United States
          Environmental Protection
          Agency
           Office of Research and
           Development
           Washington DC 20460
EPA/625/7-90/011
November 1990
xvEPA
Approaches for
Remediation of
Uncontrolled Wood
Preserving Sites

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                                   EPA/625/7-90/011

                                   November 1990
    Approaches for Remediation of
 Uncontrolled Wood Preserving Sites
Center for Environmental Research Information
    Office of Research and Development
    U.S. Environmental Protection Agency
           Cincinnati, OH 45268
                                       Printed on Recycled Paper

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                            NOTICE
    This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.

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                                    CONTENTS
Notice	ii
Acknowledgments	iv
Introduction	1
Physical and Chemical Nature of Wood Preserving Compounds	3
Sampling and Monitoring Methodologies to Determine Extent of Contamination	5
Innovative Screening Techniques for Monitoring Wood Preserving Sites	7
Modeling Wood Preserving Compound Movement	9
Treatment Technologies for Recovery, Source Control, and Ground-Water Contamination	11

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                   ACKNOWLEDGMENTS
    This document was compiled by Ed Earth of the Center for Environmental
Research Information, ORD, Cincinnati, Ohio; John Matthews of the RSKERL,
ORD (Ada, Oklahoma); and Ron Wilhelm of OS WER, Washington, DC. Other
major contributors or authors are:
    Don Oberacker, RREL,
    Bob Ambrose, ERL,
    Gary McGinnis
    Ron Sims
    Jeanette Van Emon
Cincinnati, OH
Athens, GA
Forest Products Lab
Mississippi State University
Starkville, MS
Environmental Engineering
Department, Utah State University,
Logan, UT
EMSL, Las Vegas, NV
                                 IV

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                                          INTRODUCTION
    This document provides an overview of the process of
remediation of uncontrolled wood preserving sites. Itis, in part,
a distillation of discussions which took place at a Forum on
Wood Preserving Waste held in San Francisco, California in
October, 1988.  Information from this workshop has been
updated to reflect more recent technological advances.  The
audience is comprised of individuals  with a scientific or an
engineering background who are involved with remediation at
these sites.

    This document emphasizes two important elements of the
wood preserving remediation process: 1) site specific factors
and 2)  multiple technology utilization.  Greater emphasis is
placed  on the  treatment of soils rather than ground water
treatment and containment mechanisms.  The reader is cau-
tioned that some of the soil treatment data presented may be
from only a limited number of studies and may not have
universal application.

    More detailed technical documents regarding the investi-
gation and  evaluation of wood preserving sites are being
developed.  (USEPA, 1990; NETAC, 1990)


References

USEPA, Planning Guide for Selection of Control Technologies
    for Wood Preserving Sites (Draft), Cincinnati, OH(1990).
NETAC, A Technology Overview of Existing and Emerging
    Environmental  Solutions for Wood Treating Chemicals,
    Pittsburgh, Pennsylvania (1990).

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                                 Physical and Chemical Nature of
                                   Wood Preserving Compounds
    Wood preserving compounds are generally of the follow-
ing three types:

        Organic based - creosote
        Organic based - pentachlorophenol (PCP)
        Inorganic based (Metallic salt) - primarily copper/
        chromium/arsenic (CCA)

    The physical and chemical characteristics of these waste
types differ and these differences will influence the sampling,
monitoring, and migration of the wastes as well as the choices
of remediation technologies. Inaddition.anuncontrolledwaste
site may contain wastes from one, two, or all three of the above
waste types.

    The following information is a listing of the compounds
that could generally be found in each class. Even within each
chemical class, the exact physical and chemical characteristics
will vary depending on intended use and supplier (vendor). The
reader is referred to  material safety data sheets (MSDS) for
more accurate information about commercial products.

Organic Based
    A.  Creosote - coal tar distillate mixture of over 250
individual compounds

        35% by weight aliphatic hydrocarbon (oil)
        65% by weight polynuclear aromatic
        hydrocarbons (PAHs)-including:
                 naphthalene
                 acenapthene
                 fluoranthene
                 pyrene
                 chrysene
                 carbozole
        minor compounds may include:
                 nitroquinolenes
    Table 1 lists the major components of commercial grade
creosote and Figure 1 shows the structure of the most prevalent
polynuclear aromatic hydrocarbons in this type of waste.

    Table 2 presents  some of the most important physical
properties of creosote compounds for evaluating waste distri-
bution and treatment options.

    Figure 2 shows the general relationship between the num-
ber of six membered condensed rings and physical and chemi-
cal properties.

    B. Pentachlorophenol (4-8% weight) in heavy oil carrier
mixture also includes tetrachlorophenol used to make PCP
soluble, and "higher" chlorophenols.

    Benzene, toluene, and xylene may be present in the carrier
oil. Mixtures exposed to sunlight may also contain dioxin.

    Figure 3 shows the structure and composition of penta-
chlorophenol and several related compounds.

Inorganic Based (Metallic Salt)
    A.  Copper, chromium, arsenic (CCA)--major group
    B.  Zinc, copper, arsenic
    C.  Ammonia and metal salts
    D.  Dinitrophenol, zinc, and other metal salts

References

Verschueren, K., Handbook of Environmental Data on Organic
    Chemicals, Von Nostrand-Reinhold, New York (1977)
Occupational Health Services, Material Safety Data Sheets
    Database.

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Table J. Major Components of Creosote

Creosote component                 Composition
Naphthalene                          17.0
2-Methylnaphthatene                    
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                           Sampling and Monitoring Methodologies
                             to Determine Extent of Contamination
    The investigation and monitoring of wood preserving
contamination is dependent on site specific factors such as the
chemistry of the wastes at the site and the soil characteristics.

Waste Distribution/Contaminant Behavior
    The migration of contaminants is influenced by factors
such as density and viscosity, pore space, degree of water
saturation, and organic content of the soil at the site (USEPA,
1989).

    Wood preserving waste/ground water interactions may be
classified into three general types depending on the preserva-
tive, carrier oil, and ground water chemistry.

    Immiscible
       Sinker - dense nonaqueous phase liquid (DNAPL)
       Floater - light nonaqueous phase liquid (LNAPL)
    Miscible
       Soluble
    DNAPL will sink by gravity and be located on top of a less
permeable zone. LNAPL will float on top of the water table.
Miscible compounds will be soluble in the ground water.

Chemical Characteristics
    When analyzing air, soil, or liquid for chemical constitu-
ents, one must monitor for compounds from the carrier, manu-
facturing by-products, and environmental by-products as well
as the major wood preserving compounds.

Monitoring Well Materials and  Installation
    Caution must be exercised when developing a monitoring
well so that distinct aqueous layers (LNAPL, DNAPL, ground
water) can be identified. The material comprising the monitor-
ing  well should not chemically interact with  the extracted
liquid.

Reference
USEPA, Transport and Fate of Contaminants in the Subsurface
    (EPA/625/4-89/019) Cincinnati, OH (1989).

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                                Innovative Screening Techniques for
                                 Monitoring Wood Preserving Sites
     Two innovative monitoring methods may be considered
 for use at wood preserving sites.  X-ray fluorescence can be
 utilized on CCA sites and immunoassay techniques can be
 utilized on PCP sites.

 X-Ray Fluorescence
     Field-portable X-ray fluorescence (FPXRF) is a site-
 screening procedure using a small, portable instrument (15-25
 Ibs) that addresses the need for a rapid turnaround, low-cost
 method for  the in situ analysis of inorganic contaminants.
 Traditional Contract Laboratory Program (CLP) methods of
 analysis may take 20-45 days per site to complete and the
 analysis would cost much more than FPXRF. FPXRF can
 measure inorganic elements when used with the proper radio-
 isotope source and the appropriate standards.  FPXRF is ca-
 pable of simultaneous analysis of up to six analytes at a time.
 This method is useful at various levels of analysis, with data
 quality dependent upon the extensiveness of the survey, the
 type of standards used, and the reinforcement of data by other
 collaborator^ methods.  FPXRF can be used for periodic
 monitoring as remediation proceeds.

     The following elements have been successfully analyzed
 by using FPXRF: arsenic, chromium, copper, iron, lead, and
 zinc. Though detection limits are highly matrix dependent and
 site  specific, the detection limits for these elements using
 FPXRF have  ranged from approximately 100-500 mg/kg
 (Raab, et al,  1990).

     X-ray fluorescence is based on  the fact that atoms fluo-
 resce in a unique and characteristic way.  By bombarding a
 sample with energy, the instrument causes an electronic insta-
 bility. As the instability "relaxes" to a more stable energy level,
 X-ray fluorescence is emitted. The detector senses and counts
 this spectrum of radiation which is a "fingerprint" of the specific
 analyte and, on this basis, identifies the atom.  Quantitation is
 done against a calibration curve that was generated  by the
 analysis of site-specific standards.

 Reference
Raab, G.A., R.E. Enwall, W.H. Cole, El, M.L. Faber, and L.A.
    Eccles, X-Ray Fluorescence Field Method for Screening
    of Inorganic Contaminants at Hazardous Waste Sites. In:
    Hazardous Waste  Measurements,  M.  Simmons, Ed.,
    Lewis Publishers, Chelsea, MI (1990).

Immunoassay

    Immunoassay techniques have been applied to the mea-
surement of toxic compounds in the environment.
     Advantages of immunoassays to other monitoring tech-
 niques are their speed, sensitivity, specificity, and cost-effec-
 tiveness. Further, there is no need to sample cleanup prior to
 analysis, which saves solvent costs and minimizes generation
 of hazardous wastes. Immunoassays can be used for analyzing
 a wide variety of  structures. They can be designed either as
 rapid, field-portable, semi-quantitative methods or as standard
 quantitative laboratory procedures. They are well suited for the
 analysis of large numbers of samples and often obviate the need
 for lengthy sample preparation.  They  can also be used to
 identify which samples need to be further analyzed by classical
 analytical chemistry methods,  and they are especially appli-
 cable in situations where the  analysis of an analyte by conven-
 tional methods is not possible or is prohibitively expensive
 (Van Emon, etal, 1990).

     As with any other method, immunoassays have important
 disadvantages. Immunoassays monitoring techniques are only
 applicable for water based samples at this time.  Unlike gas
 chromatography/mass spectrometry (GC/MS), they cannot be
 used when the environmental  sample contains an unknown
 compound or a complex mixture of compounds. In some cases,
 immunoassays may not be  as accurate  and precise as  the
 conventional  analytical procedures.  Because antibodies are
 subject to interferences and cross-reactivity with compounds
 other than the target analyte and must be raised and character-
 ized, more lead time is required of development of immunoas-
 says for monitoring techniques.

    Of particular importance to the characterization and
remediation of a site contaminated with wood preserving
wastes has been the development and successful demonstration
of two immunoassays for pentachlorophenol  in water.  The
demonstrations were conducted under the monitoring and mea-
surement technologies portion of the Superfund Innovative
Technology Evaluation (SITE) Program.   One method dem-
onstrated was  a 96-well plate immunoassay, designed prima-
rily for use in fixed or mobile laboratories. The detection limit
of the plate assay  is about 1 ppb.  The second method was a
field analysis kit  designed  to be used on-site to  generate
qualitative and semi-quantitative data on pentachlorophenol in
water. The detection limit of the field kit is about 30 ppb. Both
methods are commercially available.

Reference
Van Emon, J., M.E. Silverstein, W.D. Munslow, R. White, and
    E.N.  Koglin.  Demonstration of the Westinghonse Bio-
    Analytic Systems, Inc.  Field Immunoassay Method for the
    Analysis  of  Pentachlorophenol in Water  (Draft).
    EnvironmentalMonitoringSystemsLaboratory-Las Vegas,
    U.S. Environmental Protection Agency (1990).

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                      Modeling Wood Preserving Compound Movement
    In order  to assess the risk to human health and environ-
ment from exposure to wood preserving compounds, the move-
ment of waste from its source to a receiving source, such as a
surface stream or fish should be modeled.

    Pentachlorophenol movement through runoff, erosion,
leaching, and ground water transport to a surface stream has
been modeled, and the largest source of uncertainty or error in
this modeling effort  involved the effects of ionization  upon
uptake, the amount of chemical deli vered to the stream from the
site, and the effect  of daily averaging rather than volume
weighted averaging.  Further uncertainty was associated with
complications arising fromPCPbehavior within fish (Ambrose,
et al, 1988). Figure 4 illustrates the contaminant movement in
this modeling effort.

    More sophisticated models could be applied to a wood
preserving site to give better insight into the behavior of the
 wastes.  MTNTEQ-a metal speciation model is capable of
 predicting the different ionic forms of the metals and other
 complexes based on the local geochemistry. HSPF-a whole
 watershed model, which has the capability of simulating both
 land and water bodies simultaneously and could be applied to
 multiple and large scale wood preserving sites.

     Indicator compounds would need to be selected if model-
 ing creosote movement because of the difficulty of modelling
 several compounds.

 Reference

 Ambrose, E., et al.  Modeling the Transport and Fate of Wood
     Preserving Wastes in Surface Waters. Proceedings of the
     Forum on Wood Preserving Waste, San Francisco, CA
     (1988).
       Log Processing
       Area
Bloaccumulation
                                                                                      Q (dilution)
             Figure 4. Contaminant Migration from Modeled Wood Preserving Site
                                                     9

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                               Treatment Technologies for Recovery,
                      Source Control, and Ground-Water Contamination
Multiple Technology Utilization
    Most  uncontrolled wood preserving sites contain con-
taminated soils and ground water. Remedial processes for both
of these problems should be considered together.  In most
instances,  the technologies required for source control treat-
ment (involving liquid, sludges, or soil) would differ from
those required for ground water treatment. An exception to this
may be in situ biorestoration for organic contamination.  In
addition, source control measures may require combinations of
unit processes (the treatment train approach) to achieve accept-
able cleanup levels or to meet cost effectiveness criteria. This
is especially true if the site contains both metallic salts and one
of the organic classes (an exception may be vitrification). Table
3 shows several options for single technology use or treatment
train operations for various types of source control contami-
nants.

    The contaminant behavior of creosote waste lends itself to
innovative treatment concepts. Unfortunately, there are limita-
tions on treatment processes for CCA waste because metals can
not be destroyed and have different solubilities at varying pHs.

Preliminary  Screening  Methodology  for
Determining Feasible Alternatives
    Preliminary evaluation of the treatability of wood preserv-
ing surface water or extracted ground water constituents can be
made by utilizing existing software containing treatability data
from traditional treatment processes (USEPA, 1989). Innova-
tive processes such as ion exchange are also being utilized to
recover metals from groundwater contaminated  with CCA
(Hickey and Stevens, 1990).

    Soil remediation processes can also be evaluated from the
literature or from the performance of bench scale treatability
studies. The reader is referred to a more complete guide for
evaluating soil treatment technologies  (USEPA, 1988). The
soil/contaminant matrix must first be understood when  evalu-
ating potential treatment technologies. Figure 5 illustrates the
distribution of soil constituents.  The  contaminants may  be
found in any of the soil constituents.

    The soil texture or particle  size is useful in determining
whether the contaminant would be tightly bound  to the soil.
Leaching or partitioning tests can also  be utilized for this
purpose. S tabilization technology can be evaluated by compar-
ing the leachability of the soil before and after treatment.

    The following partitioning coefficients between  the fluid
and solid can be used to determine the migration potential and
treatment of potential of a constituent:
        Kow - water/oil (general literature)
        Kd - water/soil (site specific)
        Kh - water/air (general literature)


    Partitioning coefficients are beneficial in evaluating ex-
traction technologies or air stripping. A retardation coefficient
relates the relative velocity (V) of a constituent to water.

        R = y water
           V constituent

    The higher the retardation coefficient, the less likely it is
that the constituent will migrate in water. Therefore, retarda-
tion coefficients are useful in evaluating pump and treat tech-
nologies.

    The relative biodegradability of a substance can be evalu-
ated by placing the material  (slurry) in a container with or
without microbial addition and determining the degradation
over time. Air and nutrients may also be introduced.  A
complete mass balance including the volatilization pathway is
vital for performing feasibility evaluation.

    British Thermal Units (BTUs) data can be used to measure
the incinerability  of the material.  The heating value of a
compound may also be useful in this evaluation and can be
found in  the literature.  Heating  value determination is also
important when evaluating vitrification because hood systems
may be limited by the amount of heat generated.
Recovery: Pump and Treat Systems
    Nonaqueous phase liquid (NAPL) compounds such as
creosote may be recoverable if the compound is present in
concentrations above residual saturation. Normal recovery
methods involve flow path management by several methods.
NAPL moves in response to pressure gradients and gravity. The
movement and recovery is influenced by interfacial tension and
by the process of volatilization and dissolution.  Over 7,000
gallons of a coal tar liquid containing naphthalene and anthra-
cene were recovered from a site by a well recovery system
(Villaume, et al, 1983).  Two hundred fifty thousand gallons of
creosote were recovered in a drainage line system at a different
site (Union Pacific Railroad,  1989).

    Recovery operations become less efficient if the NAPL
compounds sorb to the soil formation. The extraction flow rate
during remediation may be too rapid to allow aqueous satura-
tion levels of the partitioned coefficient to be reached locally.
This will result in large volumes of extracted ground water with
low levels of contaminant concentration.
                                                      11

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 Table 3,   Technology Options for Source Control
 Contamination


  Metallic salts


  Creosote or PCP
  Metallic salts
    and Creosote
         or
  Metallic salts
    andPCP
Single Unit Operation

  Stabilization
  Vitrification

  Incineration
  Vitrification
  In situ biorestoration
  Land treatment
  Vitrification
          Treatment Train
Soil Washing  —> Stabilization
Soil Washing  —» Biotreatment
Incineration    » Stabilization
Soil Washing  —*•  Biotreatment  —* Stabilization
Land Treatment  —* Stabilization
                     Fluid
                      Soil Constituents
                                                            Soil Texture
            Figure 5. Distribution of soil constituents, contaminant may be found in any or all constituents
     The required data for evaluating the recoverability of the
material and predicting the time for restoration can be found in
the literature (USEPA, 1990).

Bioremediation

    On-site biological treatment is generally accomplished
using one of three types of systems: (1) in situ, (2) prepared bed,
or(3)biorcactor. An in situ system consists of treating contami-
nated soils in place, often with the use of naturally occurring
microorganisms to treat the contaminants.  In some instances,
supplemental populations of adapted organisms may serve to
enhance treatment. In aprepared bed system, the waste may be
                                   either physically moved from its original  site to a newly
                                   prepared area, which has been designed to enhance biological
                                   treatment and/or to prevent transport of contaminants from the
                                   site; or removed from the site to a storage area while the original
                                   location is prepared for use, then returned to the bed, where the
                                   treatment is accomplished.  Bioreactor systems typically are
                                   based on reactor designs from  chemical or environmental
                                   engineering processes and may be either unsaturated (e.g.,
                                   composting) or saturated (e.g., slurry).

                                       Before implementing a biological remediation technology
                                   for a soil contaminated with wood preserving waste, an evalu-
                                   ation of the potential of the contaminated system to accomplish
                                                         12

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detoxification and degradation of hazardous constituents present
in the waste should be conducted.  Preliminary treatability
studies can be used to evaluate detoxification and degradation
processes as they affect the fate and behavior of hazardous
constituents in a contaminated waste or soil.  Treatability
studies can provide specific information that can be used to
determine migration (leaching) potential; correlate chemical
disappearance with changes in bioassay response;  compare
treatment of different wastes under similar experimental condi-
tions; and evaluate approaches for enhancing treatment. Persis-
tent hazardous constituents that occur as co-substrates, (e.g.,
high molecular weight PAHs in wood preserving waste), in a
matrix where other hydrocarbons are serving as readily avail-
able growth substrates may be degraded through the process of
co-oxidation (Foster, 1962a,b), (Keck, et al.,1989).

    Factors that may be evaluated in laboratory and field
studies to enhance biological treatment, including degradation
and detoxification, include: (1) soil incorporation or mixing to
reduce the initial (toxic) concentration; (2) application of waste
more frequently and at lower concentrations to acclimate soils
to toxic  complex wastes and to avoid application of toxic
concentrations; (3) addition of mineral nutrients; (4) addition of
microbial carbon and energy sources to stimulate co-oxidation;
and (5) use of different soil types as the treatment medium.

    There have been few published studies concerning wood
preserving wastes in which bioassays have been combined with
chemical assays to evaluate the extent of both detoxification
and degradation of hazardous substances in soil systems and to
characterize the toxicity of potential leachates.  Chemical
analyses may be used to define the types and concentrations of
hazardous compounds in a waste or soil, but the results must be
extrapolated to estimate the toxicological effects on biological
systems (Donnelly, et al., 1986).

    Apparent degradation, expressed as changes in concentra-
tions of PAH constituents for creosote sludge and pentachloro-
phenol (PCP)-creosote mixed sludge in a sandy loam soil are
presented in Tables 4,5, and 6 (Aprill, et al., 1990). Generally,
results indicated greater apparent degradation for low molecu-
lar weight PAHs, which are non-carcinogenic, and less appar-
ent degradation for high molecular weight PAHs, which are
carcinogens or co-carcinogenic. The group of non-carcino-
genic PAHs, including naphthalene, fluorene, phenanthrene,
and anthracene, were compared with the group of carcinogenic
and co-carcinogenic  PAHs, including fluoranthene,  pyrene,
benzo(a)anthracene, and chrysene  with regard to apparent
degradation.  Results are summarized in Table 4.   Greater
apparent degradation was indicated for the non-carcinogenic
group, ranging from 54-90% of mass added for the four wastes
evaluated. The carcinogenic group of PAHs exhibited apparent
degradation ranging from 24-53% of mass added for the four
wastes. The greater apparent degradation of the non-carcino-
genic PAH was not unexpected, since these compounds serve
as carbon and energy sources for soil microorganisms, whereas
the carcinogenic PAHs generally cannot serve as ubiquitous
carbon and energy sources for soil microorganisms but are
believed to be degraded through co-oxidation processes (Park
1987a,b), (Keck,etal., 1989).

    Significant degradation of PCP and creosote compounds
was observed in a pilot-scale treatment train process consisting
of soil washing, aqueous treatment system and slurry bioreactor
(Ellis and Stinson, 1990).

    The integration of information concerning apparent degra-
dation of hazardous constituents of complex wastes with bioas-
say information represents an approach for evaluation of the
effectiveness ofbiological treatment of wood preserving wastes.
When combined with information from site and soil character-
ization studies, the data generated in treatability studies may be
used in predictive mathematical models to evaluate the effec-
tiveness ofbiological treatment for a specific site scenario and
to develop appropriate containment and monitoring strategies.
Incineration

    Organic wood preserving waste (creosote and PCP) are
amenable to incineration because of the organic structure and
heating value of the compounds.  Inorganic wood preserving
mixtures are not as amenable to incineration because  some
metals may be emitted during the combustion process. There-
fore mixtures of organic and inorganic waste  may require an
additional treatment train.

    Tables 7, 8, 9, and 10 contain incineration performance
data for organic wood preserving compounds or similar waste
types.  These data indicate that incineration was effective in
destroying or removing the compounds tested.

    Table 11 shows that some dioxins and furans were emitted
from the incineration stack. It is believed that these pollutants
were not completely destroyed because temperatures below
1800° F were prevalent in this particular incinerator.

    One processing problem that may occur with soil contami-
nated with wood preserving waste is the initial materials han-
dling operation.  Incompatible equipment design may cause
problems such as dusting or feed stock processing jams.
                                                       13

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 Table 4. Apparent Degradation of PAH Constituents* in Creosote Sludge in Unacclimated Kidman Sandy Loam Soil.
                                                                                          Waste/soil
                                     Initial waste              Initial waste/soi I          concentration
                                     concentration              concentration             at day 354
 PAtt constituents                   faigfcg^jvastef)            (me ke'Lsoiin
Naphthalene
Fluorene
Phenanlhrene
Anthracene
Fluoranthcnc
Pyrene
Bemo(a)anlhracene
Chrysene
28,000 ±
23, 000 ±
76,000 ±
15. 000 ±
72,000 ±
64, 000 ±
7,400 ±
8300 ±
1200*
5,900
15,000
6,800
17,000
12,000
1,600

      273.0 ±
      177.0 +
      833.0±
      243.0 ±
      567.0 ±
      573.0 ±
       52.5 ±
       50.5 ±
 11.5
 23.0
110.0
 11.5
  5.8
  0.7
  1.0
      n.d.§
  72.1 ±    18.9f
 500.0 ±    P8.5
 131.0 +
 397.0 ±
 353.0±
  36.0 ±
                                35.1 ±
 52.0
 90.7
 76.4
   8.0
   8.0
   Decrease
during incubation
      (%}

      100
       59
       40
       46
       30
       38
       31
       30
          Results are presented for eight PAH compounds, which represent 96% of the mass of the 14 PAHs analyzed in the waste sample
          Results are presented on a dry weight of waste or soil basis
          Results are expressed as mean concentration of three replicate analyses +. one standard deviation
          nd. snot detected (from Aprill, 1990)
Table 5.  Apparent Degradation of PAH Constituents* in PCP-Creosote Mixed Sludge in Unacclimated Kidman Sandy Loam Soil.

                                                                                         Waste/soil
                                     Initial waste              Initial waste/soil           concentration              Decrease
                                    concentration               concentration              at day 354             during incubation
PAH constituents                   (my k<> •' waste?}             fmg kg -' soill")            fmg kg -' soil f)               (%)
Naphthalene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Bemo(a)anthracene
Chrysene
42,000 ±
22,000**
52,000 ±
11,000 ±
46,000 ±
56,000 ±
16,000 ±
6,900 ±
28,000*

6200
6,800
6200
13,000
2,400
2200
       49.2 ±
      120.0 ±
       69.4 +
       73.3 +
      143.0 ±
       14.0 ±
       20.7 ±
             n.d.§
  1.7*
  0.0
  72
 63.5
  5.8
  1.6
  1.8
        n.d.~
  1.6+    1.8t
  42 ±    0.8
 17.5 ±    5.4
 55.3 ±
353.0 ±
 10.9 ±
 14.2 ±
14.7
76.4
 1.5
 1.7
      97
      97
      75
      25
      74
      22
      31
     *    Results are presented for eight PAH compounds, which represent 96% of the mass of the 14 PAHs   analyzed in the waste sample
     t    Results are presented on a dry weight of waste or soil basis
     #    Results are expressed as mean concentration of three replicate analyses + one standard deviation
     I    n.d. s not detected
     * *   One sample was analyzed (from Aprill, 1990)
Table 6. Apparent Degradation of'Four Non-carcinogenic andFour Carcinogenic PAHCompounds in Four ComplexWastes in Unacclimated Kidman Sandy
        Loam Soil During 354 Days Incubation
PAlt Group

Non-carcinogenic
         Initial concentration (mg kg'1)
         Final concentration (mg kg'1)
         Mass removed (%)

Carcinogenic
         Initial concentration (mg kg'1)
         Final concentration (mg kg'1)
         Mass removed (%)
  Creosote
   sludge
.7,527 ±  750
  703 ±  154
    54
1243 ±   19
  821 ±  183
    34
    PCP-creosote
     mixed sludee
        239+   9
         23+   8
           90
       251+  64
       118±  47
           53
                                                                (from Aprill, 1990)
                                                                    14

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 Table 7. Incineration Trial Burn Data on PCP
 Test Facility:


 Waste Description:
 Waste Analysis:

 Results:

 Waste Feed Rates:
 Incineration Conditions:
  Los Alamos National Laboratory, (DOD) Controlled Air Incinerator by Environmental Control
  Products, Model 500-T (Nominal 500 LbsJHr.),
  with Minor Modification to Factory Unit.
  Korean War-Vintage Army Ammunition Boxes Treated with Pentachorophenol (PCP), Crushed
  Chlorine Content -0.07 Percent by Weight; PCP Content - 0,103 to 0.106 Percent by
  Weight; Pine Wood with 7960  (Actual) and 9066 (dry) BTUILb
  DREfor PCP was Greater than 99.99% - No TCDD in Stack Emissions (Del. Limit 1 PPB).
  No TCDF in Stack Emissions(Det. Limit 5 PPB), Ash - Not Sampled and Analyzed
  60-100 LbslHr.
  1800 • F for a Gas Residence  Time of 15 Seconds

  (from USEPA, 1984)
Table 8. Data on Incinerating Wood Preserving Wastes
Test Facility:                            EPA Combustion Research  Facility Rotary Kiln,  Summer, 1987
Waste Description:
Analysis:
Results:
  K001 - Pentachlorophenol (PCP)  Type. Allied Chemical's American Wood Division of Timber
  Company, Richton Mississippi. Bottom Sediment/Sludge from Waste-water Treatment Containing
  PCP (including Penta  - and  Tetrachlorophenols, Volatile Organic Solvents, e.g., Benzene,
  Toluene, and Polynuclear Aromatic (PNA) Parts of Creosote)
  Soil                        40%
  Water                       30%
  Wood Chips                 10%
  Active Organics              20%
                              100%
                                        Ash Content

                                        Heating Valve
                                        PCP
                              12-51%

                              3800-8300 BTUILB.
                              970-3800 PPM
                                        Non-Detectable for all Priority RCRA Volatile and Semi-Volatile Compounds in
                                        Ash and in  Scrubber Water (Including DioxinslFurans)
                                        (from USEPA, 1988a)
Table 9. Data on Incinerating Wood Preserving Wastes
Test Facility:                          John Zink Company Rotary Kiln
Waste  Description:
Analysis:
Results:
K001-C  (Creosote Type)
Allied Chemical's Birmingham, Alabama Plant, Bottom, Sediment Sludge from
Treatment of Wastewaters from Processes using Creosote, This Material Obtained from the Pearl
River Wood Preserving Corporation, Picayune, Mississsippi
Soil
Water
Wood Chips
Naphthalene
Phenanthrene
Fluoranthene
Other Active Organics

Ash Content
Heating Value
Volatile Matter
                                                                            30.0%
                                                                            20.0%
                                                                            10.0%
                                                                            4.0%
                                                                            3.5%
                                                                            2.5%
                                                                            30.0%
                                                                          100.0%
                                                                           12-51%
                                                                           10,000-11,000 BTUILB.
                                                                           57-81%
                                      Non-Detectable for all Priority RCRA Volatile and Semi-Volatile Compounds in
                                      Ash and in Scrubber Water (Including DioxinslFurans), Stack Testing Results
                                      Not Available
                                      (from USEPA, 1990a)

                                                                  15

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TABLE 10.   Summary Results of Test Burn on Simulated Creosote  Pit Waste
Tat Conditions:                        Waste Feed Rale -121.0 Ib/hr in the Shirco Portable Pilot Test Unit
         Waste Analysis (% wl) -
         Operating Conditions -
     POIfC  ANALY7ED
     Pentachlorophenol
     Phenol
     2,4-Dimethylpltenol.
     Indeno (123-CD) Pyrene
     Bento (B) & (K) Fluoranthene
     Bemo (A) Pyrene
     Benzo (A) Anthracene/Chrysene
     Naphthalene
     Acenapihene
     Acenapthylene
     Fluorene
     Anlhracene/Phenanthrene
     Ftouranthene
     Pyrene

     'ORE calculated at detection limit
      Measured Particulate Grain Loading:
     (Corrected to 7% O})
Creosote
Pentachlorophenol
Water
Inert Dry Soil
Residence Time
Layer Thickness
Primary Chamber Temps
Secondary Chamber Temp
               Gas Phase
                Analysis
              >99.9999
              >99.9995
              >99.9999
              >99.9820
              >99.9999
              >99.9985
              >99.9999
                99.9998
                99.9999
                99.9999
                99.9999
                99.9999
                99.9998
                99.99995
                Total ppm

            0.010 grldscf
                                            (from Berdine, 1987)
         22.20%
          0.85%
          7.71%
         69.24%
        15.00 min.
          1.00 in.
       1612/1725'F
            2189°F
      Residual Ash
        Analysis
         (ppm)
          ND
          ND
          ND
         0.030
         0.120
         0.137
          ND
         0248
          ND
          ND
          ND
         0.403
         0362
         0.164
         1.464
Table 1L Incineration Dala by EPA's Tier 4 National Dioxin Study 1986-87
Tea Facility:                               Industrial Controlled Air Incinerator with Waste Heat Boiler
Waste Description:                          Paint Fillers and Dry Paint, Paint Sludge, and Wood /Plastic
Results;
Incinerator Temperatures:
    Scrap Material from Manufacture ofPCP-Treated Wood/
    PVC Plastic Coated Storm Windows, Wood Framing Treated with 0.1 LblFt3 PCP
    For an Average Feed rate of 2390 LblHr to the Incinerator:
    Total PCDD Emissions:
    2,3,7,8 TCCD
    Total PCDF Emissions:
    Ash Analyses:

    Total PCDD:
    2,3,7,8 TCCD
    Total PCDF:
    Primary Chamber:
    Secondary Chamber:
    (from  USEPA,  1987)
                                                                  1370 Micrograms/Hour (Stack)
                                                                  8.62   Micrograms/Hour (Stack)
                                                                  4600 Micrograms/Hour (Slack)
1TO302.6PPB
ND to 02
0.07 To 17.7 PPB
1100 TO 1800 °F (Avg. 1392 °F)
940 to 1820 °F (Avg. 1480 °F)
                                                                 16

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Soil Washing/Soil Flushing/Extraction

     Soil washing and extraction technologies are used to sepa-
rate contaminants from the host matrix.  These systems com-
monly utilize an extractant, a separation stage, and produce a
more concentrated waste and also less contaminated residuals.

     Onsite soil washing systems are likely to cause volume
reduction of hazardous material by separating coarse material
from fine material. Soil washing systems have been evaluated
for metal contaminated  soils (Esposito, et. al, 1989), although
their effectiveness for CCA waste  has not been evaluated.
They have also been evaluated and are commercially available
for their use as a pretreatment step in biological treatment of
creosote waste.

     The effectiveness of in-situ soil flushing systems for or-
ganic wood preserving and similar compounds is currently
being evaluated at several uncontrolled waste sites.

     Extraction systems can separate creosote or PCP waste
from contaminated soils. In a batch pilot scale test at the United
Creosote site, over 95% of the total PAH was removed from
untreated soil (Table 12). PCP removals  were 85%. Removal
efficiencies for dioxins and dibenzo furans were not as substan-

 Table 12.  Summary of Results for Solvent Extraction

                                        Untreated Soil             Treated Soil
                                           (mg/kg)                 (mg/kg)
 Compound                             Sample/Duplicate          Sample/Duplicate

 PAHs (mg/kg)
 Acenapthene                               360/200
 Acenaphthylene                             15J/8.6J
 Anthracene                                330/210
 Benzo(A)Anthracene                         100/56
 Benzo(A)Pyrene                             48/24J
 Benzo(B)Fiouranthene                        51/24J
 Benzo(G,HJ)Perylene                         20J/11J
 Benzo(K)Flouranthene                        50/28J
 Chrysene                                   110/59
 Dibenzo(A,H)Anthracene                     ND/370
 Flouranthene                               360/270
 Flourene                                  380/220
 Indeno(l,2,3-CD)Pyrene                       19J/10J
 Naphthalene                                140/69
 Phenanthrene                               590/450
 Pyrene                                    360/220

 Total PAH Conc.(mg/kg)                     2,879/2,124

 Pentachlorophenol (mg/kg)                     380/210

 Dioxins (mg/kg)
   Total TCDD                           ND(0.4)/NA
   Total PeCCD                            ND(2)/NA
   Total HxCCD                              16/NA
   Total HpCDD                             360/NA
   Total OCDD                             1300/NA
 Dibenzofurans (mg/kg)
   Total TCDF                            ND(0.2)/NA
   Total PeCDF                              1/NA
   Total HxCDF                             30/NA
   Total HpCDF                             160/NA
   Total OCDF                              160/NA
 ND = Not Detected (Detection Limit in Parentheses)

 J   = Estimated Value - The Result is Less than the Detection Limit but Greater than
      Zero (Detection Limit in Parentheses)
 NA = Not Analyzed (not part of sampling plan)

                                                   (from Litherland, 1990)
                                                         17
tial; however, the initial concentrations of these compounds
were low.

     In a bench scale study designed to extract chromium from
a contaminated soils from a mining operation, 64% of the total
chrome and 93% of chrome (VI) were extracted utilizing acid.
The original concentration of total chrome was 1467 mg/kg and
700 mg/kg of chrome (VI)  (Taylor, et al., 1990)

    Limitations on the process would be the efficiency and
costs of the extraction process to produce a clean material as
well as disposal or reuse of the extracted material.

Dechlorination
    Chemical dechlorination processes have been developed
and pilot-tested for chlorinated organic compounds. The gen-
eral chemical equations for this process are:

        ROH +KOH —> ROK +Hf)

        ArCln + ROK«->ArCln_1 OR + KC1

        (R = organic)
        (Ar = aryl)
     3.4J/3.3J
     3.0J/2.9J
      8.9/9.1
     7.9/7.6J
      12/11
      9.7/13
      12/12
      17/11
      9.1/9
     4.3J/4.4J
      11/11
     3.8J/3.8J
      11/11
     1.5J/1.5J
      13/13
      11/10

     123/110

      58/52
     ND/NA
     ND/NA
     4.8/NA
     180/NA
     690/NA

    0.015/NA
     2.6/NA
     18/NA
     75/NA
     87/NA
                         Water
                         (mg/L)
ND(0.12)
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND
  ND

   0

 0.470J
  NA
  NA
  NA
  NA
  NA

  NA
  NA
  NA
  NA
  NA
              Removal
95.7

84.7
68.8
50.0
46.9
40.0
53.1
45.6

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    Apentachlorophenol/bil waste from the Montana Pole site
was treated by a dechlorination process. Table 13 show that
reductions in the chlorine content of specific classes of com-
pounds occurred. Table 13 shows 2,3,7,8 reduction in another
study.  Table 14 shows 2, 3, 7, 8 reduction in another study
involving dechlorination processes.
                                                                  In another laboratory test utilizing KPEG for treating a
                                                              wood preserving slurry, 97% of the PCP and 59% of the total
                                                              PAHs were removed (Table 15). Dioxin removal was higher
                                                              although some initial values were low.

                                                                  Several technical considerations must be addressed when
                                                              evaluating this technology such as air emissions and toxicity of
                                                              residual by-products.
TABLE 13. Results of Laboratory Tests on PCPIOil Waste front Montana Pole Site
CDD/CDFin
Treated and
Untreated
 Waste


TCDD(2378)
TCDD (total)
PeCDD (total)
HxCDD (total)
1/pCDD (total
OCDD
TCDF(2378)
TCDF (total)
PeCDF (total)
HxCDF (total)
1/pCDF (total)
OCDF

'"ND" indicates "none detected" in excess of the minimum detectable concentration (MDC) indicated.

                                                     (from Tiernan, et al., 1989)
Untreated
Waste
OIL

282.
422.0
822.0
2982.0
20671.0
83923.0
23.1
147.0
504.0
3918.0
5404JO
6230.0
Following KPEG Following KPEG
Treatment at Treatment at
70 °Cfor 100°Cfor
15 Minutes 15 Minutes
Concentration in Parts-Per-Billion (ppb)"
ND
ND
ND
ND
11.2
65
12.1
33.3
ND
4.9
5.8
ND

ND
ND
ND
ND
225
4.40
ND
ND
ND
ND
ND
ND
                                                                                             Average
                                                                                            MDC (ppb)
                                                                                               0.65
                                                                                               037
                                                                                               0.71
                                                                                               2.13
                                                                                                028
                                                                                                0.35
                                                                                                030
                                                                                                0.76
                                                                                                1.06
                                                                                                2.62
                   Time (Hours) Following
                      KPEG Treatment'
TABLE 14. Results of Laboratory Tests of KPEG Reagent on Kent, Washington Wastes
                                                 Concentration of 2,3,7,8-TCDD (ppb)
                                                      in Treated Waste Sample
                            &                                120"                            ;
                            5.5                                 5.5
                            6.5                                 2.5
                           12.0                             ND (0.3)
•A 250-g aliquot of the waste was treated with 25g KOH, followed by 75g KPEG and 25g dimethyl sulf oxide at a temperature of 1 15°C.
'Refers to the original waste, prior to treatment.
                                                     (from Tiernan, et al., 1989)
Table IS. Dechlorination Summary Results Concentration (mg/kg)
Ptmmelcr
Towl PAH's
Pcnuchlorophcnol
Dioxins
  TCDD
  PCDD
  HxCDD
  HpCDD
  OCDD
                                    Untreated           Treated          Reduction
                                      Soil                Soil             £%}
                                     1746               721               58.7
                                     1100                31               97.2

                                       0.004            <0.0003           92+
                                       0.011            <0.0004           96+
                                       0.692            <0.0003           99+
                                       5.280b           <0.0004           99.99+
                                      16.400B           <0.0008           99.99+

                                                    (from Litherland, 1990)
                                                            18

-------
 Immobilization

     Immobilization technologies have been widely considered
 for the treatment of metals contaminated soils and sludges.
 They do not destroy the metal but decrease the leaching rate to
 an  acceptable level  by chemical reaction and surface area
 reduction. The effectiveness of these processes will be defined
 by the waste type, the binder utilized, and the leaching test that
 applied as the criterion.

     Immobilization technologies include solidification/stabi-
 lization and vitrification. The term solidification suggests the
 conversion of a liquid or a semi-solid into a solid. Many waste
 materials are amenable to solidification. The term stabilization
 refers to a chemical reaction that decreases teachability. Not all
 waste can be successfully  stabilized.  For metal waste treat-
 ment, both terms can be used, but this is not true for many
 organic wastes. Solidification/Stabilization is aresiduals man-
 agement technique that can be used as part of a treatment train
 when organics and metals are both present.

     Vitrification is a high-temperature thermal process that
 converts  sludges or soils into an obsidian-like material and
 pyrolyzes organic compounds.

     Metal waste solidification/stabilization has been demon-
 strated to be generally effective for reducing the leachability of
 several metals as evaluated by the TCLP test in the EPA's
 S.I.T.E. program and B.D.A.T.  program.  Stabilizing  CCA
 waste is more  difficult because the minimum solubilities of
 each metal is at a different pH value. Table 16 shows solidifi-
 cation/stabilization treatment data for a synthetic Superfund
 soil. Copper was successfully immobilized but variable results
 were obtained for arsenic whereas chromium data was incon-
 clusive. Variable results  for stabilization treatment of arsenic
 and chromium from wood preserving waste are also shown in
 Tables 17 and 18. Although these results are generally unsat-
 isfactory, chrome reduction and arsenic reactions with sulfide
 or iron may increase the  effectiveness of the stabilization
 process.

     There have been  several successful bench scale demon-
 strations of the vitrification process for reducing the leachabil-
                                     ity of waste containing several metals.  Arsenic may be incor-
                                     porated into the melt instead of being  volatilized (Timmons,
                                     1990).

                                         Regardless of which immobilization process is evaluated,
                                     several leach tests beyond the regulatory tests are encouraged.
                                     Both of these processes can be implemented in situ.

                                         Soh'dification/stabUizationhasnotbeenconclusivelyproven
                                     to be effective for organic waste.  Many organic compounds
                                     such as oil and grease can interfere with cementacious  reac-
                                     tions (USEPA,  1989a).  Regulatory acceptance levels have
                                     been based on destruction processes  such as incineration.
                                     These levels are based on a strong extraction test using meth-
                                     ylene chloride or hexane. In general, pozzolonic material will
                                     not form a strong bond with organic compounds and will not
                                     meet cleanup criterion.

                                         Recent research with organophilic (organic modified)
                                     clays has shown promise for reducing organic leaching because
                                     of strong bonding or reaction between the binder and waste
                                     (Soundararajan,et.al, 1990, and Sell, et.al, 1990). Polynuclear
                                     compounds and PCP have been treated with orgnaophilic clays.
                                     Table 19 shows that destruction levels were met for three of the
                                     four compounds evaluated. In another study with actual PCP
                                     waste,  reduction in the total waste analysis and TCLP were
                                     noted after stabilization with three vendors, although dilution
                                     was not considered (Table 20). Evidence of dechlorination of
                                     polychlorinated compounds has been observed in other studies
                                     but has not been evaluated in detail.

                                        The evaluation of, organophilic clays needs to go beyond
                                     regulatory testing techniques to include Fourier Transform
                                     Infrared spectrophotometry (FTTR) and mass balances. Engi-
                                     neering controls to minimize ground water contact are also
                                     suggested.

                                        Vitrification destroys organic materials by pyrolysis. The
                                     technology may be limited by the moisture content because of
                                     increased energy requirements and total organic concentration
                                     because of capture hood thermal limitations.

                                        Alternatively, recovery mechanisms such as smelting may
                                     eventually be applicable for CCA waste.
Table 16. Solidification/Stabilization Treatment Data for Synthetic Soils (TCLP Test)
                                   Raw faig/1')
ND - Non Detectable
Metal

 As
 Cd
 Cr
 Cu
 Pb
 Ni
 Zn
                Treated

 6.4,9.6          ND.ND
33.1,35.3         ND.ND
 ND, .06          .07, .07
80.7,10.0         .09, .17
19.9,70.4         ND, .37
17.5,26.8         ND, ND
359,396          .69, .74

             (from USEPA, 1988b)
                                                        19

-------
Table 17. Solidification/Stabilization Treatment Data for CCA Waste
                              E.P.Tox(mg/l)
            Element           Raw          Treated                 Binder
           Chromium          90             16.0             cement/silicate
                              90              0.5             potassium silicate
                              90            150.0             proprietary
                              90             13.4             portland cement
                              90              4.1             portland cement
            Arsenic
1.8
1.8
1.8
1.8
1.8
                                             2.3             cement/silicate
                                             0.01            potassium silicate
                                             3.0             proprietary
                                            13.8             portland cement
                                             4.3             portland cement

                                                          (from Conners, 1990)
Table 18. Solidification/Stabilization Treatment Data for CCA Waste
Compound
Arsenic
Chromium
Copper
EP.Tox(mg/l)
Raw
1.8
98.4
13.6
                                                             Treated
                                                            Vendor 2

                                                               1.4

                                                              12.4

                                                               4.7

                                                            •(from Weston, 1988)
                                      8,582

                                     18,060
                                     20,184
                                     30,460
Table 19. Solidification/Stabilization Treatment Data for Organic Waste
                                 Mean Cone.                    Mean Cone.
                                in Raw Waste                in Stabilized Waste
Com pound

Bis-2-chloro-isopropyl
  ether
iN'splhalcnc
Phcnanihrene
Bcnzo(a)anthraccnc

"Not Detected
'Value corrected for dilution
                                       ND'

                                      1,445"
                                       ND'
                                       ND'
                                                        (from Soundaarajan, et al, 1990)



 Table 20. Solidification/Stabilization Treatability Study Results for POP Waste

         Ttst Method                     Untreated                   Treated
 Total Waste Analysis (tnglkg)
 TCLP (ugll)
              521
             13,000
                                                      Vendor 1
                                                        150
                                                        190
Vendor 2
   34
  2700
Vendor 3
   51
  230
                                                           (fromEBASCO, 1990)
                                                                     20


-------
 References

 Aprill, W., R.C. Sims, J.L. Sims, and J.E. Matthews, Assessing
     detoxification and degradation of wood preserving and
     petroleum  wastes  in  contaminated   soil. Waste
     Management and Research, 8:45-65,1990.
 Berdine, S., Hazardous Waste Treatment Capabilities of the
     Shirco  Infrared Mobile Waste Processing System,
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 Conner, J., Chemical Fixation and Solidification of Hazardous
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 Donnelly, K.C., P. Davol, K.W. Brown, M. Estiri, and J.C.
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 Esposito, P., et. al., Results of Treatment of a Contaminated
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 Foster, J.W.,  Bacterial oxidation of  hydrocarbons.  In
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 Keck, J., R.C. Sims, M.  Coover,  K. Park,  and B. Symons,
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    hydrocarbons in soil. Water Research, 23 (12): 1467-1476,
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 Litherland, S., Treatment of Wood Preserving Waste Using
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Park, K.,  Degradation and  Transformation of  Polycyclic
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    Dissertation,  Department of  Civil and Environmental
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Park, K., R.C. Sims, W.J. Doucette, and J.E.  Matthews.
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Sell, N., et. al., Solidification  and Stabilization of Phenol and
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     Waste, American Society for Testing Methods, 1990.
 Soundararajan, R., Earth, E., et. al., Stabilization of Organic
     Waste Utilizing an   Organophilic   Clay, Hazardous
     Materials Control Journal, Volume 3, No. 1,1990.
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     Conference on Innovative Hazardous  Waste'Treatment
     Technologies, Philadelphia, PA, 1990.
 Tiernan, T., et.al., Laboratory and Field Tests to Demonstrate
     the Efficacy  of KPEG Reagent  for Detoxification of
     Hazardous Wastes ContainingPolychlorinated dibenzo-p-
     dioxins (PCDD) and dibenzofurans (PCDF) and Soils
     Contaminated with Chemical Wastes. Chemosphere, Vol.
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 Timmons, D., et al., Vitrification Tested on Hazardous Waste,
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    68-03-3482,1988.
                                                     21

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