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 decomposes by heating or oxidation at  temperatures greater than 1000°C,
 thermal methods  for treating  these wastes have received a large amount of
 attention.   Thermal technologies evaluated  in this document are those in which
 heat  is the major  agent  of treatment or destruction.  Technologies inlcuded in
 this  category are:

      •     Stationary rotary kiln incineration
      •    Mobile rotary  kiln  incineration
      •    Liquid injection incineration
      •    Fluidized—bed  incineration
      •     Infrared  incineration
      •    High temperature fluid wall destruction
      •     Plasma arc pyrolysis
      •    Molten salt destruction
      •    In situ vitrification
      •    Supercritical water oxidation

      EPA has  indicated that incineration is currently the only sufficiently
 demonstrated treatment technology  for dioxin-containing waste (51 FR 1733).
 RCRA  performance standards for incineration and other thermal treatment
 processes require the  demonstration of 99.9999 percent destruction and removal
 efficiency  (DRE) of  the principal  organic hazardous constituent (POHC).
 Several of the thermal technologies have demonstrated this performance on
 chlorinated compounds  of one type or another.   However,  only three,  and
 perhaps four, thermal technologies have been demonstrated to achieve this
 level of performance  on dioxin.  These technologies are the EPA mobile rotary
 kiln incinerator, Huber's high temperature fluid wall reactor,  Shirco's
 infrared incinerator, and possibly, Modar1s supercritical water oxidation
process.  Modar has not yet released data conclusively showing  six nines  DRE,
but they do claim to have achieved this performance.   Thermal technologies
that have achieved six nines DRE on PCBs include  stationary rotary kiln
incinerators, liquid injection incinerators, fluidized-bed incinerators  (the
                                      1-10

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circulating bed variation), the plasma arc process,  and the molten salt
process.  The in situ vitrification process has not  shown six nines DRE;
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 1 ppb, and then
destroyed efficiently using ultraviolet radiation.  The chemical
dechlorination process has also demonstrated a reduction of  TCDD  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
                                      1-11

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demonstrated the ability to reduce dioxin in contaminated soil to a level of
1 ppb.  Biodegradation is also a potentially attractive approach since it
presumably would not require the large energy inputs, sophisticated equipment,
and the chemical additions that the other technologies require.  However,
biodegradation, particularly in situ, has not proven to be very effective as a
dioxin destruction process.  Stabilization and/or fixation would allow the
treatment of contaminated soils in place.  Since this method does not involve
destruction of the dioxin there is always the possibility that the stabilized
waste/soil matrix will break down and the dioxin will be released.  Finally,
the last three technologies listed (two chemical degradation processes and
  i
gamma ray radiolysis) are methods that have been studied in the laboratory but
have not yet shown enough promise technically or economically to be developed
on a larger scale.  Investigation of these methods, at this time, appears to
have stopped.
     Of all the treatment technologies evaluated, none is currently
commercially available for the treatment of dioxin wastes.  The EPA mobile
incinerator has been used to treat a variety of waste forms at the Denney Farm
in Missouri, but this unit is intended to be used for research purposes and
not as a commercial treatment process.  The high temperature fluid wall
process (AER) operated by Huber at its Borger, Texas facility is permitted to
perform research on dioxin contaminated wastes and is also a research tool
which is'not intended to be used for actual waste treatment.

CONCLUSIONS
     Dioxin wastes, particularly those dioxin—contaminated soils which account
for over 98 percent of the contaminated wastes identified in Table 1.2,
contain low levels (10 to 100 ppb) of dioxins and/or dibenzofurans.
Nonetheless, many technologies, particularly the thermal destruction
technologies, require that the total quantity of the waste be treated to
destroy the extremely low dioxin fraction resulting in very high energy usage
for dioxin destruction.  In addition, when incineration and other thermal
destruction technologies are used, large quantities of exhaust gases are
generally formed.  These waste streams can contain toxic products of
incomplete combustion (PICs) and other hazardous emissions.  They and other
                                     1-12

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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.
                                     1-13

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                                  SECTION 2.0
                       REGULATIONS CONCERNING MANAGEMENT
                            OF LISTED DIOXIN WASTES
 2.1  CURRENT REGULATION UNDER RCRA
      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 Amendments list as acute hazardous
wastes certain chlorinated dibenzo-p-dioxins, dibenzofurans, and phenols (and
their phenoxy derivatives).  A complete listing was presented in Table 1.1.
When  the RCRA Amendment listing dioxin-contaminated wastes became effective on
July  15, 1985, duplicate listings of certain dioxins under RCRA and TSCA were
revoked.
      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

                                      2-1

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prohibit the landfilling of "dioxin-contaminated wastes."  However,  there is a
four year exemption for response actions taken under CERCLA Section 104 or
106.  Therefore, the land disposal of untreated (or unstabilized)
dioxin-contaminated materials will not be prohibited for CERCLA actions until
November 9, 1988.
     HSWA also state that storage (now included within the definition of land
disposal) of hazardous wastes in mines or caves is specifically prohibited
until such time as a permit has been issued under RCRA Section 3005(c).  In
addition, placement of noncontainerized, bulk solids or bulk liquid waste in
underground mines or caves is prohibited until the EPA Administrator has
determined that such placement is protective of human health.  In addition,,
HSWA specify more stringent minimum technology requirements for all new land
disposal facilities.
     The RCRA regulatory amendments of January 14, 1985 (effective
July 9, 1985), listing certain dioxin-contaminated wastes as RCRA acute
hazardous wastes, include specific provisions for the management of these
wastes.  These acute hazardous wastes are subject to the 1 kg small quantity
generator limitation, and residues in empty containers will also be
regulated.  Residues from the incineration of dioxin—contaminated soils are
listed only as toxic RCRA wastes and are not as stringently controlled.  In
addition, a proposed rule in 50 FR 37338 would also make residues from the
incineration of other dioxin-containing  wastes (F020-F027) toxic instead of
acute hazardous wastes, if the wastes contained less than 10 ppm TCDD prior to
incineration.  However, this proposed rule will most likely not be finalized
before the fall of 1986.  All persons who generate, transport, treat, store,
or dispose of the listed wastes were required to notify EPA or an authorized
State by April 15, 1985.  All hazardous waste management facilities which
treat, store, or dispose of the listed wastes, and which qualify to handle the
listed wastes under interim status, were required to notify by April 15, 1985
and submit a Part A permit application by July 15, 1985.  Even those sites
that had qualified for interim status prior to the regulatory amendments are
not allowed to handle the listed wastes unless they qualify to handle these
wastes, notify EPA or an authorized state by April 15, 1985, and submit a
Part A application by July 15, 1985.
                                      2-2

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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
    units;

     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 CFR 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 DRE 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.
                               2-3

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2.2  PROPOSED LAND DISPOSAL RESTRICTIONS

     On January 14, 1986 EPA proposed a framework for a regulatory program to
implement the congressionally mandated land disposal prohibition
[52 FR 1602].  The regulatory framework establishes a new 40 CFR Part 2b8
which specifies treatment standards and effective dates for the
dioxin-contaminated wastes and prohibits land disposal of these wastes unless
the specified treatment standards are achieved.  EPA has proposed specific
constituent screening levels in 40 CFR 268.42 for the dioxin-contaminated
wastes, F020, F021, F022, F023, F026, and F027.  Waste No. F028 is the residue
from incineration or thermal treatment of dioxin-contaminated soil to
six nines DRE.  Waste No. F028 is considered toxic (as opposed to acute
hazardous) and therefore, is not addressed by EPA in these proposed RCRA
regulatory amendments.
     The proposed  treatment standards are based on specific constituent
screening levels.  These screening levels, shown in Table 2.1, are determined
through a toxicity characteristic leaching procedure (detailed in Appendix I
of 51 FR 1750) which tests the extract of the waste for the concentration of
constituents  of concern.  The EPA procedure for.analyzing the extracts
(Method 8280) has  a detection  limit of 1.0 ppb for CDDS and CDFs.  Therefore,
at this time, the  land  disposal  restrictions specify that the residuals from
treatment of  listed dioxin wastes must contain less than  1.0 ppb of
extractable  CDD and CDFs in order for them to be land  disposed as nonhazardous
materials.  As detection limits  are lowered, the treatment standards will
approach the  constituent screening levels.  Nonetheless,  all  land disposal
must meet RCRA regulations established in the January  14, 1985 regulations.
     The proposed  regulations  specify certain prohibitions on storage.
Section 268.50 states that dioxin-contaminated hazardous  waste not meeting
specified  treatment  standards  may not be  stored  in tanks  or containers after
November 8,  1986,  unless:

      1.    The owner  or  operator  of a hazardous waste  treatment,  storage,  or
           disposal facility  stores such waste  for  90  days or  less; or
      2.    A transporter stores manifested shipments of such waste  in
           containers  at a transfer facility  for  10 days or  less;  or
                                       2-4

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    TABLE 2.1.  CONCENTRATIONS OF CONSTITUENTS OF CONCERN WHICH WILL RESULT
                IN BANNING LISTED WASTES FROM LAND DISPOSAL [51 FR 1732]
        Constituent*
Screening level (mg/1)
      2,3,7,8-TCDD
      Other TCDDs
      2,3,7,8-PeCDDs
      Other PeCDDs
      2,3,7,8-HxCDDs
      Other HxCDDs
      2,3,7,8-TCDFs
      Other TCDFs
      2,3,7,8-PeCDFs
      Other PeCDFs
      2,3,7,8-HxCDFs
      Other HxCDFs
      2,4,5—Trichlorophenol
      2,4,6,-Trichlorophenol
      2,3,4,6-Tetrachlorophenol
      Pentachlorophenol
4 x 10
4 x 10
8 x 10
8 x 10
1 x 10
1 x 10
4 x 10
4 x 10
4 x 10
4 x 10
4 x 10
4 x 10
8.0
0.04
2.0
1.0
-9
-7
-9
-7
-5
-8
-6
-8
-8
-7.
-5
*Definitions of abbreviations used above
      TCDDs and TCDFs = All isomers of tetrachlordibenzo-p-dioxins  and
                       -dibenzofurans respectively.
      PeCDDs and PeCDFs = The pentachlorodibenzo-p-dioxins  and  -dibenzofurans.
      HxCDDs and HxCDFs = The hexa-isomers.
                                      2-5

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     3.   Such waste is accumulated onsite by the operator and does  not exceed
          the applicable time limitations set forth in 40  CFR 262.34.


     The proposed regulations also provide the following variances to  the  land
disposal prohibition effective November 8, 1986:


     1.   Extensions past the effective date of the land disposal prohibition
          may be obtained from EPA on a case-by-case basis if the applicant
          demonstrates that,  among other things,  an alternative technology
          will protect human health and the environment  and that this
          alternate technology will not be available by  the effective  date
          and/or capacity for existing technologies will not  be available  by
          the effective date, however,  all efforts have  been  made to meet  the
          deadline (40 CFR 268.4).

     2.   EPA will consider petitions to allow land disposal  in particular
          limits past the effective date of the land disposal prohibition  if
          the applicant demonstrates that, among other things,  there will  be
          no adverse impact on human health and the environment and  no
          migration of hazardous constituents (40 CFR 268.5).

     3.   All wastes meeting the treatment levels specified in 40 CFR  268.42
          may be land disposed in accordance with applicable  RCRA regulations
          after November 8, 1986.

     4.   In the preamble to the proposed regulations, EPA states that a
          nationwide variance of up to 2 years may be granted if alternate
          recovery and disposal capacity is inadequate nationwide.
                                         2-6

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                                   SECTION 3.0
                       CHARACTERIZATION AND QUANTIFICATION
                             OF LISTED DIOXIN WASTES
 3.1  INTRODUCTION
      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 DRE.
 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, FO23, 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).
                                      3-1

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     In order to treat the wastes banned from land disposal  it  is necessary to
be familiar with both the characteristics and quantities of  the wastes which
are to be treated.  The following sections contain information  on the chemical
and physical properties of the constituents of concern along with the nature
of the waste matrices in which they may be found.

3.2  PHYSICAL AND CHEMICAL CHARACTERISTICS OF CONSTITUENTS OF CONCERN

Chlorinated Dibenzo-p-dioxins

     Chlorinated dibenzo-p-dioxins (PCDDs) are organic chemical compounds
consisting of two benzene rings connected by two oxygen atoms opposite one
another (see Figure 3.1).  They may contain one to eight chlorine atoms  at  any
of the eight positions on the two aromatic rings.  PCDDs can exist  in  75
possible congeneric forms, the most thoroughly studied of which is
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (U.S. EPA, 1985;  Environment
Canada, 1985).
     Chlorinated  dioxins are  formed in an exothermic reaction from chlorinated
phenols in the presence of base at elevated temperatures. Most chlorophenols
and  their chlorophenoxy derivatives, whose process wastes are covered under
the  dioxin listing rule, are manufactured under such conditions.   In
combustion processes,  such as incineration, the mechanism forming TCDD has
been estimated to take place most efficiently between 750 and 900°C, while
decomposition of  TCDD is most likely to  occur between 1200 and 1400°C
(Ahling, 1977; Junk and Richard, 1981; Redford, 1981; Shaub and Tsang,  1982).
     Physical and chemical characteristics of some PCDDs are listed in
Table  3-2.   Several properties of TCDD are significant with regard to waste
treatment.   They  include  the  following:

     •   very  low water  solubility;
     •   much  greater solubility  in organic  solvents;
     •    strong  binding  to organic matter;
     •    rapid decomposition at temperatures above  1350°C;
                                       3-4
-------
                        (a) Dibenzo-p-Dioxin
                        (a)  Dibenzofuran
Figure 3.1.
Structure of (a) Dibenzo-p-Dioxin and (b) Dibenzofuran
Source:  Environment Canada, 1985
                              3-5
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          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 1,1,1-trichloroethane and pentachlorophenol.
                                     3-7
-------
Consequently, if heats of combustion were used to determine the relative
incinerability of hazardous constituents, these compounds could be used as
Principle Organic Hazardous Constituents (POHCs) to demonstrate six 9s
destruction.
     Studies have indicated that the biodegradation of TCDD is a slow
process.  As mentioned above, the half-life of TCDD in soil has been estimated
to range from hundreds of days up to more than ten years (Young, 1976;
DiDominico, 1980).  One of the reasons that biodegradation is slow is that the
organisms cannot readily access the dioxin molecule which is usually strongly
adsorbed to soil particles (Crosby, 1985).  There has been some-recent
investigation into the ability of White Rot Fungus to degrade TCDD.  This
organism is extremely effective in biodegrading lignin.  In recent laboratory
tests it has also been effective in degrading chlorinated compounds such as
dichlorobenzene, DDT and TCDD (Bumpus, J. A., et al., 1985).
     Finally, the vapor pressure of TCDD is also very low.  A recent estimate
of this parameter was 1.5 x 10   torr (Freeman, R. A. and J. M. Schroy,
1986).  Consequently, volatilization of TCDD from waste streams or soil is not
expected to be a rapid process.  Of more concern is the wind transport of soil
particles with adsorbed TCDD.

Chlorinated Dibenzofurans (CDFs)
     Chlorinated dibenzofurans are structurally similar to PCDDs, the only
difference being that in PCDFs the two benzene rings are connected by one
oxygen atom and one carbon-carbon bond instead of two oxygen atoms.  As with
PCDDs, the number of chlorine atoms in PCDFs can vary between one and eight,
giving rise to 135 possible congeners.  Due to the similar structure of PCDDs
and PCDFs, the two compounds have similar physical and chemical properties and
also show similar toxicity and biological activity (Environment Canada, 1985;
U.S. EPA, 1985).
     PCDFs are formed as a result of the thermal oxidative cyclization of
chlorinated phenols, PCBs, polychlorinated diphenyl ethers, or chlorobenzenes
under alkaline conditions.  These are similar to the conditions under which
PCDDs are formed, and consequently these compounds are frequently found
together (U.S. EPA, 1985).

                                      3-8
-------
Chlorophenols 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  WASTE SOURCES, QUANTITIES, AND COMPOSITION

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 waste 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 1 and 2
                                      3-9
-------
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                                    3-10
-------
(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
  i
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.
                                     3-11
-------
       TABLE 3.4.  LISTING OF DIOXIN NOTIFIERS AS OF FEBRUARY 18, 1986a
    Waste Code
          Company
      Location
       F020
       F021
       F023
       F026
       F027
       F028
 Monsanto Company

 USEPA Laboratory
 Velsicol Chemical Corp.

 Koppers Company, Inc.
 Vulcan Materials Company
 USEPA Laboratory
 Reichhold Chemical,  Inc.

 FMC Corporation
 Nalco Chemical Corp.
 Velsicol Chemical Corp.
 Monsanto Company
 Ralston Purina Health Ind.
 Reichhold Chemical,  Inc.

 Monsanto Nitro Plant
, Monsanto Company
 Koppers Company
 University of Wisconsin

 USDOE Scientific Laboratory
 Maytag Company
 Vulcan Materials Company
 Sunflower Army Ammunition
   Plant

 Farmland Industries,  Inc.
 Transbag, Inc.
 Reichhold Chemical,  Inc.
Luling, Louisiana
St. Louis, Missouri
Kansas City, Kansas
Be a umont, Texa s

Montgomery, Alabama
Gainesville, Florida
Florence, South Carolina
Orrville, Ohio
Denver, Colorado
Wichita, Kansas
Kansas City, Kansas
Tacoma, Washington

Middleport, New York
Garyville, Louisiana
Beaumont, Texa s
St. Louis, Missouri
Bridgeton, Missouri
Tacoma, Washington

Townsend, West Virgina
Luling, Louisiana
Montgomery, Alabama
Gainesville, Florida
Florence, South Carolina
Orrville, Ohio
Denver, Colorado
Madison, Wisconsin
Arlington, Wisconsin
Los Alamos, New Mexico
Newton, Iowa
Wichita, Kansas
De Soto, Kansas
St. Joeseph, Missouri
Billings, Montana
Tacoma, Washington
 USDOE Scientific Laboratory    Los Alamos,  New Mexico
aDoes not include commercial treatment facilities which notified because of
 their intention to treat these wastes.
                                     3-12
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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 CDDs, 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 glycol,  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
glycol the process operates at lower temperatures and ODD 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.  In 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 as 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 aids 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 glycol and toluene or xylene was used.
                                      3-13
-------
When distillation is used to recover the solvent, CDDs and CDFs are not
recovered.  They remain either in the still bottoms or the final product.   One
manufacturer reported the use of carbon adsorption to remove CDDs and CDFs
from its product.  This, however, results in an additional spent carbon waste.
     The manufacture of hexachlorophene is accomplished by condensing
prepurified 2,4,5-TCP with formaldehyde in a mixture of concentrated sulfuric
acid and ethylene dichloride.  Because the reaction occurs at rather low
temperature and at acid pH,  no CDDs or CDFs are expected to be produced.   Past
production, when prepurified 2,4,5-TCP was not used, resulted in TCDD
contamination due to carry over of contaminants in the TCP feedstock.
Waste Characteristics—
     Since these products are no longer manufactured, the wastes requiring
disposal are primarily stored in drums or landfills.  Most of the wastes,  such
as those at the Vertac site in Jacksonville, Arkansas were generated as a
result of the manufacture of several chlorophenols and chlorophenoxy
compounds.  At this site, 2,4,5-TCP, 2,4-D and 2,4,5-T were manufactured.
Wastes from these processes, primarily toluene still bottoms, were placed in
drums which have slowly corroded.  These wastes contain toluene
(30-50 percent) (Radian, 1984) and lesser amounts of 2,4,5-TCP and
tetrachlorobenzene.  The concentration of TCDDs in this waste stream,  as
indicated in Table 3.5,ranges from 0.6 to 350 ppm.  The TCDD may not be
uniformly distributed throughout the waste liquid.  In a similar waste stream,
still bottoms from the manufacture of 2,4,5-TCP and hexachlorophene (generated
by NEPACCO, stored in Verona, MO, and disposed at Denney Farm), more than
95 percent of the 2,3,7,8-TCDD was incorporated within the solids, which
represented only 0.5 percent of the total waste stream (des Rosiers, 1985).
     Another type of waste stream covered under waste code F020 is a
non-aqueous phase leachate (NAPL) from landfills in which wastes from the
production of chlorophenols and phenoxy herbicides have been dumped along with
other types of waste including organic solvents.  The two major cases of this
are the Hyde Park Landfill in Niagra County, New York and the Love Canal
Landfill in the City of Niagra Falls, NY.  The NAPL from the Hyde Park
Landfill contains up to 20.2  ppm of 2,3,7,8-TCDD in addition to "chloro-,
bromo-, and fluororganics, PCBs, pesticidal residues, and high concentrations
of chromium, antimony, tin, arsenic, lead, zinc, mercury, aluminum,

                                      3-14
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3-15
-------
 phosphorus, and sulfides" (des Rosiers,  1985).   Analysis  of the NAPL  from the
 Love Canal Landfill revealed 203 ppb of  2,3,7,8-TCDD.  This  waste, similar to
 the Hyde Park Waste, probably also contains  a variety  of  other constituents
 such as heavy metals and PCBs which would influence the selection of  an
 appropriate treatment method.  Control of exhaust  gases from the incineration
 of such a waste stream would have to take into  account the vaporization of
 heavy metals present in the waste stream.
      Another type of waste  covered under this waste code  is  spent carbon from
 the treatment of aqueous phase leachate  from Hyde  Park and Love Canal.  The
 aqueous phase of the leachate at Love  Canal  only contains low levels of
 2,3,7,8-TCDD ( <1 ppb)  but  this would  probably  be  concentrated to levels of
 above 1 ppb upon adsorption onto the carbon.

 Waste Quantities—
      The amount of waste currently generated in this code is estimated to be
 zero  (Technical Resources,  Inc.  (TRI), 1985).   This is based upon the fact
 that  there  has been no manufacture of  2,4,5-TCP since 1983,  when Vertac ceased
 production.   The  other major manufacturer of 2,4,5-TCP, Dow, had already
 ceased production in 1979.  Wastes  from  the manufacture of 2,4,5-TCP-derived
 herbicides  such as  2,4,5-T and Silvex are also estimated to be zero since
 production  of these compounds  by major manufacturers was also ceased in 1983.
 In  addition,  future  generation of wastes  from the manufacture of these
 compounds should  be  zero since EPA issued a draft notice of intent  on January
 2,  1986 to ban all pesticide products containing 2,4,5-TCP due  to their
 contamination with 2,3,7,8-TCDD.
     Production of hexachlorophene at this time  is also zero due to  the
unavailability of 2,4,5-TCP necessary for its manufacture.  It  is possible,
however, that hexachlorophene will be manufactured in  the  future using a  new
dioxins and furans free process that Velsicol Chemical  Corp.  is interested in
developing.
     Since there are no current manufacturing sources  of waste  in this code,
the major sources of wastes  requiring treatment  are wastes which were
generated in the past and are currently being stored.   The quantity of waste
 designated as F020 is summarized in Table 1.2.   It  includes  2273 metric
 tons (MT) of still bottoms at the Vertac  site in Arkansas,  1364 MT of  NAPL at
the Hyde Park Landfill, 68 MT of NAPL at  the  Love  Canal Landfill, and  23 MT of

                                     3-16
-------
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 be
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 EPA1 s 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  as fungicides  and biocides with the majority (80 percent) being
 used as  a  wood preservative.  Since all non-wood uses of PCP 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

                                      3-17
-------
 proceeds until  approximately 3 to  7 percent tetrachlorophenol remains in the
 product.  The chlorination reaction results in the formation of up to 30 ppm
 of HCDDs along  with chlorinated furans.  2,3,7,8-TCDD, is not expected to be
 generated in the manufacture of PGP (U.S. EPA, 1985).
    • Current manufacture of PGP does not generate any dioxin-containing wastes
 (TRI, 1985).  The primary reason for this is that distillation is not part of
 the process.  At one time, however, Dow did manufacture a purified PGP
 product.  Purification of the product was achieved by distillation, and the
 still bottoms that were generated contained up to 2,000 ppm of CDDs and CDFs.
 Because of difficulties in working with the product,  however,  its production
 was soon dropped (TRI, 1985; U.S. EPA, 1985).
     The future manufacture of pentachlorophenol, however, may involve
 purification and an associated waste stream containing CDDs and CDFs.  A
                                                                         /
 regulation under the Federal Insecticide, Fungicide and Rodenticide
 Act (FIFRA) would require PGP manufacturers to reduce the concentration of
 HxCDD in PGP from a current average of 15 ppm to 1 ppm (51 FR 1434).   PGP
 manufacturers are disputing this regulation, and negotiations between them and
 EPA are currently being carried out to resolve the HSVE.  Once this
 requirement takes effect, there will be an ongoing dioxin waste stream
 associated with the manufacture of PGP unless new manufacturing processes are
 developed in which the formation of dioxins is completely avoided (Chemical
 Regulation Reporter, 1/10/86).
     Another possible source of waste in this code is from the formulation of
 pentachlorophenol products.  Eighty percent of all PGP,  however,  is used for
 wood preservation, where no formulation of PGP is required.  Non-wood uses of
 POP have been banned.  Consequently,  wastes from the  formulation of PGP are
 not expected to be generated in the future.
     The final potential source of F021 waste is the  waste from wood
 treatment/preservation facilities that use pentachlorophenol.   This waste is
 not currently covered by the dioxin listing rule.  It has been surmised,
 however, that this may be the largest source of PCDD/PCDF contaminated waste
 (des Rosiers,  1985).  This waste  is currently designated as RCRA code
KOOl-Wastewater Treatment Sludge  from Wood Preserving Processes using PGP.
The wastewater treatment sludge would most likely be  contained in a lagoon in
which other organic wastes in addition to PGP may have been placed.  In many
cases these lagoons were torched  to reduce waste volumes,  resulting in the

                                     3-18
-------
formation of PCDDs and PCDFs (des Rosiers,  1985).   The number of sites
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 PGP 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 PGP does not currently generate a
waste stream containing CDDs.  In the future, however, PCP will have to be
purified to reduce HGDD 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.
                                      3-19
-------
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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 current U.S. demand for PCP of 15,000 MT
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 HCDD.  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
                                      3-21
-------
FCDDs, both the products and the wastes may be contaminated with PCDDs.   Such
is the case with the manufacture of 2,4-D, which from process chemistry  is not
otherwise expected to be contaminated with 2,3,7,8-TCDD,  but does contain TCDD
due to the use of equipment previously used to produce 2,4,5—T (Federal
Register, 1980).  The continued manufacture of 2,4,D on 2,4,5-T contaminated
equipment would theoretically extract the residual 2,4,5-T and TCDD over
time.  There are data, however, which shows that still bottoms generated seven
years after 2,4,5-T  production ceased,  still contained 70 ppb of TCDD
(U.S. EPA, 1985).

Waste Characteristics—
     The types of waste generated under this waste code would be similar to
those generated under waste code F020, and would include  still bottoms,
reactor residues, and filter aids.  In addition, TRI stated that most of the
waste under this code would likely come from formulating processes using
equipment previously used to formulate chlorophenols and their phenoxy
derivatives.  If this is the case, washwater sludges and other equipment
cleanup wastes would also be potential waste types.
     Sampling and analysis of 2,4-Dichlorophenol still bottoms from a 2,4-D
manufacturing facility where 2,4,5-TCP had been manufactured years earlier
showed 20 ppm of CDDs and 450 ppm of CDFs (U.S.  EPA, 1985).
Waste Quantities—
     TRI estimated the quantity of waste generated under this code to be
zero.  This estimate is based on several factors.   One is the assumption that
the number of formulators of products covered by the code has been reduced
substantially, and much of the equipment of interest has been replaced,
dismantled, sold or discarded.  Another is that most of the facilities that
notified EPA that they were generating F023 also indicated that they treated
their wastes onsite, and therefore would not present a demand on offsite waste
treatment facilities.  Finally, they indicated that, for facilities that also
generate other listed dioxin wastes, it would be difficult to differentiate
these wastes from the F023 waste.
     Radian also made an estimate of the quantity of waste generated.under
this code.  Their estimate is based on the assumption that past manufacturers
and formulators of the products of concern, characterized as active, are

                                     3-22
-------
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.  As 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 FQ23.  Consequently there should De  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
                                      3-23
-------
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                                        3-24
-------
up  to 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 CDDs 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 TCDD.
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,  1985).
     The only FO27 waste being generated on an ongoing basis would be unused
pentachlorophenol.  Because of the consent decree requiring PGP manufacturers
to reduce the concentration of HCDD 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.
                                     3-25
-------
     Current and future generation of this waste code should only be
associated with the manufacture of PGP (unless the manufacture of 2,4,5-TCP
resumes).  One thousand MX appears to be the maximum annual amount that would
be generated.  It has been reported, however, that the quantity may be much
less (Industrial Economics, Inc., 1986).  Since Reichhold Chemicals recently
stopped manufacturing PGP, the demand is greater than the capacity for
production.  Consequently, the quantity of unused PGP may be less that it has
been in the past.

3.3.8  Contaminated Soils

Waste Sources—
     Soils contaminated with listed dioxin wastes are regulated as the
respective hazardous waste contaminant (50 FR 28713).  These wastes are
categorized in one of the waste codes discussed above.  They are being
discussed in this section, however, because of the difference in the physical
nature of these wastes relative to the other listed wastes, and also because
it is difficult to assess exactly which waste code is appropriate for the
contaminated soil.
     The largest known quantities of contaminated soils are in Missouri where
several horse arenas and other areas were sprayed with TGDD contaminated waste
oils.  Contamination of the waste oils with TCDD resulted from mixing these
waste oils with distillation bottoms from the manufacture of
2,4,5-trichlorophenol to be used.to produce hexachlorophene (USEPA, 1985).
     Other known sources of contaminated soil and sediment include a herbicide
manufacturing plant (Vertac Chemical Company) in Arkansas where cooling pond
sludges, equalization basin muds, and stream sediments have been contaminated
due to the leakage of wastes (such as still bottoms from the manufacture of
2,4,5-TCP) from drums stored onsite (Thibodeaux, L.J., 1983).  The improper
disposal, both onsite and offsite, of wastes from another herbicide
manufacturer in Missouri have also led to the contamination of soils in that
state.  Instances of improper disposal of waste from this site include dumping
of drummed and bulk wastes into unlined onsite trenches and lagoons, and the
disposal of drummed wastes into a trench on a farm offsite (U.S. EPA, 1985).
                                      3-26
-------
      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  organics 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 chlorophenoxy  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.
                                      3-27
-------





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 Waste  Quantities—
     It  has  been estimated that there are 500,000 MT 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
characterized.
     Wastes which are of concern for this document are  those containing an
extractable TCDD or TCDF concentration of greater than  1 ppb.   It is possible
that much of the contaminated soil will contain strongly adsorbed TCDD,  and  so
will not require treatment  with respect to the  land disposal ban.
                                     3-29
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                             REFERENCES
Adams, W.J. and D.K. Blaine.  A Water Solubility Determination of
2,3,7,8-TCDD.  Paper presented at the fifth International Symposium on
Chlorinated Dioxins and Related Compounds, Bayreuth,  Germany,
September 16-19, 1985.

Ahling, B. et. al.  1977.  Formation of polychlorinated dibenzo-p-dioxins
and dibenzofurans during combustion of a 2,4,5-T formulation.
Chemosphere 8:461-468.

Bumpus, J.A. et. al.  Biodegradation of Environmental Pollutants by The
White Rot Fungus Phanerochaete Chrysosporium.   Presented in the Eleventh
Annual Research Symposium on Incineration and Treatment of Hazardous
Waste.  EPA 600/9-85-028

Chemical Regulation Reporter, January 10, 1986.

Crosby, D.G.  The Degradation and Disposal of Chlorinated Dioxins
presented in proceedings of symposium entitled:  Dioxins in the
Environment.  Edited by Kamrin, M.A. and P.W.  Rodgers, 1985.

des Rosiers, P.E.  Memorandum to Erich Bretthauer, Chairman, ORD Dioxin
Team.  June 18, 1985.

DiDominico, A. et. al.  Accidental Release of 2,3,7,8-TCDD at Seveso,
Italy.  Ecotoxicology and Environmental Safety, 4 (3) 282-356, 1980.

Environment Canada.  Polychlorinated Dibenzo-p-Dioxins (PCDDs) and
Polychlorinated Dibenzo-Furans (PCDFs):  Sources and Releases.  Prepared
by A. Szheffield, Environmental Protection Service.  July, 1985.  EPS
5/HA/Z

Federal Register, 1980.  Storage and Disposal of Waste Material:
Prohibition of Disposal of Tetrachlorodibenzo-p-dioxin.  45 (98):  32676.
                                 3-30
-------
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 M. Arienti, GGA  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/600/9-85/013 April 1985.

Junk, G.A. and J.J.  Richard.  1981.   Dioxins Not 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.
                                 3-31
-------
Rappe, C. et. al. Dioxins, Dibenzofurans,  and other Polyhalogenated
Aromatics Production, Use, Formation and Destruction.   Ann.  NY Acad.  Sci.
320: 1-18.

Redford, D.P. et. al. 1981.  Emission of PCDD from combustion sources.
International Symp. on Chlorinated Dioxins and Related Compounds.
Arlington, VA; October 25-29.

Young, A.L. et. al.  Fate of 2,3,7,8-TCDD in the Environment:  Summary  on
Decontamination Reccomendations.  U.S.A. FA-TR-76-18,  1976.

Sittig, M.  Pesticide Manufacturing and Toxic Materials Control
Encyclopedia.  Noyes Data Corporation, Park Ridge, NJ, 1980.

Shaub, W.M. and W. Tsang.  1982.  Physical and Chemical Properties of
Dioxins in Relation to Their Disposal.  Proc. Second Intl. Symp. on
Dioxins.  Arlington, VA, October.  1981.

Stoll, Barry.  U.S. EPA Office of Solid Waste.  Telecon'with M. Arienti,
GCA Corporation Technology Division.  February 25, 1986.

Technical Resources, Inc.  Analysis of Technical  Information to Support
RCRA Rules  for Dioxins-Containing Waste Streams.  Submitted to
P.E. des Rosiers  , EPA/Office of Research and Development.  Contract No.
5W-6242-NASX.  July  31,  1985.

Thibodeaux,  L.J.   Offsite Transport of  2,3,7,8-Tetrchlorobenzo-p-dioxin
from a Production Disposal Facility.  In:   Chlorinated Dioxins  and
Dibenzofurans in the Total Environment.  C.  Gangadhar et. al. Ed.
Butterworth Publishers,   pp. 75-86, 1983.

U.S. EPA,  1978.   Report  of the  Ad Hoc Study Group on  Pentachlorophenol
and Contaminants. EPA/SAB/78/001   p. 170

U.S.  EPA Dioxin Listing Background  Document.  U.S. EPA, OSW, Washington,
D.C.,  January,  1985.

Westat, Inc. Natural  Survey of Hazardous Waste  Generators  and Treatment,
Storage and Disposal Facilities Regulated Under  RCRA  in 1981.   Prepared
 for EPA Office  of Solid Waste,  1983.

Young, A.L.  Long-Term Studies  on  the Persistence and Movement  of TCDD  in
 a Natural Ecosystem.  In: Human and Environmental Risks  of Chlorinated
Dioxins and Related Compounds.   R.E.  Tucker et. al., Ed.  Plenum
 Publishing Corp., NY  pp. 173-190.
                                  3-32
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                                   SECTION 4
                 THERMAL TECHNOLOGIES FOR LISTED DIOXIN  WASTES

     In this report, thermal technologies include incineration, pyrolysis 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, FO23,  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   )
                           DRE  = —HI-	2HL_ x  100
                                     in
               where:    W£n =  mass feed rate of one POHC in
                        the waste  stream feeding  the incinerator; and
                        wout = mass emission rate of the same POHC
                        present  in exhaust  emissions prior to release to
                        the atmosphere.
                                     4-1
-------
     Six nines (99.9999 percent DRE) must be demonstrated either on the CDDs
themselves or on a POHC that is more difficult to destroy than the  CDDs.   One
criterion EPA has used to determine the relative ease of destruction of
various toxic constituents is heat of combustion.  The lower the heat of
combustion, the more difficult it is to destroy.  Therefore, if a waste
containing HCDD is to be destroyed, the process must be able to achieve six
nines DRE on a POHC with a heat of combustion of less than 2.81 kcal/gram, the
heat of combustion of HCDD.  An example of such a compound would be
pentachlorophenol, which has a heat of combustion of 2.09 kcal/gram.
     Another criterion for evaluating incineration (or any treatment process)
with regard to dioxin wastes is that the residues of treatment must contain
less than a detectable level (1 ppb) of CDDs and CDFs in order to be
designated non-hazardous. Consequently, when evaluating the potential of some
method for treating wastes containing dioxin, it is important not only to look
at the exhaust gases but also the  scrubber water, filter residues,  and the
non-combusted, treated material if the waste is an inorganic solid such as
soil.
     Finally, with regard  to destruction by incineration, CDDs and CDFs are
assumed to be similar to polychlorinated biphenyls (PCBs).  This is because
they are both highly chlorinated compounds with similar structure and similar
heats of combustion.  In addition, incinerators  burning PCBs must achieve six
nines DRE.  As a  result, EPA has indicated that incinerators that operate in
accordance with the performance standards specified in 40 CFR 761.70 for  PCB
wastes, namely six nines DRE, have also demonstrated  their  ability  to meet the
performance standards  for  incinerators burning  dioxin wastes (51 FR 16U2).
      Incinerators burning  PCB wastes must be  operated at  1200°C with a waste
residence  time of 2  seconds  and 2  percent excess oxygen.  Alternatively,  the
incinerator may  be operated  at  1600°C, 1.5  second dwell  time and 2  percent
excess  oxygen.   It would be  expected that incinerators burning  dioxin wastes
would also have  to operate under  these conditions.
                                       4-2
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     This section includes subsections on a-variety-of thermal technologies.
Methods of incineration include:
          Stationary Rotary Kiln
          Mobile Rotary Kiln
          Liquid Injection
          Fluidized Bed
          Infrared
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
PCB waste; in these cases, the FOB data have been presented as evidence of
their performance.

4.1  STATIONARY ROTARY KILN INCINERATION

     Several commercial rotary kilns have been permitted to burn PCB wastes.
In so doing they have demonstrated six nines DRE for  PCBs,  and therefore  have
the potential to burn dioxin wastes.  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.
                                      4-3
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4.1.1  Process Description(GCA, 1985; McGaughey, et al. 1984; Bonner,
       1981; Freeman and Olexsey, 1986)

     A rotary kiln incinerator consists of a cylindrical, refractory—lined
shell that is mounted with its axis at a slight incline (less than 5 degrees
from the horizontal) and may rotate from 5 to 25 times per hour.  The
peripheral speed of rotation, which ranges from 1 to 5 feet per minute,
provides excellent mixing of wastes and combustion air.  In addition to the
kiln, the system includes a waste feed system, a secondary combustion chamber,
air pollution control equipment, and a stack.  Rotary kilns can handle a wide
variety of waste feeds.  Solids and viscous sludges are typically fed to the
upper end of the kiln by conveyor or in fiber drums, while liquids are
atomized through auxiliary burners.  Liquids are either injected into the kiln
or into the afterburner.  In the kiln, solid wastes are partially burned.  The
products are gases and inorganic ash.  The ash is removed from the kiln, and
combustion of the gaseous products is completed in the secondary combustion
chamber (afterburner) (Bonner, T. A., et al., 1981; Marson, L. and S. Urger,
1979; Mclnnes, R. B., 1979.)
     Auxiliary fuel systems are typically required to bring the kiln up to the
desired operating temperature.  Various types of auxiliary fuel systems may be
used, including dual-liquid burners designed for combined waste-fuel firing or
single-liquid burners equipped with a premix system.
     Rotary kilns may be configured either with a co-current or a
countercurrent design.  Co-current units have the auxiliary fuel burner at the
same end of the incinerator as the waste feed, whereas countercurrent units
are designed such that the combustion gases run countercurrent to the flow of
waste through the incinerator.  The countercurrent design is more advantageous
for wastes having a low heating value because temperature can be controlled at
both ends of the kiln, minimizing problems such as overheating of the
refractory lining.  Brief descriptions of two of the rotary kiln incineration
facilities that are permitted to burn PCBs are provided below.
                                      4-4
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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 afterburner 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
                                     4-5
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temperature of 1040°C, combusts the gaseous effluent from the primary
combustor.  Combustion products from the secondary combustion chamber are
contacted with a caustic and lime slurry, passed through a spray tower
scrubber, demisted, and finally discharged to the atmosphere.  Kiln
temperature, afterburner temperature, kiln and afterburner drafts, and carbon
monoxide and carbon dioxide concentration are monitored regularly.  Process
instrumentation shuts down the feed for non-compliance with regulations.
     The ENSCO incineration system can handle both solid and liquid wastes
(the kiln section is not necessary for liquid wastes).  Feed rates for PCS
wastes are typically 8,140 kg/h with supplementary fuel requirements of
3,000 kg/h with an average of 16,400 kw heat input.

Restrictive Waste Characteristics—
     The rotary kiln is capable of treating a wide variety of waste forms,
including both liquids and solids, and also drums and bulk containers.  It is
capable of handling liquids and solids independently or in combination.
     Spherical or cylindrical items may roll through the kiln before
combustion is completed (i.e., insufficient residence time).  Aqueous sludges
may form clinker or ring residue on the refractory walls due to drying of the
aqueous sludge wastes or melting of some solids.

Operating Parameters—
     Typical operating parameters for stationary rotary kiln incinerators are
summarized below (McGaughey, et al, 1984; M. M. Dillon, 1983; Bonner, 1981):
Residence Time
Incinerator
  Temperatures
Length to Diameter Ratio
Peripheral
  Rotational Speed
Incline Ratio
Ranges from a few seconds (highly
combustible gas) to a few hours (low
combustible solid waste).
Can vary from 800 to 1600°C (1470 to
2900°F) depending on requirements for a
particular waste.
Typically ranges between 2 and 10.
Ranges from 1 to 5 fpm.
•x
Ranges from 1/16 to 1/4 in./ft.
                                      4-8
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4.1.2  Technology  Performance Evaluation

     As discussed  in the previous subsection, three commercial-scale
stationary rotary  kiln incinerators have demonstrated six nines DRE (99.9999X)
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,
Arkansas.
     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
(Carnes,  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 (Carnes, 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) (Carnes,  1984;  Ross, et al., 1986;
Ross,  et al., 1984).
                                     4-9
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     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 (Games, 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-TCDD DRE 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.,
1986).
     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).
                                      4-11
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                   TABLE 4.1.1.   VERTAC STILL BOTTOM TEST BURN
Parameter
Mean Waste Feedrate (Ib/hr)
Duration of Burn (hrs)
2,3,7,8-TCDD in Feed (ng/g)
Kiln Exit Gas Temp. (°C)
Nominal Kiln
Residence Time (sec)
Afterburner Exit Gas Temp. (°C)
Afterburner Nominal Residence
Time (sec)
DRE at Kiln Exit (%)a»b
DRE at E-Duct (%)c»d
Test 1
22
12
37
980

4.9
2030

1.8
>99.99995
>99.9997
Test 2
39
6
37
990

6.0
2030

2.3
>99. 99976
>99.9997
Particulate at Stack
(tng/dscm)

Maximum 2,3,7,8-TCDD Concentration in
Scrubber Blow Down (pg/1)

Maximum 2,3,7,8-TCDD
Concentration in Ash (pg/g)
                                                             0.12


                                                              ND8
aBased on Helium tracer data

bAverage of values from two sampling trains

cAverage values from 4 sampling trains

^Based on flue gas velocity data

eUncorrectted

fCorrected to 7% oxygen

^Detection limits ranged from 5.6 to 28 pg/g

Reference:  Ross,  et'.  al.,  1986.

                                      4-12
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     Since in all cases the residues from this incinerator contained CDDs and
CDFs at levels below 1 ppb, it would be expected that these residues could be
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 CDFs
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):
4.1.3
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.

The test plan called for continuous monitoring of flue gas,  C02,
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.

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.

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 PCSs incineration.   Table  4.1.2
lists the average unit costs for PCBs wastes at the currently permitted

stationary rotary kiln facilities.
                                      4-13
-------
         TABLE 4.1.2.  AVERAGE UNIT COSTS FOR PCB WASTE DESTRUCTION AT
                         PERMITTED STATIONARY ROTARY KILN FACILITIES
PCB concentration
      range
Unit costs
 liquids
Unit costs
  solids
0 to 50 ppm

50 to 1000 ppm

1000 to 10,000 ppm

10,000 to 100,000 ppm

 100,000 ppm
0.25 $/lb

0.30 $/lb

0.35 $/lb

0.40 $/lb

0.45 $/lb
0.40 $/lb

0.45 $/lb

0.50 $/lb

0.60 $/lb

0.70 $/lb
References:  Bailey, May 1986; SCA, .May. 1986.
                                     4-14
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4.1.4  Process Status

     Land-based incineration systems with potential to treat dioxin wastes
include commercial incineration facilities which have been approved for PCS
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 PCS
wastes.  The following are the maximum feed rates for these land-based
incineration systems (GCA, 1985; Clarke, 1986):
     Rollins
     (Deer Park, TX).
     ENSCO
     (El Dorado, AK.)
     SCA
     (Chicago, XL.)
1,440 Ib/hr for solids
6,600 Ib/hr for liquids
2,500 Ib/hr for solids
5,000 Ib/hr for liquids
2,910 Ibs/hr for solids
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 ORE 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 ORE.
                                      4-15
-------
 4.2 MOBILE ROTARY KILN

      As  mentioned previously,  the EPA Mobile, Incineration System (MIS) has
 demonstrated six nines DRE on waste containing 2,3,7,8-TCDD.   ENSCO has
 developed  a modified version of the EPA mobile rotary kiln incinerator with
 improved solids handling techniques that is also capable of treating these
 wastes.  These two units are described below.
4.2.1
Process Description
     The EPA mobile unit  is  mounted on four heavy-duty  semi-trailers  which  can
 be  transported  to  a treatment  site and connected in series.   The  system
 includes a  rotary  kiln, a secondary combustion chamber,  and  a scrubber,  along
 with the following support equipment:   bulk fuel storage,  waste blending and
 feed equipment  for both liquids  and solids, scrubber solution feed  equipment,
 ash receiving drums,  stack monitoring  equipment, and an auxilliary  diesel
 power generator (IT Corporation,  1985a;  Freestone,  et al., 1985;  Freeman and
 Olexsey, 1986).  A schematic of  the EPA mobile incineration  system  is shown in
 Figure 4.2.1.
     The first  trailer consists  of a solids feed system, burners, and a  rotary
 kiln (IT Corporation, 1985a; GCA,  1985;  Freeman and Olexsey,  1986;  Freestone,
 et  al., 1985).  After being  shredded by  the shear-type  shredder (driven  by  a
 150-HP motor),  the solids  are  carried  by an enclosed conveyor to  the  hopper.
A sliding knife gate at the  bottom of  the hopper opens  to  allow the contents
 of  the hopper to empty into  the  ram feeder.  The bydraulically operated  ram
 feeder forces the  feed into  the  kiln.  The  kiln is  rated at  15 million BTU/hr
 and is capable  of  handling 150 Ibs/min of dry  solids.  Contaminated water and
 contaminated fuel  oil are  introduced directly  into  the afterburner  at  maximum
 feed rates of 3 gpm and 1.7  gpm, respectively.   The refractory lining  material
 in the kiln is abrasion-resistant,  acid-resistant,  and able  to withstand
repeated thermal cycling.  The rotary  kiln  operates  at approximately  1800°F  to
vaporize and partially combust the  incoming waste.   Incombustible
ash is discharged  directly from the  kiln.  Ducting  connects  the solids feed
system and the ash discharge system  to a  trailer-mounted, dual-manifold,  high
efficiency particulate air (HEPA)/carbon  filter  system to control fugitive
dust emissions.
                                     4-16
-------
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                             4-17
-------
     The exit gases  from the kiln pass  through  a  secondary combustion  chamber
 (SCO)  located on  the second trailer.  The  secondary combustion chamber is
 capable of providing 2.2 seconds residence time at 2200°F (1200°C)  to  complete
 the combustion process.   The refractory lining  of the SCC is coated with a
 thin layer of acid-resistant mortar.  The  flue  gases from the SCC are  cooled
 by water sprays to 190°F.  Excess water is collected in a sump.
     The cooled gases are then passed through air pollution control
 equipment.  The third trailer contains  the air  pollution control system which
 consists of a quench system with partial acid gas removal, a clean  high
 efficiency air filter (CHEAF) to remove submicron-sized particulates,  and flue
 gas instrumentation.  A  draft fan moves combustion gases through the system
 and maintains a negative pressure so that  toxics  will not escape to the
 atmosphere.
     The cleaned  gases are emitted from the system through a 40 ft  high
 stack.  Combustion and stack gas monitoring equipment are contained within the
 fourth trailer.   Carbon  dioxide and oxygen are  continuously monitored  in the
 stack.
     The ENSCO mobile incinerator is similar in design to the EPA mobile
 incinerator.  The ENSCO mobile system is capable  of incinerating 150 gal/hr of
 liquid PCS waste blend or 2 to 5 tons/hr of solid hazardous waste (Pyrotech
 Systems, 1985).  The system is mounted  on  trailers and consists of  the
 following six basic process modules:  solids incineration, liquids
 incineration, waste heat boiler, a pollution control/prime mover system,
 control room and process  laboratory, and effluent neutralization and
 concentration systems (Pyrotech'Systems, 1985;  Sickels, 1986).  A schematic of
 the process is shown in Figure 4.2.2.
     The solids incineration module consists of a rotary kiln, solids
 preparation and charging equipment, a burner, an  air blower,  and an ash
 discharge system  (Pyrotech Systems, 1985;  Sickels, 1986).  During operation,
 contaminated solids are  shredded and fed to the kiln via a ram feeder.  The
 rotary kiln is a brick-lined, carbon steel pipe measuring 30 ft in  length with
 an inside diameter of 69 inches.  It is mounted horizontally with a slight
vertical incline, and rotated by a trunnion drive mechanism.   The kiln has a
nominal solids capacity  of 3.5 tons/hr  and a nominal heat load of 15 million
Btu/hr. (Pyrotech Systems, 1985; Sickels,  1986).

                                     4-18
-------
4-19
-------
      The liquid incinerator/afterburner (SCC) is a large refractory-lined
 vessel designed to maintain a temperature greater than 2200°F (1200°C) and a
 residence time greater than 2 seconds.  It has a length of 40 ft and an inside
 diameter of 7 ft.   The nominal heat load for the SCC is 20 million Btu/hr.
 Combustion can be  enhanced by oxygen enrichment (Pyrotech Systems, 1985;
 Sickels, 1986).
      A firetube boiler is used to recover heat in the offgas stream and to
 provide the steam  required to drive the system prime mover.  A
 scrubber/ejector system acts as the system prime mover,  and also as the
 primary pollution  control device.  Thus,  an induced draft fan is not
 required.   Offgases containing particulates are driven through the ejector
 nozzle where they  are contacted with water.  Turbulent mixing occurs causing
 efficient  particulate capture (emissions  less than 0.08 gr/DSCF*).  The
 agglomerated particulate and water are subsequently removed by a horizontal
 gas water  separator (HGW) with an integral demister.   Cleaned gases are vented
 to the atmosphere.   Scrubber water is filtered to remove solids and then
 recycled to the steam ejector.   The combustion processes and emissions control
 systems are monitored and controlled by an automated system.  Fail-safe
 shut-down  occurs when the following events are detected:   loss of  combustion
 flame,  low flue pressure, secondary combustor pressurization,  or excessive
 temperature at  the  control device inlet (Pyrotech Systems,  1985; Sickels,
 1986).

 Restrictive Waste Characteristics—
     The EPA and ENSCO mobile  incinerators  are able  to handle  both solid and
 liquid  hazardous waste streams.   Bulky  solids  need  to be  fed  through  a
 specially designed  solids feed  system (described  previously) prior to  being
 fed to  the  kiln.  Wastes  with a low heating value (i.e.,  less  than
 8,000 Btu/lb) may require blending  with kerosene  prior to being  fed  to the
 combustor  (GCA, 1984).
* gr/DSCF s grains per dry standard cubic foot.
                                     4-20
-------
Operating Parameters—
     Operating parameters for the two mobile rotary kiln systems are
summarized below (U. S. EPA, 1984; Sickels, 1986; Freestone,  et al., 1985)
Waste Forms

Maximum Waste Feed Rate (Ib/hr)
  -Solids to Rotary Kiln
  -Liquids to Rotary Kiln
  -Liquids to SCC
Kiln Temperature (°F)
SCC Temperature (°F)
SCC Residence Time (sec)
                      EPA/MIS
                      Solids,
                      Liquids
                        9,000
                        1,500
                         1800
                         2200
                          2.2
ENSCO
Solids,
Liquids
10,000
 3,000
 4,000
  1800
  2200
     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, tetrachlorobenzene, and PCBs.  In
these liquid waste trial burns, 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  1 ppb or  lower concentration of residual 2,3,7,8-TCDD and
          other chlorinated dioxins and chlorinated furans in the incinerator
          ash.
                                      4-21
-------
      •    Temperature and time are the primary factors which affect
           2,3,7,8-TCDD removal efficiency.
      •    Other factors (such as  initial moisture  content,  soil  type, etc.)
           had either no effect or a minor effect on  dioxin  removal.  An
           exception was very large soil agglomerates with high initial
           moisture  content,  which require substantially longer residence time
           to achieve a uniform temperature  throughout the solid mass.

      In December 1984,  a solids feed system (see process description) was
 installed so that the MIS could be tested on dioxin-contaminated soils at the
 Denney Farm  Site in Missouri.   Prior to testing at the Denney Farm Site, a
 series of "shakedown" tests  were  performed  to  determine the  conditions
 necessary to decontaminate the soils (IT Corporation, 1985a).
      Four different types of soils were passed through the  solids feed system,
 rotary kiln,  and ash discharge system without  showing any problems which
 adversely affected  performance (IT Corporation, 1985a; U. S. EPA, 1985).
 However,  some  slagging occured as  solids were  carried over into the front end
 of the SCO where they accumulated  to a  depth of up to 9 inches.  Residence
 times  averaged  over 30 minutes with a 2000  Ib/hr feed rate.   The kiln rotated
 at 1  rpm  and discharged ash  at an  average temperature of 750°C.  Stack
 particulate  tests demonstrated that particulate emissions were well below RCRA
                 3
 limits (180 mg/m ,  corrected to 7  percent oxygen).  These data are
 summarized in Table  4.2.1.
     After completing the shakedown tests,   the MIS was transported to the
 Denney Farm Site in Missouri for a  series of dioxin trial burns (U.  S.  EPA,
 1985;  U.  S. EPA,  1984).   As  indicated in Table 4.2.2, greater than 99.9999
 percent DRE was achieved  on waste feeds of up to 2000 Ibs/hr of solids  and 230
 Ibs/hr of  liquids (IT Corporation,  1985a).   The concentration of 2,3,7,8-TCDD
 in liquid waste feed materials ranged from 225 to 357 ppm, and in the solid
 wastes from 101  to  1010 ppb  (IT Corporation, 1985a and b;  U. S.  EPA,  1985).
     In addition to the 99.9999 percent DRE, the treated  soil and process
wastewater from these burns were analyzed for a number of constituents  and
were shown to meet the delisting guidelines  (see Table 4.2.3) established by
the Office of Solid Waste (Poppiti, 1985).
                                      4-22
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         TABLE 4.2.1.
SOILS USED IN THE EPA MOBILE INCINERATOR DURING
PRELIMINARY TESTING OF THE SOLIDS FEED SYSTEM
     Soil type
            Test purpose
Particulate
 emissions
Denney Farm
Area Soil
Montmorillonite
Coral from Florida
Clarksburg
(New Jersey) Soil
    To ensure that there were
    no unusual problems with
    soil from that area; Site
    soil was very dry from being
    stored

    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, 1985a.
                                     4-23
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TABLE 4.2.3.
MISSOURI DEPARTMENT OF NATURAL RESOURCES AND EPA DELISTING
PARAMETERS FOR ORGANIC CONSTITUENTS IN INCINERATOR ASH
AND SCRUBBER WASH WATER
        Toxic Constituent
                                           Concentration

Dioxins/Dibenzofurans3
2, 3,4-Trichlorophenol
2,3, 5-Trichlorophenol
2,4, 6-Trichlorophenol
2, 5-Dichlorophenol
3,4-Dichlorophenol
2,3,4, 5-Tetrachlorophenol
2 , 3, 4, 6-Tetrachlorophenol
1,2,4, 5— Tetrachlorobenzene
1,2,3, 5-Tetrachlorobenzene
Hexachlorophene
Polychlorinated Biphenyls
BenzoC a) pyrene
Benzo (a) anthracene
Chrysene
Dibenzo(a, h)anthracene
Indeno( l,2,3-c,d)pyrene
BenzoC b) f louranthene
Ash
1 ppb
100 ppm
100 ppm
1 ppm
350 ppb
100 ppm
1 ppm
1 ppm
100 ppm
100 ppm
200 ppm
2 ppm
5 ppm
5 ppm
50 ppm
5 ppm
5 ppm
5 ppm
Scrubber water
10 ppt
10 ppm
10 ppm
50 ppb
15 ppb
10 ppm
50 ppb
50 ppb
10 ppm
10 ppm
5 ppm
1 ppm
10 ppb
10 ppb
1 ppm
10 ppb
10 ppb
10 ppb
Weighted average of TCDDs/TCDFs, PeDDs/PeDFs, and HxCDDs/HxCDFs using
 toxicity weighting factors.

Reference:  Poppiti, 1985; U.S. EPA, 1985.
                                      4-25
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              TABLE 4.2.4.   MATERIAL TO BE  INCINERATED DURING FIELD
                            DEMONSTRATION OF  THE EPA MOBILE INCINERATOR SYSTEM
       Material
    Estimated quantity
                                                           2,3,7,8-TCDD Cone.
 *Denney Farm

   Soil
   Mixed solvents  and water
   Chemical solids and  soils
   Drum remnants and trash

 Verona

   Hexane/Is opropano1
   Methanol
   Extracted still bottoms
   Activated carbon
   Decontamination solvents
   Sodium sulfate  salt  cake
   Miscellaneous trash

 *Neosho

   Spill area soil
   Bunker soil/residue
   Tank asphaltic  material

 *Erwin Farm

   Empty drums with  residue

 *Rusha Farm

   Spill area soil

 *Talley Farm

   Spill area soil

 Eastern Missouri

  Times Beach soil sample
   Piazza Road soil sample
 210  cubic yards
 2,590 gal
 31,150  Ib
 84 85-gal overpack drums
 10,000 gal
 5,000 gal
 5,000 gal
 5,000 Ib
 1,000 gal
 23 cubic yards
 84 55-gal drums
25 cubic yards
15 drums
75 gal
30 drums
10 cubic yards
10 cubic yards
3 cubic yards
3 cubic yards
 500 ppb
 Low
 1 ppb - 2 ppm
 Unknown
0.2 ppm
PPt
0.2 ppm
Unknown
Unknown
1 ppb
Unknown
60 ppb
2 ppm
2 ppm
8 ppb
Unknown
6 ppb
500 ppb
1,600 ppb
*These burns have been completed,  but the results were  not  released'in time to
be included in this document.

References:  Krogh, 1985; IT Corporation,  1985a

                                     4-2b
-------
     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,
1985):
               Kiln Temperature
               SCC Temperature
               SCC Combustion Gas
               Flow Rate
               SCC Residence Time
               Waste Feed Rate
               Auxiliary Fuel
                 -Kiln   5 to 6 million Btu/hr
                 -SCC    4 to 5 million Btu/hr
1800°F
2200°F
13,500 acfm

2.6 seconds
2000 Ib/hr (soil)
250 Ib/hr (liquid)
     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 ORE)
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, C09,
0,, NO , operating temperatures and feed rates (Hazel, 1986; Freestone',
 <£    X
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).
                                     4-27
-------
     ENSCO has constructed four mobile units; two MWP-2000 type incinerators
and two MWP-75 incinerators (McCormick, 1,986).  The MWP-75 (earlier model) was
tested on PCB-containing wastes in 1983 (Freestone, et al., 1985; GCA, 1985).
The results of these tests, listed in Table 4.2.5, demonstrated successful
(>99.9999 percent DRE) destruction of the PCBs (IT Corporation, 1985a).  One
of the MWP-2000 units, currently located at a site near Tampa, Florida, is
undergoing test burns on PCB-containing soils (McCormick, 1986).  Initially,
ENSCO encountered slagging problems similar to those experienced with the EPA
mobile incinerator (IT Corporation, 1985a; Lee, 1985).  To solve these
problems, six chutes were added to the secondary unit and a cyclone was
installed prior to the secondary unit to remove fine particulates (IT
Corporation, 1985a).  The second MWP-2000 unit was used recently to conduct a
series of trial burns at the El Dorado, Arkansas facility using
dioxin-containing wastes from the Vertac Site (Hicks, 1986).  The purpose of
these burns was to obtain RCRA certification.  The results of the dioxin trial
burns are expected to be released in late May or early June,  1986 (McCormick,
1986).

4.2.3  Costs of Treatment

     A detailed procedure for estimating the unit costs of a mobile rotary
kiln incinerator has not yet been developed.  The EPA intends to develop such
a. procedure and present it in its final report on  the Denney Farm Trial Burns
(IT Corporation, 1985a).
                                      4-28
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TABLE 4.2.5.  EMISSION DATA FOR THE ENSCO MOBILE  INCINERATOR (MWP-75;
              PCB TRIAL BURN
        Condition
     PCB ORE

     Carbon Monoxide

     Nitrogen Oxides

     Particulate

     HCl Scrubbing
                                             Result
>99.9999%

 20 ppm

 300 to 500 ppm

 Met or exceeded all standards

 99% at 1,500 Ib HCl/hr
     Reference:   Sickels,  1986; Pyrotech Systems, 1985.
                               4-29
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     Factors which need to be considered when developing a cost estimate for a
mobile incineration system are as follows (IT Corporation,  1985a).

       •     Labor is a substantial portion of the operating costs.   The
             greater the capacity of the system (e.g.,  by size or number of
             systems or through design modifications),  the lower the unit
             costs.
       •     Costs are lower if the heat and moisture content of the waste
             feed are low because of the increased feed rate that can be
             maintained (up to 200 Ib/hr).
       •     The greater percentage of time that the system is able  to process
             material, the lower the overall costs.
       •     Setup costs vary according to site design requirements, permit
             costs, etc.
       •     The longer the duration of the cleanup operations, the higher the
             costs will be.
       •     Reliability (via conservative design and redundancy) increases
             actual operating time and thereby reduces overall costs.
4.2.4   Process Status
        The  EPA mobile  incinerator was developed and tested for the purpose of
 evaluating  the technical  and economical feasibility of mobile incineration, to
 establish procedures for  obtaining Federal, State and Local permits and to
 gauge  public  reactions (IT  Corporation, 1985a; Krogh, 1985).  The intention of
 future uses of the EPA mobile  incinerator  is  to encourage commercial
 development of onsite  cleanup  technologies.   As a result of conducting
 research burns on various waste  forms, the EPA is able to provide operating
 specifications and other  valuable information to the private sector.  The EPA
 believes that, given this information, the private sector will.be capable of
 developing  improved, more reliable,  larger capacity, lower cost systems.
        ENSCO  has developed  a modified version of the EPA mobile rotary kiln
 incinerator,  with improved  solids handling techniques (Pyrotech Systems,
 1985).  ENSCO has three mobile rotary kiln units (termed the MWP-200 series),
 which  are designed to  process  3  to 4 cubic yards/hour (Hicks, 1986; McCormick,
 1986).  The MWP-2000 incinerators are capable of burning both solids and
 liquids using supplimentary fuel oil for wastes with low BTU content.
                                      4-30
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       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 May 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;  McCormicfc,
1986).
                                      4-31
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4.3    LIQUID INJECTION INCINERATION

4.3.1  Process Description

       The general components of a liquid injection (LI) incineration system
include a burner, primary combustion chamber, secondary (unfired)  combustion
chamber, quench chamber, scrubber, and stack.  The LI incinerator system can
be configured either vertically or horizontally.  With the vertical
configuration shown in Figure 4.3.1, the incinerator acts as its own stack and
a portion of the stack may serve as a secondary combustion chamber.  Vertical
units are preferred for wastes which are high in inorganic salts and ash
contents.  In contrast, horizontal incinerators are connected to tall stacks,
and may be used with low-ash wastes (Bonner, 1981; McGaughey, et al., 1984).
       To ensure efficient combustion, the liquid must be atomized prior to
entering the corabustor.  Atomization is typically accomplished either
mechanically through rotary cup or pressure  atomization systems, or via
gas/fluid nozzles using high pressure air or steam.  The distribution of spray
(by volume) is more uniform with rotary cups than with pressure or
air-atomized nozzles.  Waste feed storage and blending tanks aid in
maintaining a steady, homogeneous waste flow.   Particle size in slurries is a
critical factor  for successful operation because the burners are susceptible
to clogging by particulate or caked material at the nozzles  (McGaughey,
et al.,  1984; Bonner,  1981).
        Combustion chamber residence times generally range  from  0.5 to
2.0  seconds.  Operating temperatures depend  on  the waste type and  destruction
requirements, but typically  range from  650  to 1750°C  (1200 to 3180°F)
 (McGaughey, et al., 1984; GCA, 1985).   The  heat capacity (BTU)  of  the waste
 liquid must  be adequate for  ignition  and incineration  or a supplemental  fuel
must be added.
        Modified  LI  incineration  systems which have been used to destroy  dioxin
wastes are employed in ocean incinerators.   The Vulcanus uses a vertically
 configured system.  Two identical,  refractory-lined  furnaces are  located at
 the  stern.  Each incinerator consists of a  combustion  chamber and  a  stack.
                                       4-32
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FREE STANDING
INTERLOCKING REFRACTORY
MODULES
   TEMPERATURE MEASURING
   INSTRUMENTS
                          EFFLUENT DIRECTLY TO ATMOSPHERE    FRF(.H , lp
                          .OR TO SCRUBBERS AND STACK         . FOR TURBO -BLOWER
                                                            AND AFTERBURBER FAN
                                       AIR CONE
                                      UPPER NACELLE
         TURBO-BLOWER
   IGNITION CHAMBER

     HIGH VELOCITY
     AIR SUPPLY
   AIR-WASTE ENTRAINMENT
   COMPARTMENT
             WASTE LINE
                                                     — DECOMPOSITION CHAMBER
                                                           DECOMPOSITION STREAM
                                                          AFTER-BURNER FAN
                                        FLAME SENSITIZER



                                   TURBULENCE COMPARTMENT

                                     LOWER NACELLE


                                    AUXILIARY FUEL LINE

                                     TUBULAR SUPPORT COLUMNS
0   I  ^ 2   345 feet

 Approximate Scale
                                              ELECTRICAL POWER LINE
   Figure 4.3.1.
Vertically-oriented Liquid Injection Incinerator
[Bonner,  1981].
                                         4-33
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Electrically driven pumps are used to deliver the waste feed to the combustion
system.  A gorator (mixing device) is used to reduce solids in the waste to a
pumpable slurry (U. S. EPA, 1983; Ackerman, 1986; Ackerman, 1983).  It also
functions as a means of mixing the waste contents by recirculating the waste
through the waste tank (U. S. EPA, 1983; U. S. EPA, 1978; Ackerman, 1986;
Ackerman, 1983).
       Each incinerator is equipped at the base with three rotary cup type
burners.  Waste or fuel oil is delivered through a central tube to atomization
nozzles at the periphery of the rotating cup.  Optimal mixing of the
combustion gases is accomplished by positioning the burners tangentially to
the vertical axis of the incinerators.  Waste oil and fuel oil cannot be fed
into a burner simultaneously but alternate burners can be operated with fuel
and waste to alter required combustion temperatures.
       Expected emissions from the stack include CO-, CO, HC1, and H20
vapor.  Land—based liquid injection incineration systems require the use of a
scrubber to remove acids prior to releasing combustion gases to the
atmosphere.  Ocean incinerators do not require scrubbers because the acids are
expected to be neutralized by the ocean (U". S. EPA, 1983; Ackerman, 1986;
Ackerman, 1983).
Restrictive Waste Characteristics—
       Liquid injection incineration can only be used to dispose of
combustible liquids or slurries which have a low enough viscosity to be pumped
(i.e., less than 10,000 Standard Saybolt Units  (SSU)) (GCA, 1985; U. S. EPA,
1983; Bonner, 1981).  High viscosity also impairs atomization which can result
in lower DREs.  Liquid injection is most effective when the waste is
physically and chemically homogeneous.
       Particle size  in slurries is a critical  factor for  sustained operation
because the burner nozzles are susceptible to clogging by  particulate or caked
material (U. S. EPA,  1983; U. S. EPA, 1978; Ackerman, 1986).  A gorator can  be
used  to reduce solids in the waste to a pumpable slurry.
       The heat capacity (Btu) of the waste liquid must be adequate for
ignition and incineration, or a supplimental fuel must be  added.  If the heat
content of waste is less than 8,000 Btu/lb, then a supplemental fuel is
required.

                                     4-34
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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
     Temperature
     Air Feed Rate
     Waste Feed Rate Capacity
                         0.5 to 2.0 seconds
                         650 to 1750°C (1200 to 3180°F)
                         65,000 to 75,000 m3/hr
                         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-D)  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 lots 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).
                                     4-35
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  TABLE 4.3.1.
SUMMARY OF TEST RESULTS FOR U.S.-SPONSORED OCEAN
TRIAL BURNS USING LIQUID INJECTION INCINERATION
Date
11/74










8/77


8/82














2/83




Principal
hazardous constituents
Bis (dichloroyl) ether
Tetrachloroethane
2-Chloroethyl formate
1, 1,2-Trichloroethane
1,2,3 ,4-Tetrachlorobutane
1,2, 3-Tr ichloropropane
2,3-Dichloro-l-propanol
1, 1-Dichloroethane
1 ,2-Dichloroethane
Dichloropropene
1 ,2-Dichloropropane
2,4-D
2,4,5-T
TCDD
PGB with 1 chlorine atom
PCB with 2 chlorine atoms
PCB with 3 chlorine atoms
PCB with 4 chlorine atoms
FOB with 5 chlorine atoms
PCB with 6 chlorine atoms
PCB with 7 chlorine atoms
PCB with 8 chlorine atoms
Chlorobenzenes
with 1 chlorine atom
with 2 chlorine atoms
with 3 chlorine atoms
with 4 chlorine atoms
with 5 chlorine atoms
with 6 chlorine atoms
1 , 1-Dichloroethane
1 ,2-Dichloroethane
1,1, 2-Tr ichloroethane
Chloroform
Carbon Tetrachloride
Average %-DRE
>99. 99998
>99. 99994
>99'.9997
99.997
>99. 99992
>99.992
99.996
>99. 99992
>99. 99998
>99. 99997
99.9995
>99.999
>99.999
>99.93
>99.997
>99.9993
>99.9997
> 99. 9998
>99. 99999
> 99. 99992
>99. 99993
> 99. 99994

> 99. 9998
>99.9994
> 99. 99996
> 99. 99994
> 99. 9999
> 99. 99992
99.99994
99.99996
> 99. 999995
99.9996
99.998
References: U.S. EPA, 1983;  U.S. EPA,  1978; Lee, 1985.
                                4-36
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               TABLE 4.3.2.
SUMMARY OF OPERATING PARAMETERS FOR
HERBICIDE ORANGE TRIAL BURNS USING LIQUID
INJECTION INCINERATION ON THE VULCANUS
               Flame Temperature
               Furnace Wall Temp.
               Residence Time
                 1375-1610°C
                 1100-1200°C
                 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 summarized 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 (CBs),
tetrachlorodibenzofurans (TCDFs), and tetrachlorodiberizo-p-dioxins (TCDDs).
               TABLE 4.3.3
SUMMARY OF OPERATING PARAMETERS FOR
PCB TRIAL BURNS USING LIQUID INJECTION
INCINERATION ON THE VULCANUS
               Flame Temperature
               Furnace Wall Temp.
               Residence Time
               Feed Rate
                 1648-2048°C
                 1281-1312°C
                 1.1 to 1.5 seconds
                 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]
                                      4-37
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     Even though land-based liquid injection incinerators have not  been tested
using dioxin-containing wastesj several have demonstrated greater than  99.9999
percent DEE on PCB-wastes.  One of these is General Electric's Thermal
Oxidizer in Pittsfield, MA.  This unit, built by the John Zink Company  in
1972, is a horizontal unit with a primary combustion chamber and secondary
quiescent reactor followed by a vertical quench chamber and a scrubber.   In
1981, a PCB trial burn was conducted.  The results of this trial burn are
presented in Table 4.3.4.  As indicated in the table,  greater than  99.9999
percent DRE of PCB was achieved at a temperature of 1141 to 1262°C  and  a
residence time of 4.02 seconds.  In addition, no PCBs  were detected in  the
scrubber water discharge (Thayer, J.H. et al., 1983).
4.3.3
Costs of Treatment
     The costs of treatment will be a function largely of the type of waste
being fed to the unit.  Aqueous wastes with low Btu values will require
auxiliary fuel and consequently the costs will be higher.  Wastes with high
halogen content will also be more costly to treat because a caustic scrubber
is required to remove halogen acid gases.  A typical liquids incineration cost
for halogenated solvents containing significant amounts of water (i.e.,
greater than 50%) is $200/metric ton.  A PCB contaminated oil,  because of the
six nines DRE requirement and because PCBs are a highly toxic material may
cost $500 metric ton to incinerate. [CGA Corporation, 1984]  Incineration of
TCDD-contaminated liquids would probably have costs similar to  the latter and
not the former waste type.
4.3.4
Process Status
     There have been no liquid injection incinerators that have demonstrated
six nines DRE on wastes containing dioxin.  There are, however, at least two
liquid injection incinerators that have been permitted to burn PCB wastes.
Both of these incinerators are owned and operated by General Electric.   One is
in Waterford, N.Y., but it is apparently not available for commercial use,  and
the other is in Pittsfield, MA  (Mclnnes, R.C. and R.C. Adams 1984).   In
                                      4-38
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       TABLE 4.3.4.  SUMMARY OF LIQUID INJECTION INCINERATION TRIAL BURN
                     RESULTS FOR PCBs - GENERAL ELECTRIC,  PITTSFIELD, MA
                  Parameter
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 @ 12%
NOX Emissions
RC1 Emissions
HC1 Emissions
1,262°C - 1,
(2,303°F - 2,085°F)

4.02 sec

99.993%

9.5 - 10.5%

1.09 - 119 GPM

18.4 - 20.0%

99.999982%

99.999982%

99.82%

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
Reference:  Thayer, et al., 1983.
                                     4-39
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addition, Occidental Chemical Company is reportedly in the process of trying
to get a permit to perform test burns of non-aqueous phase leachate (NAPL)
from the Hyde Park landfill in its liquid injection incinerator
(Ghianti, S.).  The use of this unit to burn wastes containing dioxin seems
much more likely than the use of the two G.E. incinerators, since
transportation of the waste to the Occidental Facility would be minimal.
     With regard to ocean incineration, there are currently no existing
designated or approved burn sites in U.S. coastal waters.  Therefore,  the
status of this technology is uncertain at best.  Chemical Waste Management
(CWM) has conducted research burns and trial burns for PCB-containing wastes
and dioxin-containing waste.  However, there has been strong public opposition
to full-scale operation (Bond, 1984; HMIR, 1985a and b; HMIR,  1986a and b).
CWM has applied for a permit to conduct another research burn of PCBs at sea
to address public concerns about emissions and toxic effects that have been
raised by the Science Advisory Board in a 1985 report (Brown,  1986; HMIR,
1985a).  The proposed test plan includes obtaining more data on DREs for PCBs
(99.9999 percent-DRE is required by permit) (Brown, 1986).  The Science
Advisory Board believes that prior ocean incineration testing  has not
conclusively characterized emissions because effluent streams  were only
analyzed for a limited range of constituents.   During the proposed burn,  a
full GO/MS scan will be performed to address this concern (Brown, 1986).
     Additionally,  the Science Advisory Board suggested that synergistic
and/or antagonistic reactions between emitted compounds may increase the
toxicity of emissions beyond that which would be expected from the toxicities
attributed to each compound individually.   Therefore,  during the proposed
burn, concentrated samples collected from the  stack effluent will be injected
into biological organisms (in a laboratory environment) to determine the
concentrations at which the effluent emissions will cause toxic effects
(Brown, 1986).
     The U.S. EPA published the proposed permit regulations on December 16,
1985.  The comment period ended on February 15,  1986.   A final decision is
expected in May 1986.
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4.4  FLUIDIZED BED/CIRCULATING FLUIDIZED BED (CFB) SYSTEM

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.  The solid uncombustible materials in the waste become finely
suspended particulate 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 (Rasmussen,  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 is 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 beds and also has reduced
supplemental fuel requirements (Rasmussen, 1986; Freeman,  1985).
                                     4-41
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                                                 PREHEAT BURNER
     SAND'FEED
 ACCESS
 DOORS
                                                  THERMOCOUPLE
  PRESSURE
  TAP 	*•
                                            = :    _   SLUDGE INLET
                                                       FLUIDIZING
                                                       AIR  INLET
     I
                             5 feet
     Approximate Scale
Figure 4.4.1.  Cross-section of Fluidized-Bed Furnace [U.S. EPA, 1979]
                               4-42
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     Another modification of the conventional fluidized bed technique  that  has
been developed is the Circulating Fluidized Bed Combuster (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.,
1985a and b; Earner, 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; Earner, 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, 1985; Rickman, et
al.,  1985).
                                       4-43
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                     STEAM
                     DRUM
PROCESS
STEAM
FD
FAN
                                    COOLING
                                    WATER
     Figure 4.4.2.   Schematic of Circulating Bed Combustor.
                     Source:   GA Technologies,  1985.
                                                                        STACK
                                    4-44
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          TABLE 4.4.1.  COMPARISON OF CONVENTIONAL FLUIDIZED BED WITH
                         CIRCULATING FLUIDIZED BED COMBUSTOR
     Condition
Circulating fluidized bed     Conventional fluidized bed
Feeding

  No. of Inlets

  Sludge Feeding

  Solids Feed-size

Pollution Control

  POHCs


  C1,S,P

  Upset Response
1^-solid; 1-liquid

Direct

<1 in.



In moderate temp, combustor


Dry limestone in combustor

Slump bed; no release
5-solid; 5-liquid

Filter/Atomizer

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

Downstream scrubber

Bypass scrubber pollution
release
Effluent
Efficiency
Thermal
Carbon
Dry Ash

>78%
>98%
Wet Ash Sludge

>75%
>90%
Reference:  Rickman, et al., 1985
                                      4-45
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     Bottom ash is continuously removed frcta the combustor,  cooled to
approximately 200°F using a water-cooled screw conveyor and  solidified or
drummed.
     Auxiliary fuel may also be injected into the bed if required to maintain
temperature.  Retractable bayonet heat exchangers are used when combustion
heat must be removed from the combustor.  These heat exchangers are
constructed of stainless steel and use recirculated water as a coolant.
Adjustment of the heat exchanger area enables control of the combustor
temperatures (GA Technologies, 1985; Rickman, et al., 1985).

Restrictive Waste Characteristics—
     The fluidized bed incineration technique is not well—suited for
irregular, bulky solids, tarry solids, or wastes with a high fusible ash
content (Freeman, 1985; GCA, 1985).  Formation of eutectics  (compounds with
low melting or fusion temperatures) can result in bed fouling.  Problems
caused by wastes with low ash fusion temperatures can be avoided by keeping
operating temperatures below the ash fusion level or by using chemical
additives to raise the ash fusion temperature.  Waste containing bulky or
irregular solids may require pretreatment in the form of drying, shredding,
and sorting prior to entering the reactor.
     Labor utilization is high since regular preparation and maintenance of
the fluid bed must be performed.  These costs can increase dramatically if  it
becomes difficult to remove residual materials from the bed.

Operating Parameters—
     The diameter of the fluidized bed unit typically ranges from a few meters
to 15 meters.  Operating temperatures normally range from 450°C to 980°C and
are limited by the softening point of the bed media (1100°C  for sand)
(McGaughey, et al., 1984; GCA, 1985).  Residence times are generally on the
order of 12 to 14 seconds for a liquid hazardous waste.
                                     4-46
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4.4.2  Technology Performance Evaluation
     Fluidized beds have been used to 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

4.4.2.
     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 HG1 by capturing the
chlorides formed.  The following results were obtained (Rickman, et al., 1985;

Chang and Sorbo, 1985):
       NOX emissions
       SC>2 emissions

       CO emissions

       Chloride  Capture

       Flue  Gas  Emissions  (%-DRE)
              - Ethylbenzene
              - 1,1,2-trichloroethane
              - 1,2-dichloroethane
              - 1,1-dichloroethylene
              - 1,2-transdichloroethylene
              - vinyl  chloride
              - toluene
              — benzene
40 ppm (average)

250 to 350 ppm

 1000 ppm

 99%
>99.99
>99.99
>99.99
>99.99
>99.99
>99.99
>99.99
>99.99
                                      4-47
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    TABLE 4.4.2.  RESULTS OF LOW-TEMPERATURE FLUIDIZED BED TRIAL BURN USING
                  SOIL CONTAMINATED WITH CARBON TETRACHLORIDE
                  AND DICHLOROETHANE
       Condition
  Run 1
                                                                     Run 2
Fluidized Bed Temperature

Combustion Vessel
Exit Temperature

Vessel Residence Time

Feed Rate:
850°C

650°C


1.3 sec
850°C

650°C


1.3 sec
Soil
Carbon Tetrachloride
Dichloroethane
Destruction Efficiency:
Carbon Tetrachloride
Dichloroethane
10.5 kg/h
0.32 kg/h
0.035 kg/h

99.998%
99.998%
6.17 kg/h
0.40 kg/h
0.044 kg/h

99.996%
99.997%
Reference:  Freeman, 1985; Rasmussen, 1986.
                                     4-48
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     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  fluidized 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,
1986).

                                      4-49
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         TABLE 4.4.3.  PCB-CONTAMINATED SOIL TRIAL BURN TEST CONDITIONS
                       AND RESULTS FOR CIRCULATING BED COMBUSTOR
Condition/result
PCB Concentration
in soil (ppm)
Soil Feed Rate (Ib/hr)
Combustion Temperature (°F)
Surface Velocity in
Combustion Chamber (ft/sec)
% Excess Oxygen
%-DRE
PCB in bed ash (ppm)
PCB in fly ash (ppm)
Dioxin/Furan in ash (ppm)
% Combustion Efficiency
NOX (ppm)
CO (ppm)
HC1 (ppm)
Particulates (g/dry cu. ft)
Trial 1
11,000
325
1800
18.7
7.9
>99.9999
0.0035
0.066
ND
99.94
26
35
57
0.09b
Trial 2
12,000
410
1800
18.7
6.8
>99.9999
0.033
0.010
ND
99.95
25
28
202a
0.04
Trial 3
9,800
325
1800
18.1
6.8
>99.9999
0.186
0.032
• ND
99.97
76
22
255a
0.002
aHigh values resulted from intermittent limestone addition.

"Obtained from makeup test for particulates only.

Reference:  Rickman, et al., 1985; Chang and Sorbo, 1985.
                                      4-50
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                TABLE 4.4.4.   WASTE-TECH FLUIDIZED BED COSTS
                Item
                                Cost
     Operating Labor

     Consumables and Utilities

     Nonlabor (capital depreciation,
     siting cost, maintenance mat'Is,
     insurance, tax overhead)

     Limestone for Chlorine Removal,
     Waste Excavation, Ash Disposal, etc.

     TOTAL COST       c
                             0.0084   $/lb

                             0.0138   $/lb



                             0.0116   $/lb


                             0.043    $/lb

                               $150/ton
Note:  These cost estimates are for a 50 sq.ft. system with a throughput of
       9,200 Ib/hr for soils having 2 percent organics and 5 percent moisture
       content.
                 TABLE 4.4.5.   CIRCULATING FLUIDIZED BED COSTS
Feed Type
  Installed
   Capital
    Costs
  Annual
 Operating
   Costs
                                                                Total Cost per
                                                                 Unit of Feed
Chlorinated
Organic Sludge

Contaminated
Soil

Wet Sludge
$2.0 million


$1.8 million

$1.8 million
$0.25 million


$0.35 million

$0.35 million
$60/ton


$27/ton

$32/ton
Note:  Costs  are based on  the use of  a  25 million Btu/hr unit.
                                     4-51
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4.5  HIGH TEMPERATURE FLUID WALL (HTFW) DESTRUCTION -
     ADVANCED ELECTRIC REACTOR
4.5.1  Process Description  [Lee, Schofield, and Lewis, 1984; Schofield, Scott
and Dekany, 1985; Weston, Inc. 1985.]

     The HTFW reactor was originally developed by Thagard Research of Costa
Mesa, California.  The J.M. Huber Corp. of Borger, Texas has developed
proprietary modifications to this original design.  This reactor,  called the
Advanced Electric Reactor (AER), is shown in Figure 4.5.1.  The reactor is a
thermal destruction device which employs radiant energy provided by
electrically heated carbon electrodes to heat a porous reactor core.   The core
then radiates heat to the waste materials.  The reactor core is isolated from
the waste by a blanket of gas formed by nitrogen flowing radially through the
porous core walls.
     The only feed streams to the reactor are the waste material and the inert
nitrogen gas blanket.  Therefore, the destruction is by pyrolysis rather than
oxidation.  Because of the low gas flow rate and the absence of oxygen, long
gas phase residence times can be employed, and intensive downstream cleanup of
off gases can be achieved economically.
     Destruction via pyrolysis instead of oxidation significantly reduces the
concentrations of typical incineration products such as carbon monoxide,
carbon dioxide, and oxides of nitrogen.  The principal products formed during
treatment of soil contaminated with TCDD are hydrogen, chlorine (if calcium
oxide is added to the reactor, calcium chloride is formed instead),
hydrochloric acid, elemental carbon,  and free-flowing granular material
(Schofield, et. al.,  1985; Boyd, et al.,  1986; GCA, 1985)
     A process flow diagram for the AER is shown in Figure 4.5.2.   The waste,
if it is a solid, is released from an air tight feed bin through a metered
screw feeder into the top of the reactor.  If it is a liquid,  it is  fed by an
atomizing nozzle into the top of the  reactor.   The waste then passes  through
the reactor where pyrolysis occurs at temperatures of approximately 4500°F in
the presence of nitrogen gas.  Downstream of the reactor, the  product gas and
waste solids pass through two postreactor treatment zones, the first  of which
is an insulated vessel which provides additional high temperature  (2000°F)  and
                                      4-52
-------
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                                DEFLECTOR

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                                CONNECTOR
                              9. POROUS CORE
                             13. RADIOMETER PORT
                             14. BLANKET GAS INLET
                                (TYPICAL)
Figure 4.5.1.  Advanced Electric Reactor [Huber]


               4-53
-------
 POST
REACTOR
 ZONES
                  AIR TIGHT FEED BIN
                  MOUNTED ON A HOPPER
                    METERED
                    SCREW FEEDER
                   ELECTRIC
                   REACTOR
                    SAMPLE POINT I

                       / FAN     BAG FILTER
                                         SAMPLE POINT 2
                       SLIDE VALVE
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      SOLID
      WASTE
       BIN
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ACTIVATED
CARBON BEDS
1



                        CAUSTIC
                        SCRUBBER
       Figure 4.5.2.
High  temperature fluid wall process  configuration for the
destruction of carbon tetrachloride  [Huber].
                                        4-54
-------
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.
                                     4-55
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Operating Parameters—
     Typical operating parameters for the Advanced Electric Reactor are
summarized below (Freeman, 1985; Schofield, et al., 1985; Boyd,
  et al.,1986):
            Residence Time
            C100 mesh solids)
            Gas Flow Rate
            Gas phase
            Residence Time
            (at 2500° F)

4.5.2  Technology Performance Evaluation
0.1 seconds

500 scfm for 150 ton day scale
5 seconds
     In 1983, Thagard conducted a series of tests on PCB-contaminated soils
using a 3-inch diameter research reactor. (Horning and Masters, 1984; Freeman,
1985).  The results of these tests showed an average DRE of 99.9997 percent.
The destruction efficiency was found to be independent of the feed rate in the
                      "*                          #
50 to 100 g/min range at 2343°C.  Pyrolysis products other than carbon and
hydrogen chloride were not detected using a. GC with electron capture
detection.  It was concluded that the method for dispersing the feed into the
reactor needed improvement.   Problems with slagging in the reactor occurred
that were believed to be related to the small diameter of the reactor and also
to the design of the fluid wall flow.  After modifications, additional tests
on a 6-inch prototype reactor were conducted by Thagard using
hexachlorobenzene dispersed on carbon particles; 99.99991 percent destruction
efficiency was achieved (Horning and Masters, 1984).
     J.M. Huber Corporation purchased the patent rights and made further
improvements to the process (Boyd, 1986). The J.M. Huber Corporation then
began tests in its stationary reactor system which has a diameter of
12 inches.  Included in this system are:  an insulated post-reactor vessel, a
water-jacketed cooling vessel, a cyclone, a baghouse, a wet scrubber, and an
activated carbon bed (Boyd, et al., 1986; Schofield, et al., 1985; Freeman,
1985).  Several research burns have been conducted with this system
(Schofield, et al., 1985).  Results and operating parameters for pertinent
burns are summarized in Table 4.5.1.
                                     4-56
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          TABLE 4.5.1.  SUMMARY OF OPERATING PARAMETERS AND RESULTS
                         FOR HUBER AER RESEARCH/TRIAL BURNS
Condition
Reactor Core
Temperature (F)
Haste Feed
Rate (Ib/min)
Nitrogen Feed
Rate (scfm)
%-DRE
PCBs
(Sept. 1983)

4100

15.5-15.8

147.2
>99. 99999
CC14
(May 1984)

3746-4418

1.1-40.8

104.3-190.0
>99.9999
Dioxins
(Oct/Nov 1984)

3500-4000

0.4-0.6

6-10
>99.999
Reference:  Schofield, 1984; Roy F. Weston,  1985.
                                      4-57
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     A series of four trial PCB-burns were conducted during September 1983
using a synthesized mixture of Aroclor 1260 and locally available  sand to
obtain a total concentration of 3000 ppm PCBs (Schofield,  et al.,  1985;
Freeman, 1985).  After treatment, the sand had a PCB content ranging  from
0.0001 to 0.0005 ppm (0.1 to 0.5 ppb).  The destruction and removal efficiency
was measured to be  99.99960 to  99.99995 percent.   Additional studies were
conducted with the 12 inch diameter reactor using soils contaminated  with
octachlorodifaenzo-p-dioxin (OCDD) and carbon tetrachloride.   Seven nines DRE
(99.99999 percent) were reportedly achieved at feed rates  up to 2500  Ibs/hr.
J.M. Huber also maintains a 3 inch diameter mobile  reactor which was  used  for
trial burns on 2,3,7,8-TCDD-contaminated soil at Times Beach,  Missouri in
November 1984 (Roy F. Weston, 1985).  The 2,3,7,8-TCDD levels in the  soils-
ranged from 67.9 to 99.8 ppb.  A total of 63.58 Ibs of soil were processed af;
temperatures ranging from 2260° to 2315°C.
     Greater than five nines (99.999 percent) destruction  and removal
efficiency (DRE) was demonstrated during the Times  Beach trial burns  (Roy  F.
Weston, 1985).  Higher DREs could not be demonstrated due  to the inability of
the instrument detection limits to compensate for the relatively low  quantity
of contaminated soil 0\>79 ppb in 63.58 Ibs or 0.002 grams).   2,3,7,8-TCDD
concentrations were below detection limits in the treated  soil  (<0.11 ppb),
in the baghouse catch (<0.55 ppb), and in the stack emissions (<0.71  ppb).
Chlorinated organics were not detected in the stack emissions (at  a detection
limit of 25 ppb), and gaseous emissions of particulates were within EPA
standards.
     During the Times Beach trial burns, difficulties were encountered in  the
soil preparation (such as maintaining dryness and properly sized soils) which
caused Huber Corporation to delay the construction  of a 50,000 ton/yr reactor
(Technical Resources, Inc., 1985).  The U.S. Air Force recently conducted
studies related to the pretreatment of dioxin contaminated soils using the
3 inch mobile AER system at Gulfport, Mississippi (Boyd, 1986). Although  the
testing was completed in June 1985, the results are currently being reviewed
and a final report should be available in the summer of 1986.   The studies
consisted primarily of soil pretreatment techniques for more efficient
operation of the reactor (Boyd, 1986).
                                      4-58
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4.5.3  Costs 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.,  1984).
Pretreatment may be necessary for bulky wastes having a high moisture
content.  Typical energy requirements for normal soil range from 800 to 1000
kwh/ton.
     Cost estimates for processing a site containing more than 100,000 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
                                      4-59
-------
RCRA for treating dioxin-containing wastes.  The J.M. Huber Corporation
intends to use the permit for research and development of a full-scale
transportable AER.
     Huber does not intend to operate a hazardous waste disposal operation,
but rather to construct and market stationary and/or mobile units for use by
companies or organizations involved in hazardous waste destruction (Boyd,
1986).                                                                       /
                                      4-60
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4.6  INFRARED DESTRUCTION (Shirco)
4.6.1  Process Description (Daily, 1986;  Shirco,  1985;  Freeman and Olexsey,
       1986; HMIR,  1986; Technical Resources Inc.,  1985;  Daily,  1985)

     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
                                      4-61
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also are arranged to enhance gas turbulence.   Turbulence is  also provided by
combustion air from the blower which is injected into the secondary chamber
through two offset jets on each side of the chamber.   Combustion residence
times typically range from 1.5 to 2.2 seconds,  with a process  temperature
capability of up to 2,300°F.
     Exhaust gases from the secondary chamber pass through a wet scrubber for
removal of particulates.  The scrubber also cools the gases  (from incoming
temperatures of 1,000 to 2,300°F) to saturation temperature  (generally
180°F).  The gases can be subcooled to lower temperatures, but this requires a
significantly greater volume of water.  A pump is used to recirculate  the
scrubber water from a sump tank to the scrubber.  Lime may be  added to the
sump tank to remove any acid materials formed.  A blower is  used to direct the
exhaust gases through a 10 ft exhaust stack.
     Available sampling points include two standard sampling ports in  the
exhaust stack, and sampling ports in the primary and  secondary chamber exhaust
ducts*  In addition, temperatures, pressures, and flow rates are measured and
shown on a master control panel.

4.6.2  Technology Performance Evaluation

     In early June 1985, the Shirco portable pilot test unit was taken to
Times Beach, Missouri to conduct trial burns on 2,3,7,8-TCDD-contaminated
soils (ERT, 1985: Daily, 1986).  The system was set up and ready for
operations within a few hours of arrival at the site.  The testing was
conducted over a 2—day period followed by equipment decontamination
activities.  Two tests were performed, each with differing operating
parameters.  The operating parameters and the results of each  test are shown
in Table 4.6.1.
     Emissions samples were collected over a 7-hour period for Test 1
(30-minute residence time), and over a 2.5-hour period for Test 2 (15-minute
residence time)(ERT, 1985; Daily, 1986).  Continuous  samples of the thermally
treated soil were also collected during each run.  Dioxin was  not detected
(based on analytical detection limits) in the treated residual material for
either test run.  Sufficient gas sample was collected to demonstrate
destruction and removal efficiencies (DREs) for both  runs that
                                      4-62
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       TABLE 4.6.1  OPERATING PARAMETERS AND RESULTS FOR SHIRCO INFRARED
                    DESTRUCTION PILOT TESTS
   Condition
 Test 1
                                                                      Test2
TCDD in Feed
(ng/g)

Solid Phase
Residence Time
(min)

Solid Feed
Rate (Ib/hr)

Primary Chamber
Temp.-Zone A (°F)

Primary Chamber
Temp.-Zone B (°F)

Secondary Chamber
Temperature (°F)

Emissions Sampling
Duration (hours)

Particulate at
7% 02 (gr/dscf)

Gas Phase DRE of
2,3,7,8,-TCDD
  at Detection Limit
  (picograms)

Ash Analysis for
2,3,7,8-TCDD
  at Detection
  Limit (ppt)
   227



   30


  47.68


  1560


  1550


  2250
 0.0010


>99.999996

   14


    ND

    38
    156



    15


  48.12


   1490


   1490


   2235


   2.5


  0.0002


>99.999989

   8.4


   ND

   33
Reference:  ERT, 1985; Daily, 1986.
                                      4-63 ;
-------
exceeded the required 99.9999 percent DRE (when calculated at  the detection
limits).  Particulate emissions were well-below the 0.08 gr/dscf EPA
regulation requirement.

4.6.3  Costs of Treatment

     Preliminary estimates of the operating costs for infrared incineration
have been stated to be under $200/ton (Daily,  1985).  This estimate includes
the cost of insurance, obtaining permits, labor, and energy requirements.
Costs for excavation and disposal are not included in this estimate.
Construction costs for the transportable incinerator range from 2 to 3 million
dollars.

4.6.4  Process Status

     The results obtained at The Times Beach Trial Burn have demonstrated that
the Shirco Infrared Process is a viable technology for dioxin
decontamination.  The Shirco Infrared Incinerator is expected to be
commercially available in the near future (Johanson, 1986; Hill, 1986).
                                       4-64
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 4.7  PLASMA ARC PYROLYSIS

 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 atomic 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 is  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,
1984).
                                     4-65
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                                                  n
OFF GASES TO FURE
                                                             EMERGENCY CARBON FUER
                                                             GASCHROMATOGRAPH-
                                                             MASS SELECTIVITY UNIT

                                                             LABORATORY
                                                             ANALYSIS EQUIPMENT

                                                             GASCHROMATOGRAPH
                                                        SALT WATER TO DRAIN
Figure 4.7.1.   Pyroplasma process  flow diagram.

Source:   Kolak,  et  al.,  1986.
                             4-66
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     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 kg/min of waste
containing 35 to 40 percent CGI, was fed to the reactor, a scrubber water
effluent flowrate of 30 I/minute was generated (Kolak, Barton, Lee,
Peduto, 1986).

Restrictive Waste Characteristics—
                                                               i
     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 Park
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.
                                      4-67
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     Table 4.7.1 presents the results of three test burns conducted in
Kingston, Ontario using carbon tetrachloride in the feed material.   The carbon
tetrachloride was fed to the reactor along with ethanol, methyl ethyl ketone,
and water at a rate of 1 kg of CC1,/minute.  The duration of each of these
tests was 60 minutes, and stack gas flowrates and temperatures averaged
32.5 dry standard cubic meter/minute (dscm/min) and 793°C, respectively.  As
can be seen in the table, the destruction and removal efficiency (DRE) of
CC1, in each of the tests exceeded six nines which is the required DRE when
incinerating wastes containing TCDD.  In addition, the concentration of HC1 in
exhaust gases was less than the upper limit of 1.8 kg/hr required by RCRA
guidelines.  The only possible area of concern is that the concentration of
CC1, in the scrubber water is greater than 1 ppb.  Proposed regulations for
treatment of TCDD require that the residuals have less than 1 ppb of TCDD for
the residual to be nonhazardous (Kolak, Barton, Lee, Peduto, 1986).
     Table 4.7.2 contains results of other tests conducted using PCB in the
feed material.  During startup of the unit, a mixture of MEK and methanol
(MeOH) was fed to the reactor.  Once the exhaust gas attained a temperature of
1,100°C, the waste feed was switched to a blend of PCB, MEK, and MeOH.
Typical operating parameters for these tests are presented in Table 4.7.2.
Stack gases and scrubber effluents were analyzed for dioxins, furans and
benzo(a)pyre"ne, in addition to PCBs.  As indicated in Table 4.7.3, the
concentrations of these constituents in each of the residual streams is
extremely low.  The  concentrations of dioxins  in the scrubber water and the
stack gases are both in the low parts per trillion range.  As far as PCBs are
concerned, the destruction and removal efficiency in each of the tests was
greater than 6 nines, and in some cases reached 8 nines.
 4.7.3   Costs  of Treatment

     The approximate capital cost  of  a unit  similar to the one tested would be
 in the  range  of 1 to 1.5  million dollars  (Plottner, 1986).  More accurate
 figures will  be available once a commercial  unit  has  been built.  Nonetheless,
 some general  operating costs associated with using the reactor can be
 estimated.  One of the major costs would  be  the electrical power required to
 generate the  plasma torch.  If,  for example, the  currently built unit were
 used to destroy nonaqueous leachate collected  at  the  Hyde Park and Love  Canal
                                       4-68
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                TABLE 4.7.1.   CARBON TETRACHLORIDE  TEST RESULTS
Parameter
Chlorine Mass Loading (%)
Scrubber Effluent
CCl4(ppb)
mg/hr
Flare Exhaust
CC14 (ppb)
mg/hr
NOX
ppm(v/v)
Ibs/hr
CO
ppm(v/v)
Ibs/hr
HC1
mg/dscm*
kg/hr
Destruction Removal Efficiency
Test 1
35

1.27
2.29

0.83
12.1
106
1.02

48
0.28

(1)
(1)
99.99998
Test 2
40

5.47
9.85

0.43
4.9
92
0.69

57
0.26

137.7
0.25
99.99998
Test 3
35

3.26
5.87

0.63
7.2
81
0.02

81
0.37

247.7
0.44
99.99998
(1)  sample taken was invalidated due to plugging of sampling apparatus




*mg/dscm = milligrams per dry standard cubic meter.
                                      4-69
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      TABLE 4.7.2.  TYPICAL OPERATING DATA FOR PCB TESTS (ONE HOUR RUNS)

                         OPERATING DATA FOR  PCB RUN #1
Elapsed operating time:

Feed Rate
  Total Feed-
  PCB Feed

Feed Composition (mass)
Reactor Operating
Temperature

Plasma Torch Power
70 min.  at operating temperature
3.09 1/min
2.83 kg/min

0.40 kg/min

14.1% PCB
11.0% TCB
74.9% MEK/MeOH
1136°C

327 kW
Reference: Kolak, et al, 1986.
                                       4-70
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                        TABLE 4.7.3.   PCB TEST RESULTS
                                      Run 1
                    Run  2
                  Run 3
Stack Gas Parameters

Total PCB,    (1)
  g/dscm*     (2)
Total Dioxins,
  g/dscm
Total Furans,
  g/dscm
Total  BaP,
  g/dscm
   0.013
   0.013

   0.076  (3)

   0.26

   0.18
  0.46
  0.32

  0.43

  1.66

  0.45
   3.0
   0.011

   0.13

   0.30

   2.8
Scrubber Effluent Parameters

Total PCB, ppb(l)
              (2)
Total Dioxins, ppt
Total Furans, ppt
Total BaP, mg/L
   1.56
   0.06
   5.8
   1.5
   0.04
  2.15
  4.7
  259
  399
  0.92
   9.4
   0.01
   1.35
   1.35
   2.0
Destruction Removal Efficiency

PCB, Percent DRE
     (1)
     (2)
>99.99999
 99.999999
99.99994
99.99997
>99.9999
 99.999999
      (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 #1 where 0.06 ng tetra dioxin was reported.
      *g/dscm  = grams per dry  standard cubic meter

 Reference:  Kolak, et al., 1986.
                                      4-71
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Landfills, the electricity cost would amount to $200,000.  This estimate is
based on the treatment of 330,000 gallons of waste at a rate of 55 gal/hour,  a
power requirement of 327 kw, and an electricity cost of $0.10 per kilowatt/hr.
     Other operating costs include manpower (estimated to be three people),
sodium hydroxide for the scrubber, cooling water, and compressed air.  One
possible cost credit associated with this process is related to the fact that
the products of combustion of this process are hydrogen and carbon monoxide.
These materials are themselves combustible and could be used as a fuel to run
a generator.

4.7.4  Process Status

     The construction and testing of the plasma arc system is jointly
sponsored by the New York State Department of Environmental Conservation
(NYDEC) and the U.S. EPA Hazardous Waste Engineering Research Laboratory
(HWERL).  The project is comprised of four phases, which are:

     Phase 1:  Design and construction of the mobile plasma arc system by the
               contractor, Pyrolysis Systems, Inc. (PSI).
     Phase 2:  Performance testing of the plasma arc system at the Kingston,
               Ontario, Canada test site.
     Phase 3:  Installation of the plasma arc system and additional
               performance testing at Love Canal, Niagara Falls, N.Y.
     Phase 4:  Demonstration testing as designated by NYDEC.
Phase 1 took place in 1982 and Phase 2, the results of which have been
presented above, was completed in early 1986.  Phase 3 will be initiated later
in 1986.
     The plasma technology is being jointly marketed by Westinghouse Electric
Corporation Waste Technology Services Division and PSI.  Once the system has
been properly tested, they plan to lease these units to companies or
organizations that require the system for waste clean up.
     The current system is only designed to handle liquid wastes.  Future
plans by PSI and Westinghouse include the design of units which could handle
contaminated soil and other solid wastes (Haztech News, 1986).
                                      4-72
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4.8  MOLTEN SALT DESTRUCTION

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 1,450°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)j 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 (1,650°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
          X
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 oan 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
                                      4-73
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                    LIQUID WASTE FEED
                                     COMBUSTION AIR
    SOLID WASTE FEED
   MOLTEN-SALT
   LEVELCONTROL -J
           SALT QUENCHING CHAMBER
                                                     EXHAUSTSTACK
                                                       AND/OR GAS
                                                    CLEANING EQUIPMENT
                                             MOLTEN SALT DEMISTER
                                           ^SECONDARY REACTION ZONE
                                           ..-MOLTEN SALT
                                        WASTE ENTRANCE
                                                    NOT DRAWN TO SCALE
                              TO SALT RECOVERY
Figure 4.8.1.
Schematic of generalized molten salt  incinerator  design

 [Hitchcock,  1979].

               4-74
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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 period of time.  The process becomes
inefficient and/or impractical for wastes of high ash content.  Also, wastes
with 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
     Operating Temperature
     Average Residence Time
           Gas Phase
           Solid (or Liquid Phase)
     Energy Requirements
Solid or Liquid Wastes of
Low ash and water contents
800 to 1000°C
(1500° to 1850°F)
5 seconds
Hours
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-D herbicide,  tar, chloroform, perchloroethylene distillation bottoms,
trichloroethane, tributyl phosphate, and PCBs (GCA, 1985; Edwards,  1983).
                                     4-75
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      The PCB trial combustion data are presented in Table 4.8.1.  The
 destruction efficiency at  the lowest  operating  temperature  (1,300°F) exceeded
 99.99995 percent.   The average residence  time of the PCB in the melted salt
 was  0.25 to 0.50  seconds,  based on gas velocities of 1 to 2 ft/sec through the
 0.5  ft  of melt  (GCA,  1985; Edwards, 1983).
      Hexachlorobenzene (HCB)  and chlordane destruction were tested in the
 pilot plant facility  (Johanson,  1983). Feed rates  for HCB  and chlordane were
 as high as  269  Ib/hr  and 72 Ib/hr,  respectively.  Bed temperatures ranged from
 1,685°  to 1,805°F,  and residence times were close to 2 seconds.
 HCB  destruction efficiencies  ranged from nine to eleven nines DRE (99.9999999
 to 99.999999999%),  and chlordane DREs  ranged from seven to eight nines
 (99.99999 to 99.999999%).   The  results of the pilot-scale tests are summarized
 in Table 4.8.2
      Smaller scale  experiments  using 2,3,7,8-TCDD were conducted at the
 University  of Milan in Italy  (Bellobono, 1982).  A 0.8 in.  diameter by 24 in.
 high reactor was used at temperatures  ranging from 1,470°F to 2,190°F.
 Materials simulating  herbicide wastes  were prepared  by blending 50 percent
 cellulose powder, 30  percent  polyethylene, and selected herbicides.   The
 2,3,7,8-TCDD  concentration was  0.1 to  10 percent by weight.   The solids were
 pulverized  to less  than 50 mm.   2,3,7,8-TCDD destruction efficiencies ranged
 from 99.96  percent  (at  1,470°F)  to 99.98 percent at 2,190°F.

 4.8.3   Costs  of Treatment

     The molten salt  process  has not been developed to the  scale that specific
 cost projections can  be developed.  However,  the equipment  cost for  the
 200  Ib/hr capacity pilot unit has been estimated to be $1.4 million (GCA,
 1984).
     The most significant  factor that  affects the cost of molten salt
 incineration  is the frequency with which the  salt bed needs  to be  replaced.
For a high chlorine content waste,  the replacement of the bed  can  be  as high
as one pound of bed for one pound of waste destroyed (GCA,  1984).
     Costs will be higher for wastes which require auxiliary fuel  to  sustain
combustion in the molten salt  bed.   Wastes with heating values >4000  BTU/lb
should not require supplemental fuel (GCA,  1984).
                                      4-76
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   TABLE 4.8.1.   PCB COMBUSTION TESTS IN SODIUM-POTASSIUM-CHLORIDE-CARBONATE
                 MELTS  [Edwards,  1983]
Temp
          Stochiometric
               air
Concentration
of KC1, NaCl
   in melt
   (wt %)
                                               Extent of PCB
                                               destruction3..
Concentration
  of PCB in
  off-gasa
  ( g/m3)
1598
1526
1292
1643
1427
1427
145
115
160
180
125
90
60
74
97
100
100
100
>99. 99995
>99. 99995
>99.99995
>99. 99993
>99. 99996
>99. 99996
52
65
51
59
44
06
aPCBs were not detected in the off-gas, i.e., values shown are detection
 limits.

Reference:  GCA, 1985; Edwards, 1983.
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                TABLE 4.8.2.  SUMMARY OF PILOT-SCALE  TEST RESULTS
                                 PCB
                                      Chlordane
Combustor Feed Rate
  (Ib/hr)

Combustor Off-gas

  - mg/m3

  - ppmv

Baghouse

  - mg/m3

  - ppmv

Spent Melt (ppmv)

NOX (ppmv)

HC (ppmv)

Particulate (mg/m3)

DRE (%)
20.9 - 122.0





2.7 x 10~* - 7.1 x 10~2

2.3 x 10~5 - 6.1 x 10~3




  <6 x 10~6 - 1.6 x 10~4

<5.2 x 10~7 - 1.4 x 10~5

0.001 - 0.104

70 - 125

35 - 110

<6.2 x 10~3 - 0.107

11-9's - 9-9's
12.1 - 32.7





5.3 x 10~3 - 6.8 x 10~2

3.2 x ID"4 - 4.1 x 10~3




<3.6 x 10~4 -  4.4 x 10~3

<2.1 x 10~5 -  2.6 x 10~4

0.0044 - 1.2

0.5 - 630

0.4 - 60

4.1 x 10~3 - 1.75 x 10-2

8-9's - 7-9's
Note:  The pH of the liquid in a small sampling scrubber in the  off-gas  line
       remained basic throughout the test indicating essentially no HC1
       emission.
Reference:  Freeman, 1985.
                                      4-78
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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 DRE  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.
                                       4-79
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 4.9  SUPERCRITICAL WATER OXIDATION
 4.9.1  Process  Description
      The supercritical water (SCW)  oxidation process utilizes the properties
 of water at  pressures  greater than  218 atmospheres combined with temperatures
 above 374°C  to effect  oxidation of  organics  such as TCDD (Thomason and Modell,
 1984;  Josephsory,  1982).   Above these temperatures and pressures, water is in
 its supercritical  state and exhibits solubility characteristics which are the
 inverse  of normal  liquid water properties  (Thomason and Modell, 1984;
 Josephsory,  1982).   Thus,  organics  become  almost completely soluble and
 inorganic salts become only sparingly soluble and tend to precipitate.
      The steps involved in the SCW  oxidation process (as developed by Modar,
 Inc.)  are diagrammed in Figure 4.9.1.  Initially, the waste (in the form of an
 aqueous  solution or slurry)  is pressurized and heated to supercritical
 conditions by  mixing it with recycled reactor effluent (Modar, 1982; Modell,
 1984).   Compressed  air is  also mixed with  the feed to serve as source of
 oxygen for the reactions.   Oxygen and air  are miscible with water under
 supercritical  conditions,  thereby enabling the homogeneous operation of the
 process.  The  homogenized mixture is then  pumped to the oxidizer where
 organics  are rapidly (residence times average 1 minute) oxidized.  Oxidation
 is  achieved  under homogeneous  conditions (single-phase supercritical fluid)
 and therefore  higher effective oxygen concentrations and destruction
 efficiencies can be  achieved with shorter  residence times than with other
 similar processes (i.e., the wet oxidation process).
     The  release of  combustion heat from the oxidation reactions causes
 temperatures in the  oxidizer reactor to rise to 1112 to 1202°F (Modell,  1984;
 Freeman,   1985;  GCA,  1985; GCA, 1984).  The reactor effluent then enters a
 cyclone (solids separator) where inorganic salts are precipitated out (at
 temperatures above 450°C) (Modell,  1984;  GCA, 1985;  GCA,  1984;  Freeman,
 1985).  The fluid effluent of  the solid separator consists  of superheated,
 supercritical water, nitrogen, and carbon dioxide.   A portion of the
 superheated,  supercritical water is directed to an eductor  so that it can be
 recycled to heat the incoming waste feed (initial step  in the process).
Modar, Inc.  suggests that the remaining effluent,  which consists of a high
 temperature,  high pressure fluid, can be  cooled to subcritical  temperatures  in
                                     4-80
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4-81
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a heat exchanger and the resulting steam can be used with turbines to generate

energy (Modar, 1982; Modell, 1984).  However, the cost-effectiveness of the
turbine power generation system is limited to certain cases.

     The supercritical oxidation process results in conversion of carbon and
hydrogen compounds from the organic compound to CO ' and H_0 (Swanson, et

al., 1984; Josephson, 1982).  Chlorine atoms are converted to chloride ions

and can be precipitated as sodium chloride with the addition of basic

materials to the feed.  Gaseous emissions consist primarily of carbon dioxide

with smaller amounts of oxygen and nitrogen gas, which do not require

auxilliary treatment for offgases.  Solid emissions consist of precipitated

inorganic salts (chlorine produces chloride salts, nitro compounds precipitate

as nitrates, sulfur compounds as sulfates, and phosphorous compounds as
phosphates).  The liquid effluent consists of a purified water stream, which
can be used for process water.
Restrictive Waste Characteristics (Thomason and Modell, 1984; GCA, 1985; GCA,
1984; Freeman, 1985)—
     Certain restrictions exist concerning the types of waste that can be
treated using the supercritical water oxidation system.  These restrictions
are:

     1.   Organic concentrations need to be less than 20 percent by weight in
          order for the process to be cost-effective; higher concentrations
          can be diluted by mixing with dilute wastewater or with pure water.

     2.   The waste needs to be in the form of an aqueous solution or slurry.
          Solids can be mixed with water to form a slurry.

     3.   Costs are higher if the waste has a fuel value of greater than
          1750 Btu/lb, a value equivalent to that exhibited by a waste
          consisting of 10 percent by weight of benzene or its equivalent.
          This is the optimal heat for achieving a reactor exit temperature of
          600 to 650°C.  Wastes with greater than a 10 percent benzene
          equivalent should be diluted, and fuel should be added to wastes
          with less than a. 10 percent benzene—equivalent.

Operating Parameters (Sieber, 1986)—
     The following are typical operating parameters for the SCW system:
     Waste Form
     Temperature
     Pressure
     Average Residence Time
     Feed rate
Aqueous solution or slurry of organics
450 to 650°C
220 to 250 atmospheres
less than 1 minute
                                     4-82
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4.9.2  Technology Performance Evaluation

     Modar has built and tested bench scale supercritical water reactors  for
destruction of urea, chlorinated organics,  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 Hastelloy 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 TOG 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 DRE 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  Costs 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
                                      4-83
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 TABLE 4.9.1.  COMPOSITION OF FEED MIXTURES FOR TEST RUNS  [Modell,  1982]
                                                    Wt
                                                                Wt % Cl
Run  11
DDT
MEK
Run  12
1, 1, 1-trichloroethane
1,2-ethylene dichloride
1,1,2, 2-tetrachloroethy lene
o-chlorotoluene
1,2,4-trichlorobenzene
biphenyl
o-xylene
MEK
Run 13
hexachlorocyclohexane
DDT
4,4'-dichlorobiphenyl
hexachlorocyclopentadiene
MEK
Run 14
PCB 1242
PCB 1254
Transformer oil
MEK
Run 15
4,4-'dichlorobiphenyl
MEK
                                  CAH80
                                  C12H10
                                  C8H10
                                  C4H80
                                  C4HgO
                                  c!2Hxcl4-6
                                  c!2Hxcl5-8
  4.32
 95.68

100.0
   .01
   .01
   .01
   .01
   .01
   .01
   ,44
 88.48
                                                   100.0
                                                   100.0
  0.34
  2.41
 29.26
 67.99

100.0
                                                     3.02
                                                    96.98

                                                   100.0
                                                                 2.133
                                                                 2.133
                                                                 0.806
                                                                 0.739
                                                                 0.866
                                                                 0.282
                                                                 0.591
                                                                 3.284
0.69
1.00
1.57
0.65
96.09
0.497
0.493
0.495
0.505
—
                                                                 1.99
0.14
1.30
1.44


 .96


0.96
                                   4-84
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        TABLE 4.9.2.  SUMMARY OF  RESULTS:
                      I Model 1,  1982J
OXIDATION OF ORGANIC CHLORIDES
Run No.
Residence time (min)
Carbon analysis
Organic carbon in (ppm)
Organic carbon out (ppm)
Destruction efficiency (%)
Combustion efficiency (%)
Gas composition
02
C02
CH4
H2
CO
Chloride analysis
Organic chloride in (ppm)
Organic chloride out (ppm)
Organic chloride conversion (%)
GC/MS effluent analysis
Compound Ba (ppb Cl)
C
E
F
H
K
M
N
0
11
1.1

26,700.
2.0
99.993
100.

25.58
59.02
—
—
— —

876.
.023
99.997

—
—
— •
18
—
5
— .

' "
12
1.1

25,700.
1.0
99.996
100.

32.84
51.03
—
—
—

1266.
.037
99.997

— •
—
9
12
—
16
—
—
__
13 '
1.1

24,500.
6.4
99.975
100.

37.10
46.86
, —
~
—

748.
<.028
99.996

—
—
—
18
<4.
<5.
0.2
0.3
"— "-
M
1.1
<
38,500.
3.5
99 .991
100.

10.55
70.89
—
—
—

775.
.032
99.996

—
—
14
—
—
6
—
—
12
15
1.3

33,400
9.4
99.97
100.

19.00
70.20
. —
—
„ —

481.
.036
99.993

—
. —
. —
—
__
~
—
36
"""•
aCompounds searched  by GC/MS Analysis
     ei
-------
led Modar to use liquefied oxygen as the primary oxygen source.  Oxygen demand
and heat content of an organic waste are usually directly related.  Therefore,
the heating value of the waste and waste throughput can be used to make a
preliminary estimate of treatment costs.
     Table 4.9.3 presents waste treatment costs based on an aqueous waste with
a 10 percent by weight benzene-equivalent and a heat content of 1,800 Btu/lb.
This is the optimal heat content of a cold feed for this process to attain a
reactor exit temperature of 600 to 650°C (GCA, 1984).  Other factors on which
the costs in Table 4.9.3 are based are:

     (1)  the system is installed at the site of the waste generator;
     (2)  the units are owned and operated by the waste disposer; and
     (3)  the units are not equipped with power recovery turbines.

     If the waste has a fuel value of greater than 1,800 Btu/lb, the cost will
be higher per unit of waste processed (GCA, 1984).  In treating a waste with a
higher organic content, it is recommended that the waste is diluted to a
10 percent benzene-equivalent (Modell, 1984; GCA, 1984).  Therefore, the
increase in cost will be in proportion to the increase in organic content.
     If the waste has a heat content of between 5 and 10 percent
benzene-equivalent, fuel can be added to the waste to bring the heat content
up to 10 percent benzene-equivalent without appreciable cost increases (GCA,
1984: Modell, 1984).  If, however, the waste is dilute (2 to 3 percent benzene
equivalent) it is more economical to use a combination of fuel with
regenerative heat exchange (GCA, 1984: Modell, 1984).

4.9.4  Process Status

     Design of full scale units for supercritical fluid oxidations is underway
at Modar, Inc (Killiley, 1986).  Commercial units should be available in 1987
although their cost effectiveness for dioxin wastes has not been established.
Treatment of contaminated soils, without pretreatment to extract adsorbed
dioxin, would appear to be impractical.
                                     4-86
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      TABLE 4.9.3.   MODAR TREATMENT COSTS FOR ORGANIC
                    CONTAMINATED  AQUEOUS WASTES3
Waste capacity
gal/day
5,000
10,000
20,000
30,000
ton/day
20
40
80
120
Processing cost
$/galb $/tonb
$0.75 -
$0.50 -
$0.36 -
$0.32 -
$2.00
$0.90
$0.62
$0.58
$180
$120
$ 86
$ 77
- $480
- $216
- $149
- $139
aBased upon an aqueous waste with 1800 Btu/lb heating
 value and inorganic solids of between 1% and 10%.

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

Source:  Sieber, 1986.
                            4-87
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4.10  IN SITU VITRIFICATION
4.10.1  Process Description/Flow Diagram
     The basic principle of the In Situ Vitrification (ISV) process involves
placement of electrodes into a contaminated soil zone and then passing
electrical current between the electrodes.  This "joule heating" principle,
which utilizes the soil as the resistance element in an electric circuit,
creates temperatures in excess of 1,350°C and leads to the melting of the  soil
and subsequent formation of a stable/immobile molten glass or crystalline
substance.
     The basic ISV process was developed by Battelle Memorial Institute's,
Pacific Northwest Laboratories (PNL) under a funding program with the U.S.
Department of Energy's (DOE) Richland Operations Office.  This emerging
technology was developed as a potential method for the in place stabilization
of transuranic (TRU) contaminated materials (Fitzpatrick, et.al., 1984).
However, recently this concept has been envisioned as an applicable,  in situ
treatment technology for contaminated soils at hazardous waste sites.  The
overall process development and application to dioxin-contaminated soils is
described in the following narrative (Brouns, et.al., 1982; Fitzpatrick,
et.al., 1984).  Figure 4.10.1 provides a conceptual schematic diagram of a
proposed ISV system.
     The first step in the use of the ISV process requires that the boundaries
encompassing the area to be treated be clearly identified.  Once this
condition is satisfied, molybdenum or graphite electrodes are then inserted
into the contaminated soil area at the four corners of the boundary to form  a
square.  A high voltage, over 4,000 volts for a large scale vitrification
process, is then applied until a vitreous soil mass is produced.
     During the melting process, organic materials tend to pyrolyze,  rise to
the surface of the molten glass, and combust when brought into contact with
air.  Other components such as fission products,  transuranics,  heavy  metals,
and non-volatile organics become trapped in the molten soil product.   The
volatile organic combustion products are collected and treated to prevent the
transfer of pollutants from soil to air.   A hood  is placed over the area being
vitrified to perform three functions:
                                      4-88
-------
                             Support traitor
                     Off-ga» trailer	 —
            Area prepared flaked graphlto
            for vitrification/ and gloat frl
                                                                 Vitrified •oil/waste
                                       Contaminated
                                        aol/wa*te
                   \Etectrode

  Source: Adapted from Pacific Northweot Laboratory
Figure  4.10.1.
Schematic diagram of an  in situ  vitrification operation
[Hazardous Waste Consultant,  1985].
                  4-89
-------
     (1)  .to collect the gas products of the combustion reaction;
     (2)  to act as a chamber for combustion of the pyrolyzed volatile
          organics; and
     (3)  to support the electrodes placed in the soil.

     The off-gas treatment system consists of three stages.   First,  the
off-gas is cooled and scrubbed in a quencher and tandem nozzle scrubber to
remove larger particles.  The water in the gas is then removed by a  vane
separator followed by a condenser and a second vane separator.  Finally, the
gas is heated above its dewpoint to maintain an unsaturated  gas stream which
is then filtered by high efficiency particulate air (HEPA) filters.   Following
this stage the stream is discharged through a stack.  A schematic of this
off-gas treatment system is illustrated in Figure 4.10.2.

4.10.2  Technology Performance Evaluation

     Since the initiation of this program with the DOE, the  PNL has  conducted
several engineering—scale and pilot—scale tests with the ISV process on
radionuclide wastes.  Specifically, 21 engineering-scale (laboratory) tests
have been conducted which produced a vitrified mass of between 0.05  and 1.0
tons per test at a power level of 30 kW.  Pilot-scale (field) tests  have also
resulted in up to 10 tons of vitrified mass in each of the Seven tests.
     Additionally, performance studies have been conducted by PNL on four
different aspects of ISV (Buelt,  et al., 1984).  The effect  of variations in
soil types was studied to determine the scope of the potential market.
Examining the quality of the vitrified waste helped to qualify this  same
market, since determining the behavior of organic hazardous  wastes during ISV
processing could extend this market into areas such as the treatment of dioxin
contaminated soil.
     PNL have conducted experiments on nine different kinds  of radioactive
soils from all over the United States.  These tests proved there is  no
expected degradation (as measured by variations in properties and as
electrical and thermal conductivities, fusion,  temperature,  viscosity,  and
chemical composition) of the ISV systems capabilities due  to varying soil
types.   However,  ISV has only been conducted on Hanford nuclear waste soils so
conclusive data has not yet been generated.
                                      4-90
-------
                 PAHALLU QUENCHER
                 SCMUMER VANE
                 MPAMATOK AMD TANK
                                                                       STAC*
                                                     HEPA FILTERS   MUT BYPASS
CONTAINMENT MODULE
   Figure 4.10.2.   Schematic of  large-scale off-gas
                     treatment system  (JFitzpatrick,  1984) ,
                            4-91
-------
     Further analysis of the vitrified wastes indicates that the waste blocks
are expected to maintain their integrity for more than 10,000 years (Oma,  et
al., 1983).  This vitrified waste has also been shown to exhibit leach
resistance superior to marble and possess durability similar to granite
(Strachan, et al., 1980 and MCC, 1981).  It has been suggested, that for a
vitrified site with engineered barriers exposure could be reduced by a factor
of 105 for TRU wastes (Buelt, et al., 1984).  The reduction in exposure
obtained for toxic and heavy metal wastes is currently unknown.
     Experimental work on the treatment of organic and hazardous wastes (e.g.,
Go, Cd, carbon tetrachloride, and dichlorobenzene) has resulted in the
following three conclusions (Oma, et al., 1984).  First, it is apparent that
gaseous releases of combustible organics result in a higher release fraction
when implementing ISV.  Secondly, certain organics are pyrolyzed in the soil
and consequently achieve complete combustion in the off-gas hood maintained
over the  site being vitrified.  Finally, burying the wastes to a greater depth
reduces the potential for release of hazardous elements.
     While these conclusions represent distinct advantages of the system, the
process also has several limitations.  The most severe limitation restricts
the process to vitrification depths of approximately 13 meters
(40 feet)(Buelt, J., 1986).  The electrical nature of the system poses another
problem,  especially as  it relates to soil moisture.  Additionally, since the
process depends on the  conductivity of the medium being vitrified, metallic
conductors in  the soil  can  reduce efficiency.  The potential even exists for
metal  pipes or bars to  short out the electrodes or for  sealed containers
housing highly  combustible  organics  to explode.   Insulators  and void  volumes
(such  as  empty  plastic  containers)  can also  seriously affect performance.  It
is possible  to  get collapse in the molten  block  being  formed if the void
volume is greater than the  volume of molten soil  already  formed.  Some
pretreatraent of the  soil may be necessary  to minimize  this  problem.
 4.10.3  Costs of Treatment

      The cost considerations reported by PNL,  and discussed below for TRU
 wastes treated by the ISV process,  account for charges associated with site
 preparation, consumable supplies such as electrical power,  and operational
                                       4-92
-------
 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
                                        3
 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
                                    O
costs  would range from 70 to 130 £/m .  Treatment of high (greater than 25
percent) moisture content hazardous waste-PCB contaminated soil would cost
approximately  150 to 250 $/m  versus costs of 128 to 230 $/m3 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).
                                      4-93
-------
    400
    500
I
U
    200
    1OO
Portable
Generator
                               4          6           8

                                  Etectrical Rates (0/kWh)
   10
12
     Figure 4.10.3.  Cost of  insitu vitrification for Transuranic  wastes
                     as a function of electrical rates and  soil moisture
                     (Fitzpatrick,  1984).
                                      4-94
-------
4.10.4  Process Status

     As briefly indicated above in the "Cost" discussions, PNL 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 (DRE) 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.
                                     4-95
-------
                                  REFERENCES
Ackerman, D.G., L.L. Scinto, C.C. Shih, and B.J. Matthews.  TRW, Inc.  The
     Capability of Oceanic Incineration - A Critical Review and Rebuttal of
     the Kleppinger Report.  May 1983.

Ackerman, D.G. Sitex Consultants East, Inc. Draft Final Report:  The
     Capability of Oceanic Incineration - A Critical Review of the
     Kleppinger-Bond Report.  March 1986.

Bailey, William.  Rollins Environmental Services, Inc.  Telephone Conversation
     with Lisa Farrell, GCA Technology Division, Inc.  Re:  PCBs Incineration
     Costs.  May 13, 1986.

Earner, H.E., J.S. Chartier, H. Beisswenger, and H.W. Schmidt.  Lurgi
     Corporation.  Application of Circulating Fluid Bed Technology to the
     Combustion of Waste Materials.  Environmental Progress, 4(2):   125-130.
     May 1985.

Barton, Thomas G.  Mobile Plasma Pyrolysis.  Hazardous Waste,  1(2):
     237-247.  1984.

Bellobono,  I.R., E. Selli, and L. Veronese.  Destruction  of Dichloro- and
     Trichloro-phenoxyacetic acid esters containing
     2,3,7,8-Tetrachlorodibenzo-p-dioxin by Molten Salt Combustion Technique.
     Acqua-Aria.  January  1982.

Bond,  Desmond H. At-Sea Incineration  of Hazardous Wastes.  Environmental
     Science & Technology,  18(5):   148A-152A.   May 1984.

Bonner, T.A., et al.  Engineering Handbook for  Hazardous  Waste Incineration.
     Report prepared  for U.S. EPA,  Cincinnati,  Ohio.  SW-899.   June  1981.

Boyd,  J.,  H.D. Williams, and T.L. Stoddard.  Destruction  of Dioxin
     Contamination  by Advanced Electric Reactor.  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.

Boyd,  James. J.M.  Huber Corporation.  Telephone  Conversations with  Lisa
     Farrell, GCA Technology Division, Inc.  January 28,  1986; April 3", 1986;
     May  1, 1986.

Brouns,  R.A.,  and C.L.  Timmerman.   Pacific Northwest Laboratories, Richland,
     Washington.   In Situ  Thermoelectric  Stabilization  of Radioactive Wastes.
      In:   Proceedings  of  the Waste  Management  1982 Meeting in  Tucson,
     Arizona.  PNL-SA-9924.   1982.

Brouns,  R.A.,  J.L.  Buelt,  and W.F.  Bonner.  In Situ  Vitrification of Soil.    /
     U.S.  Patent 4,  376,  598.   1983.                                         /
                                      4-96
-------
Brown, William.  Chemical Waste Management, Inc.
     Lisa Farrell, GCA Technology Division, Inc.
                           Telephone Conversation with
                           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.

Games, 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.

Games, 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.

Games, 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.
     July 9, 1984.
New Units Give Boost to Sludge Incineration.
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.
                                     4-97
-------
Daily, Philip L.  Shirco Infrared Systems, Inc.  Performance Assessment of
     Portable Infrared Incinerator.  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.

Eaton, H.C., M.E. Tittlebaum, and F.K. Cartledge.  Louisiana State
     University.  Techniques for Microscopic Studies of Solidification
     Technologies.  In:  Proceedings of the llth 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.

Edwards, B.H., J.N. Paullin, K.C. Jordan.  Noyes Data Corporation, Park Ridge,
     New Jersey.  Emerging Technologies for the Control of Hazardous Wastes.
     1983.

Ellis, William D., William H. Vick, Donald E. Sanning, and Edward J. Opatkin.
     Evaluation of Stabilized Dioxin Contaminated Soils.  In:  Proceedings of
     the EPA-HWERL llth Annual Research Symposium, Cincinnati, Ohio.
     April 29-May 1, 1985.

Ellis, William.  JRB Associates.  Telephone Conversation with Lisa Farrell,
     GCA Technology Division, Inc.  May 15, 1986.

Environmental Research and Technology, Inc.  Final Report:  Onsite
     Incineration Testing of Shirco Infrared Systfems Portable Pilot Test Unit,
     Times Beach Dioxin Research Facility, Times Beach, Missouri.  Prepared
     for Shirco Infrared Systems, Inc.  Report No. 815-85^-2.
     November 14, 1985.

Fitzpatrick, V.F., et al.  In Situ Vitrification - A Potential Remedial Action
     Technique  for Hazardous Wastes.  In:  Proceedings of the 5th National
     Conference on Management of Uncontrolled Hazardous Waste Sites,
     Washington, D.C.  1984.

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

Freeman, Harry M.  Hazardous Waste Destruction Processes.  Environmental
     Progress.  Volume 2, Number 4.  November  1983.

Freeman, Harry M.  U.S. EPA, Hazardous Waste Engineering Research Laboratory,
     Thermal Destruction Branch.  Project  Summary:  Innovative Thermal
     Hazardous Waste Treatment Processes.  1985.

Freeman, Harry M., and Robert A. Olexsey.  A Review of Treatment Alternatives
      for Dioxin Wastes.  Journal of the Air Pollution Control
     Association (JAPCA), 36(1):  66-75.   January  1986.
                                     4-98
-------
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.
                                     4-99
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Hazardous Materials Intelligence Report.  First Commercial Dioxin Incineration
     Permit Granted to J.M. Huber.  January 24, 1986b.

Hazardous Materials Intelligence Report.  Opposition Raised to EPA's Ocean
     Incineration Proposal.  7(6):  2-3.  February 7, 1986c.

Hazardous Materials Intelligence Report.  EPA's Ocean Incineration Proposal
     Delayed by NOAA.  February 28, 1986d.

Hazardous Waste Consultant.  Volume 3, Issue 1, Pages 4-4 and 4-5.  McCoy &
     Associates Publication.  January/February 1985.

Hazel, Ralph.  U.S. EPA, Region VII.  Telephone Conversation with Lisa Wilk,
     GCA Technology Division, Inc.  August 4, 1986.

Haztech Notes.  Plasma Arc Technology Used to Atomize Liquid Organics.
     1(5):  33-34.  1986.

Hicks, James.  ENSCO, Inc.  Telephone Conversation with Lisa Farrell, GCA
     Technology Division, Inc.  February 5, 1986.

Hill, Michael.  Shirco Infrared Systems, Inc.  Dallas, Texas.  Telephone
     Conversation with Lisa Farrell, GCA Technology Division, Inc.
     January 14, 1986.

Hitchcock, D.A.  Solid Waste Disposal:  Incineration.  Chemical Engineering,
     86(11):   185-194.  May 21, 1979.

Horning, A.W., and H. Masters.  Rockwell International, Newbury Park,
     California.  Destruction of  PCB-Contaminated Soils With a
     High-Temperature Fluid-Wall  (HTFW) Reactor.  Prepared  for U.S. EPA,
     Office of Research and Development, Municipal Environmental Research
     Laboratory, Cincinnati, Ohio.  EPA-600/D-84-072.  1984.

IT  Corporation.  Interim Summary  Report on Evaluation of  Soils Washing and
     Incineration As Onsite Treatment Systems  for Dioxin-Contaminated
     Materials.  Prepared  for U.S. EPA, Hazardous Waste Engineering Research
     Laboratory, under EPA Contract No. 68-03-3069.   June 7, 1985a.

IT  Corporation.  Dioxin Trial Burn Data Package, EPA Mobile Incineration
     System at the James Denney Farm  Site, McDowell,  Missouri.  Prepared  for
     U.S.  EPA, Hazardous Waste Engineering Research  Laboratory, under EPA
     Contract  No. 68-03-3069.  June 21, 1985b.

Jensen,  Daniel.  GA Technologies, Inc. Telephone Conversation with Lisa
     Farrell,  GCA Technology Division,  Inc.  February 4,  1986.

Johanson,  J.G.,  S.J. Yosim, L.G.  Kellog,  and S. Sudar.  Elimination of
     Hazardous Waste by the Molten Salt Destruction  Process.  In:
      Incineration and Treatment of Hazardous Waste,  Proceedings fo  the Eighth
     Annual Research Symposium, EPA-600/9-83-003.  April  1983.
                                     4-100
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 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 Rosiers, 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.

                                     4-101
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Modar, Inc.  Brochure:  Process Description and Test Results.  1984.

Modell, Michael, Gary G. Gaudet, Glenn T. Hong, Morris Simson, and Klaus
     Biemann.  Modar, Inc.  Supercritical Water Testing Reveals New Process
     Holds Promise.  Solid Waste Management.  August 1982.

Modell, Michael, Gary G. Gaudet, Morris Simson, Glenn T. Hong, and Klaus
     Biemann.  Modar, Inc.  Destruction of Hazardous Waste Using Supercritical
     Water.  In:  Proceedings of the Eighth Annual Research Symposium on
     Incineration and Treatment of Hazardous Waste, sponsored by U.S. EPA-MERL
     and U.S. EPA-IERL.  Ft. Mitchell, Kentucky, March 8-10, 1982.
     EPA-600/9-83-003.  September 1983.

Modell, Michael, and Terry B. Thomason.  Modar, Inc.  Supercritical Water
     Destruction of Dilute Aqueous Wastes.  In:  Proceedings of the 2nd
     International Symposium on Operating European Centralized Hazardous
      (Chemical) Waste Management Facilities.   Odense, Denmark.  September 1984.

Oma, K.H., et al.  In Situ Vitrification of Transuranic Wastes:  Systems
     Evaluation and Applications Assessment.   Pacific Northwest Laboratory,
     Richland,  Washington.  PNL-4800.   1983.

Oma,  K.H., R.K. Farnsworth, and C.L. Timmerman.  Characterization  and
      Treatment  of  Gaseous Effluents  from In  Situ Vitrification.   In:
      Radioactive Waste  Management  and  the Nuclear  Fuel  Cycles, Volume 4.
      Hardwood Academic  Publishers.   1984.

Poppiti,  James. U.S. EPA.  Memorandum, Re:   RCRA  Dioxin  Delisting Petition
      for the Mobile  Incinerator System. May 23,  1985.

 Pyrolysis Systems, Inc.  Pyroplasma Waste Management Systems.  Product
      Literature.

 Pyrotech Systems,  Inc.   Mobile Waste Processor:  MWP-2000-ER.   1985.

 Rasmussen, George P.  Waste-Tech Services,  Inc.  Another  Option:   Onsite
      Fluidized Bed Incineration.   Hazardous Materials & Waste Management
      Magazine.   January-February 1986.

 Rickman, William S., Nadine D. Holder, and Derrell T. Young.  GA Technologies,
      Inc.  Circulating Bed Incineration of Hazardous Wastes.  Chemical
      Engineering Progress.  March 1985.

 Rollins Environmental Services, Inc.  Brochure on Rollins Environmtental
      Services and Capabilities.  1985.

 Ross, Robert W., II, Frank C. Whitmore, and Richard A. Carnes.  Evaluation of
      the U.S. EPA CRF Incinerator as Determined by Hexachlorobenzene
      Incineration.  Hazardous Waste, 1(4):  581-597.  1984.
                                      4-102
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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.
                                     4-103
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Swanson, M.L., J. Dollimore, and H.H. Schobert.  University of North Dakota,
     Energy Research Center.  Supercritical Solvent Extraction.  Prepared for
     U.S. Department of Energy.  DOE/FE/60181-96.  June 1984.

Technical Resources, Inc.  Analysis of Technical Information to Support RCRA
     Rules for Dioxin-Containing Waste Streams.  Submitted to Paul E. des
     Rosiers, U.S. EPA Office of Research and Development.  July 31, 1985.

Thomason, Terry B., and Michael Model1.  Modar, Inc.  Supercritical Water
     Destruction of Aqueous Wastes.  Hazardous Waste, 1(4):  453-467.  1984.

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.

U.S. EPA.  Office of Research and Development.  At-Sea Incineration of
     Herbicide Orange Onboard the M/T Vulcanus.  Prepared by TRW Inc., Redondo
     Beach, California.  EPA-600/2-78-086.  April 1978.

U.S. EPA.  Process Design Manual for Sludge Treatment and Disposal,
     EPA-625/1-97-011.  September 1979.

U.S. EPA.  Fact Sheet on the U.S. EPA Mobile Incineration System (MIS).
     April 1982.

U.S. EPA.  Office of Research and Development.  At-Sea Incineration of
     PCB-Containing Wastes Onboard the M/T Vulcanus.  Prepared by TRW Inc.,
     Redondo Beach, California.  EPA-600/7-83-024.  April 1983.

U.S. EPA, Region VII.  Status Reports on the Mobile Incinerator.
     June-December 1985.

Vick, W.H., S. Denzer, W. Ellis, J. Lambach, 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.

Vrable, D.L., and D.R. Engler.  GA Technologies, Inc.  Transportable
     Circulating Bed Combustor for the Incineration of Hazardous Waste.
     Storage & Disposal.  1985a.

Vrable, D.L., D.R. Engler, and W.S. Rickman.  GA Technologies, Inc.
     Application of Transportable Circulating Bed Combustor for Incineration
     of Hazardous Waste.  Presented HAZMAT  1985, West Long Beach, California.
     December 1985b.
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                                  SECTION 5.0
               NONTHERMAL TECHNOLOGIES FOR LISTED DIOXIN WASTES

     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 DRE, 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
judged.
                                       5-1
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5.1  CHEMICAL DECHLORINATION

5.1.1  Process Description

     Briefly stated, chemical dechlorination processes use specially
synthesized chemical reagents to destroy hazardous chlorinated molecules, or
detoxify them to form other compounds which can be considered .less harmful and
environmentally safer than the original hazardous chemical (Dillon, 1982).
The basic chemical principle of this dechlorination process involves the
gradual, but progressive, substitution of the contaminants' chlorine atoms Dy
other atoms (predominantly hydrogen).  This substitution process eventually
"deactivates" the previously hazardous chlorinated-contaminant.  (It should be
noted that dechlorination of halogenated aromatics is not a new principle but
rather a common industrial process used for production of phenolics and
certain pesticides.)
     Many researchers have, over the past years, tested various chemical
reagents for use in destroying and/or detoxifying hazardous,  chlorinated
compounds.  This research has evolved into several processes shown to destroy
polychlorinated biphenyls (PCBs) and dioxin contaminants.  The following
discussion provides a review of each of these processes,  starting with those
dechlorination processes which have been evaluated/designed for PCBs and
concluding with more recent studies on dioxin dechlorination from a soil
matrix.
     One of the first major PCB-contaminated oil dechlorination processes was
developed by the Goodyear Tire and Rubber Company (desRosiers,  1983; Weitzman,
1982).  This process was intended to remove PCBs from heat transfer fluids
using sodium naphthalene as the reagent.  The sodium naphthalene reagent is
prepared by complexing naphthalene and metallic sodium with the solvent
tetrahydrofuran (THF).  The reagent mix is reacted with the PCB-contaminated
fluid at ambient temperature and at a reagent to chlorine ratio of 50-11)0:1
(under a nitrogen blanket).  Under these conditions,  the  PCB  molecule is
stripped of chlorine to form sodium chloride and polyphenyls  which, after
quenching,  are vacuum distilled in order to recover the THF and naphthalene.
                                      5-2
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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;
Weitzman, 1986) which used a sodium-based reagent, prepared from proprietary
but nonpriority pollutant constituents (Miille, 1981).  The system operates by
mixing filtered, PCB 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 Rosiers, 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).

                                      5-3
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     In 1978, the Franklin Research Institute began studies to develop a
chemical reagent that would lead to the cleavage of the carbon halogen bonds
inherent with PCBs (Rogers, C., 1983; Klee, A., et al., 1984).  Their research
identified a chemical reagent which could be synthesized from sodium,
polyethylene glycols, and oxygen.  This dehalogenation reagent, termed NaPEG,
was formulated by mixing molten sodium (60 grams) with 1 liter of polyethylene
glycol (PEG) having an average molecular weight of 400.  Laboratory studies in
1979 effectively utilized this NaPEG reagent on dielectric fluids containing
PCBs, demonstrating the applicability of NaPEG as a dehalogenation reagent.
     In 1982, this reagent (generically referred to now as "APEG-alkali
polyethylene glycolates") was applied to dioxin-contaminated soils.  This
research, conducted by the U.S. EPA, Industrial Environmental Research
Laboratory in conjunction with Wright State University, was undertaken to
establish the effectiveness of these newly-developed APEG reagents.  Results
clearly indicated that APEG reagents could, under certain laboratory
conditions, significantly reduce the levels of TCDD (dioxin) in contaminated
soils.  The success of these studies has led the U.S. EPA, in cooperation with
Galson Research Corporation, to further evaluate the APEG chemical
dechlorination process for the destruction/detoxification of dioxins in soil
(Peterson, et al., 1985 and 1986).  These studies are now in progress.
     Scientists in Italy (specifically, at the Institute of Organic
Chemistry/University of Torino and the Sea Marconi Technologies Group) have
also recently carried out laboratory research using APEGs for the chemical
degradation of 2,3,7,8-TCDD.  Their process is similar to the Galson
Research/USEPA process, but PEGs of much higher molecular weight (1,500 to
6,000 versus 400) are used.  The PEGs are then combined with a weak base such
as potassium carbonate and an inorganic peroxide such as sodium peroxide to
form a clear solution which promotes organic dehalogenation (Tundo, P.,
et al., 1985).  This process, currently referred to as the Sea Marconi's
CDP-Process, was first conceived for the decontamination of mineral oils
contaminated by PCBs, but has also been shown to destroy 2,3,7,8-TCDD in
solvent, in  soil or on surfaces as tested at Seveso, Italy (Tumiatti, W., et
al., 1986).
                                       5-4
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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 (Weitzman, 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 (1%)—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.
                                        5-5
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     The results of several of the early 1980 laboratory research and later
laboratory/fieId testing of the APEG chemical dechlorination process are
promising.  Specifically, in the 1982 research study conducted by the U.S.
EPA/Wright State University, actual dioxin-contaminated soils were effectively
dechlorinated under certain laboratory conditions (Klee, A., 1984).  As shown
in Tables 5.1.1 and 5.1.2, dioxin (TCDD) levels in soils were reduced by 8  to
51 percent depending on the specific APEG reagent and number of days after
application that the dioxin levels were measured.  A multiple application
experiment of the K-400 (potassium-based reagent and polyethylene glycol of
average molecular weight of 400) reagent showed that an increase of from 16 to
56 percent and 25 to 68 percent could be realized by repeat application versus
a single application to the contaminated soil.
     Later laboratory research, in 1985, by the U.S. EPA/Galson Research
Corporation (using 1,2,3,4-tetrachlorodibenzo-p-dioxin) demonstrated that
chlorinated dioxin levels in soil may be further chemically reduced by
applying APEG-type reagents (Peterson, R.L.,  et al., 1985).  In situ and
slurry testing, using potassium hydroxide/polyethylene glycol 400/dimethyl
sulfoxide (KOH/PEG/DMSO) and potassium hydroxide/2-(2-methoxy ethoxy
ethanol)/dimethyl sulfoxide (KOH/MEE/DMSO) reagents, on contaminated soils
containing an initial concentration of 2000 ppb was quite favorable, as
summarized in Tables 5.1.3 and 5.1.4.  Several key features uncovered during
the experiments are as follows:

     •    Temperature increases from 20 to 70°C during the in situ process
          indicated a dramatic improvement in reaction efficiency, i.e., from
          50 to 90 percent increase.
     •    No difference between reagent formulations was noted at 70°C during
          in situ testing.
     •    Dilution of the reagent with water (to provide more contact,
          followed by evaporation of the water to encourage reaction) was not
          effective in reducing the amount of reagent required during the
          in situ processing.
     •    A removal efficiency of  99.95% TCDD (from 2000 ppb to  1 ppb) was
          realized after 12 hours at 70°C during the slurry processing.
                                      5-6
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        TABLE 5.1.1.   SUMMARY OF DATA SHOWING PERCENT REMOVAL OF TCDD
                      FROM CONTAMINATED SOILS USING APEG DECHLORINATION  PROCESS
                      (Klee,  A.  et.al., 1984).
Days after
application
7 days
28 days
ft
Timberline
K-400
45%
35%
K-120
46%
38%
Denny
K-400
c
nm
12%
K-120
51%
5%
alnitial TCDD content equalled 277  28 ppb.

 Initial TCDD content equalled 330  33 ppb.
cnm = not measured
         TABLE 5.1.2.
SUMMARY OF DATA SHOWING PERCENT REMOVAL OF TCDD
FROM CONTAMINATED SOIL AT DENNY FARM
(Klee, A., et. al., 1984)
Days after
application
1 day
7 days
14 days
21 days
28 days
Denny Farm Soil
K-400b
8%
19%
16%
25%
22%
KM-350
15%
27%
36%
42%
43%
    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.

    K—400 reagent used in these experiments (vs.  those shown in previous
    Table 5.1.1) was prepared from KOH pellets instead of a 66% aqueous  KOH
    solution.
                                       5-7
-------
TABLE 5.1.3.
SUMMARY OF RESULTS OF IN-SITU PROCESSING (PETERSON, R. L.,
et. al., 1985) - ALL SOILS.INITIALLY AT 2000 ppb.



Reagent
1:1:1 KOH/PEG/DMSO
1:1:1 KOH/PEG/DMSO
1:1:1 KOH/PEG/DMSO
2:2:2:1 KOH/MEE/DMSO/WATER
2:2:2:1 KOH/MEE/DMSO/WATER
2:2:2:1 KOH/MEE/DMSO/WATER
2:2:2:1 KOH/MEE/DMSO/WATER
2:2:2:6 KOH/MEE/DMSO/WATER
2:2:2:30 KOH/MEE/DMSO/WATER
2:2:2:30 KOH/MEE/DMSO/WATER
BLANKS - ALL


Wt%
in soil
20
20
20
20
20
20
20
20
50
20



Temp,
(°c)
20
70
70
70
70
70
70
70
70
70



Time,
(days)
7
7
1
1
2
4
7
7
7
7

Final TCDD
(avg)
Concent rat ion
(ppb)
'980
<1
5.3
3.3
2.8
2.1
1.2
2.1
18
50
<1
 TABLE 5.1.4.  RESULTS OF SLURRY PROCESSING (PETERSON, R. L., et. al.,  1985).

Reagent
1:1:1 KOH/PEG/DMSO
1:1:1 KOH/PEG/DMSO
1:1:1 KOH/MEE/DMSO
1:1:1 KOH/MEE/DMSO
1:1:1 KOH/MEE/DMSO
1:1:1 KOH/MEE/DMSO

Temp, °C
180-260
180
150
70
70
25
Reaction
Time, hrs
4
2
2
2
0.5
2
Final TCDD
Concentration, ppb
<1
<1
<1
<1
15
36
Blanks - all <1 ppb TCDD
Spikes - % recovery in soil - 0.1-5.9
                                      5-8
-------
     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 PEGs 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 5.1.1.  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.
                                      5-9
-------
                                                      180
                                                           TIME (MIN)
T s 50°C; 2.0 ml of n-decane containing 5 yg of dioxin,
0.9 g PEG 1500, 0.15 g K2C03' 0.10 g of an ether compound
and 0.10 g Na^

T s 85°C; 2.0 ml of n-decane containing 5 yg of dioxin,
2.06 g of PEG 6000, 0.53 g K2C03, and 0.37 g Na202
    Figure 5.1.1.
Degradation of 2,3,7,8-TCDD using the
CDP-Process (Tundo,, P., et al., 1985).
                             5-10
-------
TABLE 5.1.5.
           DEGRADATION OF 2,3,7,8-TCDD UNDER DIFFERENT CONDITIONS
           USING THE CDP-PROCESS (Tundo, P.  et  al, 1985)
REAGENTS (g)
IPEG 6000
Nfo3


PEG 6000
K|C°3

BuO(C>H2CH20)2I

(2.1)
(0.5)
(0.4)

(1.3)
(0.5)
(0.2)
I (0.2)
TEMPERATURE (°C) TIME (h)
85 0.5
1.0
1.5
2.0
85 0.5



DECOMPOSITION (%)
99.4
99.6
99.75
>99.9
>99.9



fPEG 6000

 K2C°3
 Ni2°2
(1.8)
(0.4)
(0.2)
                                 20
 72
192
30
50
      without n-decane: after homogenization at 80°C the reaction was
      soliiifLed by  cooling and kept at 20°C;
                                   5-11
-------
     The data indicate that the GDP process is effective  in decomposing TCDD
under laboratory scale conditions.   However,  researchers  have  questioned the
effectiveness of high molecular weight PEGs under field conditions.   Their
skepticism  concerns the ability of the high molecular  weight  PEG to  penetrate
and react with TCDD in soil raicropores (Technical Resources, Inc.  1985).
These concerns will have to be addressed by further research.

5.1.3  Cost of Treatment

     At this time, costs are very well established for  the  decontamination of
PCB contaminated oils.  These costs are dependent on several variables:

     •    concentration of pollutant;
     •    quantity and characteristics of the material  to be treated;
     •    reagent costs; and
     •    the resale value of the treated material.
     The cost of treating PCB-contaminated oil using the SunOhio PCBX  process
is reportedly about $3/gallon of contaminated oil in bulk.  However, the cost
for onsite treatment of transformers may be considerably more  depending on the
site specific situation (Marilee Fisher, SunOhio).
     Based upon the APEG laboratory (and select field)  research that has been
conducted over the past several years,  a preliminary economic  evaluation of
this dechlorination process has been attempted (Peterson, R. L., et al.,
1985).  Specifically, Galson Research Corporation, in conjunction with the
U.S. EPA-HWERL, has roughly estimated the costs for APEG dechlorination using
two hypothetical field scenarios.  These costs, as shown in Table 5.1.6,
indicate that for the in situ process (operating on a 1 acre-3 feet deep
contaminated area) vs. the slurry process (with excavation  and 3 reactor
systems operating) there is approximately a $205/ton difference.  This
difference comes from the fact that in the slurry APEG  process,  reagent
recovery is a component which accounts for recovery of  approximately
65 percent of the total cost of the in situ process. Another  source has
restated these above costs on the basis of $/acre/cm indicating that the
slurry process costs are approximately $l,000/acre/l cm penetration (Technical
Resources Inc., 1985).
                                         5-12
-------
  TABLE 5.1.6.  PRELIMINARY ECONOMIC ANALYSIS OF
                 IN SITU AND SLURRY PROCESSES
                 (Peterson, R.L.,  et al.,  1985)
Cost item
  Cost,  $/ton soil

In situ        Slurry
Capital recovery

Setup and operation

Reagent

Total costs
  31

  65

 200

 296
17

54

20

91
                       5-13
-------
5.1.4  Process Status

     As stated previously, the chemical dechlorination processes developed by
Acurex (Chemical Waste Management), SunOhio and Goodyear are exclusively for
the treatment of liquid PCB-contaminated oils.    In fact, it was noted that
the sodium-based reagent process developed by Acurex Corporation should never
be used in the field on soils due to its explosive nature (Weitzman, 1986).
     On the other hand, research using variations of APEG reagents has been
and will continue.  Specifically, Galson Research Corporation is continuing
laboratory and field testing of the treatment of dioxin contaminated soils
(Peterson, R. L., et al., 1986).  This research testing was conducted within
55-gal. mixing reactors located at Pine Bluff, Arkansas (Peterson, R.L.,
1986a).  In these reactors, the slurry process was used on soils initially
containing 100-150 ppb of  dioxin and allowed to react for approximately 3
hours at 100-150°C.  Results from this research showed a removal efficiency
of 99 percent.
     It is currently envisioned that this research will be continued using the
Electric Power Research Institute's 100-gal reactor placed on a Galson trailer
(Peterson, R.L., 1986a).  These tests are to be carried out in parallel with
an incinerator receiving the same feed stock of contaminated soil.
     Due to inability of the in situ process to reduce dioxin levels in soil
to below 1 ppb, it is expected that this variation of the technology will be
applied instead to PCB contaminated soils where residual levels of contaminant
need not be so low.

5.2  UV PHOTOLYSIS

5.2.1  Process Description
     Ultraviolet (UV) radiation is electromagnetic radiation having a
wavelength shorter than visible light,  but longer than x-ray radiation.   The
energy content of light increases as the wavelength decreases.   For wave
lengths in the UV region the energy is  sufficient to break chemical bonds and
bring about rearrangement or dislocation of molecular structures.   The energy
                                     5-14
-------
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 nm.   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 Rosiers,
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,
1978).
     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.
                                     5-15
-------
         TABLE 5.2.1.  DISSOCIATION ENERGIES FOR SOME CHEMICAL BONDS
     Bond
Dissociation
   energy
(kcal/gmol)
 Wavelength
to break bond
    (nm)
c-c
c=c
c=c
C-C1
C-F
C-H
C-N
C=N
CSN
C-0
C30 (aldehydes)
CS0 (ketones)
C-S
CSS
Hydrogen
H-H
Nitrogen
N-N
N«N
N=N
N-H (NH)
N-H (NH3)
N-0
NSO
Oxygen
0-0 (02)
-0-0-
0-H (water)
Sulfur
S-H
S-N
s-o
82.6
145.8
199.6
81.0
116.0
98.7
72.8
147.0
212.6
85.0
176.0
179.0
65.0
166.0

104.2

52.0
60.0
226.0
85.0
102.0
48.0
162.0

119.1
47.0
117.5

83.
115.
119.
346.1
196.1
143.2
353.0
246.5
289.7
392.7
194.5
134.5
334.5
162.4
159.7
439.9 ,
172.2

274.4

540.8
476.5
126.6
336.4
.280.3
595.6
176.5

240.1
608.3
243.3

344.5
248.6
240.3
Source:  Legan, R.W.  1982.
                                     5-16
-------
     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 nm 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, E.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  by
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
processes.
                                         5-17
-------
5.2.2  Technology Performance Evaluation
Syntex-IT Enviroscience—
     A commercial-scale UV degradation process was developed cooperatively by
Syntex Agribusiness and IT Enviroscience, and used by Syntex on 4,300 gallons
of still bottoms composed of roughly equal concentrations (50-55%) of
trichlorophenols and ethylene glycol derivatives (45-50%) and containing
approximately 340 ppm 2,3,7,8-TCDD.  The first step in this process involved
neutralization and extraction of the 2,3,7,8-TCDD from the still bottoms using
sulfuric acid-n-hexane-caustic soda.  Multiple (up to eight) extractions were
used to remove as much 2,3,7,8-TCDD as possible.  The hexane 2,3,7,8-TCDD
mixture was then placed in a UV batch reactor.  Isopropyl alcohol was added as
a. hydrogen donor.  Each batch was then exposed to UV irradiation for about
27 hours under conditions of turbulent mixing to insure exposure of the
2,3,7,8-TCDD to the UV radiation.  Destruction efficiencies of greater than
98.7 percent of the original 2,3,7,8-TCDD were achieved (des Rosiers, P.E.,
1983; Sawyer, C.J., 1982; Exner, J.H., 1982).
     As shown in Figure 5.2.1, the photodecomposition rate of TCDD is
pseudo-first-order over a concentration range of five orders of magnitude.  In
addition, the rate of decomposition was  found to be temperature independent,
and the reaction products were less toxic than dioxin (Exner, J.H., 1982).
The only problem with the extraction/UV  photolysis process was that four
process waste streams were generated and were still contaminated with
2,3,7,8-TCDD as well as  less toxic, but  still hazardous materials.
     These process residuals are listed  in Table 5.2.2.  They are  a result
both of the inefficiency  of  the extraction process and the need  to remove all
dioxin from process equipment.  Even though  a majority of the dioxin was
extracted from the still  bottoms,  500  gallons still remained containing 35 ppm
of  dioxin.  In addition,  5000  gallons  of waste were generated by  rinsing
equipment that was used  for  extraction and photolysis.  Even though this waste
stream only contained 20  ppb of dioxin,  1 ppb is the  level which must be
attained  to allow non-hazardous disposal.  Consequently, each  of these waste
streams was placed in a  RCRA interim status  storage facility to  await final
disposal  or destruction.
                                       5-18
-------
         0.001
                   60
120     180     240
    TIME—MIN
                                                300
Figure 5.2.1.  Rate of  dioxin disappearance via UV irradiation
               of hexane  extract of dioxin-contaminated still
               bottoms  (Exner,  J.H.,  1982).
                              5-19
-------
TABLE 5.2.2.  ESTIMATED VOLUMES AND CONCENTRATIONS OF 2,3,7,8-TCDD
              PRODUCED BY THE SYNTEX-IT PHOTOLYIC PROCESS

Treated waste
Aqueous (salt) waste
Hexane still bottoms
Equipment solvent rinses
Vo lume
(gallon)
4,000
20,000
500
5,000
2,3,7,8-TCDD
(ppb)
200
2
35,000
20
  Source:  des Rosiers, P.E.  1983.
                               5-20
-------
 Ultraviolet (UV) Ozonolysis—
      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 1 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
 1 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 unfavorable
economics.  No research efforts have directly involved 2,3,7,8-TCDD
(Worne, 1984).
                                      5-21
-------
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                                                                        _ o
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                                                                                   o
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                                                                                    o  a  o
                                                                                        O  N
                                                                                    r-t -H  O
                                                                                    (4 4->
                                                                                    B  O
s
                                                                                     oo
                           %  'QCOL
                                            5-22
-------
            UV lamps
s~
O
O
O
o
o^





— N
(
i
O
o
0
b-
b
o
o
0 0
•s*
o
0
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0
s~
0
o
o
o
0 0
"Si
o
o
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0
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Flow distributor IseSSTi-




'*Q
<-


	 Waste water in 1
1
Treated


Spent 03
Gas out
1
J.
r



water out
Solid state
controlled
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).
                        5-23
-------
Thermal Desorption/UV Photolysis—
     Based partially upon IT Corporation's past experience in the use of UV
photolysis for the chemical degradation of 2,3,7,8-TCDD-contaminated materials
(as discussed above), recent laboratory and onsite pilot scale experiments
have been undertaken to confirm or deny the applicability of an extension  of
the UV photolysis process (Technical Resources Inc., 1985; Helsel, R., 1986).
Specifically, a system comprised of a thermal desorber, followed by a solvent
based absorption/scrubbing system and a UV photolytic unit (as shown in
Figure 5.2.4), was tested on contaminated soil containing Herbicide Orange.
In the laboratory tests, key process design and operating parameters were
established using a GIZ aliphatic hydrocarbon  soltrol 170 (a product of
Phillips  Petroleum) for absorption/scrubbing.  These tests indicated that a
TCDD removal efficiency of greater than 99 percent was achieved across both
scrubber  stages.
     Following these  tests,  a  pilot-scale  field demonstration system was
tested on soils  during May-June  1985 at the Naval  Construction Battalion
Center (NCBC)  in Gulfport, MS  (Helsel, R.,  1986).   During these  tests,  a
 series of five desorption and  three photolysis runs were  made.   The  untreated
 soil consisted of sand,  shells,  cement stabilized soil,  and traces  of asphalt;
 a composite was  prepared,  which was considered representative of the various
 portions of the contaminated site.  The  composite soil was air dried;  crushed
 to less than 1/4 inch (to enable passage through the  desorber feed mechanism);
 and thoroughly blended with TCDD.  Analysis of five separate drums indicated
 approximately 250 ppb 2,3,7,8-TCDD with good uniformity.  The total quantity
 of soil processed during each run, which lasted from 6 to 12 hours, ranged
 from 200 to 500 pounds.  Samples of treated soil and scrubber solvent before
 and during photolysis were taken and analyzed for  2,3,7,8-TCDD within 3 days
 to provide information for adjusting test conditions, as necessary, for
 succeeding runs.
       Results  of the  pilot-scale field tests indicate  that the goal  of  less
 than  1 ppb residual  2,3,7,8-TCDD in the soil  was achieved for all desorption
 runs, with  desorber  operating temperatures ranging from  460°  to  500°C  and
  feedrates  ranging  from 30 to  100 pounds/hour. The photolysis system
  demonstrated  that  99 percent  reduction of the 2,3,7,8-TCDD  to less  than  1 ppb
 could be achieved  in 6 hours, with a corresponding 85 to 95  percent reduction
 of 2,4,5-T and  2,4-D, respectively.
                                       5-24
-------
    Purge Gas Makeup
         Purge Gas
Contaminated
   Soil
   Heat
Thermal


Desorber
             Treated Soil
                                                    t
                                                Vent Gas


                                                Treatment
                                Purge Gas Recycle
                           organic/water
                              vapors
    Purge Gas,


    Cooling, and


Scrubbing System
                                   e
                                   at
                                   a
                                   v
                                                 •o
                                                  0)
                             Solvent Makeup
                                                          water condensate
                                                                i
                                              Water

                                              Treatment
                                                         aqueous discharge
                                                UV System
                                                   I
                                              Solvent purge




   Figure 5.2.4.   Thermal desorption, solvent absorption/scrubbing,

                  UV photolysis process schematic (des Rosiers,

                  P.  E.,  1985).
                                 5-25
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5.2.3  Cost of Treatment

     Several estimates of the cost to treat the 4300 gallons  of 2,3,7,8-TCDD
contaminated still bottoms using the Syntex-IT process  have been presented in
the literature.  These estimates have ranged from $500,000 (Waste Age,  1980)
to over one million dollars (Chemical Engineering,  1980).
     The UV ozonation process has been proven effective for aqueous solutions
of PCBs, and is reported to be competitive with activated  charcoal for
cleaning up contaminated wastewater (Edwards, B.H., 1983;
Swarzgn, E.M., 1982).  Specific capital cost estimates  for treating PCBs,
suggest that approximately $300,000 is required for a 150,000 gpd wastewater
treatment plant, with reduction of PCBs from 50 ppb to  1 ppb  (Arisman,
R.K., 1980).  Table 5.2.3 identifies design specifications and cost data for
the ULTROX treatment process.  However, as with the direct UV process,  it is
proven only for liquids and no work on 2,3,7,8-TCDD has been reported.
     Finally, precise costs associated with the thermal desorption/UV
photolysis system have not yet been developed.  It is estimated, however, that
the cost would range from $250 to $l,250/ton of soil treated (Technical
Resources, Inc. 1985).

5.2.4   Process Status
                         I'
     Presently, little development data and/or progress have been reported on
those processes designed primarily for PCBs.  However,  it has been indicated
that further  field  and demonstration  testing  of thermal desorption/UV
photolysis on Johnston Island in the  Pacific  was reportedly scheduled for
early  1986  (Helsel,  R.,  1986).   During these  tests,  it is anticipated that a
series  of seven desorption tests on contaminated coral-derived soil will
occur.   Following these  tests,  it is  expected that an engineering/economic
analysis of the system will  be performed.
                                     3-26
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TABLE 5.2.3.
DESIGN  SPECIFICATIONS, CAPITAL, AND O&M COSTS  FOR
40,000  AND  150,000 GPD ULTROX TREATMENT PLANTS
(50 ppm PCS feed-1 ppm PCB effluent)
               Reactor

        Dimension, Meters (LxWxH)
        Wet Volume, Liters
        UV Lamps; Number 65 W
            Total Power, kw'

             Ozone Generator

        Dimensions, Meters (LxWxD)
        kg Ozone/day
        Total Energy required
            (kwh/day)
                DESIGS SPECIFICATIOSS

                      40,000 GPD
                     (151,400 LPD)
                   Automated System

                   2.5 x 4.9 x 1.5
                       14,951
                        378
                         25
                             150,000 GPD
                             (567,750 LPD)
                           Automated System

                           4.3 x 8.6 x 1.5
                                56,018
                                 1179
                                  80
        Reactor
        Generator
       O £ H Costs/Day
     1.7 x 1.8 x 1.2
          7.7
          768

BUDGETARY EQUIPMENT PRICES

       40,000 GPD

       $94,500
        30,000
TOTAL $124,500
                                          2.5
                                             x 1.8 x 3.1
                                               28.6
                                               2544
                                                        TOTAL
                                             150,000 GPD

                                             $225,000
                                               75,000
                                             $300,000
Ozone Generator Power
UV Lamp Power
Maintenance
(Lamp Replacement)
Equipment Amortization
(10 Yrs @ 10%)
Monitoring Labor
TOTAL/DAY
Cost per 3785 Liters
(with monitoring labor)
(without monitoring labor)
$4.25
15.00
27.00
41.90
85.71
$173.86
$4.35
$15.60
48.00
84.20
97.90
85.71
$331 .41
$2.21
$1.64
  Source:   Arisman,  R.1L.  and Musick,  R.C.,  1980.
                                    5-27
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5.3  SOLVENT EXTRACTION
5.3.1  Process Description
     Solvent extraction, as discussed here,  involves contacting contaminated
soil with solvents which preferentially desorb the contaminant(s) molecules
from the soil matrix.  As such, solvent extraction is not a complete treatment
technology but a pretreatment step in an ultimate treatment process train.
     There are several requirements for the successful application of solvent
extraction to dioxin contaminated materials (soils).  First,  a favorable
equilibrium is needed to provide a considerable transfer of the dioxin
molecules from the solid phase to the liquid phase .  Second,  it is important
that the rates at which dioxin molecules transfer into the solvent be fast
enough so that the overall process occurs in a reasonable length of time.
Finally, to achieve high removal efficiencies, the amount of pollutant removed
must be proportional to the amount on the soil resulting in a geometric
reduction in the concentration of dioxin molecules (Weitzman,  1984).
     These requirements suggest that a desirable solvent would have the
following properties (Weitzman, 1984; Firestone, 1984):
     •    the ability to reduce the concentration of the original dioxin
          molecules in  the soil to an acceptable level;
     •    nonflammability for safety in the field;
     •    a low latent  heat of vaporization and a low boiling point for ease
          of recovery;
     •    a low toxicity;
     •    a -low cost;
     •  .  commercial availability; and
     •    compatibility with other treatment schemes, such as photolysis,
          incineration, or biodegradation following extraction.

     Usually more than  one wash will be needed, leading to the use of multiple
batch processes or  continuous  countercurrent processes.  Soil preprocessing,
contacting devices, and solvent recycling are  likely features of any solvent
extraction unit.  Preprocessing will probably  involve the particle size

                                     5-28
-------
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 is 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.
                                     5-29
-------
                                                             
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     Specifically, IT Enviroscience performed tests 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 60% to over 90% of the 2,3,7,8-TCDD could be removed by the Soils Washing
System, inmost cases (soils initially containing over 100 ppb of dioxin)  the
washed soil would still contain residual dioxin in excess of the 1 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 (33% less than 5 microns, 26% 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
                                     5-31
-------
chromotography revealed that approximately 85 percent of the applied TCDD was
recovered.  In 1978, Ward and Matsumura extracted 2,3,7,8-TCDD from lake
sediments with concentrations of 0.71, 1.0 or 1.83 ppm incubated from 1 hour
to 589 days.  A sequential scheme of acetone, chloroform:methanol (4:1),
hexane:acetone (5:1), and chloroform was used with recoveries in the range of
90 to 98 percent (Ward, 1978).  Both the Kearney, and Ward and Matsumura
experiments showed a decrease in extraction efficiency with increased
incubation periods, illustrating the increased difficulty of desorbing
2,3,7,8-TCDD with time (Philipp, 1981).  Finally, in 1980, Tiernan et al.
found it necessary to use the Soxhlet extraction procedure to remove
2,3,7,8-TCDD from finely ground soil.  This is a lengthly procedure using pure
methylene chloride for up to 3 days with recoveries of around 100 percent
(Vanness, 1980).
     Though 2,3,7,8-TCDD has a very low solubility in water (7 to 20 ppt)
(Marple, 1986;  Adams and Elaine, 1986), micellar solubilization in a water
medium has been attempted.  Aqueous solutions of cationic, anionic, and
nbnionic solvents were tested in 1978 by Botre et al. on soil from Seveso,
Italy.  The cationic solvent, 1-hexadecylpyridinium chloride (CPC) proved to
be the best solubilizing agent of those tested, with 75 percent of the
2,3,7,8-TCDD on the soil being solubilized.  The other solubilizing agents
tested were sodium dodecyl sulfate (SDS), methanol, and polyoxyethylene
sorbitan monooleate (Tween 80).  Table 5.3.1 summarizes the results of these
experiments.

5.3.3  Cost of Treatment                                         .

     At the present time, due to the uncertainties involved in the use of this
pretreatment technology, no definitive cost data have been made available.
However,  it is reportedly an expensive means of pretreating
dioxin-contaminated soils because of the high costs associated with the
solvents  themselves and the high expected consumption rates needed for
adequate  extraction.
                                       5-32
-------















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5.3.4  Process Status

     More laboratory tests need to be made to determine the applicability of
extraction procedures to the wide range of dioxin-contaminated soil types.
For instance, high organic content soils are known to be harder to wash than
sandy soils.
     Though organic solvents have been identified with high removal
efficiencies (in certain cases), the level of soil cleanup necessary will
determine their applicability.  Also, cleaning soils to 1 ppb or below has not
yet been established as feasible.  In addition,  the solvent which is used in
actual cleanup situations must be non-hazardous.  Residual concentrations of
solvents such as methylene chloride or carbon tetrachloride in soil would be
unacceptable.  Selection of the proper solvent also depends upon the final
treatment or disposal scheme.  The chemical CPC, for instance, is very
sensitive to photodegradation (Botre, 1978).
     Finally, pilot scale and full-scale testing is needed to resolve problems
such as soil handling and preprocessing, as well as safety hazards involved in
the increased mobility of 2,3,7,8-TCDD in the dissolved state.

5.4  BIOLOGICAL TREATMENT

5.4.1  Process Description
     Biodegradation is the molecular breakdown of an organic substance by
living organisms.  During biodegradation, the decomposition which occurs
results in less complex compounds which could be of either less or more
toxicity.  The principal factors which control microbial degradation are:
moisture levels, organic content, oxygen levels, temperature,  pH, and nutrient
sources.
     Biological treatment of wastes can be accomplished in a number of
different modes.  These include in situ aerobic'degradation, pretreatment
(e.g., by photolysis or ozonation) followed by biodegradation, anaerobic
degradation, and activated sludge.  Processes such as activated sludge, for
which the waste must generally be in an aqueous form, are standard methods for
treating domestic wastewater.  For treating dioxin waste, which is frequently

                                     5-34
-------
found in a soil matrix, in 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 become 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 2,3,7,8-TCDD
sprayed as a constituent of defoliants was  still present 12 to 14 years after
application (Young, 1983).  Although natural degradation seems to proceed

                                      5-35
-------
fairly rapidly at first, it slows or completely stops after only a few
months.  This decrease in degradation is probably due to the affinity  of
2,3,7,8-TCDD for soil and organic matter.  Any use of biodegradation as a
treatment process for 2,3,7,8-TCDD in soil will have to overcome this
adsorption phenomenon.
     Microbial metabolism of 2,3,7,8-TCDD has been shown to occur both in soil
and aquatic environments.  The species responsible for degradation were not
always reported.  Table 5.4.1 lists some of the microbial strains which are
known to degrade 2,3,7,8-TCDD.  Other researchers have identified soil
micro-organisms with 2,3,7,8-TCDD degrading capabilities (Phillippi, 1982;
Camoni, 1982).
     The information available in the literature is incomplete with regard to
the specific micro-organisms which have the capability for 2,3,7,8-TCDD
degradation, their intermediate metabolites, and end products of
biodegradation.
     The process of 2,3,7,8-TCDD biodegradation currently appears to be one  of
co-metabolism.  That is, 2,3,7,8-TCDD is not metabolized directly as a food  or
energy source, but is degraded by metabolic enzymes generated during the
metabolism of other organics.  The degree of 2,3,7,8-TCDD biodegradation  which
can occur has been reported to vary for different micro-organisms.

5.4.2  Technology Performance Evaluation

Past Research--
     Research on the degradation of 2,3,7,8-TCDD has been going on for a
number of years.  Work prior to 1980 monitored various aspects of
biodegradation in the soil environment.  Much of this early work is subject  to
dispute because biodegradation was inferred from the "disappearance" of
2,3,7,8-TCDD.  It is now known that 2,3,7,8-TCDD binds tightly to soils and
that biodegradation rates are much lower than early reports indicated. Other
researchers followed the metabolism of carbon 14 labeled 2,3,7,8-TCDD  or
measured the formation of 2,3,7,8-TCDD metabolites.  The following discussion
summarizes a literature review of past research on soil biodegradation of
2,3,7,8-TCDD (Esposito, 1980).
                                      5-36
-------
    TABLE 5.4.1.   MICRO-ORGANISMS WITH KNOWN CAPABILITY FOR
                  DEGRADING 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN


                                             Researcher
Nocardiopsis sp.

Bacillus megaterium

Beijerinckia B8/36a

Pseudomonas, sp.

Biejerinckia, sp.a

Phanerochaete chrysosporiumc
Matsumura, 1983.

Matsumura, 1983,

Klecka, 1980.

Klecka, 1979.

Klecka, 1980.

Bumpus, et'al., 1985.
aOxidation of dibenzo-p-dioxin and several mono-, di-, and
 trichlorinated dibenzo-p-dioxins was reported.

''Metabolism of dibenzo-p-dioxin was observed.

cWhite rot fungus.
                               5-37
-------
     A 1973 study by researchers at the Agricultural Research Center in
Beltsville, Maryland monitored 2,3,7,8-TCDD degradation in two soils with
                                                            14
2,3,7,8-TCDD concentrations of 1,  10,  and 100 ppm,  and with   C-labeled
concentrations of 1.78, 3.56, and 17.8 ppm (Kearney, 1972).  Soil samples were
                           14
monitored for evolution of   C0_ as an indication of microbial
degradation, but very little was detected and no metabolites were found in
2,3,7,8-TCDD treated soil after 1-year.
     Camoni, et al., investigated the influence of organic compost additions
to 2,3, 7,8-TCDD-contaminated soils from Seveso, Italy.  The organic compost
was used to provide active micro-organisms to stimulate biodegradation.  The
researchers concluded that organic compost addition had little effect on the
degradation of 2,3, 7,8-TCDD.  Initial concentrations of TCDD in soil were
100 ppb.  At the end of the experiment, extracted 2,3,7,8-TCDD was about 73
percent of that extracted initially for the compost treated soil, and 88
percent of initial levels for untreated soils.
     Hutter and Phillippi of the Microbiological Institute of Zurich,
Switzerland found aerobic microbial degradation of 2,3,7,8-TCDD in liquid
media or soil to be very low under laboratory conditions.   Approximately
1 percent of the input material was degraded after several months of
incubation to an apparent hydroxlated 2,3,7,8-TCDD metabolite.  Initial
2,3,7,8-TCDD concentrations were not reported.
     Ward and Matsumura (1978) from the University of Wisconsin studied the
fate of TCDD using aquatic sediment and lake water.  Under experimental
conditions the half-life of TCDD was approximately 600 days.   Maximum levels
of metabolite production were reached between 19 to 39 days of incubation.
The level of metabolite production amounted to 1 to 4 percent of the original
TCDD level.
     Other researchers who have investigated biodegradation of 2,3,7,8-TCDD
include:  Bartleson, et al., 1975; Commoner and Scott, 1976;  Pocchiari,  1978;
and Salkinoja-Salonen, 1979.  As noted, Esposito, et al.,  1980,  has summarized
the work published by these researchers.  The indications  are that
biodegradation will proceed slowly in soils and may be stimulated by addition
of nutrients and organics.
                                        5-38
-------
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
             14
converted to   CO_ 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 C0_.  This conclusion is based on more

                                     5-39
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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
ineffective.
     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.
                                     5-41
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 TABLE 5.4.3.  EFFECT OF SOLVENTS ON METABOLISM OF TCDD BY BACILLUS MEGATERIUM

               IN YEAST-SOYBEAN MEDIUM (Quensen and Matsumura, 1983)




                             Amount of radiocarbon recovered (%)


                   Aqueous phase           Solvent phase


  Treatment      Aa          Bb       Metabolites     TCDD         Total
Ethyl acetate 4.3 + 1.3  12.4 + 16.5


DMSO          1.9 + 1.4   1.1 +  0.5


Ethanol       5.9 + 2.3   1.4 +  1.6


Corn oil      0.2 + 0.2   1.0 +  1.0
8.9 + 3.5   51.8 + 27.5  77.4 + 15.6


8.9 i 0.9   81.9 + 13.1  93.7 + 10.3


1.6 + 0.2   90.0 _+  6.6  98.8 +  3.0


   c        92.0 +  1.1  93.2 +  2.3
aExtracted medium.


"Aqueous layer formed during evaporation of solvents.



cThin-layer chromatographic analysis was not possible because of interference
 oy cne corn oil.

 The amount of solvent used was 1 mL per 50 mL culture.  Values are means + SD-
 sample sxze — 2.                                                         —   '
                                     5-42
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Kearney and Plimmer (Kearney, 1984)—
     A biological process to detoxify 2,3,7,8-TCDD-contaminated 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 organics 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 1 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 1 month;
     •    80 percent degradation of PCB over 1 month;
                                     5-43
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     •    60 percent degradation of 2,3,7,8-TCDD over 1 month;  and
     •    75 percent degradation of PCP over 1 month.

For all compounds, most of the decomposition occurred during the first  day  or
two in the soil.
     This process is limited in applications to dioxin molecules that are in
solution with a proton donor and is most effective when 2,3,7,8-TCDD
concentrations do not exceed 1 ppm.  The UV pretreatment  step cannot be
applied to 2,3,7,8-TCDD-contaminated soil because UV radiation does not
penetrate below the soil surface.

Loper (Poiger, 1983; Loper,  1985)—
     Research is being conducted on yeast at the University of Cincinnati.
Loper hopes to genetically alter yeast to include a gene  for a liver enzyme
(p450 mono—oxygenase) that is able to degrade dioxin molecules.   Degradation
of dioxin molecules has been observed in dogs and rats due  to liver enzymes.
Results are not available at this time.

Research on TCDD Surrogates—
     Compounds such as chlorophenols, chlorobenzenes and  the herbicides
2,4,5-T and 2,4-D are structurally similar to chlorinated dioxins, and
therefore micro-organisms that have the ability to degrade these compounds  may
have the ability to degrade TCDD as well.  In addition, since TCDD is a
byproduct of manufacturing chlorophenols and 2,4,5-T, these compounds are
frequently found at waste sites along with TCDD.  Several groups have
conducted research on the biodegradation of these types  of compounds.   These
research projects are summarized in Table 5.4.4.  Most of these projects are
currently only at the laboratory scale and many of them are not necessarily
directed toward the treatment of waste containing TCDD.   Nonetheless, further
research may  indicate that TCDD can be degraded by these  processes.
                                      5-44
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5.4.3  Costs of Treatment

     Costs associated with biological treatment of TCDD will undoubtedly be
expensive, but given the high cost associated with other treatment
alternatives, biological treatment is expected to be very competitive.
In-situ treatment would be the least expensive method.   Operations would be
similar to an intensive agricultural process, with regular tilling,
fertilizing, and irrigation.  Adaption of activated sludge to treatment  of
2,3, 7, 8-TCDD-contaminated soils would be much more expensive.  If the soil
were excavated and suspended in an aeration tank, aeration costs would be very
high.  Activated sludge would be most cost-effective if applied to
2,3,7,8-TCDD which had been solvent extracted from the  soil.

5.4.4  Process Status

     At this point in time, biodegradation as a process for treating wastes
containing TCDD is still very much in its infancy.  Certain types of
micro-organisms have shown the ability to degrade TCDD  in laboratory
cultures.  With respect to actual wastes such as contaminated soil, biological
treatment has not been demonstrated to be effective. The major obstacle has
been that it has been difficult to make TCDD bioavailable.  Since TCDD adsorbs
strongly to soils, cellular uptake is severely limited.  One organism
discussed above, the white rot fungus (P. Chrysosporium), has the ability to
degrade recalcitrant insoluble substrates such as lignin by secretion of
extracellular enzymes.  Because of this ability, it has been suspected that
this fungus might have the ability to degrade 2,3,7,8-TCDD and other
haloorganics which are resistant to degradation by other micro-organisms.
Some initial data have indicated that P. Chrysosporium has a potential for
degrading TCDD to nontoxic end products.  Even these data, however, are
inconclusive, since only 5 percent of the degradation end products were
measured as C02 after 60 days.  Much additional work must be carried out
before P. Chrysosporium can be used to treat actual waste.  Research will be
carried out in the near future to determine the survivability of the
micro-organism in a soil environment.  In a  lab-scale  study, moisture,
                                        5-46
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 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 TGDD.  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
 testing.
     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 TGDD 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
 environment.                                      .
     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
          concentrations.

 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.
                                         5-47
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5.5  STABILIZATION/FIXATION

5.5.1  Process Description

     Stabilization/fixation processes are used to render immobile the
hazardous constituents which may be present in liquids,  sludges,  or solids.
Stabilization refers to processes which physically change or encapsulate the
waste through mixing with additives and binders.  Fixation involves a chemical
interaction between the waste and a chemical binding agent.  Stabilization
techniques are only interim measures.  The stabilized wastes must be
subsequently disposed at an EPA-approved hazardous waste landfill,  or
subjected to further treatment.
     Several types of stabilization/fixation technologies exist,  including:
cement-based, lime-based (pozzolanic), thermoplastic and thermosetting organic
polymers, macroencapsulation, self-cementing, glassification, and other more
recently developed techniques (Tittlebaum, et al., 1985).  Table  5.5.1 lists
some of the stabilization/fixation techniques in these categories.   Most must
be considered stabilization techniques; fixation processes are rare.
     Stabilization materials can be either organic or inorganic;  inorganics
are more commonly used and include Portland cement, pozzolanic materials with
or without lime or cement, and sorbent clays (Hazardous Waste Consultant,
1985; Spooner, 1985; GCA, 1985).  Organic materials include asphalt,
polyethylene, urea formaldehyde, and other thermoplastic and thermosetting
polymers (Hazardous Waste Consultant, 1985; Spooner, 1985; GCA, 1985).  The
performance of most of these materials over time has not been fully
demonstrated.
Organic Materials—
     One common technique for stabilizing organic contaminants is blending
them into resins and then solidifying the mixtures (GCA,  1985).   Plastic
solidifying agents fall into two main categories, thermoplastics and
thermosets.  Thermoplastics are materials that become fluid upon heating and
include asphalt, polyethylene, polypropylene, and nylon.   Thermoplastic
techniques generally call for the waste to be dried, heated, dispersed through
the heated plastic matrix, and then cooled (solidified) and placed in
                                     5-48
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          TABLE 5.5.1   SUMMARY OF STABILIZATION PROCESSES FOR TREATING
                        HAZARDOUS WASTES (M. E., Tittlebaum, et al., 1985)
Classification
     Process sponsor
     (process name)
   Stabilization agents
  Wastes
  treated
Cement-based
Lime-based or
pozzolanic
Thermoplastic
Thermosetting
polymer

Macro-
encapsulation


Se1f-cement ing


Classification

Other
Chemfix
Stablex (Sealo.safe)
Stabatrol  (Terra-Tite)

Dravo Lime (Calcilox)
International Mill Service
IU Conversion Systems
Soil Recovery Systems
Sludgemaster

Werner and Pfleiderer
Southwest Res.earch Inst.
(Sulfex)

Dow Chemical
Newport News Industrial

Environmental Protection
Polymers
TRW Systems

Sludge Fixation Technology
(Terra-Crete)

None specified

ARDECCA

Anschutz Corp. (Ansorb)
Cement, soluble silicates
Cement, flyash
Cement, additives

Lime, additives
Lime
Lime
Lime
Lime, additives

Asphalt
Sulfur, modifiers
Polyesters, polyvinyls
Polyesters

.Polyolefins

High-density polyethylene

Calcium sulfite or sulfate


Glass or ceramics

Proprietary

Clay-like material
 Inorganics
 Inorganics
 Inorganics

 FGD sludges
 Metal  slags
 FGD sludges
 Misc.
 Misc.

 Misc.
 Misc.
Radioactive
Radioactive

Soluble
toxics
Misc.

FGD sludges
Radioactive

Oil field
wastes
Misc.
                                      5-49
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containers.  Thermosets include urea formaldehyde, polyester,  and phenolic and
tnelamine resins.  Thermoset techniques call for the waste to be mixed with the
thermoset prior to reaction of the mixture to form a solid matrix through
crosslinking reactions.  This matrix will remain solid throughout subsequent
heatings.  Containers may or may not be needed with thermosets.
     In early work, asphalt and bitumen were the most widely applied materials
for solidifying organics (GCA, 1985).  These fixative materials are chemically
stable and low in cost.  At low waste-to-fixative loadings, these materials
were generally found to exhibit acceptable solidification properties (e.g.,
good solid product formation and dimensional stability remained upon immersion
in water).  However, for high contaminant loadings (above about 30 percent by
weight), or, in general, for most organics of lower molecular weight, high
vapor pressure or hygroscopic nature, these materials often yielded
unacceptable products.  More recently, these products have been replaced by
thermoplastic or thermosetting resins; e.g., linear polyethylene has been
employed as a stabilizer for certain organics (GCA, 1985).
     Soil stabilization chemicals are also available that react with moisture
in the soil or an aqueous catalyst to form a hydrophobic crosslinked
polymer-based gel  (GCA, 1985).  The semi-solid gel forms in situ coats and
binds the soil particles together.  The chemical and water (or catalyst)
mixture is sprayed on  cultivated or loosened soil to react with the upper
3 to 4 inches of soil.  The resulting gel-soil mixture then becomes a barrier
to water infiltration.
     Commonly offered  grouts include organic polymers based on acrylaraides,
polyurethanes, urea, and phenolics.  The advantages some of the chemical
grouts offer are that  they are easy to mix, they penetrate soil much like
water (since they are  polar and have a viscosity similar to water), they can
be applied by spraying, and they are generally nontoxic when handled
properly.  The grouts  form highly stable compounds of extended but unknown
life.  However, grouts are sensitive to freeze-thaw and wet-dry conditions,
and some grouts will deteriorate under ultraviolet light and other degradative
mechanisms.
                                     5-50
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Inorganic Stabilizers—
     Lopat Enterprises, Inc., of As bury Park% New Jersey has developed a
product called "K-20"  (McDaniel, 1983).  K-20 is an inorganic mixture of at
least eight chemicals  (McDaniel, 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 (GoIdensohn, 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 tl.«- 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. EP.A, 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:

     e    evaluating the cost-effectiveness of the processes;
     •    developing optimum soil/stabilizer ratios and mixing  conditions; and
     •    assessing the viability of successful field implementation.
                                     5-51
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     Soil from three Missouri dioxin sites were tested with both stabilization
techniques.  As summarized in Table 5.5.2, each soil had different
properties.  Cement-based stabilization samples were prepared at optimum
moisture, but with varying cement contents.  Tests were performed for
freeze-thaw susceptability, leachability, and 7-day unconfined, comprehensive
strength (Vick, 1985).  The freeze-thaw and wet-dry test results were
satisfactory for the portland cement process.  However, significant loss (by
weight-percentage) of the sample was observed during weathering processes
followed by an aqueous  leaching process.  Percent weight loss in the
soil/cement samples ranged from 6 to 18 percent for the Minker sample,
13  to  16 percent for the Piazza Road sample, and 16 to 27 percent for the
Sontag Road sample (Vick, 1985; Technical Resources, 1985J.  The leachability
test results are summarized in Table 5.5.3.  The results suggest that the
leachate concentration  may be limited by the decreased aqueous solubility of
2,3,7,8-TCDD in the range of 2 to 3 ppt in the leachate from the matrix
(Technical Resources, Inc., 1985).
     A cationic, slow-setting emulsion (CSS-lh) was used for the emulsified
asphalt  samples.  A slow setting emulsion is preferred for dense-graded
aggregate  soils such as the Missouri soils used during these tests.   Initial
tests  for wet-dry stability, dry density, moisture content, and air void,
indicated  that the emulsified asphalt did not produce acceptable results
(Vick, 1985; Ellis, 1986).  Therefore, formula modifications using lime
additives  (calcitic lime, calcium hydroxide) were developed to modify the soil
prior  to asphalt addition (Ellis^ 1986).  Addition of  1.5 percent lime and the
use of the SS-lh  (nonionic, slow-setting  emulsion) instead of  the CSS-lh
emulsified asphalt, dramatically improved the results of the soil/asphalt
sample tests  (Vick, 1985).  The optimum  asphalt percentage was found  to be
nine percent residual asphalt (Vick, 1985).
     Lopat,  Inc. has  recently completed  tests of  the K-20 process on
contaminated soils  from Times Beach.  The  data from these tests have not been
of sufficient  quality to permit an  accurate  assessment of the  process with
respect  to the encapsulation of dioxin.   Lopat plans to conduct further tests
on dioxin-contaminated soils when samples are made  available  (Flax,  1986).    j
                                      5-52
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        TABLE 5.5.2.   SOIL TYPES USED TO TEST PORTLAND CEMENT
                      AND EMULSIFIED ASPHALT/LIME STABILIZATION
                      TECHNIQUES
 Site
     Description
                                      Soil  type
                    TCDD
                concentra t ion
Minker
Piazza
Road

Sontag
Road
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
loam
700 ppb




640 ppb


 32 ppb
(Technical Resources, Inc., 1985)
                                 5-53
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   TABLE 5.5.3.  SUMMARY OF LEACHABILITY TEST RESULTS FOR PORTLAND CEMENT
                   STABILIZED AND NATIVE UNSTABILIZED MISSOURI SOILS3
                   (Technical Resources, Inc., 1985)
Soil
collection
site
Minker
Minker
Piazza
Piazza
Sontag
Sontag
Material
leached
Unstabilized
Soil/cement
Unstabilized
Soil/cement
Unstabilized
Soil/cement
Mass TCDD
leached
(ng)
9.5 + 4.7
28 ± 8
3.9
36 + 12
3.4
8 +. 4b
Cone. TCDD
in leachate
(ng/L)
2.4 + 1.2
2.3 £ 0.7
1.0
2.6 + 0.9
0.91
0.6 + 0.4
Mass TCDD leached per
unit mass of soil
(ng/g)
0.095 + 0.047
0.012 +_ 0.003
0.039
0.016 + 0.006
0.034
0.004 +_ 0.002
aMean values of triplicate measurements, unless indicated.

bOne of the three replicates was below detection limit; listed value is a
 mean of two measurements.
                                       5-54
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 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
 soils).

 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,
 1986).
     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.
                                     5-55
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5.6  CHEMICAL DEGRADATION USING RUTHENIUM TETROXIDE

5.6.1  Process Description

     Ruthenium tetroxide is a powerful oxidizing agent.   It  is more  effective
than either hypochlorite or permanganate in attacking aromatic substances.
The reagent can be used in solution with water or with organic solvents which
demonstrate no nucleophilic character such as chloroform, methylene  chloride,
acetic acid, fluorotrichloromethane, and nitromethane.
     Degradation using ruthenium tetroxide is by aromatic ring cleavage.   In
tests where chlorophenols were treated with ruthenium tetroxide,  all of the
aromatic ring carbons were accounted for as carbon dioxide,  and  the  aromatic
chlorosubstituents gave rise to chloride ions.  A similar analysis of the
degradation products of TCDD was not carried out in this study due to
analytical difficulties related to the low solubility of the compound.  It was
inferred, however, that because of the close chemical and structural
similarities between TCDD and chlorophenols that they would  be degraded in a
similar manner (Ayres, 1985).
     One factor affecting the rate of pollutant degradation  using ruthenium
tetroxide (RuO,) is temperature.  In one set of experiments, the rate of
pollutant degradation increased 2.4-fold per 10 °C rise  within the test
temperature range (Ayres, 1981a; des Rosiers, 1983).

5.6.2  Technology Performance Evaluation

     Studies have been performed on soils contaminated with Agent Orange.
These soil samples, containing approximately 70 ppb of TCDD, were obtained
from Eglin Air Force Base in Florida.  After treatment of the extracted
material with excess ruthenium tetroxide for 1 hour at 76°C  in carbon
tetrachloride, TCDD was no-longer detectable (detection limit of 10 ppb).
When water was used as the solvent instead of CCl^ the degradation of TCDD
was noticable, but not nearly as great as with CCl^.  An experiment was  also
performed in which an excess of sodium hypochlorite and hydrated ruthenium
tetroxide were added to the same soil samples along with carbon tetrachloride
as the solvent.   In this case, the degradation was similar to that attained  by
using excess ruthenium tetroxide in the presence of CCl^ (Ayres, 1985).
                                      5-56
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     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 minutes 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 Rosiers, 1986).

5.7  CHEMICAL DEGRADATION USING CHLOROIODIDES

5.7.1  Process Description
     A method for the degradation of substances containing both aromatic rings
and ether bonds was reported in 1979 (Botre, 1979; des Rosiers, 1983;
Esposito, 1980).  This is of current interest because 2,3,7,8-TCDD contains
                                     5-57
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two aromatic rings connected by two ether bonds.   The method utilized
chloroiodides attached to quarternary ammonium salt surfactant molecules  to
rupture the ether bonds, and thus split the 2,3,7,8-TCDD molecule into smaller
fragments.  End products are chlorophenols and related compounds.  The
mechanism of the ether bond rupturing is thought to be the loss of an iodine
atom from the surfactant (Corwell, 1957), and subsequent formation of reactive
hydrogen iodide at a location in an aqueous solution near the 2,3,7,8-TCDD
molecule (Botre, 1979).  Hydrogen iodide by itself is known to rupture ether
bonds, but usually only in a strongly acidic environment.  However, the
formation of the hydrogen iodide in close proximity to the 2,3,7,8-TCDD
molecule seems to be the key factor.
     One method of 2,3,7,8-TCDD degradation described involves the extraction
of 2,3,7,8-TCDD from soil using aqueous solutions of surfactants containing
chloroiodide groups (Botre, 1979; des Rosiers, 1983, Esposito, 1980).  The
aqueous residues from the soil washings are extracted with benzene, methanol,
or methylene chloride.  These extracted  liquids containing the 2,3,7,8-TCDD
may require evaporation under reduced pressure to concentrate the solution and
thus enhance the reaction by bringing the 2,3,7,8-TCDD molecule and
chloroiodide-bearing surfactant molecules into more frequent contact.
     The  chloroiodide derivatives producing the most promising results for the
cleavage  of ether bonds are alkyldimethylbenzylammonium  (benzalkonium)
chloroiodide,  and 1-hexadecylpyridinium  (cetylpyridinium) chloroiodide (CPC).
The low solubilities of these chloroiodides in water can be increased with the
addition  of micellar solutions pf the same surfactants with chloroiodide
groups.   Micellar solutions consist  of  large  polymeric particles  (clusters) of
 the  surfactants.  Common solubilizing agents  are  benzalkonium chloride, used
 to enhance the solubility of benzalkonium chloroiodide,  and cetylpyridinium
 chloride,  used to enhance the  solubility of cetylpyridinium chloroiodide.
      Surfactant micellar solutions  of 2,3,7,8-TCDD  without chloroiodides are
 stable when  stored  in the dark,  but decompose when exposed to sunlight or UV
 irradiation  (Botre,  1978).  This form of treatment  seems to be appropriate and
 effective for the  decontamination of buildings,  furniture, etc.,  where
 surfactant contact  accompanied by exposure to UV is possible  (Botre,  1978).
 However,  the use of chloroiodides has  been shown to be effective in the
                                      5-58
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 decomposition of 2,3,7,8-TCDD without irradiation.   This  latter method
 utilizing chloroiodides  is  therefore  more  suitable  for degrading bulk
 solutions.

 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 Rosiers,  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.
                                     5-59
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5.7.3  Costs of Treatment

     Since no commercial applications exist for the  use  of chloroiodides to
destroy TCDD, the economic feasibility cannot be estimated with any degree of
confidence.  Some cost factors of significance include:

     1.   the excavation and pretreatment of contaminated soil with a
          solubilizing solution;
     2.   washing of the solution from the soil;
     3.   extraction of 2,3,7,8-TCDD from the solution and concentration by
          evaporation; and
     4.   stringency of conditions needed to achieve a 1 ppb level with
          chloroiodide extracts.
5.7.4  Process Status

     As stated earlier, the potential for the use of micellar surfactant
solutions (with a UV source) may apply in decontaminating surfaces of
buildings,  furniture,  and other personal belongings.  The addition of
9 chloroiodides may improve the application of surfactant micellar solutions
for this  type of decontamination.  The decomposition of 2,3,7,8-TCDD by
chloroiodides (without a light source) has been proven in laboratory
experiments.  However,  it has not  been demonstrated that TCDD levels can be
 lowered to  less than  1 ppb  in soils.  Additional bench scale testing is needed
 for further optimization of processes, perhaps including the possibility of
 in-situ decontamination of  contaminated  soil.  In situ decontamination using
 solubilizing agents may not be  feasible  because  it  raises the possibility of
 causing the transport of 2,3,7,8-TCDD from soils into ground water and surface
 water.  Chloroiodides have  not  destroyed all  TCDD in clean  liquid solutions,
 and it is unlikely that near  100%  destruction in contaminated soils could be
 achieved.
                                         5-60
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 5.8  GAMMA RAY RADIOLYSIS

 5.8.1  Process Description

      Gamma rays are electromagnetic waves of energy (photons) similar to
 x-rays, 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.
                                     5-61
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5.8.2  Technology Performance Evaluation

     Gamma ray radiolysis is. used on a commercial basis for many purposes,
including thickness measurements in process control and for the sterilization
of disposable medical products.  The use of gamma rays for the degradation of
chlorinated hydrocarbon wastes appears to be limited to investigations in
research laboratories where the wastes were dissolved in various solvents
(Fanelli, 1978; Buser, 1976; Craft, 1975).  In each of the laboratory
investigations, the major degradation pathway appears to be the dechlorination
of the compounds to lower chlorinated compounds.
     The effect of gamma rays on 2,3,7,8-TCDD dissolved in organic solvents
was investigated in a series of preliminary experiments in Italy in 1978
(Fanelli, 1978).  The investigators dissolved 2,3,7,8-TCDD in either ethanol,
acetone, or dioxane at a concentration of 100 ng/ml (ppb).  Irradiations  of
0.5 ml samples were accomplished with a  10,000 Curie Cobalt-60 source.  The
dose rate was  106 rad/hour.  It was found that the disappearance of
2,3,7,8-TCDD is directly related to the  total dose of radiation absorbed  and
to the solvents used.  About 97 percent  of  the 2,3,7,8-TCDD was degraded  after
30 hours when  ethanol was the  solvent.   Thus, the concentration of
2,3,7,8-TCDD was reduced from  100  ppb to about 3 ppb.  Degradations of
80 and 70 percent, respectively, were achieved  in 30 hours when acetone and
dioxane  were the solvents,  as  shown in Figure 5.8.1.
     From the  experiments described above,  it seems clear that .the  type of
solvent  used  is  important for  the  efficiency of  the degradation process.
There was no  irradiation testing of 2,3,7,8-TCDD in contaminated  soil  samples
without  solvents,  although  the authors  indicated in their 1978 paper  that
further  studies  were  in progress to verify  the  possible  application of gamma
rays to  the degradation of  2,3,7,8-TCDD  in  contaminated  soil  samples.
      In  earlier  related work in 1976,  gamma ray experiments with
octachlorodibenzo-p-dioxin  and octachlorodibenzofuran dissolved  in benzene  and
hexane  at a concentration  of 25 mg/L  (ppm)  were conducted (Buser,  1976).
After 4  hours  of gamma irradiation,  80  percent  of the octachlorodibenzo-p-
dioxin was  converted to dioxin molecules containing  5,  6, or  7  chlorine atoms
per molecule.
                                      5-62
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                                                             Ethanol
                        10               20

               Total absorbed dose  (million rads;
                                          30
Figure 5.8.1.
Effect of Gamma Ray irradiation on 2,3,7,8-TCDD
concentration in ethanol, acetone and dioxane
[Fanelli, 1978].


              5-63
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     The potential for destroying pesticides using gamma ray  radiation was
investigated in 1975 at the Georgia Institute of Technology (Craft,  1975).
Significant destruction of compounds such as pentachlorophenol,  2,4,5-T,  and
2,4,-D were obtained, but no change in PCBs or mixtures  of compounds such as
"Herbicide Orange" could be detected.  These researchers concluded that,
because of the inefficiency of radiation in destroying mixtures  of pesticides
and dioxin molecules, radiation treatment of chlorinated hydrocarbons is  not
economically feasible.

5.8.3  Costs of Treatment

     A prototype gamma ray radiolysis facility has been built at the Sandia
National Laboratory.  The facility is capable of treating about  4 tons per  day
of digested and dewatered sewage sludge at a dosage of 1 million rad. Sludge
                                                                   3
is passed by the radiation source in a bucket conveyor (1 to  1.5 ft
buckets).  The capital cost of the facility is about $3 million and the
processing cost is about $50 per ton (Pierce, 1984).  For larger facilities
(50 to 60 TPD), the  processing cost could conceivably be reduced to as low as
$10 per ton (Pierce, 1984).
5.8.4  Process Status

     In  summary,  the development of gamma ray technology for the destruction
of  2,3,7,8-TCDD is in the research stage.  Based on some limited data, it
appears  that  dechlorination occurs most readily when dioxin molecules are
dissolved in  certain solvents.  If this technique were used for large
quantities  of contaminated soil, some method of removing the 2,3,7,8-TCDD from
the soil (e.g., solvent extraction) would probably be required before gamma
ray irradiation.
     If  further studies show  that direct irradiation of 2,3,7,8-TCDD-
contaminated  soils also dechlorinates the dioxin molecule, then it may be
possible to remove the contaminated soil and treat it at an irradiation
 facility,  before  replacement  at the site.  Because of the heavy radiation
 shielding  required,  it  is not practical to  treat  large  quantities of  soil with
 portable units  (Craft,  1984).
                                     5-64
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     Further research is needed to verify the possible  application of gamma
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).
                                    5-65
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                                  REFERENCES

Acurex, Cincinnati, Ohio.  Communication with representative.  17 May 1984.

Arisman, R.K., and R.C. Musik (General Electric Company); J.D. Zeftack,
     T.C. Grose (Westgate Research Corporation).  Experience in Operation of a
     UV-Ozone (ULTROX) Pilot Plant for Destroying PCBs in Industrial Waste
     Effluent.  Presented at the 35th Annual Purdue Industrial Waste
     Conference.  May 1980.

Ayres, D. C., C. M. Scott.  Oxidative Control of Organosulfur Pollutants.
     Environmental Science & Technology, 13(11):1383.  November 1979.

Ayres, D. C.  Destruction of Polychlorodibenzo-p-dioxins.  Nature, 290:323.
     26 March 1981a.

Ayres, D. C.  Ruthenium Tetroxide Destroys Dioxin.  The Oxidative Control of
     Aromatic Pollutants.  Platinum Met. Rev.,  25(4):160.  1981b.

Ayres, D. C., D. P. Levy and C. S. Greaser.  Destruction of Chlorinated
     Dioxins and Related Compounds by Ruthenium Tetroxide.  In:  Chlorinated
     Dioxins and Dibenzofurans in the Total Environment II.  Butterworth
     Publishers, Stoneham, MA.  1985.

Banerjee, S., S. Duttagupta, A. M. Chakrabarty.  Production of Emulsifying
     Agent During  Growth of Pseudomonas Cepacia with 2,4,5-Tri-
     chlorophenoxyacetic Acid.  Arch. Microbiology,  135:110-114.  1983.

Bartleson, F. D.,  Jr., D. D. Hanison, and J. B. Morgan.  Field Studies of
     Wildlife Exposed to TCDD-Contaminated  Soils.  U.S. Air Force Armament
     Laboratory, Eglin Air Force Base, Florida.  1975.

Berry, R. I. New Ways to Destroy PCBs.  Chemical Engineering, 88(16):37-41.
     August  10,  1981.

Bolton,  L.   Seveso Dioxin:  No Solution in  Sight.  Chemical Engineering,
      85(22):78.   1978.

Botre,  C. et al.   2,3,7,8-TCDD Solubilization  and  Photodegradation  in Aqueous
      Solutions.  Environmental Science and  Technology.   12(3):335-336.
      March  1978.

Botre,  C., Memoli, A.,  and Alhaique,  F.  Environmental  Science and  Technology,
      13(2):228.   1979.

Bumpus,  J.A.,  Tien, M.,  Wright, D.A.  and Aust,  S.D.   Biodegradation
      of Environmental Pollutants  by  the White  Rot  Fungus Phanerocheate
      chrysosporium.  Presented  at EPA HWERL llth Annual Research Symposium,
      Cincinnati, OH, April 29-May 1,  1985.
                                      5-66
-------
Bumpus, J.A., Tien, M., Wright, D.A. and Aust, S.D.  Oxidation of
     Persistent Environmental Pollutants by a White Rot Fungus.  Science,
     _228:1434-1436.  1985.	

Buser, Hans-Rudolph.  Preparation of Qualitative Standard Mixtures of
     Polychlorinated Dibenzo-p-dioxins 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
    i 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.  USAF 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. F., 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.
                                    5-67
-------
Crosby, D.G., and A.S. Wong.  Photodecomposition of Chlorinated
     Dibenzo-p-dioxins.  Science.   173:748-749.   August  20,  1971.

Crosby, D.G.  Conquering the Monster:   The Photochemical Destruction  of
     Chlorodioxins.  In;  Disposal and Decontamination of Pesticides.  ACS
     Symposium Series 73.  Washington, DC.  1978.

Davis, L.  Sybron Corporation.  Personal communication to B.  Farino,
     GCA Technology Division, Inc.  9  January 1984.

des Rosiers, P.  Remedial Measures for Wastes Containing Polychlorinated
     Dibenzo-p-dioxins (PCDDs) and Dibenzo-furans (PCDFs):  Destruction,
     Containment or Process Modification.  Annals of Occupational  Hygiene,
     27(l):57-72.  1983.

des Rosiers, P.  Environmental Engineering and Technology, Office  of  Research
     and Development, EPA.  Communication.  21 May 1984.

DiDominico, A., et al.  Accidental Release of 2,3,7,8-tetrachlorodibenzo-p-
     dioxin (TCDD) at Seveso, Italy.  Ecotoxicology and  Environmental Safety,
     4(3):282-356.  1980.

Eaton, H. C., M. E. Tittlebaum, and F. K. Cartledge.  Louisiana  State
     University.  Techniques for Microscopic Studies of  Solidification
     Technologies.  Proceedings of the llth 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.

Edwards, B.H., J.N. Paullin, and K. Coghlon-Jordon.  Noyes Data  Corporation.
     Emerging Technologies  for the Control of Hazardous  Wastes,  pp.  76-87,
     105-108, 119-122.   1983.

Ellis, William D., William  H. Vick, Donald E. Banning, and Edward  J.  Opatkin.
     Evaluation of Stabilized Dioxin Contaminated Soils.  Proceedings of the
     EPA-HWERL llth Annual  Research Symposium, Cincinnati, Ohio.  April 29-May
     1,  1985.

Ellis, William.  JRB Associates.  Telephone Conversation with Lisa Farrell,
     GCA Technology Division, Inc.  May  15, 1986.

Esposito, M. P., et al.  Dioxins.  EPA-600/2-80-197.  1980.

Esposito, M. P., et al.  PEDCo Environmental, Inc.  Dioxins:  Vol. I, Sources,
     Exposure, Transport, and Control.   Prepared for IERL.  EPA-600/2-80-156.
     June 1980.

Esposito, M.P., T.O.  Tiernon, and F.E. Dryden.  Dioxins.  EPA 600/2-80-197.
     pp. 263-264.  November 1980.

Exner, J.H.  et al.  Process for Destroying Tetrachlorodibenzo-p-dioxin in a
     Hazardous Waste.   Paper Presented in Detoxification of Hazardous Waste.
     Chapter 17.  Ann Arbor Science, Ann Arbor, Michigan.  1982.
                                    5-68
-------
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) :1126r-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.

Gilman, 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,  1983.

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.
                                         5-69
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Jackson, N. E.  SunOhio.  Paper presented to the Annual Conference of the
     Southeastern Electric Exchange.  April 1981.

Jiranders, J.  Lopat Enterprises, Inc., Asbury Park,  New Jersy.   Telephone
     conversation with T. Murphy, GCA/Technology Division.   8 May 1984.

Karns, J. S., S. Duttagupta, A. M. Chakrabarty.  Regulation of 2,4,5-Trichloro-
     phenoxyacetic Acid and Chlorophenol Metabolism in Pseudomonas Cepacia
     AC1100.  Applied and Environmental Microbiology, 46(5):1182.  November
     1983a.

Karns, J. S., J. J. Kilbane, S. Duttagupta, A. M. Chakrabarty.  Metabolism of
     Halophenols by 2,4,5-Trichlorophenoxyacetic Acid—Degrading Pseudomonas
     Cepacia.  Applied and Environmental Microbiology, 46(5):1176.  November
     1983b.

Kearney, P. C., et al.  Persistence and Metabolism of Chlorodioxins in Soils.
     Environmental Science and Technology.  6(12):1017-1019.  1972.

Kearney, P. C. Agricultural Research Center, Beltsville, Maryland.  Personal
     communication with M. Button, GCA Technology Division, Inc..
     18 January 1984.

Kellogg, S. T., D. K. Chatterjee, A. M. Chakrabarty.  Plasmid—Assisted
     Molecular Breeding:  New Technique for Enhanced Biodegradation of
     Persistent Toxic Chemicals.  Science, 214:1133-1135.  December 1981.

Kilbane, J. J., D. K. Chatterjee, J. S. Karns, S.T. Kellogg, A. M. Chakrabarty.
     Biodegradation of  2,4,5-Trichlorophenoxyacetic Acid by a Pure Culture of
      Pseudomonas  Cepacia.  Applied  and Environmental Microbiology, 44:72.
      June  1982.

Kilbane,  J.  J., D. K. Chatterjee, A. M. Chakrabarty.  Detoxification of
      2,4,5-Trichlorophenoxyacetic Acid from Contaminated Soil by  Pseudomonas
      Cepacia.   Applied  and Environmental  Microbiology, 45:1697.   May 1983.

Kircher,  J. F., and R. E. Bowman.   Effects of  Radiation on Materials and
      Components.   Reinhold Publishing  Corp., New York.   1964.

Kitchens,  Judith. Atlantic Research  Corporation.  Personal  Communication.
      1986.

Klecka, G. M.,  and D. T. Gibson. Metabolism  of Dibenzo-p-dioxin and
      Chlorinated  Dibenzo-p-dioxins  by a Beijerinckia Species.   Appl. and Env.
      Microbiology, 39(2):288-296,  1980.

Klecka, G. M.,  D. T.  Gibson.   Bacterial Degradation  of Dibenzo-p-dioxin  and
      Chlorinated  Dibenzo-p-dioxins.  Prepared for  Environmental Research Lab.
      EPA-600/4-81-016.   March 1981.

Klee, Albert,  et  al.   Report  on the Feasibility of APEG Detoxification of
      Dioxin-Contaminated Soils.   U.S.  EPA-IERL/ORD.   EPA-600/2-84-071.
      March 1984.
                                        5-70
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Legan, R.W.  Ultraviolet Light Takes on CPI Role.  Chemical Engineering,
     9(2):95-100.  January 25, 1982.

Lubowitz, 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.

Malone, 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 1981.

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 1986a.

Philippi, Martin, et al.  Fate of 2,3,7,8-TCDD in Microbial Cultures and in
     Soil Under Laboratory Conditions.   Ferns 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.
                                      5-71
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Quensen, J. F., and F. Matsumura.  Oxidative Degradation of 2,3,7,8-tetra-
     chlorodibenzo-p-dioxin by Microorganisms.   Environmental  Toxicology.
     2(3):261-268.  1983.

Quensen, J. F.  Dept. of Crop and Soil Sciences, Michigan State University.
     Personal Communication with M. Arienti, GCA Technology Division,  Inc.
     April 29, 1986.

Quensen, J.  Pesticide Research Center, East Lansing, Michigan.  Personal
     communication with M. Button, GCA Technology Division, Inc.
     17 January 1984.

Rogers, C. J.  Chemical Treatment of PCBs in the Environment.   Paper presented
     at 8th Annual Research Symposium on Incineration and Treatment of
     Hazardous Waste.  EPA-600/9-83-003.  April 1983.

Rogers, C. J.,  et al.  Interim Report on the Feasibility of Using UV
     Photolysis and APEG Reagent for Treatment of Dioxin Contaminated Soils.
     Project Summary.  EPA-600/S2-85/083.  December 1985.

Salkinoja-Sabnen, M.  University of Helsinki, Finland.  Microbial Dechlorin-
     ation of Chloro-Organics.  Presentation given at U.S. EPA Offices,  IERL,
     Cincinnati, Ohio.  December 1979.

Sawyer, C.J.  Environmental Health and Safety Considerations for a Dioxin
     Detoxification Process.  In:  Detoxification of Hazardous Waste.
     Chapter 18.  1982.

Sferra, P.  U.S. EPA Hazardous Waste Engineering Research Laboratory.
     Personal Communication with M. Arienti, GCA Technology Division, Inc.
     April 29, 1986.

Smith, Robert L., David T. Musser, Thomas J. DeGrood.  ENRECO, Inc.  In-Situ
     Solidification/Fixation of Industrial Wastes.  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.

SunOhio,  Canton, Ohio.  Marketing Brochure.  1985.

SunOhio,  Canton, Ohio.  Communication with representative.  17 May 1984.

Swarzgn,  E.M., and D.G. Ackerman.  Interim Guidelines for the Disposal/
     Destruction of PCBs and PCB Items by Nonthermal Methods.
     EPA-600/2-82-069.  April 1982.

Technical Resources,  Inc.  Analysis of Technical Information to
     Support RCRA Rules  for Dioxins-containing  Waste Streams.  Final Draft
     Report submitted to Paul E. des Rosiers, Chairman, U.S. EPA - Dioxin
     Advisory Group.   July 31,  1985.
                                  5-72
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Telles, 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
     Environmental Control, 15(2):179-211.   1985.
          in
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.
     Engineering.  1981.
Pollution
Vanness, G. F., 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.
                                    5-73
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Waste Age.  Destroying Dioxin:  A Unique Approach,  pp.  60-63.   October 1980.

Weitzman, L.  Acurex Corporation, Cincinnati, Ohio.   Telephone  conversation
     with M. Jasinski, GCA Technology Division,  Inc.  4  June 1986.

Weitzman, L.  Treatment and Destruction of Polychlorinated Biphenyls  and
     Polychlorinated Biphenyl-Contaminated Materials. In; Detoxification of
     Hazardous Waste, Chapter 8.  1982.

Weitzman, L.  Acurex Waste Technologies, Inc.  Telephone conversation with
     T. Murphy, GCA Technology Division, Inc.  19 January 1984.

Worne Biotechnology, Medford, New Jersey.  Personal  communication with
     Dr. Worne.  1984.

Young, A. L., et al.  Fate of 2,3,7,8-Tetrachlorodibenzo-p-dioxin
     (TCDD) in the Environment:  Summary of Decontamination Recommendations.
     USA FA-TR-76-18.  1976.

Young, A. L.  Long-Term Studies on the Persistence and Movement of  TCDD in a
     Natural Ecosystem:  In;  Human and Environmental Risks of  Chlorinated
     Dioxins and Related Compounds.  R. E. Tucker, et al., editors.   Plenum
     Press, New York, New York.  pp. 173-190.  1983.

Zepp, R.G., and D.M. Kline.  Rates of Direct Photolysis  in Aquatic  Environment.
     Environmental Science and Technology.  ll(4):359-366.  April 1977.
                                  5-74
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                                   SECTION 6
                    FACTORS AFFECTING TECHNOLOGY SELECTION

     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.

6.1  TECHNICAL REQUIREMENTS FOR PROCESS SELECTION

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

     1.    Has the technology demonstrated  that  it can achieve  99.9999 percent
          DRE on CDD (or similar compounds)?
                                      6-1
-------
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     2.   Has the technology demonstrated that residues  contain less  than
          1 ppb CDDs and GDFs?
     3.   Can the treatment unit or process be transported to the waste  site?
     4.   Can the process be used on in situ wastes or must the waste material
          first be removed and then fed to the unit?
     5.   Can the treatment process handle wastes of all physical states or  is
          it limited to just liquids or just solids (and to what extent  is
          pretreatment possible and/or justified)?
     6.   Is the process a final treatment/destruction process or just a
          temporary, or pretreatment process?

     Responses to the above considerations have been provided in matrix  form
in Table 6.3, Treatment Technology Selection Chart, for  each of the
technologies discussed in Sections 4 and 5.  A discussion of this table  and
its significance with regard to the assessment and selection of particular
technologies is provided below.

6.1.1  Demonstration of Six Nines DRE
     The dioxin listing rule specifies that incinerators and other thermal
treatment units must achieve 99.9999 percent (six nines) destruction and
removal efficiency (DRE) for CDDs and CDFs in order to become fully
permitted.  Three technologies have demonstrated this level of performance.
These are the EPA mobile (rotary kiln) incinerator, the Shirco infrared
incinerator, and the Huber Advanced Electric Reactor (AER).  Achievement of
six nines DRE was obtained by Huber on tests of its small-scale stationary
research reactor located at its Borger, Texas facility.  Due to the
concentration of TCDD in the waste feed, their pilot scale, transportable unit
was only able to demonstrate five nines DRE.  Another technology that has
reportedly achieved six nines DRE on CDDs is the supercritical water oxidation
process.  Data to indicate the exact conditions under which this was achieved
have not yet been released by the developer of the process.
     In addition to those processes that have demonstrated six nines DRE on
CDDs and CDFs, processes that have demonstrated six nines DRE on compounds
that are at least as difficult to destroy as CDDs and CDFs, such as PCBs, may

                                      6-6
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6-7
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also have potential for use.  In particular,  those processes  that  have  TSCA
permits to treat PCBs, which include several  rotary kiln and  liquid injection
incinerators, may be able to burn listed dioxin waste if their previous trial
burn demonstrates the six nines performance standard on compounds  such  as  PGBs
(51 FR 1733).
     Processes that have achieved six nines ORE on CDDs and CDFs,  or on PCBs,
have demonstrated that they can technically be considered as  candidates for
treating listed dioxin wastes.  Other factors that will affect the selection
of an appropriate technology are considered below.

6.1.2  Demonstration of Treatment Residuals with Less Than 1  ppb of CDQs/CDFs

     The proposed land disposal restrictions specify that the residuals from
treatment of listed dioxin wastes must contain less than 1 ppb of  extractable
CDDs (and CDFs) in order for them to be land disposed as nonhazardous
materials.  Not only must the gases exiting an incinerator or thermal
treatment process be virtually free of CDDs and CDFs, but so  also  should be
the treated ash, scrubber water, filter residues, and other residuals.   In
some cases, the amount of dioxin in the waste feed may not be great enough to
allow demonstration of six nines ORE, however, the concentration of dioxin in
the treated residues may still be reduced to below detection  limits (1  ppb).
Two examples of this occurrence are the test burns at the Combustion Research
Facility and the test burns using the Huber transportable AER.  In both of
these cases, the concentration of dioxin in the residual streams was below
detection limits, but six nines was not demonstrated because  the analytical
detection limits were not low enough.  Nonetheless, the data  seemed to
indicate that the treatment processes were effective (Ross et al., 1986; Roy
F. Weston, 1985).
     In addition, for nonthermal treatment methods such as chemical
dechlorination, destruction and removal efficiency (DRE) is not an applicable
measure of performance.  A more appropriate measure is the residual
concentration of contaminants in the treated waste.  Nonthermal treatment
processes that can achieve  less than 1 ppb of CDDs and CDFs in the treated
waste have presumably demonstrated their potential for use on actual dioxin
wastes.
                                     6-8
-------
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 which" 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

                                      6-9
-------
process has been much more successful to date, both in terms of destruction of
dioxin, and in terms of cost.  The estimated cost for the batch reactor
process is less, primarily because the chemical reagent can be recovered when
the process is conducted in the laboratory under enclosed and controllable
conditions.  However, when the reagent is added directly to the soil as it is
in the field, it cannot be recovered.  The cost savings associated with the
offsite treatment approach offset the cost of excavation.  In general, an in
situ process is desirable whenever there is a large quantity of contaminated
soil in which the level of contamination is not extremely high ( 10 to 100
ppb).  In these cases the quantity of soil that would have to be excavated to
destroy a small quantity of dioxin may not be justified.

6.1.5  Waste Physical Form

     The physical form of a waste will have a large effect on the choice of an
appropriate  treatment technology.  As indicated  in Table 6.1, the largest
quantity of  dioxin-bearing waste  falls into the  category of  contaminated
soils.  The  second  largest quantity  falls  into the category  of organic
liquids.   These include  still bottoms and  other  process wastes  from  the
           f
manufacture  of  2,4,5-trichlorophenol and chlorophenoxy  herbicides, and non
aqueous phase  leachate  from  the landfilling of waste  from  these manufacturing
processes.   The quantity of  contaminated soil is estimated to  be at  least
500,000 metric  tons (MT),  while the  maximum  quantity  of organic  liquid waste
currently  awaiting  treatment is estimated  to  be  approximately  7,500  MT.
Consequently,  it would be expected that  the  development of technologies  to
treat contaminated soil is much more important  than the development  of
 technologies to treat organic liquids.   Conversely,  the organic liquids  are
 generally contaminated with CDDs and CDFs  to a much higher degree  than are the
 contaminated soils.  In addition, since they are liquids,  their mobility,  if
 released to the environment is higher.   Therefore,  it is important to develop
 technologies to treat both types of waste.
      Several of the technologies are designed to be used specifically for the
 treatment of either solids or liquids.   For solids, these include in situ
 vitrification, infrared incineration,  and stabilization/fixation.   For
 liquids, these include plasma arc pyrolysis,  liquid injection incineration and
                                       6-10
-------
 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
  1
 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 TCDD.   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 characteristics and process capabilities must  be
 carefully evaluated before the appropriate treatment technology  can  be  applied.
                                     6-11
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6.1.6  Pretreatment Versus Final Treatment/Destruction

     Two of the processes in Table 6.3 are not classified as final treatment
processes; e.g., solvent extraction and stabilization/fixation.  Solvent
extraction is potentially a very attractive method of separating CDDs and CDFs
from soil or other waste matrices so that a less voluminous waste stream
containing a higher concentration of contaminant may undergo final
treatment/destruction.  Solvent extraction will always be followed by another
process such as liquid injection incineration or photolysis as was done in the
case of the 4300 gallons of still bottoms at the Syntex plant.  Unfortunately,
solvent extraction has not yet been demonstrated capable of removing CDDs to
residual  levels below 1 ppb.
     Stabilization/fixation is generally a temporary process.  It, like
landfilling, contains the waste, but does not generally involve destruction or
true chemical fixation of the contaminants.  Processes such as this may be
useful in cases where contamination or release rate levels are low.  In the
end, however, it should be recognized that a final treatment/destruction
process,  in which CDDs and CDFs are destroyed, may be required.
 6.2  COST OF TECHNOLOGY

     Another important factor in the  selection of a treatment  technology,
 although not listed in Table  6.3,  is  the cost of treating  the  waste.  Many  of
 the  technologies discussed are innovative technologies  for which accurate
 estimates of treatment costs  have not yet been developed.   In  general,
 however, thermal technologies are the most expensive to use, particularly  for
 certain dioxin wastes such as contaminated soils, since high energy input  is
 required to treat small quantities of contaminants.  In addition, thermal
 technologies generally require the use of expensive equipment  to treat  both
 the  waste  itself and the off  gases and other residuals  that result.  However,
 one  cannot  generalize with respect to thermal technologies either, since there
 may  be a wide  range of costs  depending on the physical  form of the waste and
 the specific technology used.  For example, rotary kiln incineration of
 contaminated soil may cost 800 to 900 dollars/ton, while liquid injection
 incineration of a halogen-containing liquid waste may cost 200 dollars/ton.

                                      6-12  ,
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     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 of a treatment
method, but at this time the demonstration of technical and environmental
effectiveness appears to a more overriding concern.  Technology must 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
DRE 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.

                                     6-13
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                                  REFERENCES

Boyd, James.  Huber Corporation.  Telephone conversations with Lisa Farrell,
     GCA Technology Division, Inc.  January 28, 1986; April 3, 1986;
     May 1, 1986.

Gianti, S.  U.S. EPA Region II.  Telephone conversation with M. Arienti,
     GCA Technology Division,'Inc.  March 6, 1986.

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 the U.S. EPA, Office of Research and
     Development, Hazardous Waste Engineering Research Laboratory, under EPA
     Contract No. 68-03-3267, Work Assignment Nos. 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.

Technical Resources, Inc.  Final Draft Report:  Analysis of Technical
     Information to Support RCRA Rules for Dioxin-containing Waste Streams.
     Submitted to Paul E. des Rosiers, Chairman, U.S. EPA - Dioxin Advisory
     Group.  July 31, 1985.
                                      6-14
                                      . GOVERNMENT PRINTING OFFICE* 1987-748-121/40718
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