27679
                          WLB:TDI1:01
                    LISTING BACKGROUND DOCUMENT  FOR
                  DINITROTOLUENE,  TOLUENEDIAMINE AND
                    TOLUENE DIISOCYANATE PRODUCTION1
   Kill:   Product  washwaters  from the production of dinitrotoluene
          via nitration of  toluene (C,T)
   K112:   Reaction by-product  water  from the drying  column in
          the production of  toluenediamine via hydroyenation uf
          dinitrotoluene (T)
   K113:   Light ends  from the  purification of toluenediamine
          in the production  of toluenediamine via hydrogenation
          of dinitrotoluene  (T)
   K114:   Vicinals  from the
          in the production
          of dinitrotoluene
purification of toluenediamine
of toluenediamine via hydrogenation
(T)
   K115:   Heavy ends from the purification of toluenediamine
          in the production of toluenediamine via hydrogenation
          of dinitrotoluene (T)
   K116:   Organic condensate from the solvent recovery column in
          the production of  toluene diisocyanate via phosgenation
          of toluenediamine  (T)
   -One waste from TDI  production (EPA Hazardous Waste No.  K027,
    Centrifuge and distillation residues from toluene diisocyanate
    production)  was previously listed.  A background document for
    this listing has been available in the public docket at EPA
    Headquarters and at EPA regional libraries since May 19,  1980.

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                        TABLE OF CONTENTS








                                                             PAGE



   I. Summary of Basis for Listing                             1






  II. Sources of the Wastes                                    2



      A. Profile of the Industry                               2



      B. Manufacturing Processes                               4



         1. Nitration of toluene to form dinitrotoluene (DNT)  5



         2. Hydrogenation of DNT to form toluenediamine (TDA)  8



         3. Formation of toluene diisocyanate (TDI) from TDA  12






 III. Composition of the Wastes                               16






  IV. Waste Management                                        22





   V. Basis for Listing                                       27



      A. Hazards Posed by the Wastes                          27



      B. Degree of Hazards Posed by These Wastes              34



      C. Mismanagement                                        37



      D. Environmental Effects of the Hazardous Constituents  40



      E. Health Effects of the Hazardous Constituents         43






  VI. References                                              51





 VII. Appendix I                                              52






VIII. Appendix II                                             53

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I.    Summary of Basis for Listing


         The above-listed solid wastes resulting from the nitration

of  toluene to produce dinitrotoluene (DNT), from the hydrogenation of

DNT to toluenediamine (IDA)/ and from the reaction of IDA with phosgene

to form toluene diisocyanate (TDI), are hazardous solid wastes.
                                                  ft,^rft.-fiOn of "toluCnC
Administrator has determined that wastes from the a-bove—§>i=-e>ee-s«es

pose a substantial present or potential hazard to human health or

the environment when improperly transported, stored, disposed of

or otherwise managed, and therefore should be subject to appropriate

management requirements under Subtitle C of RCRA.JThis conclusion

is based on the following considerations:

     1)  Wastes from the production of dinitrotoluene, toluene-
         diamine, and toluene diisocyanate typically contain
         significant concentrations of one or more of the toxic
         compounds: 2 ,4-dinitrotoluene, 2,6-dinitrotoluene, 2,4-
         toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine,
         2-amino-l-methylbenzene (o-toluidine) , 4-amino-l-methyl-
         benzene (p_-toluidine) , aniline, carbon tetrachloride,
         tetrachloroethylene, chloroform, and phosgene.

     2)  A number of these compounds — namely, 2,4-dinitrotoluene,
         2,4-toluenediamine, o-toluidine, chloroform, carbon  tetra-
         chloride, and tetrachloroethylene — have been  identified
         by the Agency's Carcinogen Assessment Group (CAG) as known
         or potential carcinogens.  In addition, several of these
         compounds have been shown to  be mutagens in bacterial or
         mammalian test systems, and cause reproductive, terato-
         genic, or otherwise chronic systemic effects.

     3)  Dinitrotoluene product washwaters  (waste Kill)  are also
         corrosive (pH = 1 - 2), due to the high concentrations of
         sulfuric and nitric acids.

     4)  These wastes are  produced in  large amounts: an  approximate
         total of 647,000  kkg of DNT,  TDA, and TDI production wastes
         are generated annually.

     5)  These toxicants,  moreover, are mobile and persistent  in  the
         environment.  In  fact, a  number of these toxicants have  been
         found in drinking water or surface water, as well as  in  air,
         and,  thus, have been shown to leach and be  sufficiently
         persistent to escape into the environment and present  a

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         substantial  hazard to human health or the environment,
         if  improperly managed,  such as disposal in unlined surface
         impoundments, or inadequate incineration.


II.   Sources of the Wastes^


     A.   Profile of the Industry


         The manufacture of toluene diisocyanate (TDI)  from toluene

involves the production of dinitrotoluene (DNT) and toluenediamine

(IDA) as intermediates.  As of 1983, five domestic companies were

producing TDI at seven locations (see Table 1).


         Two other major manufacturers produce DNT and/or TDA

primarily for sale to TDI manufacturers.  The Air Products plant

at Pasadena, TX is a key supplier of DNT and TDA, while the duPont

plant at Deepwater, NJ is also a major producer of DNT.  There are

several other producers of DNT and TDA; however,  their production

levels may be quite low, and some are producing TDA for captive use

in the manufacture of dyes or other chemical products.  (Table 4,

which later discusses quantity and management data for the waste

streams of concern, includes not only data based  upon the  production

volumes of the DNT and TDA produced for captive use in TDI production,

but  also includes  the production volumes of the DNT and TDA produced

for  sale to other  facilities as  intermediates  in  TDI production.)


         TDI production  capacity in the U.S.  was  315,000 kkg  in

1983.  The U.S. International Trade Commission reported the total

production of TDI  (80:20 mixture of the 2,4-  and  2,6-  isomers)
 2The  information presented  in this section  is  taken  in  large  part
  from a  1983 report prepared by S-Cubed.

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        TABLE 1 - PRODUCERS OF TOLUENE UIISOCYANATE {TDI}1
PRODUCER
Mobay Chemical Corp.
Bay town, TX
Mobay Chemical Corp.
New Mart insville, WV
ol in Corp.
Lake Charles, LA
Olin Corp.
Moundsville, WV
BASF Wyandotte Corp.
Geismar, LA
Dow Chemical
Freeport, TX
Rubicon Chemicals
Geismar, LA
TOTAL
RAW
MATERIAL
toluene
toluene
dinitro-
toluene
toluene
dinitro-
toluene
toluene
diamine
toluene
PRODUCTS2
1,2,3
1,2,3
2
2
2
2
2
CAPACITY3
(106 kg/yr)
59
57
45
34
57
4b
18
315
      manufacturers of TDI are listed within this table.   Other
 manufacturers produce DNT and/or TDA intermediates but do not
 produce TDI (see text).

2Key to Products:
 1 = pure 2,4-TDI
 2 = 80:20 mixture of 2,4- and 2,6-TDI
 3 = 65:35 mixture of 2,4- and 2,6-TDI

3Nameplate capacity for TDI production as of 1983 (SRI International,
 1983 Directory of Chemical Producers - United States, Stanford
 Research Institute, Menlo Park, CA,  1983).

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domestically in 1980, 1981, and 1982.  Reported production data



for DNT and IDA were less specific.  However, based upon reaction



stoichiometry and estimates of process yields from process residuals



reported by manufacturers, it was possible to estimate the amounts



of DNT and IDA (as the 80:20 mixture of the 2,4- and 2,6- isomers)



produced in association with these levels of TDI in 1980, 1981,



and 1982.  In particular, the production estimates are:






                PRODUCTION ESTIMATES (in kkg)



                     1980       1981       1982



           DNT      344,000    346,000    337,000



           TDA      215,000    216,000    210,000



           TDI      267,000    268,000    261,000






Five of the seven TDI-manufacturing plants produce only an 80:20



mixture of 2,4-TDI and 2,6-TDI, while two plants produce an 80:20



mixture, a 65:35 mixture of 2,4-TDI and 2,6-TDI, as well as pure



2,4-TDI.  Almost all TDI  is used to make polyurethanes, including



polyurethane foam products (85% of production), coatings, elastomers,



and adhesives.






     B.  Manufacturing Processes



         The manufacture of toluene diisocyanate typically involves



three distinct continuous chemical processes:



         1.  nitration of toluene to form dinitrotoluene (DNT);



         2.  hydrogenation of DNT to form toluenediamine (TDA); and



         3.  reaction of TDA with phosgene to form TDI.



As shown in Table 1, four TDI plants begin the production process



with toluene and incorporate all three of these steps, two plants

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purchase DNT for use as a raw material, and one purchases TDA for


use as a raw material.  The Air Products plant at Pasadena, TX,


with a reported annual capacity for TDA of 57,000 kkg, is a key


supplier of TDA, as well as DNT.  The duPont plant at Deepwater,


NJ, is also a major producer of DNT.



         The following is a description of the major commercial


processes utilized in the manufacture of DNT, TDA, and TDI.



     1.  Nitration of toluene to form dinitrotoluene (DNT)


         In general, toluene is nitrated with nitric acid  in the


presence of sulfuric acid, which acts as a solvent and a catalyst


Increasing the acidity and temperature increases the degree of


nitration.  The dinitration of toluene is represented by the


overall reaction:

            CH3                         CH3


                . 2HN03


                  M i t T i r
         Toluene   Ir-fd           Dinitrotoluene
                   C a               (DNT)


         As shown in Figure 1, sulfuric and nitric acids are


added to a recycled acid stream to form the nitrating solution.


This solution is combined with toluene in the nitration reactor.


The reactor is jacketed, and continuously cooled to remove  the


heat of reaction.  The reactor contents must be vigorously  agitated


because toluene is not very soluble in the mixed acids.  Most


TDI manufacturers use either nitration-grade toluene  (99.8%


purity) or highly refined toluene  (99.5+% purity) as a feedstock.



         The two-phase product from the nitration reactor  is

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                  Vent  Gas
Wflshwater
   Kill
                               Acid Recovery Water
                                                                      ONT
                                                                    Product
r-'iqure  1.   Typical  Process Flow  niar\rf\m  for  UKJ Nitration ot Toluene

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allowed to separate into organic and acid layers.  Spent acid



from the acid separation unit is sent to a recovery unit where



water (a by-product of the nitration reaction) is separated and



re-used in the washing process.   The recovered acid solution is



reconstituted into a nitrating solution containing the desired



concentrations of sulfuric and nitric acids.  After addition of



make-up sulfuric and nitric acids, the nitrating acid solution



consists of about 50% sulfuric acid, 20% nitric acid, 12% nitro-



sylsulfuric acid, and 8% nitroorganics.





         The organic layer contains the desired dinitrotoluenes,



as well as side products of reaction, and is subjected to purifica-



tion.  A two- or three-stage washing process is typically employed



to remove water-soluble organic by-products and any remaining spent



acid from the crude DNT product stream.  The first washing step



utilizes an alkaline wash solution containing sodium hydroxide,



ammonium hydroxide, or sodium carbonate to remove acidic by-products.



Water from the acid recovery unit is usually combined with additional



water, if necessary, and is then re-used in the remaining washing



steps.  Washwaters from the washing process are combined and form



a major waste from the toluene nitration process (Kill in Figure 1).





         Vent gases from the nitration reactor and other units may



be scrubbed with water to remove acid fumes.  Scrubber waters, if



generated, are typically utilized subsequently for product washing.





         The dinitrotoluene (DNT) product consists of about 96% 2,4-



and 2,6-DNT, and 4% of other isomers, primarily 2,3- and 3,4-DNT (see



Figure 2).  Operating conditions are controlled so as to reduce the

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formation of trinitrotoluene.  Several oxidized by-products, including
nitrocresols, nitrophenols, and nitrobenzoic acids, also result,
however.  These may constitute up to 2% of the product mixture.

     2.  Hydrogenation of DNT to form toluenediamine (TDA)
         The reduction of DNT to TDA occurs in liquid (often
methanolic) phase hydrogenation at high temperature and pressure,
and occurs according to the  following reaction:
             CH3
                  (N02)2 + 8H2  Catalyst.   [Gj—(NH2)2

       Dlnitrotoluene                 Toluene Oianrine
           (DNT)                          (TDA)
         Hydrogenation  is not specific, and results  in  the  reduction
of any nitroaromatic compound to the corresponding amine  (occurring
without  rearrangements).   For this reason,  the isomeric distribution  of
the TDA  product  is  iaentical to that of the DNT used as a  raw  material.

         The crude  diamine  product may contain partially  reduced
compounds  (nitroamino  toluenes), and small  amounts of cyclohexane
derivatives  that  result from aromatic  ring  hydrogenation.   Hydrogen-
ation  proceeds  through the  intermediate  formation  of nitroso (R-NO)
and hydroxylaraine (R-NH-OH)  intermediates.   In addition,  polymeric
condensation species of azo (R-N=N-R)  or  hydrazo  (R-NH-NH-R) linkages
may be  formed.   A flow diagram  for  a typical  hydrogenation process
 is shown in  Figure 3.

         The DNT feed  is dissolved  in  solvent,  typically methanol,
 combined with  the catalyst (either  palladium on  carbon  or Raney

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2,5-ONT
 0.5%
2.4-DNT
  77%
2,67DNT
  19*
3,4-DNT
2,3-DNT
  1.0%
        Figure 2.  Isomer Protluction  in  the Nitration of  Toluene

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                                                                    By-Product
                                                                    i   Water

                                                                        K1I2
                                                                                  u)
                                                                                 I iyht
                                                                                  Umls
                                                                                  K113
                                             Vicinals

                                              K114
Make-Up
Solvent
DNT-
                             Recycled
                             Solvent
                 Catalyst
                      M2-
                               Reactor
Catalyst

Recovery
                                     Recycled
                                                  Spent
                                                Catalyst
                                     Catalyst
                                                                                                            IDA

                                                                                                          Product
                                                                                                        c
                                                                                                        E
                                                                                                        fO
                                                                                                        t-
                                                                                                        nt
                                                                                                        OL
                                                                                                        01
                                                                                                       to

                                                                                                        a*
                                                                                                      T
                                                                                                   Heavy Cnds
                                                                                                       K115
             Fifjnr/e  3.   Typical Process Flow  Diagram for the  Hyrirogenat ion  of" DNT  to TIJA

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nickel),  and sent to a pressurized reactor,  where hydrogen is

introduced.   The operating temperature of the reactor is between

90 and 190°C at a pressure of about 6 atmospheres.   The output from

the reactor  is sent to a catalyst recovery unit where recovery is

accomplished by centrifugation,  filtration,  or settling, and the

recovered catalyst is sent back  to the reactor.  Small amounts of

the catalyst may be lost as fines in the crude product stream or

intentionally discarded as a portion of the  recovered catalyst

stream.  New catalyst is then added so as to retain catalyst activity.


         The crude TDA product then goes through a series of distill-

ation columns to remove the following components:

         1.   solvent (generally  methanol) from the solvent recovery
              column, which is recycled;
         2.   by-product water (K112, resulting from the hydrogenation
              reaction) from the TDA drying  column;
         3.   light ends (K113) from the light ends separation column;
         4.   vicinals (process residuals resulting from the separation
             of the ortho isomers from the desired product isomers)
             (K114) from the vicinals separation column; and
         5.   heavy ends (K115) from the residue separation column.

As illustrated  in Figure 3, by-product water  is the second distill-

ation product (K112).  It contains toluenediamines and toluidines,

as well as methylcyclohexanes and small amounts of methanol.


         Low-boiling by-products, or light ends (K113), are typically

separated in a  third distillation column as a gaseous overhead stream.

Although these  wastes come off the distillation column as gases because

of the high temperatures employed in distillation, they quickly condense

to liquids  (their natural state) on contact with the surrounding lower

temperatures.   This stream contains primarily  toluenediamines and

toluidines, but also contains aniline and water.
                              11

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         The fourth distillation column separates out the
toluenediaraines with ortho amine groups (vicinals), which boil
at slightly lower temperatures (2,3-TDA boiling point = 255°C;
3,4-TDA boiling point = 265°C) than the desired product amines
(2,4-TDA boiling point = 292°C; 2,6-TDA boiling point = 292°C)
(K114 of Figure 3).  If not separated from the TDA product  stream,
the ortho (2,3- and 3,4-) diamines form cyclic ureas  in the
subsequent phosgenation reaction  (see below), resulting in
reduceu product yield, and increased amounts of "heavy ends"
residue from the TDI purification process.
         The residue separation column  is  the final distillation
step, and the  "heavy ends" (K115  of Figure  3) are  removed at  this
point.  The heavy  ends consist  primarily of  toluenediamines.

      3.  Formation  of  toluene  diisocyanate  (TDI)  from TDA
         TDI results  from  the  reaction  of  TDA with phosgene:
             CH3
                  (NH2)2 + 2COC12
           Toluene        Phosgene       Toluene
           Diamine                    Diisocyanate
            trn A\                        (TDI}
            ^ ' >»" /
This  reaction  proceeds at  atmospheric pressure  and without a
catalyst.   A typical  process flow diagram is shown in Figure 4.

          It is necessary to  use TDA of high isomeric purity to
 reduce  side reactions.  2,3- and 3,4-TDA form methylbenzimidazolone
 in preference  to the diisocyanate, reducing the reaction yield:
                               12

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                                        Vent Gas
    Vent.Gas
Water
   HC1  Solutl m
   (Coproduct)
 T
Phosyene
Recycle
                                                Organic
                                                 Liquid
                                                  K116
                                             (condonscice)
     Phosyene
     So1utior
     Phosgene
                                                               Product  TOI
                                                                   fa
                                                                                 c
                                                                                 O
                                                                                 n>


                                                                                  O
                                                                                  i
                                                                                 
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                                                      2HC1
                                             H

          "faluene-2,    Phosgene         Cyclic Urea
          3-Qi ami ne              (Methyl-benzimi dazolone}


In addition,  the imidazolone combines with TDI, forming intractable

sludges, which present physical removal problems.  Therefore, the

IDA feed to this process is usually of very high isomeric purity;

it consists of an  80:20 (+_ 11) mixture of the 2,4- and 2,6-isomers.


         The TDA is dissolved in chlorobenzene, o-dichlorobenzene,

or other solvents.  This solution is combined with phosgene  (either

in solution with the same solvent or as a liquid) in phosgenation

reactors.  The phosgene feed may contain low molecular weight

chlorinated hydrocarbons (primarily carbon tetrachloride) impurities.


         Phosgenation is accomplished  in a series of phosgenators,

with increasing temperatures in each successive phosgenator.  Phosgene

liquid  is fed into the bottom of the phosgenators.  Phosgenator  vent

gases are typically sent through a condenser, the condensate returned

to the  phosgenator, and uncondensed gases sent to a phosgene and HC1

by-product recovery system.


         The crude TDI product that exits from the phosgenation

reactors undergoes stepwise distillation to separate the  following

components:

         1.  phosgene, from the phosgene recovery column, which
              is recycled to the phosgenation reactors;
         2.  by-product HCl from the scrubber system;
         3.  solvent, from the solvent  recovery  column, recycled
              to the phosgenators;


                              14

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         4.  organic liquid (condensate) containing chlorinated
              hydrocarbon impurities and excess phosgene (K116),  from
              the solvent recovery and subsequent separation columns;
         5.  TDI residue (K027, currently regulated in CFR 261.32),
              the heavy ends from the residue separation column;  and
         6.  purified TDI product.

Figure 4 provides a representative process flow diagram for separa-

tion of these components (the seven TDI plants surveyed demonstrated

slightly different processes).


         In the process shown in Figure 4, phosgene and by-product

HCl are distilled from the product stream at relatively low tempera-

tures, combined with vent gases from the phosgenation reactors, and

fed to the phosgene/HCl recovery section, where phosgene is absorbed

in the process solvent, and HCl is subsequently absorbed in water.

The phosgene/solvent solution is then stripped of phosgene with

a gas, and the phosgene is condensed out of this gas stream and

recycled to the phosgenators.  Vent gases that have been stripped

of phosgene are commonly sent to a final scrubber for HCl recovery.

These gases are scrubbed with water or a caustic solution to

remove the remaining traces of phosgene.  Carbon adsorption is

also employed to remove trace chlorinated organics from vent

gases.  HCl may be utilized in other processes within the plant,

or marketed.


         After separation of phosgene and HCl from the crude

product stream, a second distillation step is carried out for

recovery of the process solvent as an overhead stream from the

solvent recovery column.  Further distillation of this stream may

be needed to separate a liquid containing chlorinated hydrocarbon

impurities and excess phosgene originally associated with the


                              15

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phosgene feed, from the solvent.  The resulting condensate (K116



in Figure 4) therefore contains chlorinated hydrocarbons, phosgene,



and some residues of the solvent used in the process.





         The final separation removes the TDI product from the



higher-boiling distillation bottoms (the currently regulated waste,



K027).  As discussed above, these still bottoms are expected to



contain polymeric condensation by-products, TDA, and TDI.





         The TDI product (80:20 mixture of 2,4- and 2,6-isomers)



may be subjected to further distillation steps to produce both a



pure 2,4-TDI product and a 65:35 mixture of the 2,4- and 2,6-



isomers, but these distillations do not produce wastes.





III. Composition of the Wastes3





         The nitration of toluene creates one major waste stream,



the product washwaters from washing the crude DNT product (Kill).



Because of the relatively high concentrations of sulfuric and



nitric acias {ranging from 1 - 4%), this waste stream also is



corrosive, due to its pH of between 1-2.  In addition, this



waste stream is toxic; the hazardous constituents, as determined



from RCRA Section 3007 questionnaires and sampling and analysis,



are expected to be dinitrotoluenes (about 0.1%), of which 0.08%



of the waste is 2,4-DNT, and 0.02% is 2,6-DNT.  in addition,



this waste is expected to contain dinitrocresols (about 0.06%,



primarily 2 ,6-dinitro-p_-cresol); mononitrotoluenes (about 0.005%);



and mononitrophenols, dinitrophenols, nitrobenzoic acids, and
3see footnote 2.





                              16

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mononitrocresols (about 0.007%, combined).4 (See Tables 2 and 3.)


         A second major aqueous waste is the reaction by-product

water from the hydrogenation of DNT to TDA (K112).  This waste

contains a substantial concentration of 2,4- and 2,6-TDA (ranging

from 0.05 - 0.3%), 3,4-TDA (ranging from 0.05 - 0.3%), as well as

£-toluidine (ranging from 0 - 0.06%) and £-toluidine (ranging from

0 - 0.04%), which are the hazardous constituents of concern.  In

addition, one manufacturer reported methylcyclohexylamine and

methylcyclohexanone as components of this waste stream.4


         Purification of the crude TDA product by distillation

produces "light ends", "vicinals", and a "heavy ends" waste stream.

The light ends (K113) typically consist of 3,4-TDA (ranging from

0 - 37.5%) and 2,4- and 2,6-TDA (ranging from 0 - 37.5%); o-toluidine

(ranging from 0.6 - 6%) and £-toluidine (ranging from 0.4 - 4%);

and aniline (ranging from 0.01 - 0.1%), the hazardous constituents

of concern.


         The hazardous constituents from the vicinals waste

stream from the purification of crude TDA  (K114) are 2,4- and

2,6-TDA  (ranging from 4.5 - 50%); 3,4-TDA  (ranging from 45 -

95%); o-toluidine (ranging from 0-3%) and p_-toluidine (ranging

from 0 - 2%).


         2,4- and 2,6-TDA (ranging from 10 - 50%), and 3,4-TDA
4We are not proposing to list these additional compounds as hazardous
 constituents at this time since we currently have insufficient data
 on concentrations and/or toxicity to justify such listing; however,
 in the future,  if we do receive more information on them, we will
 then make a determination as to whether or not they should be listed


                              17

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    TABLE  2:  APPROXIMATE  AVERAGE  COMPOSITION  OF  DNT WASHWATER1
       Constituent
  Dinitrotoluenes
   (see  Figure 2  for  approximate
   isomer  distribution)

  Mononitrotoluenes
   (see  Figure 2  for  approximate
   isomer  distribution)

  Dinitrocresols
   (mostly 2,6-dinitro-p_-cresol)

  Nitrophenols
   (including di-  and mono-nitrophenols)

  Other  nitroaromatics,  including
   nitrobenzoic acids and nitrocresols
          TOTAL ORGANICS
Concentration (ppm)
        1U85



          45



         600


          35


          35



        1800
T-S-CUBED, 1983
                              18

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        J: COMPOSITION OF MAJOR WASTE STREAMS FHDM PLANTS THAT MANUFACTURE DNT, TDA  & TDI
WASTE STREAM
DESIGNATION
Kill






K112





K113






K114






K115



K116



K0272

!
DESCRIPTION
(Figs. 1,3,4)
DNT Washwater






Byproduct water from
the TDA drying column




Light ends from the
purification of
crude TDA




Vicinals from the
purification of
crude TDA




Heavy ends from the
purification of
crude TDA

Organic liquid con-
taining chlorinated
hydrocarbon impurities

Heavy ends from the
purification of
crude TDI
TYPE
Aqueous
liquid
(pH=l-2)




Aqueous
liquid




Organic
liquid





Viscous
organic
liquid/
solid



Viscous
organic
liquid

Organic
liquid


Viscous
organic
liquid
MAJOR CONSTITUENTS
CONSTITUENT
Dinitrotoluenes ,
N i tr ophenol i cs

Inorganics^
H2S04 + HN03
Sulfate +
Nitrate Salts
Toluenediamines
2,4-TDA & 2,6-TDA
3,4-TDA (& 2,3-TDA)
Toluidines
o-toluidine
p_-toluidine
Toluenediamines
2,4-TDA & 2,6-TDA
3,4-TDA (& 2,3-TDA)
Toluidines
o-toluidine
pj-toluidine
Aniline
Toluenediamines
2,4-TDA & 2,6-TDA
3,4-TDA (& 2,3-TDA)

Toluidines
o-toluidine
p_-toluidine
To luened i ami nes
2,4-TDA & 2,6-TDA
3,4-TDA (& 2,3-TDA)
Spent Catalyst (Ni)
Carbon tetrachloride
Tetrachlorcethylene
Chloroform
Phosgene
Polymerized TDI
TDI

ESTIMATED
CONCENTRATION
RANGE (%)
0 - 0.3


1 - 4



0.1 - 0.6
0.05 - 0.3
0.05 - 0.3
0 - 0.1
0 - 0.06
0 - 0.04
0-75
0 - 37.5
0 - 37.5
1-10
0.6 - 6
0.4 - 4
0.01 - 0.1
0-95
4.5 - 50
45 - 95

0-5
0-3
0-2
10 - 50
10 - 50
0 - 2.5
0-5
0-75
0-15
0-7
0-30
50 - 100
0-50

^Inorganic composition varies between plants depending on the degree to which acids (H2SO4
  + HN03)  in the crude DNT product are neutralized by alkaline washwaters.
2This waste is currently regulated in 40 CFR 261.32.
                                              19

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(ranging from 0 - 2.5%), are the hazardous constituents of concern



of the TDA "heavy ends" (K115).  In addition, TDA polymers and



other high-boiling residues, and small amounts of catalyst fines



(most commonly Raney nickel) are present.5  None of the TDI



manufacturers reported specific polymeric components; however,



the process chemistry indicates that the major polymerics are



toluenediamines of short length with azo (-N=N-) or hydrazo



(-NH-NH-) linkages.





         The TDI purification processes additionally generate an



organic liquid waste stream (K116) of small volume but containing



10 - 30% phosgene, and chlorinated hydrocarbons, principally carbon



tetrachloride (ranging from 0 - 75%), as well as tetrachloroethylene



(ranging from 0 - 15%), and chloroform (ranging from 0 - 7%), as



the hazardous constituents.  One manufacturer employs a vacuum



ejector which uses toluene as the motive fluid/ thus introducing



toluene (about 60%, with this system) into this waste.5





         The final major waste from the production of TDI is the



"heavy ends" from purification of crude TDI.  This waste stream



is currently regulated in 40 CFR 261.32 as "K027, Centrifuge and



distillation residues from toluene diisocyanate production".  This



waste contains TDI, TDA, TDI polymers, and high-boiling by-products



from the phosgenation reaction.  None of the TDl plants currently



operating reported specific component information on this waste.



However, one manufacturer (whose plant closed in 1981) reported



the following composition for this waste stream.
5see footnote 4.
                              20

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     COMPONENT                             CONCENTRATION (%)

     Isocyanurates (TDI triraer)                   45

     Carbodiimides                               40

     Ureas                                       10

     Methyl-benzimidazolones                      5

This appears to be a representative composition for an aged TDI

residue {one that has been stored for several days, resulting in

polymerization of the TDI monomer).6


         Approximately 647,000 kkg of the TDI production wastes dis-

cussed above are generated annually.  (This volume does not include

the approximately 21,000 kkg of the currently regulated EPA Hazardous

Waste No. K027, discussed above.)  This volume is broken down by

waste stream as follows (total estimated generation, in kkg):

         Kill - 427,000

         K112 - 195,000

         K113 -     240

         K114 -   3,700

         K115 -  21,000

         K116 -     150

As seen above, a number of hazardous constituents are present in

high concentrations in the wastes.  Therefore, if the wastes were

improperly managed, there is the potential that relatively  large

amounts of these constituents could escape to the environment.

Table 3 is a summary of waste composition data for the wastes,

as supplied by the manufacturers and derived from the literature.
     listing background document for EPA Hazardous Waste No. K027
 estimated a slightly different composition for this waste.


                              21

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         The potential environmental and human health effects of



these compounds are discussed in Section V.





         In addition, there are a number of minor process waste



streams, including aqueous wastes from steam ejector systems for



vacuum distillation columns, scrubber wastewater, spent vacuum pump



oil, spent catalyst, and spent activated carbon from the treatment



of aqueous wastes or air emissions.  These wastes are extremely varia-



ble in quantity and composition, depending on the process flow scheme



and unit operations utilized.  They are not generated industry-wide



on a regular basis, and have not been fully characterized.  There-



fore, we are not proposing to list these minor process waste streams



at this time; however, if in the future more information becomes



available, we will then make a determination on whether there is



sufficient justification for listing.





IV.  Waste Management?





         Table 4 presents a summary of management information con-



cerning these wastes.  They are managed by a variety of techniques.





         In most plants, DNT washwater (Kill) and TDA reaction



by-product water (K112) are treated by biological and/or physical-



chemical treatment, and then discharged to surface waters.  At



least one manufacturer, however, uses a deep well injection



system for these wastewaters.





         Although no information was specifically collected from
 See footnote 2.
                              22

-------
         TABLE 4:  SUMMARY OF QUANTITY AND MANAGEMENT DATA FOR MAJOR WASTE STREAMS
                        FROM PLANTS THAT MANUFACTURE DOT, TDA & TDI
WASTE
DESIGNATION
Kill



K112




K113


K114




K115


K116
K0274




GENERATION RATE
(kg of waste/kg TDI
Produced)
1.1 - 2.0



0.44 - 1.23




0.004 - 0.012


0.012 - U.065




0.02 - 0.25


0.0003 - 0.007
0.09 - 0.28




TOTAL ESTIMATED
GENERATION1
(kkg/yr)
427,000



195,000




240


3,7UO




21,OOU


150
21,000




MANAGEMENT
SEQUENTIAL TECHNIQUES USED2
NTRL, BIOL, CRBN, DSWR
NTRL, CRBN, STLG, DSWR
SIMP, DWI
Unknown
NTRL, BIOL, CRBN, DSWR
BIOL (SIMP), DSWR
CTRT, CR8N, NTRL, DSWR
SIMP, DWI
Unknown
SIMP, DWI
INCN
Unknown
KCRY
MKTD
INCN-OFST
FUEL
Unknown
INCN
LDFL-OFST
Unknown
INCN
INCN
A***********************
PILE, LDFL-OFST
FUEL
PILE, LDFL
USE (%)3
60
11
4
25
27
29
19
4
21
71
8
21
23
21
18
17
21
76
3
21
100
35
********
18
12
1
^Total waste stream quantity generated in association with the production of TDI and
  intermediates, based on 19 BO production figures.
     to management techniques:
 BIOL = Biological wastewater treatment  CRBN = Carbon adsorption
 CIRT = Chemical treatment               DSWR = Discharge to surface waters
 DWI  = Deep well injection              FUEL = Used as a fuel in a boiler or other device
 INCN = Incineration                     LDFL = Landfill
 MKTD = Marketed as a by-product         NTRL = Neutralization
 •OFST = Off-site unit process (all management techniques on-site unless specified otherwise)
 PILE = Storage in a pile or a shed      RCRY = Unspecified recovery of waste
*******CONFIDENTIAL BUSINESS INFORMATION
 STLG = Settling                         SIMP = Surface impoundment

'^Percentage of total generated waste treated by the sequence of techniques indicated.

4This waste is currently regulated in 40 CFR 261.32.
                                             23

-------
the two major manufacturers of DNT and TDA for non-captive use,

some general knowledge of their management techniques was available

from other sources.  The duPont plant at Deepwater, NJ (manufacturer

of DNT only), utilizes their patented PACT® process for treatment of

combined washwaters, including the washwater and the acid recovery

wastewaters from their DNT production.  This treatment process in-

volves neutralization with lime, primary clarification, combined

activated sludge/powdered activated carbon treatment, and discharge

to surface waters.  Management techniques utilized at the Air Products

plant at Pasadena, TX (manufacturer of DNT and TDA) are not specifically

known, but may include a deep well injection system for aqueous wastes.


         Wastes K113, K114, K115 result from product purification.

Waste K113, the light ends, may be combined with waste K112, if

mostly aqueous, for treatment and discharge to surface waters.

Some plants, however, separate this waste to include very little

water, and incinerate it.  *************************************f


         Waste K114, the vicinals, consists primarily of the ortho

(2,3- and 3,4-) toluenediamines, which have slightly lower boiling

points than the desired product (2,4- and 2,6-TDAs).  Because of

this,  the ortho TDAs can be recovered and marketed as a by-product.

However,  it has also been reported to be used as a fuel or incinerated.


         The TDA heavy ends (waste K115) are usually incinerated;

however,  some landfilling is also practiced.  (Three manufacturers

did not report its generation; they apparently allow high-boiling
* indicates that this is CONFIDENTIAL BUSINESS INFORMATION and is
in the record for this rulemaking.


                              24

-------
polymeric residue in the TDA product to continue on to the phosgenation



process, ultimately increasing the quantity of TDI heavy ends.)





         The TDI purification processes additionally generate an



organic liquid waste stream (K116) of small volume but containing



phosgene and chlorinated hydrocarbons (and, in the case of one



manufacturer, toluene).  Most facilities dispose of this residue



by incineration, either on-site or off-site.





         Management of the TDI heavy ends (K027), currently regulated



in 40 CFR 261.32, varies, including both incineration and landfill.
One other plant reported utilization of this residue as a fuel but



provided no details.





         In addition to these major waste streams, several minor



process waste streams were reported by TDI manufacturers.  These



include aqueous wastes from steam ejector systems for vacuum



distillation columns, scrubber wastewater, spent vacuum pump oil,



spent catalyst, and spent activated carbon from the treatment of



aqueous wastes or air emissions.  These wastes are extremely



variable in quantity and composition, depending on the process



flow scheme and unit operations utilized.





         Aqueous waste streams are typically combined, sent to



biological and/or physical chemical wastewater treatment systems,



and then discharged to surface waters.  Aqueous cleanup wastes



are probably sent to the same wastewater treatment facilities as



aqueous process wastes.  Data regarding the use of impoundments in
                              25

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the treatment of aqueous wastes were reported by two manufacturers:

*******************************************************************

*************************************



         Spent vacuum pump oil is typically very small in volume

and is incinerated.



         Spent catalyst from the DNT hydrogenation process was

reported as a waste stream by only one manufacturer.  However,

the literature and experience with similar processes suggest
                         •
that spent catalyst is frequently a waste stream in this process.

Raney nickel appears to be the most widely used catalyst although

the possible use of palladium on carbon is suggested in the

literature.  Due to the inherent value of the metal components

in these catalysts, the spent catalyst is often reclaimed.



         Very little information was supplied by the manufacturers

regarding spent activated carbon quantities and management.

However, economics often favor thermal regeneration of spent

activated carbon.



         Some of the manufacturing products, if discarded for

any reason, including if the product is off-specification, are

currently regulated in 40 CFR 261.33(£): U105, 2,4-dinitrotoluene;

U106,  2,6-dinitrotoluene;  U221, toluenediamine; and U223, toluene

diisocyanate.  Section 261.33(f) only pertains to the discarded

commercial chemical products, manufacturing chemical intermediates,

or off-specification commercial chemical products, container residues,

and spill residues.
                              26

-------
V.   Basis for Listing


     A.  Hazards Posed by the Wastes


         1)  Waste No. Killi  Product washwaters from the production
of dinitrotoluene via nitration of toluene.

         The nitration of toluene to produce dinitrotoluene requires

highly acidic conditions.  Because of the high {up to 4%) concen-

tration of nitric and sulfuric acids, this waste is corrosive, with

a pH between 1-2.  Therefore, this waste meets the corrosivity

characteristic (40 CFR 261.22) and is thus defined as hazardous.


         In addition, this waste is expected to contain significant

concentrations of 2,4-dinitrotoluene, a mutagen as well as having

evidence of carcinogenicity,  as determined by the Agency's Carcinogen

Assessment Group  (GAG);  and 2,6-dinitrotoluene, an experimental muta-

gen  (i.e., positive  in in_ vitro or other short term tests).   {See

Section V.B. for  discussion of toxic levels).  Both are currently

listed as  toxic constituents in Appendix VIII of 40 CFR 261.


         As discussed above, a total of 427,000 kkg of waste  Kill

is estimated to be generated per year, based on 1980 TDI production

figures, with 2,4-dinitrotoluene and 2,6-dinitrotoluene constituting

0.08%  and  0.02%,  respectively.  Thus, approximately 342 kkg of

2,4-DNT and 85 kkg of 2,6-DNT  could potentially escape  into the

environment from  this waste.


         Although experimental environmental persistence data is  not

currently  available  for  dinitrotoluenes,  they have  been demonstrated

to be  both sufficiently  mobile to  leach out of  improperly  disposed
                               27

-------
wastes, and sufficiently persistent to remain  in the environment

long enough to cause substantial hazard, especially as a water

contamination problem.  This conclusion is supported by the detection

of these toxic materials in United States tap  water, ambient water

and finished effluent (see Sections V.C. and D.).


         These factors, as well as the toxicity of these constitu-

ents (discussed in detail in section V.E.), contribute to  the

potential hazards posed by this waste, justifying a hazardous

waste listing.


         2)  Waste No. K112, Reaction by-product water from the
drying column in the production of toluenediamine via hydrogenation
of dinitrotoluene.

         This waste is expected to contain significant concentra-

tions of 2,4- and 2,6-toluenediamine (TDA) and 3,4-TDA, which are

currently listed (as toluenediamine) as toxic  constituents in

Appendix VIII of Part 261, and o- and p_-toluidines, which we are

proposing to add to Appendix VIII.  Of these compounds, 2,4-TDA

and o-toluidine have been determined by the Agency's CAG as having

evidence of carcinogenicity; 2,4-TDA is also reported to be mutagenic,

In addition, 2,6- and 3,4-TDA have been found  to be experimental

mutagens; while p_-toluidine was found to cause chronic blood effects,

in addition to causing hepatomas in mice.  (See Section V.B. for

discussion of toxic levels.)


         A total of 195,000 kkg of this waste  is estimated to be

generated annually, based on 1980 TDI production figures, with 2,4-

and 2,6-TDA constituting between 0.05 - 0.3%;  3,4-TDA ranging between

0.05 - 0.3%; and £- and p_-toluidine constituting between 0 - 0.06%


                              28

-------
and 0 - 0.04%, respectively.  Thus, there is a potential for escape

of these constituents into the environment from waste K112 up to

the following amounts (based upon the higher concentration limit}:

     2,4- and 2,6- TDA    585 kkg

     3,4-TDA              585 kkg

     o-toluidine          117 kkg

     £-toluidine           78 kkg

         Because of the high concentrations of these constituents,

and since wastewater treatment and surface impoundment are commonly

used management techniques, there is a high risk of their escaping

into the environment.  Several of these constituents are both acute

and chronic toxicants (see Section V.E.), so a serious potential hazard

is presented by their release into the environment.  These constitu-

ents, moreover, are all mobile in the environment  (based on their

solubility in water and in other solvents), and some are expected to

be persistent (see Section V.D.); in addition, they are generated in

large quantities.  Therefore, if improperly managed, they are likely

to enter into, and remain in the environment, posing substantial

risk.  These considerations justify a hazardous waste listing.


         3)  Waste No. K113, Light ends from the purification of
toluenediamine in the production of toluenediamine via hydrogen-
ation of dinitrotoluene.

         This waste is expected to contain significant concentrations

of 2,4-, 2,6-, and 3,4-TDA; o- and £-toluidine; and aniline.  The

potential hazards of the TDAs and toluidines to human health and the

environment are outlined above.  Aniline is carcinogenic in rats,

teratogenic, and chronically toxic.  (See Section  V.B. for discussion

of toxic levels.)


                              29

-------
         A total of 240 kkg of this waste is estimated to be generated

annually, based on 1980 TDI production figures, with 2,4- and 2,6-TDA

constituting between 0 - 37.5%; 3,4-TDA ranging up to 37.5%; o- and

£-toluidine constituting between 0.6 - 6% and 0.4 - 4%, respectively;

and aniline constituting between 0.01 - 0.1%.  Thus, there is a potential

for release of these constituents into the environment from waste K113

up to the following amounts (based upon the higher concentration limit):

     2,4- and 2,6- IDA    90 kkg

     3,4-TDA              90 kkg

     o-toluidine          14 kkg

     £-toluidine          10 kkg

     aniline            0.24 kkg

         Because of the high concentrations of these constituents,

and since surface  impoundments are a commonly used management tech-

nique, there  is a  high risk of their escaping  into the environment.

Several of  these constituents are acute and/or chronic toxicants (see

Section V.E.), so  a serious potential hazard  is presented by their

release  into  the environment, should improper management occur.  These

constituents, moreover, are all mobile in the  environment (based on

their solubility in water and  in other solvents), and  some are  expected

to be persistent (see Section V.D.).  In addition, they are  likely  to

enter into, and remain in the1 environment,  posing substantial risk.

These considerations justify  a hazardous waste listing.


         4)   Waste No. K114,  Vicinals from  the purification  of
toluenediamine  in  the production of  toluenediamine via hydrogenation
of dinitrotoluene.

         This waste is expected  to contain  significant concentra-

tions of 2,4-,  2,6-, and  3,4-TDA, and o- and  p_-toluidine.   (See


                               30

-------
Section V.B. for discussion of toxic levels.) The potential

hazards to human health and the environment of TDAs and toluidines

have already been discussed above.


         A total of 3700 kkg of this waste is estimated to be

generated annually, based on 1980 TDI production figures, with 2,4-

and 2,6-TDA constituting between 4.5 - 50%; 3,4-TDA ranging up to

95%; and o_- and p_-toluidine constituting between 0-3% and 0-2%,

respectively.  Thus, there is a potential for release of these

constituents into the environment from waste K114 up to the

following amounts (based upon the higher concentration limit):

     2,4- and 2,6- TDA    1850 kkg

     3,4-TDA              3515 kkg

     o_-toluidine           111 kkg

     £-toluidine            74 kkg


         Because of the high concentrations of these constituents,

and since these constituents are all acute and/or chronic toxicants

(see Section V.E.), a serious potential hazard is presented by their

release into the environment.  These constituents are all mobile in the

environment (based on their solubility in water and other solvents),

and some are expected to be persistent (see Section V.D.); in addition,

they are generated in large quantities.  Therefore, they are likely to

enter into, and remain in the environment, posing substantial risk.

These considerations support a hazardous waste listing.


         5)  Waste No. K115, Heavy ends from the purification of
toluenediamine in the production of toluenediamine via hydrogenation
of dinitrotoluene.

         This waste is expected to contain significant concentrations


                              31

-------
of 2,4-, 2,6-, and 3,4-TDA.  (See Section V.B. for discussion of toxic

levels.)  The potential hazards of TDA to human health and the

environment are outlined above.


         A total of 21,000 kkg of this waste is estimated to be

generated annually, based on 1980 TDI production figures, with

2,4- and 2,6-TDA constituting between 10 - 50%; and 3,4-TDA

ranging up to 2.5%.  Thus, there is a potential for release of

these constituents into the environment from waste K115 up to

the following amounts (based on the higher concentration limit):

     2,4- and 2,6- TDA  10,500 kkg

     3,4-TDA               525 kkg

         Because of the high concentrations of these constituents

and because these constituents are all acute and/or chronic toxicants

(see Section V.E.), a serious potential hazard is presented by their

release into the environment.  These constituents moreover, are all

mobile in the environment (based on their solubilities in water and

other solvents), and some are expected to be persistent (see Section

V.D.); in addition, they are generated in large quantities.  Therefore,

they are likely to enter into,  and remain in the environment if there

is improper management,  posing substantial risk.  These considerations

justify a hazardous waste listing.


         6)  Waste No. K116, Organic condensate from the solvent
recovery column in the production of toluene diisocyanate via
phosgenation of toluenediamine.

         This waste is expected to contain significant concentra-

tions of carbon tetrachloride,  tetrachloroethylene, chloroform,

and phosgene.   All of these, except phosgene,  have been identified
                              32

-------
as potential human carcinogens by the Agency's CAG;  in addition, they



are chronically toxic.   Phosgene is extremely dangerous as an acute



toxicant at low concentrations in air.  All of these constituents



are currently listed in 40 CFR Appendix VIII.  (See  Section V.B. for



discussion of toxic levels.)





         A total of 150 kkg of this waste is expected to be generated



annually, based on 1980 production figures, with carbon tetrachlonde



constituting up to 75%, tetrachloroethylene up to 15%, chloroform



up to 7%, and phosgene up to 30%.  Thus, there is a  potential for the



escape of these constituents into the environment from waste K116 up



to the following amounts (based on the higher concentration limit):



     Carbon tetrachloride      113 kkg



     Tetrachloroethylene        23 kkg



     Chloroform                 11 kkg



     Phosgene                   45 kkg



         Carbon tetrachloride, tetrachloroethylene,  chloroform, and



phosgene are all volatile, and, at such high concentrations, may



result in inhalation exposure.  In addition, although their solubility



is limited, they have been shown to migrate  into the environment; also,



they are persistent in aqueous environments, and mismanagement of this



waste could result in significant human exposure by this route as well.



In fact, all of these toxicants (except phosgene) have been detected



in various samples at the Love Canal  site  (U.S. EPAd, 1980), demonstra-



ting their mobility and persistence  in  the environment.





     A further risk to human health  and the  environment may be posed



by improper incineration of these compounds.  Improper incineration
                              33

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of the chlorinated hydrocarbons, including carbon tetrachloride,



tetrachloroethylene, and chloroform could cause exposure to unburned



toxicants in the wastes, and exposure to products of incomplete



combustion,  including phosgene and hydrochloric acid.





         Therefore, because of the high concentrations of these



toxicants in the waste, and their ability to migrate and persist



in the environment, a serious potential hazard is presented by



their release into the environment.  These considerations justify



a hazardous waste listing.





     B.  Degree of Hazard of These Wastes



         The Agency has determined that several of the hazardous



constituents in these wastes are toxic.  For example, the Agency's



Carcinogen Assessment Group (CAG) has determined that 2,4-TDA and



o-toluidine are potential human carcinogens; several of these toxi-



cants are experimental mutagens; and several are reproductive or



teratogenic toxins, or otherwise cause chronic or acute systemic



effects.





         A semi-quantitative assessment was made of  the degree  of



hazard posed by these wastes, if mismanaged.  For each constituent



of concern, an allowable daily  intake  (ADI), or the  10~6 excess



cancer risk level virtually safe dose  (VSD) was calculated  (see



Appendix I).  The methods used  for these calculations are those



used to calculate Water Quality Criteria (U.S. EPAf, 1980).  These



doses are listed in column 5 of Table  5.  2,6-DNT and 2,6-TDA



have other chronic systemic effects.   For these chemicals an ADI



was estimated from animal studies  (U.S. EPAf, 1980).





                              34

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                                          TABLE 5
WASTE
Kill

K112



K113




K114



K115

K116
TOXICANT
OF
CONCERN
(TOG)
2,4-DNT
2,6-DNT
2,4- + 2,6-TDA
3,4-TDA
o-toluidine
Pj-toluidine
2,4- + 2,6-TDA
3,4-TDA
aniline
o-toluidine
pj-toluidme
2,4 + 2,6-TDA
3,4-TDA
o-toluidine
£-toluidine
2,4 + 2,6-TDA
3,4-TDA
Carbon
tetrachloride
Tetrachloro-
ethylene
Chlorofonn
(TOC) /Waste
%
0.08
0.02
0.03
0.03
0.06
0.04
37.5
37.5
0.1
6
4
47.5
2.5
3
2
50
2.5
up to 75
up to 15
up to 7
Estimated
Daily
Exposure
(DE)
mg/day3
0.030
0.007
0.10
(0.05)c
0.10
0.02
0.013
12.5 (6.3)c
12.5
0.03
2
1.3
16 (8)c
0.8
1
0.7
13 (6.5)c
0.8
25
5
2.3
ADI, (A) or
VSD, (V) at
the 10~6 Cancer
Risk Level
rag/day13
2.6 x 10-4 (V)
2.1 (A)
3 x 10~6 (V)
-
2.9 x ID"4 (V)
-
3 x 10-6 (V)
-
2.3 x ID"3 (A)
2.9 x 10~4 (V)
-
3 x 10~6 (V)
-
2.9 x ID"4 (V)
-
3 x ID'6 (V)
-
8.5 x ID"4 (V)
18 x 10-4 (V)
3.8 x ID"4 (V)
DE/
ADI
or
VSD
100
10-3
104
-
700
-
2 x 106
-
13
0.7 x!04
-
3 x 106
-
3000
-
2 x 106
-
3 x 104
2.5 x 103
5 x 103
b "-" = NO ADI for cancer potency estimate available,
c If 50% of the reported mixture is 2,4-TDA.
                                            35

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          For  each  toxicant of concern,  a daily exposure  dose  was



 estimated  by  use of the plausibly-occurring mismanagement  scenario



 outlined  in Appendix  I.  The resulting  values are listed in column  4



 of Table  5.   For each toxicant, a crude estimate of the  risk  of chronic



 systemic  or carcinogenic effects was obtained by comparing this estimated



 daily exposure with the ADI or VSD.  These comparisons are shown  in



 column  6  of Table  5.






         Ambient Water Quality Criteria (AWQC) have been established



 (see 45 FR 79318,  November 28, 1980) for four of the toxicants of



 concern in the wastes which we are proposing to list, namely, 2,4-DNT;



 carbon  tetrachloride; tetrachloroethylene; and chloroform.  The AWQC



 developed  for these substances to protect against a 10"^ excess



 cancer  risk to humans resulting from the consumption of  water and



 aquatic organisms  are 0.11, 0.4, 0.8, and 0.19 ug/1, respectively.





         As seen in Table 5, these toxicants are present in the wastes



 at concentrations  107 - 109 times higher than the AWQC;  in addition,



 their solubility is many times greater than the AWQC.  Thus, even



 though soil attenuation factors, such as soil binding, biodegradation,



 and other environmental degradative processes are expected to decrease



 the amount of the  toxicants available for migration, these toxicants



 are expected to present a substantial hazard, since only a small fraction



need migrate from  the wastes and reach environmental receptors to pose



 the potential for substantial harm.






         The Agency thus concludes that the concentrations of 2,4-DNT,



 2,4- and 2,6-TDA, o-toluidine,  carbon tetrachloride, tetrachloro-



ethylene and chloroform may occur in the listed wastes at levels



of regulatory concern.



                              36

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         Although the Agency was not at this time able to make a quali-



tative evaluation of the levels of concern for 3,4-TDA and p_-toluidine,



we believe that the toxic effects of these substances (see Section V.E.)



are such as to warrant their designation as toxicants of concern.





         In the case of aniline and 2,6-DNT, the ratio of estimated



to allowable daily exposure is not high.  However, the Agency judges



that their toxic properties, and their demonstrated persistence



(i.e., they have been found in ground and surface water and/or soil),



provide sufficient grounds to warrant their inclusion.





     C.  Mismanagement





         A number of environmental damage incidents have occurred



due to mismanagement of either DNT, TDA, or TDI wastes,  or other



wastes containing the hazardous constituents found in wastes from



DNT, TDA, or TDI production.  These incidents show either that these



wastes can cause substantial harm if mismanaged, or that the



constituents of concern are mobile and persistent upon migration.





         DNT waste products have been discharged into surface water



or sewage by industries that manufacture dyes,  isocyanates, polyur-



ethanes,  and munitions.  As a result of the routine discharge to



surface waters of its plant process water containing residues of



DNT by the Milan Army Ammunition Plant in Milan, Tennessee, wells



in the installation in the vicinity of the industrial lagoons



were found to have residues of DNT (U.S. EPAc,  1980).



         2,4-DNT has been detected both in ambient waters and in



industrial effluents (U.S. EPAe, 1979).
                              37

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          In Abbeville,  LA,  groundwater was found to be contaminated
 by a number of  substances,  including  2,4-DNT at a concentration
 of 31 ug/1, about  280 times the  AWQC  level.   Twenty-two wells exist
 within 1/4  mile of the  site;  the distance to the drinking water
 supply is  300 yards.   The source of the contamination  is an  open pit
 for disposal of oil-based mud and storage tanks.
          2,6-DNT has  been detected in  the water effluent of  a tri-
 nitrotoluene plant in Virginia,  in pond effluent of a  DNT plant,
 as well  as  in tap  water  in  the united  States,
 indicating  both the mobility  and the persistence of DNT in the
 environment (U.S.  EPAa,  1980).

         Both o- and  £-toluidines  have  been  detected in  quite a
 few  samples of  ground water and  surface  water,  as  well  as  in
 chemical plant  effluents  (U.S. EPAa, 1980).

         An industrial facility  allegedly dumped  sludge  from  aniline
 production  in two  open pits prior  to 1952.   In  subsequent years,  the
 the  area was used  for waste disposal until the  site was  closed  in
 July,  1974.  Surface  water, groundwater, and soil  are suspected  to  be
 contaminated by aniline.

         In measurements made during the National  Organics Monitoring
 Survey of 113 public water systems sampled, 11 of  these  systems
detected carbon  tetrachloride at levels at or exceeding  the recommended
safe limit.   Carbon tetrachloride has  also been detected in school and
basement air samples taken at the Love Canal site  (U.S.  EPAd, 1980).

         Tetrachloroethylene has  been  detected in school and basement
                              38

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air, basement sumps, and solid surface samples at Love Canal



sites  (U.S. EPA, 1980d).  It has been detected in a number of



drinking water samples  (U.S. EPAa, 1980).





         Chloroform has been detected in basement sumps and school



and basement air at the Love Canal site (U.S.  EPAd, 1980).





         (A large number, more than 60, of additional damage



incidents relating to contamination by carbon tetrachlonde,



tetrachloroethylene, and chloroform are appended to this listing



Background Document.)





         Thus, if waste disposal sites are improperly designed or



managed - for example, sited in areas with highly permeable soils or



constructed without effective natural or artificial liners - there



is a possibility of escape of waste constituents to ground water or



surface water, and, in the case of the volatile constituents, to



the atmosphere as well.





         A further possibility of substantial hazard arises during



transport of these wastes to off-site disposal facilities.  The



damage incidents described above in fact demonstrate hazards which



may arise during off-site transportation and management.  Some of



the toxicants of concern in these wastes are persistent, biodegrade



slowly, and can thus cause substantial harm to human health and



the environment (see Section V.D.).






         Another risk to human health and the environment may be



posed by improper incineration of some of these compounds.  Improper



incineration of the chlorinated hydrocarbons, including carbon





                              39

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tetrachloride, tetrachloroethylene, and chloroform could cause exposure

to unburned toxicants in the wastes, and exposure to products of

incomplete combustion, including phosgene and hydrochloric acid.


     D.  Environmental Effects of the Hazardous Constituents


         The environmental effects described here are more fully

discussed in the Health and Environmental Effects Profiles.8


         Dinitrotoluenes (DNT) would be expected to biodegrade to a

limited extent.  The nitro groups retard biodegradation and studies

with soil microflora have shown that mono- and di- substituted nitro-

benzenes persist for more than 2 months (U.S. EPAa, 1980).  It has

been reported that dinitrotoluenes are decomposed very slowly in

a reservoir; biodegradation by Azotobacter has also been reported

to be slow (U.S. EPAe, 1979).

         As indicated by the solubility of 2,4-DNT (270 mg/1 in

water at 22°C; readily soluble as well in ethanol, ether and carbon

disulfide (U.S.  EPAa, 1979) and of 2,6-DNT (soluble in ethanol),

DNTs (constituents of waste Kill), if inadequately disposed, may

be dissolved found within mixed wastes and leach out of these

wastes into the ground water, causing a contamination problem,

especially since they are not readily biodegradable, so are

likely to persist.


         The toluenediamines (TDA) are constituents of wastes

K112, K113, K114, and K115.  2,4-TDA is very soluble in hot water,

alcohol, and ether; 2,6-TDA is soluble in water and alcohol; and
8These documents are available in the RCRA Docket, and at EPA
 regional libraries.

                              40

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 3,4-TDA  is very soluble  in water  (CRC, 1968).  Although monitoring



 data are not available for these  substances, they are capable of



 causing water contamination problems by being dissolved within



 mixed wastes, and leaching out of these wastes into waterways,



 from improperly designed and managed waste disposal sites.





         Some studies have shown  that o- and £-toluidine would not



 significantly biodegrade by activated sludge in a week, although



 aniline activated sludge and £-nitroaniline activated sludge



 degraded them (U.S. EPAa, 1980).



         In the absence of adequate data, it is difficult to



 estimate the half-life of the toluidine biodegradation in ambient



 aquatic media.  However, the fact that both isomers have been



 detected in quite a few samples of ground water and surface



 water (U.S. EPAa, 1980), demonstrates both the mobility and



 persistence of the toluidines.





         Aniline is very water soluble (35,000 ppm at 25°C)



 (U.S. EPAb, 1980).  Soils of organic content may retain aniline;



 clays of high surface area (montmorillonite) will also have some



 retention capacity (U.S. EPAa, 1980).  Aniline has a low vapor



pressure of 1 mm Hg at 35°C and 10 mm Hg at 70°C (U.S. EPAa,



 1980),  so it is unlikely to volatilize from water or soil into



the atmosphere.   All of these factors contribute to aniline's



potential persistence in the environment.





         Carbon tetrachloride, a constituent of waste K116, is



very soluble in water (800 mg/1 at 20°C,  Verschueren,  1977).  It



 is nondegradable in water, with a hydrolytic breakdown half-life





                              41

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 of  70,000 years, and  tends to remain  indefinitely at  the bottom  of



 water courses  (U.S. EPAb, 1980).  It  is also extremely volatile  (90



 mm  Hg at 20°C, Verschueren, 1977), and therefore, could present



 an  inhalation  hazard.  In the incineration of carbon  tetrachloride-



 containing wastes, phosgene, a highly toxic gas, is emitted under



 incomplete combustion conditions.  All of these  factors demonstrate



 that carbon tetrachloride is both mobile and extremely persistent



 in  the environment.






         Tetrachloroethylene, another constituent of  waste K116,



 is  volatile (vapor pressure = 37.6 mm Hg at 40°C).  Its water



 solubility is  150 mg/1, and it has been detected in a number of



 drinking water samples (U.S. EPAa, 1980).  All of these factors



 demonstrate that tetrachloroethylene is both mobile and very



 persistent in  the environment.






         Chloroform, a constituent of waste K116 , is  also very



mobile and persistent in the environment.  it is very water-



 soluble (8,200 mg/1, U.S. EPAe,  1979), and also very volatile,



with a vapor pressure of 200 mm Hg at 25°C (U.S. EPAa, 1980).



Chloroform is stable under normal environmental conditions.



When exposed to sunlight, it decomposes slowly in air, but is



relatively stable in water.   The measured half-life for hydrolysis



was found to be 15 months (U.S.  EPAa, 1980).





         Phosgene,  also found in waste K116,  has high acute



toxicity and has been used as a  nerve gas by  the military.   It



 is extremely volatile (1215  mm Hg at 20°C).   It is only slightly



soluble in  water (Windholz,  1976) and would  most likely volatilize





                              42

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 from wastes, causing an air pollution problem  if not properly
 contained on disposal.

     E.  Health  Effects of the Hazardous Constituents
         1.  Dinitrotoluenes
             a.   2,4-Dinitrotoluene  (2,4-DNT)  is absorbed by ingestion,
 inhalation, and  through the skin.  The EPA's Carcinogen Assessment Group
 (CAG) determined  that 2,4-DNT is a potential human carcinogen,  inducing
 liver and kidney  carcinoma and (benign) mammary tumors in rats  and
 mice.  2,4-DNT is mutagenic in several assay systems.  Chronic
 exposure causes decreased sperm production and testicular atrophy
 in rats, and may  produce methemoglobinemia, anemia, jaundice, and
 liver damage in animals and humans; alcohol aggravates its toxic
 effects.  In addition, the oral toxicity hazard of 2,4-DNT is
 very high (Sax, 1979).
         The Occupational Safety and Health Administration (OSHA)
 has set the permissible exposure limit (PEL) for 2,4-DNT in air
 at 1.5 mg/m3 as the time-weighted average (TWA).
         The Ambient Water Quality Criterion to protect humans  from
 the effects of 2,4-DNT has been set at 0.11 ug/1.  A 24-hour average
concentration of 620 ug/1, not to exceed 1,400 ug/1, has been set
as the EPA's Water Quality Criterion to protect freshwater life
from the toxic effects of 2,4-DNT.  2,4-DNT is a priority pollutant
under Section 307(a) of the Clean Water Act (CWA).

             b.  2,6-Dinitrotoluene (2,6-DNT) is absorbed by ingestion,
inhalation,  and through the skin.  it produces benign tumors in rats,
and is mutagenic in several strains of Salmonella typhimurium without
                              43

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metabolic activation.  it causes metheraoglobinemia in cats, dogs,



rats, and mice.  When administered orally to these animals for a



maximum of thirteen weeks, the major effects seen, in addition to



the blood effects, were depressed spermatogenesis, liver and



kidney degeneration, bile duct hyperplasia, and incoordination



and rigid paralysis of the hind legs.  2,6-DNT is listed as



having a high toxicity via ingestion (Sax, 1979).



         The OSHA PEL for 2,6-DNT in air is 1.5 mg/m3 (TWA).



         2,6-DNT is a priority pollutant under Section 307(a) of



the CWA.





         2.  Toluenediamines



             a.  2,4-Toluenediamine (2,4-TDA) is absorbed by ingestion,



inhalation, and through skin contact.  It is carcinogenic in rats



and mice.  2,4-TDA has been identified by the Agency's CAG as a



potential human carcinogen.  It is a frameshift mutagen in bacterial



and insect test systems, and causes cell transformation.  The results



of a dominant lethal test, however, were negative.  2,4-TDA is



hepatotoxic to rats and mice, and causes renal disease.



         2,4-Toluenediamine has also been designated as moderately



toxic when inhaled (Sax, 1979).



         There are no Federal guidelines or standards for exposure



to 2,4-TDA.



             b.  2,6-Toluenediamine (2,6-TDA) is positive in the Ames



Salmonella assay system in the presence of enzyme activators, as



well as in a cell transformation system.  Reduced weight gain,



nephrosis, and hyperplasia were found in rats and mice administered



3,000 - 10,000 ppm of 2,6-TDA in the diet for 3 months.  Among these





                              44

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 animals,  diffuse  bilateral  adenomatous  hyperplasia of  the  thyroid



 was  seen  in  70% of male  rats  fed  3000 ppm.  At  lower dose  levels,



 other  studies  have not identified adverse effects.






             c.   3,4-Toluenediamine  (3,4-TDA) produces positive



 mutagenic response in some  assay  systems.   Female rats receiving



 33.3 or 50 mg/100 kg body weight  of  3,4-TDA by  gavage  twice



 daily  for 5  days  developed  duodenal  ulcers; single subcutaneous



 injections of  62.5 - 500 mg/kg of 3,4-TDA to male and  female



 rats resulted  in  gastric and  duodenal lesions.






          3.  Toluidines  (aminoroethylbenzenes)



             a.   o-Toluidine  (2-amino-l-methylben2ene) is absorbed



 both orally  and dermally.   o-Toluidine  is metabolized, and excreted



 mainly through urine.  it has been identified by the Agency's CAG



 as a potential human carcinogen.  In the Ames test, o-toluidine



 only exhibits a positive mutagenic response when a special "activator"



 is added.  There  is evidence of transplacental migration of o-toluidine



 or its metabolites.  Induction of fetal tumors  has also been observed.



 Other chronic effects observed experimentally are bladder lesions



 and  other bladder abnormalities, methemoglobinemia, sulfhemoglobinemia,



 and  increased levels of cytochrome oxidase.   o-Toluidine has also



 been designated as highly toxic via oral, and moderately toxic



by dermal routes of exposure (Sax, 1979).



         The OSHA PEL for o-toluidine is 5 ppm  in air (TWA).



         The American Conference of Governmental Industrial



Hygienists (ACGIH) recommends an 8-hour threshold limit value



 (TLV) at 2 ppm (TWA).
                              45

-------
             b.  p-Toluidine (4-amino-l-methylbenzene) is absorbed by
ingestion and dermally.  It is metabolized, and excreted primarily
in the urine.  2~Toluidine nas been tested for carcinogenicity in
male rats and in female mice, and increased the incidence of hepatoma
in mice only.  £-Toluidine caused methemoglobineraia in cats when
intravenously injected.  p_-Toluidine has also been designated as
highly toxic by ingestion (Sax, 1979).
         The FDA has established a tolerance of 0.1% for p_-toluidine
in D and C green dye No. 6.

         4.  Aniline is absorbed orally, dermally, and through inhala-
tion.  It is rapidly absorbed into the blood stream and metabolized
in the liver.  The metabolites are excreted in the urine.  Aniline
is carcinogenic in rats, with statistically significant increases
of fibrosarcomas and sarcomas of the spleen and in multiple body
organs.  Aniline can cross the placental barrier and form methemo-
globin in the fetus, affecting its development.  Aniline also has a
number of chronic effects, including methemoglobinemia and anemia.
At higher exposure levels, cardiotoxic effects, hepatic injury,
splenic hemosiderosis,  fatigue, headache,  irritability, dizziness,
insomnia, and paresthesias are noted.  Aniline has been designated
as highly toxic through oral and inhalation routes of exposure
(Sax, 1979).
         The maximum allowable concentration in class I waters
used for drinking water in the U.S.  is 5 mg/1.

         5.  Carbon tetrachloride has been  identified by the
Agency's Carcinogen Assessment Group  (CAG)  as  a potential human
                              46

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carcinogen.  Retarded fetal development, fetal liver changes,



and slight fetotoxicity have been demonstrated in rats.  Chronic



effects include fatigue, lassitude, giddiness, anxiety, headache,



paresthesias, muscular twitching, increased reflex excitability,



moderate jaundice, hypoglycemia, anorexia, nausea, diarrhea, mild



anemia, cardiac and kidney pain, dysuria, slight nocturia, and



blurred vision.  Adverse effects of carbon tetrachloride on liver



and kidney functions and on the respiratory and gastrointestinal



tracts have also been reported.  Death has been caused in humans



at small doses.  Obese individuals are especially sensitive to



the toxic effects of carbon tetrachloride.  Carbon tetrachloride



is considered a high systemic poison hazard through ingestion



and inhalation (Sax, 1979).



         The OSHA PEL for carbon tetrachloride in air is 10 ppm  (TWA).



         The Ambient Water Quality Criteria for carbon tetrachloride



designed to reduce the excess human cancer risk is 0.4 ug/1.



         Carbon tetrachloride is a priority pollutant under Section



307(a) of the CWA.





         6.  Tetrachloroethylene has been identified by the Agency's



CAG as a potential human carcinogen.  it is a mutagen in bacterial



assays.  It is also chronically toxic to dogs, causing kidney and



liver damage, and to humans, causing impaired liver function.  In



mice and rats, tetrachloroethylene has caused toxic nephropathy.



Subjective central nervous system complaints were noted in workers



occupationally exposed to tetrachloroethylene.  Exposure to tetra-



chloroethylene is reported to cause alcohol intolerance to humans.



         Tetrachloroethylene is designated as moderately toxic by





                              47

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inhalation, oral, subcutaneous, intraperitoneal, and dermal routes,



and highly toxic via the intravenous route of exposure  (Sax, 1979).



         The AGCIH TLV for tetrachloroethylene in air is 670 mg/m3.



         The Ambient Water Quality Criterion for tetrachloroethylene



designed to reduce the excess human cancer risk is 0.8  ug/1.



         The Water Quality Criterion to protect saltwater aquatic



life from the toxic effects of tetrachloroethylene is 79 ug/1 as a



24-hour average, not to exceed 180 ug/1 at any time; for freshwater



aquatic life, the the draft criterion is 310 ug/1 as a  24-hour



average, not to exceed 700 ug/1 at any time.  Tetrachloroethylene



is a priority pollutant under Section 307(a) of the CWA.





         7.  Chloroform has been identified by the Agency's CAG as



a potential human carcinogen.  Chloroform induces hepatocellular



carcinomas in mice, and kidney epithelial tumors in rats.  It is



also a teratogen: chloroform induces fetal'abnormalities (acaudia,



imperforate anus, subcutaneous edema, missing ribs, and delayed



ossification) in rats.  In addition, it is fetotoxic to rats and



rabbits.  Other chronic effects include liver necrosis  and kidney



degeneration.  It is absorbed by ingestion, inhalation, and dermally.



A small fraction of absorbed chloroform is metabolized  by mammals.



Alcohol, and high fat and low protein diets reportedly  enhance



the toxic effects of chloroform.  Chloroform is designated as



moderately toxic by oral and inhalation routes (Sax, 1979).



         The OSHA PEL for chloroform in air is 2 ppm (TWA).



         The FDA prohibits the use of chloroform in drugs, cosmetics,



or food contact material.



         The Ambient Water Quality Criterion for chloroform designed





                              48

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to reduce the excess human cancer risk is 0.19 ug/1.



         The Ambient Water Quality Criterion for chloroform to



protect freshwater aquatic life is 500 ug/1 (24-hour average),



not to exceed 1,200 ug/1 at any time.  To protect saltwater



aquatic life, the criterion is 620 ug/1 (24-hour average), not to



exceed 1,400 ug/1 at any time.  Chloroform is designated a priority



pollutant under Section 307(a) of the CWA.





         8.  Phosgene (this discussion is taken from sax, 1979)  is



highly toxic by inhalation and highly irritating to the eyes and



mucous membranes.  Within the lungs, phosgene decomposes to carbon



monoxide and hydrochloric acid.  Because there is little irritation



to the respiratory tract, its warning properties are very slight.



The liberation of hydrochloric acid in the lung tissues results



in pulmonary edema, which may be followed by bronchopneumonia,



and occasionally lung abcess.  Degenerative changes in the nerves



have also been reported.



         Concentrations of 3 - 5 ppm phosgene in air causes irrita-



tion of the eyes and throat, with coughing; 25 ppm is dangerous



for exposure lasting 30 - 60 minutes, and 50 ppm is rapidly fatal



after even short exposure.  There may be no immediate warning



that dangerous concentrations are being breathed.  After a latent



period of 2 - 24 hours,  the patient complains of burning in the



throat and chest,  shortness of breath and increasing dyspnea.



There may be moist rales in the chest.  Where the exposure was



severe, the development of pulmonary edema may be so rapid that



the patient dies within 36 hours after exposure.  In cases where



the exposure was less,  pneumonia may develop within several





                              49

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days.  In patients who recover,  no permanent residual disability



is thought to occur.
                              50

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                          VI.  References
           ^1 R~uber ComPany-  Handbook of Chemistry  and  Physics.
           ed.  The Chemical Rubber Company, Cleveland, OH.   1968.


      ?*!!' *' Ifvin9-  Dangerous Properties of Industrial  Materials.
      5tn ed.  van Nostrana Reinhold Co., New York. - 1979. -


      S-Cubed.  Analysis of RCRA Solid Wastes from the Industria
      Organic Chemicals inaustrv;  Toluene Diisocyanate.  -prSTTST
                                                        .         narv

      INFORMATION^      °A'  September' 1983'  (CONFIDENTIAL BUSINESS
      nco   °ufiCe x°f S°lld WaSte' Hazardous and Industrial Waste
      Division.  Hazardous Waste Incidents (unpublished, open file).




      U.S. EPAa.   Office of Solid Waste.  Appendix A - Health and

      Environmental Effects Profiles.   Washington, B.C.  October 30,
      1980, and subsequent revisions.


      U.S. EPAb.   Office of Solid waste.  Appendix B - Physical

          1C                                 Constituents! "W^hlnntnn ,
 ?'    ^ri'Th^AC;   211  a"d  SPecial  Materials  Control Division.   Damages
      u"?i.         Caused by  Hazardous  Material  Sites.   EPA/430/980/004.
      Washington,  D.C.  May  1980.   --          /»ou/uui.



 8*    nA?'  EPAd\  Genfric  Chlorinated  Organic Waste Streams.   Background
      Document, Appendix D.  Washington,  D.C. - T980: -      Kgrouna


                  Office ,?f  Water.  Water-Related  Environmental  Fate

                     P°11UtantS ^olume  II).   Washington,  D.C. -
10'  2:?o EnAfi'-.°fJ1Ce °f Water Ouality Regulations and  Standards.
     Water Quality Criteria.  45 Federal Register 79318-79379
     Washington, D.C.  November 28, 1980.   -


11.  U.S. EPAg.  Office of Solid Waste.  Solid Waste Data:  A Compil-

                   P^^^^^               Management Within ^niL*
12 '   XS!?!!11!!;*11',,*";1'  Ha"dbo°k of Environmental Data on Organic
                     Nostrand Reinhold Co., New York. - 1977. — -


                                Merck Inde'" 9th ed-
                              51

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                            Appendix I



                      MISMANAGEMENT SCENARIO





     The wastes under consideration are assumed to constitute 5%



of the wastes disposed in a sanitary landfill receiving predominantly



domestic refuse.  The mean density of the refuse  is 415 kg/m3 (U.S.



EPAg, 1981), and the depth of the landfill is assumed to be 6 meters



(20 feet).  Therefore, per square meter of the landfill, there are



121 kg of the industrial waste (0.05 x m2 x 6m x  415 kg/m3).  Rain-



fall, estimated at 1000 l/m2/year (U.S. EPAg, 1981), is estimated to



migrate through the landfill.  AS a worst case, it is assumed that



all of the toxicant contained in the industrial waste dissolves



in the rainfall percolating through the landfill  over its 70-year



operational lifetime.  Thus, if the waste contains 0.08% of a



toxicant, the toxicant available for leaching per square meter



of landfill (0.08 kg toxicant/100 kg waste x 127  kg waste x 106



mg/kg = 1.02 x 105 mg) is dissolved in 70 x 103 liters of leachate,



resulting in an average concentration of 1.46 mg  toxicant per liter



of leachate.  Assuming a 100-fold attenuation between the generating



site and a ground water,  the drinking water concentration would be



0.015 mg/1.  The estimated daily intake of a person drinking this



water would be 0.015 mg/1 x 2 I/day = 0.030 mg/1.  These estimated



exposures are listed in column 4 of Table 5.
                              52

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