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.
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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
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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.
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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)
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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
-------
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
-------
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
-------
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,
Proceedings of Third International Hazardous Materials
Management Conference, Long Beach, California, 1987.
Conner, J., Chemical Fixation and Solidification of Hazardous
Waste, Van Nostrand Reinhold, New York, New York,
1990.
Donnelly, K.C., P. Davol, K.W. Brown, M. Estiri, and J.C.
Thomas, Mutagenic activity of two soils amended with a
wood-preserving waste. Environmental Science and
Technology, 21:57-72,1986.
EBASCO, Coleman Evans Treatability Study, EPA Contract
68-01-7250,1990.
Ellis, W.D. and M. Stinson, S.I.T.E. Demonstration of a Soil
Washing System by BIOTROL at a Wood Preserving Site
in New Brighton, Minnesota. Presented at the American
Institute of Chemical Engineers' National Meeting, San
Diego, CA, 1990.
Esposito, P., et. al., Results of Treatment of a Contaminated
Synthetic Soil, Journal of Air Pollution Control
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Foster, J.W., Bacterial oxidation of hydrocarbons. In
Oxygenases (Hayaishi, O., ed.) Academic Press, Inc.,
New York, 1962b.
Foster, J.W., Hydrocarbons as substrates for microorganisms.
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Serology, 28:211-274,1962a.
Hickey, T. and Stevens, D., Recovery of Metals from Water
Using Ion Exchange, Proceedings of Second Forum on
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EPA/540/2-90/010, Philadelphia, Pennsylvania, 1990.
Keck, J., R.C. Sims, M. Coover, K. Park, and B. Symons,
Evidence for cooxidation of polynuclear aromatic
hydrocarbons in soil. Water Research, 23 (12): 1467-1476,
1989.
Litherland, S., Treatment of Wood Preserving Waste Using
Innovative Techniques. Proceedings of Wood Preserving
Waste Treatment Forum, Forest Products Laboratory,
Mississippi State University, 1990.
Park, K., Degradation and Transformation of Polycyclic
Aromatic Hydrocarbons in Soil Systems. Ph.D.
Dissertation, Department of Civil and Environmental
Engineering, Utah State University, Logan, Utah, 1987.
Park, K., R.C. Sims, W.J. Doucette, and J.E. Matthews.
Biological transformation and detoxification of 7,12-
dimethylbenzanthracene in soil systems. Journal Water
Pollution Control Federation, 60:1822-1825,1988.
Sell, N., et. al., Solidification and Stabilization of Phenol and
Chlorinated Phenol Contaminated Soil, Proceedings of
Second International Symposium on Stabilization/
Solidification of Hazardous, Radioactive, and Mixed
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.
Taylor, M., J. Wentz, and E. Earth, Chromium Recovery and
Stabilization, Abstract Presented at Second Forum
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.
18,1989.
Timmons, D., et al., Vitrification Tested on Hazardous Waste,
Pollution Engineering Journal, Volume 22, Number 6,
1990.
Union Pacific Railroad, Milestone III Report, Union Pacific
Laramie Tie Plant, In Situ Treatment Process
Development Program, 1989.
USEPA, Controlled Air Incineration of Pentachlorophenol
Treated Wood, EPA/600/S2-84-089, Cincinnati, Ohio,
1984.
USEPA, National Dioxin Study-Tier4-Combustion Sources,
Final Report- Test Sites 2, EPA/540/4-84/014k, Research
Triangle Park, North Carolina, 1987.
USEPA, Technology Screening Guide for Treatment of
CERCLA Soils and Sludges, EPA/540/2-88/004,1988.
USEPA, Pilot Scale Incineration of Wastewater Treatment
Sludges from Pentachlorophenol Wood Preserving
Processes, Final Report, EPA Contract 68-03-3267,
Cincinnati, Ohio, 1988a.
USEPA, Evaluation of Solidification/Stabilization as a Best
Demonstrated Available Technology for Contaminated
Soils, Hazardous Waste Engineering Research Lab,
Cincinnati, Ohio, 1988b.
USEPA, Water Engineering Laboratory Treatability Database,
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Stabilization, Hazardous Waste Engineering Research Lab,
Cincinnati, Ohio, 1989a.
USEPA, Basics of Pump and Treat Ground Water
Remediation Technology (EPA/600/8-90/003), 1990.
USEPA, Incineration of CreosoteandPentachlorophenol Wood
Preserving Wastewater Treatment Sludges, EPA/600/S2-
89/060, Cincinnati, Ohio, 1990a.
Villaume, et al., Recovery of Coal Gasification Wastes: An
Innovative Approach, Proceedings of Third National
Conference on Aquifer Restoration and Ground Water
Monitoring, Columbus, OH, 1983.
Weston, Palmetto Woods Treatability Study, EPA Contract
68-03-3482,1988.
21
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