Document Reference:
   Alliance Technologies Corp. 'Technical Resource Document: Treatment
Technologies for Dioxin-Containing Wastes." Technical Report EPA/600/2-86/096.
                  244pp. October 1986.
              EPA LIBRARY NUMBER:

           Super-fund Treatability Clearinghouse - FCFR-3 ,q,
                               U,S. Environmental Protection Agency
                               Region 5, Library (PL-!?1)
                               77 West Jackson D;.v  -  < 2'h Floor
                               Chicago, IL 60604-:^ " "


Treatment Process:      Thermal Treatment - Circulating Bed Combustion

Media:                  Soil/Generic

Document Reference:     Alliance Technologies Corp. "Technical Resource
                        Document:  Treatment Technologies for Dioxin/
                        Containing Vastes."  Technical Report
                        EPA/600/2-86/096.  244 pp.  October 1986.

Document Type:          EPA ORD Report

Contact:                Harold Freeman
                        U.S. EPA, ORD
                        26 W. St. Clair Street
                        HWERL-Thermal Destruction Branch
                        Cincinnati, OH 45268

Site Name:              Denny Farm Site, MO (Non-NPL)

Location of Test:       Denny Farm, MO

BACKGROUND;  GA Technologies conducted the circulating bed combustor (CBC)
pilot scale tests using PCB-contaminated soils.  This treatability study
compiles available information on those technologies for dioxin containing
solids, liquids and sludges, many of which are in early stages of develop-
ment.  Discussion of the CBC pilot test is contained in this abstract.
Other technologies in this document are discussed in Document Numbers
FCFR-4 and FCFR-6.  Technologies evaluated were those that destroy or
change the form of dioxin to render it less toxic.  Those technologies not
tested on dioxin-containing wastes had been tested on PCB-containing
wastes.  The report divides the technologies into thermal and non-thermal
groups for discussion.  It was noted that incineration was the only suffi-
ciently demonstrated technology for treatment of dioxin containing wastes
(51 FR 1733) and RCRA Performance Standards for Thermal Treatment require
99.9999 percent destruction removal efficiency (ORE) of the principal
organic hazardous constituent (POHC).  Factors which affect the selection/
use of a particular technology are discussed.  Technical performance for
treating a specific waste type and costs are both considered in this
discussion.  A summary of dioxin treatment processes, their performance/
destruction achieved, and estimated costs are provided in Table 1.  QA/QC
is not discussed.
OPERATIONAL INFORMATION;  GA Technologies conducted trial burns on PCB-
contaminated soil with 9800 to 12,000 ppm of PCB.  Auxiliary fuel was used
to maintain the bed temperature at 1600  to 1800°F.  A soil feed rate of
325 to 410 pounds per hour was used.
PERFORMANCE;  A destruction efficiency exceeding six nines (99.9999 per-
cent) was achieved.  Costs of fluidized bed treatment are dependent on fuel
requirements,  scale and site conditions.  Cost estimates of from $27/ton to
$150/ton are provided for various assumptions.
3/89-35                                            Document Number:  FCFR-3

   NOTE:  Quality assurance of data may not be appropriate for all uses.


 Analytical data is provided in the  treatability  study  report.  The
 breakdown of the contaminants  by treatability  group  is:

 Treatability Group             CAS  Number         Contaminants

 W02-Dioxins/Furans/PCBs         1336-36-3          Total PCBs
 Note:   This  is  a  partial  listing  of  data.  Refer  to  the document  for  more
3/89-35                                            Document Number:  FCFR-3

   NOTE:  Quality assurance of data may not be appropriate for all uses.

                                         TABLE 1
  Process Name

Stationary Rotary
Kiln Incineration
Mobile Rotary
Kiln Incineration
Liquid Injection
Infrared Incinerator
High Temperature
Fluid Wall (Huber AER)
Molten Salt
(Rockwell Unit)

Water Oxidation

Plasma Arc
Solvent Extraction

UV Photolysis
Chemical Dechlor-
ination APEG processes
Biological in situ
addition of microbes
Degradation using
Ruthemium Tetroxide

Degradation using
  Performance/Destruction Achieved

Greater than 99.999 DRE demonstrated
on dioxin at combustion research
Greater than 99.9999 DRE for dioxin
by EPA unit; process residuals
Ocean incinerators only demonstrated
99.9 on dioxin-containing herbicide
Greater than 99.9999 DRE demonstrated
on PCBs
Greater than 99.9999 DRE on
TCDD-contaminated soil
Greater than 99.999 DRE on TCDD-
contaminated soil
Up to eleven nines DRE on
99.9999 DRE on dioxin-containing
waste reported by developer

Greater than 99.9999 destruction of
PCBs and CC14
Greater than 99.9% destruction on
PCB-contaminated soil
Still bottom extraction:  340 ppm
TCDD reduced to 0.2 ppm; 60-90%
removal from soils.
Tests using cement decreased
leaching of TCDD
Greater than 98.7% reduction of TCDD
Reduction of 2,000 ppb TCDD to below
1 ppb for slurry (batch process)
50-60% metabolism of 2,3,7,8-TCDD
using white rot fungus
Reduction of 70 ppb TCDD to below
10 ppb in 1 hr

Up to 92% degradation on solution
of TCDD in benzene
$0.25 - $0.70/lb
for PCB solids

$200 - $500/ton
$60 - $320/ton

$200 - $1,200
per ton
$300 - $600/ton


$0.32 - $2.00/
$300 - $l,400/ton

$120 - $250/M3


$250 - $l,200/ton
$296/ton for  in  situ,
$ 91/ton for  slurry


3/89-35                                            Document Number:  FCFR-3

   NOTE:  Quality assurance of data may not be appropriate for all uses.

Treatment  Process:


Document Reference:
Document Type:

Site Name:
Location of Test:
Thermal Treatment - Pyrolysis


Alliance Technologies Corp. "Technical Resource
Document:  Treatment Technologies for Dioxin-
Containing Wastes."  Technical Report
EPA/600/2-86/096.  244 pp.  October 1986.

EPA ORD Report

Harold Freeman
HWERL-Thermal Destruction Branch
26 W. St. Clair Street
Cincinnati, OH 45268

Times Beach, MO (NPL)

Times Beach, MO
BACKGROUND;  This report focuses on the pilot scale Advanced Electric
Reactor (AER).  This treatability study compiles available information on
those technologies for dioxin containing solids, liquids and sludges, many
of which are in early stages of development.  A discussion of the AER pilot
test is contained in this abstract.  Other technologies in this document
are discussed in Document Numbers FCFR-3 and FCFR-6.  Technologies evalu-
ated were those that destroy or change the form of dioxin to render it less
toxic.  Those technologies not tested on dioxin-containing wastes had been
tested on PCB-containing wastes.  The report divides the technologies into
thermal and non-thermal groups for discussion.  It was noted that inciner-
ation was the only sufficiently demonstrated technology for treatment of
dioxin containing wastes (51 FR 1733) and RCRA Performance Standards for
Thermal Treatment require 99.9999 percent destruction removal efficiency
(ORE) of the principal organic hazardous constituent (POHC).  Factors which
affect the selection/use of a particular technology are discussed.  Techni-
cal performance for treating a specific waste type and costs are both
considered in this discussion.  A summary of dioxin treatment processes,
their performance/destruction achieved, and estimated costs are provided in
Table 1.  QA/QC is not discussed.
OPERATIONAL INFORMATION:  The AER, owned and operated by J.M. Huber
Corporation, was used to treat, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD).
It was also used in other tests including tests at Gulfport, Mississippi,
but these tests reported only removal efficiencies.  Only two data points
are present from the Times Beach trials, one from the treated soil and one
from the baghouse catch.
    The AER was operated at 3500°F-4000°F.  Heating was accomplished using
electrically heated carbon electrodes.  A nitrogen purge gas provided the
3/89-36                                            Document Number:  FCFR-4

   NOTE:  Quality assurance of data may not be appropriate for all uses.

 reaction  atmosphere.   Since  oxygen was  not present,  it was  run  in  a
 pyrolytic manner.
 PERFORMANCE;   High  DREs  could not be  demonstrated due to  the  low amount  of
 contamination  (79 ppb  in the influent soil).  One limitation  of the AER  is
 that  it cannot  handle  two-phase materials such as sludge.   Soils should  be
 dried and sized (smaller than 10 mesh)  before being  fed into  the reactor.
 Another limitation  is  that other types  of incineration processes are more
 cost  effective  for  high  BTU  content material.  Since no supplementary  fuels
 are required,  this  process is better  suited  for low  BTU material.  A cost
 estimate  guideline  is  included.  Recently the U.S. EPA and  the Texas Water
 Commission jointly  issued J.M. Huber  Corporation a RCRA permit which
 authorizes the  incineration  of any non-nuclear RCRA  hazardous waste in the


 Analytical data is  provided  in the treatability study report.  The
 breakdown of the contaminants by treatability group  is:

 Treatability Group             CAS Number        Contaminants

 W02-Dioxins/Furans/PCBs        1746-01-6         2,3,7,8-Tetrachloro-

                               1336-36-3         Total PCBs
Notes  This is a partial listing of data.  Refer to the document for more
3/89-36                                            Document Number:  FCFR-4
   NOTE:  Quality assurance of data nay not be appropriate for all uses.

                                         TABLE 1
  Process Name
Stationary Rotary
Kiln Incineration
Mobile Rotary
Kiln Incineration
Liquid Injection

Infrared Incinerator
High Temperature
Fluid Wall (Huber AER)
Molten Salt
(Rockwell Unit)
Water Oxidation
Plasma Arc
Solvent Extraction
UV Photolysis
Chemical Dechlor-
ination APEG processes
Biological in situ
addition of microbes
Degradation using
Ruthemium Tetroxide
Degradation using
  Performance/Destruction Achieved
Greater than 99.999 ORE demonstrated
on dioxin at combustion research
Greater than 99.9999 ORE for dioxin
by EPA unit; process residuals
Ocean incinerators only demonstrated
99.9 on dioxin-containing herbicide
Greater than 99.9999 DRE demonstrated
on PCBs
Greater than 99.9999 DRE on
TCDD-contaminated soil
Greater than 99.999 DRE on TCDD-
contaminated soil
Up to eleven nines DRE on
99.9999 DRE on dioxin-containing
waste reported by developer
Greater than 99.9999 destruction of
PCBs and
                                        $0.25  -  $0.70/lb
                                        for  PCB  solids

                                        $200  -  $500/ton
                                        $60  -  $320/ton

                                        $200 - $1,200
                                        per  ton
                                        $300 - $600/ton


                                        $0.32  - $2.00/
                                        $300 - $l,400/ton

                                        $120 - $250/M3

Greater than 99.9% destruction on
PCB-contaminated soil
Still bottom extraction:  340 ppm
TCDD reduced to 0.2 ppm; 60-90%
removal from soils.
Tests using cement decreased            NA
leaching of TCDD
Greater than 98.7% reduction of TCDD    $250 -  $l,200/ton
Reduction of 2,000 ppb TCDD to below
1 ppb for slurry (batch process)
50-60% metabolism of 2,3,7,8-TCDD
using white rot fungus
Reduction of 70 ppb TCDD to below
10 ppb in 1 hr
Up to 92% degradation on solution
of TCDD in benzene
                                        $296/ton  fo-r  in situ,
                                        $ 91/ton  for  slurry
3/89-36                                            Document Number:  FCFR-4
   NOTE:  Quality assurance of data may not be appropriate for all uses.


 Treatment Process:      Physical/Chemical - Dechlorination

 Media:                  Soil/Generic

 Document Reference:     Alliance Technologies Corp.  "Technical  Resource
                         Document:   Treatment Technologies  for Dioxin-
                         Containing Wastes."  Technical Report
                         EPA/600/2-86/096.   244 pp.   October  1986.

 Document Type:           EPA ORD Report

 Contact:                Harold Freeman
                         U.S.  EPA,  ORD
                         HWERL-Thermal Destruction Branch
                         26 W.  St.  Clair Street
                         Cincinnati,  OH 45268

 Site Name:               Denny Farm Site,  MO (Non-NPL)

 Location of  Test:        Denny Farm,  MO

 BACKGROUND;   This  document summarizes several case  studies on the  applica-
 tions of the Alkali Polyethylene Glycolate  (APEG) treatment  process  applied
 to  dioxin-contaminated  soil.   This treatability study  compiles  available
 information  on  those technologies  for dioxin containing solids,  liquids and
 sludges,  many of which  are in early  stages  of development.   A discussion  of
 the APEG technology is  contained in  this abstract.   Other  technologies  are
 discussed in Document Numbers  FCFR-3 and FCFR-4.  Technologies  evaluated
 were those that destroy or change  the form  of dioxin to render  it  less
 toxic.   Those technologies not tested on dioxin-containing wastes  had been
 tested on PCB-containing wastes.   The report divides the technologies into
 thermal  and  non-thermal groups for discussion.  It was  noted that  incinera-
 tion was  the only  sufficiently demonstrated  technology  for treatment of
 dioxin containing  wastes (51  FR 1733)  and RCRA Performance Standards for
 Thermal Treatment  require  99.9999  percent destruction  removal efficiency
 (DRE) of  the principal  organic hazardous constituent (POHC).  Factors which
 affect the selection/use of a  particular technology  are discussed.  Techni-
 cal  performance for treating a specific waste type and  costs are both
 considered in this  discussion.   A  summary of dioxin  treatment processes,
 their performance/  destruction achieved, and estimated  costs are provided
 in Table  1.   QA/QC  is not  discussed.
 OPERATIONAL  INFORMATION;   This  document summarized several case studies on
 the applications of  the  Alkali  Polyethylene  Glycolate  (APEG) treatment
 process applied to  dioxin-contaminated soil.   All data  are either  bench or
 pilot scale.   Two different molecular weight  APEG reagents were used.
Three tests  were K-400  (potassium-based reagent and  polyethylene glycol of
average molecular weight of 400) and  two tests were  K-120.   It  is  unclear
whether the  waste matrix was a  solvent, soil,  or contaminated debris.   All
analyses reported were  total waste analyses.
3/89-38                                            Document Number:  FCFR-6

   NOTE:  Quality assurance of data may not be appropriate for all uses.

 PERFORMANCE;  The document concludes that this technology has a potential
 for treating soil contaminated with dioxins.   Efficiencies improve with
 increased temperature.   Costs for the slurry  process is estimated at
 $91/ton and for the in  situ process of $296/ton.


 Analytical data is provided in the treatability study report.   The
 breakdown of the contaminants by treatability group is:

 Treatability Group             CAS Number        Contaminants

 W02-Dioxins/Furans/PCBs        1336-36-3          Total PCBs
                                1746-01-6          2,3,7,8-Tetrachlorodi-
Note:   This  is  a  partial  listing  of  data.  Refer  to  the  document  for  more
3/89-38                                            Document Number:  FCFR-6
   NOTE:  Quality assurance of data may not be appropriate for all uses.

                                         TABLE  1
                           SUMMARY  OF  DIOXIN TREATMENT PROCESSES
   Process  Name

 Stationary Rotary
 Kiln  Incineration
Mobile Rotary
Kiln  Incineration
Liquid Injection

Infrared Incinerator
High Temperature
Fluid Wall (Huber AER)

Molten Salt
(Rockwell Unit)

Water Oxidation

Plasma Arc
Solvent Extraction
UV Photolysis
Chemical Dechlor-
ination APEG processes
Biological in situ
addition of microbes
Degradation using
Ruthemium Tetroxide
Degradation using
   Performance/Destruction Achieved

Greater  than 99.999 ORE demonstrated
on dioxin at combustion research
Greater  than 99.9999 ORE for dioxin
by EPA unit; process residuals

Ocean incinerators only demonstrated
99.9 on dioxin-containing herbicide
Greater  than 99.9999 ORE demonstrated
on PCBs
Greater  than 99.9999 ORE on
TCDD-contaminated soil
Greater  than 99.999 ORE on TCDD-
contaminated soil
Up to eleven nines ORE on
99.9999 ORE on dioxin-containing
waste reported by developer
Greater than 99.9999 destruction of
PCBs and
Greater than 99.9% destruction on
PCB-contaminated soil
Still bottom extraction:  340 ppm
TCDD reduced to 0.2 ppm; 60-90*
removal from soils.
Tests using cement decreased
leaching of TCDD
Greater than 98.7% reduction of TCDD
Reduction of 2,000 ppb TCDD to below
1 ppb for slurry (batch process)
50-60% metabolism of 2,3,7,8-TCDD
using white rot fungus

Reduction of 70 ppb TCDD to below
10 ppb in 1 hr
Up to 92% degradation on solution
of TCDD in benzene
$0.25 - $0.70/lb
for PCB solids

$200 - $500/ton
$60 - $320/ton

$200 - $1,200
per ton
$300 - $600/ton


$0.32 - $2.00/
$300 - $1,AGO/ton

$120 - $250/M3


$250 - $l,200/ton
$296/ton for in situ,
$ 91/ton for slurry


3/89-38                                            Document Number:  FCFR-6
   NOTE:  Quality assurance of data nay not be appropriate for all uses.

united states
Environmental •>rotect on
~iazaraoL,s vVaste Engineering
^esear:"i Laooratory
Cincinnati OH 45268
E=>A SCO 2-36
Octooe^ ' 985
Research and Development
Technical Resource

Technologies for

                                      October 1986

                   Mark Ar1ent1
                   Lisa W1lk
                   Michael Jasinski
                   Nancy Prom1nsk1
        Alliance Technologies Corporation
                Bedford,  MA  01730
          EPA Contract Number 68-03-3243
                 Project Officer

                 Harry M. Freeman
        Alternative Technologies Division
 Hazardous- Waste Engineering Research Laboratory
              Cincinnati, OH.  45268
             CINCINNATI, OHIO  45268

     As hazardous waste continues to be one of the more prominent
environmental concerns to the people of the United States and other countries
throughout the world, there are continuous needs for research to characterize
problems and develop and evaluate alterantives to addressing those problems.
The programs of the Hazardous Waste Engineering Research Laboratory are
designed to contribute to satisfying these research needs.

     This Technical Resource Document for Treatment Technologies for Dioxin
Containing Wastes compiles available information on those technologies.  It is
intended to provide support for the land disposal prohibition, currently being
considered by the EPA, and to provide technical information for those
individuals and organizations concerned with the subject waste streams.  Those
wishing additional information on the various technologies should contact the
Hazardous Waste Engineering Research Laboratory.
                                              Thomas R. Hauser
                              Hazardous Waste Engineering Research Laboratory


Number                                                                    Page

 3.1      Structure of (a)  Dibenzo-p-dioxin and  (b)  dibenzofuran   .  .      3-5

 4.1.L    Schematic of Rollins Environmental Services'  incinerator.  .      4-6

 4.1.2    Schematic of ENSCO stationary incinerator  	      4-7

 4.1.3    Simplified schematic of CRF rotary kiln	      4-10

 4.2.1    Schematic of EPA mobile incineration system 	      4-17

 4.2.2    Schematic of ENSCO MWP-2000 mobile rotary  kiln incinerator.      4-19

 4.3.1    Vertically-oriented liquid injection incinerator  	      4-33

 4.4.1    Cross-section of fluidized bed furnace  	      4-42

 4.4.2    Schematic of circulating bed combustor  	      4-44

 4.5.1    Advanced electric reactor (AER) 	      4-53

 4.5.2    High temperature fluid vail process configuration for
            the destruction of carbon tetrachloride  	      4-54

 4.7.1    Pyroplasma process flow diagram	      4-66

 4.8.1    Schematic of generalized molten salt incinerator design.. .       4-74

 4.9.1    Process schematic for oxidation of an aqueous waste with
            a heating value of 1750 Btu/lb	       4-81

 4.10.1   Schematic of an in situ vitrification operation 	       4-89

 4.10.2   Schematic of large scale off-gas treatment system 	       4-91

 4.10.3   Cost of in situ vitrification for transuranic wastes as a
            function of electrical rate and soil moisture 	        4-94

Number                                                                    Page

 1.1    Dioxin Contaminated Wastes  Listed  as  RCRA Hazardous Wastes,
          January 14,  1985, 50 FR 1978	    1-2

 1.2    Summary of Dioxin Waste Sources  and Quantities   ........    1-6

 1.3    Summary of Treatment Processes   	    1-7

 2.1    Concentrations of Constituents  of  Concern Which  Will  Result
          in Banning Listed Wastes  from Land  Disposal [51  FR  1732]   .  .    2-5

 3.1    Basis for Listing Wastes [50 FR 1978]	    3-2

 3.2    Physical and Chemical Characteristics of Some
          CDDs and CDFs	    3-6

 3.3    Physical and Chemical Characteristics of Some
          Chlorophenols and Chlorophenoxy  Compounds 	    3-10

 3.4    Listing of Dioxin Notifiers as  of  February  18,  1986	    3-12

 3.5    Constituents of Waste Code F020	    3-15

 3.6    Constituents of Waste Code F021	    3-20

 3.7    PCDD and PCDF Concentrations in Manufactured Products and
          Chemical Intermediates  	    3-24

 3.8    Characterization of Some Soils  Contaminated with
          Diozin Constituents 	 .....      3-28

 4.1.1  Vertac Still Bottom Test Burn	     4-12

 4.1.2  Average Unit Costs for PCB Waste Destruction at Permitted
          Stationary Rotary Kiln Facilities 	 .      4-14

 4.2.1  Soils Used in the EPA Mobile Incinerator During Preliminary
          Testing of the Solids Feed System	      4-23

                              TABLES  (continued)
 4.7.2    Typical Operating Data for  PCB  Tests  (One Hour Runs)	    4-70

 4.7.3    PCB Test Results	    4-71

 4.8.1    PCB Combustion Tests  in Sodium-Potassium-Chloride-Carbonate
            Melts	    4-77

 4.8.2    Summary of Pilot-Scale Test Results	    4-78

 4.9.1    Composition of Feed Mixtures for  Test Runs	    4-84

 4.9.2    Summary of Results:  Oxidation  of Organic Chlorides	   4-85

 4.9.3    Modar Treatment Costs for Organic Contaminated Aqueous
            Wastes	    4-87

 5.1.1    Summary of Data Show  Percent Removal  of TCDD From
            Contaminated Soils  Using  APEG Dechlorination Process   .  .  .    5-7

 5.1.2    Summary of Data Showing Percent Removal of  TCDD  From
            Contaminated Soil at Denny Farm	    5-7

 5.1.3    Summary of Results of In-Situ Processing -  All Soils
            Initially at 2000 ppb	    5-8

 5.1.4    Results of Slurry Processing	    5-8

 5.1.5    Degradation of 2,3,7,8-TCDD Under Different Conditions
            Using the CDP-Process	     5-11

 5.1.6    Preliminary Economic  Analysis of  In  Situ and Slurry
            Processes	     5-13

 5.2.1    Dissociation Energies for Some  Chemical Bonds ...  	     5-16

 5.2.2    Estimated Volumes and Concentrations of 2,3,7,8-TCDD
            Produced by the Syntex-IT Photolytic  Process  	   5-20

 5.2.3    Design Specifications, Capital, and  O&M Costs for 40,000
            and 150,000 GPD ULTROX Treatment Plants  	     5-27

 5.3.1    Solubilization of TCDD	   5-33

 5.4.1    Micro-organisms with  Known Capability for  Degrading
            2,3, 7,8-Tetrachlorodibenzo-p-dioxin	   5-37

                                  SECTION  1
                               EXECUTIVE  SUMMARY


     The 1984 Hazardous and Solid Waste Act Amendments to the Resource
Conservation and Recovery Act (RCRA) directed 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 enactment of the Amendments for EPA to regulate
the land disposal of these identified wastes (with some exceptions).  In the
event that the Agency has not issued regulations by that time (November 1986),
land disposal of all specified dioxin-containing waste streams automatically
will be banned.
     An important aspect of the land disposal restrictions is the
identification and evaluation of alternative technologies that can be used to
treat the listed wastes in such a way as to meet proposed treatment levels
which EPA has determined are protective of human health and the environment.
If alternatives to land disposal are not available by November 1986,  it may be
necessary to extend the deadline for the restrictions on land disposal.  The
purpose of this document is to identify and evaluate alternative  technologies
that remove and/or destroy dioxih and related compounds from  listed dioxin
wastes in order to achieve constituent levels that allow the  safe land
disposal of the treated residues.
     A number of potential technologies  exist  for  treating wastes containing
dioxin.  Because many of the technologies  are  currently in early stages of
development, it is not possible to  fully assess  the  effectiveness of these

                JANUARY 14, 1985, 50 FR 1978
 waste no.
                    Hazardous Waste from Nonspecific Source
Hazardous waste
  F020*     Wastes** from the production or manufacturing use of       (H)
            tri- or tetrachlorophenol, or of intermediates
            used to produce their derivatives.**

  F021*     Wastes** from the production or manufacturing use of       (H)
            pentachlorophenol (POP), or of intermediates used to
            produce its derivatives.

  F022*     Wastes** from the manufacturing use of tetra-, penta-,      (H)
            or hexachlorobenzene under alkaline conditions.

  F023*     Wastes** from the production of materials on equipment     (H)
            previously used for the production or manufacturing
            use of tri- or tetrachlorophenols.***

  F026*     Wastes** from the production of materials on equipment     (H)
            previously used for the manufacturing of tetra-,
            penta-, or hexachlorobenzene under alkaline conditions.*

  F027*     Discarded unused formulations containing tri-, tetra-,      (H)
            or pentachlorophenol or discarded unused formulations
            derived from these chlorophenols.****

  F028      Residues resulting from the incineration or thermal        (T)
            treatment of soil contaminated with EPA hazardous
            waste F020, F021, F022, F023, F026, and FU27.
*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

wastes requiring treatment at this tine are wastes such as still  bottoms  and
reactor residues that were generated in the past and remain to be treated.
The only process waste stream that is still being generated, and  may continue
to be generated in the future, is from the manufacture of pentachlorophenol
(POP).  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 1.2 shows estimated waste quantities for each of the waste codes.
Several items associated with the information 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 contaminated soil will  meet EPA
delisting requirements.  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 contaminated 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 1.2 could have a significant impact on  future  treatment
practices.  As shown in the table, there are more than 500,000 metric  tons
(MT) of dioxin-contaminated soil that may require treatment.  This  quantity is
considerably greater than the estimated maximum  7500 HI of  process  wastes,
such as still bottoms currently requiring treatment and the estimated  2500 HI
of industrial process wastes  that will be generated in  future  years.
Consequently, 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  capable of removing the
toxic constituents from the soil and  thereby reducing  the total  volume of
waste requiring final detoxification/destruction.


     As mentioned previously, a number of  technologies for treating dioxin
waste are evaluated  in this document.   A summary of the status of these
technologies is provided  in Table  1.3.   Because studies have shown that dioxin


                                       TABLE  1.3.   SUMMARY  OF  TREATMENT  PROCESSES
Procea* name
Stetionery Sotary
Kiln Incineretion

Mobil* Sotary
Kiln Incineration

Liquid Injection

(Circulating ted

High Temperature
Fluid Hell
(Huber AES)
weate atreama
Solid*, liquida. aludgea

Solid* , liquid*, aludge*

Liquida or aludge* with
viacoaity lea* than
10,000 aau
(I.e., pumpable)

Solid*, aludge*

Primarily for granular
contaminated aoila,
but may alao handle
Stage of
Several approved
and commercially
available unita for
PCBa; not yet uaed
for dioxlna
EPA mobile unit la
permitted to treat
dioxin waataa;
EH8CO unit ha* bean
demonstrated on PCS
Pull *c*l* land-
baaed unita permit-
ted for PCS*; only
ocean loclneretor*
have bandied dioxin
GA Technologlea
mobile circulating
bed combuator he*
a T8CA permit to
burn PCS* anywhere
ia the nation; not
teated yet on dioxin
Huber etationary
unit i* permitted
to do research on
deatruction achieved Coat
Greater than aix nine* DU for 10.25 - |0.70/lb
PCBa; greater than five ninea for PCS aolida
DU demonatrated on dioxin at
combuation reeearch facility

Greater than aix nine* DU for HA*
dioxin by EPA unit; proceaa
realdual* dellated

Greater than aix ninea DU on *200 - 1500/ton
PCB waatee; ocean Inclneretora
only demonatrated three ninea
on dioxin containing herbicide

Greater than aix ninea DSE .60 - »320/ton
demon* treted by CA unit on for CA unit

Pilot acal* mobile unit 1300 - i600/con
demonatrated greater then five
nine* DU on TCDD - contaminated
Treated w**te material
(aah), acrubber vaatewater.
particulate from air
filtera. gaaeoue product*
of combuation
Same ea above.

Seme ea ebove, but e*h i*
u*uelly minor becauae
aolid feeda are not

Treated waate (aah), parti-
culataa from air filtera

Treated waite (olid*
perticulatea from baghouae,
                    liquida                   dioxin wa*t*e;
                                              pilot *cale mobile
                                              reactor ha* been
                                              teated at aeveral
                                              location* on dioxin
                                              contaminated eoila

Infrared Incinerator Contaminated aoil*/*ludgee Pilot acal*. port-
(Shirco)                                      «bl« uolt teated on
                                              waat* containing
                                              diosln; full acal*
                                              unita heve been
                                              uaed In other appli-
                                              cation*; not yet
                                              permitted for TCDD
                                                                  aoil  at Time* Beech (79 ppb
                                                                  reduced to below detection)
                                                                  Greater  than aix ninea DSE on
                                                                  TCDD-contaminated aoll
Treatment  coata
are 1200 - t1,200
per ton
                  gaaeoua  effluent (primarily
Treated material (aah);
particulate* captured  by
acrubber (aeparated from
acrubber water)
•Not available


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      - «•  * — •.
       'J1" li*:S
       U - 'III
            ^ 1:1:=  \\\li\    i\-tii**

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                       *• » •»• «*• «»•• • •»• c e f
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                5  :Fss

•••truct loo »ehl«»«4

 circulating bed variation), the plasma arc process,  and the molten salt
 process.   The  in situ vitrification process has not  shown six nines UKE;
 however,  it is as much a stabilization process as it is a destruction
 process.   Therefore, the primary objective of this technology is to prevent
 the  leaching 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 secondary concern (as long as
 volatilized dioxin is captured and subsequently destroyed).
     Nonthermal technologies evaluated include the following:

     •     Chemical dechlorination
     •     Ultraviolet (UV) photolysis
     •     Solvent extraction
     •     Biodegradation
     •     Stabilization/fixation
     •     Chemical degradation using ruthenium tetroxide
     •     Chemical degradation using chloroiodides
     •     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
being field tested on dioxin-contaminated soil.  As indicated in Table 1.3,
preliminary field data on the thermal desorption/UV photolysis process
indicate that dioxin was desorbed from soil to a level below I ppb, and then
destroyed  efficiently using ultraviolet radiation.  The chemical
dechlorination process has also demonstrated a reduction of TCUD in soil  to
below 1 ppb, but only on a laboratory scale.
     The other nonthermal processes have not shown as much promise with regard
to treating dioxin waste.  Solvent extraction is a potentially useful
technology since it could,  if successfully applied to soil treatment, reduce
the volume of the waste stream that requires final treatment/destruction by
several orders of magnitude.   Unfortunately, this technology has not yet


associated waste streams are themselves subject to costly treatment
processes.  Therefore, technologies such as solvent extraction or desorption,
which separate the toxic constituents .-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
reaction to public opposition to the transport of dioxin waste from source to
waste treatment facilities, and should continue to be encouraged.
     In addition, because of the large volume 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 materials into the
environment is minimized.  Most of the technologies in this category, such as
biodegradation, in situ vitrification, chemical dechlorination, and
stabilization in the near future have not yet been sufficiently demonstrated.
Use in the near future seems improbable without more intense development of
these technologies.  Steps should be taken to encourage  these developments.
     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 generally  calls for  less
extensive handling and pretreatment.  Technologies, such as plasma arc
pyrolysis and supercritical water oxidation, appear to be capable  of treating
these wastes, and their development should be  fostered,  as  should  other
reasonable activities aimed at the development of emerging  technologies.

                                  SECTION 2.0
                            OF LISTED DIOXIN WASTES

     Certain dioxin contaminated wastes originally regulated under the Toxic
Substance Control Act (TSCA), 40 CFR Part 775, were listed as hazardous wastes
under the Resource Conservation and Recovery Act (RCRA) on January 14, 1985,
50 FR 1978.  The January 14, 1985 RCRA Anendments list as acute hazardous
wastes certain chlorinated dibenzo-p-dioxins, dibenzofurans, and phenols (and
their phenoxy derivatives).  A complete listing was presented in Table I.I.
When the RCRA Amendment listing dioxin-contaminated wastes became effective  on
July 15, 1985, duplicate listings of certain dioxins under RCRA and TSCA were
     The inclusion of these dioxin-contaminated wastes under the RCRA regula-
tions was mandated by the RCRA statutory amendments entitled the Hazardous and
Solid Waste Amendments of 1984 (HSWA), signed into law November 8, 1984 as
Public Law 98-616.  HSWA, among other things, mandate a RCRA listing status
for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-contaminated wastes, stringent
technical requirements for land disposal facilities, an expanded definition  of
land disposal, and various land disposal bans and restrictions.
     HSWA state that in the case of any hazardous waste which is prohibited
from one or more methods of land disposal, the storage of such hazardous waste
is prohibited unless such storage is solely for the purpose of the
accumulation of such quantities of hazardous waste as are necessary to
facilitate its proper recovery, treatment, or disposal.  In order for interim
storage of these wastes to be excluded from this prohibition, it must be
demonstrated that the storage is solely for the purposes of facilitating
proper recovery, treatment, or disposal.  HSWA also specify a two year
(24 months)  period during which EPA must decide whether or not to completely


Pertinent regulatory  provisions are summarized below.
     2,3,7,8-TCDD-contaminated wastes resulting from the production or
     manufacturing  use  of several chlorophenols and chlorobenzenes,
     including  contaminated soil, are added to the list of RCRA regulated
     acute  hazardous wastes (RCRA hazardous waste numbers F020, F021,
     F022,  F023, F026,  F027, F028); RCRA regulated quantity for small
     quantity generators is 1 kilogram of 2,3,7,8-TCDD-
     contaminated material;

     2,3,7,8-TCDD wastes may be disposed only in fully permitted RCRA
     (Part  B) land  disposal facilities (interim status land disposal
     facilities are not acceptable);

     Interim status facilities that may be acceptable for the management
     of  2,3,7,8-TCDD wastes include surface impoundments (for wastewater
     sludge; managed pursuant to 40 CFR 264.231), enclosed waste piles
     (pursuant  to 40 CFR 264.250(c), tanks (pursuant to 40 CFR 264.200),
     containers (pursuant to 40 CFR 264.175), incinerators (if certified
     pursuant to 265.352), and thermal treatment units (if certified
     pursuant to 265.383);

     A waste management plan is required for all land disposal facilities
     that submit Part B of their RCRA permit application.  The waste
     management plan will specifically address the means by which  the
     waste  will be managed safely at the land disposal facility;

     2,3,7,8-TCDD wastes may not be stored or disposed of in unlined

     Interim status incinerators and interim status thermal treatment
     units  are  allowed  to burn 2,3,7,8-TCDD wastes if they are
     "certified" by the Assistant Administrator for the EPA Office of
     Solid  Waste and Emergency Response, pursuant to 40 CFK 265.352 and
     .383,  respectively as meeting 40 CFR Part 264, Subpart 0, RCRA
     performance standards;

     Incinerators and thermal treatment units that are used to burn
     2,3,7,8-TCDD wastes must achieve a ORE of 99.9999 percent (i.e., six
     nines  DRE); and

     Residue resulting  from incineration or thermal treatment  of
     dioxin-containing  soils (F028) must be, at a minimum, managed at a
     RCRA interim status land disposal facility.


        Constituent*                             Screening level  (mg/1)

      2,3,7,8-TCDD                               4 x 10~9
      Other TCDDs                                4 x 10~7
      2,3,7,8-tteCDDs                             8 x 10~9
      Other PeCDDs                               8 x 10~7
      2,3,7,8-HxCDDs                             I x 10~7
      Other HxCDDs                               1 x 10~5
      2,3,7,8-TCDFs                              4 x 10~8
      Other TCDFs                                4 x 10~6
      2,3,7,8-PeCDFs                             4 x 10~8
      Other PeCDFs                               4 x 10~8
      2,3,7,8-HxCDFs                             4 x 10~7
      Other HxCDFs                               4 x 10~5
      2,4,5-Trichlorophenol                      8.0
      2,4,6,-Trichlorophenol                     0.04
      2,3,4,6-Tetrachlorophenol                  2.0
      Bentachlorophenol                          1.0
^Definitions of abbreviations used above
      TCDDs and TCDFs "All isomers of tetrachlordibenzo-p-dioxina and
                       -dibenzofurans respectively.
      PeCDDs and PeCDFs " The pentachlorodibenzo-p-dioxins and -dibenzofurans.
      HxCDDs and HxCDFs * The hexa-isomers.

                                  SECTION 3.0
                            OF LISTED DIOXIN WASTES

      The  purpose of  this  section is to characterize the wastes described by
 RCRA codes  F020, F021, F022, F023, F026, and F027.  These codes describe
 wastes  from the production and manufacturing use of tri-, tetra-, and
 pentachlorophenols and from the manufacturing use of tetra-, penta-, and
 hexachlorobenzenes under  alkaline conditions and elevated temperatures.  These
 wastes  include still bottoms, reactor residues, untreated brines, spent filter
 aids, spent carbon adsorbents, and sludges resulting from wastewater
 treatment.   They also include wastes resulting from the production of
 materials on equipment previously used for the production and manufacturing of
 tri-  and tetrachlorophenols, and formulations containing these chlorophenols
 and their derivatives.  Waste code F028 is a treatment residue from
 incineration or thermal treatment of dioxin-containing soil to six nines DR£.
 It  is designated a toxic  and not an acute hazardous waste, and therefore is
 not addressed in this document.  The untreated soils, however, that have been
 contaminated by spills of wastes in codes F020, F021, F022, F023, F026 and
 F027  are defined as hazardous (50 FR 28713) and are addressed.
      As shown in Table 3.1, the basis for listing each of these wastes and for
 banning them from land disposal is the expected or known presence of
 significant  quantities of tetra-, penta-, and hexachlorodibenzo-p-dioxins
 (CDDs) and chlorinated dibenzofurans (CDFs).  These compounds are among the
most  potent  animal carcinogens known and are potential human carcinogens in
addition to  being extremely persistent in the environment.  These wastes may
also contain significant concentrations of tri-, tetra-, and
pentachlorophenols and their chlorophenoxy derivatives, some of which are
potential human carcinogens (2,4,6-TCP) and/or are suspected of causing liver
and kidney damage  (U.S.  EPA, 1985).

                                         TABLE 3.1 (continued)
EPA code
Waste code description
Hazardous constituents for which listed
 F023      Wastes  (except wastewater and spent carbon
           from hydrogen chloride purification)  from
           the production of materials on equipment
           previously used for the production or manu-
           facturing use (as a reactant, chemical  in-
           termediate, or component in a formulating
           process) of tri-and tetrachlorophenols.
           (This listing does not include wastes from
           equipment used only for the production  or
           use of  hexachlorophene from highly purified

 F026      Wastes  (except wastewater and spent carbon
           from hydrogen chloride purification)  from
           the production of materials on equipment
           previously used for the manufacturing use
           (as a reactant, chemical intermediate,  or
           component in a formulating process) of
           tetra-, penta-, or hexachlorobenzene  under
           alkaline conditions.

 F027      Discarded formulations containing
           tri-, tetra-, or pentachlorophenol or
           discarded formulation containing hexa-
           chlorophene synthesized from prepurified,
           2,4,5-trichlorphenol as the sole component.
 F028      Residues  resulting  from the  incineration  or
           thermal treatment of  soil contaminated  with
           EPA Hazardous Waste Nos. F020, F021,  F022,
           F023, F026,  and F027.
                                       Tetra-, and pentachlorodibenzo-p-dioxins;
                                       tetra- and pentachlorodibenzofurans; tri-
                                       and tetra-chlorophenols and their
                                       chlorophenoxy derivative acids, esters,
                                       ethers, amines, and other salts.
                                       Tetra-, penta-, and hexachlorodibenzo-p-
                                       dioxins; tetra-, penta-, and hexachlorodi-
                                       Tetra-, penta-, and hexachlorobibenzo-p-
                                       dioxins; tetra-, penta-, and hexachlorodi-
                                       benzofurans; tri-, tetra-, and pentachloro-
                                       phenols and their chlorophenoxy derivative
                                       acids, esters, ethers, amines, and other

                                       Tetra-, penta-, and hexachlorodibenzo-p-
                                       dioxins; tetra-, penta-, and hexachlorodiben-
                                       zofurans; tri, tetra-, and pentachlorophenols
                                       and  their chlorophenoxy derivative acids,
                                       esters, ethers, amines, and other salts.

                        (•) Dibenzo-p-Dioxin
                        (a)  Dibenzofuran
Figure 3.1.  Structure of (a) Dibenzo-p-Dioxin and (b) Dibenxofuran
             Source:  Environment Canada, 1985

      •    low vapor pressure;
      •    absorption of ultraviolet radiation; and
      •    low rate  of biodegradation.
      PCDDs are  characterized by low polarization which results in a very  low
 water solubility, but  a much higher solubility in organic solvents.  The  water
 solubility of 2,3,7,8-TCDD has been measured by a number of investigators.
 Recently derived estimates have been in the range of 7 to 20 parts per
 trillion.   In contrast, the solubility of TCDD in organic solvents such as
 benzene, xylene, and  toluene ranges from 500 to 1,800 ppm.  This results  in a
 log  octanol/water partition coefficient of up to nine.  Consequently, in  the
 environment TCDD is not generally found at high concentrations in aqueous
 media.  Instead, it  is bound to the organic matter in soil where it may remain
 for  long periods of time.  The half-life of TCDD in soil has been estimated to
 range  between 1.5 and  10 years (U.S. EPA, 1985), but the results of one recent
 study  indicated virtually zero degradation of TCDD after being in the soil  for
 twelve years.   In addition, the TCDD had only moved about 10 centimeters  over
 this period of  time (Freeman & Schroy, 1986).
     Another  property of TCDD is that it absorbs ultraviolet light strongly
 with a wavelength of maximum absorption lying within the sunlight region
 (above 290 nm).  As a result, TCDD has been shown to degrade significantly
 when exposed  to light of this wavelength in the presence of a hydrogen donor
 such as hexane or some other organic solvent.  Tests have shown that when a
 hydrogen doner is not present,  degradation of TCDD is negligible (Crosby,
 D. G., 1985).  Photolytic degradation was applied to 4,300 gallons of still
 bottoms containing 343 ppm of 2,3,7,8-TCDD.  The dioxin was first extracted
 from the still bottoms using hexane, and then the extract was irradiated  with
 ultraviolet light; 99.9 percent destruction of TCDD was achieved.  This
 process will  be described in more detail in Section 5.
     One of the most important properties of TCDD with respect to treatment is
 that it is destroyed at temperatures between 1200 and 1400°C (Shaub and Tsang,
 1982).  When chlorinated compounds are incinerated at lower temperatures,
 however,  dioxins may be formed in large quantities.  The heat of combustion of
 PCDD is 2.81 kilocalories per gram which is greater than the heat of
combustion of compounds such as I,I,1-trichloroethane and pentachlorophenol.


 Chlorophenola and Chlorophenoxy Compounds

      In general these compounds are water soluble,  and in wastes  they
 concentrate in the aqueous phase where they are biodegradable  by  adapted
 microorganisms (U.S. EPA, 1985).  The biodegradation half-life of 2,4,5-T and
 Silvex in water is expected to be one to three weeks.   The  same compounds have
 a  similar half-life due to biodegradation in soils.   2,4,5-TCP, however, has
 been  shown to be persistent in some soils.   In one  case,  where the  initial
 concentration of 2,4,5-TCP in soil was 5000 ppm, the concentration after three
 years was still 1 to 20 ppm (Lautzenheiser, 1980).
      Other properties of these compounds include relatively low volatility,
 ability to be adsorped by organic matter such as activated  carbon,  and
 susceptibility to photolytic degradation (U.S. EPA, 1985; Lautzenheiser,
 1980).  Chemical and physical characteristics of these compounds  are listed in
 Table 3-3.


 3.3.1  Sources of Data

     The primary source of data utilized for waste quantity estimates was  a
 report prepared by Technical Resources, Inc. (TRI), entitled,  "Analysis of
 Technical Information to Support RCRA rules for Dioxins - Containing Waste
 Streams".  This report evaluated previous estimates of waste quantities made
 by Radian (Radian, 1984), and determined that they reflected past practices.
 TRI presented revised waste generation quantities based on more current
 information on manufacturing processes obtained by talking to  industry
 contacts.  Their estimates appear to be the best available at this time;
 however, where additional information was available, changes have been made to
 their estimates.
     There are several other sources of data which may be used in the future
 to obtain better estimates of the quantity of vaste containing dioxin.  One of
 these is EPA's Dioxin Strategy.  Tiers one, two and three of  the Dioxin
 Strategy encompass sites where 2,4,5-TCP and its pesticidal derivatives were
produced or formulated and also sites where wastes from  these  processes were
disposed.   Close to 100 potential sites were identified  in Tiers  I and 2

 (Radian,  1984);  a  report will be issued in the near future containing
 information  related to the extent of contamination at these sites.   The
 information  in this report will hopefully contain data which will allow for a
 better estimate  of waste quantities and characteristics, particularly for
 those sites  where waste was disposed (Korb, 1986).
     Another potential but unused source of data is RCRA Biennial Reports.
 These reports are  filed biennially by hazardous waste treatment, storage and
 disposal  facilities.  EPA has indicated that the data from the 1983 reports
 are  not very accurate both because of a poor response rate, and also because
 data reported to states were not carefully verified prior to sending data
 summaries to EPA headquarters (Stoll, 1986).  In addition, at the time of the
 1983 report, the dioxin waste codes (F020-F028) had not yet been developed.
 Consequently, the 1983 report only contained data concerning the "U" waste
 codes for tri-, and tetra-, and pentachlorophenol and their pesticide
 derivatives  2,4,5-T and Silvex.  These waste codes have now been replaced by
 F027.  The 1985 Biennial Reports will contain data on the quantities of waste
 in codes F020-F028 that were treated, stored or disposed in 1985.  These data
 should be available in the fall of 1986.  Whether these data will be better
 than the data from the 1983 Biennial Reports is unknown at this time.
     Finally, facilities that handle (generate, store, treat, or dispose)
 wastes covered under the dioxin listing rule were required to notify EPA by
 April 15, 1985.  Information contained in the notifications does not at this
 time include data on the quantities of waste generated or stored, but  it does
 indicate which waste codes the facility handles, and it also includes  data to
 indicate the waste treatment and storage capacity at these facilities.  TRI
utilized this information to estimate the quantities of F027 waste that will
 require treatment.
     A recent listing of the dioxin waste notifiers is presented in
Table 3.4.  This listing is updated monthly as new facilities notify,  or as
 facilities that do not belong on the list are deleted.  It is expected that
information regarding the quantities of wastes handled by these facilities
will be assembled in the future.

 3.3.2  Waste Code F020

 Sources of Waste—
      This waste code  includes wastes from the production and manufacturing of
 tri- or tetrachlorophenols or intermediates used to produce their
 derivatives.   The major  derivatives include phenoxy compounds such as
 2,4,5,-trichlorophenoxyacetic acid (2,4,5,-T), 2-(2,4,5-trichlorophenoxy)
 propionic acid (Silvex), and hexachlorophene.
      The  manufacture  of  2,4,5-TCP is accomplished by the alkaline hydrolysis
 of tetrachlorobenzene.   The primary wastes from the process include
 distillation  bottoms  from solvent recovery, spent filter aids, and reactor
 bottoms.   These wastes,  in addition to the product itself, will be
 contaminated  with CODs,  CDFs and chlorophenols.  The amount of CDDs formed in
 the process is dependent upon reaction temperature, which in turn is dependent
 upon the  solvent used (methanol, ethanol, ethylene giycol, toluene or
 isomyl/amyl alcohols).   When methanol or water are used as the solvent, the
 process operates at around 220-300°C, a temperature at which lab experiments
 have shown the formation of 1.6 g TCDD per kg of 2,4,5-TCP.  Using ethylene
 giycol the process operates at lower temperatures and CDD formation should be
 lower (U.S. EPA,  1985).
      2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol are most efficiently
 produced  by the  chlorination of phenol.  la this process more 1,3,6,8-TCDD
 than 2,3,7,8-TCDD is  formed.  These products also contain up to 50 ppm of CDFs.
      The manufacture  of  2,4,5-T and other phenoxy compounds utilize 2,4,5-TCP
 as  one of  their  starting materials.  Since TCDD contaminates 2,4,5-TCP, and
may also  be generated in the formation of the phenoxy compound itself, it is
expected  to be present in both the product and the wastes from its
manufacture.   Phenoxy herbicides such a* 2,4,5-T and Silvex are synthesized oy
 reacting  the  appropriate chlorophenol with a haloalkanoic acid under alkaline
reflux conditions.  These conditions are conducive to the formation of CDDs
and CDFs.  Careful control of reaction time, temperature,and pH are said  to
have  an effect in reducing the formation of TCDDs.  Wastes from the process
include caustic  scrubber water, spent filter aide and/or carbon adsorbent, and
distillation  bottoms  from solvent recovery.  Solvents used are similar to
those used in the production of 2,4,5-TCP.  Formerly methanol was used, and
more  recently a mixture of ethylene giycol and toluene or xylene was used.

                                                 TABLE  3.5.    CONSTITUENTS  OF  WASTE  CODE F020
Other Pouible
              Herbicide  Manufacture
              (•tilt botto**,  and
              reactor icaidue*
              fro* the Mnufacture
              of 2,4.5-T.  2,*,5-TCP
              •nd He*actlorophene)
Non-Aqueou* Fh**e
Le*ch*te (fro*
di*poaal of w**te
fro* Manufacture of
2,4,5-T and phenoxy
herbicide* - Love
Canal. Hyde Perk)
                       60-1290 ppm
0.6-350 pp*
             Filter Aid*
             in 2,4,5-TCP

             Filter Cake
             fro* Heiechlorophene

             Spent Carbon
             fro* treet*ent of
             •queou* leachate.
                                    0.2-20.2 pp*
                                        0.008-300 pp*
                                        8-2000 ppb
                       untreated wa*te,
                       0.004-0.017 ppb;
                       trected vatte.
                        0.010 ppb
•  Hethanol
   ethylene glycol
•  2,4,5-TCP
e  trichloro*ni*ole*
•  tetrachloro-

•  *i*il*r to w**te*
   described *bove
•  heevy *et*l*
   - *nti*ony
   - *r*enic
   - lead
   - nercury
   - alu*inu*
   - chro*im
•  fluoroorg*nic*
•  bro*oorg*nic*
•  phoaphide*
a  culfide*
•  PCS

a  lnorg»nic Solid*
a  chlorophenol*
                                 •   Inorgcnic Solid*
                                 a   chlorophenol* or
                                    organic colvent*

                                 •   Spent Carbon
                                 •   chlorphenol* end
                                    other orginici

de* Holier*,  1985;
R*di*n,  1984;
U.S.  EPA,  198)
                                                                    U.S.  EPA,  198)
                                                       99. SZ
                                                                                                                          U.S. EPA, 1985
                                                                                                            U.S. EPA, 1985
                                                                                                            U.S. EPA, 1985

 spent carbon from the  treatment of aqueous phase leachate from the Love Canal
 Landfill.   The  TRI report  did not include an estimate of the quantity of spent
 carbon from treatment  of aqueous phase  leachate at the Hyde Park Landfill.
 EPA Region II personnel have indicated  that there are currently several
 dumpsters  of spent carbon  at the site that Calgon (the manufacturer of the
 carbon)  will not  accept for regeneration because of possible dioxin
 contamination.  Aqueous phase leachate  is still being generated at a rate of
 approximately 5000 gallons per day, so  spent carbon will also continue to oe
 generated  and require  treatment (Gianti, 1986).
   ,   In  addition  to the non-aqueous phase leachate that is currently stored in
 lagoons  at Hyde Park,  an additional 40  to 200 gallons per day are continuing
 to be  collected.   At an average rate of 120 gallons per day, 200 MT would be
 collected  in one  year.  The period of time over which NAPL will continue to be
 generated  is not  known (Gianti, 1986).
     In  addition  to these major sources of waste, there are probably other
 smaller  sites where 2,4,5-TCP and derivatives were manufactured or formulated
 in the past and wastes are currently stored.  Possible locations of these
 sites  have  been and are being identified through EPA1s Dioxin Strategy and
 also through the  provision that all potential handlers of dioxin wastes notify
 EPA  of their activities.  Data on the quantity of wastes at these "other"
 sites, however, are not currently available.  TRI estimated that the quantity
 of F020  waste at  these miscellaneous sites is 500 MT.

 3.3.3  Waste Code  F021

 Sources  of Waste—
     This waste code encompasses wastes from the production and manufacturing
 of pentachlorophenol.  Pentachlorophenol (PGP) and its sodium salt have
 various  uses  a* fungicides and biocides with the majority (80 percent) being
 used as  a wood preservative.  Since all non-wood uses of PGP will be banned as
 a  result of  a notice of intent to cancel made by EPA on January 8, 1986
 (Chemical Regulation Reporter,  1/10/86), it is expected that all future uses
will be  as a wood  preservative.
     The manufacture of pentachlorophenol can be accomplished either by the
chlorination of phenol or by the alkaline hydrolysis of hexachlorobenzene.  In
the United States,  the former method is used.  The chlorination usually


 formation of PCDDs  and  PCDFs  (des Rosters, 1985).  The number of sices
 containing these  sludges may exceed 100; however, no estimates of the quantity
 of sludges has  been made.  In addition, 23 damage incidents related to wood
 treating  operations using PCP were included in the Listing Background
 Document.   These  damage incidents include cases where sludges and wastewaters
 were  stored onsite  and contaminated soil and water.  This waste stream is
 being included  in this discussion due to its possible listing as a "dioxin
 waste" to  be  banned from land disposal.

 Waste Characteristics—
      As mentioned above, the manufacture of PCP does not currently generate a
 waste stream  containing CDDs.  In the future, however, PCP will have to be
 purified  to reduce  HCDD concentrations from 15 ppm to 1 ppm.  Radian estimated
 the composition of  a waste stream generated as a result of the purification of
 PCP by distillation (Radian, 1984).  This waste stream would consist primarily
 of organic  solids (nonvolatile), various chlorinated phenols and organic
 solvents as indicated in Table 3.6.  In addition, a small fraction of the
 waste would consist of residual catalyst (aluminum chloride), and total CDDs
 could reach 2,000 ppm.  Future purification of PCP will probably not be by
 distillation, but instead by a solvent extraction and crystallization
 process.  The wastes from this process are assumed to be similar to those
 generated by  distillation (TRI.1985).
      Waste  from wood treatment facilities is expected to contain a large
 variety of constituents.  The exact composition of the waste will vary from
 facility to facility, but in all cases will be a sludge with varying
 concentrations of water, chlorophenols, and creosote.  Organometallic
 compounds such as copper and zinc naphthalenates and arsenicals are also
expected to be potential constituents, in addition to PCBs and waste
 solvents.  The source of CDDs and CDFs in these wastes would be from the
 inherent contamination of PCP with these compounds.  Higher concentrations may
 be present  if waste pits and lagoons containing these wastes were torched  to
reduce volume.

 Waste  Quantities—
     The  only current manufacturer of PCP is Vulcan Materials  Company.
 Previous manufactures include Dow, which ceased production in  1980, and
 Reichhold Chemicals, Inc. which ceased production in 1985 (TRI,  1985).  TRI
 estimated that Vulcan would fill the cArrent U.S.  demand for PCP of 15,000 hi
 per year.  If this is the case, and if purification results in a waste stream
 of 5 percent of the end product, the quantity of waste generated through
 purification will be 750 MT per year.
     Wastes from formulation of PCP are not expected to be generated  in the
 future since all PCP is expected to be sold directly to wood preservers.
 Previous to the ban of non-wood uses of PCP, however, 20 percent of  the PCP
 was formulated into products for herbicidal, antimicrobial, and disinfectant
 use (Chemical Regulation Reporter, 1/10/86).  These uses are  assumed to have
 resulted in the generation of 350 MT per year of scrubber water sludges
 contaminated with PCP and HCDO.  Three hundred fifty MT are estimated for the
 past years (1985) formulation activities, and another 350 MT  for the  current
 years activities.  Therefore, as indicated previously in Table 1.2,  700 MT of
 waste code F021 presently require treatment.

 3.3.4  Waste Code F022

     The Radian Report (Radian, 1984) states that there are no known
 commercial activities with the processes encompassed by this waste code.   The
 compound, 2,4,5-trichlorophenol, was manufactured by the alkaline hydrolysis
 of tetrachlorobenzene which would subject its wastes to inclusion in this
 waste code, in addition to waste code F020.  Since 2,4,5-TCP is not being
manufactured at this time, no wastes are currently being generated.
 Potentially generated wastes, and wastes generated by this process in the past
 are discussed previously under waste code F020.

 3.3.5  Waste Code F023

 Sources of Waste—
     Production trains are often used for the  production of chemicals whose
manufacture necessitates the use of similar process  equipment.  In the
manufacture of chemicals on a production train previously contaminated with

 currently  using contaminated equipment and generating contaminated wastes.   In
 addition,  they assumed that current production levels are equal  to the
 greatest past production levels.  These assumptions would seemingly lead to  an
 upper  bound estimate of the quantity of F023 waste generated.  The actual
 quantity probably  lies between TRI's estimate of zero and Radians estimate of
 573 MT per year.

 3.3.6  Waste Code  F026

     The only manufacturing process that involves the manufacturing use of
 tetra-, penta-, or hexachlorobenzenes is the manufacture of
 2,4,5-Trichlorophenol.  Aa mentioned above, the manufacture of 2,4,5-TCP
 involves the alkaline hydrolysis of tetrachlorobenzene.  Wastes  from the
 production of materials on equipment previously used to manufacture 2,4,5-TCP,
 however, is regulated under waste code F023.  Consequently there should oe  no
 F026 waste generated..

 3.3.7  Waste Code  F027

 Sources of Waste—
     This waste code encompasses discarded, unused formulations of tri-,
 tetra-, and pentachlorophenols and their derivatives.  These wastes arise
 either because the product is off specification, the product was manufactured
 but then its use was banned, or an excess amount was produced or acquired.
 Because most of these compounds are no longer being manufactured, these wastes
 are not currently  being generated.  The exception to this, as mentioned above,
 is pentachlorophenol which is still manufactured, and so wastes from unused
 formulations may continue to be generated.  For the other compounds of concern
 unused formulations which have been generated in past years may still  lie in
 storage and eventually require final destruction/disposal.

Waste  Characteristics--
     Measured concentrations of CDDs and CDFs in the products of concern are
presented in Table 3.7.  As indicated by the data in this table, the
concentration of CDDs in these products can range from non-detectable  levels

 up co hundreds  of ppm.  The actual concentration will vary from batch to
 batch,  and compound to compound.  In addition, the products may have contained
 higher concentrations of CDOs in the past than they have more recently.   For
 example,  the mean concentrations of 2,3*7,8-TCDD in Agent Orange and Agent
 Purple  (both mixtures of 2,4,5-T and 2,4-D) in the 1960s were 1.98 and 32.8
 ppm  respectively  (Young, 1983) while it was claimed that those prepared in the
 1970s  contained less than 0.1 ppm (Rappe, 1979).  Despite this claim there may
 still  remain quantities of waste in storage with substantial levels of TCUO.
 For  example, the  Tennessee Valley Authority (TVA) currently has 21 drums of
 herbicide  orange,  one of which contains 5.6 ppm of 2,3,7,8-TCDD (TRI, 19U3).
     The  only F027 waste being generated on an ongoing basis would be unused
 pentachlorophenol.  Because of the consent decree requiring POP manufacturers
 to reduce  the concentration of HCDO in their product from 15 ppm to 1 ppm,
 this waste  will be of less concern than it has been in the past, since the
 majority  of the HCDD will be incorporated in the purification wastes.
     The physical  forms of these wastes will vary from case to case.
 Pentachlorophenol  is commonly applied to wood as a 5 percent suspension in
 fuel oil  (sometimes blended with creosote) or dissolved in an organic solvent
 (Chemical  Products Synopsis, 1983).  The other products are generally marketed
 as emulsifiable concentrates.  These concentrates are prepared by dissolving
 the  active  ingredient (15-80 percent) and a surface active agent (less than
 5 percent)  in a water emulsifiable organic solvent.  The surface active
 emulsifiers are generally polyethylene and polypropylene glycols, calcium
 sulfonates or various soaps (Sitig, 1980).

Waste Quantities—
     TRI estimated the quantity of waste code F027 in storage to be  1,000 MT
 per year.  This estimate was based on a review of data contained in the Dioxin
Waste Notifications.  They estimated that the amount of waste generated that
would place a demand on treatment capacity was equivalent to the storage
capacity at facilities notifying EPA that they were handling waste code F027.
Their estimate does not include facilities which reported capacity for waste
treatment within the plant site because the waste generated at  these
facilities would not place a demand on offsite treatment.

     Large quantities of contaminated soils and sediments also exist in New
York State.  Two landfills, Hyde Park and Love  Canal, were used for the
disposal of organic solvents and wastes from the production of chlorophenols
and phenoxy herbicides.  The Hyde Park landfill is estimated to contain
approximately 120 kg of TCDD; leakage of wastes from these landfills has
resulted in the contamination of surrounding soils and  sediments.  It is
believed that there are 55,000 cu yds of stream bed  sediments contaminated
with an average of 70 ppb of TCDD (USEPA, 1985).

Waste Characteristics—
     Waste soils, sediments and other solid materials that have been
contaminated with dioxin may have varied compositions and concentrations of
dioxin.  As indicated in Table 3.8 concentrations of TCDD  in  soils and  other
solids range from nondetectable (ND) to greater than 26 ppm.  The contaminated
materials at some of the sites include not only granular materials such as
soils and sand, but also asphalt, vegetation, rocks  and gravel.  These
materials may require special procedures to remove and/or  destroy  the TCDD.
Incinerators many times require the feed material to be of a  certain size and
consistency.  Consequently, some sort of pretreatment to reduce  size and
produce a more uniform feed may be necessary for the treatment of  these wastes.
     One of the most significant characteristics of TCDD on  soils  is its very
high soil/water partition coefficient.  As shown in Table  3.2 the  log of the
partition coefficient can be as high as seven.   The conclusions  of a recent
study indicate that the most important factor affecting both  the concentration
of TCDD in soils, and its partitioning between soil and water is  the presence
of other organic* in the soil.  The data indicated that in soils with  higher
concentrations of solvent-extractable organics (particularly  halogenated
semivolatiles) the TCDD concentrations in water extracts were greater.   They
further suggested that it is other organic contaminants in the wastes  and not
the total organic carbon and clay content of soils that affects  the mobility
of TCDD (Jackson, D. R. et al, 1985).  This would mean that  in cases where
wastes from the manufacture of chlorophenols or chloropnenoxy herbicides were
disposed or leaked into soil media along with other organic  wastes,  TCDD may
be much more mobile than would be normally expected.  In cases where
chlorophenols and organic solvents are not present in the wastes,  the TCDD may
be much more strongly bound to the soil, and much more difficult to desorb.


Waste Quantities—
     It has been estimated that there are 500,000 HI of dioxin-contaminated
soils in Missouri, 160,000 MT at Times Beach alone (Radian,  1984).   Radian
made a rough estimate of the total quantity of dioxin-contaminated  soil  in the
U.S. by assuming an average site size (5 acres with a 1.5 ft.  depth) and
multiplying this by the number of tier 1, 2, and 3 sites identified in the
Dioxin Strategy.  Their result was 2.3 million MT.  Because  of the
uncertainties in making an estimate such as this, 500,000 MT was used as the
minimum quantity of dioxin-contaminated soils currently requiring treatment in
the United States.  This is the number that is presented in Table 1.2.  It
will be possible to make a more accurate estimate of the quantity of
contaminated soil after the sites identified in the Dioxin Strategy are better
     Wastes which are of concern for this document are those containing an
extractable TCDD or TCDF concentration of greater than 1 ppt>.  It is possible
that much of the contaminated soil will contain strongly adsorbed TCOD, and so
will not require treatment with respect to the land disposal ban.

Freeman, R.A. and J.M. Schroy.  Modeling of the Transport of 2,3,7,8-TCDD
and Other Low Volatility Chemicals in Soils Environmental Progress,
5  (1),  1986.

GCA Technology Division.  Assessment of Treatment Alternatives for Wastes
Containing Helogenated Organics.  U.S. EPA Contract No. 68-01-6871.
October, 1984.

Gianti, S.  U.S. EPA, Region II.  Telecon with H. Arienti, GCA Technology
Division.  March 6, 1986.

ICF, Incorporated.  The RCRA Risk/Cost Analysis Model Phase III Report.
Submitted to U.S. EPA Office of Solid Waste, Economic Analysis Branch.
March 1, 1984.

Industrial Economics, Inc.  Regulatory Analysis of Proposed Restrictions
on Land Disposal of Certain Dioxin-Containing Wastes.  Draft Final report
prepared for EPA, Office of Solid Waste.  January, 1986.

IT Enviroscience, Inc.  Study of Potentially Hazardous Waste Streams for
the Industrial Organic Chemical Manufacturing Industry, 1982.

Jackson, D.R. et. al.  Leaching Potential of 2,3,7,8-TCDD in Contaminated
Soils.  In proceedings of the Eleventh Annual Research Symposium on Land
Disposal of Hazardous Waste.  EPA/600/9-8S/013 April 1985.

Junk, G.A. and J.J. Richard.  1981.  Dioxins Mot Detected in Effluents
from Coal/Refuse Combustion.  Chemosphere 10:1237-1241.

Korb, Barry.  U.S. EPA.  Telecon with M. Arienti, GCA Technology
Division.  February 10, 1986.

Lautzenheiser, J.G. et. al.  Non Aquatic Fate and Environmental Bruden of
2,4,5-T, 2,4,5-TP and 2,4,5-TCP.  Prepared  for U. S. EPA Contract No.
68-01-3867.  September, 1980.

Marple, L. et. al.  Water Solubility of 2,3,7,8-Tetrachlorodibenzo-p-
dioxin.  Environmental Science and Technology.  20 (2)  1986.

Mill, T. SRI International, Menlo Park, CA

Radian Corporation.  Assessment of Treatment Practices For  Proposed
Hazardous Waste - Listings F020, F021, F022, F023, F026, F027, and F028.
EPA Contract No. 68-02-3148.  September, 1984.

                                  SECTION 4

     In this report, thermal technologies  include  incineration, pyro lysis and
other processes in which heat is the major agent of destruction.  As mentioned
in Section 3, laboratory studies have  shown  that CDDs  break  down  rapidly when
subjected to temperatures above 1,200°C.   As a result,  high  temperature
incineration and other thermal methods have  received much attention with
regard to treatment of waste containing CDDs.   This attention has led  to the
development by EPA of a mobile incineration  system designed  specifically for
research on wastes containing dioxin and other toxic substances.  This mobile
incinerator has demonstrated greater than  six nines  (99.9999 percent)
destruction and removal efficiency (DRE) of  wastes containing CDDs, and has
led EPA to propose in their January 14, 1986 ruling  on land  disposal of waste
containing dioxins (FR, Vol. 51, No. 9) that incineration (or an  equivalent
thermal technology) be used as the treatment technology for  these wastes.
     Incineration and other thermal treatment of RCRA-listed dioxin wastes
(codes F020, F021, F022,  F023, F026, F027) must be done in accordance  with  the
criteria specified under 40 CFR Parts  264.343 and  265.362 in the  dioxin
listing rule.  These criteria specify  that processes burning these  wastes must
achieve a DRE of 99.9999 percent for each  principal  organic  hazardous
constituent (POHC) designated in its permit.  DRE  is determined from the
following equation:

                                 (W.   - W    )
                           DRB .              « 100
               where:     W^a • macs feed rate of one POHC in
                         the waste stream feeding the incinerator; and
                         Woug • mass emission rate of the same POHC
                         present in exhaust emissions prior to release to
                         the atmosphere.

      This  section includes subsections on a variety of  thermal technologies.
Methods of incineration include:

          Stationary Rotary Kiln       *
          Mobile Rotary Kiln
          Liquid Injection
          Fluidized Bed
Other thermal destruction technologies include:
          High Temperature Fluid Wall
          Plasma Arc
          Molten Salt
          In Situ Vitrification
          Supercritical Water Oxidation

     Each subsection contains a process description, an evaluation of the
performance of the technology with regard to chlorinated dibenzo-p-dioxins
(CDDs) or similar compounds,  an assessment of treatment costs,  and a
discussion of the status of the technology.  Not all of these  units have been
tested using dioxin waste, but most of them have at least been tested using
PCS waste; in these cases, the FOB data have been presented as evidence of
their performance.


     Several commercial rotary kilns have been permitted to burn FOB wastes.
In so doing they have demonstrated six nines ORE for PCBs, and therefore  have
the potential to burn dioxin waste*.  These units are:   the Rollins
incinerator in Deer Park, Texas; the SCA incinerator in Chicago, Illinois;  and
the ENSCO incinerator in El Dorado, Arkansas.  None of  these units has been
demonstrated using dioxin wastes; however, the EPA Combustion Research
Facility in Jefferson, Arkansas, which operates a rotary kiln incinerator,
recently conducted test burns of dioxin wastes.   Even though this is not  a
commercial incineration facility, the data that were generated by the dioxin
burns are included to indicate the performance of a rotary kiln.

Rollins (Rollins, 1985; M. M. Dillon, 1983; Gregory,  1981)--

     The configuration of the Rollins stationary incinerator is shown in
Figure 4.1.1.  Solids or sludges are conveyed to the rotary kiln in fiber
drums or 55 gallon metal drums.  Certain solids (such as capacitors,) need to
be preshredded prior to being fed into the kiln.  Liquid wastes can be fed
directly into the afterburner section.  The liquids are atomized using
compressed air, which produces a rotary action in the combustion zone.
     The combustor is a Loddby furnace measuring 1.6m diameter by 4.9m long.
The  fterburner zone measures 4 x 4.3 x 10.6m.  Natural gas and/or No. 2 fuel
oil are used as ignition fuel and also as a supplementary fuel if necessary.
Combustor temperatures can reach 1500°C, and afterburner temperatures average
1300°C.  Residence times in the afterburner range from 2 to 3 seconds.  Kiln
residence times vary widely according to the form of the waste, with residence
time being a function of design, solids content and viscosity.  Combustion
gases from the afterburner pass through a combination venturi
scrubber/absorption tower system in which particulates and acid gases are
removed from the gas stream.  A fraction of the scrubbing water is dosed with
lime and returned upstream of the venturi throat to increase scrubbing
efficiency.  Induced draft fans are used to drive the scrubber gas stream to
the atmosphere.

ENSCO (M. M. Dillon, 1983; McCormick, 1986)—

     A schematic of the ENSCO incineration facility is shown in Figure 4.1.2.
Drummed wastes are fed to an enclosed shredder where solids drop  into a  hopper
and are conveyed by an auger into the rotary kiln.  Liquid wastes are mixed
with the shredded solids and conveyed to the kiln or injected  directly  into
the combustion chamber.  The air in the enclosed shredder is drawn  by a  fan
into the rotary kiln.
     The rotary kiln measures 2.1m in diameter by 10.4m  long and  is  angled
slightly so that the solid residue flows by gravity to the ash drop.  Flue
gases from the kiln are ducted to the 85 cubic meter combustion chamber where
fuel (often an organic waste) is burned to create a high temperature zone
(outlet temperature 1250°C).  This afterburner, which  possesses an outlet


  Sludge, semi-solids,
  contaminated dirt

       Capacitors, ballasts, drums, etc.

              Totally enclosed  shredder
         Liquid  organic waste—y

         Liquid  aqueous waste -v\
         Combustion air
                         Liquid aqueous waste
                      i— Liquid organic wastes (fuel)
                                 Rotary kiln
                                 2.1 * 10.4 m
                                 Ferrous metal
                                   recovery —
                         Combustion air  4-
Exhaust air
                          84.9  m3
  Chemical encipsubtion
  of scrubber sludge and
  ash for landfill
   Deep well injection
   of brine
Sludge lagoon
                     84.9 m3 Secondary
                      I    chamber
         , Oemister
                                                                              Lime mixing
                                                                      Stack drain
                Figure 4.1.2.  Schematic  of ENSCO stationary  incinerator [M.M.  Dillon,  1983].

 4.1.2  Technology Performance Evaluation

     As  discussed in the previous subsection, three commercial-scale
 stationary rotary kiln incinerators have demonstrated six nines ORE (99.9999%)
 for PCBs and are permitted to burn PCBs.  Trial burns of dioxin wastes have
 not been conducted at any of the commerical-scale stationary rotary kiln
 incinerators due to strong public opposition*  However, trial burns of
 dioxin-containing wastes have been performed using the stationary rotary kiln
 incinerator at the U.S. EPA Combustion Research Facility (CRF) in Jefferson,
     The CRF is a 3100 sq.ft. permitted experimental facility built for the
 purpose of conducting pilot scale incineration burns and evaluating whether
 incineration is an effective treatment/disposal option for various types of
 hazardous waste.  During September 1985, trial burns were conducted at the CRF
 using dioxin-containing toluene still bottoms (Ross, et al., 1986).  These
 were generated by the Vertac Chemical Company in Jacksonville, Arkansas and
 stored there pending an EPA decision on appropriate treatment/disposal.
     The CRF contains two pilot-scale incinerators and associated waste
 handling, emission control, process control,, and safety equipment
 (Games, 1984).  Additionally, onsite laboratory facilities are available to
 characterize the feed material and process performance samples.  As shown in
 Figure 4.1.3, the main components of the CRF incineration system include a
 standard rotary kiln incinerator, an afterburner and a conventional air
 pollution control system (Games, 1984; Ross, et al., 1986;
 Ross,  et al., 1984).  Waste fed into the kiln flows countercurrent to  the
 primary burner (concurrent configuration is also possible).  The
 monitoring/control equipment for the kiln includes a propane meter, a  pitot
 tube to monitor primary combustion air, a shielded thermocouple to control
 temperature, and monitoring equipment for combustion gas composition and flow
 rate.   Organic components are determined by extractive sampling through a
 heat-traced sampling line and a liquid impinger (from EPA Method 5) or a
 volatile organic sampling train (VOST) (Games, 1984; Ross, et al., 1986;
Ross,  et al., 1984).

     Following combustion in the kiln, the combustion gases are directed
 through a refractory-lined transfer duct to the afterburner.  A shielded
 thermocouple  is used to control temperature in the afterburner.  Surface
 temperature,  exit gas temperature and combustion gas composition and flow rate
 are monitored.  Exhaust gases are cleaned in the air pollution control system
 which consists of a variable throat venturi scrubber, a fiberglass reinforced
 polyester wetted elbow, a packed tower caustic scrubber, and an induced draft
 fan (Carnes,  1984; Ross, et al., 1986; Ross, et al., 1984).
     A total  of four trial burns were performed in 1985 between September 4th
 and September 21st.  These included a blank burn to establish .background
 emission levels, a short-duration (4 hrs.) burn to establish feed capabilities
 and to test the sampling protocol, and two full waste burns (10 hr. duration)
 to establish  the DREs for dioxin (Ross, et al., 1986).
     The results of the two full waste burns are presented  in Table 4.1.1.
 The data show that the 2,3,7,8-TCDO ORE was greater than 99.9997 percent as
 measured in the virtual stack (E-DUCT) which would correspond  to the stack of
 an actual hazardous waste incinerator.  The reason six nines DRE could not be
 established was that the detection limits experienced in the sampling and
 analysis protocols used were not sufficiently  low (Ross, et al., 1986; Carnes,
 1986).  Despite this, it was concluded from the data in the study that
 "incineration under the conditions existing in the CFR pilot incineration
 system for these tests is capable of achieving 99.9999 percent dioxin DRE"
 (Ross, et al., 1986).  It was further concluded that land-based incineration
 should be considered a viable disposal method  for the Vertac still bottoms
waste given that appropriate safeguards are employed (Ross, R. W., et al.,
     The concentrations of 2,3,7,8-TCDD and other CDDs and  CDFs were also
measured in the scrubber blowdown water and kiln ash (Ross, et al.,  1986).
The maximum concentration of 2,3,7,8-TCDD detected in the  scrubber blowdown  •
was 0.12 picograms per milliliter (approximately 0.1 ppt).  In most  samples of
blowdown, all forms of CDDs were undetected at detection limits of 0.006  to
0.020 pg/ml.  In one sample, however, 0.78 pg/ml of Octa-CDD was detected.  No
2,3,7,8-TCDF was detected in any blowdown samples.  Total  TCDF was  detected  at
0.20 pg/ml in all 4 samples.  Tetra-, penta-,  hexa- and hepta- CDD and  CDFs
were not detected in any of the kiln ash samples at detection limits ranging
from 1.3 to 37 picograms per gram (ppt).

     Since  in all cases the residues from this incinerator contained CDDs and
CDFs at levels below I ppb, it would be.expected that these residues could De
land disposed in accordance with the screening levels proposed in 51 FR 1602.
These screening levels are based on the use of a different analytical method
(Method 8280) than used in the present situation.  Therefore,  definite
conclusions cannot be made.  Nonetheless, the concentrations of CDDs and CUFs
detected in the treatment residues indicate that a high degree of destruction
did occur.
     Several problems encountered during the trial burns should be mentioned.
These include (Ross, et al.,  1986):

     I.   Waste was fed into the kiln through a water-cooled feed lance using
          a Moyno cavitation pump.  The lance frequently became clogged due  to
          carbon-buildup from coking of the waste material.
     2.   The test plan called for continuous monitoring of flue gas, CO^,
          02, CO and NOX, at the stack with one set of emission analyzers
          and at the kiln exit and afterburner exit on a time-share basis with
          another set.  However, only one set of emission analyses was
          operational during most of the test series.  Therefore, no kiln
          emission monitoring data were obtained.  Very little simultaneous
          afterburner exit and stack data were obtained.
     3.   An air leak in the sample transfer line from the afterburner exit  to
          the monitors caused the data to be "substantially compromised".
          Also,  difficulties were encountered while monitoring by means of the
          isokinetic Method 5 sampling train (MM5).  The glass frit  in the MM5
          train condensor/XAD2 sorbent cartridge frequently became plugged.
          Most exhaust and stack sampling was at less than 50 percent
          isokinetic, which compromises the particulate emission results.

4.1.3     Costs of Treatment

     Currently,  there are no stationary kilns permitted to burn dioxin
wastes.  Thus,  no costs are available.  However, these costs would  be expected
to be similar to or greater than the costs for PCBs incineration.  Table 4.1.2
lists the average unit coats for PCBs wastes at the currently permitted
stationary rotary kiln facilities.

4.1.4  Process Status

     Land-baaed incineration systems with potential to treat dioxin wastes
include commercial incineration facilities which have been approved for PCB
disposal, in addition to RCRA hazardous wastes.  These incinerators are
operated by Rollins Environmental Services (Deer Park, Texas),  ENSCO
(El Dorado, Arkansas) and SCA (Chicago, Illinois).  Each of these systems
contains a rotary kiln incinerator followed by an afterburner section which
can also be used independently as a liquid injection incinerator.
     The Rollins and ENSCO facilities can accept both liquid and solid wastes,
but the SCA incinerator has only been approved for the disposal of liquid PCB
wastes.  The following are the maximum feed rates for these land-based
incineration systems (GCA, 1985; Clarke, 1986):

     Rollins                         1,440 Ib/hr for solids
     (Deer Park, TX).                6,600 Ib/hr for liquids
     ENSCO                           2,500 Ib/hr for solids
     (El Dorado, AK.)                5,000 Ib/hr for liquids
     SCA                             2,910 Ibs/hr for solids
     (Chicago,  IL.)                  6,300 Ibs/hr for liquids

Although none of these facilities has conducted trial burns for the
destruction of dioxin-contaminated waste, their ability to demonstrate six
nines DRE for PCBs suggests that they would be able to destroy dioxins.
Results of trial burns using the CRF pilot-scale rotary kiln incinerator  show
the potential for dioxin destruction at the RCRA regulated DRE.




ITHC. NO.. SOj. Oj. CO COjl

            Figure  4.2.1.   Schematic of  EPA  mobile incineration system  [U.S.  EPA,  1984].

                                 "1 DEAERATOR

                                            WASTE HEAT
                  •T——"     PUILtH
                                          I   BLOWOOWN
                              •TLTRATION AIR
                               Rowrr KILN
                    •——1  _^~    "NJ 1^


                           	J^CIRC TANK
                Figure 4.2.2.  Schematic flow diagram of ENSCO MWP-2000 Mobile Rotary Kiln Incinerator
                             [Pyrotech Systems, 1985].

Operating Parameters—
     Operating parameters for the two mobile rotary  kiln systems are
summarized below (U. S. EPA, 1984; Sickels,  1986;  Freestone, et al.,  1985):

                                EPA/MIS                  ENSCO

Waste Forms                     Solid*,                  Solids,
                                Liquids                  Liquids

Maximum Waste Feed Rat* (Ib/hr)
  -Solids to Rotary Kiln          9,000                  10,000
  -Liquids to Rotary Kiln                                 3,000
  -Liquids to SCO                 1,500                   4,000

Kiln Temperature (°F)              1800                    1800

SCC Temperature (°F)               2200                    2200

SCC Residence Time (sec)            2.2                       2

     Severe weather conditions can effect the operation of the mobile

incinerator.  For instance,  extremely cold weather during the  initial stages

of the EPA Mobile incinerator trial burns on the Denney Farm site  caused the

No. 2 diesel fuel to gel, hydraulic fluids to thicken,  and water  lines to

freeze (IT Corporation, 1985a; Krogh, 1985).

4.2.2     Technology Performance Evaluation

     Initial trial burns with the EPA mobile incinerator were  conducted in

Edison, New Jersey using surrogate compounds to mimic RCRA-listed constituents
such as dichlorobenzene, trichlorobenzene, tetracblorobenzene,  and PCBs.  In

these liquid waste trial burn*, up to six nines DRE of PCBs was  demonstrated.

Following this,  laboratory studies were conducted to establish optimum

conditions for treating soils contaminated with dioxin.  The following

conclusions were made based on these studies (IT Corporation,  1985a):
          Thermal treatment of contaminated Missouri soils was capable of
          achieving I ppb or lower concentration of residual 2,3,7,8-TCOO and
          other chlorinated dioxins and chlorinated furans in the incinerator


         TABLE 4.2.1.
     Soil type
            Test purpose
Denney Farm
Area Soil
Coral from Florida
(New Jersey) Soil
    To ensure that there were
    no unusual problems with
    soil from that area; Site
    soil was very dry from being

    Planned to be used as the
    Solids Carrier in Test 1
    of Solids Trial Burn

    Potential Future Use of
    EPA/MIS for U.S. Air Force
    on Johnston Island
    Contaminated Coral

    Readily Available Soil
    in the Missouri Area
18 mg/Nm3
                                                                17 mg/Nm3
                                                                9 mg/Nm3
Not Available
Reference:  IT Corporation, I985a.

TABLE 4.2.3.
        Toxic Constituent
                                                 ScruDoer water
2, 3, 5-Trichlorophenol
2 , 4, 6-Trichlorophenoi
2, 5-Dichlorophenol
2, 3, 4, 5-Tetrachlorophenol
1,2,4, 5-Tetrachlorobenzene
1,2,3, 5-Tetrachlorobenzene
Polychlorinated Biphenyla
BenzoC a) anthracene
DibenzoCa, h) anthracene
IndenoC 1,2, 3-c,d) pyre ne
BenzoC b)f louranthene
I ppb
100 ppm
100 ppm
1 ppm
350 ppb
100 ppm
I ppm
I ppm
100 ppm
100 ppm
200 ppm
2 ppm
5 ppm
5 ppm
50 ppm
5 ppm
5 ppm
5 ppm
10 ppt
10 ppm
10 ppm
50 ppb
15 ppb
10 ppm
50 ppb
5U ppb
10 ppm
10 ppm
5 ppm
1 ppm
10 ppb
10 ppo
I ppm
10 ppb
10 ppb
10 ppb
•Weighted average of TCDD«/TCDF», PeDDa/PeDFs, and HxCDDs/HxCDFs using
 toxicity weighting factor*.

Reference:  Poppiti, 1985; U.S. EPA, 1985.

     Average operating parameters during the trial burn for dioxin-contaminated
 soil and  liquids were as follows (IT Corporation, 1985 a and b;  U.  S.  EPA,

               Kiln Temperature        '            1800°F
               SCC Temperature                      2200°F
               SCC Combustion Gas                   13,500 acfm
               Flow Rate
               SCC Residence Time                   2.6 seconds
               Waste Feed Rate                      2000 Ib/hr (soil)
                                                    250 Ib/hr (liquid)
               Auxiliary Fuel
                 -Kiln   5 to 6 million Btu/hr
                 -SCC    4 to 5 million Btu/hr

     Following the successful (demonstrating  99.9999 percentDRE) completion
of these preliminary trial burns, additional test burns were planned  for the
EPA/MIS as summarized in Table 4.2.4.  As noted  in the table, burns of the
material from five of these sites (Denney Farm, Neosho, Erwin Farm, and Talley
Farm) have been completed.  The total amount of dioxin-contaminated material
that was successfully burned (i.e., achieved greater than six nines DRE)
included 2 million pounds of soils and  180,000 pounds of liquids (Hazel, 1986;
Freestone, 1986).  The material from the remaining sites listed in Table 4.2.4
is scheduled to be burned as soon as funding becomes available  (Hazel, 1986).
Currently, the amount of dioxin-contaminated material that remains to be
burned includes 600,000 pounds of soil  and 80,000 pounds of  liquid wastes
(Hazel, 1986).
     During the incineration of the dioxin-contaminated wastes  from  these
sites, several parameters were monitored continuously, including:  CO, CO.,
0_, NO , operating temperatures and feed rates (Hazel, 1986; Freestone;
1986).  Built-in safety controls cause  the operations to stop if any  of  these
parameters are not within the proper range (Hazel, 1986).  In addition,  the
waste residues from the burns (i.e., ash and water) are continually
monitored.  To date, dioxin has never been found in the burn residues (Hazel,
1986).   More detailed data will be available in  the Final  Report  scheduled for
release within the next few months (Freestone, 1986).

              PCB TRIAL BURN
        Condition                            Result

     PCB ORE                     >99.9999Z

     Carbon Monoxide              20 ppm

     Nitrogen Oxides              300 to 500 ppm

     Particulate                  Met or exceeded all  standards

     HC1 Scrubbing                99Z at 1,500  Ib UCl/hr

     Reference:   Sickels,  1986;  Pyrotech Systems,  1985.

       Initially, ENSCO encountered slagging problems which were  solved by
adding six chutes to the secondary unit and a cyclone was installed prior to
the secondary unit to remove fine particulates (Pyrotech Systems,  1985).
These modifications increase the treatment costs.
       One of the MWP-2000 units is currently located at a site near Tampa,
Florida where it is being used to clean up a site containing liquids
contaminated with chlorinated organics (McCormick, 1986; Lee, 1985).  A second
MWP-2000 unit located at the El Dorado, Arkansas facility (i.e.,  the location
of the ENSCO stationary rotary kiln system) has just completed a series of
dioxin trial burns using wastes from the Vertac Site.  The results are
expected to be released in Nay 1986 (McCormick, 1986).  The construction of
the third MWP-2000,  a computer-operated unit, is not complete yet.  Upon
completion, this third unit is scheduled to undergo tests by the Air Force  to
handle dioxin-contaminated coral at Johnston Island (Lee, 1985; McCormicK,

                         OR TO SCRUBBERS AND STACK
            WASTE LINE
                                                    — DECOMPOSITION CHAMBER
                                                         DECOMPOSITION STREAM
                                                         AFTER-BURNER FAN




0^12345 fttt

 Appro*imote Scon
                                              ELECTRICAL POWER LINE
   Figure 4.3.1.   Vertically-oriented Liquid  Injection Incinerator
                    [Bonner,  1981].

 Operating  Parameters—
      Typical  operating parameters for the vertically-configured LI  incinerator
 on the  Vulcanus are as follows (U. S. EPA, 1983; U.  S.  EPA,  1978):

      Residence Time                0.5 to 2.0 seconds
      Temperature                   650 to 1750°C (1200 to 3180°F)
      Air Feed Rate                 65,000 to 75,000 m3/hr
      Waste Feed Rate Capacity      7 to 10 tons/hr

 4.3.2    Technology Performance Evaluation

      The only documented burns of waste containing dioxins in a liquid
 injection incinerator are those that took place on board incinerator ships.
 These burns took place between July and September 1977.  Three shiploads
 (totalling approximately 10,400 metric tons) of U.S. Air Force stocks of
 Herbicide Orange were incinerated by the M/T Vulcanus in the Pacific Ocean
 west  of Johnston Atoll (U. S. EPA, 1978).  A summary of the DREs achieved in
 these burns and other U.S.-sponsored ocean burns is presented in Table 4.3.1.
 Operating parameters for these Herbicide Orange trial burns are summarized in
 Table 4.3.2.
      The Herbicide Orange stock consisted of an approximately 50-50 volume
mixture of the n-butyl esters of 2,4-dichlorophenoxyacetic acid (2,4-0) and
 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) (U. S. EPA, 1978).  A small
 quantity of the stock contained a 50-50 volume mixture of 2,4-D and the
 iso-octyl ester of 2,4,5-T.  Certain lot* also contained 2,3,7,8-TCDD ranging
 in concentration from 0 to 47 ppm (with an average concentration of 1.9 ppm).
Drums containing the waste stock and waste handling equipment were rinsed with
diesel fuel which was subsequently mixed with the waste feed to increase its
 heating value for incineration (U. S. EPA, 1978).


               Flame Temperature              1375-1610'C
               Furnace Wall Temp.             UOO-1200°C
               Residence Time                 1.0 to 2.0 seconds
               Reference:  U. S. EPA, 1978

     During the period from December 1981 through January 1982, the first
ocean burn of PCBs was performed in U.S. waters (U. S. EPA, 1983).  A second
shipload of PCB-containing wastes were incinerated aboard the M/T Vulcanus
during August 15-31, 1982 (U. S. EPA, 1983).  Operating parameters for the
PCBs burns are sunmarized in Table 4.3.3.  An EPA-sponsored test project was
performed during the second PCBs trial burn to measure emissions of
polychlorinated biphenyls  (PCBs), chlorobenzenes (CBa),
tetrachlorodibenzofurans (TCDFs), and tetrachlorodibenzo-p-dioxins (TCDDs).

                             PCB TRIAL BURNS USING LIQUID INJECTION
                             INCINERATION ON THE VULCANUS

               Flame Temperature              1648-2048°C
               Furnace Wall Temp.             1281-1312°C
               Residence Time                 1.1 to 1.5 seconds
               Feed Rate                      5.23-6.79 mt/hr
               Reference:  U. S. EPA, 1983.
     No TCDDs were detected in any sample of waste or stack gas during  the
tests.  Detection limits for the waste ranged from less than 2 ppb to less
than 22 ppb.  TCDFs, however, were detected in the waste feed at ppb  levels
and in the stack gas at low ppt levels. [USEPA, 1983]

Trial burn results
Temperature Inside the Reactor Chamber

Residence (Dwell) Time of Combustion Products

Combustion Efficiency

Oxygen Concentration during PCB Incineration

Waste Oil Firing Rate

PCB Concentration in Oil

Average PCB Destruction Efficiency

Average PCB Destruction and Removal Efficiency

HC1 Scrubber Efficiency

Particulate Emissions @ 12Z
NOX Emissions
RC1 Emissions

HC1 Emissions

Reference:  Tnayer, et al.. 1983.
1,262°C - 1,
(2,303°F - 2,085°F)

4.02 sec


9.5 - 10.51

1.09 - 119 GPM

18.4 - 20.OZ




0.543 Ib/hr
0.0361 gr/dscf

18.3 ppm
0.43 Ib/hr

0.000304 ppm
0.00002542  Ib/hr

0.2752  Ib/hr


 4.4.1     Process Description

      The  fluidized bed incinerator uses"high temperature oxidation under
 controlled conditions to destroy organic constituents in liquid,  gaseous,  and
 solid waste  streams.  It is typically used for slurries and sludges.
      As shown in Figure 4.4.1, a typical fluidized bed incinerator consists of
 a vertical refractory-lined cylindrical vessel containing a bed of inert
 granular material (typically, sand) on a perforated metal plate.   The waste
 (in the form of either gas, liquid, slurry, or sludge) is usually injected
 into or just above the stationary bed.  The granular bed particles are
 fluidized  by blowing air upward through the medium.  The resulting agitation
 ensures intimate mixing of all waste material with combustion air (McGaughey,
 et al., 1984; Bonner, 1981).
      A burner located above the bed is used to heat the bed to start-up
 temperature.  The large mass and high heat content of the bed causes the waste
 to rapidly combust which, in turn, transfers heat back to the bed.  The
 maximum temperature of the granular bed is limited by the softening point of
 the bed material (for sand this temperature is 1100°F).  The residence time of
 waste material  in the bed typically ranges from 12 to 14 seconds for liquid
 wastes.  TV* solid uncombustible materials in the waste become finely
 suspended  particul*te matter which is separated in a cyclone while the exhaust
 gases pass through an afterburner to destroy vapor-phase residuals (McGaughey,
 et al., 1984; Bonner, 1981).
      Waste Tech Services, Inc. has developed a Low-Temperature Fluidized Bed
 that  functions  similarly to the conventional fluidized bed except that a
 higher air volume is forced through the bed material (Rasaussen, 1986;
 Freeman, 1985).  Also, the bed is composed of a mixture of a granular
 combustion catalyst and limestone.  Limestone is continuously added  to the  bed
 and the bed material ia periodically drained from the vessel. A multicyclone
 system employing a baghouse to clean the flue gas is used for air-pollution
control.   The Waste-Tech fluidized bed is able to operate at lower
temperatures than conventional fluidized bed* and also has reduced
supplemental fuel requirements (Rasmussen, 1986; Freeman, 1985).

      Another modification of  the conventional fluidized bed technique  that  has
 been developed is  the  Circulating Fluidized Bed Com buster (Figure 4.4.2).   It
 utilizes contaminated  soil as  the bed material and air flow rates 3 to 5 times
 greater than conventional  systems (Rickman, et al., 1985; Vrable, et al.,
 I985a and b; Barner, 1985).  The high air flow causes increased turbulence
 which allows for efficient  combustion at much lower operating temperatures
 without requiring  the  use  of an afterburner.  A comparison of the circulating
 fluidized bed combustor with the conventional fluidized bed is shown in
 Table 4.4.1.
      The startup combustor burner consists of a natural gas fuel system
 (Rickman,  et al.,  1985; Vrable, et al., 1985a and b; Barner, 1985).  It has a
 4 to 6 hour  cold startup  period, and an approximately 30 minute hot restart
 (with a refractory temperature at or greater than 1400°F).  The startup burner
 is generally idle  during waste burning unless the waste feed is interrupted
 and it is  required to maintain a low combustor temperature.  The combustor is
 a carbon-steel tube with  refractory lining which consists of an
 erosion-resistant inner layer and a thermal insulating outer layer.  Prior to
 being injected into the combustion chamber the waste feed is mixed with hot
 recirculating solids from  the cyclone.  Both the waste feed and the
 recirculated solids are introduced into the combustion chamber.  Liquid and
 slurry waters are pumped from stirred tanks whereas a metering screw is used
 to convey  solids and sludges.
      The combustor has primary and secondary air ports through which
 fluidizing air is provided by a constant-speed, motor-driven forced-draft fan
 (GA Technologies,  1985; Rickman, et al., 1985).  The high air velocity (15 to
 20  feet/second) entrains both the bed and the combustible waste which rise
 through the  reaction zone to the top of the combustion chamber and pass into a
hot cyclone.
     The cyclone is constructed of carbon-steel and lined with castable
refractory lining.   The function of the cyclone is to separate bed material
from the combustion gases and recirculate these solids to the combustion
chamber.  The hot  combustion gases flow to an off-gas heat exchanger where
they are cooled to 375°F and then directed to baghouse filters to remove any
residual products  of incomplete combustion (GA Technologies, I9bi; Ricwnan, et
al., 1985).

Circulating fluidized bed     Conventional fiuidized  bed

  No. of Inlets

  Sludge Feeding

  Solids Feed-size

Pollution Control



  Upset Response




1-solid; 1-liquid



5-solid; 5-liquid


<0.5-0.25 in.
In high temp, combustor
or afterburner

Downstream scruboer

Bypass scrubber pollution

Wet Ash Sludge

Reference:  Rickman, et al., 1985

4.4.2  Technology Performance Evaluation

     Fluidized beds have been used Co treat municipal wastewater treatment
plant sludges, oil refinery waste, pulp and paper mill waste,  pharmaceutical
wastes, phenolic wastes, and methyl methacrylate.  Pilot-scale demonstrations
have been performed for other hazardous wastes.   Currently,  there are more
than 25 circulating bed combustors operating in the U.S.  and Europe.  However,
there are currently no units operating commercially as hazardous waste
incinerators (Freeman, 1985; Rickman, et al., 1985).
     The low-temperature fluidized bed combustor (designed by Waste Tech
Services, Incorporated) was used to conduct trial burns on soil contaminated
with carbon tetrachloride and dichloroethane (Freeman, 1985).  Only four nines
DRE was demonstrated.  The results of these tests are summarized in Table
     GA Technologies has conducted trial burns on its pilot scale circulating
bed combustor using chlorinated organic liquid wastes.  The combustor was
operated at 1540 to 1600°F with a gas velocity of 11 to 12 feet/second and 45
to 60 percent excess air.  Limestone was injected into the incinerator  with
the liquid waste feed to prevent the formation of HC1 by capturing the
chlorides formed.  The following results were obtained (Rickman, et al., 19»5;
Chang and Sorbo, 1985):
       NOX emissions                           40 ppm (average)
       SC>2 emissions                           250 to 350 ppm
       CO emissions                             1000 ppm
       Chloride Capture                         99Z
       Flue Gas Emissions (Z-DRE)
             - Ethylbenzene                    >99.99
             - 1,1,2-trichloroethane           >99.99
             - 1,2-dichloroethane              >99.99
             - l,l-dichloroethylene            >99.99
             - 1,2-transdichloroethylene       >99.99
             - vinyl chloride                  >99.99
             - toluene                         >99.99
             - benzene                         >99.99

     The pilot-scale unit was also used to conduct  trial  burns on
PCB-contaminated soil (Rickman, et al., 1985;  Chang and Sorbo, 1985).  An
auxilliary fuel was used to maintain bed temperature at 1600  to  1800°F.  A
destruction efficiency exceeding six nines (99.9999 percent)  was achieved.  A
summary of the test conditions and results is  given in Table  4.4.3.

4.4.3.  Costs of Treatment

     The costs for the conventional fluidized  bed are dependent  on fuel
requirements, scale, and site conditions.  However, the costs are generally
comparable with conventional rotary kiln incineration technology.  Waste-Tech
Services, Inc. lists the costs in Table 4.4.4  as being typical for their
low-temperature fluidized bed (Freeman, 1985).
     Costs for the circulating bed combustor vary according to the size of the
incineration unit, and the type of waste being processed.  Estimated costs for
a 25 million Btu/hr unit are given in the Table 4.4.5 (Freeman,  1985):

4.4.4  Process Status

     Currently, there are several fluidired bed combustors operating
worldwide.  Although fluidized beds have been used  in various industries,  at
the present time there are not any fluidized beds operating commercially as
hazardous waste incinerators.  However, the fluidized bed, particularly the
circulating fluidized bed, appear to have  significant potential for  future use
in the destruction of hazardous wastes.
     The low-temperature fluidized bed  developed by Waste Tech  Services
requires additional testing  and/or development, but could potentially be used
for the destruction of dioxin  contaminated wastes.
     A stationary pilot scale  circulating  fluidized bed  unit  capable of
incinerating a ton per hour  of hazardous waste  is  in operation  at the GA
Technologies test facility.  A transportable  incinerator has  also been
constructed for use in onsite  demonstrations  on PCBs contaminated wastes.
Although dioxin trial burns  have  not been  conducted, GA  Technologies would be
interested in performing dioxin testing if funding were  available (Jensen,


                 TABLE 4.4.4.    WASTE-TECH FLUIDIZED  BED COSTS
                Item                   .               Cost
     Operating Labor                               0.0084  t/lb

     Consumables and Utilities                     0.0138  t/lb

     Nonlapor (capital depreciation,
     siting cost, maintenance mat'Is,
     insurance, tax overhead)                      0.0116  $/lb

     Limestone for Chlorine Removal,
     Waste Excavation, Ash Disposal, etc.          0.043   $/lb

     TOTAL COST                                     $150/ton
Note:  These cost estimates are for a SO sq.ft. system with a throughput of
       9,200 Ib/br for soils having 2 percent organics and 5 percent moisture
                       Installed              Annual            Total Cost per
Feed Type               Capital              Operating           Unit of Feed
                         Costs                 Costs
Organic Sludge       $2.0 million           $0.25 million             $60/ton

Wet Sludge
$1.8 million
$1.8 million
$0.35 million
$0.35 million
Note:  Costs are based on the use of a  25 million Btu/hr  unit.

                                           3. POWER CLAMP

                                           9. POROUS CORE
                                          13. RADIOMETER PORT
                                            . BLANKET GAS INLET
             Figure 4.5.1. Advanced Electric Reactor [Huber],

residence time (5 seconds).   The second postreactor treatment  zone  is
water-cooled, and its primary purpose is to cool the gas  prior to downstream
particulate cleanup.
     Off gas cleaning equipment includes a cyclone to collect  particles which
do not fall into the solids bin, a bag filter to remove fines, an aqueous
caustic scrubber for acid gas and free chlorine removal,  and two banks of five
parallel activated carbon beds in series for removal of trace  residual
organics and chlorine.
     The stationary pilot scale reactor which has been used for testing
various wastes at their Borger, Texas facility consists of a porous graphite
tube, 1 foot in diameter and 12 feet high, enclosed in a hollow cylinder with
a double wall cooling jacket.  This pilot unit is capable of processing 5000
tons/yr of waste.  Huber also has a 3 inch diameter mobile unit which has been
transported to hazardous waste sites for testing purposes.  Test results are
described below.

Restrictive Waste Characteristics—
     The AER cannot currently handle two-phase materials (i.e.,  sludge); it
can only burn single-phase materials consisting of  solids, or  liquids,  or
gases alone (Schofield, 1985; Boyd, 1986).  Generally, a solid  feed must be
free flowing, nonagglomerating, and smaller than 100 mesh  (less  than  149
micrometers or 0.0059 inches) (GCA, 1985; Shofield,  1985).  However,  depending
on the required destruction, solids larger than 100 mesh (but  smaller than
10 mesh) may be suitable.  Soils should be dryed and sized before  being fed
into the reactor.
     Also, the Huber process is not cost competitive with  standard thermal
destruction techniques (such as the rotary kiln)  for materials with a high Btu
content (Schofield, 1985; Boyd, 1986).  It is  cost-effective  for wastes with  a
low Btu content (i.e., PCBs and dioxin) because unlike standard thermal
destruction techniques, the Huber process does not require supplementary fuels
to obtain the necessary Btu content for incineration.

                         FOR HUBER AER RESEARCH/TRIAL BURNS
Reactor Core
Temperature (F)
Waste Feed
Rate (Ib/tnin)
Nitrogen Feed
Rate («cfm)
(Sept. 1983)
>99. 99999
(May 1984)
(Oct/Nov 1984)
Reference:  Schofield, 1984; Roy F. We•ton, 1985.

 4.5.3  Costa  of  Treatment

      Operating costs will vary depending on the quantity of material  to  be
 processed and the characteristics of the waste feed (Lee,  et al.,  iy«4).
 Pretreatment  may be necessary for bulky wastes having a high moisture
 content.  Typical energy requirements for normal soil range from 8UO  to  1000
      Cost estimates for processing a site containing more than 100,QUO tons of
 waste material were approximately $365 to $565/ton in 1985 (Lee,  et al.,  1984;
 Freeman and Olexsey, 1986).  The cost breakdown for this estimate was
 12 percent for maintenance, 7 percent labor, 29 percent energy,  18 percent
 depreciation  and 34 percent for other costs (permitting, setup,
 post-treatment,  etc.).  These costs have recently been updated.   The  new costs
 are expected  to  be released in May 1986 (Boyd, 1986).

 4.5.4  Process Status

     The J.M. Huber Corporation purchased the patent rights from Thagard
 Research Corporation.  Huber then modified the design of the reactor
 (primarily the feed tube and the core design) to improve the efficiency  of the
 reactor, extend  the lifetime of the electrodes and core material, and to
 reduce sticking  of vitreous material on the core walls (which lowers
 efficiency) (Boyd,  et al., 1986).
     Huber maintains two fully-equipped reactors at their pilot facility in
 Borger, Texas (Schofield, et al., 1985).  The smaller reactor, which is
 equipped for mobile operation, has a 3-inch core diameter and a capacity of
 0.5 Ib/min..  The larger reactor is commercial scale with a 12-inch core
 diameter and a capacity of 50 Ib/min.  Both of these reactors are used
 primarily for research purposes.  In May 1984, the Huber reactor was  certified
 by the EPA under TSCA to burn PCB wastes.  Recently, the U.S. EPA and the
Texas Water Commission jointly issued J.M. Huber Corporation a RCRA permit
which authorizes the incineration of any non-nuclear RCRA hazardous waste
 (including dioxin-containing wastes) in the Huber Advanced Electric
Reactor (AER)(HMIR,  1986).  This was the first commercial permit issued under

 4.6.1  Process Description (Daily, 1986; Shirco,  1985;  Freeman and Olexsey,
        1986; HMIR, 1986; Technical Resources Inc.,  19b5; Daily, iy»5)

      Shirco Infrared Systems, Inc. has developed a portable  infrared
 incineration system, which can be transported in a 45 ft trailer.  The major
 components of the system include a feed metering system, an  infrared  primary
 chamber furnace, a combination propane-fired/infrared secondary chamber, a
 venturi scrubber system, blower and heating control systems,  and  a monitoring
 and control system.
      The waste material is fed by bucket or inclined conveyor onto a  metering
 conveyor which controls the amount and rate of waste feed  into the primary
 furnace.  The primary furnace chamber is constructed of carbon steel, lined
 with multiple layers of ceramic fiber blanket-insulation mounted  on stainless
 steel studs and retained with ceramic fasteners.  The external dimensions  of
 the primary chamber are 2.5 ft x 9 ft x 7 ft, and it weighs  (installed)
 3,000 Ibs.  Infrared heating elements, consisting of silicon carbide  rods  with
 external electrical connections at each end, are spaced along the length of
 the furnace.  The chamber can be heated to temperatures ranging  from  500 to
 1,050°C.  Residence times for the feed material are variable ranging  between
 10 and  180 minutes. The temperatures and times will depend on the
 characteristics of the waste.
     Following combustion, the ash (or processed material) is conveyed to  the
end of the furnace where it drops off the belt and passes  through a chute  into
 an enclosed, tapered hopper.  A discharge screw conveyor controls transport  of
 the discharged material from the hopper into sealed collection drums.
     Combustion air is forced through a combustion air preheater and then
 injected at 10 points along the length of the primary chamber furnace.
Depending on the waste characteristics, the exhaust gases  may be directed  to a
secondary combustion chamber to complete gas-phase combustion reactions.
     The secondary chamber is a rectangular carbon steel box lined with a
ceramic fiber blanket insulation.  The secondary chamber weighs  1,500 Ibs  and
has external dimensions of 3 ft x 9 ft x 3 ft.  Combustibles in the gas are
ignited via a propane-fired burner and are maintained at a predetermined
setpoint temperature using an array of silicon carbide heating elements which


                    DESTRUCTION PILOT TESTS
Condition Test 1
TCDD in Feed
(ng/g) 227
Solid Phase
Residence Time
Uin) 30
Solid Feed
Rate (Ib/hr) 47.68
Primary Chamber
Temp. -Zone A (°F) 1560
Primary Chamber
Temp. -Zone B (°F) 1550
Secondary Chamber
Temperature (°F) 2250
Emissions Sampling
Duration (hours) 7
Particulate at
7Z 02 (gr/dscf) 0.0010
Gas Phase DRE of
2, 3, 7, 8, -TCDD >99. 999996
at Detection Limit
(pic OR rams) 14
Ash Analysis for
2,3,7,8-TCDD ND
at Detection
Limit (ppt) 38
>99. 999989
Reference:  ERT, 1985; Daily, 1986.


 4.7.1  Process Description

 Operation  and Theory—
      In this process waste molecules are destroyed by the action of a thermal
 plasma  field.  The field is generated by passing an electrical charge through
 a  low pressure air stream, thereby ionizing the gas molecules and generating
 temperatures up  to 10,000'C.
      A  flow  diagram of the plasma pyrolysis system is shown in Figure 4.7.1.
 The plasma device is horizontally mounted in a refractory-lined pyrolysis
 chamber with a length of approximately 2 meters and a diameter of 1 meter.
 Liquid  wastes are injected through the colinear electrodes of the plasma
 device  where the waste molecules dissociate into their atonic elements.  These
 elements then enter the pyrolysis chamber which serves as a mixing zone where
 the atoms recombine to form hydrogen, carbon monoxide, hydrogen chloride and
 particulate carbon.  The approximate residence times in the atomization zone
 and the recombination zone are 500 microseconds and 1 second, respectively.
 The temperature  in the recombination zone is normally maintained at
 900-1,200°C  (Barton, 1984).
      After the pyrolysis chamber, the product gases are scrubbed with water
 and caustic  soda to remove hydrochloric acid and particulate matter.  The
 remaining gases, a high percentage of which are combustible, are drawn by  an
 induction fan to the flare stack where they are electrically ignited.  In  the
 event of a power failure, the product gases are vectored  through an  activated
 carbon  filter to remove any undestroyed toxic material.
      The treatment system that is currently being used  for  testing purposes  is
 rated at 4 kg/minute of waste feed or approximately 55  gal/hour.  The  product
 gas production rates are 5-6 m /minute prior to flaring.  To facilitate
 testing, a flare containment chamber and 30 ft stack have also been  added  to
 the system.  The gas flow rate at the stack exit is approximately
 36 m  /minute (Kolak, Barton, Lee, Peduto, 1986).
     A  major advantage of this system i* that it can be moved  from waste  site
 to waste site as desired.  The entire treatment system,  including a
 laboratory, process control and monitoring equipment, and transformer and
switching equipment, are contained on a 45 ft tractor-trailer  bed  (Barton,

      Two residual streams  are generated by this process.  These are the
 exhaust gases  released  up  the stack as a flare, and the scrubber water
 stream.  Since the product gas  (after scrubbing) is mainly hydrogen, carbon
 monoxide,  and  nitrogen,  it burns with a clean flame after being ignited.
 Analysis of  the  flare exhaust gases, presented in the following section,
 indicates  virtually complete destruction of toxic constituents.
      The scrubber water stream  is composed mainly of salt water from
 neutralization of HC1 and  particulates, primarily carbon.  Analyses of the
 scrubber water for the  waste constituent of concern (e.g., carbon
 tetrachloride  (CC1.) and PCB in the feed material) have shown that the
 constituents were present  at low ppb concentrations.  The quality of scrubber
 water generated  would depend on the water feed rate and corresponding product
 gas  and scrubber waste  flowrates.  During a test in which 2.5 Itg/min of waste
 containing 35  to 40 percent CC1, was fed to the reactor, a scrubber water
 effluent flowrate of 30 I/minute was generated (Kolalc, Barton, Lee,
 Peduto,  1986).

 Restrictive Waste Characteristics—
      The reactor as it  is  currently designed can only be used to  treat  liquid
 waste streams  with viscosities  up to that of 30 to 40 weight motor oils.
 Particulates are removed by a 200 mesh screen prior to being fed  into  the
 reactor.  Contaminated  soils and viscous sludges cannot be treated.  The TCDD
 wastes  for which this technology has potential include nonaqueous phase
 leachate such  as that which has been generated at the Love Canal and Hyde  Par It
 Landfills, unused liquid herbicide solutions such as herbicide orange,  and
 possibly still bottoms  from herbicide production.

 4.7.2   Technology Performance Evaluation

     The plasma  arc system has  been tested using several  liquid  feed materials
 including carbon tetrachloride  (CC1,), polychlorinated biphenyls  (PCBs),  and
methyl ethyl ketone (MEK). It has not been tested on wastes or other materials
 contaminated with TCDD.  However, because of the structural similarity between
TCDD and PCBs,  the  data presented should provide some indication as to the
potential of this  technology towards destroying TCDD.

Chlorine Mass Loading (Z)
Scrubber Effluent
Flare Exhaust
CC14 (ppb)
Destruction Removal Efficiency
Test 1



Test 2



Test 3



(1)  sample taken was invalidated due to plugging of sampling apparatus

*mg/dscm " milligrams per dry standard cubic meter.

                        TABLE 4.7.3.   PCB TEST RESULTS
                                      Run 1
                  Run 2
                                                                       Run 3
Stack Gas Parameters
Total PCB, (1)
g/dscm* (2)
Total Dioxins,
Total Furans,
Total BaP,


0.076 (3)










Scrubber Effluent Parameters

Total PCB, ppb(l)
Total Dioxins, ppt
Total Furans, ppt
Total BaP, mg/L
Destruction Removal Efficiency

PCB, Percent DRE
                                   >99. 99999
     (1)  These values are based upon mono-decachlorobiphenyl.
     (2)  These values are based upon tri-decachlorobiphenol.
     (3)  No tetra or penta dioxins were detected at 0.05 ng on a GL column,
          except for run tl where 0.06 ng tetra dioxin was reported.
     *g/dscm • grams per dry standard cubic meter

Reference:  Kolak, et al., 1986.


 4.8.1  Process Description

      The molten salt destruction process has been under development by
 Rockwell International since 1969 (Edwards, 1983).  The original intent was to
 use the process to gasify coal.  A variety of salts can be used, but the most
 recent studies have used sodium carbonate (Na-CO-) and potassium carbonate
 (K2C03) in the i,450°F to 2,200*F temperature range.
      In addition to the Rockwell process, another molten salt process is under
 development.  The State of New Jersey in late 1982 issued a contract to the
 Questex Corporation of New York to evaluate a mobile offsite earth
 decontaminator (MOSED), a waste treatment unit based on the molten salt
 destruction  principle*  A status report on the development of this device was
 presented at the 1985 Hazpro Conference (Leslie, 1985).
      As shown in a schematic of the Rockwell process (Figure 4.8.1), the waste
 is  fed to the bottom of a vessel containing the liquid salt along with air or
 oxygen-enriched air. The molten salt is maintained at an average temperature
 of  900°C (l,650°F).  The high rate of heat transfer to the waste causes rapid
 destruction.  Hydrocarbons are oxidized to carbon dioxide and water.
 Constituents of the feed such as phosphorous, sulfur, arsenic, and the
 halogens react with the salt (i.e., sodium carbonate) to form inorganic salts,
 which are retained in the melt.  The operating temperatures are Low enough to
 prevent NO  emissions (Freeman, 1985; GCA, 1985; Edwards, 1983).  Any gases
 that  are formed are forced to pass through the salt melt before being emitted
 from  the combustor.  If particulates are present in the exhaust gases, a
 venturi scrubber or baghouse may be used (GCA, 1985; Edwards, 1983).
      Eventually, the build-up of inorganic salts must be removed from the
molten bed to maintain its ability to absorb acidic gases.  Additionally,  ash
 introduced by the waste must be removed to maintain the fluidity of the bed.
 Ash concentrations in the melt must be below 20 percent to preserve  fluidity
 (Edwards,  1983).
     Melt removal c*n be performed continuously or  in a batch mode.
 Continuous removal is generally used if the waste feed rates are high.   The
melt  can be quenched in water and the ash can be  separated by filtration while

 the  salt remains in solution.  The salt can then be recovered and recycled.
 Salt losses, necessary recycle rates, and recycling process design are
 strongly dependent on the waste feed characteristics (GCA, 1985; Freeman,
 1985; Edwards, 1983).

 Restrictive Waste Characteristics—
     The ash content of the melt should be limited to 20 percent in order to
 maintain fluidity for a reasonable per.od of time.  The process becomes
 inefficient and/or impractical for wastes of high ash content.  Also, wastes
 wj.th a low water content are destroyed more effectively.

 Operating Parameters (Freeman, 1985; GCA, 1985)—
     The following are typical parameters for the molten salt incinerator:

     Waste Form                      Solid or Liquid Wastes of
                                     Low ash and water contents
     Operating Temperature           800 to 1000°C
                                     (1500° to 1850°F)
     Average Residence Time
           Gas Phase                 5 seconds
           Solid (or Liquid Phase)   Hours
     Energy Requirements             Fuel to burn waste
                                     (if not combustible)
                                     Electric power for blowers

4.8.2  Technology Performance Evaluation

     Rockwell International has built two bench scale combustors  (0.5 to 2
 Ib/hr), a pilot plant (55 to 220 Ib/hr), and a portable unit  (500  Ib/hr)
 (Edwards, 1983).  They have also built a 200 Ib/hr coal gasifier  based on the
molten salt process.
     Many wastes have been tested in the bench scale unit.  Chemical warfare
agents GB, Mustard HD, and VX have been destroyed at efficiencies  ranging from
99.999988 to 99.9999995 percent.  Other chemicals that  have been destroyed
using the molten salt combustion process include: chlordane,  malathion, Sevin,
DDT,  2,4-0 herbicide, tar, chloroform, perchloroethylene  distillation bottoms,
trichloroethane, tributyl phosphate, and PCBs  (GCA,  1985;  Edwards, 1983).

                 MELTS  [Edwards, 1983]
of KC1, NaCl
in melt
(wt Z)
Extent of PCB
>99. 99995
>99. 99995
>99. 99995
>99. 99993
>99. 99996
>99. 99996
of PCB in
( g/m^
aPCBs were not detected in the off-gas, i.e., values shown are detection

Reference:  GCA, 1985; Edwards, 1983.

 4.8.4   Process Status

     Rockwell has constructed several molten salt units of varying sizes.   The
 company has conducted extensive tests in two sizes of units; bench-scale
 combustors for feeds of up to 10 Ib/hr wastes, and a pilot-scale unit for
 feeds of up to 250 Ib/hr of wastes (Freeman, 1985).
     Several developments will be needed if molten salt combustion is to be
 applied to dioxin-contaminated wastes.  The 99.9999 percent ORE  required by
 the current RCRA regulations must be demonstrated for dioxins, and additional
 testing with dioxin-contaminated wastes (both liquids and solids) needs to be
 performed on a larger scale.  Research to develop more economical construction
materials may also be required.
     As indicated above, molten salt combustion is not currently practical for
 the treatment of dioxin-contaminated wastes.  Additional research and
 development is required, but Rockwell has no plans for such further activity.
 The status of the New Jersey MOSED unit is not known.

       WASTE (10* ORGANIC)
                                               RECYCLE EDUCTOR
                                 k TURBINE    ^-^
                                                   HIGH PRESSURE
                                                   LI QUID-VAPOR
                   LOW PRESSURE
         Figure 4.9.1.
Process schematic for  supercritical oxidation of an aqueous waste with
a heating value of 1750 Btu/lb  (Modeli,  et al., 19U4J.

 4.9.2   Technology  Performance Evaluation

     Modar  has  built and tested bench scale supercritical water reactors  for
 destruction of  urea, chlorinated organips, and dioxin-containing wastes.
 Skid-mounted, transportable systems with a capacity of  50 gal/day have been
 designed as well as larger-scale stationary units.
     A  reactor, constructed of Iconel 628 and measuring 19.6 inches long with
 an  inside diameter of 0.88 inches, was used to investigate urea destruction
 (GCA, 1985; GCA, 1984).  Additional tests of the supercritical water oxidation
 process were conducted using a similarly constructed Haste Hoy C-276 reactor
 with dimensions of 24 inches in length and 0.88 inch inside diameter (GCA,
 1985; GCA,  1984).  Tests on chlorinated organics were performed with this
 reactor.  Table 4.9.1 summarizes the compositions of the various waste feeds
 used in the test runs.  Liquid influents and effluents were analyzed for total
 organic carbon  TOC by GC/MS (Modell, 1982).  Gaseous effluents were analyzed
 by  GC for low molecular weight hydrocarbons (Modell, 1982).  The results of
 these analyses  and the calculated destruction and removal efficiencies (DREs)
 are shown in Table 4.9.2.  Chlorinated dibenzo-p-dioxins were searched for
 specifically, but none were found in the effluents.
     A laboratory-scale trial burn was conducted using a feed consisting of
 synthesized dioxin added to trichlorobenzene (at 100 ppm concentrations)
 (Killiley,  1986).  According to Modar, the process achieved greater than six
 nine's ORE  based on the analytical detection limits for gas and liquid
 effluents (Killiley, 1986).  Modar has performed studies on dioxin-
 contaminated soils for private clients, including a field demonstration using
 their pilot scale unit for the New York Environmental Conservation Department
 (Killiley,  1986).  Although the results of these tests are not available for
 release at  this time, the DREs for TCDD were reportedly greater than 6 nines
 (Killiley,  1986).

4.9.3  Costa of Treatment

     The most significant operating cost factor is the cost of oxygen  consumed
 (GCA,  1985).  Although compressed air can be used as the source of oxygen, the
cost of power as well as the high capital cost of appropriate compressors  has




(2) 99.997

• *oo

, oxf~^-<2

. o^Q — Q



— -






99 .991





9.4 .



— •
— —


Waste capacity
gal /day
Processing cost
$0.75 -
$0.50 -
$0.36 -
$0.32 -

$180 -
$120 -
$ 86 -
$ 77 -

*Based upon an aqueous waste with 1800 Btu/lb heating
 value and inorganic solids of between IX and 10Z.

''Does not include energy recovery value of approximately
 $0.05 per gallon.

Source:  Sieber,  1986.

    8«w«* Adapted from
                        "•"»»••* Laboratory
figure 4.10.1.
Schematic diagram t%e
                   Con.u™ .lnnt

                ICMMfft »»«rt
                MMIUkTO* *« TANK
                                                            MLfT •*»***
   Figure 4.10.2.  Schematic of  large-scale  off-gas
                    treatment system (Jitzpatrick, 1984),

 costs  such  as  labor and annual equipment charges (Oma,  et al.,  1983).
 Specifically,  for variations in manpower levels, power  source costs, and
 degree of heat  loss it was determined that the costs for TRU waste
 vitrification  ranges from 160 to 360 $/m  to vitrify to a depth of
 5 meters.   These costs are a function of*many variables but are most  sensitive
 to variations  in the amount of moisture in the soil and the cost of electrical
 power in the vicinity of the process.  Figure 4.10.3,  developed by  PNL,
 illustrates the variation in total costs as a function  of both  electrical
 power costs and moisture content of TRU soil experimentally treated.   The
 vertical line represents the value beyond which it is more cost effective to
 lease a portable generator.
     Recently, PNL has assessed the cost implications for ISV  treatment of
 three additional waste categories; i.e., industrial sludges and hazardous
waste (PCB) contaminated soils at both high and low moisture contents (Buelt,
J., 1986).  Representatives at PNL indicated that for industrial sludges with
moisture contents of 55 to 75 percent (classified as a slurry), the total
costs would range from 70 to 130 $/m .  Treatment of high (greater than 25
percent) moisture content hazardous waste-PCB contaminated soil would cost
                            3                               3
approximately 150 to 250 t/m  versus costs of 128 to 230 i/m  for low
(approximately 5 percent) moisture content PCB contaminated soil.
     As these recent data and past TRU waste cost data  suggest, the moisture
content of the contaminated material is particularly important  in influencing
treatment costs.  High moisture content increases both  the energy and length
of time required to treat the contaminated material.  Furthermore,  PNL
representatives suggest that treatment costs are also influenced by the degree
of off-gas treatment required for a given contaminated material (i.e., ISV
application to hazardous chemical wastes will likely not require as
sophisticated an off-gas treatment system as would TRU waste treatment).

4.10.4  Process Status

     As briefly indicated above in the "Cost" discussions,  PML has recently
assessed the treatment and costs associated with hazardous  waste contaminated
soils (Buelt, J., 1986).  During the summer of 1985,  tests  were conducted for
the Electric Power Research Institute (EPRI) on PCS contaminated soil.   Note
that while the draft report on these tests has been completed, it has not been
published and/or made available to date.  However,  an EPRI  project summary
publication, dated March 1986, entitled "Proceedings:  1985 EPRI PCB Seminar"
(EPRI CS/EA/EL 4480) has recently been made available to EPRI members.
Preliminary results suggest that a destruction/removal efficiency (ORE) of six
to nine nines was achieved from the off-gas treatment system overall, and that
a vitrification depth of 2 feet was achieved.  Additional information will
soon be available to the public.  PNL expects to continue with research in the
area of hazardous waste soils.

Brown, William.  Chemical Waste Management,  Inc.  Telephone Conversation with
     Lisa Farrell, GCA Technology Division,  Inc.  March 28, 1986.

Buelt, J.L., et al.  Battelle Memorial Institute, Pacific Northwest
      Laboratories, Richland, Washington.  An Innovative Electrical Technique
     for In-Place Stabilization of Contaminated  Soils.  In:  Proceedings of
     the American Institute of Chemical' Engineers  1984 Summer Meeting  in
     Philadelphia, Pennsylvania.  1984.

Buelt, J.L.  Battelle Memorial Institute,  Pacific Northwest Laboratories,
     Richland, Washington.  Telephone Conversation  with Michael  Jasinski, GCA
     Technology Division, Inc.  1986.

California State Air Resources Board.  Technologies for the Treatment  and
     Destruction of Organic Wastes as Alternatives  to Land Disposal.   1982.

Carnes, Richard A., and Frank C. Whitmore.  Characterization  of  the  Rotary
     Kiln Incinerator System at the U.S. EPA Combustion Research
     Facility (CRF).  Hazardous Waste, 1(2):  225-236.   1984.

Carnes, Richard A.  U.S. EPA, Combustion Research  Facility.   U.S.  EPA
     Combustion Research Facility Permit Compliance Test  Burn.   In:
     Proceedings of the Eleventh Annual Research Symposium on Incineration  and
     Treatment of Hazardous Waste, sponsored by U.S. EPA-HWERL.   Cincinnati,
     Ohio, April 29-May 1, 1985.  EPA/600/9-85/028.  September 1985.

Carnes, Richard A.  U.S. EPA, Combustion Research  Facility.   Telephone
     Conversation with Lisa Farrell, GCA Technology Division,  Inc.
     January 29, 1986.

Chang, Daniel P.Y., and Nelson W. Sorbo.  University of  California,  Department
     of Civil Engineering.  Evaluation of a Pilot  Scale  Circulating Bed
     Combustor with a Surrogate Hazardous Waste Mixture.   In:   Proceedings of
     the Eleventh Annual Research Symposium on Incineration and Treatment of
     Hazardous Waste, sponsored by U.S. EPA-HWERL.  Cincinnati, Ohio,
     April 29-May 1, 1985.  EPA/600/9-85/028.  September 1985.

Chemical Engineering.  New Units Give Boost to Sludge Incineration.
     July 9, 1984.

Clark, W.D., J.F. La Fond, O.K. Moyeda, W.F. Richter, W.R. Seeker, and
     C.C. Lee.  Engineering Analysis  of Hazardous Waste Incineration; Failure
     Mode Analysis  for Two Pilot Scale  Incinerators.  In:  Proceedings of  the
     Eleventh Annual Research Symposium on  Incineration and Treatment of
     Hazardous Waste, sponsored by U.S. EPA-HWERL.  Cincinnati, Ohio,
     April 29-May 1, 1985.  EPA/600/9-85/028.  September 1985.

Daily, Philip L.  Shirco Infrared Systems,  Inc.  Performance Assessment of
     Portable Infrared Incinerator.   Storage & Disposal.  1985.

Freestone, F., R. Miller, and C.  Pfrommer.   Evaluation of Onsite  Incineration
     for Cleanup of Dioxin-Contaminated Materials.   In:  Proceedings  of  the
     International Conference on New Frontiers for  Hazardous  Waste  Management,
     sponsored by:  U.S. EPA-HWERL, NUS Corporation,  National Science
     Foundation, and American Academy of Environmental Engineers.   Pittsburgh,
     Pennsylvania, September 15-18, 1985.  EPA/600/9-85/025.   September  1985.
Freestone, Frank.  U.S. EPA-HWERL, Edison,  New Jersey.  Telephone Conversation
     with Lisa Wilk, GCA Technology Division, Inc.   August  5, 1986.

GA Technologies, Inc.  Brochure:   Circulating Bed Waste Incineration.  1984.

GCA Technology Division.  Screening to Determine the Need  for Standards  of
     Performance for Industrial and Commercial Incinerators.   Prepared for the
     U.S. EPA, Office of Air Quality Planning and Standards,  under EPA
     Contract Nos. 68-02-2607 and 68-02-3057.  January 1979.

GCA Technology Division.  Draft Final Report:  Technology  Overview -
     Circulating Fluidized Bed Combustion.   Prepared for U.S. EPA, Office of
     Research and Development, under EPA Contract No. 68-02-2693,
     GCA-TR-81-91-G.  August 1981.

GCA Technology Division.  Utilization of Non-Land Disposal Alternatives to
     Handle Superfund Wastes.  Prepared for the U.S. EPA,  Office of Solid
     Waste, Waste Management and Economics  Division.  July 25, 1984a.

GCA Technology Division.  Final Report:  Technical  Assessment of Treatment
     Alternatives for Wastes Containing Halogenated Organics.  Prepared for
     U.S. Environmental Protection Agency,  Office of Solid Waste, Waste
     Treatment Branch, under EPA Contract No. 68-01-6871,  Work Assignment
     No. 9.  GCA-TR-84-149-G.  October  1984b.

GCA Technology Division.  Detailed Review Draft Report:  Identification of
     Remedial Technologies.  Prepared for U.S. EPA, Office of Waste Programs
     Enforcement, under EPA Contract No. 68-01-6769, Work Assignment
     No. 84-120.  GCA-TR-84-109-G-(0).  March 1985.

Gregory, R.C.  Rollins Environmental Services, Inc.  Design  of Hazardous  Waste
     Incinerators.  Chemical Engineering Progress.  April 1981.

Hazardous Waste Consultant.  Stabilizing Organic Wastes:  How Predictable Are
     The Results?  Volume 3, Issue 3, Pages  1-18 to  1-19.  May/June  1985.

Hazardous Materials Intelligence Report.  EPA Incineration Test, Public
     Hearing on AL Waste Law Amendments.  December 6,  1985a.

Hazardous Materials Intelligence Report.  EPA to Issue  Permits  for Ocean
     Incineration Tests.  December 6, 1985b.

Hazardous Materials Intelligence Report.  Texas Company Markets  Transportable
     Infrared Incinerator.  January  10,  1986a.


 Johanson,  Kenneth.  Shirco Infrared Systems, Inc., Dallas,  Texas.   Telephone
      Conversations with Lisa Farrell, GCA Technology Division,  Inc.
      February  20, 1986; April 1, 1986; April 3, 1986; April 23,  1986;  and
      May 5,  1986.

 Josephson, Julian.  Supercritical Fluids.  Environmental Science &
      Technology.  October 1982.

 Killiley,  William.  Modar, Inc.  Telephone Conversation with Lisa Farrell,  GCA
      Technology Division, Inc.  February 25, 1986.

 Kolak, Nicholas P., Thomas G. Barton, C.C. Lee, and Edward F. Peduto.   Trial
      Burns - Plasma Arc Technology.  In:  Proceedings of the U.S. EPA Twelfth
      Annual Research Symposium on Land Disposal, Remedial Action.
      Incineration and Treatment of Hazardous Waste.  Cincinnati, Ohio.
      April 21-23, 1986.

 Krogh, Charles.  CH2M Hill.  Memorandum to Katie Biggs (EPA VII), Steve
      Wilhelm (EPA/VII), and John Kingscott (EPA/HQ).  Re:  Technical Briefing
      on the Mobile Incinerator Project.  June 7, 1985.

 Lee,  Anthony.  Technical Resources, Inc.  Analysis of Technical Information to
      Support RCRA Rules for Dioxins-containing Waste Streams.  Final Draft
      Report submitted to Paul E. des Hosiers, Chairman, U.S. EPA - Dioxin
      Advisory Group.  July 31, 1985.

 Lee,  Kenneth W., William R. Schofield, and D. Scott Lewis.  Mobile Reactor
      Destroys Toxic Wastes in "Space".  Chemical Engineering.  April 2, 1984.

 Leslie, R.H. Development of Mobile Onsite Earth Decontaminator, In:
      Proceedings of the Hazardous '85 Conference, Baltimore, Maryland.
      May 1985.

 Materials Characterization Center (MCC).  Nuclear Waste Materials
      Handbook—Waste From Test Methods.  Department of Energy, Washington,
      D.C.  DOE/TIC-11400.  1981.

 Marson, L. and S. Unger.  Hazardous Material Incinerator Design Criteria,
      prepared by TRW, Inc. for the U.S. EPA Office of Research and
      Development, EPA-600/2-79-198.  October 1979.

 McCormick, Robert.  ENSCO, Inc.  Telephone Conversation with Lisa  Farrell, GCA
      Technology Division, Inc.  May 7, 1986.

 McGaughey, J.F., M.L. Meech, D.G. Ackerman, S.V. Kulkarni, and M.A. Cassidy.
      Radian Corporation.  Assessment of Treatment Practices  for Proposed
      Hazardous Waste Listings F020, F021, F022, F023, F026, F027,  and  F028.
      Prepared for U.S. EPA under EPA Contract No. 68-02-3148, Work Assignment
      No. 10.  September 1984.

M.M. Dillon, Ltd.  Destruction Technologies for Polychlorinated  Biphenyls
      (PCBs).  Prepared for Environment Canada, Waste Management  Branch.   1983.


Ross, R.W., II, T.H.  Backhouse,  R.N.  Vogue, J.W. Lee, and L.R. Waterland.
     Acurex Corporation,  Energy  & Environmental Division, Combustion Research
     Facility.  Pilot-Scale Incineration Test  Burn of TCDD-Contaminated
     Toluene Stillbottoms from Trichlorophenol Production from the Vertac
     Chemical Company.   Prepared for  U.S. EPA, Office of Research and
     Development, Hazardous Waste Engineering  Research Laboratory, under EPA
     Contract No. 68-03-3267,  Work Assignment  0-2.  Acurex Technical Report
     TR-86-100/EE.  January 1986.

Roy F. Weston, Inc. and York Research Consultants.  Times Beach, Missouri:
     Field Demonstration of the  Destruction of Dioxin in Contaminated  Soil
     Using the J.M. Huber Corporation Advanced Electric Reactor.
     February 11, 1985.

SCA, Inc., Customer Service Department.   Telephone Conversation  with Lisa
     Farrell, GCA Technology Division, Inc.  Re:  PCBs  Incineration Costs.
     May 9, 1986.

Schofield, William R.,  Oscar T.  Scott, and John  P. DeKany.   Advanced Waste
     Treatment Options:  The Huber Advanced Electric  Reactor and The Rotary
     Kiln Incinerator.   Presented HAZMAT Europa  1985  and HAZMAT
     Philadelphia 1985.

Shih, C.C., et al.  Comparative  Cost  Analysis and Environmental  Assessment  for
     Disposal of Organochloride  Wastes.   Prepared by  TRW,  Inc.  for the U.S.
     EPA Office of Research and  Development,  EPA-600/2-78-190.   August 1978.

Shirco Infrared Systems,  Inc.  Dallas, Texas.  Brochure:   Shirco Incineration
     System - Process Description and Component  Description.  1985.

Sickels, T.W.  ENSCO's Modular Incineration System:   An Efficient  and
     Available Destruction Technique for Remedial Action at Hazardous Waste
     Sites.  Preprinted Extended Abstract of Paper  Presented Before the
     Division of Environmental Chemistry, American  Chemical Society,   191st
     National Meeting, New York, New York:  Vol 26,  No. 1.  April 13-18, 1986.

Sieber, F.  Modar, Inc.  Correspondence with  N.F. Surprenant, GCA Technology
     Division, Inc.  May 29, 1986.

Smith, Robert L., David T. Musser, Thomas J.  DeGrood.  ENRECO,  Inc.   In Situ
     Solidification/Fixation of  Industrial Wastes.  In:  Proceedings  of the
     6th National Conference on Management of Uncontrolled Hazardous  Waste
     Sites, Washington, D.C.  November 4-6, 1985.

Spooner, Philip A.   Science Applications  International Corporation (SAIC).
     Stabilization/Solidification Alternatives for Remedial Action.

Strachan, D.M., R.P. Turcotte, and B.O.  Barnes.  MCC-1:  A  Standard Leach  Test
     for Nuclear Waste Forms.  Pacific Northwest Laboratory, Richland,
     Washington.  PNL-SA-8783.   1980.

                                  SECTION  5.0

     This section reviews nonthermal technologies for treating  dioxin wastes.
Several of the technologies involve the addition of chemical  reagents to
degrade or destroy dioxin, e.g. chemical dechlorination,  ruthenium tetroxide
degradation, and degradation using chloroiodides.  Two technologies,
ultraviolet (UV) photolysis and gamma ray radiolysis, involve the application
of electromagnetic radiation to break down dioxin and other contaminants.
There is also a subsection covering biodegradation.  The  remaining two
treatment technologies discussed, solvent extraction and  stabilization/
fixation, are not destructive technologies, but rather represent pretreatment
and temporary measures, respectively, for managing dioxin wastes.
     The technologies that are included in this section are not evaluated in
the same manner as the thermal technologies.  Thermal technologies are
primarily evaluated on the basis of six nines ORE, where  DRE is a function of
the concentration of a contaminant in the exhaust gas from the  process.   With
nonthermal treatment there are generally no exhaust gases of significance.
There are,  however,  other treatment effluents and residues which are  major
potential sources of dioxin emissions.  Since EPA has proposed that these
residues must contain less than 1 ppb of CDDs or CDFs in  order to be  land
disposed, this will be the main criterion on which these  technologies will be

The use of the priority pollutant, naphthalene, proved to be a source of
concern. Subsequent dechlorination processes were designed to utilize
alternate reagents.  For example, the Acurex Waste Technologies Corporation
(now Acurex Corporation) developed a process (Dillon, 1982; desRosiers,  1983;
Ueitzman, 1986) which used a sodium-based reagent, prepared from proprietary
but nonpriority pollutant constituents (Miille, 1981).  The system operates by
mixing filtered, PCS contaminated oil with the sodium-based reagent in
processing tanks where the chemical reaction occurs.  The two streams leaving
the reactor are a treated oil containing no PCBs and a sodium hydroxide
effluent.  The entire PCB destruction process was designed to occur under an
inert nitrogen atmosphere, however, Acurex found that this inert nitrogen
blanket was not essential (Weitzman, 1986).
     The SunOhio PCBX process, approved by USEPA in 1981, is a continuous,
closed loop process utilizing a proprietary reagent to strip chlorine atoms
from PCB molecules, converting the PCBs to metal chlorides and polyphenyl
(polymer) compounds (Dillon, 1982; Jackson, 1981; SunOhio, 1985).
PCB-contaminated mineral/bulk oils are first treated to remove moisture and
gross contaminants.  The PCB-contaminated oil  is then mixed with the
proprietary reagent and sent to the reactor where PCB destruction occurs.  The
mixture is then centrifuged, filtered, and vacuum-degassed.  Effluent streams
include treated oil, and polyphenyl/salt residues.  The  latter are  solidified
and then typically sent to a landfill.  The entire  system is mobile,  as it  is
mounted on 40-foot tractor trailers.  SunOhio  commercially  operates five
mobile units.
     Only limited information has been  found relating to  the  PPM process;
however, more is expected in the near future.  From the  available  information,
this mobile process destroys PCB contaminated  oil  through the aid  of a
proprietary sodium reagent (M. M. Dillon,  1982; des Hosiers,  1983).  The
reagent is added to the contaminated oil and left  to react.   The solid  polymer
formed by the reaction is filtered out  of  the  oil.   While this polymer  is
reportedly a regulated substance,  it has been  found to contain no  PCBs  and can
readily be disposed of (M. M. Dillon, 1982).   PPM  currently has under
development a dechlorination process designed  to work on soils.  However,  no
information is available on the process (personal  conversation with
L. Centofanti, PPM).


 5.1.2  Technology Performance Evaluation

      The Acurex process,  while only applicable  to contaminated PCB oils, has
 been extensively evaluated and is  now commercially available via Chemical
 Waste Management (Weitrman,  1986).  Tests'by  Acurex, during an EPA
 demonstration in the early 1980's, proved that  this technology is effective in
 treating PCB-contaminated oils containing approximately  1,000 ppm to
 10,000 ppm (IZ)—reducing the PCB  concentration to below detectable limits,
 about 1 ppm (Weitzman,  1982).
      The SunOhio PCBX process has  and will continue to be used only on liquid
 hydrocarbon streams  (i.e.,  oil).   The process cannot be  used to treat
 contaminated soils.   At present no tests have been performed on 2,3,7,8-TCDD,
 and it appears  that  this  technology will continue to be  used only on PCB
 contaminated oils or fluids  (SunOhio,  1984).  This process has reduced PCB
 contaminated transformer  oil  from  500 ppm to  below detectable limits (1 ppm)
 in just one pass through  the  system (Weitzman,  1982).  By passing a
 contaminated oil through  the  system three times, it is believed that the PCB
 concentration can be reduced  from  3,000  ppm to  below 2 ppm  [Dillon, 1982;
 Jackson,  1981].
      Performance data regarding the Goodyear process are limited.  However,
 available  information indicates that  this process is capable of treating oils
 containing  300 to 500 ppm PCBs down to less than 10 ppm  (Weitzman, 1982;
 Berry,  1981).  The contaminated transformer or  heat transfer oil is purified
 to  this level within approximately 1  hour at ambient temperature.  Like the
 Acurex/Chemical Waste Management and SunOhio dechlorination processes, the
 Goodyear process  has  only been demonstrated to  be applicable to treatment of
 PCB-contaminated  oils.
     The "APEG-type"  processes  have been laboratory and, in select situations,
 field tested on  PCBs  and 2,3,7,8-TCDD-contaminated soil  samples (Klee, A., et
 al., 1984;  Peterson,  R., et al., 1985  and 1986; Rogers,  C. J., et al., 1985;
Rogers, C. J., 1983).  The APEG reagents used in these experiments have varied
over the several  recent years  of research from  the NaPEG-type, sodium-based
reagents used in  PCB destruction,  to the KPEG-type, potassium-based reagents
proven more efficient in 2,3,7,8-TCDD-type destruction.

         TABLE 5.1.1.
(Klee, A. et.al., 1984).
Days after
7 days
28 days
Tim her line*
 alnitial TCDD content equalled 277  28 ppb.

  Initial TCDD content equalled 330  33 ppb.
  not * not measured
                       (Klee, A., et. al., 1984)
Days after
1 day
7 days
14 days
21 days
28 days
Denny Farm Soil3
a   The anomalies in the apparent decrease of the TCDD level of K-400 treated
    sample at day 14 was found not to be statistically significant.

b   K-400 reagent used in these experiments (vs. those shown in previous
    Table 5.1.1) was prepared from KOH pellets instead of a 66Z aqueous KOH

      Additionally,  it should  be  noted  that during the summer of 1985,
 APEG-type reagents  were  tested by the U.S. EPA at the Shenandoah Stables
 dioxin-contaminated site to evaluate the dechlorination potential of these
 reagents on 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) under field
 conditions (Rogers,  C. J., 1985).  Results of these tests were not as
 promising as in the  past using APEGs in the laboratory.  Specifically,  the
 APEG reagents were  deactivated due to  the fact that APEG is moisture
 sensitive.   The soil moisture at Shenandoah was determined to be on the order <
 of 18 to 21 percent  by weight.   These  results, while not favorable, did point
 out that APEGs  are extremely hygroscopic and that contact with moisture will
 eventually result in the deactivation of the APEG reagent.
      Finally,  results of the use of the Sea Marconi CDP-process are presented
 in Figure 5.1.1 and  Table 5.1.5.  Figure 5.1.1 shows that, at least in the
 beginning,  the  disappearance of  2,3,7,8-TCDD from the reaction mixture is
 linear with respect  to time (Tundo, P., et al., 1985).  The figure also
 indicates that  mixtures  containing higher weight PEG* promote a much more
 rapid decomposition  of TCDD than mixtures containing lower weight PEGs.  When
 a  PEG with  a molecular weight of 6,000 is used (square data points), greater
 than 99 percent decomposition of TCDD occurs in 30 minutes, while the use of a
 PEG with a molecular weight of 1,500 (circular data points) requires over two
 hours for an equivalent  level of degradation.  However, the reaction rate is
 also a function of temperature, and the reaction using PEG 6000 was carried
 out at 85°C  versus 50°C  for the  PEG 1500 reaction.  Therefore, based on
 the data presented in Figure 5.1.1, it is difficult to assess the full effects
 of higher molecular  weight PEGs.
      The  data in Table 5.1.5 show the effect of temperature and different
mixtures  of  reagents on the decomposition of TCDD.  The first set of data
 represents the  same  conditions (PEG 6000 at 85°C) as those used to generate
 the square data points in Figure 5.1.I.  As already mentioned, these
conditions result in rapid decomposition of TCDD.  The second set of data
points was generated using a smaller quantity of PEG 6000 and adding a butyl
ether compound  to the reaction mixture.  With this combination of reagents,
greater  than 99.9 percent decomposition of TCDD occurred in 30 minutes.  For
the third set of data, the reaction temperature was only 20°C, and the
decomposition of TCDD was much slower than for all of the other uses.  Only
50 percent decomposition occurred in 192 hours.


               USING THE CDP-PROCESS  (Tundo, P. et al,  1985)
IPEG 6000

85 0.5
(PEG 6000
2 3
Na 0
Buu(cH CH 0)
IPEG 6000
2 3
(1.3) 85 0.5 >99.9

2H (0.2)
(1.8) * 20 72 30
(0.4) 192 50

      without n-decane: after  homogenization  at 80°C  the reaction was
      solidified by cooling and  kept at 20*C;

                 (Peterson, R.L.,  et al.,  1985)
                               Cost,  $/ton soil

Cost item                    In situ        Slurry

Capital recovery               31             17

Setup and operation            65             54

Reagent                       200             20

Total costs                   296             91

 corresponding  to  the absorption of a quantum (photon) of light  is 95 kilo
 calories per gram-mole for UV light with a wave length of 3,900 angstroms and
 is  142  kilocalories per gram-mole for a wave length of 2,000 angstroms.
     Table  5.2.1  lists the dissociation energies for many common chemical
 bonds,  along with the wavelength corresponding to the energy at which UV
 photons will cause dissociation.  As can be seen from the data  in Table  5.2.1,
 bond dissociation energies range from a low of 47 kcal/gmole for the peroxide
 bond to a high of 226 kcal/gmole for the nitrogen triple bond.   Of particular
 interest in the case of dioxins is the C-C1 bond, with a dissociation energy
 of  81 kcal/gmole, corresponding to an optimum UV wavelength of  353 run.   For
 reference purposes,  this can be compared to the violet end of the visible
 spectrum with a wavelength of about 420 nm.  Thus, the UV radiation of
 interest is in the electromagnetic spectrum close to visible light.  This  fact
 is  important because it means that sunlight, which radiates strongly in the
 near visible wavelengths, might be a good source of UV photons which are
 capable of degrading many molecules.
     It is not surprising then, that the use of sunlight to degrade certain
 toxic molecules has been noted by several researchers (des Hosiers,
 P.E., 1983; Zepp, R.G., 1977, Esposito, M.P., 1980; Crosby, D.G.,  1971).  In
 the case of 2,3,7,8-TCDD and other related compounds, the apparent mechanism
 is  that a terminal C-C1 bond is broken by UV radiation, thus "dechlorinating
 the molecule" and converting it into less toxic compounds.  (Note that this
 reaction mechanism is very similar to that of chemical dechlorination; i.e., a
gradual and progressive substitution of the chlorine atoms.)
     Efficient degradation appears to require the presence of a hydrogen
donor,  because while UV can cause the cleavage of the C-C1 bond, recombination
can take place.  However, if a hydrogen donor is present, it will  also react
and replace the chlorine on the molecule.  For example, several researchers
have noted that pure 2,3,7,8-TCDD and other chlorinated compounds  degrade
slowly or not at all when placed on inorganic substrates,' but when suitable
hydrogen donors are present, degradation in sunlight can be rapid  (Crosby,
     UV has been commercially used to kill micro-organisms such  as bacteria,
protozoa,  viruses, molds, yeasts, fungi, and algae.  Applications  include
process and drinking water disinfection and sterilization, pretreatment prior
to reverse  osmosis,  and general algae and slime control.

      Recently,  UV  photolysis has been viewed as a potential large-scale
 commercial mechanism  to degrade toxic wastes.  In attempting to obtain a
 simple,  inexpensive,  and effective soil detoxification method,  the University
 of Rome  evaluated  the use of various cationic, anionic, and nonionic
 surfactants  to  solubilize 2,3,7,8-TCDD in an aqueous solution prior to
 photodegradation with sunlight or artificial UV light (Botre, C.,  1978).   Of
 the four surfactants, 1-hexadecyclpyridium chloride or cetylpyridium chloride
 (CPC)  was found to be the most effective solubilizing agent, as well as  having
 the ability  to  enhance the  subsequent photochemical degradation of
 2,3,7,8-TCDD.   Other  solvents examined included sodium dodecyl sulfate (SDS),
 polyoxyethylene sorbitan monoleate (Teewn 80) and methanol.
      In  1975, Velsicol Chemical Corporation (Chicago) experimented with
 removing 2,3,7,8-TCDD contamination from stockpiles of "Agent Orange", a
 defoliant used  in  Viet Nam  (Crosby, D.G., 1978; des Rosiers, P.E., 1983).  The
 2,3,7,8-TCDD molecule was extracted by using n-heptane as a solvent, and
 exposing the solution to UV photolysis at 300-320 on wavelength.  The process
 resulted in  a reduction from 1,900 ppb of 2,3,7,8-TCDD in the stockpiles to
 less than 50 ppb in end products (Zepp, R.G., 1977; Esposito, M.P., 1980).
 However,  the process was not considered practical, and soon was discontinued.
     Another UV degradation process that was developed in the early 1980s oy
 the Atlantic Research Corporation was named Light Activated Reduction of
 Chemicals (LARC).  This process involves bubbling hydrogen into an aqueous
 solution containing chlorinated hydrocarbons and then irradiating the solution
 with ultraviolet light to declorinate the contaminants.  Work on this process
 was stopped  several years ago for economic reasons (Kitchens, 1986).
     More recently, three UV based processes have been described in the
 literature which may be viable for large-scale degradation of 2,3,7,8-TCDD, as
 well as  other toxic chlorinated hydrocarbons.  There are:

     •    the Syntex - IT Enviroscience process which involves UV photolysis
          preceded by solvent extraction,
     •    UV photolysis in combination with ozonation, and
     •    UV photolysis preceded by thermal desorption.

 Section  5.2.2 contains a discussion of the performance of  these three

          100 c:
120     180     240
Figure 5.2.1.  Rate of dioxin disappearance via UV  irradiation
               of hexane extract of dtoxin-contaminated still
               bottoms (Exner, J.H., 1982).

 Ultraviolet (UV)  Ozonolysia—
      In 1979,  it  was shown (see  Figure  5.2.2) by the California Analytical
 Laboratories and  the Carborundum Company  that ultraviolet activated ozone
 could successfully degrade 2,3,7,8-TCDD from the 1 ppb levels in solution to
 less than 0.4 ppb (Edwards, B.H.,  1983).*  The procedure utilized to produce
 the results shown in Figure 5.2.2  consisted of bubbling ozone gas through the
 TCDD solution,  which was  then passed by UV lamps.  The UV radiation lamps not
 only degraded the 2,3,7,8,-TCDD  directly, but integrated with ozone to enhance
 the oxidation of  the 2,3,7,8-TCDD.  No  information was available regarding the
 waste products that  were  generated from this process.
      UV ozonolysis has also been tested extensively in degrading PCBs down to
 levels of I ppb.   An "ULTROX" pilot plant at a General Electric (GE) plant in
 Hudson Falls,  New York, and another smaller installation at the Iowa
 Ammunition Plant,  Burlington,  Iowa, have  proven the technical feasibility of
 this  process  on PCBs (Arisman, R.K., 1980; Edwards, B.H., 1983; Swarzgn,
 E.M.,  1982).   Both of these plants mixed  wastewater containing PCBs with
 ozone,  then exposed  the mixture  to UV radiation in a mixing tank.
 Figure  5.2.3  shows a schematic of  the pilot plant set up by GE to demonstrate
 the ULTROX UV/ozone  system for PCBs.
      Another UV ozonolysis process is called the "Oxyphoton" process.  The
 process  was reportedly capable of  destroying a wide variety of toxic or
 organic  compounds  including PCBs,  chlorinated dioxins, DDT, and many types of
 halogenated aliphatic and  aromatic compounds (Worne, 1984).  The process is
 carried  out in  stainless  steel reactors and is capable of treating 60 to
 1,800 gallons per  hour of  waste  fluids.  Liquid waste containing a proprietary
 catalyst  is spray-atomized and premixed under pressure with oxygen containing
 I to 2 percent  ozone prior to passage through the high intensity ultraviolet
 (UV)  light.
     One  advantage to this vapor phase  reaction process over the conventional
 liquid phase UV light processes  is the  rapid disintegration of the waste.
Reaction  rates  are generally  reported in  the millisecond range.  Presently,
 the oxyphoton process is on the "back burner", possibly because of unfavoraole
economics.  No  research efforts have directly involved 2,3,7,8-TCDD
(Worne, 1984).

            UV lamp*
O 0
V ^
O 0
V _J*
Flow distributor


— — Wa«te water in

Spent Oj

water out

Solid state
gear pump
Figure 5.2.3.
Schematic of top view of ULTROX pilot
plant by General Electric (Ozone sparging
system omitted) (Edwards, B. H., 1983).

    Purge Gas Makeup
                                               Vent Gas
         Purge Gas
                               Purge Gas Recycle^
   Purge Gas,
   Cooling, and
Scrubbing System
             Treated Soil
                             Solvent Makeup
                                                          water condensate
                                                          aqueous discharge
                                                UV System
                                               Solvent purge
   Figure 5.2.4.
Thermal desorption, solvent absorption/scrubbing,
UV photolysis process schematic  (des  Rosiers,
P. E., 1985).

                 40,000 AND  150,000 GPD ULTROX TREATMENT  PLANTS
                  (50  ppm  PCB  feed-1 ppm PCS effluent)
                                        40,000 GPD             150,000 GPO
                                       (151,400 LPD)            (567,750 LEO)
               Rtaetor               Automated System         Automated System

        Dimension, Meters  (LxNxH)       2.5 x 4.9 x 1.5          4.3 x 8.6 x 1.5
        Net Voltm, Liters                14,951                  56,018
        UV Lamps; Number 65 W               378                     1179
            Total Power,  lew                 25                       80

             Oaone Generator

        Dimensions, Meters (LxHXD)      1.7 x 1.8 x 1.2          2.5 x 1.8 x 3.1
        kg Oaone/day                       7.7                     28.6
        Total Energy required               768                     2544
                                BOXEPUCf EQUIPMBir PRICES

                                        40,000 GPD               150,000 GPD

        Reactor                          $94,500                  $225,000
        Generator                         30,000                    75,000
                                mao.  $124,566            TOIAL  $300,000

        0 t M Costs/Day

        Oaone Generator Power              $4.25                    $15.60
        UV Lamp Power                     15.00                     48.00
           (Lamp Replacement)              27.00                     84.20
        Equipment Mortlzation
           (10 Yrs • 10%)                  41.90                     97.90
        Hanitoring Labor                   'S-71                     85.71
                             lOaL/DAJf   $173,86                   $331.41

        Cost per 3785 Liters
        (with monitoring labor)            $4.35                     $2.21
        (without monitoring labor)          $2.2Q _ $1.64
  Source:   Arlsman,  R.IL  and Mustek»  R.C.,  1980.

reduction of soils to enhance optimum solvent/soil  contact.   Solvent  recycling
allows reuse of expensive solvents and lowers concerns  about  disposal of
contaminant-containing solvents.   Distillation or vacuum stripping  are  the
usual, methods for cleaning solvents.  In either case,  the result  is a
concentrated volume of contaminant for eventual treatment or  disposal
(Weitzman, 1984; Firestone, 1984).
     EPA has developed a mobile soils washing system (MSWS)  process for
extracting dioxin and other contaminants from soil.  The EPA-developed  MSWS
contains two basic components, as summarized below  from IT Corporation, 1985
and as shown in Figure 5.3.1.  These components are a Drum Screen Scrubber  and
a Counter-Current Chemical Extractor.  The Drum Screen unit automatically
loads previously excavated soil (particle sizes less than 1 inch) into the
system where it passes through high pressure streams of extractant solution
and a "soaking zone".  The high pressure streams are designed to wash sands
and stones and to separate fines for further, high energy extraction.  Sands
and stones are discharged from the Drum Screen and the fines are pumped
continuously into the Counter-Current Extractor, which consists of four
high-shear mixing chambers.  As the fine soil (less than 2 mm) leaves each
chamber, it is separated from its solvent carrier  before it enters the next
chamber.  The design capacity of the MSWS ia 18 cubic yards of soil  per hour.

5.3.2  Technology Performance Evaluation

     Solvent extraction of chemical substances  from soil has been  commonly
used in the mining industry and has been demonstrated  for extraction of
bitumen from tar sands (Cotter, 1981).  Currently, the  only  full-scale process
that has attempted to use solvent extraction for dioxin molecules  dealt  with a
contaminated slurry.  In this instance, the  dioxin molecule  (2,3,7,8-TCDD) was
extracted from distillation still bottoms at the Syntex Agribusiness facility
in Verona, Missouri.  IT Enviroscience was contracted  by Syntex  to develop a
safe and effective method for removing approximately 7  kg of dioxin  from about
4600 gal of waste (Exner, J.H., et  al  1982).  The  treatment  process  designed
by IT involved the separation (extraction) of  dioxin using a solvent,  followed
by the photolytic dissociation of the  carbon-halogen bond  (see Section 5.2).
The solvent extraction phase of this project,  as briefly described below,
involved several laboratory, miniplant, and  scale-up  operations.

      Specifically,  IT Enviroscience performed teats on hexane,  tetrachloro-
 ethylene and o-xylene to determine which solvent would best remove  the  dioxin
 molecule and,  once  removed, would allow the dioxin molecule to be effectively
 degraded via the photolytic step.  Their results showed that hexane extraction
 of  the  subject wastes performed better overall than the other two solvents.
 Based upon these results, a large-scale reactor vessel was designed and
 constructed.   In 1980, this reaction vessel processed several 160-gal batches
 of  the  dioxin-containing waste resulting in a reduction of 2,3,7,8-TCDD-
 concentrations of from 340 to 0.2 ppm via six hexane extractions.
      IT Corporation, under the auspices of EPA, has also prepared additional
 laboratory experiments to assess the suitability of the EPA Mobile  Soils
 Washing System (MSWS) for use in extracting dioxin from contaminated soils (IT
 Corporation, 1985).  The MSWS was designed to use water, or water with
 non-toxic and/or biodegradable additives, as an extractant solution.
 Non-hazardous additives are required because some residual solution will
 always  remain with the discharged soil.  Because of this requirement, various
 additives,  such as surfactants and fuel oil, were evaluated in the laboratory
 for the removal of dioxin from soil.  Although laboratory results indicated
 that  602 to over 902 of the 2,3,7,8-TCDD could be removed by the Soils Washing
 System, in most cases (soils initially containing over 100 ppb of dioxin) the
 washed  soil would still contain residual dioxin in excess of the I ppb
 guideline for decontamination.  Similarly, while other experiments using Freon
 and Freon-methanol combinations proved promising, the target residual dioxin
 levels  could not be achieved under the test conditions.  It was  concluded that
 the major obstacle to removing dioxin from the soils was that dioxin binds
 strongly to small soil particles.  The soils on which the MSWS was  tested were
 from  the Denney Farm in Missouri.  These soils contained a  high  percentage  of
 extremely fine materials (33Z less than 5 microns, 262  less than 1 micron).
 For materials with  larger grain size, such as  sands and gravels, the process
 may be  viable  (IT Corporation, 1985).
      In other  laboratory experiments, both aqueous and organic solvents have
 been  tested on 2,3,7,8-TCDD-contaminated soil.  In 1972, Kearney used a 1:1
 hexane: acetone solvent solution on 2,3,7,8-TCDD (labeled with carbon
isotopes)  in loamy sand and silty clay-loam soils.  Electron-capture gas

                       TABLE 5.3.1.  SOLUBILIZATION OF TCDD (Botre, C.,  et al.  1978)

Tween 80
21 w/v0
on soila
Surfactant TCDD
cone (X)
0.02M 75
0.02M 71
U w/v0 72
on pure TCDD^
21 w/vc

     •Each  90-g  sample  contained  initially 6.3  yg  of TCDD.

     blnitial  amount  of TCDD:  40.90  pg.

     cPercent  weight  to volume

 found in a soil matrix, io situ degradation is  a more practical alternative.
 In addition to the various modes of treatment,  biodegradation can be effected
 by a number of different types of micro-organisms.  These include:
     •    aerobic bacteria;
     •    anaerobic bacteria;
     •    yeast; and
     •    fungi.

 Following a discussion of the environmental degradation of  TCDD,  examples  of
 research on the application of several of these modes of treatment  and types
 of micro-organisms will be presented.
     Degradation of 2,3,7,8-TCDD is a slow process,  overall,  in the natural
 environment.  Natural degradation is primarily  due to biodegradation and
 photochemical (UV) breakdown.  A wide variety of  half-lives have been
 reported.  The observed half-life for uncontrolled biodegradation of
 2,3,7,8-TCDD has been reported as 225 and 275 days by the U.S.  Air  Force
 (Young,  1976), although a separate analysis of  the same data yielded
 half-lives ranging from 190 to 330 days (Commoner, 1976).  Another  study
 reported that half-life is affected by concentration, being greatly reduced at
 high concentrations (Bolton, 1978).  In fact, half-lives are probably
 significantly greater than those reported, as most early research did not
 account for the strong tendency for 2,3,7,8-TCDD  to bind to soil particles.
 Strongly bound 2,3,7,8-TCDD would not have been detected analytically and
 biodegradation assumed incorrectly to be the cause of  its absence.
     Studies at Seveso, Italy indicate that the half-life of 2,3,7,8-TCDD
 increases with its time in the soil, because of its tendency to became more
 tightly bound to soil and organic matter (DiDominico,  1980).  DiDominico found
 that half-life calculations made 1-month after the Seveso accident  predicted a
 10 to 14-month half-life, but 17 months after the accident, the half-life  of
2,3,7,8-TCDD in the soil had increased to more than 10 years.
     In a study performed for the Air Force, 99 percent of  the 2,3,7,o-TCDD
sprayed as a constituent of defoliants was still present 12 to 14 years after
application (Young, 1983).  Although natural degradation seems to proceed



Nocardiopsis sp.                         Matsumura,  1983.

Bacillus negaterium                      Matsumura,  1983.

Beijerinckia B8/36*                      Klecka,  1980.

Pseudomonas, sp.b                        Klecka,  1979.

Biejerinckia, sp.*                       Klecka,  1980.

Phanerochaete chrysosporiumc             Bumpus,  et al., 1985,

'Oxidation of dibenzo-p-dioxin and several mono-, di-,  and
 trichlorinated dibenzo-p-dioxins was reported.

^Metabolism of dibeozo-p-dioxin was observed.

cWhite rot fungus.

 Ongoing Research—
     There  have been several more recent research projects concerning the
 biodegradation of 2,3,7,8-TCDD and related compounds.  Some of the more
 significant ones are discussed below.

 White Rot Fungus (Bumpus et al., 1985)—
     One method that has received a large amount of attention has involved the
 study of the ability of the fungus,  P. chrysosporium. to degrade recalcitrant
 organopollutants, one of these being 2,3,7,8-TCDD.  P. chrysosporium is a
 lignin-degrading white rot fungus.  This organism secretes a unique hydrogen
 peroxide-dependent oxidase capable of degrading lignin, a highly complex,
 chemically resistant, nonrepeating heteropolymer.  The enzyme catalyzes the
 formation of carbon-centered radicals which react with oxygen to initiate
 oxidation.  The low molecular weight aromatic compounds formed may then
 undergo further modification or ring cleavage and eventually be metabolized to
 carbon dioxide.
     Several properties of P. chrysosporium make it a candidate for the
 degradation of the more recalcitrant organopollutants such as 2,3,7,8-TCDD,
 DDT, lindane and PCBs.  First of all, the organism is able to degrade  lignin,
 chlorinated lignin and chlorinated lignin-derived by-products of the Kraft
 pulping process.  Secondly, low levels of pollutant (such as may exist in
 contaminated soil) do not repress the production of enzymes required for
 degradation.  Thirdly, the organism is not substrate-specific and therefore
 can attack and degrade a wide variety of structually diverse, recalcitrant
 compounds.  Finally, P. chrysosporium is a highly successful competitor  in
 nature, especially when the carbon source is lignin.  Consequently,
 competition by other organisms will be minimal  if wood chips or sawdust  are
 added as a supplement to the waste material.
     Results of laboratory tests using P. chrysosporium to degrade  several
 different compounds are shown in Table 5.4.2.   In 10 ml cultures containing
 1.25 nmoles of the   C-labeled 2,3,7,8-TCDD substrate, 27.9 pmoles  were
converted to   C02 within 30 days and 49.5 pmoles within  60 days,
representing 4.96 percent metabolism.  The remaining  carbon atoms  should have
either been incorporated into the organism or been present as  intermediates  in
the pathway between 2,3,7,8-TCDD and CO..  This conclusion  is  based on more


 detailed  studies  of  the degradation of DDT which indicated that after 30 days
 4 percent of  the  original DDT was evolved as CO,, when approximately
 50 percent of the DDT  had been degraded.  In the case of DDT, greater than
 99 percent degradation had  occurred after 75 days.

 Matsumura and Quensen  (Quensen and Matsumura;  1983, Quensen, 1986)—
      Research has been conducted at the Pesticide Research Center of Michigan
 State University  in  which low concentrations of 2,3,7,8-TCDD were metabolized
 by pure cultures  of  Nocardiopsis spp. and Bacillus megaterium.  In these
 experiments TCDD  in  solvent was added to flasks containing the pure cultures,
 and after a period of  1 week, the contents were extracted and analyzed  for
 TCDD and  metabolites.
      Several  conclusions were drawn from the study.  One of these, as
 substantiated by  detail in Table 5.4.3, is that the choice of solvent used  to
 dissolve  TCDD and add  it to the culture medium has a significant effect on  the
 degradation of TCDD.   The use of ethyl acetate or dimethyl sulfoxide (DMSO)
 resulted  in significantly higher degradation than when corn oil or ethanol
 were  used.  Another  conclusion that was drawn  is that lowering of alternative
 carbon sources increases the degradation of TCDD.  The proportion of TCDD
 metabolized by B. Megaterium increased dramatically when the amount of  soybean
 extract in the medium  was reduced from 1.6 to  0.4 percent and ethyl acetate
 was  used  as the solvent.  Finally, analog-induced metabolism of TCDD by
 including  napthalene or dibenzofuran in the culture medium proved to be
      In addition  to  the pure culture experiments, TCDD degradation  in  soil  by
 naturally  occuring micro-organisms was also studied.  TCDD was added  to three
 different  types of soil and after 0, 2, 4, and 8 months of  incubation,  soil
 samples were  extracted and  the levels of TCDD  and metabolites were
 determined.   Very little metabolism of TCDD occured  in any of  the  soils over
 the  8 month period.  This was true regardless  of which solvent was  used to  add
TCDD  to the soil  system.  Dimethyl sulfoxide,  ethyl  acetate and  10  percent
ethanol were  used.   They surmised that the resistance to degradation  was  due
to the fact that  TCDD  binds tightly to soil thereby  limiting  the  rate of
cellular uptake.

Kearney and PIinner (Kearney, 1984)—
     A biological process Co detoxify 2,3,7,8-TCDD-contamiaated soils  is  being
evaluated at the Agricultural Research Center in Beltsville, Maryland.  Work
is based on the observation that soil micro-organisms have the ability to
degrade highly chlorinated organica that have been pretreated  with
ultra-violet (UV) radiation.  Pretreatment with UV radiation removes chlorine
from the 2,3,7,8-TCDD molecule in the presence of a proton donor,  and
the resulting dibenzo-p-dioxin molecule can then be biodegraded.
     Laboratory studies have involved subjecting solutions of  chlorinated
organics to UV radiation before adding them to the soil where  biodegradation
could take place.  Kearney and his colleagues have since experimented with a
prototype system that includes a 55-gallon stainless steel drum as a holding
tank and a commercial water purifying unit as the UV source.  Kearney's
process focuses on cleaving  the chlorine-carbon bonds in the chlorinated
organic compounds by the following procedures:

     1.   Expose a dilute aqueous solution (i. e., 1 ppm 2,3,7,8-TCDD) to
          ultra-violet light (UV) for at least I hour
          (Photo-Chemical Reaction).
     2.   While irradiating, bubble oxygen through the solution to speed up
          the chlorine-carbon bond break up (Ozone Reaction).
     3.   Pour or spray irradiated solution over soil containing the test
          micro-organisms (Biodegradation).
     4.   Determine the percent degradation by monitoring the amount of carbon
          dioxide generated.

Recent studies (1981) have yielded the following results:

     •    80 percent degradation of 2,4,5-T over I month;
     •    80 percent degradation of PCB over I month;

University of
Illinois Medical

Michigan State

Sybron Corpora! io
Saiam. Virginia

Syatema. Inc..
Ualdwick, H.J.

Louie iana State
Haaardoua Uaste
leaearch Center

Univeraity of
research ha* bean
funded (or TCDD

phenol a

n, 1,4-Dichlorophenol

acetone; methylene
chloride; n-butyl
alcohol; 1 ,4-dichloro-
2,4-D and 2.4.J-T

2,4-D; J,5-
Type/Heme of
Cepacia. AC1100




(only identifiable
at the genua

plant aludge waa
the aource of
Type of
developed by
acclimation to
2,4.5-T in a
chemoatat; bacteria
alao can be applied
to aoil

would probably
involve the use
of an anaerobic

addition of microbes
in powdered form to
contaminated aite

activated sludge
ayatem from which
mlcro-organiama are
injected into
laboratory acale
batch reactora

reactora and
Performance Reference
up to 98X Ghoaal, et al..
degradation of 1985; Kilbane
2,4.5-T; et al.. 1985;
reduction of Tomasek and
2,4.5-T in aoil Chakrabarty,
from 1000 ppm 1985
to 10 ppm in
one week
capable of Tiedje, 1984
removing chlorine
atoma from the
lab teat ing hes Davia, 1984;
shown degradation Goldsmith, 1986
at 1.4-OCP
coocantrationa of
50-100 ppm
600-700 ppm of Macatsa, 198}
reduced to leaa
than 6 ppb for
induatrial orgaoics
demonstrated toy end Mitre,
growth of micro- 1986
organisms uaing
2,4-D aa aola
carbon aourca

micro-organiama Kim and Heier,
were capable of 1986
utilising 2.4-D
•nil 1 5-DT.B IS
                                                     innoculating after
                                                     acclimation, the
                                                     Paeudomonaa apeciea
                                                     waa predominant
the aola aubatrate
at concentreciona
between 10ug/l end

temperature, pH, and wood chip type and size  (the substrate on which the
micro-organism is grown) will be varied to  determine optimum growth conditions
(Sferra, 1986).  After this,  the white rot  fungus will  be tested in soil plots
containing TCDD.  This means  that the  application of even a promising
micro-organism such as P. Chrysosporium to*  actual waste will not occur  for
several years,  and only then  if it proves to  be  successful in lab-scale
     Several treatment methods described above have been demonstrated to be
applicable to the treatment of compounds that are similar to 2,3,7,8-TCDD,
such as chlorophenols and 2,4,5-T.  They have not, however, been tested either
in the lab or the field on waste containing TCDD.  In the case of the Sybron
Corporation work, it has been difficult to  obtain samples of waste with which
to test their process in the  lab, and  it has  also been  difficult to test their
process at actual sites of TCDD contamination (Goldsmith,  1986).  One of the
reasons for the difficulty in testing  microbial  processes on actual waste
sites is the issue of releasing genetically altered micro-organisms  to  the
     In summary, the feasibility of biodegradation of 2,3,7,8-TCDD as  a
treatment technology is still in question.  Most investigations have  been
performed in the laboratory,  and the efficiency of a large scale treatment
process is unknown.  There are many advantages associated with biotreatment
which make continued investigation advisable:

     •    The end products of complete biodegradation are nontoxic.
     •    Some processes may be accomplished onsite without soil excavation.
          However, use of solvents which could potentially cause uncontrolled
          mobilization of 2,3,7,8-TCDD must be avoided.
     •    Biological treatment appears to be effective at low 2,3,7,8-TCD

In addition, biotreatment could  be coupled with other  treatment processes  to
make them both more efficient.  For instance, the sodium polyethylene  glycol
(NaPEG) process might be modified  to  in-situ  treatment with the use of
micro-organisms to degrade the dechlorinating solvent  and the residual
nonchlorinated and less chlorinated dibenzo-p-dioxins.

                        HAZARDOUS WASTES  (M.  E. Tittlebaum, et al., 1985)
Lime-based or
Process sponsor
(process name)
Chemf ix
Stablex (Sealosafe)
Stabatrol (Terra-Tite)
Dravo Lime (Calcilox)
International Mill Service
IU Conversion Systems
Soil Recovery Systems
Werner and Pfleiderer
Southwest Research Inst.
Dow Chemical
Newport News Industrial
Stabilization agents
Cement, soluble silicates
Cement, fly ash
Cement, additives
Lime, additives
Lime, additives
Sulfur, modifiers
Polyesters, polyvinyls
FGD sludges
Metal slags
FGD sludges



Environmental Protection
TRW Systems

Sludge Fixation Technology

None specified


Anschutz Corp. (Ansorb)
.Polyolefins                 Soluble
High-density polyethylene   Misc.

Calcium sulfite or sulfate  FGD sludges
Glass or ceramics


Clay-like material

Oil field

 Inorganic  Stabilizers—
      Lopat Enterprises,  Inc., of Asbury Park, New Jersey has developed a
 product  called "K-20"  (McDaniel, 1983).  K-20 is an inorganic mixture of at
 least eight chemicals  (McOaniel, 1983).  No further information on its content
 is  available at this time.  Lopat, Inc.', has a patent pending for K-20, which
 was originally developed as a sealant  for leaky basements (Goldensohn, 1983).
 Recent investigations  have shown evidence that dechlorination of chlorocarbon
 contaminants may occur when K-20 is used as an encapsulant (Jiranders, 1984).

 Pretreatment Requirements/Restrictive Waste Characteristics—
      Stabilization is more frequently used for inorganics because organics
 tend  to  interfere with the physical and chemical processes which are necessary
 to  bind  the materials  together (Spooner, 1985; Hazardous Waste Consultant,
 1985;  GCA, 1985).  Wastes with greater than 10 to 20 percent organic content
 are generally not recommended for treatment by stabilization.

 5.5.2  Treatment Performance Evaluation

      In  1985,  the Solid Waste Research Division of the Disposal Branch of the
 U.S. EPA sponsored a study to find the optimum mixture of asphalt and soil
 cement that will stabilize 2,3,7,8-TCDD-contaminated soil (Vick, 1985).  The
 Portland Cement Institute and the Asphalt Institute will be reviewing the
work.  In t!.'  laboratory, stabilized soil underwent a leach test designed by
Battelle- Columbus Laboratory.  A structural integrity test was suggested, but
not undertaken, because  the soils are not expected to be subject to  large
 loads  (even though strength tests are often an indication of durability).
     JRB Associates, under the sponsorship of the U.S. EPA, conducted a  field
 test of cementious and asphaltic stabilization techniques in the State of
Missouri during 1985 (Vick, 1985; Ellis, 1986).  The objectives of this
testing program included:

     •    evaluating the cost-effectiveness of the processes;
     •    developing optimum soil/stabilizer ratios and mixing conditions; and
     •    assessing the viability of successful field implementation.

       TABLE 5.5.2.
 Soil type

Residential area with
steep, sloping banks
that drain into a
nearby creek

Roadside material
Roadside material,
with considerably
greater percentage
of fine particles
(salt and clay) than
Piazza Road sample
Sandy loam
Sandy loam
Sandy silty
   700 ppb

   640 ppb

    32 ppb
(Technical Resources, Inc., 1985)

The University of Maryland is currently performing  controlled tests on the
ability of K-20 to decontaminate soils by encapsulation and/or dechlorination
using several chlorinated hydrocarbons including 2,3,7,8-TCDD.  The U.S. EPA
in Cincinnati, Ohio is also running some tests on the  ability of K-20 to
degrade 2,3,7,8-TCDD in soil.  The results of the last two sets of tests may
help to evaluate the effectiveness of this encapsulation agent.

5.5.3  Costs of Treatment

     To date, stabilization/fixation processes have not been fully tested  and
cost effectiveness has not been documented.  Organic wastes are generally more
practically disposed of via other technologies such as incineration.  Fixation
becomes more cost-effective when the organic content of the waste is  small,
thereby making incineration less feasible (e.g., 2,3,7,8-TCDD-contaminated

5.5.4  Process Status

     Application of stabilization/fixation processes to organic wastes  is a
relatively recent development, because organic wastes generally lend
themselves better to other treatment processes such as incineration or
biodegradation.  Preliminary studies of contaminated soil suggest  that  an
emulsified asphalt-lime combination may be an effective interim remedial
measure for stabilization of dioxin-contaminated soils (Vick, 1985;  Ellis,
     Further studies plan to investigate the  leaching potential and
performance of formulations using uncompacted soils (Vick, 1985).   Future
goals are to develop a procedure whereby temporary in-situ stabilization could
be followed by soil/stabilizer removal and complete stabilization or fixation
at an offsite facility.

      Tests  have  also  been done on synthetic wastes containing PCDDs.  In one
 of these  experiments,  2,7-DCDD, when mixed with RuO, in a carbon
 tetrachloride  solution was determined to have a half-life of 215 minutes at
 30°C;  the half-life decreased to 38 minuses at 50°C.  The oxidation of
 2,3,7,8-TCDD proved to be a slower reaction; at 20°C it had a half-life of
 560 minutes, while at  70°C the half-life decreased to slightly less than
 15 minutes.

 5.6.3  Costs of  Treatment

     Due  to the  current level of development of this technology, no cost data
 are available.   Major  costs would be for energy to heat up the material to be
 treated,  and the cost  of the chemical reagents.  Pretreatment, extraction and
 post-treatment costs are unknown.

 5.6.4  Process Status

     To date,  this method of degrading TCDD has only been performed on  a
 laboratory scale.  While these studies have shown that RuO, has  the ability
 to degrade 2,3,7,8-TCDD, the reaction end products have not been identified.
 In addition, the only  work reported has involved either the use  of water or
 CC1, as the solvent.   Water is not very effective, and the application  of
 carbon tetrachloride to soil would not be environmentally acceptable.   Thus,
 the use of other solvents should be investigated.
     This technology will require considerable work before it can be  applied
 in the field.  The high cost of ruthenium tetroxide and the toxicity  of
 process residuals may  limit application of this technology.   Its potential  (if
 any) probably  lies in  the area of detoxification of glassware or purging of
 industrial reactors (des Hosiers, 1986).


 5.7.1  Process Description

     A method  for the  degradation of substances containing both aromatic  rings
and ether bonds  was reported in 1979 (Hotre,  1979;  des Rosiers,  1983;
Esposito, 1980).  This is of current interest  because  2,3,7,8-TCDD  contains

 decomposition of 2,3,7,8-TCDD without irradiation.   This  latter method
 utilizing chloroiodides is therefore more suitable  for  degrading bulk
 5.7.2  Technology Performance Evaluation

     No commercial processes utilizing chloroiodides for  decomposition  of
 2,3,7,8-TCDD are known to exist.  However,  experiments  illustrating  the use of
 surfactants containing chloriodides for the cleavage of ethers have  been
 accomplished.  These experiments have been performed on substances such as
 xanthene, benzofuran, and 2,3,7,8-TCDD (Botre,  1979).  All substances tested
 confirmed that chloroiodides aided in the decomposition.   This discussion will
 be  limited to the results from experiments on 2,3,7,8-TCDD.
     In one study, solutions containing 2,3,7,8-TCDD in benzene  were vacuum
 evaporated and the residues were treated with aqueous surfactant solutions
 (Botre, 1979).  Two chloroiodide derivatives were used in the surfactant
 solutions:  benzalkonium chloroiodide, and cetylpyridinium chloroiodide.  When
 benzalkonium was used, a 71 percent decomposition of 2,3,7,8-TCDD was
 observed.  When cetylpyridinium chloroiodide was used,  a  92 percent
 decomposition of 2,3,7,8-TCDD was achieved.  Reaction products  included
 chlorophenols, phenols, and 2-phenoxychloro-phenols.  Quantitative information
 was not available for these substances.  The results were obtained under  ideal
 conditions,  so extrapolations to actual decontamination should be made  with
 great care.
     Contaminated soil samples from Seveso, Italy were also treated
 (Botre, 1979; des Roaiers, 1983; Esposito, 1980).  Samples were  prepared by
 treating the soil with solutions containing surfactant micelles with
 chloroiodides and micelles without chloroiodides.  A benzalkonium chloride
micellar solution showed approximately a 14 percent decomposition of
 2,3,7,8-TCDD.  A solution containing benzalkonium chloroiodide in a micellar
 solution showed a decomposition of 52 percent of 2,3,7,8-TCDD.  Thus,  the
 addition of chloroiodides to micellar surfactant solutions greatly enhances
 the decomposition of 2,3,7,8-TCDD.  This study did not specify whether or not
 exposure to UV radiation occurred.  UV radiation may or may not enhance
 decomposition significantly, depending on  the experimental configuration.


 5.8.1  Process Description
     Gamma rays are electromagnetic waves of energy  (photons) similar to
 x-raya, except that they are commonly generated  in different ways and are of
 much higher energy.  In fact, gamma rays  possess the highest energy levels of
 all radiation in the electromagnetic spectrum.   Gamma rays are emitted from
 the nucleus of radioactive substances as  a result of transitions of protons
 and neutrons between two energy levels of the nucleus.  X-rays, on the other
 hand, are the result of the de-excitation of electrons  to a  lower energy
 state.  The energy of gamma rays ranges between  10 thousand electron volts
 (KeV) and 10 million electron volts (MeV).
     The mechanism of gamma ray interaction with matter is a complex function
 of the radiation energy and the atomic number of the material  (Kircher,
 1964).  At low energies, the gamma photon is completely absorbed by an
 electron and the electron is ejected from the atom (photoelectric effect).   At
 higher energies,  the photon can eject more strongly  bound electrons, with the
 photon being scattered at a reduced energy (Compton  effect).   The scattered
 photon can also interact with electrons.   At still higher energies, the gamma
 ray can interact with a nucleus and be absorbed, resulting  in  the production
 of two particles, a positive and a negative electron (pair production).  The
minimum photon energy for pair production is 1.02 MeV.
     In each of the mechanisms described  above,  energetic electrons are
 produced, and it is this internal electron bombardment that  actually  causes
 chemical changes in a material irradiated by gamma rays*  Rupture of  chemical
 bonds results from the electron bombardment; thus organic  hydrocarbons can be
effectively degraded by gamma radiation.
     Commercial sources of gamma radiation generally are  unstable  isotopes of
 cesium and cobalt.  Gamma rays from cesium and cobalt-60  sources  have  energies
 in the range of 0.40 to 1.33 MeV.  In this range, the  primary  mechanism of
gamma ray interaction with matter is the  Compton effect.

                       10              20

               Total absorbed dose (million rads)
Figure 5.8.1.  Effect of Gamma Ray irradiation on 2,3,7,8-TCDD
               concentration in ethanol, acetone and dioxane
               [Fanelli, 1978J.


     Further research is needed to verify the  possible application of g<
ray radiolysis in the destruction of dioxin molecules in soils.  Based on
experimental data,  it appears that a minimum dosage  of 30 million rad of
radiation is required to reduce the 2,3,7,8-TCDD  level from 100 ppb to 30 ppb.
(Fanelli, 1978).

Bumpus, J.A.,  Tien,  M.,  Wright,  D.A.  and Aust, S.D.  Oxidation of
     Persistent Environmental  Pollutants by a White Rot Fungus.  Science.
     2^8:1434-1436.   1985.

Buser,  Hans-Rudolph.  Preparation of  Qualitative Standard Mixtures of
     Polychlorinated Dibenzo-p-dioxinsJ and Dibenzofurans by Ultraviolet and
     -Irradiation of the Octachloro Compounds.  Journals of Chromatography.
     129:303-307.  1976.

Centofanti, L.  PPM, Inc.  Personal Communication.   1986.

Camoni, I., et al.  Laboratory Investigation  for the Microbial Degradation of
     2,3, 7,8-tetrachlorodibenzo-p-dioxin in Soil by  Addition of Organic
     Compost.   In;  Chlorinated Dioxins and Related  Compounds:  Impact on the
    . Environment.  0. Hutzinger, et al.,  editors.  Pergammon Press,  New York,
     New York.  pp.  95-103.  1982.

Chakrabarty, A. M.  University of Illinois Medical Center  at Chicago.
     Personal communication with M. Sutton, GCA Technology Division, Inc..
     17 January  1984.

Chatterjee, D. K., A. M. Chakrabarty.  Generic Rearrangements  in Plasmids
     Specifying Total Degradation of  Chlorinated Benzoic Acids.   Mol.  Gen.
     Genet, 188:279-285.  1982.

Chatterjee, D. K., A. M. Chakrabarty.  Genetic Homology Between Independently
     Isolated Chlorobenzoate-Degraditive Plasmids.  Journal of Bacteriology,
     153(1):532.  January 1983.

Chemical Engineering.   Commercial Scale Ultraviolet Destruction of Dioxin.
     88(18):18.  September 7, 1981.

Commoner, B., and R. E.  Scott.  Center for the Biology of Natural Systems,
     Washington  University, St. Louis, Missouri.   USAP Studies on the
     Stability and Ecological Effects of TCDD (Dioxin):  An Evaluation
     Relative to the Accidental Dissemination of 2,3,7,8-TCDD at Seveso,
     Italy.   1976.

Corwell, D.,  Yamasaki,  R. S.  Journal of Chemical Physics, 2(5):1064-1065.
     November 1957.

Cotter,  J.  L., et al.   TRW, Inc., Redondo Beach, CA.  Facilities Evaluation of
     High Efficiency Boiler Destruction PCB Waste - Research Brief.  January
     to  April 1980.  EPA Reprot No.  EPA-600/7-81-031.  NTIS.  1981.

Craft, T. P., R.  D. Kimbrough,  and C. T. Brown.  Georgia  Institute  of
     Technology.  Radiation Treatment  of High Strength Chlorinated  Hydrocarbon
     Wastes.  U.S. EPA  Report.EPA-660/2-75-017.  July 1975.

Craft, T.F.   Georgia Institute  of Technology.  Telephone  communication.
     May 1984.

 Fanelli, R., C. Chiabrando,  M.  Salmona,  S.  Garattini, and P. G. Calders.
      Degradation of 2,3,7,8-Tetrachlorodibenzo-p-dioxin in Organic Solvents by
      Gamma Ray Irradiation.   Experentia.  34(9):1126-7.  September 9, 1978.

 Firestone,  F.   Oil and  Hazardous Materials  Spills Branch.  Telephone
      conversation with  T.  Murphy,  GCA/Technology Division.  19 January 1984.

 Fisher,  Marilee.   SunOhio,  Inc.  Personal Communication.  1986.

 Flax,  L.  Lopat Enterprises,  Inc.   Telephone Conversation with Lisa Farrell,
      GCA Technology Division,  Inc.  May  19, 1986.

 Furukawa,  K.,  A.  M. Chakrabarty.   Involvement of Plasmids in Total Degradation
      of  Chlorinated Biphenyls.  Applied  and Environmental Microbiology,
      44(3):619.   September 1982.

 Ghosal,  D.,  et al.   Microbial Degradation of Halogenated Compounds.  Science,
      220:   135-228.

 Gibson.   Personal communication with M.  Sutton, GCA Technology Division, Inc.
      17  January 1984.

 Oilman,  W.  S.  United States Testing Company, Inc., Chemical Services Division.
     Report  of Test, January 4, 1983, February  7, 1983, February 17, 1983, May
      31,  1983, June 13, 1983, August 4,  1983, August 19, 1983, August 23,
      1983, October  13,  1983, October 21, 1983, December 22, 19*3.

 Goldensohn,  R.  Red Tape Slows Jersey Inventors' PCB eater.  Sunday Star-
     Ledger, Neward, NJ, 70(223):68.  9 October 1983.

 Goldsmith, D.  Environmental Engineer, Sybirn Corporation.  Personal
     Communication  with M. Arienti, GCA Technology Division.  April  29,1986.

Hay, A.  Disposing  of Dioxins by Oxidation.  Nature, 290:294.  March 26, 1981.

Hazardous Waste Consultant.  Stabilizing Organic Wastes:  How Predictable
     Are The Results?  Volume 3, Issue 3, Pages 1-18 to 1-19.  May/June  1985.

Helsel, R., et al.   Technology Demonstration of a Thermal Desorption/UV
     Photolysis Process for Decontaminating Soils Containing Herbicide
     Orange.   Preprint extended abstract.   Presented before the Division of
     Environmental  Chemistry.  American  Chemical Society.  New York.
     April 1986.

Hutter, R., and M.  Philippi.  Studies on Microbial Metabolism of TCDD
     Under Laboratory Conditions.    In;  Chlorinated Dioxins and Related
     Compounds:   Impact on the Environment.  0. Hutzinger, et al., editors.
     Pergammon Press, New York, New York.   pp. 87-93.  1983.

IT Corporation.   Interim Summary Report  on  Evaluation of Soils Washing  and
     Incineration as On-Site Treatment Systems  for Dioxin-Contaminated
     Materials.  EPA Contract No.  68-03-3069.   1985.

Legan, R.W.  Ultraviolet Light Takes on CPI Role.  Chemical Engineering,
     9(2):95-100.  January 25, 1982.

Lubovitz, H. R., et al.  Contaminant Fixation:   Practice and Theory.  Land
     Disposal of Hazardous Waste.   Proceedings  of the Tenth Annual Research
     Symposium.  EPA-600/9-84-007.   April 1984.

Nalone, P.  U.S. Army Engineer Waterways Experiment Station, Vicksburg,
     Mississippi.  Telephone conversation with  R. Bell, GCA/Technology
     Division.  27 March 1984.

McDaniel, P.  Inventors Say They Can Neutralize Dioxin.  Asbury  Park Press,
     Asbury Park, NJ.  p. A4.   12  June  1983.

Miille, G. J.  Acurex Corporation.   Paper presented to  the PCB Seminar,
     sponsored by the Electric Power Research Institute.  December  19bl.

M. M. Dillon, Ltd.  Destruction Technologies for Polychlorinated Biphenyls
     (PCBs).  Prepared for Environment  Canada,  Waste Management  Branch.   1982.

Peterson, R. L., et al.  Chemical Destruction/Detoxification of  Chlorinated
     Dioxins in Soils.  Paper presented at Eleventh Annual Research Symposium
     on Incineration and Treatment of Hazardous Waste.  EPA-600/9-85-028.
     September 1985.

Peterson, R. L., et al.  Comparison of  Laboratory and Field Test Data  in the
     Chemical Decontamination of Dioxin Contaminated  Soils Using the Galson
     PKS Process.  Preprinted Extended  Abstract.  Presented  before  the
     Division of Environmental Chemistry.  American Chemical Society.
     New York.  April 1986.

Peterson, R.L. Galson Research Corporation, E.  Syracuse,  NY Telephone
     Conversation with M. Jasinski, GCA Technology Division,  Inc.  June 19£ba.

Philippi, Martin, et al.  Fate of 2,3,7,8-TCDD  in Microbial  Cultures  and in
     Soil Under Laboratory Conditions.   Fens Symp.,  Vol.  12,  Iss. Microbial
     Degradation Xenobiotics Recalcitrant Compd.  pp.  221-3.   1981.

Philippi, M., et al.  A Microbial Metabolite of TCDD.   Experientia,
     38:654-661.  1982.

Pierce, F.  Sandia National Lab.  Telephone Communication.   May 1984.

Pocchiari, F.  2,3,7,8-Tetrachlorodibenzo-p-dioxin Decontamination.  In:
     Chlorinated Phenoxy Acids and Their Dioxins.  Ramel,  editor.  Ecol.
     Bulletin (Stockholm), 27:67-70.  1978.

Poiger, H., et al.  Special Aspects of Metabolism and Kinetics of 2,3,7,8-TCDD
     in Dogs and Rats - Assessment of Toxicity of 2,3,7,8-TCDD Metabolites  In
     Guinea Pigs.  In:  Chlorinated Dioxins and Related Compounds:  Impact  on
     the Environment.  0. Hutzinger, et al., editors.  Pergammon Press, New
     York, New York.  pp.  317-324.   1983.

 Tellea, R. W., et al., Review of Fixation Processes to Manage  Hazardous Organic
     Waste.  Draft Report.  Carlton Wiles, Project Officer,  MERL, Cincinnati,
     Ohio.  April 1984.

 Tieran, T. 0., et al.  Dioxins.  Industrial Environmental Research  Laboratory,
     Office of Research and Development, Cincinnati, Ohio.  EPA-600/2-80-197.
     November 1980.

 Tieran, T. 0.  Chlorodibenzodioxins and Chlorodibenzofurans:  An Overview,
     Detoxification of Hazardous Waste.  Ann Arbor Science,  Ann Arbor,
     Michigan,  p. 245.  1982.

 Tittlebaum, Marty E., et al.  State-of-the-Art on Stabilization of
     Hazardous Organic Liquid Wastes and Sludges.  In:  Critical Reviews  in
     Environmental Control, 15(2)-.179-211.  1985.

 Tridje, J.  Michigan State University.  Personal communication with M.  Sutton,
     GCA/Technology Division.  18 January 1984.

 Tundo, P.  Chemical Degradation of 2,3,7,8,-TCDD By Means of Polyethylene-
     glycols in the Presence of Weak Bases and an Oxidant.  In; Chemosphere.
     Volume 14, No. 5, pp. 403-410.  1985.

 Tumiatti, W.  Site Decontamination and Chemical Degradation of PCDFs and
     PCDDs Coming From Pyrolysis of PCBs.  Preprinted Extended Abstract.
     Presented Before the Division of Environmental Chemistry.  American
     Chemical Society.  New York.  April 1986.

 U.S. Army Engineers, Waterways Experiment Station, Environmental Laboratory,
     Vicksburg, Mississippi.  Guide to the Disposal of Chemically Stabilized
     and Solidified Waste.  Report prepared for U.S. EPA, Solid and Hazardous
     Waste Research Division, Municipal Environmental Research Laboratory,
     Cincinnati, Ohio.  EPA-IAG-D4-0569.  September 1982.

 Valentine, R.S.  LARC-Light Activated Reduction of Chemicals.  Pollution
     Engineering.  1981.

 Vanness, G. P., et al.  Tetrachlorodibenzo-p-Dioxins  in Chemical Wastes,
     Aqueous Effluents and Soils.  Chemosphere.  9(9):553-63.  1980.

 Vick, W.H., S. Denzer, W. Ellis, J. Lambauch, and N. Rottunda.  Evaluation of
     Physical Stabilization Techniques for Mitigation of Environmental
     Pollution from Dioxin-Contaminated Soils.  Interim Report:  Summary of
     Progress-To-Date.  Submitted to EPA-HWERL by SAIC/JRB Associates, EPA
     Contract No. 68-03-3113, Work Assignment No. 36.  June 1985.

Ward, C. T., et al.  Fate of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (2,3,7,8-TCDD)
     in a Model Aquatic Environment.  Archives of Environmental Contamination
     and Toxicology.  7:349-357.  1978.

                                   SECTION  6

     Section 3 contained information on the quantities and  types  of  dioxin
wastes generated by industrial processes and residuals identified as sources
of dioxin-containing waste.  Table 6.1 summarizes information on  their
sources, their usual physical form, and estimates of present  and  future
quantities of wastes generated within each EPA waste code.  Sections 4 and  5
contained information on the technical aspects of a number  of potential
treatment technologies for these wastes.  This information  is summarized in
Table 6.2.
     The purpose of this section is to review this previously developed
information and identify factors which would affect the selection/use of a
particular technology for treating a specific waste type.   This document has
been concerned largely with the assessment  of the technical factors  relating
to treatment technology performance.  However, both technical performance and
cost will generally be considered when selecting the most appropriate process
for a -specific waste stream.  Both are considered in the following discussions.


     Key factors which should be considered in assessing the  technical
applicability of treatment technologies to specific waste streams include:

     I.    Has the technology demonstrated that it can achieve 99.9999 percent
          ORE on CDD (or similar compounds)?

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                             _      ^ _ jj.0|   J0} ng „„,„ ,,, UW|(J j,,MJO     p»AOjdd» |>J>A>S   tatpnii 'ipinbi) *ipi|os    Xjcioi  XJiuoiitij
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                                                    TABLE  6.2  (continued)
Proceaa name
UV Photolysis
APEC procaaaea
• inimical
waste streams
Liquids, atill bottoms,
and aoila can be treated
if dioxin ia firat
extracted or deiorbed
into liquid
Contaminated aoil (other
variation! of the proceaa
uaed to traat PCS-conta-
minated oila)
Research haa bean directed
Stage of
Pull scele aolvent
proceaa waa uaed to
treat 4,300 gallona
of atill bottom! in
1980; thermal de-
aorpt ion/UV procaaa
currently undergoing
aecond timid teit
Slurry proceea
currently being
field teated at
pilot acala; in aitu
procaaa haa bean
teatad in the field
destruction achieved
Greater than 98. 7S raduction of
TCDD uaing aolvent extraction/
UV proceaa - raaiduala con-
tained ppm concantrationa of
TCDD; thermal daaorption/UV
proceaa demonstrated reduction
of TCDO in aoil to below 1 ppb
Laboratory reaearch hae
demonstrated reduction of
2,000 ppb TCDD to below 1 ppb
for slurry (batch proceaa);
laboratory and field teating
of in aitu proceaa not aa
SO-60X metabolism of
Coat of treeting
the 4,300 gallona
of atill bottom!
using solvent
extraction/UV waa
SI million; ther-
mal deaorpt ion/UV
eatimated to coat
t296/ton for in
aitu APRC proceaa;
|9l/ton for
alurry (batch)
Solvent extrect ion/UV
process genereted treated
atill bottoms, a solvent
extract atream, and an
aqueous sslt streem;
thermel desorption/UV
•trea* and a solvent
Treated soil containing
chloride aalta (reagent
ia recovered in the
•Lurry proceaa)
Degradation-         toward in aitu treatment   acala-field teating  TCDD in a week  long period
primarily in aitu    of contaminated aoila -    in next year or two  under leb conditiona uaing white
addition of microbe! liquid! era alao poaiibla                       rot  fungua -  reduction to
                                                                     below 1 ppb not achieved
Degradation uaing
lutbenium Tatroxida
Degradation uaing
                     Liquid or aoil  waataa  -
                     poaalble moat affactlva
                     in decontaminating
                     furniture, othar  aurtacaa

                     Liquid or aoil  -  thought
                     to be mo»t applicable  to
                     decontaminating furniture
                     and buildinga
Laboratory acale -
no work reported
alnca 1*6)
Laboratory acala -
no work reported
aince 198)
Reduction of 70 ppb TCDD to
below 10 ppb in 1 hr (on aoil
Up to 92X degradation on
aolution of TCDD in banxene  -
reduction! to below 1 ppb were
not demon!treted
                                                                                                                        as aoil or water with TCDD
                                                                                                                        metabolites depending on
Treeted medium plui the
aolvent which has been
edded (weter, CCI4); TCDD
and products not known

Treated waste medium;
degredetion end producta
are chlorophenola
      Ray Radiolyaii Liquid waste atreama (haa  Laboratory raaearch;  97X deatruction of  2,3,7,8-TCDD  Coat for aewage
                     been applied to sewage     no reaeerch          in ethanol  after 30 houra -      die infect ion
                     aludge diainfection)
currently being
                                                                     100  ppb  to  )  ppb
                                                   Leai chlorinated dioxin
                                                   molecules sre  the degrede-
                                 fscility  treating  tion end product! in add-
                                 4  tone  per  day  ii  it ion to the treated waata
                                 |40  per ton; TCDD  medium
                                 treetment would be
                                 more expenaive

                                TABLE 6.3.   TREATMENT  TECHNOLOGY SELECTION  CHART
Ho* dmon-
niaae Ml on Procaaa can Can treat
dioiU and/or be carried aolida Can treat
reduction of Ha a danao- Mobil* or out in aitu auch •• liquid* Currant IT being I* • pre-
dioxlo in atratad aix traoaportabl* (without aoila and and lev io**ati«*tad treacnant or
residual* to nine* Ml proceaa can be excavation heavy «i*co*ity "ith regard to temporary I* • final
»««*••• ••»•» 1 H* of KM conatructed of .oil) .ludge* sludge* dioxin «..t* proceaa proce.a
Stationary rotary kiln X X° X X
Mobil* rotary kiln I* I I X" I I
Liquid injection incinerator I X
fluidiaod bed f circulating bed IX X» I
•igb tao»>eratura fluid wall         I*            X          I                       X"         X           X                           x
(Huber AM)

Infrared incinerator (Shirco)       I                        I                       x                      X                           X

rlaama arc                                       II                                  IX                        * ' I

Molten aalt        ,                              I          I*                      x(         X                                       x

Supercrlticel voter'                I«         ,             X                       X*         Xn          X                           X

!• *itu "vitrification                                                    IX                                                  X

Solvent a*tractloo                                                                  XB         X           X            X

Stebilisatlon/iixatio*                                                   IX                      IX

UV pbotoly*!*                      ic                                               X4         X           X                           X

ChaeUcel decblorination (APIC)      X«                       x           x1          X»         I           X                           X

                                                                        X           X»         I           X                           X

      iun> tatroxida                                                                  Xh         X                                       X

Cnloroiodidee                                                                       X          Xh                                      X
•tP4 BObila rotary kiln.                                                  fThere exiat* botb an in  situ end a batch  reactor procaaa.
•Tbair atationary unit ia permitted to do raeaarch on dloxio waatea.         (High eah vaate* nay poae problaaia.
cDe»eloper ha*  indicated thia,  but pr***nt*d no data.                       hlndicatae primary vaet*  type.
dU»ing laboratory ecele equipment.                                         'solid* only treated if aon« aorc of axtractioo/daaorptlon
•One developer  ie deaigning a noblie unit.                                  procaaa r*w>vea the dioxin fron aoil.

 6.1.3  Mobile/Transportable Technology

     The ability to bring the waste treatment unit to the waste site is very
 important, particularly when treating "dioxin" waste.  The transportation of
 dioxin waste is very controversial, and has been opposed
 by the public in several instances.  For example, an attempt was made to
 obtain permission to transport dioxin-containing leachate to the SCA
 incinerator in Chicago.  Illinois residents strongly objected to this, and
 local authorities indicated that drastic measures would be used to block the
 effort (Gianti, 1986).  As a result, many of the developing thermal and
 nonthermal technologies are being designed to function as mobile/transportable
 units that can be taken to the waste site.  The units that are mobile are
 identified in Table 6.3.  Stationary treatment facilities, even though they
 are able to demonstrate high levels of destruction, may not be fully utilized
 for highly toxic dioxin wastes.
     In addition to avoiding the risk of spillage during transportation,
 another advantage of the use of a mobile unit is that the cost of transporting
 the waste to the treatment facility is eliminated.  For each of these reasons,
 processes that are designed to be mobile appear to be more useful for treating
 listed dioxin wastes.

 6.1.4  In Situ Technology

     Similarly, processes than can treat the waste in situ may also be
 advantageous.  In situ processes are aimed primarily at contaminated  soil.
Most processes require that the soil be excavated and then be  fed to  the
 treatment process.  A process in whicfc" the excavation step is  eliminated may
 be more environmentally and economically acceptable  than a process  that  relies
 on excavation of the waste*  Not only  is excavation  expensive, but  it may also
 result in the dispersal of contaminated soil particles and greater  human
 exposure to the contaminant.  Processes with the potential for in situ use
 include chemical dechlorination, in situ vitrification, biodegradation,  and
 stabilization/fixation.  Chemical dechlorination, using potassium polyethylene
glycol (KPEG), has been tested both as an  in situ and a batch  reactor type of
process.  As indicated in Section 5, the batch reactor variation of the


 gamma ray radiolysis.  Other technologies, including both fluidized bed and
 rotary kiln incineration, chemical dechlorination, and the high temperature
 fluid wall process  have been used to treat both liquid and solid wastes.
 Finally,  other processes are designed to be used primarily for either liquids
 or solids,  but if certain pretreatment measures are applied, they may be able
 to treat  both waste forms.  For example,  ultraviolet (UV) photolysis is only
 effective in treating waste streams that the radiation can penetrate, such as
 a  nonabsorbing liquid.  If, however, the contaminant is first desorbed, either
 thermally or using  an organic solvent, a contaminated soil waste can be
 treated using this  technology.
      Perhaps the most important factor with regard to the physical properties
 of a  waste  stream is that each waste stream must be treated individually, and
 variations in waste characteristics fully assessed, to ensure that
 unanticipated difficulties do not arise.  Even though pilot or laboratory
 scale data may indicate that a certain waste form is easily treatable,
 processing of the actual waste stream may pose problems.  One example of this
 is the trial burns  of Vertac still bottoms at the Combustion Research
 facility.  The waste stream, on the basis of preliminary evaluations, was
 originally pumped through a feed lance into the rotary kiln without dilution
 or mixing with fuel.  However, the lance frequently became inoperative due to
 clogging  and carbon buildup, and the waste feed had to be interrupted  so the
 lance  could  be cleaned.  The problem was finally rectified by diluting the
 waste  with water prior to pumping it into the kiln (Ross et al.,  1986).
 Another example is  the application of KPEGs directly to soil (in  situ) to
 dechlorinate TCDO.  In the lab, the process was fairly successful, but when
 applied in the field the KPEG reagent was seriously degraded by moisture in
 the soil, and the resulting degradation of TCDD was minimal.  A third  example
 involves  the Huber  AER.  This unit was originally tested on very  granular,
 uniform materials such as sand.  In reality, all contaminated solids or  soils
 are not as dry and  uniformly graded as sand.  Consequently, when  the Huber
 reactor was  tested  on actual waste, there were problems with the  feed
mechanism.  Special pretreatment measures to produce a granular,  free-flowing
 feed had  to  be incorporated (Boyd et al., 1986).
     To summarize,  waste characteristic* and process capabilities must be
carefully evaluated before the appropriate treatment technology can  be applied.

      The  cost  of  treating dioxin-containing waste is very much affected by the
 high  level  of  risk associated with the treatment of these waste streams and
 their residuals.  Generally, processing of these wastes requires the
 imposition  of  extraordinary and often redundant measures to ensure that risks
 are not incurred  by workers and the general population.  One example of this
 was the attempted incineration several years ago of 6,000 gallons of solvent
 waste contaminated with  14 ppb of TCDD.  The Dioxin Disposal Advisory Group
 (DDAG) recommended incineration of the waste at the ENSCO incinerator in
 Arkansas.   ENSCO  usually charges $325 per 55-gallon drum of hazardous waste,
 but in this case  they would have charged $45,000 for the waste plus a $150,000
 surcharge because it contained dioxin (Technical Resources, Inc. 1985)*  This
 amounts to  a unit cost of approximately $30/gallon ( $1,500 per 55-gallon
 drum)  or $6,000/ton for  10 Ib/gallon waste.  In the end, however, ENSCO
 refused to  accept the waste because of overwhelming public opposition (and
 implied liability).
      Cost will always be an important factor in the selection pf a treatment
 method, but at this time the demonstration of technical and environmental
 effectiveness  appears to a more overriding concern.  Technology oust be fully
 demonstrated for  treating dioxin wastes if public concerns are to be addressed
 and reconciled with the need for effective treatment.

 6.3   SUMMARY

      Each of the  technical and cost factors discussed  above will affect the
 final  selection of a technology to treat the waste.  It is important to keep
 in mind that the  field of dioxin waste treatment  is in a developmental stage.
At the present time, only a few of the technologies have demonstrated  6 nines
ORE on CDDs and CDFs, although many of the technologies are now undergoing
performance testing using dioxin waste, or will undergo testing in  the near
 future.  In addition, with the ban on land disposal of dioxin wastes scheduled
to go  into effect in November 1986, work on the development of additional  new
technologies for  treating these wastes can be expected-to accelerate.
Information in this document represents .the developmental status of dioxin
waste  treatment technologies in the spring of 1986; revisions will  be  required
as anticipated technical advances are made in the future.