United States
                   Environmental Protection
                   Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati, OH 45268
                   Research and Development
EPA/600/S2-86/096  Feb. 1987
<>EPA         Project Summary

                   Technical  Resource
                   Document:  Treatment
                   Technologies for
                   Dioxin-Containing  Wastes
                   Marc Breton, Mark Arienti, Paul Frillici, Michael Kravett, Steven Palmer,
                   Andrew Shayer, and Norman Surprenant
                     The 1984 Hazardous and Solid Waste
                   Act Amendments to the Resource Con-
                   servation and Recovery Act (RCRA) di-
                   rected  EPA to ban certain dioxin-
                   containing wastes from land disposal
                   unless EPA determines that restrictions
                   on land disposal of these wastes are
                   not needed to protect human health
                   and  the environment. Congress,
                   through the 1984 Amendments, fixed a
                   deadline of 24 months from the enact-
                   ment of the Amendments for EPA to
                   regulate the land disposal of these iden-
                   tified wastes (with some exceptions). In
                   the event that the Agency has not is-
                   sued regulations by that time (Novem-
                   ber 1986), land disposal of all specified
                   dioxin-containing waste streams  auto-
                   matically will  be banned.
                     An important aspect of the land dis-
                   posal restrictions is the  identification
                   and evaluation of alternative technolo-
                   gies that can be used to treat the listed
                   wastes in such a way as to meet pro-
                   posed treatment levels which EPA has
                   determined are protective of human
                   health and the environment. If alterna-
                   tives to land disposal are not available
                   by November 1986, it may be necessary
                   to extend the deadline for the restric-
                   tions on land disposal. The full report
                   identifies and evaluates alternative
                   technologies  that  remove and/or de-
                   stroy dioxin  and related compounds
                   from listed dioxin  wastes in order to
                   achieve constituent levels that allow
                   the safe land disposal of the treated
                   residues.
  This Project Summary was devel-
oped by EPA's Hazardous Waste Engi-
neering Research Laboratory, Cincin-
nati,  OH, to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).

Scope
  A number of potential technologies
exist for treating wastes  containing
dioxin. Because many of the technolo-
gies  are currently in developmental
stages, it is not possible to assess fully
the effectiveness of these technologies
at this time. Further testing of a technol-
ogy in the future may, for example, indi-
cate that a technology is or is not practi-
cal on a full scale. In  addition, several
new  technologies for treating dioxin
wastes may emerge for which informa-
tion  is not currently available. Conse-
quently, it must be emphasized that the
information discussed here represents
that which was available in the spring of
1986.
  Technologies under evaluation are
those that destroy dioxin or somehow
change its form so that it is less toxic.
Temporary management  methods,
such as storage in mines, are not evalu-
ated because these methods only
involve  moving the waste without
changing the chemical form and charac-
teristics of the waste. The majority of
the technologies are those whose per-
formance has been tested on dioxin-

-------
containing wastes. Those that have not
been  tested on dioxin-containing
wastes have, at  least, been  tested on
PCB-containing wastes. Because of the
similarity of PCBs  and dioxins, these
technologies should also be applicable
to dioxin  wastes.  Technologies  that
have been developed to full scale as
well as those only investigated in the
laboratory are included. This is primar-
ily because,  as mentioned previously,
this  field  is rapidly evolving.  Many of
the technologies  that are now only in
the laboratory stage may be  standard
technologies for treatment  of these
wastes in the future.

Definition of Dioxin Waste
  The  term "dioxin waste" is  meant to
include those RCRA wastes  listed as
EPA hazardous waste Numbers F021,
F022, F023, F026 and F027. As shown in
Table  1, these waste codes are desig-
nated as "acute hazardous" and include
wastes from the production and manu-
facturing  use of  tri-, tetra-,  and  pen-
tachlorophenols,  wastes from the man-
ufacturing use of tetra-, penta-,  and
hexachlorobenzene under alkaline  con-
ditions, and also discarded, unused for-
mulations containing tri-, tetra-,  and
pentachlorophenols. Soil that has been
contaminated by improper manage-
ment of these wastes is also encom-
passed by these waste codes. Residue;;
from the  incineration of this  contami-
nated  soil are designated as  toxic in-
stead of acute hazardous and are  cov-
ered under waste code F028.
  The wastes described by these waste
codes  are listed  hazardous wastes pri-
marily because they contain one  of a
number of forms of dioxin.  The term
"dioxin" has  been used very loosely. It
encompasses a family of aromatic com
pounds known chemically as dibenzo-p
dioxin. The forms of dioxin that are of
most environmental  concern  are  the
chlorinated dioxins, in which a chlorine
atom occupies one or more of the avail
able eight positions on the double  ben
zene ring  structure. Thus, there are 7Ei
possible chlorinated dioxin com
pounds, the most toxic of  which is
2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD). Throughout the full report, vari
ous terms will be used to refer to certain
types of dioxin.   When only the word
"dioxin" is used, it refers to chlorinated
dioxin compounds in general. Other
commonly used abbreviations are:
  PCDDs     =all isomers of chlori-
              nated dibenzo-p-
              dioxins
                                        Table 1.
   EPA
hazardous
waste no.
          Dioxin Contaminated Wastes Listed as RCRA Hazardous Wastes, January 14 1985
          50 FR 1978
                     Hazardous Waste From Nonspecific Source
                                 Hazardous waste
                                                                     Hazard
                                                                     code
               Wastes** from the production or manufacturing use of tri-         (H)
               or tetrachlorophenol, or of intermediates used to produce
               their derivatives. **

               Wastes** from the production or manufacturing use of           (H)
               pentachlorophenol (POP), or of intermediates used to pro-
               duce its derivatives.

               Wastes** from the manufacturing use of tetra-, penta-, or         (H)
               hexachlorobenzene under alkaline conditions.

               Wastes** from the production of materials on equipment         (H)
               previously used for the production or manufacturing use
               of tri- or tetrachlorophenols.***

               Wastes** from the production of materials on equipment         (H)
               previously used for the manufacturing of tetra-, penta , or
               hexachlorobenzene under alkaline conditions. *

               Discarded unused formulations containing tri-, tetra-, or           (H)
               pentachlorophenol or discarded unused formulations
               derived from these chlorophenols.****

               Residues resulting from the incineration or thermal treat-          (T)
               ment of soil contaminated with EPA hazardous waste F020,
               F021, F022, F023, F026, and F027.

   *A proposed regulation [50 FR 37338] would make residues from the incineration of these
    wastes (if the waste contained less than or equal to 10 ppm TCDD prior to incineration)
    toxic instead of acute hazardous.
  **Except wastewater and spent carbon from hydrogen chloride purification.
 ***This listing does not include wastes from the production of hexachlorophene from highly
    purified 2,4,5-trichlorophenol.
****This listing does not include formulations containing hexachlorophene synthesized from
    prepurified 2,4,5-trichlorophenol as the sole component.
(H) = Acute Hazardous Waste
(T) = Toxic Waste
  F020*
F02V
F022*
F023*
F026*
F027*
F028
   CDDs      =all isomers  of tetra-,
               penta-, and
               hexachlorodibenzo-p-
               dioxins
   TCDD    , = the 2,3,7,8- isomer
   PeCDD,    I
   HxCDD,    r = the penta-, hexa-, and
   and OCDDJ  octachloro compounds
Other toxic constituents that may be
present in the listed dioxin wastes are
chlorinated dibenzofurans (CDFs),
chlorophenols, and chlorophenoxy
compounds.

Waste Sources, Characteristics,
and Quantities
  The  waste codes  included in the
dioxin  listing encompass process
wastes from  the production of  various
chlorophenols,  primarily  2,4,5-
trichlorophenol  and  pentachlorophe-
                                      nol, and chlorophenoxy pesticides such
                                      as 2,4,5-T and Silvex. As  indicated in a
                                      report  prepared by Technical  Re-
                                      sources, Inc. for the EPA Office of Solid
                                      Waste,  the  manufacture of most of
                                      these compounds has been stopped.
                                      For example, 2,4,5-trichlorophenol has
                                      not been manufactured for several
                                      years. As a  result, the majority  of the
                                      dioxin-bearing process wastes requir-
                                      ing treatment at  this  time are wastes
                                      such  as still bottoms  and  reactor
                                      residues that were generated in the past
                                      and remain to be treated. The only proc-
                                      ess waste stream  that  is still  being
                                      generated, and may continue to be gen-
                                      erated in the future, is from the manu-
                                      facture  of pentachlorophenol (PCP).
                                      However, by far the largest quantity of
                                      dioxin-bearing wastes that have  been
                                      identified are the contaminated soils

-------
such as those at Times Beach, Missouri,
and various  other CERCLA sites
throughout the country.
  Table 2 shows estimated waste quan-
tities for  each  of the waste codes. Sev-
eral items associated with the informa-
tion in the table should be noted. One is
that no sources have yet been identified
for waste codes F022 and F026. Another
is that waste code F028 is not included
because it  is  expected  that  residues
from  future incineration of contami-
nated  soil will meet EPA delisting re-
quirements. Finally, contaminated soils
are placed in a separate category both
because  of  their unique physical form
relative  to most process wastes, and
also because a large fraction of the con-
taminated soils  are at  CERCLA sites
whose wastes will not be affected by the
RCRA land  disposal  restrictions until
November 1988.
  The estimates of the quantities of
wastes  generated  within  each waste
category in Table 2 could have a signifi-
cant impact on  future treatment prac-
tices. As shown in  the table, there are
more than 500,000 metric tons of
dioxin-contaminated  soil that may re-
quire treatment. This quantity is consid-
erably greater than  the estimated maxi-
mum 7500 MT of process wastes, such
as  still bottoms currently  requiring
treatment and the estimated 2500 MT of
industrial process wastes  that will be
generated  in future years.  Conse-
quently, it would appear that treatment
technologies  capable of treating  soil
wastes are of most importance at this
time, particularly  those technologies,
such as solvent extraction, that are ca-
pable of removing the toxic con-
stituents from the soil and thereby re-
ducing the  total volume  of waste
requiring final detoxification/destruc-
tion.

Technologies for Treating
Dioxin Wastes
  As mentioned previously, a number
of technologies  for treating dioxin
waste are evaluated in this document. A
summary of the status of these tech-
nologies is provided in Table 3. Because
studies have shown that dioxin decom-
poses by heating  or  oxidation at tem-
 Table 2.    Summary of Dioxin Waste Sources and Quantities
                                                                                             Quantity generated
                                                                                               (metric tons)
Waste
code
Waste source
Physical form
Present
(or stored)
Future
n
 F020        Manufacture of herbicides such as
             2,4,5-T, 2,4,5-trichlorophenol, hex-
             achlorophene; disposal of wastes
             in uncontrolled landfills or stor-
             age areas
  F021        Manufacture of pentachlorophe-
             nol: wastes from purification;
             wastes from formulation
  F022         No known sources at this time

  F023         Production of chemicals on equip-
              ment formerly used to manufac-
              ture F020 compounds, e.g., 2,4-D
              on 2,4,5-T equipment
  F026        No known sources at this time

  F027        Discarded formulation of in-,
              tetra-, and pentachlorophenols
              and their derivatives
              Contaminated soil from improper
              disposal and spills of F020-F027**


    *NA-Not applicable.
   **Not listed as a specific waste code.
   **Only from pentachlorophenol products.
           Still bottoms containing or-
           ganic solvents and chloro-
           phenols
         - Nonaqueous phase leachate
           (NAPL) containing solvents,
           chlorophenols, heavy metals
         - Carbon used to treat aqueous
           leachate

         - Still bottoms or other con-
           centrated materials contain-
           ing nonvolatile organic solids
           and chlorinated solvents and
           phenols
         - Sludges  from formulation

         - NA*

         - Similar to F020 wastes - still
           bottoms, reactor residues
           containing chlorophenols and
           organic solvents, and wash
           water sludges from formula-
           tion

         - NA

         - Active ingredient in an emul-
           sifiable concentrate, as a salt
           or an ester, or dissolved in
           an oil (such as in the case of
           pentachlorophenol)

          - Soils containing low concen-
           trations  of dioxins and re-
           lated compounds
   NAPL      -1,450
   Other      -  550
 0-200
Unknown
   Still bottoms-0
   Formulation waste-
   700
            0

          0-600
   750
Unknown
    0

  0-600
         1000-2000
                                                                                          500,000
                             0-1,000**'
                                                                                                               Unknown

-------
Table 3. Summary of Treatment Processes
Applicable
Process name waste streams
Stationary Rotary Solids, liquids, sludges
Kiln Incineration




Mobile Rotary Kiln Solids, liquids, sludges
Incineration





Liquid Injection In- Liquids or sludges with
cineration viscosity less than
10,000 ssu
(i.e., pumpable)



Fluidized-bed In- Solids, sludges
cineration (Circu-
lating Bed Com-
bustor)




High Temperature Primarily for granular con-
Fluid Wall (Huber taminated soils, but may
AER) also handle liquids







Stage of Performance/
development destruction achieved Cost
Several approved Greater than six nines ORE $0.25-$0.70/lb for
and commercially for PCBs; greater than five PCB solids
available units for nines ORE demonstrated
PCBs; not yet on dioxin at combustion
used for dioxins research facility

EPA mobile unit Greater than six nines ORE NA*
is permitted to lor dioxin by EPA unit;
treat dioxin process residuals delisted
wastes; ENSCO
unit has been
demonstrated on
PCB waste
Full scale land- Greater than six nines ORE $200-$500/ton
based units per- on PCB wastes; ocean in-
mitted for PCBs; cinerators only demon-
only ocean incin- strated three nines on
erators have han- dioxin containing herbi-
dled dioxin cide orange
wastes
GA Technologies Greater than six nines ORE $60-$320/ton for
mobile circulating demonstrated by GA unit GA unit
bed combustor on PCBs
has a TSCA per-
mit to burn PCBs
anywhere in the
nation; not tested
yet on dioxin
Huber stationary Pilot scale mobile unit $300-$600/ton
unit is permitted demonstrated greater than
to do research on five nines ORE on TCDD -
dioxin wastes; contaminated soil at
pilot scale mobile Times Beach (79 ppb re-
reactor has been duced to below detection)
tested at several
locations on
dioxin contami-
nated soils
Residuals
generated
Treated waste material
(ash), scrubber waste-
water, paniculate from
air filters, gaseous
products of combus-
tion
Same as above.





Same as above, but
ash is usually minor
because solid feeds
are not treated



Treated waste (ash),
particulates from air
filters





Treated waste solids
(converted to glass
beads), particulates
from baghouse,
gaseous effluent (pri-
marily nitrogen)




Infrared Incinerator Contaminated soils/sludges  Pilot scale,
(Shirco)                                       portable unit
                                              tested on waste
                                              containing
                                              dioxin; full scale
                                              units have been
                                              used in other ap-
                                              plications; not
                                              yet permitted for
                                              TCDD
                                             Greater than six nines ORE
                                             on TCDD-contaminated
                                             soil
                                             Treatment costs
                                             are $200-$ 1,200
                                             per ton
                                             Treated material (ash)
                                             particulates captured
                                             by scrubber (sepa-
                                             rated from scrubber
                                             water)
Molten Salt (Rock-
well Unit)
Solids, liquids, sludges;
high ash content wastes
may be troublesome
Pilot scale unit
was tested on
various wastes-
further develop-
ment is not
known
Up to eleven nines ORE on
hexachlorobenzene;
greater than six nines ORE
on PCB using bench scale
reactor
NA
           Spent molten salt cor
           taining ash, particu-
           lates from baghouse

-------
Table 3. (continued)
Applicable
Process name waste streams
Supercritical Water
Oxidation






Plasms Arc Pyroly-
sis


In Situ Vitrification



Solvent Extraction






Stabilization/Fixa-
tion




UV Photolysis









Chemical
Dechlorination-
APEG processes



Aqueous solutions or slur-
ries with less than 20 per-
cent organics can be
handled




Liquid waste streams (pos-
sibly low viscosity sludges)


Contaminated soil - soil
type is not expected to af-
fect the process


Soils, still bottoms






Contaminated soil





Liquids, still bottoms, and
soils can be treated if
dioxin is first extracted or
desorbed into liquid







Contaminated soil (other
variations of the process
used to treat PCB-contami
nated soils)



Stage of
development
Pilot scale unit
tested on dioxin-
containing
wastes- results
not yet published



Prototype unit
(same as full
scale) currently
being field tested
Full scale on ra-
dioactive waste;
pilot scale on or-
ganic contami-
nated wastes
Full scale still
bottoms extrac-
tion has been
tested-pilot scale
soils washer
needs further in-
vestigation
Laboratory scale
using cement and
emulsified as-
phalt; lab tests
also using K-20

Full scale solvent
extraction/UV
process was used
to treat 4,300 gal-
lons of still bot-
toms in 1980;
thermal desorp-
tion/UV process
currently under-
going second
field test
Slurry process
currently being
field tested at
pilot scale; in situ
process has been
tested in the field

Performance/
destruction achieved
Six nines ORE on dioxin-
containing waste reported
by developer, but not pre-
sented in literature; lab
testing showed greater
than 99.99% conversion of
organic chloride for
wastes containing PCB
Greater than six nines de-
struction of PCBs and CCI4


Greater than 99.9% de-
struction efficiency (DE)
(not offgas treatment sys-
tem) on PCB-contaminated
soil
Still bottom extraction:
340 ppm TCDD reduced to
0.2 ppm; 60-90% removal
from soils, but reduction
to below 7 ppb not
achieved

Tests using cement
showed decreased leach-
ing of TCDD, but up to
27% loss of stabilized ma-
terial due to weathering
followed by leaching
Greater than 98.7% reduc-
tion of TCDD using solvent
extraction/UV process-
residuals contained ppm
concentrations of TCDD;
thermal desorption/UV
process demonstrated re-
duction of TCDD in soil to
below 7 ppb


Laboratory research has
demonstrated reduction of
2,000 ppb TCDD to below
7 ppb for slurry (batch
process); laboratory and
field testing of in situ
process not as promising
Cost
$0.32-$2.00/gal-
lon
$77-$480/ton





$300-$1,400/ton


$120-$250/m3



NA






NA





Cost of treating
the 4,300 gallons
of still bottoms
using solvent ex-
traction/UV was
$1 million; ther-
mal desorption/
UV estimated to
cost $250-$!, 250/
ton

$296/ton for in
situ APEG proc-
ess; $91 /ton for
slurry (batch)
process


Residuals
generated
High purity water, in-
organic salts, carbon
dioxide, nitrogen





Exhaust gases (H2 and
CO) which are flared
and scrubber water
containing particulates
Stable/immobile
molten glass; volatile
organic combustion
products (collected
and treated)
Treated waste mate-
rial (soil, organic liq-
uid); solvent extract
with concentrated
TCDD


Stabilized matrix (soil
plus cement, asphalt.
or other stabilization
material); matrix will
still contain TCDD

Solvent extraction/UV
process generated
treated still bottoms, a
solvent extract stream.
and an aqueous salt
stream; thermal des-
orption/UV generates
a treated soil stream
and a solvent extract
stream

Treated soil contain-
ing chloride salts
(reagent is recovered
in the slurry process)




-------
Table 3. (continued)
Process name
Applicable
waste streams
Stage of
development
Performance/
destruction achieved Cost
Residuals
generated
Biological
Degradation-
primarily in situ
addition of mi-
crobes
Chemical Degrada-
tion using Ruthe-
nium Tetroxide
Chemical Degrada-
tion using
Chloroiodides
Research has been di-
rected toward in situ treat-
ment of contaminated
soils-liquids are also pos-
sible
Liquid or soil wastes-pos-
sible most effective in de-
contaminating furniture
other surfaces
Liquid or soil-thought to
be most applicable to de-
contaminating furniture
and buildings
Currently labora-  50-60% metabolism of
tory scale-field
testing in next
year or two
Laboratory scale-
no work reported
since 1983
Laboratory scale-
no work reported
since 1983
2,3,7,8-TCDD in a week
long period under lab con-
ditions using white rot
fungus-reduction to
below 1 ppb not achieved

Reduction of 70 ppb TCDD
to below 10 ppb in 1 hr
(on soil sample)
Up to 92% degradation on
solution of TCDD in ben-
zene-reductions to below
1 ppb were not demon-
strated
NA        Treated waste
          medium such as soil
          or water with TCDD
          metabolites depend-
          ing on microorgan-
          isms

NA        Treated medium plus
          the solvent which has
          been added (water,
          CCI4); TCDD end prod-
          ucts not known

NA        Treated waste
          medium; degradation
          end products are
          chlorophenols
Gamma Ray Radi-
olysis
Liquid waste streams (has
been applied to sewage
sludge disinfection)
Laboratory re-
search; no re-
search currently
being conducted
97% destruction of 2,3,7,8-
TCDD in ethanol after 30
hours- 100 ppb to 3 ppb
Cost for sewage
disinfection facil-
ity treating 4 tons
per day is $40 per
ton; TCDD treat-
ment would be
more expensive
Less chlorinated
dioxin molecules are
the degradation end
products in addition to
the treated waste
medium
*Not available
peratures greater than 1000°C, thermal
methods for treating these wastes have
received a  large amount of attention.
Thermal technologies evaluated in this
document are those in which heat is the
major agent of treatment or destruction.
Technologies  included in this category
are:
  • Stationary rotary kiln incineration
  • Mobile  rotary kiln incineration
  • Liquid injection incineration
  • Fluidized-bed incineration
  • Infrared incineration
  • High temperature fluid  wall de-
    struction
  • Plasma  arc pyrolysis
  • Molten  salt destruction
  • In-situ vitrification
  • Supercritical water oxidation
  EPA has indicated that incineration is
currently the  only sufficiently demon-
strated treatment technology for dioxin-
containing  waste (51 FR 1733). RCRA
performance standards for incineration
and other thermal treatment processes
require  the  demonstration  of 99.9999
percent destruction  and  removal effi-
ciency (DRE)  of the principal organic
hazardous constituent (POHC). Several
of the  thermal technologies  have
                       demonstrated this performance on
                       chlorinated compounds of one type or
                       another. However, only three, and per-
                       haps  four, thermal technologies have
                       been demonstrated to achieve this level
                       of performance on dioxin. These tech-
                       nologies are the EPA mobile rotary  kiln
                       incinerator,  Huber's high temperature
                       fluid wall reactor, Shirco's infrared in-
                       cinerator, and possibly, Modar's super-
                       critical water oxidation process. Modar
                       has not yet  released data conclusively
                       showing six nines DRE, but they do
                       claim to have achieved this  perform-
                       ance. Thermal technologies that have
                       achieved six nines DRE on PCBs include
                       stationary rotary kiln incinerators, liquid
                       injection incinerators, fluidized-bed in-
                       cinerators (the circulating bed varia-
                       tion),  the plasma arc  process, and  the
                       molten salt process. The in situ vitrifica-
                       tion process  has not  shown  six nines
                       DRE; however, it is as much a  stabiliza-
                       tion process as it is a  destruction proc-
                       ess. Therefore, the primary objective of
                       this technology is to prevent the leach-
                       ing of dioxin or other toxic constituents
                       from  the treated soil;  whether the
                       dioxin is driven  out of the soil  by
                       volatilization or merely contained
                                       within the vitrified material is a second-
                                       ary  concern (as long as  volatilized
                                       dioxin is captured and subsequently de-
                                       stroyed).
                                          Nonthermal technologies evaluated
                                       include the following:
                                          •  Chemical dechlorination
                                          •  Ultraviolet (UV) photolysis
                                          •  Solvent  extraction
                                          •  Biodegradation
                                          •  Stabilization/fixation
                                          •  Chemical degradation using ruthe-
                                            nium tetroxide
                                          •  Chemical degradation  using  chlo-
                                            roiodides
                                          •  Gamma  ray radiolysis
                                          Of the nonthermal technologies,
                                       those  that  have shown the most
                                       promise and the highest level of recent
                                       investigation  and testing are chemical
                                       dechlorination and UV photolysis. Both
                                       of these technologies are currently be-
                                       ing field tested on dioxin-contaminated
                                       soil. As indicated in Table 3, preliminary
                                       field data on  the thermal desorption/UV
                                       photolysis process indicate that dioxin
                                       was desorbed from soil to a level below
                                       1  ppb,  and then destroyed efficiently
                                       using ultraviolet  radiation. The chemi-
                                       cal dechlorination process  has also

-------
demonstrated a reduction of TCDD in
soil to below 1 ppb, but only on a labo-
ratory scale.
  The other nonthermal processes have
not shown as much  promise with re-
gard to treating dioxin waste. Solvent
extraction is a potentially useful tech-
nology since it could, if successfully ap-
plied to soil treatment, reduce the vol-
ume of the waste stream that requires
final treatment/destruction by several
orders  of magnitude. Unfortunately,
this technology has  not yet demon-
strated  the ability  to  reduce dioxin in
contaminated soil  to a level of  1 ppb.
Biodegradation is also a  potentially at-
tractive approach  since it presumably
would not require  the large energy in-
puts, sophisticated equipment, and the
chemical additions that the other tech-
nologies require. However, biodegrada-
tion, particularly in situ, has not  proven
to be very effective as a dioxin destruc-
tion process. Stabilization and/or fixa-
tion would allow the treatment  of con-
taminated soils in place. Since  this
method does not involve destruction of
the dioxin there is always the possibility
that the stabilized waste/soil matrix will
break down and the dioxin will be re-
leased. Finally, the last three technolo-
gies listed (two chemical degradation
processes and gamma  ray radiolysis)
are methods that have been studied in
the laboratory but have not yet shown
enough promise technically or econom-
ically to be developed on a larger scale.
Investigation of these methods, at this
time, appears to have stopped.

   Of  all the treatment  technologies
evaluated none is currently commer-
cially  available for  the treatment of
dioxin wastes. The EPA mobile incinera-
tor has been used to treat a variety of
waste forms at the Denney Farm in Mis-
souri, but this  unit is intended to be
used for research purposes and not as a
commercial treatment  process. The
high temperature fluid wall process
(AER) operated by Huber at its Borger,
Texas facility is permitted to perform re-
search on dioxin contaminated wastes
and is also a research tool which  is not
intended to be used for actual waste
treatment.

Conclusions
  Dioxin  wastes, particularly those
dioxin-contaminated soils which ac-
count for over 98 percent of the contam-
inated wastes identified  in Table 2, con-
tain low levels (10 to 100 ppb) of dioxins
and/or  dibenzofurans. Nonetheless,
many technologies, particularly the
thermal  destruction technologies, re-
quire that the total quantity of the waste
be treated to destroy the extremely low
dioxin fraction resulting  in very high en-
orgy usage for dioxin destruction. In ad-
dition,  when  incineration and  other
thermal  destruction technologies are
used, large quantities of exhaust gases
are  generally formed. These waste
streams can contain toxic products of
incomplete  combustion  (PICs)  and
other hazardous emissions. They and
other associated  waste streams are
themselves subject to costly treatment
processes. Therefore, technologies
such as solvent extraction or desorp-
tion, which  separate  the toxic con-
stituents from the waste matrix prior to
final  treatment should  receive further
investigation
  Most of the emerging technologies
are being designed for operation at the
waste source. This trend to portable or
field-erected technologies reflects a re-
action to public opposition to the trans-
port of dioxin waste from source to
waste treatment facilities, and should
continue to be encouraged.
  In addition, because of the large vol-
ume of soil contaminated  by relatively
low concentrations of dioxin, it is also
important to investigate methods of in-
situ treatment. These methods would
limit the handling of the waste so that
further dispersion of contaminated ma-
terials into the environment is  mini-
mized. Most of the technologies in this
category,  such as biodegradation, in
situ vitrification, chemical dechlorina-
tion, and stabilization in the near future
have not yet been sufficiently demon-
strated. Use in the  near future seems
improbable  without  more intense de-
velopment of these technologies. Steps
should be taken to encourage these de-
velopments.

  The treatment of dioxin contaminated
liquids and low viscosity sludges does
not appear to be as large a problem as
is the treatment of contaminated soils.
This is primarily because the quantity of
liquids and sludges is much lower, and
also because the liquid waste form gen-
erally calls for less extensive handling
and pretreatment. Technologies,  such
as plasma arc pyrolisis and supercritical
water oxidation, appear to be capable of
treating these wastes, and their devel-
opment should be fostered, as should
other reasonable activities aimed at the
development of emerging technologies.
                                           Mark Arienti, Lisa Wilk, Michael Jasinski, and Nancy Prominski are with GCA
                                             Corporation, Bedford, MA 01730.
                                           Harry Freeman is the EPA Project Officer (see below).
                                           The complete report,  entitled  "Technical Resource Document:  Treatment
                                             Technologies for Dioxin-Containing Wastes," (Order No.  PB 87-110 813/
                                            AS; Cost: $24.95, subject to change) will be available only from:
                                                  National Technical Information Service
                                                  5285 Port Royal Road
                                                  Springfield, VA 22161
                                                  Telephone: 703-487-4650
                                           The EPA Project Officer can be contacted at:
                                                  Hazardous Waste Engineering Research Laboratory
                                                  US.  Environmental Protection Agency
                                                  Cincinnati, OH 45268

-------
                                      Center for Environmental Research                                                BULK RATE
                                      Information                                                              pnr,T r     rccc  o\m
                                      Cmonnat, OH 452(^8                                                      POSTAGE & FEES  PAID
                                                                                                                       E PA
                                                                                                                 PERMIT No.  G-35
Official Business
Penalty for Private Use $300

EPA/600/S2-86/096

-------