registry of
     Toxic Effects of  Chemical Substances.  1977.

9.   U.S. EPA States Regulations Files, January,  1980.

-------
                 LISTING BACKGROUND  DOCUMENT
                     PRIMARY LEAD  SMELTING
Surface  impoundment solids contained  in  and  dredged  from surface
impoundments  at  primary lead smelting  facilities.(T)
Summary  of  Basis for Listing
     The  smelting of primary lead produces  a  number  of

wastewaters  and  slurries, including acid  plant  blowdown,

slag  granulation water, and plant washwater.  These  waste-

waters  and  slurries are sent to treatment and storage

impoundments to  settle out the solids.  The solids may  be left

in the  lagoons,  or they may be periodically dredged  and

disposed  of  elsewhere.



     The  Administrator has determined that  the  solids con-

tained  in and  dredged from surface impoundments used to

treat or  store wastewaters and slurries from  primary lead

smelting  may pose a present or potential hazard to human

health  or the  environment when improperly managed and

therefore should  be subject to appropriate management

requirements  under Subtitle C of RCRA;  This  conclusion

is based on  the  following considerations:
         1.   The  waste contains significant concentra-
              tions  of  the toxic heavy metals, lead  and
              cadmium.

-------
                Significant  concentrations of lead and
                cadmium  have been shown to leach from samples
                of  the waste which were subjected to an extrac-
                tion  procedure  designed to predict the release
                of  contaminants to the environment.  If the
                wastes are not  properly managed, leachate
                could migrate from the waste disposal site
                and contaminate underlying drinking water
                sources.  Further, lead and cadmium do not
                degrade,  so  that  contamination,  and the oppor-
                tunity for contaminant contact with living
                receptors, will be long-term.
               Estimates  indicate  that  large  quantities'
               of the waste  are  generated  each year
               (more  than 49,100 tons  in 1978) and that the
               typical waste management  practices may be
               inadequate to prevent  substantial  environ-
               mental harm caused  by  lead  and  cadmium
               migration.
Manufacturing Process and Sources  of  Hazardous  Wastes  (1)
     The primary lead facilities  that  generate  the

hazardous wastes that concern EPA  are  four  integrated

lead smelter/refineries.  These facilities  are  located  in

Missouri and Idaho.  Production capacity  ranges from  110,000

to 225,000 tons per year.  Total  primary  lead production

(from the four integrated smelter/refineries, two  smelters

and one refinery) was 611,650 tons in  1977.  Forecasts  indicate

that domestic demand will increase to  1,030,000 -   2,340,000

tons in the year 2000.
                             -t-
                             --SO2.-

-------
    All  domestic smelters and refineries  produce  lead




by  pyrometallurgical smelting and refining  processes.   The




major  process  steps are the same at all  the  smelters, with




the exception  that those that treat non-Missouri ore




concentrates  use auxiliary operations  to recover valuable




metals  or remove undesirable impurities.  The  following  is




a step-by-step description of the manufacturing process




as  presented  in Figure 1.   This description  includes the major




process steps  for all' primary lead smelting  and refining plants.








    During  the smelting process, concentrates produced  by




the beneficiation of various lead bearing ores are converted  to




an  impure lead bullion suitable for refining.  The ore concen-




trate  is  the major feedstock material.  Other  raw materials




that may  be  added during the process include iron, silica,




limestone flux, coke, soda, ash, pyrite, zinc, caustic, and




particulates and sludges collected in  pollution control devices.




The ore concentrate and the pollution  control  dusts and  sludges




are the primary sources of lead and cadmium  found in the




settled solids from the surface impoundments.






    The  first of the processes in smelting  is sintering,  an




operation which agglomerates the fine  particles,  converts  metallic




sulfides  to oxides,  drives off volatile metals, and eliminates




most of the sulphur  as sulphur dioxide.  Off-gases from




sintering  may  contain sulphur  dioxides in concentrations that

-------

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                                                          WASTE
                                                      ATHOSPHCR1C EMISSION
                                                      SOLID WASTE
                                               I
                                       Figure i,  v   Flow  chart  depicts primary  lead  smelting
                                and refining,( umbers correspond to process numbers  in  text
                                and also~correspond to step process"in tliis document.  The first three
                                steps produce the hazardous miscellaneous  slurries of concern.)

-------
are  practical for recovery.  Of  particular  concern,  though,  are




the  lead  and  cadmium entrained in  those  off-gases.   Four




plants  have  sinter machines designed  to  produce an  off-gas




containing  enough sulphur dioxide  to  permit  recovery of




sulphur as  sulphuric acid.  The  sulphur  recovery operation




generates a  stream of weak acid  called acid  plant "blowdown".




The  acid  plant blowdown stream contains  lead and cadmium.




Neutralization of the blowdown with lime  usually generates




a slurry  destined for an on-site surface  impoundment.




This waste  stream, resulting from  the sulphur  recovery




operation,  requires proper management.






     In the  second step in primary lead  smelting and refining,




sinter  is charged to the blast furnace and  smelted  to crude




lead bullion  that can be further refined.  During this




reduction process, the components  of  the  sinter are  separated




into four distinct layers, bullion, speiss,  matte and slag.




The  two layers of concern are the  bullion layer and  the  slag




layer which  result from the interaction  of  fluxes and




metal impurities.  The crude lead  bullion is charged to




dressing  (the fourth step in this  process.)  The blast furnace




slag may  be  disposed of or sent  to a  zinc fuming furnace (an




interim step) for recovery of lead and zinc,  rather  than




opting  for  direct disposal.  The zinc fuming process, in turn,




also generates a slag.   Blast furnace slag and  zinc  fuming




slag disposal practices are similar.  The waste is  either

-------
sent directly  to  a  slag  pile or granulated in a water  jet




before being transported  to  the slag pile.  The granulation




process  cools  newly  generated,  hot slag with a water spray.




Slag granulation  water is  often transported to surface impound-




ments for  settling.
     The blast  furnace  bullion undergoes "dressing" (Step 4)




to remove common metallic  impurities.   Dross separated from




the lead bullion ,must be  further  treated in a reverberatory




drossing furnace (Step  5)  to  recover metal  values.   Rough-




drossed lead bullion, still  containing  copper,  is decopperized




(Step 6) before further refining.   One  of  three usual processes




is then used to remove  metals  that  cause lead to harden.   This




process is called softening  (Step 7).   Softened lead bullion




contains precious metals,  gold, and silver,  which are




recovered for their economic  value  through  the  Parkes




desilverizing process (Step 8).   To remove  the  excess zinc




added during desilverization,  a dezincing  process (Step 10)




which removes the bismuth, which  is in  excess of the 0.15




percent specification for  desilvered and dezinced lead bullion.




Lead bullion from dezincing or debismuthing  is  combined with




flux to remove remaining impurities before  casting  (Step  11)




and, finally, the refined  lead bullion  is  cast  into ingots




for sale (Step 12).
     The listed hazardous wastes generated  by  primary lead

-------
smelting  plants  are settled solids  from  surface  impoundments.




The  impoundments are used to collect  solids  from miscellaneous




slurries,  such  as acid plant blowdown, slag  granulation




water  and  plant  washings .  Plant washing  is  a  housekeeping




process;  plant  washdown normally contains  a  substantial




amount  of  lead  and other process material.









    Data  indicate that in 1978 four  integrated  smelter/refineries




that process  lead ore concentrates  combined  to produce more




than 49,100  tons of impoundment solids considered  hazardous.




The  data  also indicate that the bulk  of  this waste  is generated




and  managed  at  three plant locations.








    The  waste  contains high concentrations  of lead  and  cadmium.




The  presence  of  such high concentrations  of  toxic  metals




in a waste stream in and of itself  raises  regulatory concerns.




Furthermore,  distilled water extraction  test data  indicate




that these dangerous condstituents  may leach from  the waste




in harmful concentrations unless the  wastes  are  properly




managed •








Waste  Generation and Management (1)








    As previously mentioned,  the miscellaneous  slurries




generated  by  primary lead smeltering  plants  are  settled  in

-------
surface impoundments.  Typically a minimal  effort  is expended

for impoundment site selection.  Site  selection  is based

primarily on convenience.  Site preparation usually consists

of simply scooping out earth to form impoundments.   EPA is

unaware of any sealants or liners being  employed beneath

disposal areas.  Leachate or groundwater monitoring is  not

adequately utilized, or not utilized at  all.

     Four facilities have surface impoundments.  Currently,

some of the impoundments ar,e d.redged of  their  accumulated,

solids on an "as needed" basis.  Dredging is done  with

common equipment at frequencies from once per  year  to once

every 3 years or longer.  The dredged  material is  either

dumped beside the impoundment or trucked to  an on-site  dump.

Some of this material may be recycled  to sintering  if it

contains enough metals.*

Hazardous Properties of the Waste (3)



     EPA has sampled process wastewater  before and  after

treatment in an effort to quantify the amounts of  lead  and

cadmium likely to be in the waste. The settled solids are

assumed to contain the pollutants removed from the  process

wastewater.  The data are summarized as  follows:
*See "Response to Comments" at the  end  of  this  document  for  a
 discussion on the coverage of those materials  recycled  back
 to the process.
                               -•309-

-------
plant A
    Flow  =  1,300,000 gpd (gallons per day)
Metal
Cd
Pb
Inrluent
Concentration
0.89 ppm
17 ppm
Effluent
Concentration
0.044 ppm
0.925 ppm
Difference i
0 . 84 6 ppm
16.075 ppm
Lbs/day in
solids
9.172
174.3
Plant  B
     Flow =  280,000 gpd
Influent Effluent Ibs/day in|
Metal Concentration Concentration Difference solids |
Cd
Pb
i 111
15 ppm | 0.43 ppm I 14.57 ppm | 34 j
1 III
i iii
50 ppm | 0.39 ppm I 49.61 ppm |115.85 1
! Ill
1 1 1 i
     Based  on  continuous year round plant operation, these




data  show that approximately 3300 Ibs/yr of cadmium accumu-




late  in  an  impoundment in Plant A and approximately 12,400




Ibs/yr accumulate in Plant B.  Lead in the impoundment




solids from Plant A accumulates at a rate of almost 64,000




Ibs/  yr,f and  at  a rate of almost 42,300 Ibs/yr at Plant B.




Should only one percent of each metal leach from the settled




solids from Plant B,  the result would be 124 Ibs/yr of cadmium
                              -SOI-

-------
and 423  Ibs/yr  of  lead  potentially available to the environment

from  that  one  plant.
     The  above  evidence  indicating that significant amounts

of lead and cadmium  are  present  in the settled solids is

supported  by  actual  waste  analyses which reveal that the

waste does in fact contain  high  concentrations of these

toxic heavy metals.   The Calspan Corporation tested samples

of the impoundment dredgings  at  two ^plants  and found the

following  concentrations of  lead and  cadmium:(2)




Hazardous  Constituents of Impoundment  Dredgings (ppm)
                  Cd                Pb
              I    700          |      115,000
Plant I                        I
              I    640          |      140,000
Plant II      I
     Calspan Corporation also subjected  a  sample  of  the  waste

believed to be representative of  the  lagoon  dredgings  to a

water extraction to determine whether  the  toxic heavy  metals

could leach from the waste.  Approximately 50  grams  of a

sample was placed in a 200 milliliter  jar  and  two  parts  by

weight of water were added.  The  bottle  was  gently agitated

on a rotary tumbler for 72 hours.  The extract was then

filtered through a 0.45 micron micropore filter and  the

filtrate was analyzed for heavy metals.  This  waste  leached
                               - "8/0-

-------
11  ppm  of  cadmium (1,100 times  the  amount  permitted  by  the

National Interim Primary Drinking Standard)  and  4.5  ppm of

lead  (90 times the amount permitted  by  the National  Primary

Drinking Standard).   Therefore, cadmium and  lead  are likely

to  be leached from the waste in harmful concentrations  even

when  they  are placed in a monodisposal  site  subject  to  mild

environmental conditions.  If these  wastes are placed in

acidic  environments  such as disposal sites subject to acid

rainfall or co-disposal with acids,  the concentrations  will

probably be higher,  since lead and cadmium compounds are

generally  more soluble in acid than  in  distilled  water.
     The  hazard associated with leaching of hazardous

constituents from the impoundments during  the  interim storage

period  is the migration of those constituents  to ground and

surface waters.  The miscellaneous slurries are probably

composed  of  particulates of various sizes, ranging from dust

particles to fine slag from slag granulation water.  The

potential of hazardous constituents to be  released from

the matrix is influenced by the physical form  of the waste.

For instance,  wastes composed of fine particles provide

greater surface area on which a solubilizing medium can act

and therefore the probability is increased that hazardous

constituents will leach from the waste.  Contaminant-bearing

leachate  can then migrate to ground and surface water.
                             -X-
                             -•311-

-------
     Thus, improper  disposal  of  surface impoundment solids
may result in  contamination of  ground and surface waters by
lead and  cadmium.  Aquatic  species might be affected,
and, where ground  and  surface waters  are sources of drinking
water, ingestion of  the  contaminants  by humans could
occur.  For this reason,  proper  waste management is essential
and of major concern to  EPA.(2)
     Present management  practices  appear  to  be  inadequate
to prevent contamination  of ground and  surface  waters  used
as drinking water sources.  Presently,  if  solids  are  allowed
                                                V
to settle in unlined and  unsealed  impoundments  in areas
with permeable soils, the  solubilized lead and  cadmium in
the liquid phase could migrate  from  the site  to  an aquifer.
Groundwater contamination  might also occur if the dredged
solids are dumped on permeable  soils since no provision
presently appears to be made to prevent percolation of
rainfall through the waste or to collect  resulting leachate.
Surface waters may become  contaminated  if run-off from
dumping sites and overflow from impoundments  are  not  controlled
by appropriate diversion  systems.(2)
     Compounding this problem, and an  important  consideration
for the future, is the fact that should  lead  or  cadmium
escape from the disposal site, they will  not  degrade  with
                             -vt-
                               -•311-

-------
 the passage of time, but  will provide a potential source of



 longterm contamination.
     Further, as indicated  previously,  the cadmium and




 particularly the lead  found  in  the  impoundments are generated




 in very substantial quantities.   Large  amounts of each of




 these metals are thus  available  for  potential  environmental




 release..  The large quantities  of  these contaminants  pose




 the danger of polluting  large areas  of  ground  and surface




 waters.  Contamination could  also  occur for  long  periods




 of time, since large amounts  of  pollutants are available




 for environmental loading.   The  attenuation  capacity  of




 the environment surrounding  the  disposal  facility could




 also be reduced or exhausted  by  such large quantities  of




 of pollutants. All of  these  considerations increase  the




 possibility of exposure  to  harmful constituents in the




 wastes, and in the Agency's  view, demand  recognition.








 Adverse Health Effects Associated with  Lead  and Cadmium








     Lead  and cadmium  are toxic  heavy metals that  threaten




 both human health and  that of other  organisms.  The  hazards




of human exposure to lead include neurological damage, renal




damage and adverse reproductive  effects.   In addition, lead




is carcinogenic to laboratory animals,  and relatively  toxic

-------
to  freshwater  organisms.   It also bioaccumulates in many




species.  Additional  information on lead can be found in




Appendix A.  Cadmium  (see  Appendix A for more information)




also can cause  toxic  effects in many species.   It is bio-




accumulated  at  all  trophic levels and has been shown to be




mutagenic and  teratogenic  in laboratory animals.
     Hazards associated  with  exposure  to lead and cadmium




have been recognized  by  other  regulatory programs.   For




example, Congress designated  lead  and  cadmium as priority




pollutants under §307  of  the  Clean Water Act.   The




Occupational Health and  Safety  Administration has a final




exposure standard for  lead and  a draft  standard has been




developed for cadmium  under §6  of  the  Occupational  Safety




and Health Act of 1970.   The  states  of  Maine,  Vermont,  New




Mexico, Missouri, Massachusetts, Minnesota,  Oklahoma,  Oregon,




and California either  regulate  or  are  considering regulation




of lead and cadmium as hazardous waste.   The implications of




these regulations or considerations  thereof  are obvious:




unregulated lead and cadmium management  is a real and  recog-




nized hazard.
                              -•3H-

-------
                          References
1.  USEPA, IERL/ORD and  Office  of Solid Waste.   Assessment
   of Solid Waste Management Problems  and Practices  in
   Nonferrouse  Smelters.   Prepared by  PEDCo Environmental
   Inc., Contract No. 68-03-2577.   November 1979.

2.  USEPA, Office of  Solid Waste.   Assessmet of Hazardous
   Waste Practices in the Metal Smelting and Refining
   Industry.  Prepared  by Calspan Corporation.  Contract
   No.  68-01-2604.   April,  1977.

3.  USEPA, Office of  Water Planning and Standards,  Effluent
   Guidelines Division.,  Draft Development Document  for
   Effulent-Limitations Guidelines and Standards  for the
   Nonferrous'Metals Manufacturing Point Source Category.
   September, 1979.

-------
                     Response to Comments
1.   One commenter indicated that the listed waste (surface




    impoundment solids contained in and dredged from surface




    impoundments at primary lead smelting facilities) was




    recycled at his facility and, therefore, should not be




    listed as a hazardous waste.




           The Agency has concluded that it does have juris-




    diction under Subtitle C of RCRA to regulate wastewater




    treatment sludges and other waste materials that are




    used,  reused, recycled or reclaimed.  Furthermore,  it




    has reasoned that such materials do not become less




    hazardous to human health or the environment because they




    are intended to be used,  reused, recycled or reclaimed




    in lieu of being discarded.   Although the materials




    recycled and reclaimed may not  pose a hazard,  the accumu-




    lation,  storage and transport of a  hazardous waste  prior




    to use,  reuse,  recycle or reclamation will present  the




    same hazard as  they would prior to  being discarded.   In




    addition, the act of use,  reuse, recycling or  reclamation,




    in many  cases,  poses a hazard equivalent to that encountered




    if the waste were discarded.   Thus, the Agency believes




    it has a strong environmental rationale for regulating




    hazardous wastes that are  used,  reused,  recycled or




    reclaimed.

-------
      For the particular  waste at issue,  the Agency recog-




nizes that it is a wastewater  treatment  sludge and for




most or all of its existence  prior to being recycled,  it




is deposited in a.surface  impoundment where the potential




for leaching of the hazardous  constituents  is real and




significant.  Consequently, the  waste must  be considered




a hazardous waste in  this  environment; to  avoid listing




it as a hazardous waste would  be  unjustified.   Likewise,




if the waste is piled  and .stored. o:n  the land,  prior to




recycling, the potential  of leaching  of its hazardous




constituents into the  environment would still  prevail  and




avoiding its regulations  would be unjustified.




      The key question, therefore, is not whether  or not




it is a hazardous waste and should be listed  as a  hazardous




waste, but whether or  not  or  to  what  degree it  should  be reg-




ulated during recycling;  that  is,  should the  recycling




process and facility be considered a  hazardous  waste




management operation and  facility required  to  obtain




interim status and eventually  a  permit and  required  to




meet the standards set forth  in  Parts 264 and  265  of the




regulations.  At this  time, the  Agency has  deferred




regulation of such facilities  because it recognizes  that




the full set of Subtitle  C management requirements  may




not be necessary.   As  and when it  concludes that regulation




of these facilities is necessary,  it  will terminate  this

-------
deferral and  impose  either the requirement of Parts 264 and 265




(as well as 122)  or  special  tailored requirements under




Part 266.




      At this  time,  applicable requirement of Parts 262




through  265 and 122  will  apply insofar as the accumulation,




storage  and transportation of  hazardous wastes that are




used, reused,  recycled  or  reclaimed.   The Agency believes




this regulatory coverage  and  the  above described deferral




of regulated coverage is  appropriate  to the  subject




wastes.  These sludges  are hazardous  insofar as  they are




being accumulated and stored  in surface impoundments and




insofar  as they may  be  stored  in  piles prior to  recycling.




Therefore, these  sludges  should be  listed as hazardous




waste.   These  sludges may  not  pose  a  substantial hazard




during their recycling  and, even  though listed as




hazardous waste,  this aspect of their  management is not




now being regulated.

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                LISTING  BACKGROUND DOCUMENT

             PRIMARY  ZINC SMELTING AND REFINING


    Sludge from treatment of process wastewater and/or
    acid plant blowdown  (T)

    Electrolytic  anode  slimes/sludges (T)

    Cadmium plant  leach  residue (iron oxide) (T)

Summary of Basis for Listing

    The primary zinc  industry is  comprised of 7,plants that

employ one of two  major  zinc  manufacturing processes--electro-

lytic or pyrometallurgical processing.  The five electrolytic

and  two pyrometallurgical  plants recover zinc metal from ore

concentrates.  Cadmium and lead  contaminants found in the raw

materials are carried  through numerous processes and are sub-

sequently found in  high  concentrations in the wastewater treat-

ment sludge generated  by  the  treatment of process wastewater

and/or acid plant  blowdown, in the  electrolytic  anode slimes/

sludges and in cadmium plant  leach  residue (iron oxide).

    The Administrator has determined that these wastes are

solid wastes which  may pose a substantial present or potential

hazard to human health or  the environment when improperly

transported, treated,  stored,  disposed of or otherwise managed,

and therefore should be subject  to  appropriate management

requirements under  Subtitle C of RCRA.   This conclusion is

based on the following considerations:

   1)   The wastes  contain significant concentrations of the
   toxic heavy metals cadmium and  lead.

   2)   Cadmium and lead have  been  shown to leach from
   samples of  these wastes in significant concentrations

-------
    when the samples were subjected to a distilled  water
    extraction procedure.

    3)  Electrolytic anode slimes/sludges and cadmium  plant
    leach residue are generated at a rate of 2,600  tons/year,
    and 200/tons year, respectively.  Sludge from the  treat-
    ment of process wastewater and/or acid plant blowdown is
    generated at a rate greater than 11,000 tons/year.  Such
    large quantities of wastes containing high concentrations
    of hazardous constituents increases probability of damage
    to human health and the environment under improper dis-
    posal conditions.

    4)  These wastes are currently stockpiled on site and/or
    hauled off-site to landfills, in a manner that could
    allow the cadmium and lead in the wastes; to leach to
    groundwater.

Industry Profile and Manufacturing Process

    Five plants produce zinc by the electrolytic process,  and

two plants produce zinc by pyrometallurgical techniques (3).

Locations of the plants, capacities and products are given

in Table 1.

    Electrolytic plants (not including the one new plant in

Tennessee) account for approximately 9 percent of the total

solid waste generated although they represent about 49

percent of the industry's production of slab zinc.   The two

pyrometallurgical plants account for 91 percent of  the solid

waste, although they represent only 51 percent of the produc-

tion of zinc (3).

   Electrolytic Process

       At four of the electrolytic zinc plants, actual production

rates range from 41,800 tons to 82,100 tons of slab zinc per

year.   These four plants account for approximately 268,300

tons of the total annual primary zinc production, or about

49 percent  of  the industry total.   The fifth plant  has come

-------
                             LOCATIONS,  CAPACITIES AND PRODUCTS OF PRIMARY
                                     ZINC SMELTERS AND REFINERS (3)
Company and Location
Pr oces s
De script Ion
 Capaci ty
(tons/year)
   Produc t
Araax, Inc.
  East St. Louis,  111
Electrolytic
   82,000
Slab zinc, cadmium,  zinc  sulfate,
  and sulfuric acid
Asarco, Inc .
  Corpus Christ!,  Tex
The Bunker  Hill  Co.
  Silver  King,  Idaho
National  Zinc  Co.
   Bartlesville,  Okla
Electrolytic
Electrolytic
ElectrolytIc
  108,000
  108,000
   55,000
Slab zinc, zinc  alloys,  zinc sul-
  fate,  cadmium,  and  sulfuric aci
Slab zinc, zinc alloys,  cadmium,
  and sulfuric acid
                                                                                                    c
                                                                                                    0
Zinc dust, zinc slab,  zinc  alloys,
  cadmium, cobalt cake,  copper/
  lead/nickel cake, and  lead  silve
  res Idue
 New  Jersey Zinc Co
   Palmer ton,  Pa.
 St.  Joe Minerals Corp
   Monica,  Pa.
Pyrometallurgical
Pyrometallurgical
  113,500
  250,200
Slab zinc, zinc alloys, zinc  dust
  and pellets, zinc oxide,  ferro-
  alloy, and sulfuric acid
Slab zinc, zinc alloys, zinc  oxide
  cadmium, ferrosi1icon, mercury,
  and sulfuric acid
 Jersey Miniere Co.
   Clarksville, Tenn.
Electrolyt ic
   90,000
Slab zinc, cadmium, sulfuric acid

-------
on-line recently, and production figures are not  yet  avail-




able (3).  Electrolytic processing basically involves  dissolv-




ing the zinc in a sulfate solution followed by electrolytic




deposition of zinc (3).  Process flow (see Figure 1)  at  the




plants is very similar, with some variation^).




     The sources of solid waste generated by the  electrolytic




process are: (1) treatment of preleach residue (this




operation occurs at only one plant), (2) the collection  and




treatment of acid plant blowdown and miscellaneous slurries,




(3) the cleaning of the electrolysis cells (anode slimes/




sludges), and (4) the filtration of the leach solution.




     The preleach process is used by one electrolytic plant




with an annual production of 62,300 tons.  Preleaching removes




excess magnesium from the incoming zinc concentrates.  Magnesium




is not electrolyzed but accumulates in the system; therefore




the zinc concentrates having high magnesium levels must be




preleached before further processing.   The preleach step




involves the reaction of sulfuric acid and a bleed stream




from the acid plant (i.e.,  acid plant  blowdown—a weak acid




stream) with a portion (up to 100%) of the incoming concentrates




to solubilize the magnesium.  The insoluble concentrate containing




zinc is separated and continues through the process.  The solu-




bilized material containing magnesium and the acidic preleach




solution enter a lined surface impoundment, from which it is




pumped to a  wastewater treatment plant (WWTP).   The sludge that




settles in the impoundment  is periodically removed and placed in




the WWTP.   This  sludge,  together with  the sludge produced from

-------
cess
sster
       PRELEACH
         PLANT
             UNDERFLOW
              SOLIDS TO
              COPPER OR
               . LEAD
              REFINERY
               SOLIDS TO
               CADMIUM
                PLANT
                              STORAGE
                                                     WATER
                                      GAS
                              ROASTER
                          i
                         DUST
                       COi_L£CTlON
                              CLASSIFIER
                                  &
                              BALL MILL
              CALCINE
                DUST
                    I
                   ACtO
                   PLAffT
H -SO4
                                                                            Acid  Plant
                                                                           Blowdown
                              LEACHING
                        zmc SOLUTION FROM
                          CADMIUM PLANT
THICKENERS
     &
  FILTERS
                 'Process
                 Wastewater
   ZINC
 SOLUTION
PURIFICATION
                             ELECTROLYSIS
               ZINC OXIDE
  CATHODE
  MELTING
  FURNACE
              WATER
  ZINC DUST
                                                 SPEKT CELL ACID
                                                                Anode  Slimes/Sludges
  CASTING
                           SLAB  ,r

                               BLOCKS
COOUNG TOWER
  SLOWDOWN
                                   OTHER
                                   SHAPES
           FICBRE    j.        ELECTROtTTIC  ZUC  flSBBCTIBU  PIOCESS

-------
the neutralization and precipitation  reactions  in  the  WWTP,

is continuously removed and hauled  to  an  off-site  landfill

operated by a private contractor.   At  the  plant  that uses

preleaching, the WWTP sludge also contains  solids  from acid

plant blowdown, anode slimes (electrolytic  cell  cleanings),

and miscellaneous slurries.  The available  information indicates

that 9,400 tons of WWTP sludge is generated  annually by  this

plant (^).

    All  zinc concentrates received  at  zinc  plants  are  roasted

to drive off sulfur and convert the zinc  sulfide in the  con-

centrate to an impure zinc oxide called calcine  (3).   The

conversion to calcine in the roaster produces a  roaster  off-

gas stream containing enough sulfur dioxide  to permit  sulfur

recovery as sulfuric acid.  All electrolytic plants treat the

roaster  offgas in sulfuric acid plants to produce  a salable

sulfuric acid.  The acid production results  in a weak  acid

waste stream from the scrubbing columns that clean the off-gas.

This waste is referred to as a bleed stream  or acid plant

blowdown.  The acid plant blowdown  is  neutralized  and  thickened,

and the  solids are allowed to settle in ponds (3).  Whether or

not the  solids are being stored for recycling, the solids do

constitute a solid waste as defined by §261.2*.  Treatment of
    *The Agency has concluded that it does have jurisdiction under
Subtitle C of RCRA to regulate wastewater treatment  sludges and
other waste materials that are used, reused, recycled or reclaimed.
Furthermore, it has reasoned that such materials do  not become
less hazardous to human health or the environment because they
are intended to be used, reused, recycled or reclaimed  in lieu
of being discarded.  Therefore, at this time, applicable require-
ments of Parts 262 through 265 and 122 will apply insofar as the
accumulation, storage and transportation of hazardous wastes
that are used, reused, recycled or reclaimed.

-------
the  acid  plant blowdown generates an estimated 1,400 tons of

sludge  per  year,  (3) which has been designated as hazardous.

    All electrolytic plants also generate a waste of anode

slimes  or sludges from cleaning of the electrolytic cells.

Anode  slimes/sludges consist of gangue material that is

passed  through earlier process steps but is not plated

out, or electrolyzed,  in the electrolysis step.  It is

estimated that anode slimes/sludges make up 2,600 tons of

the  annual  solid  waste produced (3).  This waste is also

designated  as  hazardous.*

    Pyrometallurgical Process

    There are  two pyrometallurigical zinc plants with a combined

annual  production rate of about 261,000 tons of zinc metal (3).

These  plants  account for approximately 51 percent of the total

production  of  zinc metal by the primary zinc industry, but 91

percent of  the total soldi waste produced by the industry.

Although  the  two  plants use the same basic processes (see Fig-

ure  2), they  differ greatly in the quantities of solid waste

generated and  in  the ultimate disposal or control of the waste (3)

    Pyrometallurgical processing entails the following steps:

sintering,  retorting,  refining and casting.  Sintering develops

the  desired characteristics for pyr©metallurgical smelting of the

calcine by  processing  the calcine in a sinter machine where the
    *A11  electrolytic plants also generate a leach residue
from filtration  of  the leach slurry, which is not currently
listed as hazardous  and will not be further discussed in  this
background document.
                               -SIS'-

-------
               ZINC CONCENTRATES
WATER
1

SLUDGE < COLLECTION *
WASTEWATER
TO TREATMENT
r
CONCENTRATE
DRYING
\
ROA!
CALC
COKE 	 "*>

SINTE
RESIDUE
1
COKE-r 	 *•
RESIDUE ,^ 	 	 ,
TREATMENT <
i *
• FERROSILICON
ZINC-POOR WATER •*•
RESIDUE TO
LEAD REFINERY
REDU
FURN
i

WATER GAS
! t
» DUST A
>'tH ^ COLLECTION p|
:iNE CADMIUM
r PLANT

niwtj • — ,'P- COLLECTION ^°^

CADMIUM PLANT j 	 j
r 1 i
CTJON >^ZINC OXIDE


r
CASTING 1 	 	 COOLING TOWER
CASTING | ^ SLOWDOWN
SLAB
BLO
'
CKS
l '
OTHER
SHAPES
kCID 	 te.H50,
JVNT

^ Acid Pla
Elcwdown
IS
^ By-product
^^ C^T-fJ TT«^.4-A
Solid '/aste
FIGURE  2.     PYROMETALLTJRGICAL
           ZINC  PRODUCTION PROCESS

-------
calcine  burns  autothermally and is fused  into  hard,  permeable

sinter.  Retorting consists of reducing the calcine  in  the

sinter with .carbon in a retort to produce  zinc metal.   Pre-

heated feed  of sinter and coal or coke is  fed  into the  top of

the retort;  the temperature reaches 1300°C-1400°C inside.

Because  of  the zinc's low boiling point (906°C), it  is  vola-

tilized  as  soon as it is formed.  In this  way  the zinc  is

purified by  separating it from the gangue  material in the

calcine.•  Zinc from the retort smelting may need further

purification  for some commercial uses.   The zinc Is  purified

by distillation in a graphic retort.  Molten zinc from  the

graphic  retort is either case pure into bars or blocks  or is

alloyed  with  other metals and case.

    The  sources of solid waste generated by the pyr©metallurgical

process  which  are hazardous are:  (1) collection and treatment

of acid  plant  blowdown, and (2) leaching of high-cadmium dusts

in the cadmium plant (3).*

    Both pyrometallurgical plants treat roaster off-gas in

their sulfuric acid plants to control sulfur dioxide emissions.

The process  is the same as the one described above for  electrolytic

plants.  The acid plants produce a salable sulfuric  acid and

a bleed  stream (acid plant blowdown) that must be neutralized.

One plant neutralizes the blowdown with lime,  which  leads to

the generation of an estimated 10,000 tons per year  of  settled


    *Two other wastes generated by this process (i.e.,  residue
    the production of zinc  oxide in Waelz Kins (one plant
only) and furnace residue from the operation of retort  and
oxidizing furnaces)  are not  currently listed as hazardous and
will not be further discussed in this background document.

-------
sludge, half  of  which  is  recycled to the process.  The sludge




contains  significant concentrations of cadmium and lead and




is designated  as  hazardous.




     The  other pyrometallurgical  plant uses the acid plant




blowdown  to cool  and humidify  the roaster off-gas in a humi-




difying scrubber.   Acid plant  blowdown from the scrubber is




thickened and  then  cooled  before  being recycled to the




scrubber.  A  bleed  stream  from the  thickener bottoms is sent




to the cadmium plant for cadmium  recovery.   This  acid plant




process generates no wastes.




     Both of  the  pyrometallurgical  plants operate cadmium




plants to process dusts with high cadmium content that are




collected from the  sinter  machine off-gas. •  Processing in




the cadmium precipitation  to produce  a cadmium sponge.   The




leaching  steps produce  two residues.   One contains relatively




large quantities  of lead,  silver, and  gold,  and is sold as a




by-product.   The  other  residue constitutes  a solid waste




that contains cadmium and  lead  and  is  generated at a  rate of




200 tons  per year.(3) The  latter  residue  has been classified




as hazardous.




Waste Generation  and Management (3)




     At both the  electrolytic  and pyrometallurgical  facilities




off-gases from the roaster are  treated  in sulfuric acid




plants to control sulfur dioxide  emissions.   This process




generates acid plant blowdown  which may  be  mixed  with the




process wastewater prior to treatment  by  lime  precipitation.

-------
The resulting sludge  contains significant levels of lead and




cadmium and is designated as hazardous.




    Electrolytic  refining generates a waste of anode slimes/




sludges from cleaning the electrolytic cells.  These slimes/




sludges consist  of  gangue material that has passed through




the earlier process  steps but was not plated out in the




electrolysis step.   This  waste also contains significant




amounts of; lead  and  cadmium and- is designated as hazardous.




    , Pyrometallurgical  plants process' high cadmium dusts




collected from the  sinter baghouse to recover cadmium.




Processing involves  acid  leaching which produces two residues.




One contains significant  amounts of lead, silver and gold;




this residue is  sold  as a by-product.  The other residue is a




solid waste designated  as hazardous because of its lead and




cadmium content.




    Current solid  waste  control practices are fairly uniform




throughout the zinc  industry.  Of the total solid waste gen-




erated, about 90 percent  is controlled through on-site  stockpiling,




1 percent is removed  by private and municipal organizations




and individuals  for  various uses (such as winter road sand),




and the remaining  3  percent is hauled and landfilled by private




contractors.



    Control Practices  at Electrolytic Plants (3)




    Electrolytic zinc  plants produce solid waste consisting




of anode "siimes/sludges", neutralized acid plant blowdown,




surface impoundment  dredgings, wastewater treatment sludge,




and goethite residue.

-------
     Two of the electrolytic plants  use wastewater  treatment




plants  (WWTP) to treat plant wastewater and various  process




sludges.  At both of these plants the WWTP sludge is




removed and hauled to off-site landfills.  One of the  two




plants  removes this sludge continuously as it is filtered




(dewatered).  There is no on-site storage or disposal  at this




plant.  This particular sludge contains solids from anode




sludge, neutralization of aci-d plant blowdown, impoundment




dredgings, and sludge generated from the treatment, of  a




preleach slurry.  The other plant using a WWTP piles WWTP




sludge  on-site temporarily for drying prior to removal and




transportation to an off-site landfill.  This particular




sludge  contains solids from the neutralization of acid plant




blowdown and solids precipitated from plant runoff and washdown




At this plant, anode sludge is not treated in the WWTP but




is stockpiled on site.  The WWTP sludge from these two plants




amounts to about 31 percent of the solid waste generated at




electrolytic plants.   All of this sludge is hauled to  off-site




landfills, either immediately or after temporary on-site




storage.  Because the WWTP at each of these plants treats




acid plant blowdown,  the WWTP sludges generated containing




cadmium and lead, are considered hazardous.




     Two of the remaining three electrolytic plants stockpile




dredgings from surface impoundments on-site.   One of these




plants generates two  additional solid wastes that none of




the other plants generate.  These two wastes, goethite and a




sulfur residue,  are also stockpiled on-site.
                                 -330-

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     Three  of Che four electrolytic  zinc  plants  operating

 through  1978 used lined surface  impoundments.   Two  of  these

 plants use  synthetic liners; the  other  uses  a  clay  liner.

 The fourth  plant has an unlined  surface impoundment.   Moni-

 toring wells are used by at least one plant. (3)*

     It  is  assumed(3) that the fifth plant,  one  which  has

 recently come on-line and will have  a WWTP,  will generate a

 ,sludge which will be removed to  an off-site  landfill.   It, is

 .also assumed(3) that this plant will use 'a, lined surface
                                    «r
 impoundment which treats the anode sludge, acid  plant  blowdown,

 impoundment dredgings, and plant  wastewater  in  the  WWTP.

 These assumptions, based on plant similarities  indicated  in

 the available literature(3), were necessary  to  estimate

 quantities  of solid waste generation at this new facility.

 In order to avoid underestimation, the  new plant  is also

 assumed  to  generate a solid waste (such as goethite residue)

 that is  stockpiled on-site.

     Control Practices at Pyrometallurgical  Plants

     The two pyrometallurgical zinc plants produce  acid plant

 blowdown, furnace (retort, oxide, and Waelz  kiln) residue,

 scrap furnace brick, and a cadmium plant residue.   One  of

 these plants has a relatively small solid waste  stockpile.

 The other pyrometallurgical plant has an extremely  large

 stockpile of solid waste.   This plant alone  generates  about

 89 percent  of the solid waste produced  by all primary  zinc
"""  *The groundwater monitoring system at this one  plant  may
Qot be sufficient  to  adequately monitor leaching  from  the
surface impoundment.

-------
plants(3).  Solid waste stockpile  sites  are  selected  primarily




for convenience.  No site preparation  is  conducted  other




than clearing and grubbing.




     Both plants have surface impoundments.   The  impoundment




at one plant is lined with synthetic material;  the  impoundment




at the other is not lined.  At one plant, the impoundment




collects acid plant blowdown and plant water.   At the  other




plant, acid plant blowdown is not  slurried to the impoundment,




but is instead sent to the c'admium plant  for  further .processing.




Dredgings from both impoundments are controlled on-site.  One




plant recycles all dredgings to the process;  the  other  recycles




about half of the dredgings and stockpiles the  remainder.  One




of the plants also stockpiles cadmium  plant  residues on-site.




    These plants do not use surface water control by collection




and diversion ditching to its fullest  potential.^)  Neither do




the plants currently use barriers  to prevent  seepage from




solid waste stockpiles, or wells to monitor or  collect  any




seepage or leachate(S).






Hazardous Properties of the Wastes




     The Administrator has classified  the process wastewater




and/or acid plant blowdown treatment sludge, electrolytic




anode slimes/ sludges, and the cadmium plant leach  residue




(iron oxide) as hazardous because of the  high levels of




toxic cadmium and lead found in the wastes.    In EPA's  "Assessment




of Hazardous Waste Practices in the Metal Smelting  and  Refining




Industry," Calspan Corporation tested  samples of  the wastes

-------
and performed  extraction tests on the wastes  using  distilled

water as the extraction medium (1).  The  results  are  as
follows :
Sludge  from  acid
  plant blowdown
  (Electrolytic
   Plant)
                   Waste Analysis  (ppm)    Extract  Analysis  (ppm)
                      Cd
 550
     Pb

     98
   1750
 18,100
                           Cd
                                         2.1
                                         1.0
Sludge  from  acid
  plant  blowdown
  (Pyrometallur-
   gical Plant)
Anode  slimes/
  sludges
 Cadmium Plant
  Residue
2000
 640
   4350
   4280
<0.01 -
1.3
  12
1400
 280
170,000
 89,000
215,000
   12
2.0
<0.01
9.0
       Calculations of sludge contents from  1ime-and-settie

wastewater  treatment also indicate that  significant  amounts

and concentrations of lead and cadmium are present  in  these
wastes  (2)

Plant
//I

#2
Contaminants
Cadmium
Lead
Cadmium
Lead
                  Percent in Sludge
                        4.0%
                        2.5%
                        2.6%
                        1.7%
        Cadmium and lead are always  expected  to  be in the

sludges  after treatment because 1)   the  treatment  processes are

designed to  remove such elements  from  the  wastewater to meet

-------
effluent  standards,  and  2)   cadmium and  lead will not be lost

(e.g., volatilized)  in  the  treatment process.

      Based  on  the  data  presented  above,  the  waste is  classified

as hazardous because  it  contains  significant concentrations

of cadmium  and  lead  which are  toxic and  because  the extraction

tests  performed  on these wastes  indicate that  the cadmium

and  lead  may be  in a  soluble form and  could  be released  to

the  environment  in harmful  concentrations.   The  fact  th'at

water  extractions  of  the wastes have shown that  the wastes

could  leach potentially hazardous  concentrations  of toxic

metals indicates that under  the mildest  environmental  condi-

tions  (e.g., neutral  pH  rainfall)  at a, mono-disposal  site,

the  wastes  may leach  contaminants  to the  groundwater  in  con-

centrations which  would be  harmful  to  human  health and the

environment.  Where  conditions tend  to be acidic,  the  release

of these  heavy metals over  the lifetime  of a landfill  is

expected  to be even higher  than indicated by the  water extrac-

tion  data,  since cadmium and lead  solubilities increase  with

a decrease  in pH (4),__/

        On-site  stockpiling is most  likely not an  environmen-

tally acceptable means of disposing  of a  waste which  contains
     _J The Agency has determined to list wastes from primary
zinc smelting and refining as a "T" hazardous waste, on  the
basis of lead and cadmium constituents, although  these con-
stituents are also measureable by the EP toxicity character-
istic.   The Agency believes that there are factors  in addition
to metal concentrations in leachate which justify the "T"
listing.  Some of these factors are to the high concentrations
of lead and cadmium in actual wastes streams, the non-degrada-
bility of these substances and indications of lack  of proper
management of the wastes in actual practice.

-------
significant  concentrations of toxic heavy metals  that have




been  shown to  migrate from the waste.  Surface water can




become contaminated  with contaminants from these  wastes via




runoff from  rainfall.  Similar hazards exist if these waste




are disposed of  in improperly managed landfills or surface




impoundments;  leaching, run-off, or overflow may  result in




contamination  of  surface and groundwaters.




   The cadmium  and  lead that may migrate from the waste to




the environment  as a result of improper,disposal  practices




are heavy metals  that persist in the environment  and therefore"




may contaminate  drinking water sources for extremely long




periods of time.   Cadmium is toxic to practically all systems




and functions  of  the human and animal organism(5).  Acute




poisoning may  result from the inhalation of cadmium dusts




and fumes (usually cadmium oxide) and from ingestion of




cadmium salts(6).   Lead is poisonous in all forms; it is one




of the most  hazardous of the toxic metals because it accumu-




lates in many  organisms and the deleterious effects are




numerous and severe.  Lead may enter the human system through




inhalation,  ingestion or skin contact.  Ingestion of contami-




nated drinking water is a possible means of exposure to




humans as a  result of improper management of these wastes.




Additional information on the adverse health effects of




cadmium and  lead  can be found in Appendix A.




   The hazards associated with exposure to cadmium and lead




have  been recognized by other regulatory programs.  Lead and

-------
cadmium are listed as Priority Pollutants  in accordance  with




§307(a) of the Clean Water Act of 1977.  Under  §6 of  the




Occupational Safety and Health Act of 1970, a final standard




for occupational exposure to lead has been established (7).




Also, a national ambient air quality standard for lead has




been announced by EPA pursuant to the Clean Air Act (7).




    In addition, final or proposed regulations of the State of




California, Maine, Massachusetts, Minnesota, Missouri, New




Mexico, Oklahoma and Oregon define cadmium and I ead-cont'aining




compounds as hazardous wastes or components thereof (8).   EPA




has proposed regulations that will limit the amount of cadmium




in municipal sludge which can be landspread on crop land (9).




The Occupational Safety and Health Administration (OSHA) has




issued an advance notice of proposed rulemaking for cadmium




air exposure based on a recommendation by the National




Institute for Occupational Safety and Health (NIOSH)  (10).




EPA has prohibited ocean dumping of  cadmium and cadmium




compounds except as trace contaminants (11).   EPA has also




promulgated pretreatment standards for electroplaters which




specifically limit discharges of cadmium to Public Owned




Treatment Works (12).

-------
                          References

 1.   U.S. EPA, Office  of  Solid  Waste.   Assessment of Hazardous
       Waste Practices  in the Metal Smelting and Refining
       Industry..   Calspan Corporation,  EPA Contract Number
       68-01-2604,  April  1977,  Volumes  II and IV.

 2.   U.S. EPA, Effluent  Guidelines  Division, Draft Development
       Document  for Effluent Limitation Guidelines and New
       Source Performance Standards for the Major Nonferrous
       Metals Segment  of  the Nonferrous Manufacturing- Point
       Source Category.   Washington,  D.C.   September,  1979.

 3.   U.S. EPA, Office  of  Solid  Waste.   Assessment of Solid Waste
       Management  Problems  and  Practices in Nonferrous Smelters.
       PEDCo Environmental  Inc.   Washington, D.C.  November,
       1979.,

 4.  Pourbaix, Marcel.   Atlas of  Electrochemical  Equilibria in
       Aqueous Solutions, London,  Pergamon Press, 1966.

 5.  Wladbott, G.L.   Health  Effects  of  Environmental Pollutants.
       St. Louis,  C.V.  Mosby Company,  1973.

 6.  Gleason, M., R.E.  Gosselin,  H.C.  Hodge, B.P.  Smith.   Clinical
       Toxicology  of Commercial  Products.   Baltimore,  The
       Willaims  and Wiltkins Co.,  1969.  3rd Edition.

 7.  U.S. Department of  Interior,  Bureau of Mines.  Mineral
       Commodity Summaries,  1979.

 8.  U.S. EPA State  Regulations  File,  January 1980.

 9.  44 .FR 53449.

10.  44 _FR 5434.

11.  38 £R 28610.

12.  40 CFR, Part 413.

-------
Response  to  Comments  to  Proposed  Regulations

     Comments  were  received  from three  companies  pertaining

to  the  listing  of  wastes  from  the primary  zinc  industry.

The  comments  address  the  following  general  points:

     1.  Listed  wastes are recycled  and  not  discarded.

     2.  Listed  wastes are being stored  on-site  but  will
        eventually  be recycled.

     The  Agency has concluded  that  it  does  have  jurisdiction

under Subtitle  C of RCRA  to  regulate wastewater  treatment

sludges and  other waste materials  that  are  used,  reused,

recycled  or  reclaimed.  Furthermore, it has reasoned that

such materials  do not become less hazardous to human health

or  the  environment  because  they are intended to  be  used,

reused, recycled or reclaimed  in  lieu  of being discarded.

Although  the  materials recycled and reclaimed may not pose a

hazard, the  accumulation, storage and  transport  of  a hazardous

waste prior  to use, reuse,  recycle or reclamation will present

the same hazard as  they would  prior to being discarded.  In

addition,  the act of use, reuse,  recycling or reclamation,

in many cases, poses a hazard  equivalent to that encountered

if the waste  were discarded.   Thus, the Agency believes it

has a strong  environmental rationale for regulating hazardous

wastes that are used,  reused,  recycled or reclaimed.

     For the  particular wastes at issue, the Agency recognizes

that these wastes for  most or  all of its existance  prior to

being recycled is deposited in a  surface impoundment when  the

-------
potential  for  leaching of the hazardous constituents  is  real




and  significant.   Consequently, the waste must  be  considered




a hazardous  waste  in this environment; to avoid  listing  it  as




a hazardous  waste  would be unjustified.  Likewise,  if  the




waste  is  piled and stored on the land, prior to  recycling,




the  potential  of  leaching of its hazardous  constituents  with




in to  the  environment would still prevail and avoiding its  regu'




lation, would ,be unjustified.




     The  key 'question, therefore, is not wnether, or not  it




is a hazardous waste and should be listed as a hazardous




waste, but whether or not to what degree it should be regu-




lated  during recycling; that is should the  recycling process




and  facility be considered a hazardous waste management  opera-




tion and  facility  required to obtain interim status and  event-




ually  a permit and required to meet the standards set forth




in Parts  264 and  265 of the regulations.   At this time,  the




Agency has deferred regulation of such facilities because it




recognizes that the full set of Subtitle C  management require-




ments  may  not  be necessary.  As and when it concludes that




regulation of  these facilities in necessary, it  will terminate




this deferral  and  impose either the requirements of Parts 264




and  265 (as  well as 122) or special tailored requirements




under  Part 266.



    At this time,  applicable requirements  of Parts 262




through 265  and 122 will apply insofar as the accumulation,




storage and  transportation of,hazardous wastes that are  used,

-------
reused, recycled or reclaimed.  The Agency believes this




regulatory coverage and the above described deferral of




regulated coverage in appropriate to the subject wastes.




These sludges are hazardous insofar as they are being ac-




cumulated and stored in surface inpoundments and insofar




as they may be stored in piles prior to recycling.   There-




fore, these sludges should be listed as hazardous waste.




These sludges may not:pose a substantial hazard during their




recycling and, even though listed as hazardous  waste,  this




aspect of their management is not now being regulated.

-------
Emi
              LISTING BACKGROUND  DOCUMENT

                SECONDARY  LEAD  SMELTING


ssion control dust/sludge  from  secondary lead  smelting  (T)
Waste leaching solution  from  acid  leaching  of  emission
control dust from secondary lead  smelting  (T)


I.   Summary of Basis  for  Listing

     The emission control  dust/sludge  from  reverberatory  furnace

smelting of secondary  lead products  is  generated  when  lead,

cadmlunij and chromium  contaminants  found in the  source materials

are entrained in the furnace  fumes  during  the  smelting process

and subsequently collected by air  pollution control  equipment.

Dry collection methods generate a  dust  as  a solid  residue;

wet collection methods generate a  sludge as a  solid  residue.

The sludge is usually  land disposed  as  a waste.   The dust  is

usually recycled for further  lead  smelting;  before recycling,

however, the dust may  be leached with  acid  for zinc  recovery,

and the resulting waste  acid  leaching  solution containing

cadmium, chromium and  lead is  land  disposed.  The  Administrator

has determined that these  dusts/sludges and the  waste  acid

leaching solutions from  acid  leaching  of these dusts/sludges

are solid wastes which may pose a  substantial  present  or  poten-

tial hazard to human health or the  environment when  improperly

transported, treated,  stored,  disposed  of  or otherwise managed,

and therefore should be  subject to  appropriate management

requirements under Subtitle C  of RCRA.  This conclusion is

based on the following considerations:

     1)    The emission control dusts/sludges contain significant

-------
           concentrations  of the toxic heavy metals  lead,
           cadmium  and  chromium.

      2)    Waste  leaching  solutions from acid leaching of  the
           emission control dusts/sludges likewise contain
           significant  concentrations of lead, cadmium, and
           chromium,  since the  acid leaching medium  solubilizes
           these  heavy  metals.

      3)    The  hazardous  constituents of these waste streams
           may  migrate  from the  waste in harmful concentrations,
           since  distilled water extraction procedures performed
           on  samples of  the emission control dust and sludge
           leached  significant  concentrations of cadmium and
           lead from  the  sludge  and ,significant concent rat ions
           of  lead,  cadmium,  and chromium fr.om the dust.

      4)    The  emission control  sludge and the waste leaching
           solutions  are  typically disposed of in unlined
           lagoons,  thus  posing  a realistic possibility of
           migration  of lead, cadmium and chromium to under-
           ground drinking water sources.  Further,  these
           elemental  metals persist in the environment, thereby
           posing a real  danger  of long-term contamination.

      5)    Very large quantities of these emission control dust/
           sludges  are  generated annually (7,151,600 metric
           tons  of  sludge  and 127,158,700 metric tons of  dust
           in  1977)  and are available for disposal as solid
           waste.   There  is thus greater likelihood  of large
           scale  contamination of the environment if these
           wastes are not  managed properly.

I.    Industry  Profile  and Manufacturing Process

      Eighty-two  plants located  in 27 states manufacture

secondary  lead products.   The major  production centers are

located in the Great Lake States,  in Texas  and in Louisiana

(1,5).  Plant  locations by state are shown in Table 1.

      Plant capacities  range  from 25,000 to  40,000 metric tons

of lead per year (1, 5).    The total  quantity of lead produced

by the secondary lead  industry  was  769,000  metric tons in

1978  and the estimate  for  1979  is  760,000  metric tons (4).

-------
                          Table 1 (1)
       Distribution  of  Secondary Lead Smelters by State
State                            No. of Plants

Alabama                                2
California                             8
Colorado                               2
Delaware                               1
Florida                                3
Georgia                                3
Illinois                               7
Indiana                                4
Kentucky                               1
Louisiana                              2
Maryland                               1
Massachusettes                         2
Michigan                               4
Minnesota                              1
Mississippi                            1
Missouri                               2
Nebraska                               2
New Jersey                             3
New York                               4
North Carolina                         2
Ohio                                   6
Pennsylvania                           7
Texas                                  9
Tennessee                              2
Virginia                               1
Washington                             1
Wisconsin                              1

-------
     Four  products  are  manufactured in the secondary lead




industry:  refined lead,  lead  oxide, antimonal lead and lead




alloy.   Individual  plants  may produce any or all of the




products.  As  shown  in  Figure 1,  the source materials will




vary for each.   Discarded  batteries comprise the major source




material.  Other source  materials  are lead residues,  lead




slags and  scrap  iron.




II.  Generation  and  Management  of  Listed  Waste Streams




1.   Emission  Control Dust/Sludge




     Emission  control dust/sludge  is generated from the




manufacture of refined  lead,  lead  oxide,  and lead  alloy in




reverberatory  furnaces.  In the production process,  "soft




lead" (low antimony  lead)  is  smelted in a  reverberatory




furnace  from lead residues, scrap  lead, and  in the  case of




lead alloy, recycled secondary  lead  emission control  dust is




a  source material.   The  soft  lead  is then  further  processed




to either refined lead or  lead  oxide.  In  the  scrubbing of




reverberatory  furnace emissions, cadmium,  chromium  and  lead




entrained in the fumes are collected by either wet  scrubbing




or by baghouse, resulting  in  a  sludge  or  dust  that  may  be




discarded.   The Agency attributes  the  presence of  lead,




cadmium and chromium in  the waste  stream  to  their  presence in




the source materials.  (See p.  10  below confirming  the  presence




of these heavy metals in the  waste  stream  in significant




concentrations.)
                              -•3HH-

-------
                                                                            WASTE BATTERIES
 I

00
                                                   LEAD RESIDUES
                WASTE
                SOLIDS
DAGHOUSE
                                         EMISSIONS
                                                                  H,O
                                                  BATTERY
                                                  CRACKING
                         H,O
                             SCRUBBER
                                \
                          LIQUOR TO RECYCLE
            "^Sludge
               to
            Lagoon
REVERBERATORY
   FURNACK
                                       SLAQ
                                 i
                              REMELT
                              KKTTLB
                            REFINED LEAD
                                                          SOFT LEAD
       \
                          BARTON
                         OXIDATION
                         LEAD OXIDE
                                                  ,O -f ELECTROLYTE
                                                   TO TREATMENT.
                                                                                                CASINOS TO DISPOSAL
                                                                                       SCRAP IRON
                                                                                 Li
 BLAST
FURNACE
                                                                                           EMISSIONS
                                                 ANTIMONIAL
                                                    LEAD
                                                                                         At.Cu
                         ANTIMONIAL LEAD
BAQHOUSE
B^MMMBW^^fr
WASTE
SOLIDS
                                                                                                    LIQUOR TO RECYCLE
                                                                              t
                                                                         Slud)
                                                                       ** to
                                                                       Lagoon
                                                     SCRUBBER
                                                M,O
                                                                                                                  EMISSIONS
                                                                           i
                                                     RCMELT
                                                     KCTTLK
                         LEAD ALLOY
                                     FIGURE i
                           SECONDARY  LEAD/ANTIMONY  SREltlMC  PROCESS

-------
      Three  plants  in the industry use wet scrubbing which


generates a  sludge.   The sludge is typically disposed in


unlined  lagoons  (1,5).


      Dry collection  methods  (i.e., baghouses) are used by all


other  plants,  generating a  dust as a solid residue.  This dust


is available  for disposal or for recycling.


2.    Waste  Leaching  Solution


      Emission  control  dusts  are often recycled for use as input


material for  lead  alloy  ("white metal")  production.  The recy-


cling  process, however,  generates a separate waste stream which


is listed along with  emission  control dust/sludge.  Before


the dust is recycled  to  the  remelt kettle for lead alloy produc-


tion,  it is leached  with dilute sulfuric  acid to  remove  zinc.


The waste leaching solution  contains chromium,  cadmium,  and  lead


leached  from the emission control dust.


      With regard to  the  management of the waste leaching


solution, EPA  is presently aware  that a  plant in  New Jersey
                                                     •

receives secondary lead  emission  dusts  for recycling.   The


dusts  are leached, and the waste  acid solution  is disposed of


on-site in unlined lagoons (3).   EPA presently  lacks information


on other waste leaching  solution  generating  locations  and


management practices.


     The Agency wishes to make  clear that it is not regulating


those wastes which are recycled directly  to  the process  as a


hazardous waste.  However, if  the dusts are  stored prior to
                             -*-

-------
recycling,  they are defined  as  solid  wastes  and are subject

to Subtitle C jurisdiction.*

3.   Secondary Lead Smelting  Industry Waste  Generation Levels
     and Trends

     Generation of emission  control  dust/sludges  from

reverberatory furnaces  is  already  very substantial, and is

expected to increase in  the  future.   Table  2 shows  the historic

sludge/dust generation  from .wet  and  dry scrubbing of

reverberatory furnaces  (5).   Historic quantities  are given

for 1967 and 1977 as well  as  minimum  and  maximum  generation

projections predictions  for  1980,  1984,  and  1987.   The total

dust/sludge generation  for 1977  (dry  weight  basis)  was

127,158,700 metric tons.   While  not  all of  these  materials

are disposed (due to dust  recycling),  it  is  nevertheless  clear

that substantial quantities  of wastes  are  generated annually.**

     These  quantities can  be  expected  to  incr ease — part icular ly

dust generation.  First, New  Source Performance Standards
 *At this  time,  requirements of Parts  262  through  265  and
122 will apply to the accumulation,  storage,  and  transportation
of hazardous wastes that are used,  reused,  recycled  or reclaimed.
The Agency believes this regulatory  coverage  is  appropriate  to
the subject waste.  These dusts/sludges  are defined  as hazardous
only if  they are being accumulated  and  stored  in  piles prior to
recycling.  These dusts may not pose  a  substantial hazard  during
their recycling  and, even though  listed  as  a  hazardous waste,  this
aspect  of  their  management is not now  being regulated.

**The Agency presently lacks data to  estimate  the  percentage
of secondary lead smelting emission  control dust  which is
recycled,  although a major percentage  of dusts  generated
may be  recycled.  In light of the large  quantities of  dust
generated, the Agency believes large  amounts  of  these
dusts are  managed as wastes, and  not  recycled.

-------
                                 SECONDARY LEAD INDUSTRY  -  (dry  weight  basis)  (5)
            I
            I
            I
Illinois    |3-04
Kansas      |3-04
Pennsylvania|3-04
          "T
 State
I    SCC  Code
I
Process
                                                                Total  Sludge/Dust Generation
                                                                   (10^ metric  tons/year)
                                                   Historic
                                                 1967
                         1977
                                   Minimum Scenario
                        Maximum  Scenario
                                                           I
                                                      1980 |    1984
                                   	1
                                   1987  I   1980
                                 1984
                                                                                  1987
                         Wet Controls
Alabama
Arizona
California
Indiana
Lousisiana
Minnesota
Mississippi
Missouri
Nebraska
N. Jersey
Ohio
Tennessee
Texas
Virginia
Washington
J3-04
13-04
13-04
J3-04
13-04
13-04
13-04
I 3-04
j 3-04
J3-04
J3-04
|3-04
 3-04
 3-04
 3-04
                                                4964.2
-004-02|Reverberatory  furnacel 4505
-004-02JReverberatory  furnacel   27
-004-02|Reverberatory  furnacel  431
       I
       |     Total  sludge  from
       I       wet  controls
       I
       |Dry Controls
       I
-004-02jReverberatory  furnacel
-004-02|Reverberatory  furnacel
-004-02JReverberatory  furnacel
-004-02 IReverberatory  furnacej 1849
-004-02jReverberatory  furnacel 2481
-004-02JReverberatory  furnacel 1327
-004-03jReverberatory  furnacel  541
-004-03|Reverberatory  furnacel 2173
-004-02|Reverberatory  furnacel 7380
-004-02JReverberatory  furnacel 1856
-004-02|Reverberatory  furnacel  550
-004-02|Reverberatory  furnacel 5403
-004-021Reverberatory  furnacel62043
-004-02|Reverberatory  furnacel 1187
.5
.5
.2
                                                        6490.8
                                                          39.6
                                                         621.2
                                 6924
                                   42
                                   662
~T
  I
  I
.31
.21
• 7|
    7718.4
      47.0
     738.7
                                                      8314.
                                                        50.
                                                       795.
T
 I
 I
0|
61
7|
                                                                                7755.2
                                                                                  47.3
                                                                                 742.2
                                                                                          8644.6
                                                                                            52.6
                                                                                           827.3
                                                               9311.7
                                                                 56.7
                                                                891.2
                        7151.6
                 660
                   8
                 360
   .0
   .3
   .5
   .6
   .2
   • 3|
   .61
   .51
   .81
   • 2|
   .0|
   .0|
   .21
   .91
     •004-02jReverberatory furnace
            I
            |     Total  dust from
            |       dry  controls
340.7|
                                                      T
                                                                        I
                                                                 7629.21  8504.1
                                                                        I
                                                                        I
                                                                        I

                                                          950.8j  1014.31  1130.6
                                                           11.9|     12.7J    14.2
                                                          519.3J    554.0J   617.5
                                                         2664.6|  2842.61  3168.6
                                                         3574.5j  3813.21  4250.51
                                                         1912.1|  2039.81  2273.71
                                                          780.2|    832.31   927.8|
                                                         3131.2|  3340.3|  3723.4|
                                                        10633.1|  11343.31  12644.2J
                                                         2674.1|  2852.71  3179.9J
                                                          792.3J    845.2J   942". l|
                                                          778.4J    830.4J   925.61
                                                        89382.4J  95352.4|106288.1|
                                                         1711.4J  1825.7J  2035.1J
                                                          490.81    523.61   583.7|
                   1
             9160.31   8544.7
                   1
                   1
                                                                         9524.5
                                                                                                  10259.6
             1217
               15
              665
             3413
             4578
             2449
              999
             4010
            13619
             3425
             1014
              997
           114489
             2192
              628
                                                             1
                                                             1
                                                           8J
                                                           3|
                                                           1|
                                                           ij
                                                           51
                                                           2J
                                                           41
                                                           .71
                                                           .9J
                                                           .31
                                                           .81
                                                           .0J
                                                                                1136.0
                                                                                  14.2
                                                                                 620.5
                                                                                3183.7
                                                                                4270.8
                                                                                2284.6
                                                                                 932.2
                                                                                3741.1
                                                                               12704.5
                                                                                3195.0
                                                                                 946.6
                                                                                 930.0
                                                         9106794. 7
                               T
                                               88163.81120007.11128022
                                                      I         I
    ~~~1	
5|142705. | 53716
 I         I
                                                         1|
                                                         7J
                                                                2044.8
                                                                 586.4
                                                                        T
                                                           "1	
                                                           8|143385.1
                                                             I
                                                   1266.3    1363.9
                                                     15.9      17.1
                                                    691.6     744.9
                                                   3548.8|   3882.7
                                                   4760.5J   5127.9
                                                   2546.51   2743.1
                                                   1039.11   1119.3
                                                   4170.21   4492.0
                                                  14161.5|  15254.3
                                                   3561.51   3836.3
                                                   1055.21   1136.6
                                                   1036.71   1116.6
                                                 119042.7|128228.7
                                                   2279.31   2455.2
                                                    653.71    704.1
                                                                                                 I	
                                                                                         159829.5|172162.7
                                                                                                 I
                                                 T
Total sludge/dust|93128
from wet/dry     J	
controls
                                                      |127158.7 135651
                                                      |
                                        II
                                       7 J151209.1 1145319
                                        II
                                                                            ~1	
                                                                              I
                                                                            8|151929.8
                                                                              I
                                       1
                                       1
                              169354.  1274758.7
                                       1

-------
 Wl
 ill  limit particulate  emissions  from new reverberatory furnaces,

resulting in increased  collection  of  particulate wastes.   Since
                                                 /

baghouses are the most  cost-effective means  of  meeting NSPS,

it is expected that dry  collection of emissions will  continue

to be used in the industry  and  lead  to increased generation

of emission control dusts  (5).

     Production of secondary  lead  is  also increasing,  again

with  the likely result  of  increasing  emission control

dust/sludge generation.  Secondary lead  production  in  fact

increased by 200% between  1969  and 1979  (5).  Projected

dust/sludge generation  levels (estimated  on  a minimum/maximum

basis) are 145,319,800 - 274,475,700  metric  tons (dry  weight)

by 1987 (Table 2).*

Ill.  Hazardous Properties of  the Wastes

1.   Concentrations of Lead,  Cadmium  and  Chromium  in  the  Waste
     Stre ams.

     Agency data indicates  that significant  levels  of  the toxic

metals lead, cadmium and chromium  are found  in  the  emission

control dust/sludge.   As indicated in Table  3,  lead may comprise

as much as 5 - 10% of the entire waste  stream.   Chromium  and

lead  concentrations are also high  (although  nowhere near  so

elevated):
 *The  Agency does not presently  have  data showing
quantities of waste leaching  solution generated.   Increased
rate  of emission control dust  recycling  may,  however,  lead
to increased generation of waste  leaching solution.

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                            Table  3
Emission Control Sludge
From Soft Lead Smelting

Emission Control Dust
From Lead Alloy Smelting
Waste Analysis (ppm)

 Cd       Pb      Cr
 340    53,000    30
 900   120,000
150
     The Agency does not have  heavy metal  concentration data

for the waste leaching  solution.   Concentrations  of  these

heavy metals in the waste leaching solution,  however,  can  be

expected to be significant since  the  acid  leaching medium  will

solubilize heavy metals fairly aggressively  --  indeed,  it  is

intended to perform this function.  Some concrete  idea  of

concentrations in the waste leaching  solution can  be  gained

from comparision of a distilled water  extract of  emission

control dust presented  in Table 4  below.   Since lead,  cadmium,

and chromium are more soluble  in  acid  than in distilled water

(7,8), the concentrations of these constituents in the  dilute

sulfuric acid leaching  solution can be  expected to be  at

least as great as, and more likely higher  than  concentrations

in the distilled water  extract.

2.   Propensity of Lead, Cadmium, and  Chromium'to  Migrate  From
     the Wastes in Dangerous Concentrations  and Possible Path-
     ways of Exposure of Improperly Managed  Wastes.

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     The presence of such  high  concentrations  of  toxic  metals

in a waste stream may pose a  serious  threat  to human  health

and the environment should these  toxic metals  be  released.

Furthermore, distilled water  extraction test data  indicate

that these toxic constituents may leach from the  waste  in

harmful concentrations unless the wastes are properly managed.

Thus, a distilled water  extract from  samples of the secondary

lead emission control dust and  emission control sludge  presented

in Table 3 indicates that  lead, cadmium, and (in  the  case of

the emission 'dust) chromium may solubilize from the waste in

concentrations several orders of magnitude greater than

Interim Primary Drinking Water  Standards.  See Table 4  (1).
Emission Control Sludge
From Soft Lead Smelting

Emission Control Dust
From Lead Alloy Smelting

Interim Primary Drinking
Water Standard
                           Table 4
                                           Distilled Water
                                        Extract Analysis  (ppm)
                                        Cd
230
.01
          Pb
         2.5
24.0
 .05
           Cr
          .05
12 .0
 .05

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     While  the  Agency  has  not performed any analyses of  the



waste acid  leaching  solution, as noted above, the Agency



believes  lead,  chromium  and  cadmium concentrations in waste



acid leaching  solution will  probably be higher than in the



distilled water  extract  of  the emission control dust.  Further-



more, since the  waste  leaching solution may be disposed of



in liquid form,  i.e.,  with  harmful  constituents already solu-
                                   /\

bilized and available  for migration into the environment,



there is  a  corresponding dang.er  of  exposure to harmful concen-



trations  of these metals if  the  waste  is improperly managed.



     Thus,  these wastes may  leach  harmful  concentrations  of


lead, cadmium,  and chromium  even under relatively mild  environ-



mental conditions.   If these  wastes are exposed to more acidic


disposal  environments, for example  disposal environments  sub-



ject to acid rainfall, these  metals would  most likely be



solubilized to  a greater degree  than in the distilled water


since lead, cadmium  and chromium (and  their oxides)  are more



soluble in acid  than in distilled water (6,7,8).   (See  Table  1



indicating that  a number of  secondary  lead  plants are located



in states known  to experience  acid  rainfall including New Jersey



Ohio, Illinois, and  Indiana.)



     A further  indication of  the migratory  potential  of the



waste constituents is  the physical  form of  the waste  itself.


These waste dust/sludges are  of a fine particulate composition,



thereby exposing a large surface area  to any percolating  medium,
                             -ve-

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and increasing  the  probability  for  leaching  of  hazardous




conBtituents from the  waste  to  groundwater.   Waste  acid




leaching solution,  as  noted  above,  is  disposed  of in  liquid




form with harmful constituents  directly  available for  migration.




     The Agency  thus believes that  emission  control  sludge/dust,




and waste acid  leaching  solution  may pose a  threat  of  serious




contamination to groundwater unless proper waste management




is assured.  These  wastes  do not  appear  to be properly managed




at the present  time.   Thus,  present industry practices of




disposing of these  wastes  in unlined lagoons (see pp.  5 and  7




above) may well  not be environmentally sound.   For  example,




location of disposal sites in areas with permeable  soils




could permit contaminant-bearing  leachate from  the  waste to




migrate to the  groundwater in harmful  concentrations.  This




is a particular  concern  for  lagoon-disposed  wastes  because a




large quantity  of liquid is  available  to percolate  through




the solids and  soil beneath  the fill,  increasing heavy metal




solubilization  and  migration.



     The Agency  is  also  concerned that the lagooned  wastes




could contaminate surface  waters  if not  managed to  prevent




flooding or total washout.   While the  Agency is not  aware




whether disposal lagoons presently  have  diking  or other con-




trol mechanisms  to  prevent washout, it is certainly possible,




given the number of sites, that in  some  cases,  present flood-




control measures are inadequate.  Nor  can proper flood manage-




ment (or leachate control, for  that matter)  be  assured without




regulation.






                           -vf-

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     Another  pathway  of  concern is through airborne exposure

to lead,  chromium,  or  cadmium particulates escaping from

emission  control  dust.   These particulates could escape if

waste dusts are piled  in  the  open, or placed in uncontrolled

landfills.  Although  the  Agency is not aware whether waste

dusts are managed in  this manner,  this type of improper manage-

ment situation appears plausible in light  of the large quantitiei

of emission control dust  generated annually.

     Should lead, cadmium, 'or chromium escape from the disposal

site, they will persist in  the  environment and therefore may

contaminate drinking  water  sources for extremely long  periods

of time.  Cadmium is  bioaccumulated at all trophic levels  (9,

10).  Lead can be bioaccumulated and  passed along  the  food

chain but not biomagnified.   (Although bioaccumulation of

chromium  occurs,  the  process  does  not play a major role in

determining the fate  of chromium.)


3.   The  Large Quantities  of  Waste Dust/Sludge Generated Are
     A Further Factor  Supporting a "T" Listing of  These Wastes

     The Agency has determined  to  list secondary lead  emission

control sludge/dust as a  "T"  hazardous waste,  on the basis of

lead, chromium, and cadmium constituents,  although these

constituents are also measurable by  the EP toxicity character-

istic.   Moreover, concentrations of  these  constituents

in an EP extract from waste streams  from individual sites

might be less than 100 times  interim  primary drinking  water
                              -vf-
                               -SSH-

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standards  (although the Agency's own extraction data suggests




that extract  concentrations may exceed  the  100  x benchmark for




some generators).   Nevertheless, the Agency believes that  there




are factors in  addition to metal concentrations in  leachate




which justify the  "T"  listing.   Some of these  factors  already




have been  identified,  namely the high concentrations of  cadmium




and chromium,  and  especially lead in actual waste streams,  the




non-degradability  of  these substances,  and  indications of  lack




of proper  management  of the wastes in actual practice.




     The quantity  of  these wastes generated is  an additional




supporting factor.




     As indicated  above,  secondary lead emission control




sludge/dust is  generated  in very substantial quantities, and




contains very high  lead concentrations, as  well as  elevated




concentrations  of  cadmium and  chromium.  (See  p.  10  above.)




Large amounts  of each  of  these  metals are thus  available for




potential  environmental release.   The large quantities of




these contaminants  pose the danger of polluting large  areas




of ground  or  surface  waters.   Contamination could also occur




for long periods of time,  since large amounts  of pollutants




are available  for  environmental loading.  All  of these consid-




erations increase  the  possibility of exposure  to the harmful




constituents  in the wastes,  and in the  Agency's view,  support




a "T" listing.



IV.   Hazards Associated With Lead,  Chromium and Cadmium




     Lead is  poisonous  in  all  forms,  and  is one of  the most




hazardous of  the toxic  metals because it  accumulates in  many

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organisms.   Its  deleterious  effects are numerous and severe.


Lead may  enter the  human  system through inhalation, ingestion


or skin contact.


     Chromium is  toxic  and  poses a hazard if contaminated


drinking  water is ingested  by  humans.   It is also toxic to


lower  forms  of aquatic  life.   Cadmium  is toxic to practically


all systems  and  functions of human and animal organism (9).


Acute  poisoning  may  result  from the inhalation of cadmium


dusts  and fumes  (usually  cadmium oxide) ,and  from ingestion


of cadmium salts  (10).  Additional information on the adverse


health effects of cadmium, chromium, and  lead can be found


in Appendix  A.


     Lead, cadmium,  and chromium historically have been regarded


as toxic.  Thus, EPA has  established maximum concentration


limits for lead, cadmium  and chromium  in  effluent limitations


guidelines adopted pursuant to  Section 304 of the Clean Water


Act, and  under National Interim Primary  Drinking  Water  Stand-


ards adopted pursuant to  the Safe  Drinking Water  Act.   Lead


also is regulated under the New Source Performance Standards


of the Clean Air Act.


     The Occupational Safety and  Health  Administration  (OSHA)


has set a work place standard  for  exposure to lead.


     In addition, several states  that  are currently  operating


hazardous waste management programs specifically  regulate


cadmium,  chromium, and lead containing compounds  as  hazardous
                           -vt-
                            -•356-

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wastes or components  thereof.   These  states  include  Maryland,




Minnesota, New Mexico,  Oklahoma  and California  (final  regula-




tions), and Maine,  Massachusetts,  Vermont, and  Louisiana



(proposed regulation).
                             -yf-

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                            Refer ences
 1.   U.S. EPA, Office  of  Solid  Waste.   Assessment of Hazardous
      Waste Practices in  the  Metal  Smelting and Refining
      Industry.  Calspan  Corporation.   EPA Contract Number
      68-01-2604, April 1977,  Volumes  II and IV.

 2.   U.S. EPA, Effluent  Guidelines  Division,  Draft Development
      Document for Effluent Limitation  Guidelines and New
      Source Performance  Standards  for  the Major Nonferrous
      Metals Segment of the Nonferrous  Manufacturing Point
      Source Category.  Washington,  D.C.   September, 1979.

 3.   U.S. EPA, Office  of  Solid  Waste.   Assessment of Solid
      Waste Management  Problems  and  Practices  in Nonferrous
      Smelters.  PEDCo  Environmental,  Inc.  EPA Contract
      Number 68-03-2577.   November,  1979.

 4.   U.S. Deparment of Interior, Bureau of Mines.  Mineral
      Commodity Summaries, 1980.  December, 1979.
 5.   U.S. EPA, Office of Solid Waste.   Background  Document
      for Comprehensive Sludge Study Relevant  to  Section
      8002 (9) of the Resource Conservation  and Recovery  Act
      of 1976 (P.L. 94-580).  SCS Engineers.   EPA Contract
      Number 68-01-3945.  December, 1978.  Volume 2,  App.  E.

 6.   Handbook of Chemistry and Physics,  52nd  Edition.
      Cleveland, The Chemical Rubber Company,  1971-72.

 7.   The Merck Index.  8th Edition, 1968.

 8.   Pourbaix, Marcel.  Atlas of Electrochemical Equilibria
      in Aqueous Solutions, London, Pergamon Press,  1966.

 9.   Waldbott, G.L. Health Effects of Environmental  Pollutants
      St. Louis, C.V. Mosby Company, 1973.

10.   Gleason, M., R.E. Gosselin, H.C. Hodge,  B.P.  Smith.
      Clinical Toxicology of Commercial  Products.  Baltimore,
      The Williams and Wilkins Co., 1969.  3rd Edition.

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