EPA/600/2-88/055
September 1988
CHARACTERIZATION AND LABORATORY SOIL TREATABILITY
STUDIES FOR CREOSOTE AND PENTACHLOROPHENOL
SLUDGES AND CONTAMINATED SOIL
by
Gary D. McGinnis
Hamid Borazjani
Linda K. McFarland
Daniel F. Pope
David A. Strobe!
Mississippi Forest Products Utilization Laboratory
Mississippi State University
Mississippi State, Mississippi 39762
Project CR-811498
Project Officer
John E. Matthews
Robert S. Kerr Environmental Research Laboratory
P.O. Box 1198
Ada, Oklahoma 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ADA, OKLAHOMA 74820
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
SPRINGFIELD. V*. 22161
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
RTNO.
600/2-88/055
2.
IfNT'S ACCESSION NO.
9 10 99 2 QMS
6 AND SUBTITLE
CHARACTERIZATION AND LABORATORY SOIL TREATABILITY
STUDIES FOR CREOSOTE AND PENTACHLOROPHENOL SLUDGES
AND CONTAMINATED SOIL
5. REPORT DATE
September 1988
6. PERFORMING ORGANIZATION CODE
H. Borazjani, L.K. McFarland, D.F. Pope
and D.A. Strobel
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND ADDRESS
Mississippi Forest Products Utilization Laboratory
I Mississippi State University
Mississippi State, MS 39762
10. PROGRAM ELEMENT NO.
CBWD1A
11. CONTRACT/GRANT NO.
CR-811498
12. SPONSORING AGENCY N/VME AND ADDRESS
Robert S. Kerr Environmental Research Lab. - Ada, OK
U.S. Environmental Protection Agency
Post Office Box 1198
Ada, OK 74820
13. TYPE OF REPORT AND PERIOD COVERED
- Report. (1 Q/a7-Q6/flfl )
14. SPONSORING AGENCY CODE
EPA/600/15
15. SUPPLEMENTARY NOTES
Project Officer: John E. Matthews, FTS: 743-2333
16'-ABSffff(Ji''mat1on is presented from characterization and laboratory treatability phases
of a 3-phase study pertaining to on-site treatability potential of soils containing
hazardous constituents from wood-treatment waste (EPA-K001). Specific information
contained includes: 1) literature assessment of soil treatability potential for wood
«ing chemicals; 2) sludge/soil characterization data for 8 wood treating sites;
) degradatjon/toxicity data for wood treating chemicals in soils from 4 sites.
terature data indicated that creosote/PCP waste constituents may be treatable in
soil. Each sludge characterized contained the PAH constituents; relative concentratior
of individual compounds varied among sludges. PCP sludges contained PCP, OCCD, and
traces of hepta/hexa dioxins and corresponding furans.
PAH's with 2 rings generally exhibited half lives < 10 days. Three ring PAH's
generally exhibited longer half lives < 100 days. Four or five ring PAH's exhibited
half lives >^ 100 days; in specific cases, some 4 or 5 ring PAH's exhibited half lives
< 10 days. PCP half lives varied from 20 to > 1000 days in different soils. PCP was
transformed slowly in soils with no prior long term exposure to PCP. Microbial plate
counts used in this study did not appear to be closely related to transformation rates
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDEIMTIFIERS/OPEN ENDED TERMS c. COSATI Field/Croup
18. DISTRIBUTION STATEMENT
TO THE PUBLIC.
19. SECURITY CLASS (Tills Report)
21. NO OF PAGES
liL
20. SECURITY CLASS (This page)
UNrLASSIFTEn.
22. PRICE
EPA Fofm 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
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NOTICE
The information in this document has been funded wholly or in part
by the United States Environmental Protection Agency under Cooperative
Agreement CR-811498 with Mississippi State University. It has been
subjected to the Agency's peer and administrative review, and it has
been approved for publication as an EPA document. Mention of trade
names or commercial products does not constitute endorsement or
recommendation for use.
ii
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ABSTRACT
This report presents information from the first two phases of a three-
phase study pertaining to on-site treatability potential of soils containing
hazardous constituents from wood-treatment waste (EPA-K001).
Phase I studies involved: (1) developing a soil treatability database
from the literature for creosote and pentachlorophenol wood treating chemicals,
«
and (2) obtaining baseline data on qualitative and quantitative distribution
of wood treating chemicals contained in samples of contaminated soils and
sludges collected at eight wood treating sites located in the southeastern
United States. Phase II studies involved developing soil transformation,
soil transport, and toxicity information for selected wood treating solution
constituents identified in these samples. Phase III studies currently underway
nvolve comprehensive field evaluation of soil treatability of creosote and
pentachlorophenol waste constituents at one of the eight sites studied in
Phases I and II.
This report contains:
1. A literature assessment of soil treatability potential for wood
treating chemicals;
2. Sludge and soil characterization data for eight wood treating
sites; and
3. Treatability information pertaining to degradation and toxicity
of wood treating chemicals in soils from four of the sites.
The literature assessment indicated that creosote and pentachlorophenol
waste constituents may be treatable in soil. Each of the eight K001 sludges
characterized contained the PAH class of semivolatile constituents; however,
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relative concentrations of individual PAH compounds varied among different
sludges. PCP sludges contained pentachlorophenol , octachlorodibenzo-p-dioxin
(OCDD), and traces of hepta and hexa dioxins and the corresponding furans.
PAH's with two rings generally exhibited half lives less than ten days.
Three ring PAH's generally exhibited longer half lives in most cases, but
less than one hundred days. Four or five ring PAH's exhibited half lives
of one hundred days or more; however, in specific cases, particular four or
five ring PAH's exhibited half lives less than ten days. PCP half lives
varied from twenty days to over a thousand days in different soils. PCP
was transformed very slowly in soils with no prior long term exposure to
PCP.
Low concentrations of OCDD apparently were transformed slowly in three
of the four soils tested. In the soil that had previous long term exposure
to PCP, OCDD exhibited a half life less than one hundred days even at the
highest concentration tested. However, results were variable, and more in-
formation must be obtained before a definite conclusion can be made on OCDD
transformation rates in soils.
Microorganism population counts of the type used in this study did not
appear to be closely related to transformation rates.
vi
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TABLE OF CONTENTS
PAGE
Notice ±i
Foreword ii±
Acknowledgments iv
Abstract v
List of Figures. . • viii
List of Tables . ix
1. Introduction 1
Objectives 2
Evaluation Approach 2
Waste Characterization 5
Soil Characterization 6
Waste Loading Rate Determination 6
Waste Treatment in Soil 7
2. Conclusions 9
3. Literature Review 10
Introduction 10
Wood-Preserving Industry 12
Characteristics of the Organic Wood Preservatives. ... 13
Characteristics of Wood-Preserving Waste 21
Decomposition/Immobilization of PCP and Creosote
Components in Soil 27
Bioaccumulation/Toxicity of PCP and Creosote 46
4. Experimental Section 57
Introduction 57
Site Selection Criteria 57
Site, Soil, and Sludge Characterization 58
Laboratory Treatability Studies 59
5. Results and Discussion 60
Site and Soil Characterization 60
Laboratory Transformation/Degradation Studies 77
References 110
Appendix 119
Summary 138
vii
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LIST OF FIGURES
FIGURE PAGE
1. Principal cuts produced in coal-tar distillation .... 20
2. Proposed route for decomposition of
pentachlorophenol 29
3. Proposed mechanism for the microbiological
degradation of anthracene 39
4. Bacteria counts from all eight sites at 1% and
0% loading rates after the final addition of the
standard mixture ........ 80
5. Acclimated bacteria counts from all eight sites
at 1% and 0% loading rates after the final addition
of the standard mixture 81
VI 1 1
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LIST OF TABLES
TABLE PAGE
1. Volume of wood commodities treated in 1978 12
2. Comparison of composition of commercial grade and
purified grade pentachlorophenol 15
3. Chlorodioxin isomer distributions in commercial grade
PCP (Dowicide 7) and PCP-Na samples 15
4. Physical properties of PCP .* 17
5. Chemical composition of a United States and a German
creosote. 19
6. Physical properties of creosote and its fractions ... 22
7. American Wood-Preservers' Association specifications
for creosote-coal tar solutions 23
8. Properties of 16 priority pollutant PAH compounds ... 24
9. Daily discharge of creosote wastewater pollutants by
the wood-preserving industry 28
10. Degradation of pentachlorophenol in soil 34
11. Kinetic parameters describing rates of degradation of
PAH and phenolic compounds in soil systems 41
12. Toxicity of various dioxin isomers to experimental
animals 52
13. Health effects of chemical constituents of creosote . . 54
14. Site location in Major Land Resource Areas 61
15. Overall field evaluation site soil composition 62
16. Soil concentration of PCP at the proposed field
evaluation sites 68
17. Soil concentration of PAH's at the proposed field
evaluation sites 69
18. Soil concentration of octachlorodibenzo-p-dioxin at
the proposed land treatment sites 70
19. Microbial plate counts at proposed field evaluation
sites 71
1x
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TABLE PAGE
20. Nitrogen and phosphorous at the eight selected sites. . 71
21. Characteristics of the eight sites used in this
study ........ 73
22. Composition of the sludges e . . . 74
23. Chemical composition of the sludges 74
24. Concentration of PCP and total PAH's in each sludge
sample. ...... 75
25. Concentration of creosote and PCP in sludges from the
selected sites. ...«,. 76
26. Minor components present in sludge 78
27. Concentration of metals in each sludge sample ..... 79
28. Kinetic data for PAH degradation/transformation in
Gulfport soils 82
29. Kinetic data for PAH degradation/transformation in
Columbus soils . . . . 83
30. Kinetic data for PAH degradation/transformation in
Grenada soils ...... 84
31. Kinetic data for PAH degradation/transformation in
Chattanooga soils 85
32. Kinetic data for PAH degradation/transformation in
Wilmington soils 86
33. Kinetic data for PAH degradation/transformation in
Meridian soils 87
34. Kinetic data for PAH degradation/transformation in
Atlanta soils .., 88
35. Kinetic data for PAH degradation/transformation in
Wiggins soils 89
36. Kinetic data for PCP degradation/transformation in
site soils 90
37. Kinetic data for PAH degradation/transformation in
Columbus soils 92
38. Kinetic data for PAH degradation/transformation in
Grenada soils 95
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TABLE PAGE
39. Kinetic data for PAH degradation/transformation in
Meridian soils 98
40. Kinetic data for PAH degradation/transformation in
Wiggins soils 101
41. Kinetic data for PCP degradation/transformation in
site soils 104
42. Kinetic data for OCDD degradation/transformation in
site soils 105
*
43. Starting and peak microbe counts 106
xi
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SECTION 1
INTRODUCTION
Land Treatment is the hazardous waste management technology
pertaining to application/incorporation of waste into the upper layers
of soil for the purpose of degrading, transforming, and/or immobilizing
of hazardous constituents contained in applied waste (40 CFR Part 264).
Land treatment systems have been used for a variety of industrial
*
wastes; however, application of hazardous industrial waste using a
controlled engineering design and a management approach has not been
widely practiced. This is due, in part, to the lack of a comprehensive
technical information base concerning the behavior of hazardous
constituents as specifically related to current regulatory requirements
(40 CFR Part 264) concerning the treatability in soil, i.e.,
degradation, transformation, and immobilization, of such constituents.
Soil treatment systems that are designed and managed based on a
knowledge of soil-waste interactions may represent a significant
technology for treatment and ultimate disposal of selected hazardous
wastes in an environmentally acceptable manner.
In this research project, representative hazardous waste (K001)
from wood-preserving processes was evaluated for potential treatment in
soil systems. A literature assessment was conducted as an aid in the
prediction of the treatment potential for this type of waste in soil.
The literature assessment also was used as a guide to design an
experimental approach to obtain specific treatability -information
pertaining to degradation, transformation, and immobilization of
hazardous constituents in soil.
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OBJECTIVES
The overall objective of this study is to evaluate the efficacy of
land treatment as an on-site management alternative for contaminated
soil and sludges containing pentachlorophenol and creosote from wood-
treating plants. This project involves three phases: a characterization
phase, a treatability screening phase, and a field evaluation phase.
1. Characterization Phase. The characterization phase involved
obtaining baseline data on the qualitative and quantitative distribution
of wood-treating chemicals contained in representative samples of
contaminated soils and sludges collected at eight wood-treating plants
located in the southeastern United States. Samples of soil and sludges
from each site were collected and characterized using scientifically
documented physical and chemical procedures.
2. Treatability Screening Phase. This phase involved laboratory
evaluations of the treatment potential of creosote and pentachlorophenol
sludges and contaminated soil collected from each selected site.
3. Field Evaluation Phase. The final phase of this project
involves a field evaluation study at one of the eight selected sites.
This phase is currently in progress.
EVALUATION APPROACH
Standards for demonstrating treatment of hazardous wastes in soil
are promulgated in 40 CFR Part 264.272 . The standards require
demonstration of degradation, transformation, and/or immobilization of a
candidate waste in the treatment soil. Demonstration of
degradation/transformation of waste and waste constituents is based on
loss of parent compounds within the soil/waste matrix. "Complete
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3
degradation" is the term used to describe the process whereby waste
constituents are mineralized to inorganic end products, generally
including carbon dioxide, water, and inorganic species of nitrogen,
phosphorus, and sulfur. The rate of degradation/transformation may be
established by measuring the loss of parent compound from the soil/waste
matrix with time. "Transformation" refers to partial degradation in the
soil which converts a substance into an innocuous form, or which
converts wastes into environmentally safe forms (Huddleston et al.,
1986). Ward et al. (1986) also discussed the difference between rates
of mineralization (for complete degradation) and rates of biotransform-
ation. "Immobilization" refers to the extent of retardation of the
downward transport, or "leaching potential," and upward transport, or
"volatilization potential," of waste constituents. The mobility
potential for waste constituents to transfer from the waste to water,
air, and soil is affected by the relative affinity of the waste
' constituents for each phase, and can be characterized in column and
;
' batch reactors. Therefore, demonstration of soil treatment requires an
: evaluation of degradation, transformation, and immobilization processes,
i and the quantification of the processes for obtaining an integrated
5 assessment of the design and management requirements for successful
assimilation of a waste in a soil system.
I The requirement for demonstrating treatment, i.e., degradation,
transformation, and/or immobilization, can be addressed using several
approaches. Information can be obtained from several sources, including
literature data, field tests, laboratory analyses and studies,
theoretical parameter estimation methods, and, in the case of existing
land treatment units, operating data. Information presented in the
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Literature Review of this report addresses information obtained from the
literature. Specific information obtained from literature sources
includes quantitative degradation, transformation, and immobilization
information for waste-specific hazardous constituents in soil systems.
The two organic hazardous waste types from the wood-treating industry--
creosote sludge and pentachlorophenol sludge--are considered.
At this time the U.S. EPA (1986b) considers the use of information
from the literature only to be insufficient to support demonstration of
treatment of hazardous wastes in soil. A laboratory experimental
approach used during this project for obtaining additional data
concerning soil treatability for the two hazardous wastes selected for
study is presented.
The regulations also require that the effect of design and
management practices on soil treatment be evaluated. Design and
management practices specifically identified in the regulations include
waste application rate (loading rate) and frequency of waste
application.
The experimental method used in this study compared the rates of
degradation of selected components in creosote and pentachlorophenol
using eight soil types. Initial studies used a standard mixture of
technical grade creosote^ and pentachlorophenol (standard mixture) in
order to compare each site using a common waste. Further studies were
done to determine the rate of degradation of sludges from each site in
(.ho soil at tho site.
lor each hazardous waste and soil type selected, treatment was
evaluated as a function of waste loading rate and* time. Chemical
analyses over time were used to characterize treatment effectiveness.
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The experimental approach described above was used to determine
whether the hazardous waste could be degraded in each selected soil
type, to determine how-
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PAH's. For this study, the amounts of pentachlorophenol and
octachlorodibenzo-p-dioxin in pentachlorophenol sludges were used as the
key parameters.
SOIL CHARACTERIZATION
Eight wood treating sites located in the southeastern United States
were selected for study. Sites were selected having a variety of soil
types in order to determine how the rates of degradation are affected by
factors in the soil, such as the organic carbon and clay content. The
eight soil types selected are characterized in detail in Soil
Characterization.
WASTE LOADING RATE DETERMINATION
Loading rate (mass/area/application, or mg waste/kg soil) was the
first design parameter evaluated. To evaluate the extent and efficacy
of treatment, it is necessary to ensure that bacteria capable of
utilizing wood treatment chemicals as substrates exist in the soil.
The evaluation of the impact of hazardous wastes on indigenous soil
microbial populations is important, especially for these wastes, which
contain hazardous constituents specifically designed to inhibit
biological activity.
The microbial assay used in this study involved plate counting of
*
colony forming units. This was done using a variety of media in order to
determine the number of acclimated fungi, actinomycetes, and bacteria in
each site soil in the presence of wood-preserving waste.
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WASTE TREATMENT IN SOIL
| The degradation potential of organic hazardous constituents in
I waste applied to soil is critical since degradation usually represents
Is the primary removal mechanism for these constituents. The basis for
£
! biodegradation coefficient measurements was the determination of soil
; concentrations of specific constituents as a function of time. In order
to compare data using different soil types and concentrations, a first
order kinetic rate for the process was used.*The first-order reaction-
rate constant was used to calculate half-lives for each parameter. The
half-lives calculated provided quantitative information for evaluating
the extent and rate of treatment, and for comparing treatment
effectiveness for each waste/soil combination as a function of design
and management factors. Results and discussion concerning degradation
of four of the K001 wastes selected for study are presented in the Waste
Degradation Evaluation. It should be noted that the use of first-order
kinetics was done to compare the rates at various sites and does not
necessarily mean that the particular compound was undergoing a first-
order reaction at a particular site.
According to current regulations, a hazardous waste cannot be
applied to land unless hazardous constituents contained in the waste are
reduced in toxicity as a result of treatment. Therefore, conversion of
hazardous constituents to less toxic intermediates within the soil
treatment medium currently is under evaluation. Information concerning
the toxicity reduction in each waste/soil combination is being evaluated
using results from an acute toxicity assay (Microtox assay) as the
measurement criteria. Results from the toxicity reduction experiments
will be presented in a subsequent report.
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Evaluation of treatment also involved an investigation of the
extent of migration of each hazardous waste. A loading rate based on
biodegradation potential was selected for each soil/waste combination
using data generated in an earlier study (Sims et al.s 1987). The
leaching potentials are being characterized for these loading rates in
laboratory soil-column studies. Results from the column experiments
also will be presented in a subsequent report.
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*
I
SECTION 2
CONCLUSIONS
Specific conclusions based on results of this research project to date
include:
1. Creosote and PCP wood treating waste contaminants can be
transformed in soil systems; however, loading rates and
previous exposure of the soil to particular types of waste
are important factors in site-specific transformation rates
for individual contaminants.
2. Higher molecular weight PAH compounds and PCP usually are
transformed more slowly than lower molecular weight PAH's;
all of these compounds can be transformed more rapidly under
good site management conditions.
3. Populations of PAH and PCP acclimated microorganisms can be
expected to increase markedly when these compounds are applied
to soil; however, population counts of the type used in this
study are not closely related to transformation rates for
these compounds.
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10
SECTION 3
LITERATURE REVIEW
INTRODUCTION
Treatment in soil systems may represent a significant engineering
method for control/treatment and ultimate disposal of selected hazardous
constituents in applied waste. Land application for the assimilation
and treatment of hazardous constituents is a potentially significant
cost-effective, environmentally safe, low energy technology that has
been successfully used for a multitude of domestic and industrial
wastes. Soil systems for treatment of a variety of industrial wastes,
including food processing, organic chemical manufacturing, coke
industries, textiles, and pulp and paper have been utilized for many
years (Overcash and Pal, 1979). However, Phung et al. (1978) reported
that routine application of industrial hazardous wastes onto the soil
surface and incorporation into the soil for treatment is not widely
practiced, except for the oil refining industry. There are few
definitive data in the literature, quantifying treatment rates in
full-scale soil treatment systems (Huddleston et al., 1986).
Land treatment is defined in RCRA as "the hazardous waste
management technology pertaining to application and/or incorporation of
waste into the upper layers of the soil in order to degrade, transform,
or immobilize hazardous constituents contained in the applied waste" (40
CFR Part 264, Subpart M). Land treatment also has been defined as "a
controlled application of hazardous wastes onto or into the aerobic
surface soil horizon, accompanied by continued monitoring and
fc
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11
management, in order to alter the physical, chemical, and biological
state of the waste via biological degradation and chemical reactions in
the soil so as to render such waste nonhazardous" (Brown et al., 1980).
The current regulatory requirement for demonstrating treatment,
i.e., degradation, transformation, and/or immobilization of hazardous
waste constituents in soil systems, can be addressed using several
approaches. Information concerning each treatment component can be
t?
obtained from several sources including literature data, field tests,
laboratory studies, laboratory analyses, theoretical parameters,
estimation methods, and, in the case of existing land treatment units,
operating data (40 CFR Part 264.272). It is suggested that a
combination of data sources be utilized; e.g., literature data,
laboratory analyses, laboratory studies and field verification tests; to
strengthen confirmation of hazardous constituent treatment efficiency.
The availability and completeness of existing literature data influences
the need for further collection of performance data. The U.S. EPA
considers the use of only literature data to be insufficient to support
a demonstration treatment at the present time.
In this project, hazardous waste from eight wood-preserving sites
was used to evaluate the land treatment potential of these types
of waste in various soil types. A comprehensive assessment of
literature available for both waste types, pentachlorophenol and
creosote, was conducted as an aid in making these evaluations.
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12
WOOD PRESERVING INDUSTRY
Introduction (Burdell. 1984)
Wood preserving in the United States is a hundred-year-old
industry. Wood is treated under pressure in cylinders with one of four
types of preservatives: 1) creosote, 2) pentachlorophenol in petroleum,
3) water solutions of copper, chromium, and arsenic (CCA), and 4) fire
retardants.
The 1978 volume of wood commodities treated is shown in Table 1
(USDA, 1980).
Table 1. Volume of wood commodities treated in 1978.
Product
Crossties, switch
ties, and land-
scape ties
Poles
Crossarms
Piling
Lumber and
timbers
Fence posts
Other products
Total (1980)
Creosote sol
103,138
18,237
41
9,993
10,780
4,584
7,815
154,587
Volume treated
utions Penta
___ i nnn m •?+•
449
41,905
1,615
1,154
21,209
10,983
2,681
79,996
with
Inorganic saltsa
•
2,498
4,038
29
943
73,317
4,461
7,616
92,903
aThe main inorganic salts are copper, chromium, and arsenic.
About 99% of the creosote solutions, 90% of the penta, and all of
the arsenical salts in the preceding tabulation are applied by pressure
methods in closed systems. A small amount of creosote and about 3.8
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13
million pounds of penta are applied by commercial thermal and dip
treatment methods in open tanks.
Basic Wood-Treating Process
The basic oil-preservative wood-treating cycle begins by placing
either seasoned or green wood into a pressure cylinder. If green
materials are used, they can be artificially seasoned in the cylinder
with steam and either oil preservative or hydrocarbon vapor. Then an
initial air pressure (vacuum or positive pressure) is introduced into
the system. Next the preservative is pumped into the cylinder and the
pressure increased until a predetermined liquid volume is absorbed into
the wood. The pressure is released and the preservative is pumped back
into the tanks. A final vacuum is applied to remove most of the free
liquid on the surface.
The organic preservative most used is coal tar creosote, a by-
product from the production of coke from coal. When coal tar is
distilled, the 200° to 400°C fractions are creosote. Creosote is
mostly aromatic single to multiple ring compounds. Over 200 different
components have been identified in creosote.
Pentachlorophenol dissolved in No. 2 fuel oil carrier is the second
most common organic wood preservative. Technical grade PCP is about 85
to 90% pure PCP plus various levels of other chlorinated phenolic
compounds.
CHARACTERISTICS OF THE ORGANIC WOOD PRESERVATIVES
The two major organic wood preservatives used in the United States
are pentachlorophenol (PCP) and creosote.
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14
Technical-grade PCP used for treating wood contains 85 to 90% PCP.
The remaining materials in technical grade PCP are 2,3,4,6-
tetrachlorophenol (4 to 8%), "higher chlorophenols" (2 to 6%), and
dioxins and furans(0.1%). The tetrachlorophenol is added to PCP to
increase the rate of solubilization.
The other contaminants found in technical-grade PCP are formed
during manufacture. In the United States PCP is manufactured from
phenol by a catalytic chlorination process. During chlorination, the
temperature must be maintained above the melting point of the products
formed; this, it is felt, contributes to the side reaction that gives
rise to contaminants, including traces of trichlorophenol, chlorinated
dibenzo-p-dioxins, chlorinated dibenzofurans, chlorophenoxy phenols,
chlorodiphenyl ethers, chlorohydroxydiphenyl ethers, and traces of even
more complex reaction products of phenol. Chlorodibenzodioxins and
furans are the by-products about which there are the greatest concerns.
Analyses of PCP have revealed that the principal chlorodibenzodioxin and
chlorodibenzofuran contaminants are those containing six to eight
chlorines. The highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
has not been identified in any sample of PCP produced in the United
States that has been analyzed (USDA 1980). The composition of a sample
of commercial PCP and of a sample of purified PCP is given in Table 2.
A representative distribution of isomers is given in Table 3 (U.S. EPA
1978).
The physical properties of a compound play an important role in how
the compound behaves under different conditions. These properties
i"
influence the mobility of a compound in air or water, its ability to
adsorb to surfaces, and its susceptibility to degradation. These
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15
Table 2. Comparison of composition of commercial grade and purified
grade pentachlorophenol (U.S. EPA 1978).
Component
Pentachlorophenol
Tetrachlorophenol
Trichlorophenol
Chlorinated phenoxyphenols
Octachlorodioxin
Heptachlorodioxins
Hexachlorodioxins
Octachlorodibenzofuran
Heptach lorodibenzofurans
Hexachlorodibenzofurans
^Sample 9522A.
bTechnical grade PCP purified
Tables. Chlorodioxin isomer
Analytical
Commercial3
(Dowicide 7)
88.4%
4.4% .
0.1% *
6.2%
2500 ppm
125 ppm
4 ppm
80 ppm
80 ppm
30 ppm
by distillation.
distributions in
results
Purifiedb
(Dowicide EC-7)
89.8%
10.1%
0.1%
15.0 ppm
6.5 ppm
1.0 ppm
1.0 ppm
1.8 ppm
1.0 ppm
commercial grade PCP (Dowicide 7)
and PCP-Na samples (Buser
1975, 1976).
Chlorodioxin
1,2,3,6,7,9-C16D
1,2,3,6,8,9-C16D
1,2,3,6,7,8-C16D
1, 2,3,7, 8,9-Cl60
1,2,3,4,6,7,9-C17D
1,2,3,4,6,7,8-C170
1,2,3,4,6,7,8,9-C18D
PCPa PCP-Nab
(ppm) (ppm)
1 0.5
3 1.6
5 1.2
0 0.1
63 16.0
171 22.0
250 110.0
aDowicide 7 (commercial PCP).
bSodium salt of PCP.
-------
16
factors are important because they relate to the route and rate of
exposure by which a compound might be received by man or other
organisms. Some of the selected physical properties of pentachloro-
phenol are given in Table 4.
Pentachlorophenol is quite stable. It does not decompose when
heated at temperatures up to its boiling point for extended periods of
time. Pure PCP is considered to be rather inert chemically (Bevenue and
Beckman, 1967). The chlorinated ring structure tends to increase
stability, but the polar hydroxyl group tends to facilitate biological
degradation (Renberg, 1974). It is not subject to the easy oxidative
coupling or electrophilic substitution reactions common to most phenols.
All monovalent alkali metal salts of PCP are very soluble in water, but
the protonated (phenolic) form is virtually insoluble. Hence, transport
of PCP in water is related to the pH of the environment.
Pentachlorophenol is moderately volatile and a closed system should
be used when heating environmental samples or recoveries will be poor
(Bevenue and Beckman, 1967). By contrast to other chlorinated organic
compounds of low vapor pressure, PCP can be lost from soils by
volatilization (Briggs, 1975).
Creosote
*•
The other major organic wood preservative used in the United States
is creosote. Creosote, in contrast to PCP, is a very complex mixture of
organic compounds produced from coal.
At least 200 chemical compounds have been identified in creosote.
Although the chemical composition of this material varies for reasons
discussed above, it is generally agreed that creosote contains several
-------
17
Table 4. Physical properties of PCP (Crosby 1981; Bevenue
et al. 1967).
Property
Value
Empirical formula
Molecular weight
Melting point
Boiling point
Density
pKA (25°)
Partition coefficient (Kp), 25°
Octanol-water
Hexane-water
Vapor pressure, Torr (mm hg)
0°C
20°C
50°C
100°C
200°C
300°C
Solubility in water (g/L)
0°C
20°C
30°C
50°C
70°C
Solubility in organic solvents
(g/lOOg solvent]
in methanol 20°C
in methanol 30°C
in diethylether 20°C
in diethylether 30°C
in ethanol 20°C
in ethanol 30°C
in acetone 20°C
in acetone 30°C
in xylene 20°C
in xylene 30°C
in benzene 20°C
in benzene 30°C
in carbon tetrachloride 20°C
in carbon tetrachloride 30°C
C6C15OH
255.36
190°C
293°C
1.85 g/cc
4.7(7-4.80
1760 ,
1.03 x 10*
10
1.7 x
1.7 x
3.1 x 10
0.14
25.6
758.4
0.005
0.014
0.020
0.035
0.085
57
65
53
60
47
52
21
33
14
17
11
14
2
3
10'5
-4
-3
-------
18
thousand different compounds which could be identified with 6C/MS. Most
of these are present in very small amounts. The major components
of a typical creosote of U.S. origin and one of German origin
are shown in Table 5. There are some rather striking differences
between the two types of creosote in the levels of particular polycylic
aromatic hydrocarbons and in the overall levels of total PAH's.
The greater part of the composition of creosote consists of neutral
fractions. Tar acids, such as phenol and the cresols, as well as such
tar bases as pyridenes, quinolines, and acridines, constitute a rather
small percentage of the total weight of creosote.
A schematic of the distillation processes is presented in Figure 1.
Creosote is a blend of the various distillates designed to impart
specific physical characteristics that meet standards of the American
Wood-Preservers' Association (AWPA).
Compared to the starting material, the yield of fractions that are
blended to make creosote ranges from 25 to 40%, depending upon the point
at which distillation is terminated. Both the yield and the chemical
and physical properties of the various fractions are influenced by the
characteristics of the coal from which the tar originates, the type of
equipment used in the distillation process, and the particular process
used.
There were 64 producers of coal tar in the United States in 1972
and 24 tar distillation plants producing creosote (U.S. EPA, 1975).
Because their chemical composition and properties are not uniform,
creosote and blends of creosote and coal-tar are normally described in
f
terms of their physical properties. American Wood-Preservers'
Association specifications for creosote for various uses are given in
-------
19
Table 5. Chemical composition of a United States and a German creosote.
Compound or component
Naphthalene
Methyl naphthalene
Diphenyl dimethylnaphthalene
Biphenyl
Acenaphthene
Dimethylnaphthalene
Diphenyloxide
Dibenzofuran
Fluorene-related compounds
Methyl fluorenes
Phenanthrene
Anthracene
Carbazole
Methy 1 phenan threne
Methyl anthracenes
Fluoranthene
Pyrene
Benzofluorene
Chrysene
Total
U.S. creosote3
3.0
2.1
--
0.8
9.0 ,
2.0
—
5.0
10.0
3.0
21.0
2.0
2.0
3.0
4.0
10.0
8.5
2.0
3.0
90.4
German creosote13
7.3
4.2
3.2
—
4.1
~
3.4
—
9.6
—
12.6
—
—
5.4
—
6.8
5.0
4.6
2.8
69.0
al_orenz and Gjovik, 1972.
"Becker, 1977.
-------
20
Coal Tar
1
CD
mmmm
^••B
£3
GO
1
Pitch
.Chemical
Oil
_Top-of-
Column Oil
_ Uncorrected
Creosote Oil
-Heavy Oil
Figure 1. Principal cuts produced in coal-tar distillation.
-------
21
Table 6. Similar standards have been promulgated by the American
Society for Testing and Materials (ASTM) and the General Services
Administration (GSA).' The principal differences among creosotes for the
three uses shown are in specific gravity and the fraction of the oil
distilled within various temperature ranges.
A comparison of physical properties of creosote and creosote/coal
tar mixtures as shown in Table 7 indicates much higher distillation
f
residue for coal tar. A list of the properties of some of the 16
priority pollutant PAH compounds found in creosote is given in Table 8
(Sims et al., 1987).
Another group of compounds which have been identified in creosote
and which are related to the PAH's are the azaarenes which make up
approximately 0.13% of creosote (Adams et al., 1984). These compounds
are polycyclic hydrocarbons containing nitrogen (e.g., quinoline and
acridine).
CHARACTERISTICS OF WOOD-PRESERVING WASTES
There are several sources of contamination at wood-treating sites.
During the treatment cycle, waste water with traces of preservative in
water is produced from several sources, from the live steaming of the
wood, from vapor drying or oil seasoning, from vacuum condensate, from
steam and oil leaks around the system, from cleanup, and from
contaminated rain water. Treatment of this plant water produces sludges
that are classified by EPA as K001, Hazardous Waste.
Prior to the environmental rules on wastewater discharge, the
treating plant wastewater effluent generally went directly to surface
drainage or a stream. A large number of the plants had sumps or ponds
-------
22
Table 6 . Physical properties of creosote and its fractions. (USDA 1980)
American Wood-Preservers' Association Standards
Pl-65*
P7-72
P13-65C
Water % volume
Xylene, insoluble, % by wt.
< 1.5
< 0.5
< 1.0
< 0.5
< 1.5
< 0.5
Specific gravity 38/15.5°C
Whole creosote
Fraction 235-315°C
Fraction 315-355°C
Residue above 355°C
> 1.050
> 1.027
> 1.095
> 1.060
> 1.080
> 1.030
> 1.105
> 1.160
Distillation, % by wt.
Min. Max.
Min. Max.
Min. Max.
Up to 210°C
235°C
270°C
315°C
355°C
2.0
12.0
20.0 40.0
45.0 65.0
65.0 82.0
1.0
10.0
65.0
2.0
12.0
20 ..0 40.0
45.0 65 .0
65.0 75.0
For land and fresh water use.
For brush or spray application.
For marine (coastal water) use.
-------
23
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to trap the heavy oil residuals before discharging to a creek or to the
publicly-owned treating works (POTW). Ponds ranged from less than an
acre to eight acres., Normally the ponds were lined with the local
soils. Typical constituents present in creosote wastewater are given in
Table 9.
Normal wood-treatment operations create additional preservative
waste. Treating tanks and cylinders have to be cleaned periodically to
maintain quality standards. In the past these preservative sludges were
used as fuel or for road paving or were buried at the facility.
Preservative-contaminated soil is another source of environmental
concern. Treated material is withdrawn from the cylinder and moved by
rails to storage areas. During transportation the preservative drips
from the treated wood onto the soil along the track. The areas around
storage, treating, and unloading tanks have had minor preservative
spillage from broken pipes, bleeding of treated wood, etc. These areas
can be rather large, especially in the older railroad and pole plants.
DECOMPOSITION/IMMOBILIZATION OF PCP AND CREOSOTE COMPONENTS IN SOIL
Pentachlorophenol
A large number of studies on biodegradation of PCP in soil have
been done. The sequence of reactions that have been shown to occur is
summarized in Figure 2. In soil, PCP undergoes a reversible methylation
reaction to form pentachloroanisole, but this reaction apparently is not
part of the main decomposition pathway. The main route for
decomposition is not through the methyl derivative, but through PCP
-------
28
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30
(Kaufman, 1978; Matsunaka and Kuwatsuka, 1975). The route of
decomposition involves dechlorination leading to a series of partial
dechlorinated products, such as 2,3,5,6-tetrachlorophenol.
The second step in the decomposition reaction involves an oxidation
step to form substituted hydroquinones or catechols, such as 2,3,4,5-
tetrachlorocatechol. The oxidation product then undergoes ring
cleavage, ultimately forming C0£ and an inorganic chloride ion.
Mobility, persistence, and fate of PCP in soils depend on physical
and chemical characteristics of the soil as well as the prevailing
microbial population.
Hilton and Yuen (1963) compared soil adsorption of PCP to the soil
adsorption of a number of substituted urea herbicides. They found that
the adsorption of PCP was the highest of all compounds studied.
Choi and Aomine (1972, 1974, 1974a) studied the interaction of PCP
and soil in detail. Adsorption and/or precipitation of PCP occurred to
some extent on all soils tested. Choi and Aomine (1974) concluded in a
study of 13 soils that adsorption of PCP depended primarily on the pH of
the system. The more acid the soil, the more complete was the "apparent
adsorption" of PCP. Different mechanisms of adsorption dominate at
different pH values. It should be noted that PCP is an acid which forms
a salt at the higher pH's. In the salt form, PCP would be more soluble
tf
in water but also more polar. In acid clays "apparent adsorption"
involved the adsorption on colloids, and precipitation in the micelle
and in the external liquid phase. Organic matter content of soils is
important to adsorption of PCP at all ph values. Soil containing humus
always adsorbs more PCP than soil treated with H0 to remove organic
-------
31
matter. Later investigations led to the conclusion that adsorption of
PCP by humus is important when the concentration is low, but at higher
concentrations the inorganic fraction increases in importance.
Three of four allophanic soils showed a significant increase in PCP
adsorption at higher temperatures, while the fourth soil showed a
decrease (Choi and Aomine, 1974a). The difference between the three
soils and the fourth soil could be explained by assuming that andosols
chiefly adsorb PCP as anions; whereas, the ma/or factor influencing PCP
adsorption by the fourth soil, showing a decrease with increasing
temperature, is due to Van der Waal's force. Decreasing the
concentration of chlorides or sulfate ions also increases the adsorption
of PCP to soil. These results indicate the occurrence of competition
between inorganic anions and PCP anions for adsorption sites on the soil
colloid.
The persistence of PCP in soil depends on a number of environmental
factors. Young and Carroll (1951) noted that PCP degradation was
optimum when the moisture content of soil was near saturation.
Kuwatsuka and Igarashi (1975) reported that the degradation of PCP is
faster under flooded conditions than under upland conditions. Loustalot
and Ferrer (1950) found that the sodium salt of PCP was relatively
stable in air-dried soils, persisted for 2 months in soil of medium
moisture content, and for 1 month in water-saturated soil. Although the
rates of degradation may be maximized at the higher moisture values,
these conditions would not be suitable for land treatment because of the
increased potential for migration.
-------
32
There are several factors in soil which affect the persistence of
PCP. PCP is broken down slower in heavy clay than in sandy or sandy
clay soils (Loustalot and Ferrer, 1950). This could be due to factors
in the soil or to a slower oxygen transfer in the soil. An extensive
study of the soil variables affecting the rate of degradation of PCP was
carried out by Kuwatsuka and Igarashi (1975). The rate was correlated
with clay mineral composition, free iron content, phosphate adsorption
coefficients and cation exchange capacity of the soil, while the
greatest effect was correlated with organic matter. According to these
authors, little or no correlation could be found with soil texture, clay
content, degree of base saturation, soil pH, and available phosphorus.
The preponderance of information indicates that microbial activity
plays an important part in the degradation of PCP in soil. PCP decays
more rapidly when the ambient temperature approaches the optimum value
for microbiological activity (Young and Carroll, 1951). Ide et al.
(1972) found no decay in sterilized soil samples. These factors suggest
that microorganisms play an important role in PCP degradation (Kuwatsuka
and Igarashi, 1975; Young and Carroll, 1951). Kuwatsuka and Igarashi
(1975) studied degradation of PCP in soils collected from flooded and
upland areas. Upland soils degraded PCP more rapidly in the laboratory
when studied in the aerated condition, while soils obtained from flood
conditions degraded PCP more rapidly when tested in the flooded stage.
Thus, PCP-degrading microorganisms present in the soil survived the
transfer to the laboratory and were most active when placed in an
environment to which they were adapted.
-------
33
A summary of the literature values for the persistence of PCP in
soil is presented in Table 10. The persistence ranged between 22 days
and 5 years. The 5-year value obtained by Hetrick (1952) was from dry
soil sealed in a jar and probably does not represent a realistic
evaluation of the environmental half-life. Thus, PCP can be considered
moderately persistent under most conditions.
Numerous degradation products have been isolated from PCP-treated
soil. Ide et al. (1972) identified 2,3,4,5-, 2,3,5,6-, 2,3,4,6-tetra-
chlorophenol; 2,4,5- and 2,3,5-trichlorophenol; 3,4- and
3,5-dichlorophenol; and 3-chlorophenol. Similar products were obtained
by Kuwatsuka and Igarashi (1975), who also identified pentachloroanisole
as a PCP degradation product. This reaction is reversible and
pentachloroanisole can subsequently degrade back to PCP. Demethylation
and methylation of phenolic groups in biological systems are well known
(Williams, 1959). Ide et al. (1972) found 2,3,4,5-, 2,3,5,6- and
2,3,4,6-tetrachloroanisoles; 2,3,5-trichloroanisole; 3,4- and
3,5-dichloroanisoles; and 3-chloroanisole as methylated products of PCP
in incubated soil. Based on the results obtained from these
investigations, Matsunaka and Kuwatsuka (1975) proposed the soil
degradation pathway shown in Figure 2. An excellent review of the
parameters important for degradation of pentachlorophenol in soil can be
found in a review by Kaufman (1978).
Many types of bacteria and fungi are capable of degrading
pentachlorophenol, including Pseudomonas, Aspergillus, Trichoderma, and
Flavobacterium. Chu and Kirsch (1972) isolated a bacterial culture by
continuous flow enrichment that was capable of metabolizing PCP as a
sole source of organic carbon. The morphological and physiological
-------
34
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36
characteristics of the organisms suggest a relationship to the "'
saprophytic coryneform bacteria. Chu and Kirsch (1973) established that
the organism was responsive to enzyme induction with PCP as the inducer.
Lesser induction occurred with 2,4,6-trichlorophenol. The degradation
products resulting from the metabolism of PCP by this organism were not
characterized.
Kirsch and Etzel (1973) derived a microbial population capable of ;
rapid PCP degradation from a soil sample obtained on the grounds of a
wood products manufacturer. When fully acclimated, the populations were !
r
dosed with 100 mg/liter of PCP and 68% of the PCP was degraded in 24
hours. These cultures were most effective when the PCP was the sole
source of carbon.
Watanable (1973) reported penta degradation in soil samples
perfused with 40 mg/liter PCP. Bacteria isolates capable of PCP
decomposition were derived from a soil perfusion enrichment culture.
Degradation and complete dechlorination occurred after 2 to 3 weeks of
incubation. The bacterium was characterized as a Pseudomonas sp. or an
organism from a closely related genus. Tetrachlorodihydroxyphenols and
their monoethyl ethers were tentatively identified as a metabolic
product of PCP by Aspergillus sp. (Cserjesi, 1972). A soil bacterium
isolated by Suzuki and Nose (1971) was capable of degrading PCP. The *
major metabolites were pentachloroanisole and dimethyl ether; a minor
metabolite was tetrachlorohydroquinone.
More recently Edgehill (Edgehill et al., 1984) isolated a soil
bacterium capable of utilizing PCP as a sole source of carbon. The
organism was a member of the coryneform group of bacteria, probably the
genus Arthrobacter.
-------
37
It is clear that bacteria and fungi capable of degrading PCP exist
In nature. However, the number of species and their population may be
limited. In most cases where rapid degradation of PCP by microorganisms
«•*
has been demonstrated, the source of inoculum was from areas where PCP
had been used for a long time.
Creosote Components
The major components of creosote are the polycyclic aromatic
hydrocarbons (PAH's) with trace amounts of phenols and azaarenes. A
wide range of soil organisms, including bacteria, fungi, cyanobacteria
(blue-green algae), and eukaryotic algae, have been shown to have the
enzymatic capacity to oxidize PAH's. Prokaryotic organisms, bacteria,
and cyanobacteria use different biodegradation pathways than the
eukaryotes, fungi, and algae, but all involve molecular oxygen.
Tausson (1950) first demonstrated that several PAH's, Including
naphthalene, anthracene, and phenanthrene, can serve as substrates for
some soil organisms and are "completely" metabolized. Groenewegen and
Stolp (1981) isolated microorganisms that can use the compounds
mentioned above as their sole C source. However, they could show
degradation of some of the less-water-soluble PAH's, such as
benz(a)anthracene and benzo(a)pyrene (BaP), only when the PAH's were
mixed with soil, water, and a substance to stimulate growth of
oxygenase-active organisms. Shabad et al. (1971) discussed a number of
experiments that demonstrated bacterial degradation of BaP in soil.
They reported 50-80% destruction of BaP over a period of "several" days
by bacteria in soil contaminated with shale oil containing high
concentrations (up to 20,000 yg/kg) of BaP. Shabad et al. also found
-------
38
that the capacity of bacteria to degrade BaP increased with BaP content
in the soil and that microflora of soil contaminated with BaP were more
active in metabolizing BaP than those in "clean" soil. Cerniglia and
••1
Crow (1981) demonstrated the metabolism of naphthalene, biphenyl, and
BaP by a number of different species of yeast, some of which were
previously reported in high numbers in oil-polluted soils. Cerniglia
and Gibson (1979) reported the degradation of BaP by a filamentous
fungus, and Dodge and Gibson (1980) demonstrated the degradation of
benz(a)anthracene by the same fungal species.
Cerniglia and Gibson (1979) reported that the metabolites formed
during the degradation of BaP by a fungus were very similar to those
formed during BaP metabolism in mammals. Such metabolites are probably
responsible for the carcinogenicity of BaP. However, Shabad et al.
(1971) reported that extracts of a medium containing BaP were less
carcinogenic to mice (Mus spp.) after microbial degradation than before
degradation. A more complete review of earlier research (before 1970)
on microbial oxidation of PAH's was presented by Gibson (1972).
Biochemical pathways for the degradation of a number of PAH's by soil
microorganisms have been proposed by Fernley and Evans (1958), Evans et
al. (1965) and Gibson et al. (1975). One proposed mechanism for the
reaction is shown in Figure 3.
Generally, rates of degradation for PAH compounds decrease as the
molecular weight increases; rates of degradation are faster in soil than
water; and overall rates of degradation are faster where there is an
acclimated bacteria population (Herbes et al., 1980). These
observations had also been made earlier (Sims and Overcash, 1983).
-------
39
Anthracene
HO H
1,2-Dihydro-1,2-
dihydroxy-anthracene
3-Hydroxy-2-
Naphthoic Acid
COOH
OH
Salicylic Acid
•OH
•OH
Catecnol
Figure 3. Proposed mechanism for the microbiological
degradation of anthracene (Rogoff 1961).
-------
40
Compounds such as naphthalene, phenanthrene, and anthracene, which
are readily metabolized, are relatively water soluble, while persistent
PAH's, such as chrysene and benzo(a)pyrene, have a lower water
••«*
solubility (Table 11). Exceptions exist with pyrene and fluoranthene in
that these compounds are more soluble than anthracene and yet have not
been found by some researchers (Groenewegen and Stolp, 1981) to be
appreciably metabolized by soil microorganisms. Other factors that may
affect the persistence of PAH compounds are insufficient bacterial
membrane permeability to the compounds, lack of enzyme specificity and
lack of aerobic conditions (Overcash and Pal, 1979).
Two sets of studies were recently completed by Buiman et al. (1985)
to assess PAH loss from soil. In the first, a mixture containing levels
of 5 and 50 mg/kg of eight PAH's [naphthalene, phenanthrene, anthracene,
fluoranthene, pyrene, benzo(a)anthracene, chrysene and benzo(a)pyrene]
was added to soil and the concentration of each compound was monitored
with time. In the second experiment, 14C labeled benzo(a)pyrene and
anthracene were added to unacclimated agriculture soil in biometer
flasks. The distribution of 14C as volatile, adsorbed, and degraded
products was determined in sterilized and biologically active soil. In
the first set of studies, naphthalene, phenanthrene, anthracene, pyrene,
and fluoranthene disappeared rapidly from soil during an initial period
of 200 days or less. A loss of 94 to 98 percent occurred during this
period and approximated first-order kinetics, in some cases following a
lag period. With the exception of anthracene, the first-order kinetic
rate constants were the same for 5 and 50 mg-kg"1 additions of PAH.
Following the initial period, the remaining 2-6 percent of the added PAH
-------
41
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was lost at a much reduced rate, and the first-order rate constants
tended to be higher with the 50 mg'kg"* addition than the 5 mg*kg~*
addition of PAH.
Losses of dhly 22 to 88 percent were observed for
benzo(a)anthracene, chrysene, and benzo(a)pyrene, and only one kinetic
period was identified within the 400-day incubation period. With
chrysene, the first-order kinetic rate constants were the same at the 5
and 50 mg'kg"1 levels of addition; however, for benzo( a) anthracene and
benzo(a)pyrene the rate constants differed. The disappearance of
benzo (a) anthracene approximated first-order kinetics; however, a zero-
order kinetics was found for the disappearance of benzo(a)pyrene and
chrysene.
The mechanisms of disappearance of anthracene and benzo(a)pyrene
were assessed in a second set of studies using 14C labeling. The
results indicated that biological activity was responsible for some of
the loss of anthracene from soil; however, binding to soil solids and
volatilization (either as anthracene or as metabolites) were identified
as the major loss mechanisms. Identification of loss mechanisms for
benzo(a)pyrene was less successful due to the small amount of
benzo(a)pyrene that disappeared during the incubation period. Binding
of benzo(a)pyrene to soil solids appeared to be the major mechanism
involved, while microbial transformation of the compound was minimal.
Tortensson and Stenstrom (1986) have cautioned, however, that an
indirect measurement of mineralization such as liberated ^C02 from a
l^C-labeled compound may not always be reliable. They recommend that
the rate of transformation of a substance be defined by direct
-------
45
measurement of its disappearance. Liberation of labeled CO^ may not be
concurrent with transformation because transformed compounds may not be
further degraded to labeled C02 during the time frame of the study.
Some PAH's with more than four rings are not known to be utilized
as a sole carbon source but have been reported to be co-metabolized with
other organic compounds. This process involves the concurrent
metabolism of a compound that a microorganism is unable to use as a sole
source of energy along with metabolism of a carbon source capable of
sustaining growth. In a study by McKenna and Heath (1976), the
co-metabolism of refractory PAH compounds in the presence of two- and
three-ring PAH compounds was investigated. The degradation of pyrene,
3,4-benzpyrene, 1,2-benzanthracene, and 1,2,5,6-dibenzanthracene in the
presence and in the absence of phenanthrene was measured. Separate
cultures of Flavobacterium and Pseudomonas were maintained in the
presence of each of the PAH compounds. Both Flavobacterium and
Pseudomonas exhibited negligible utilization of the refractory PAH
compounds in the absence of phenanthrene. However, Flavobacterium, in
the presence of phenanthrene, was able to significantly degrade all four
test compounds. Co-metabolism by Pseudomonas was not observed. In a
_™ similar experiment PAH compound degradation by a mixed culture was
= measured. For each PAH compound studied, one container of inoculum
I
[ received naphthalene as a growth substrate while a second container
? "•*
I , received phenanthrene as a growth substrate. Cometabolism of pyrene,
I •*"•
I ^ 1,2-benzanthracene, 3,4-benzpyrene, and 1,2,5,6-dibenzanthracene by the
: Jr mixed culture was exhibited in the presence of either naphthalene or
W phenanthrene.
JBR
-------
46
The fate of PAH compounds In terrestrial systems has been reviewed
by Sims and Overcash (1983), Edwards (1983), and Cerniglia (1984).
These reviews present additional information on PAH degradation.
The types of phenols present in creosote in general are more
readily degraded than PAH's or PCP. The effect of phenols on soil
microorganisms is dependent on the soil concentration or amount added
(Overcash and Pal, 1979). At low doses (0.01-0.1 percent of soil
weight), the phenol serves as an available substrate, and there is an
increase in microbial numbers. As the dose level is increased (0.1-1.0
percent of soil weight), an increasingly strong inhibitory or
sterilizing effect is noted. At these levels, a partial sterilization
occurs in which there is a depression in microbial numbers, but not a
complete die-off. After a period of time, microbes adapt or phenol is
lost through sorptive inactivation or volatilization and a regrowth of
population occurs.
BIOACCUMULATION/TOXICITY OF PCP AND CREOSOTE
Plant/Animal Uptake of PCP
Information on the uptake and translocation of PCP by plants is
limited, and there is no information on the metabolism of PCP by plants.
Jaworski (1955) found less than 0.01 mg/kg PCP in cottonseed oil of
field-grown plants sprayed with *4C-PCP. Similarly, Miller and
Aboul-Ela (1969) could not detect PCP in cottonseed kernels of open
bolls on sprayed plants. However, in contrast to Jaworski (1955), they
found some translocation of PCP or a possible metabolite within the
plants. PCP residues definitely existed in seed from bolls that were
closed at the time of treatment. Miller and Aboul-Ela (1969) also
-------
47
observed the movement of 14C-labeled PCP in the first two leaves of
cotton within 1 hour of treatment. After 8 hours, radioactivity was
distributed througji all the veins of treated leaves, but there was no
movement of radioactivity out of the treated leaves even after 8 days.
Hilton et al. (1970) studied the distribution of radioactivity in
sugar cane following either foliage or root application of 14C-PCP. With
leaf application, 100% of the radioactivity was found in the treated
leaf after 2 weeks. After 8 weeks, 84% of the activity was in the
treated leaf with minor amounts in all plant parts except roots. Root
application was studied by growing plants in a nutrient solution
containing 14C-PCP for 4 weeks. Approximately 90% of the original
radioactivity was recovered from the plants after 4 weeks, with over 99%
found in the root system.
Uptake of PCP by animals can occur by inhalation, oral ingestion
(including consumption of PCP-contam.inated food and licking or chewing
I m treated wood) and dermal absorption by direct contact with treated wood.
j There is some evidence that PCP may be a metabolic product of other
j environmental contaminants, but the significance of this source is not
i known. Koss and Koransky (1978) demonstrated the formation of PCP from
* = hexachlorobenzene in rats, mice, hens, and trout. Hexachlorobenzene
I - occurs widely in the environment, and low-level residues are frequently
j encountered in animal tissues. The rate of PCP formation from
hexachlorobenzene is slow compared to the rate of PCP elimination.
Thus, the levels of hexachlorobenzene encountered in tissues are not
^. sufficient to account for the levels of PCP generally found.
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48
Many phenols undergo conjugation reactions in animals (Williams,
1959). These reactions include the formation of glucuronides, ethereal
sulphates, and monoesters of sulfuric acid. Some PCP is excreted
unchanged, and the amount that is metabolized or conjugated depends on
the species.
Approximately 40% of the 14C-labeled PCP given to mice and rats
was excreted unchanged in the urine (Ahlborg et al., 1974). 14C-
tetrachlorohydroquinone accounted for 5% of the excreted radioactivity
in rats and 24% in mice. Larsen et al. (1972) found that 50% of the
radioactivity of orally administered *4C-PCP was excreted in the urine
of rats in 24 hours and 68% was excreted in 10 days. Between 9 and 13%
was excreted in the feces. Tissue analysis showed small amounts of 14C
activity in all tissues, with the highest level in liver, kidneys, and
blood. In blood, 99% of the radioactivity was in the serum. A
two-compartment urinary excretion pattern was proposed that had a
10-hour half-life for the first 2 days, followed by a 102-day half-life.
Braun et al. (1976) studied the pharmacokinetics and metabolism of
PCP in rats and monkeys. Excretion of 14C from the labeled PCP was
mainly through the urine in both species. In the monkeys, only PCP was
found; while in rats, PCP, tetrachlorohydroquinone, and the glucuronide
conjugate of PCP were found. Residues were high in liver, kidneys, and
blood, thus agreeing with Larsen et al. (1972). It was suggested that
there was reversible binding of PCP to blood proteins. The half-life
ranged from 13 to 17 hours in rats and from 72 to 84 hours in monkeys.
This work failed to confirm the presence of the long half-life
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49
compartment suggested by Larsen et al. (1972). The short half-lives of
PCP suggest that there will be no buildup of residues to a toxic level
with continuing intake of PCP.
Toxic Effects of PCP
The widespread use of PCP as an antimicrobial agent and the
likelihood of commercial products being contaminated with certain highly
toxic polychlorinated dibenzo-p-dioxins and dibenzofurans necessitate a
review of the toxicological information currently available. Although
this review is primarily concerned with data on PCP per se,
available data on commercial samples are included, for comparative
purposes.
Oral Toxicity--The 1050 for PCP in male rats has been reported as
78 mg/kg (Deichmann et al., 1942), 90 mg/kg (Gabrilevskaya and Laskina,
1964), 146 mg/kg and 205 mg/kg, the last being Dowicide EC-7 (USDA,
1980), For the female rat, it was 135 mg/kg (Dow Chemical Co. Summary,
1969) and 175 mg/kg (EC-7) (Gaines, 1969).
The 1050 for mice was reported as 130 ^ 9.5 mg/kg (Pleskova and
Bencze, 1959); for rabbits, 100-130 mg/kg (Deichmann et al., 1942); for
guinea pigs, 250 mg/kg (Gabrilevskaya and Laskina, 1964); and for swine,
120 mg/kg (Harrison, 1959). Dreisbach (1963) has estimated an LD50 dose
for man to be as low as 29 mg/kg.
These data suggest that PCP has moderate acute oral toxicity, but
that the LD$Q value may vary with the quality and quantity of
contaminants. Man appears to be more susceptible than the rodent and
the female to be more susceptible than the male.
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50
Skin Absorption—When PCP in an organic solvent was applied to
rabbit skin under occlusion for 24 hours, 200 mg/kg was lethal, but 100
mg/kg and 50mg/kg were not (Dow 1969). The LD5Q for rats has been
reported as 96 mg/kg, 105 mg/kg, and 320 mg/kg (Demidenko, 1966; Noakes
and Sanderson, 1969; Gaines, 1969) and that for mice as 261 _+ 39 mg/kg
(Pleskova and Bencze, 1959).
Subcutaneous Injection—The LD50 for rats was 100 mg/kg, for
rabbits 70 mg/kg (5% in olive oil) (Deichmann et al., 1942), and for
mice 63 +_ 3.2 mg/kg (Pleskova and Bencze, 1959).
Intravenous Injection—The lowest dose of PCP reported to kill
rabbits was 22 mg/kg (Kehoe et al., 1939) when it was instilled as a 1%
aqueous sodium pentachlorophenate.
Inhalation—Exposure to 5 mg/1 dust for one hour did not kill male
and female rats (Reichhold Chemicals, 1974). Demidenko (1969) reported
the LD5Q by inhalation to be 225 mg/kg for rats and 355 mg/kg for mice.
The exposure concentration and the calculations to arrive at the 1.050
dose were not given in the abstract. Workers have reported that the
dust is irritating to the mucous membrane of the nose and throat.
Irritancy Tests—Rabbit eyes exposed to solid material showed
slight conjunctiva! and slight iritic congestion. Exposure of rabbit
skin under occlusion caused minimal irritation on intact skin and
slightly more on abraded skin (Dow, 1969).
Commercial samples have produced chloracne in the rabbit ear
bioassay; whereas, the purified material has not. Positive reactions
have been produced by topical or oral application (Johnson et al.,
1973). Allergic contact dermatitis has not been a problem in handling
the chemical.
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51
Mutagenic-Cytotoxic Potential--PCP has not shown mutagenic activity
in the Ames test (Anderson et al., 1972), the host-mediated assay
(Buselmaier et al., 1973), or the sex-linked lethal test on drosophila
(Vogel and Chandler, 1974).
Teratogenic and Embryotoxic Potential--PCP did not cause
deformities, but it was highly embryolethal and embryotoxic following
oral administration to rats of 15, 30, or 50 mg/kg per day on days 6-15
of gestation. No effects were produced at 5 mg/kg (Schwetz and Gehring,
1973; Schwetz et al., 1974). Purified PCP, with its low nonphenolic
content, was slightly more toxic than the commercial grade (Schwetz et
al., 1974).
Oral administration of PCP to golden Syrian hamsters at levels
ranging from 1.25 to 20 mg/kg daily from days 5 to 10 of gestation
resulted in fetal deaths and/or resorptions in three of six test groups.
PCP was found in the blood and fat of the fetuses (Hinkle, 1973).
Pregnant rats (Charles River-CD Strain) were given 60 mg/kg of
labeled PCP on days 8 through 13 of gestation and were sacrificed on the
20th day. Only a small amount of PCP crossed the placental barrier and
only slight teratogenic effects were noted (Larsen et al., 1975).
One of the concerns in use of technical grade PCP is the presence
of trace contaminants including the chlorinated dioxins and furans.
Limited toxicity data on two of the dioxins present in technical grade
PCP—hexachlorodibenzo-p-dioxin and octachlorodibenzo-p-dioxin—are
given in Table 12.
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52
Table 12. Toxicity of various dioxin isomers to experimental animals.
Compound
LD-50
Teratogenic Embryo
Effect1
Toxicity1
2,7-Dichlorodi-
benzo-p_-dioxin
2,3,7.8-Tetrachloro-
dibenzo-p_-dioxin
Hexachlorodibenzo-p_-
dioxin
Octachlorodibenzo-p_-
dioxin
ing/kg Body wt.
1,000
0.0006
100
1,000
None
0.001
0.1
None
None
0.00003
0.0001
100
Acnegenic
Effectb
mg/kg/day mg/kg/day mg/liter
None
0.00004
0.01
None
Source: Modified from Alliot, 1975.
Values denote the lowest dosage or concentration which gives rise to the
corresponding effect.
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53
Plant/Animal Uptake of Creosote
There is very little information on bioaccumulation/toxicity of
creosote (Brown et al., 1984). The limited information on plant/animal
uptake has recently been reviewed by the USDA (1980). There is
considerably more information on the bioaccumulation/toxicity of the
individual PAH's found in creosote. Edwards (1983), in a comprehensive
review of PAH's in the terrestrial environment, summarizes the sources
and fate of these compounds in the environment. His conclusions
regarding the uptake, translocation, and metabolism in vegetation were
1) Some terrestrial plants can take up PAH's through their roots
• and/or leaves and translocate them to various other plant
parts.
2) Uptake rates are dependent on PAH concentrations, solubility,
phase (vapor or particulate), molecular size, support media
anchoring the plants, and plant species.
3) PAH's may concentrate in certain plant parts more than in other
parts.
4) Some PAH's can be cataboVized by plants.
The health effects of the major PAH constituents in creosote are
summarized in Table 13.
**.
i SS,
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54
Table 13. Health effects of chemical constituents of creosote (U.S. EPA 1984),
2.
Compound
Effect
1. Unsubstituted 6-membered aromatic ring systems
chrysene
pyrene
benzo(a)pyrene
benzo(e)pyrene
benzc(a)anthracene
benzo(a)phenanthrene
naphthalene
phenanthrene
anthracene
dibenzanthracene
acenaphthene
triphenylene
Unsubstituted aromatic
mutagenic initiator, carcinogenic
co-carcinogen [with fluoranthene
benzo(a)pyrene], mutagenic
mutagenic carcinogenic, fetotoxic,
teratogenic
carcinogenic, mutagenic
mutagenic, carcinogenic
initiator, mutagenic
inhibitor
initiator, mutagenic
mutagenic
mutagenic
mutagenic
mutagenic
ring systems containing 5-numbered rings
fluoranthene
benz(j)fluoranthene
fluorene
co-carcinogenic, initiator, mutagenic
carcinogenic, mutagenic
mutagenic
-------
Table 13. (continued)
55
Compound
Effect
37 Heterocyclic nitrogen .bases
quinoline
indole
benzocarbazoles
isoquincline
1-methyl isoquinoline
3-methyl isoquinoline
5-methyl quinoline
4-methyl quinoline
6-methyl quiholine
isoquinoline
isoquinoline
isoquinoline
isoquinoline
5-methyl
7-methyl
6-methyl
1,3-dimethyl
acridine
carbazole
carcinogenic
mutagenic
carcinogenic
mutagenic
possibly carcinogenic
possibly carcinogenic
possibly carcinogenic
possibly carcinogenic,
possibly carcinogenic
possibly carcinogenic
possibly carcinogenic
possibly carcinogenic
possibly carcinogenic
mutagenic
mutagenic
mutagenic
4. Heterocyclic oxygen and sulfur compounds
coumarone
thionaphthene
5. Alkyl substituted compounds
No effects found in the literature
for this structural class.
1-methyl naphthacene
2-methyl anthracene
methyl fluoranthene
1-methyl naphthalene
2-methyl naphthalene
ethyl naphthalene
2,6-dimethyl naphthalene
1,5-dimethyl naphthalene
2,3-dimethyl naphthalene
2,3,5-trimethyl naphthalene
2,3,,6-trimethyl naphthalene
methyl chrysene
1,4-dimethyl phenanthrene
1-methylphenanthrene
mutagenic
mutagenic
possibly carcinogenic
inhibitor
inhibitor
inhibitor
inhibitor
inhibitor
accelerator
inhibitor
accelerator
initiator
initiator, mutagenic
mutagenic
-------
56
Table 13. (continued)
Compound
Effect
6. Hydroxy compounds
phenol
p-cresol
o-cresol
m-cresol
7. Aromatic amines
promoter
promoter
promoter
promoter
NH2
2-naphthylamine
p-toluidine
o-toluidine
2,4-xylidine
2,5-xylidine
8. Paraffins and naphthenes
carcinogenic
carcinogenic
carcinogenic
carcinogenic
carcinogenic
n (n is large, e.g., greater than 15)
No effects found in the literature for this structural class.
-------
57
SECTION 4
EXPERIMENTAL SECTION
INTRODUCTION
This project was started on February 15, 1985 and consists of three
phases: Phase I--site selection and characterization studies for
defining selected soil and sludge characteristics at eight wood-treating
sites; Phase II--laboratory treatability studies for determining rates
of microbiological degradation or other transformation processes, soil
transport properties of creosote and pentachlorophenol, and toxicity of
the water-soluble fraction of waste soil mixtures; and Phase III--a
field evaluation study at one of the eight wood-treating sites. The
following is a summary of the experimental methods for the
characterization phase and the laboratory treatability phase for four of
the eight sites. A detailed methodology is presented in Appendix A.
SITE SELECTION CRITERIA
Eight wood-treating sites were selected in the southeastern United
States, each having a different soil type. At each plant a site was
selected approximately 1/2 to 1 acre in area which could be used for the
field evaluation. The sites were selected using the following criteria:
1. Site must have a source of sludges, preferably a separate
source for PCP and creosote sludges.
2. Site should have low level exposure to PCP and creosote so that
an acclimated bacteria population is available, but there
should not be high levels of contamination within or below the
treatment zone.
•A
-------
58
3. There must be a method of collecting and disposing of run-off
water from the site.
SITE, SOIL, AND SLUDGE CHARACTERIZATION
During the first visit to each plant site, one or more potential
demonstration sites were selected and composite soil samples were
collected. Soil samples were collected at 0-6 inches and 6-12 inches
and subsequently analyzed for creosote and pentachlorophenol. Based on
the chemical analysis, microbial population, and initial observations,
one potential field evaluation site was selected at each plant location.
A second visit to each site was made in order to do a thorough site
assessment as well as more complete chemical and microbiological
characterization of the site soil. Soil samples were collected using a
systematic sampling plan. The exact number of samples depended on the
size of the area. The samples were then composited and analyzed.
A third visit was made to each site for soil evaluation. Soil
profiles were examined at each site in freshly excavated pits and they
were described and sampled using standard methods (Soil Survey Staff,
1951). Soil morphological descriptions included horizonation, Munsell
color, texture, horizon boundaries, consistency, coarse fragments, root
distribution, concretions and pedological features. Each horizon was
sampled for laboratory analyses. Detailed analytical procedures used at
each site are given in Appendix A.
-------
59
— LABORATORY TREATABILITY STUDIES
Transformation/Degradation Using a Standard Creosote/PCP Mixture:
Experiment I
Phase II involved laboratory treatability studies for determining
rates of degradation/transformation, soil transport properties of
creosote and pentachlorophenol, and toxicity of the water-soluble
fraction of waste soil mixtures. As a preliminary experiment to
determine possible loading rates, sampling times, refine experimental
techniques, and compare results in different soils using a common waste,
an initial set of degradation/transformation experiments was conducted
by applying, at 1% of the soil dry weight, a mixture of technical-grade
pentachlorophenol and creosote at 200 and 2000 ppm, respectively
*-
"• (standard mixture) to a sample of each site's soil. Samples of each
_. soil were taken at 0, 30, 60, and 90 days for chemical and
~ microbiological analysis.
;f Transformation/Degradation of Site Specific Sludges; Experiment II
The second part of the laboratory degradation studies involved
studying the kinetic rates using soil and sludges from the same site.
The objective was to assess the feasibility of land treatment of the
sludge present at a site in the soil at that site. Three sludge loading
rates were tested, and the study was replicated three times. Soil
samples were taken at 0, 30, 60, and 90 days for chemical and
microbiological analysis.
-------
60
SECTION 5
RESULTS AND DISCUSSION
SITE AND SOIL CHARACTERIZATION
The eight sites investigated represented very diverse soil,
geologic, climatic, and environmental conditions. The sites ranged from
near sea level in Gulfport, Mississippi and Wilmington, North Carolina
to elevations above 1000 feet at Atlanta, Georgia. The study areas were
located in six Major Land Resource Areas (MLRA) of the United States as
shown in Table 14.
The sites encompassed several geomorphic landforms ranging from
fluvial terraces to upland ridges. Soil parent materials
varied from sandy Coastal Plain sediments and silty Peoria loess to
granite gneiss residuum as shown in Table 15.
A brief discussion of the pertinent characteristics of each site is
presented in the following paragraphs.
Grenada, MS--Moderately well-drained Loring soil comprises the
site. Silt content exceeded 70% in the surface horizons and increased
at deeper depths in the lower sola. Maximum clay content occurred in the
Btxl horizon at depths of 16-26 inches. The fragipan horizons (Btxl,
Btx2) had very low hydraulic conductivity and tended to perch water
above the fragipan during the wetter winter and spring months. These
layers greatly reduced downward leacheate movement. The surface horizon
was strongly acid and pH levels increased with depth. Acidity (H)
decreased in the deeper horizons as pH increases. Exchangeable Al
levels reached a maximum level in the Btxl horizon at depths of 16-26
inches, comprising 30.7% of the cation exchange capacity. Mg and Ca
-------
61
f T
Table 14. Site location in Major Land Resource Areas,
Site
MLRA
Grenada, MS
Gulfport, MS
Wiggins, MS
Columbus, MS
Atlanta, GA
Wilmington, NC
Meridian, MS
Chattanooga, TN
134 - Southern MS Valley Silty Uplands
152A • Eastern Gulf Coast Flatwoods
133A - Southern Coastal Plain
133A - Southern Coastal Plain
136 - Southern Piedmont
153A - Atlantic Coast Flatwoods
133A - Southern Coastal Plain
128 - Southern Appalachian Ridges and Valleys
-------
62
Table 15. Overall field evaluation site soil composition.
Site
-h
Grenada, MS
Gulfport, MS
Wiggins, MS
Columbus, MS
Atlanta, GA
Wilmington, NC
Meridian, MS
Chattanooga, TN
Soil
Grenada silt loam
Smithton
McLaurin sandy loam
Latonia loamy sand
Urban land
Urban land
Stough sandy loam
Urban land complex
Sand3
16.06
57.04
72.55
80.03
--
91.5
60.2
13.01
Silt3
70.17
28.88
24.16
16.42
—
6.0
31.4
46.77
Claya
13.77
14.08
3.29
3.55
—
2.5
8.4
40.22
3These samples were taken from the surface to a depth of 5 inches.
-------
63
were the dominant metallic cations with levels increasing with depth.
Electrical conductivity levels were low indicating no salt toxicity
problems. Maximum total S content of 0.018% occurred in the surface
horizon. Water holding capacity was high in the surface horizon. The
clay fraction of the surface soil was dominated with kaolinite and mica
(illite) with illite increasing in the subsoil and kaolinite decreasing.
Gulfport, MS—The site had 7 to 8 inches of mixed fill-soil
overlying a poorly drained Smithton sandy loam soil. The site had slow
runoff and subsoils that were moderately slow permeable subsoils.
Maximum clay content (24.6%) occurred in the fill-soil capping and
abruptly decreased to 3% in the subjacent, original surface horizon.
K Calcareous shells were common in the fill-soil, and were also mixed to
the 7- to 12-inch layer. The calcareous materials were part of the
- fill-soil placed over the natural soil. The water table is near the
— surface during the wetter months. The added calcareous materials
f* resulted in high levels of exchangeable Ca to depths of 38 inches which
produced high base saturation levels and high pH levels (6.3 to 7.7).
Low levels of Na were detected. Electrical conductivity values
reflected the influence of the calcareous materials. Cation exchange
•^ capacity values were less than 6 me/100 g below depths of 12 inches.
Total S levels were low with a maximum of 0.018% occurring in the A
horizon at depths of 7 to 12 inches. The soil had relatively high
\ available water holding capacity. Kaolinite was the dominant clay
w- mineral in the surface horizon and subsoil. The fill-soil capping
contained small amounts of smectite.
.
* ' j~~
I f"
-------
64
Wiggins, MS--Deep, well-drained McLaurin sandy loam soils dominated
this site. These soils had slow to medium runoff and moderate
permeability. The soil was very strongly to strongly acid throughout
the 60-inch solum. The soil was poly-genetic with two distinct clay
maxima in the argillic horizon. Maximum clay content of 36.7% occurred
at depths of 39 to 60 inches. The soil had low base saturation and
cation exchange capacity, and electrical conductivity values reflected
the low soluble salt content. The surface horizon had a high saturated
conductivity value with variations in the subsoil due to the two clay
maxima. The soil had low S contents with a maximum value occurring in
the 39- to 60-inch horizon. The subsoil had low water holding capacity.
Kaolinite was the dominant clay mineral in the surface and subsoil with
i
lesser amounts of vermiculite-chlorite integrade. *
Columbus, MS—A deep, well-drained sandy Latonia soil with •
moderately rapid permeable subsoil and slow runoff comprised the study :
f
area. The soil had loamy sand textures to a depth of 40 inches where •
i
gravelly sands occur. A maximum clay content of 7.5% occurred at depths •
of 17 to 25 inches. The soil was medium to strongly acid throughout the
profile. Higher Ca levels were present in the upper horizons due to
|
prolonged additions of leacheate from treated-wood products. The soil ;
had elevated organic matter contents in the surface horizon from ,. i
*.
cultural additions which resulted in higher cation exchange capacity. •
Electrical conductivity values reflected the low soluble-salt content, |
with the highest levels in the surface horizon due to the added
leacheate. Low contents of Mg, K, and Na were present throughout the
-------
65
profile. The highest S content of 0.095 occurred in the surface
horizon. Kaolinite was the dominant clay mineral in the surface and
subsoil horizons.
Atlanta, 6A—The site had been truncated and the soil solum removed
by cutting which exposed the subsoil C horizon and weathered saprolite
parent material. The surface had accumulated organic carbon from
additions of material in the pole yard. The partially weathered
saprolite had high bulk density values and was firm in place, but tends
to be loose when disturbed. The saprolite had low saturated hydraulic
conductivity. The loose upper horizon had sandy loam textures. Clay
content was less than 6% in the material sampled. The material was very
strongly acid in the lower depths. Calcium is the dominant exchangeable
cation. Cation exchange capacities are very low reflecting the low clay
content. Kaolinite was the dominant clay mineral.
Wilmington, NC—The site was comprised of made land with 1 to 3
feet of sandy fill material over poorly drained sediments. The water
table appeared to be affected by tidal fluctuations of the adjacent Cape
Fear River. A water table at 21 inches and saturated sands below
limited the depth of sampling. The soil had sand textures throughout
the profile with a maximum clay content of 2.5% occurring in the surface
horizon. The profile was moderately alkaline to neutral. Organic
carbon had accumulated in the surface horizons from added materials.
Calcium was the dominant exchangeable cation with low contents of other
bases. Cation exchange capacity was essentially due to the added humus
material, and value were less than 1 me/100 g at depths below 10 inches.
Higher electrical conductivities occur in the upper layers analyzed due
to added materials. The soil material had extremely high permeability
-------
66
with saturated hydraulic values of 34 inches/hr at depths below 10
inches. The material had low water-holding capacity below the surface.
A complex mineral suite comprised the small clay fraction with kaolinite
the dominant mineral.
Meridian, MS--Somewhat poorly drained Stough soils comprised the
study area. These soils had slow runoff, moderately slow permeability,
and were formed in thick beds of fluvial sediments. The soil had sandy
loam upper horizons and loamy textured subsoils. Maximum clay content
of 21.8% occurred at depths of 23 to 35 inches. Slightly firm, brittle
horizons occurred at depths below 15 inches which tend to perch water
during wet periods. The soil was strongly to very strongly acid
throughout the profile. Acidity and calcium dominated the cation
exchange complex. Kaolinite dominated the clay fraction of the surface
and subsoil.
Chattanooga, TN--The site was located in a soil area mapped as
urban land. The surface layer (0-4 inches) was a compacted mixture of
limestone gravel and silty clay. The subsoil was a thick argil lie
horizon of silty clay and silty clay loam textures with slightly firm
consistency. The surface horizon was mildly alkaline due to the
limestone gravel additions, and the underlying profile was very strongly
acid. The site was well-drained with no evidence of free water at
depths of 90 inches. The soil had high bulk density and low saturated
hydraulic conductivity. Available water-holding capacity was low.
Maximum clay content of 49.2% occurred at depths of 38 to 44 inches.
Exchangeable Ca, base saturation, and electrical conductivity were
influenced by the limestone gravel in the surface horizon. Exchangeable
-------
f
f 67
aluminum comprised a significant proportion of the cation exchange
complex in the subsurface horizons. The soil had a complex clay mineral
suite dominated by-kaolinite.
The general soil type and the amounts of sand, clay, and silt for
each location are summarized in Table 15.
Chemical Analysis of Wood-Treating Chemicals in the Soil
One of the main concerns in selecting a field evaluation site for
this study was levels of background chemicals in the soil. Chemical
analyses of the amount of pentachlorophenol, creosote, and
i octachlorodibenzo-p-dioxin at various depths are summarized in Tables
=
~ 16-18. Grenada, Gulfport, and Columbus had no detectable levels of
pentachlorophenol below 10 inches. The Wiggins site had
pentachlorophenol down to 20 inches, while the other sites had
detectable levels down to 60 inches or to ground water. The detection
limit for pentachlorophenol in soil was 27 ppb. Soil from Grenada,
Gulfport, Atlanta, Meridian, Wiggins, and Chattanooga had no detectable
levels of PAH's below 10 inches while those from Columbus and Wilmington
had PAH's down to 20 inches or deeper. Octachlorodibenzo-p-dioxin
levels at the soil surface (0-6 inches) varied from none detected to
2.38 ppm (Table 18). The soil and sludge detection limits for the
individual PAH's, OCDD, and for PCP are given in Appendix A.
Microbial plate counts for soils at each site are presented in
Table 19. Counts of bacteria were done on potato dextrose agar (PDA),
alone, or with various additives. This data provides an approximate
number of total soil bacteria and fungi, as well as the number of soil
bacteria that can tolerate or utilize creosote or pentachlorophenol.
-------
68
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70
Table 18. Soil concentration of octachlorodibenzo-p-dioxin at the
proposed land treatment sites (0 to 6 inches).
Octachlorodibenzo-p-dioxin
(ppm)a
Grenada
Gulfport
Wiggins
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
0.12
0.37
0.22
0.24
0.077 ^ 0-19
0.034 + 0.22
2.13 +0.34
NO*
NO
0.36 + 0.57
aThese samples represent soil at 0 to 6 inches and are the average of a
minimum of three replicates _+ standard deviation.
bND = Not Detected.
-------
71
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The nitrogen and phosphorous contents for the soil at each site are
given in Table 20.
Sludge Characterization
Each plant site had different types of sludges. Six of the plants
had open lagoons of creosote and/or pentachlorophenol; one site had
three lagoons which were segregated into pentachlorophenol,
pentachlorophenol in a heavy oil, and creosote; two other plants had no
lagoons but had areas of dried sludge and contaminated soil (see Table
21).
The water content, total organic and inorganic materials, pH, and
total organic carbon are summarized in Table 22. Water contents of
these samples varied from 26.6 to 74.58%. The total organic material
ranged from 8.96 to 68.0%. The pH varied from 3.00 to 7.20. The more
acidic sites contained large amounts of PCP. The total organic carbon
varied from 4.02 to 49.79%. The wide variation in inorganic solids is
not surprising since these sludges are stored in large open lagoons.
The pH is related to the concentration of PCP in sludge and probably is
also affected by the soil pH. The high levels of organic materials are
mainly the heavy oils used to dissolve PCP for treating wood and the
aliphatic fraction found in creosote.
Total phenolics, oil and grease, nitrogen phosphorus, and chloride
content of the sludges are summarized in Table 23. Concentrations of
pentachlorophenol and polycyclic aromatic hydrocarbons in the sludges
are given in Table 24. A more detailed list of the individual j
I
concentration of PAH's in each sludge is given in Table 25. j
-------
73
Table 21. Characteristics of the eight sites used in this study.
•*
Site
location
Grenada, MS
Gulf port, MS
Wiggins, MS
. Size &
age of plant
100 acres
78 years old
100 acres
80 years old
100 acres
15 years old
Preservative
used
Both penta-
chloropenol
and creosote
Both penta-
chlorophenol
(65%) and
creosote (35%)
Both penta-
chlorophenol
Number & type
of lagoons
Lagoons are closed;
contaminated soil
and sludge are
present
Large lagoon of
mixed preservatives
and contaminated
soil
Individual lagoons of
1) pentachlorophenol,
Columbus, MS
Atlanta, GA
Wilmington, NCa
Meridian, MS
Chattanooga, IN
15 acres
63 years old
125 acres
61 years old
76 acres
62 years old
(60%) and
creosote (40%)
Creosote
(100%)
Both penta-
chlorophenol
(80%) and
creosote (20%)
Both penta-
chlorophenol
and creosote
Both penta-
chlorophenol
(25%) and
creosote (75%)
Creosote (100%)
2) pentachlorophenol
in heavy oil, and
3) creosote
Contaminated soil and
lagoon
Contaminated soil and
lagoon
Lagoons are closed
but contaminated soil
is available
Large lagoon and con-
taminated soil
available
Enclosed lagoons and
contaminated soil
^ aThis site has been an active land farming site for 1 1/2 years.
'»•
f
-------
74
Table 22. Composition of the sludges.3
Grenada
Gulf port
Wiggins 11°
Wiggins #2^
Wiggins #3d
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
Water
content
(X)
74.58
30.62
36.07
31.56
36.52
34.44
69.10
26.60
48.27
67.35
Total
organic
materials
(X)
24.31
68.00
40.58
26.02
27.80
61.11
23.76
8.96
50.00
15.74
Inorganic
solids
(X)
1.11
1.38
23.35
42.42
35.68
4.45
7.14
64.44
1.73
16.91
PH
6.30
4.80
3.00
3.50
5.70
5.90
5.00
7.20
4.00
7.10
Total
organic
carbon
(X)
7.37
22.50
37.85
49.45
36.03
49.79
25.33
4.02
31.96
14.61
Table 23. Chemical composition of the sludges.3
Inorganic
Site
Grenada
Gulf port
Wiggins #1°
Wiggins #2J;
Wiggins #3d
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
Total
phenol ics
(%)
.0041
.0097
.0045
.0130
.0171
.0224
.0120
.0007
.0114
.0003
Oil and
grease
(%)
9.74
44.03
15.86
22.57
17.90
44.60
14.17
0.44
35.34
3.68
Nitrogen
(ppm)
7562
2949
1119
1141
640
2951
1730
1283
3621
2090
Phosphorous
(Ppm)
236
506
446
477
261
270
316
435
213
417
chloride
content
(ppm)
267
440
361
753
825
49
278
1138
220
28
3A11 data reported on the starting weight of sludge.
'•'Lagoon contains mainly pentachlorophenol.
^Lagoon contains mainly pentachlorophenol in a heavy oil.
Lagoon contains mainly creosote.
' "f
! I
I
-------
75
Table 24. Concentration of PCP and total PAH's in each sludge sample.3
Site
Grenada
Gulfport
Wiggins #1
Wiggins #2
Wiggins #3
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
^
Pentachlorophenol
(ppm)
6,699
5,656
29,022
30,060
1,893
NDC
51,974
NO
13,891
NO
Polycyclic aromatic
hydrocarbons0
(ppm)
96,078
101,023
20,463
47,075
114,127
475,372
119,546
• 10,007
119,124
72,346
Octachloro-
dibenzo-p-
dioxin
(ppm)
23
215
114
125
21
NO
160
NO
160
NO
aThese values are the means of two replicates and are determined on a
dry basis. All were determined by capillary column gas
chromatography.
bTotal of the 17 major polycyclic aromatic hydrocarbons found in
creosote.
CND = Not detected. See Appendix A for detection limits.
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77
The results in Table 24 are obtained by capillary column gas
chromatography while the results in Table 25 are obtained using GC/MS.
Gas chromatography/mass spectrometry was also used to identify some of
the minor constituents in the sludges. The results are summarized in
Table 26.
The trace metal content of the sludges are summarized in Table 27.
The most common metals found at most wood-treating plants are mixtures
of copper chromium and arsenic salts. None of the sludges had high
levels of chromium and arsenic. None of the sites had used fire
retardant treatments (2nCl2).
LABORATORY TRANSFORMATION/DEGRADATION STUDIES
Transformation/Degradation Using a Standard Creosote/PCP Mixture;
Experiment I
The results of Experiment I are shown in Figures 4 and 5 for
the microbiological data, and Tables 28 through 36 for transformation/
degradation rates.
Gulfport soil was able to transform all the PAH's analyzed, with
only two (pyrene and benzo-a-pyrene) having relatively slow breakdown
rates. Columbus soil was able to transform all PAH's but anthracene,
though at somewhat slower rates than Gulfport for most PAH's. Gulfport
and Columbus developed higher levels of acclimated organisms than the
other sites, possibly accounting for the better transformation. Soil
from the other sites transformed most of the lower molecular weight
PAH's readily. Many of the higher molecular weight PAH's (fluoranthene,
pyrene, 1,2-benzanthracene, chrysene, and benzo-a-; yrene) tended to
transform slowly if at all. Pyrene and fluoranthene were perhaps the
most recalcitrant.
-------
78
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SU-
24-
14-
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14-
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04-
04-
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?t
1% Loading
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L
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to
24
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1**
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0% Loading
f
ITT] o
90
0*
P^?| 120
Oi u»
180
I S
Figure 4. Bacteria counts from all eight sites at 1% and 0% loading
rates after the final addition of the standard mixture.
aTotal bacteria counts on PDA media.
-------
81
1% Loading
24
XA
2d
24
14
14
1.4
1.2
14
04-
O4-
02-
00
*
?
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4£
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«o
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0% Loading
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24-
24-
1.4-
04-
02-
00
IBO
Hfh
Ou Or
CT71 0 P>TTJ 90
00
MI m c» ch u
j^v! 80 Pg^l 120 B89 IM
Figure 5. Acclimated bacteria counts from all eight sites at 1% and
0% loading rates after the final addition of the standard
mixture.
aBacteria acclimated to both PCP and creosote.
-------
82
Table 28. Kinetic data for PAH degradation/transformation in
Gulfport soils.
Compounds
Naphthalene
2-Methylnaphthalene
1-Methyl naphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Loading
Dry Wt.
(%)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.193
-0.190
-0.183
-0.179
-0.170
-0.200
-0.192
-0.192
-0.203
-0.179
-0.184
-0.024
-0.001
-0.194
-0.189
-0.002
-0.174
T 1/2
(days)
4
4
4
4
4
3
4
4
3
4
4
29
1155
4
4
365
4
-------
83
,„
*
Compounds
•
^ — ~— — — — __
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
_
Loading
Dry wt.
(*)
~
•
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
—
-0.332
-0.328
-0.316
-0.025
-0.042
-0.014
-0.063
-0.039
-0.061
NTa
-0.009
-0.012
-0.012
-0.015
-0.014
-0.009
-0.286
T 1/2
(days)
—
'• .—
2
2
2
28
16
50
11
18
11
NT
81
59
58
47
49
82
2
• .
•J
NT = no transformation observed,
-------
84
Table 30. Kinetic data for PAH degradation/transformation in
Grenada soils.
Compounds
Naphthalene
2-Methyl naphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Loading
Dry Wt.
(«)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.191
-0.189
-0.181
-0.178
-0.235
-0.202
-0.255
-0.258
-0,267
-0.241
-0.056
NTa
-0.002
NT
NT
-0.006
-0.166
T 1/2
(days)
4
4
4
4
3
3
3
3
3
3
12
NT
289
NT
NT
116
4
aNT = no transformation observed.
-------
85
"'
in
Compounds
Naphthalene
2-Methylnaphthalene
1-Methyl naphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Loading
Dry Wt.
(*)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-lj
-0.132
-0.193
-0.187
-0.181
-0.009
-0.010
-0.013
-0.015
-0.011
-0.008
NTa
-0.001
NT
-0.002
NT
NT
-0.008
T 1/2
(days)
5
4
4
4
77
72
52
47
63
91
NT
990
NT
3655
NT
NT
84
aNT = no transformation observed.
-------
86
Table 32. Kinetic data for PAH degradation/transformation in
Wilmington soils.
Compounds
Naphthalene
2-Methylnaphthalene
1-Methyl naphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-gh i -pery 1 ene
Loading
Dry Wt.
(*)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.193
-0.196
-0.188
-0.185
-0.186
-0.013
-0.137
-0.009
-0.010
NTa
-0.180
-0.004
-0.001
NT
-0.004
-0.180
-0.114
T 1/2
(days)
4
4
4
4
4
52
5
79
68
NT
4
189
1085
NT
158
4
6
aNT = no transformation observed.
-------
87
Table 33. Kinetic data for PAH degradation/transformation in
Meridian soils.
Compounds
Naphthalene
2-Methy Inaphthal ene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Loading
Dry Wt.
(%)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.185
-0.186
-0.179
-0.186
-0.174
-0.255
-0.262
-0.258
-0.217
NDa
-0.177
NTb
NT
NT
NT
NT
NO
T 1/2
(days)
4
4
4
4
4
3
3
3
3
NO
4
NT
NT
NT
NT
NT
NO
aND = not detected.
= no transformation observed.
-------
38
Table 34. Kinetic data for PAH degradation/transformation in
Atlanta soils.
Compounds
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Loading
Dry Wt.
(%)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.181
-0.181
-0.178
-0.171
-0.164
-0.020
-0.193
-0.254
-0.024
-0.175
-0.174
NTa
NT
NT
NT
NT
-0.167
T 1/2
(days)
4
4
4
4
4
35
4
3
29
4
4
NT
NT
NT
NT
NT
4
aNT = no transformation observed.
-------
89
Table 35. Kinetic data for PAH degradation/transformation in
Wiggins soils.
Compounds
Naphthalene
2-Methylnaphthalene
1-Methyl naphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-gh i -pery 1 ene
Loading
Dry Wt.
(%}
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.318
-0.313
-0.301
-0.294
-0.299
-0.338
-0.319
-0.329
-0.342
-0.309
-0.305
NTa
NT
-0.006
NT
-0.302
-0.284
T 1/2
(days)
2
2
2
2
2
2
2
2
2
2
2
NT
NT
117
NT
2
2
aNT = no transformation observed.
-------
90
Table 36. Kinetic data for PCP degradation/transformation
in site soils.
Site
Gulf port
Grenada
Columbus
Atlanta
Wiggins
Chattanooga
Wilmington
Meridian
Loading
Dry Wt.
(*)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.0107
-0.0024
NTa
NT
NT
-0.0027
-0.0022
-0.0009
T 1/2
(days)
64
289
NT
NT
NT
259
320
815
aNT = no transformation observed,
-------
91
PCP transformation occurred in Gulfport, Grenada, Chattanooga,
Wilmington, and Meridian soils. PCP half life was 64 days in Gulfport
soil, but well over 100 days for the other soils. Columbus, Atlanta,
and Wiggins soil exhibited no transformation of PCP.
The results of this preliminary experiment indicate that all of the
compounds studied can be transformed in soils at practically useful
rates under the appropriate conditions. Microorganism counts of the
type used in this experiment do not appear to be extremely accurate
indicators of potential breakdown rates for particular compounds.
However, there is some tendency for soils with higher populations of
acclimated microorganisms to transform more of the different PAH's in
creosote sludge at practically useful rates. This might be due to
larger numbers of particular microorganisms or to a more diverse array
of microbial species.
Since some of the soils exhibited no breakdown of. particular PAH's,
it would be desirable to test a range of loadings in subsequent
experiments to see if lower loading rates might allow enhanced
transformation in these soils.
Transformation/Degradation of Site Specific Sludges: Experiment II
The results of Experiment II are shown in Tables 37 through 42
for transformation/degradation kinetic data and Table 43 for
microbiological data.
The total PAH breakdown was similar in soils from all four sites
for similar loading concentrations. The individual PAH's can be
divided into three groups; those with half lives of ten days or less,
those with half lives of one hundred days or less, and those with half
-------
92
n
|able 37. Kinetic data for PAH degradation/transformation in Columbus soils.
95%
Confidence Interval
Lower Limit
Loading
Compounds Dry Wt.
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
^nzo-a-pyrene
«izo-ghi-perylene
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
K
(day-1)
-0.535
-0.536
-0.531
-0.513
-0.508
-0.187
-0.202
-0.204
-0.039
-0.015
-0.020
-0.013
-0.003
-0.002
-0.007
NT
NDb
T 1/2
(days)
1
1
1
1
1
4
3
3
18
46
35
53
231
347
102
NT
NO
K
(day-1)
-0.573
-0.551
-0.537
-0.520
-0.517
-0.288
-0.242
-0.241
-0.064
-0.020
-0.024
-0.024
-0.007
-0.006
-0.011
NT
NO
T 1/2
(days)
1
1
1
1
1
2
3
3
11
35
30
29
100
122
61
NT
NO
Upper Limit
K
(day-1)
-0.498
-0.521
-0.524
-0.507
-0.498
-0.086
-0.162
-0.167
-0.014
-0.010
-0.016
-0.003
NTa
NT
-0.002
NT
NO
T 1/2
(days)
1
1
1
1
1
8
4
4
50
68
43
248
NT
NT
301
NT
NO
aNT = no transformation observed.
bND = not detected.
-------
93
Compounds
Naphthalene
2-Methy1 naphtha 1ene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluorantnene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
(day-1) (days)
1.0
1-.
.0
1.0
1.0
1.0
1.0
1-^
.0
1.0
1/k
.0
1 —
.0
1 —
.0
1 —
.0
1 —
.0
1,-
.0
1-.
.0
1f\
.0
1rt
.0
-0.049
-0.096
-0.207
-0.149
-0.074
-0.028
-0.325
-0.022
-0.027
NT
-0.009
-0.002
-0.002
-0.001
-0.002
NT
NT
14
7
/
3
<«J
5
w
9
25
2
b
31
25
NT
75
289
433
578
365
NT
NT
-0.072
-0.169
-0.252
-0.228
-0.152
-0.041
-0.040
-0.031
-0.041
NT
-0.015
-0.004
-0.004
-0.004
-0.004
NT
NT
10
4
3
3
5
17
17
22
17
NT
48
165
187
173
173
NT
NT
-0.025
-0.023
-0.162
-0.070
NT
-0.014
-0.025
-0.013
-0.014
NT
-0.004
-0.001
NT
NT
NT
NT
NT
28
29
4
10
NT
- 50
28
52
50
NT
169
1155
NT
NT
NT
NT
NT
-------
94
(cSnt'^ed? f°r PAH ^'"on/transformation in Columbus ,„„.
95% Confidence Interva1
- Loading
Compounds Ory Wt
(%) *
__
Naphthalene 3.0
2-Methyl naphthalene a!o
1-Methylnaphthalene 3.0
Biphenyl 3>0
Acenaphthylene 3*0
Acenaphthene 3*0
Dibenzofuran 3,'o
Fluorene 3^0
Phenanthrene 3.*0
Anthracene 34*0
Carbazole 3^*0
Fluorantnene 3*0
Pyrene 3;0
1,2 Benzanthracene 3.0
Chrysene 3^0
Benzo-a-pyrene 3^0
Benzo-ghi-perylene 3.0
K
(day-1)
.
-0.050
-0.029
-0.018
-0.012
-0.006
-0.006
-0.005
-0.003
-0.001
-0.004
-0.008
-0.007
-0.007
-0.002
-0.007
NT
-0.004
T 1/2
(days)
__
14
24
39
57
112
124
147
224
578
173
90
107
99
315
98
NT
158
K 7 1/2 —j<~
(day-1) (days) (day-1) Jdays) I i
-0.066
-0.037
-0.024
-0.023
-0.008
-0.007
-0.007
-0.004
-0.004
-0.007
-0.011
-0.010
-0.011
-0.009
-0.015
NT
-0.011
11
19
28
30
89
96
99
169
173
96
62
67
62
82
47
NT
61
-0.033
-0.021
•0.011
-0.001
-0.005
-0.004
-0.002
-0.002
NT
-0.001
-0.004
-0.003
-0.003
NT
NT
NT
NT
21
33
61
578
147
169
301
347
NT
866
169
267
248
NT
NT
MT
Pi 1
NT
-------
95
Table 38. Kinetic data for PAH degradation/transformation in Grenada soils.
95%
Confidence Interval
Lower Limit
Loading
Compounds Dry Wt.
Naphthalene
2-Methy 1 naphtha 1 ene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
£enzo-a-pyrene
ftenzo-gh i -pery 1 ene
(*)
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
K
(day-1)
-0.531
-0.529
-0.498
-0.484
-0.154
-0.163
-0.160
-0.161
-0.126
-0.067
-0.255
-0.011
-0.010
-0.001
-0.004
-0.001
-0.001
T 1/2
(days)
1
1
1
1
4
4
4
4
5
10
3
65
68
3466
173
3466
770
K
(day-1)
-0.560
-0.549
-0.519
-0.486
-0.279
-0.251
-0.243
-0.257
-0.215
-0.142
-0.378
-0.014
-0.013
-0.004
-0.007
-0.002
-0.006
T 1/2
(days)
1
1
1
1
2
3
3
3
3
5
2
51
53
169
95
433
126
Upper Limit
K
(day-1)
-0.502
-0.508
-0.476
-0.482
-0.030
-0.075
-0.077
-0.065
-0.038
NTa
-0.132
-0.008
-0.007
NT
-0.001
NT
NT
T 1/2
(days)
1
1
1
1
23
9
9
11
18
NT
5
91
95
NT
866
NT
NT
aNT = no transformation observed.
bND = not detected.
-------
96
,„ Grenada soils.
.
~
Loading
Compounds Ory Wt
(%) '
— — ..
-
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenapntnene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Huoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
_
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
— •— V__M«.
— — — — — _
—
• __
95%
— |
Confidence Interval
i/ , . ._ Lower Limit
(day-1)
-0.568
-0.562
-0.532
-0.510
-0.518
-0.577
-0.568
-0.579
-0.058
-0.026
-0.539
-0.019
-0.016
-0.007
-0.007
NT
NT
" .
T 1/2
(days)
""^"••™^-™— •—•••_
1
1
1
1
1
1
1
1
2
27
1 '
36
45
107
102
NT
NT
— — — — — _
K
(day-1)
™^~"™™^"^^"^"^^^"^™™^^^^
-0.596
-0.581
-0.549
-0.520
-0.519
-0.577
-0.573
-0.584
-0.076
-0.037
-0.555
-0.027
-0.023
-0.011
-0.011
NT
NT
-'
TT72~
(days)
™*™^"p™^— •— ^—
1
1
1
1
1
1
1
1
9
19
1
25
30
66
64
NT
NT
— — — —
|
Upper Limit i
K — ^- !
(day-1)
^^^""^"^^""•^"^^^^^^^^
-0.540
-0.543
-0.515
-0.501
-0.516
-0.577
-0.564
-0.575
-0.040
-0.016
-0.524
-0.011
-0.008
-0.002
-0.003
NT
NT
_
TT7T I
(daysj j
— i
I j
1 j
1 i
i :
i 1
i
i \
i
17 1
1 i
65 j
86 ]
285 d
248 }
:
1
;;
i s
U
L
N
,,
fi
h
h
|;
|\
NT j|-«
NT 'f.
i
-------
97
soll,
952 Confidence Interval
Compounds
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
T 1/2
(days)
3.0
3-,
.0
3»
.0
3f*
.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3 —
.0
3.0
3.0
3.0
3.0
3.0
NDb
NO
NO
-0.523
NO
NO
-0.006
NO
-0.095
-0.087
NO
-0.033
-0.033
-0.030
-0.010
NT
NO
NO
ND
NO
1
NO
NO
116
ND
7
/
8
w
NO
21
21
23
72
NT
NO
~T
(day-1)
- — .
NO
ND
NO
-0.524
NO
NO
-0.009
NO
-0.351
-0.348
ND
-0.049
-0.036
-0.038
-0.016
NT
ND
~ 1 I/?
(days)
•
NO
ND
NO
1
NO
NO
75
NO
2
2
ND
14
19
18
43
NT
ND
upper L
(day-1)
— '
NO
ND
ND
-0.522
ND
NO
-0.003
NO
NT
NT
NO
-0.017
-0.029
-0.022
-0.010
NT
ND
imit
"I1 1/2
(days
~
ND
ND
ND
1
ND
ND
248
ND
NT
NT
ND
42
24
31
72
NT
ND
-------
98
Table 39. Kinetic data for PAH degradation/transformation In Meridian solH.
95% Confidence Interval
Compounds
Loading K T 1/2
Dry Wt. (day-1) (days)
Lower Limit
K
(day-1)
(days)
Upper Limit.
i<
(day-1)
aNT = no transformation observed.
bND = not detected.
(daysj
• •
Naphthalene
2-Methylnaphthalene
1-Methyl naphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Oibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
. _
"• !»
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
—— ^— •.
-0.542
-0.490
-0.490
-0.166
-1.551
-0.523
-0.544.
-0.544
-0.136
-0.180
NOD
-0.017
-0.013
-0.005
NT
NO
NO
—
1
1
1
4
1
1
1
1
5
4
NO
41
53
139
NT
NO
NO
— — — — — — .
— —— — — — — .
-0.551
-0.513
-0.514
-0.626
-0.586
-0.532
-0.548
-0.548
-0.284
-0.407
NO
-0.036
-0.022
-0.012
NT
NO
NO
„.
• i
1
1
1
1
1
1
1
1
2
2
NO
19
32
58
NT
NO
NO
— — — — •
— — — — ^— _
-0.533
-0.467
-0.466
NTa
NT
-0.515
-0.537
-0.539
NT
NT
NO
NT
-0.003
NT
NT
NO
NO
— •— — — ^_
.
1
1
1
NT
NT
1
1
1
NT
NT
NO
NT
205
NT
NT
NO
NO
•^•^•m^WMHBB
-------
99
Tab'e 39' (co^SeSr '" PAH d~-""n~,.on 1n Merjd(an ,01)!
; Compounds
Naphthalene
& lynenyI
Acenaphthy]ene
Acenaphthene
Oibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Huoranthene
Pyrene
1,2 Benzanthracene
Chrysene
|Benzo-a-pyrene
'Benzo-ghi-perylene
Loading
Dry Wt.
(%)
•
1.0
1.0
1JK
.0
1.0
1.0
1.0
1.0
1.0
1.0
1*»
.0
1.0
1.0
1/%
.0
1»
.0
1-»
.0
In
.0
1f\
.0
K
(day-l)
-0.108
-0.096
-0.091
-0.086
-0.083
-0.101
-0.109
-0.107
-0.018
-0.025
-0.096
NT
NT
-0.048
-0.043
NT
NT
T
I
(c
- .— .
6
V
7
8
8
8
\j
7
6
w
7
38
28
7
NT
NT
15
16
NT
NT
uower
(day-l)
""
-0.285
-0.272
-0.264
-0.026
-0.256
-0.028
-0.289
-0.286
-0.044
-0,161
-0.273
NT
NT
-0.146
-0.142
NT
NT
Limit
T 1/2
(days)
— •
2
b
3
w
3
«J
27
3
25
2
t,
2
16
4
3
NT
NT
5
*j
5
NT
NT
Upper
K
(day-l)
' ' .
kIT
Nl
KIT
Nl
HIT
NT
NT
NT
NT
HIT
NT
NT
NT
NT
MT
NT
NT
NT
MT
NT
NT
NT
NT
Limit
T 1/2
(days)
— .
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
;
-------
100
Table 39. Kinetic data for PAH degradation/transformation in Meridian soils.
(continued)
-
95%
Confidence Interval
Lower Limit
Loading
Compounds Dry Wt.
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Oibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
(*)
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
K
(day-1)
-0.606
-0.577
-0.557
-0.516
-0.539
-0.124
-0.070
-0.082
-0.086
-0.124
-0.585
-0.008
NT
-0.060
-0.062
NT
NO
T 1/2
(days)
1
1
1
1
1
6
10
8
8
6
1
90
NT
12
11
NT
NO
K
(day-1)
-0.637
-0.586
-0.561
-0.520
-0.547
-0.267
-0.221
-0.253
-0.242
-0.274
-0.592
-0.019
NT
-0.206
-0.216
NT
NO
T 1/2
(days)
1
1
1
1
1
3
3
3
3
3
1
37
NT
3
3
NT
NO
Upper Limit
K
(day-1)
-0.574
-0.567
-0.553
-0.512
-0.531
NT
NT
NT
NT
NT
-0.579
NT
NT
NT
NT
NT
NO
T 1/2
(days)
1
1
1
1
1
NT
NT
NT
NT
NT
1
NT
NT
NT
NT
NT
NO
-------
101
Table 40.
Kinetic data for PAH degradation/transformation in Wiggins soil
95% Confident TnfarvnT
. Compounds Dry w"9
1 (X)
1 '
Naphthalene 0 33
2-Methy]naphtnalene 0.*33
l-Methylnaphthalene 0 33
Biphenyl 0 33
Acenaphthylene 0*33
, Acenaphthene 033
i Dibenzofuran 0*33
r Fluorene n'->->
*. «•«•• \.n%_ ri v^
f Phenanthrene 0*33
& Anthracene n'^o
* Carbazole 0 33
T- Fluoranthene n'^
Pvrpnp J
* rjrrene 0.33
5 1,2 Benzanthracene 0.*33
: Chrysene 0>33
>Benzo-a-pyrene 0*33
Benzo-ghi-perylene o.*33
K
(day-1)
-0.523
-0.518
-0.492
-0.490
-0.150
-0.270
-0.271
-0.277
-0.178
-0.164
-0.174
rt A o A
-0.024
-0.122
-0.016
-0.260
NO5
NO
T 1/2
(days)
~
1
1
1
1
5
3
3
3
4
4
4
29
6
43
3
NO
NO
aNT = no transformation observed.
DND = not detected.
Lower
K
(day-1)
-0.529
-0.522
-0.505
-0.496
-0.565
-0.422
-0.421
-0.434
-0.258
-0.248
-0.276
-0.035
-0.221
-0.106
-0.391
NO
NO
Limit
r i/i
(days)
1
1
1
1
1
2
2
2
3
3
3
20
3
7
2
NO
NO
K" •"
(day-1)
-0.518
-0.514
-0.479
-0.485
-0.266
-0.119
-0.121
-0.120
-0.097
-0.081
-0.072
-0.013
-0.023
NTa
-0.129
NO
NO
r 1/2
(days)
1
1
1
1
3
6
6
6
7
9
10
53
30
NT
5
NO
NO
-------
102
Table 40. Kinetic data for PAH degradation/transformation in Wiggins soils.
(continued)
Loading
Dry Wt.
Compounds
Naphthalene
2-Methyl naphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
(*)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
K
(day-1)
-0.117
-0.119
-0.266
-0.258
-0.253
-0.017
-0.012
-0.012
-0.012
NT
NT
-0.012
NT
-0.001
NT
NT
-0.525
T 1/2
(days)
6
6
3
3
3
41
58
58
58
NT
NT
58
NT
693
NT
NT
1
95%
Confidence Interval
Lower Limit
K
(day-1)
-0.267
-0.263
-0.412
-0.391
-0.384
-0.143
-0.029
-0.032
-0.310
NT
NT
-0.023
NT
-0.007
NT
NT
-0.544
T 1/2
(days)
3
3
2
2
2
5
24
22
2
NT
NT
30
NT
99
NT
NT
1
I
Upper Limit i
K
(day-1)
NT
NT
-0.119
-0.125
-0.123
NT
. NT
NT
NT
NT
NT
-0.001
NT
NT
NT
NT
-0.506
T I/I '
(days; '
I
NT
NT
6
6
6
NT
NT
NT
NT
NT
NT
693
NT
NT
NT
NT
1
JL
*
-------
103
Compounds
Naphthalene
Dry §
/„ K T 1/2
(day-1) (days)
_, r.. WMU i cue
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
n
1,2 Benzanthracene
ru-
nzo-a-pyrene
nzo-ghi-perylene
3.0
3.0
3.0
3 A
.0
3.0
3.0
3.0
3**
.0
3 A
.0
3f\
.0
3rt
.0
3 A
.0
3rt
.0
3f%
.0
1 n
J.U
3.0
JA
.0
-0.202
-0.201
-0.155
-0.564
-0.542
-0.040
-0.025
-0.030
-0.034
-0.014
-0.013
-0.015
-0.002
-0.005
-0.001
-0.190
NO
3
3
w
4
1
x
1
X
17
28
23
20
50
53
46
347
139
7
4
NO
^ TtTF" ^PPer Limit
'««*•") (*y.) (4-1) J4?,
-0.315
-0.311
-0.280
-0.565
-0.548
-0.059
-0.043
-0.048
-0.052
-0.023
-0.020
-0.032
-0.007
-o.on
-0.007
-0.376
NO
2
2
2
1
1
12
16
14
13
30
35
22
99
63
99
2
NO
-0.089
-0.091
-0.031
-0.563
-0.536
-0.022
-0.007
-0.013
-0.016
-0.005
-0.006
NT
NT
NT
NT
-0.004
NO
8
8
22
1
1
32
99
53
43
139
116
NT
NT
NT
NT
173
NO
-------
104
Table 41. Kinetic data for PCP degradation/transformation in site soils.
95% Confidence Interval
Site
Meridian
Grenada
Columbus
Wiggins
Loading
Dry Wt.
(*)
3.0
1.0
0.3
3.0
1.0
0.3
3.0
1.0
0.3
3.0
1.0
0.3
-
K
(day-1)
NTa
-0.0096
-0.0152
-0.0335
-0.0131
-0.0152
-0.0018
NT
-0.0006
-0.0066
-0.0076
-0.0060
T 1/2
(days)
NT
72
43
21
53
46
385
NT
1087
105
91
116
Lower
K
(day-1)
NT
-0.0176
-0.0206
-0.0482
-0.0263
-0.0178
-0.0028
NT
-0.0021
-0.0200
-0.0235
-0.0217
Limit
T 1/2
(days)
NT
30
34
14
26
39
248
NT
334
35
29
32
Upper t
K
(day-1)
NT
-0.0015
-0.0115
-0.0188
NT
-0.0125
-0.0009
NT
NT
NT
NT
NT
.imit
T 1/2
(days)
NT
462
60
37
NT
55
758
NT
NT
NT
NT
NT
aNT = no transformation observed.
-------
105
2
s)
Meridian
Grenada
Columbus
Wiggins
1.
sons.
3.0
1.0
0.3
3.0
1.0
0.3
3.0
1.0
0.3
3.0
1.0
0.3
NTa
NT
-0.1251
-0.0152
-0.01973
-0.0006
NT
-0.001
NT
NT
NT
-0.0009
NT
NT
6
46
35
1161
NT
663
NT
NT
NT
766
NT
NT
-0.1959
-0.0178
-0.03935
-0.0053
NT
-0.004
NT
NT
NT
-0.0023
NT
NT
4
39
18
130
NT
160
NT
NT
NT
301
NT
NT
-0.0543
-0.0125
-0.00011
NT
NT
NT
NT
NT
NT
NT
NT
NT
13
55
6301
NT
NT
NT
NT
NT
NT
NT
aNT = no transformation observed.
-------
106
Table 43. Starting and peak microbe counts.3
Media
P
C
C+P
NA
PDA
PDAA
Loading
Dry Wt.
(%)
0.3
1.0
3.0
0.3
1.0
3.0
0.3
1.0
3.0
0.3
1.0
3.0
0.3
1.0
3.0
0.3
1.0
3.0
Columbus
Start
.07A
.02A
.01A
.50A
.47A
.50A
.09A
.01A
.01A
.67A
.88A
.74A
.90A
.91A
.57 A
.05A
.02A
.01A
Peak
.15A
.10A
.148
.50A
2. 008
2.008
.858
.398
.118
2.608
2.108
1.708
2.408
2.508
2.908
.05A
.04A
.058
Grenada
Start
.05A
.04A
.05A
.84A
1.20A
.70A
.06A
.04A
.04A
.48 A
.92A
.52A
1.10A
1.40A
1.10A
.04A
.04A
.02A
Peak
4.408
6.908
4.808
9. 408
7.608
7.108
4.408
8.208
5.808
8.408
6.908
9.608
10.008
9.108
9. 508
1.108
.708
.308
Meridian
Start
.31A
.33A
.24A
2.70A
2.20A
2.90A
.29A
.30A
.23A
3.20A
3.00A
3. 60 A
3.20A
2. 98 A
3.30A
.13A
.13A
.10A
Peak
2.108
4.108
5.108
3.50A
3.808
4.608
2.608
4. 008
4.608
3.40A
4.15A
4.808
3.20A
4.508
6.406
.17A
.13A
.198
Wiggins
Start
.22A
.09A
.05A
.40A
.20A
.26A
.27A
.10A
.05A
.42A
.39A
.05A
.51A
.29A
,27A
.05A
.05A
.07A
Peak
5.10B
6.106
4.10B
4.20B
3.00B
3. 90S
5.50B
6.40B
4.70B
5.10B
5. SOB
4. 708
5.70B
6.10B
5. 308
.16A
.11A
.07A
aStarting and peak microbe count means within a site, media, and loading rate are not
different by Duncan's Multiple Range Test (P = 0.05) if followed by the same letter.
-------
107
lives of more than one hundred days. Naphthalene, 2-methylnaphthalene,
1-methylnaphthalene, biphenyl, acenaphthalene, acenaphthene,
dibenzofuran, and fluorene have half lives of ten days or less in most
cases. Phenanthrene, anthracene, carbazole, and fluoranthene have half
lives between ten and one hundred days in most cases. Pyrene,
1,2-benzanthracene, chrysene, benzo-a-pyrene, and benzo-ghi-perylene
have half lives greater than one hundred days in most cases. In several
j
cases these last five showed essentially no breakdown within the time
frame of the experiment.
The breakdown rates of individual PAH's were apparently related to
molecular size and structure, as noted in previous studies. The zero to
ten day half life group contained compounds with two aromatic rings, the
ten to one hundred day half life group contained compounds with three
aromatic rings, and the one hundred plus day half life group contained
compounds with four or more aromatic rings. However, some of the
larger, most recalcitrant compounds apparently were broken down readily
in some situations. This gives hope that even the most persistent PAH's
might yield to biological remediation techniques under the right
conditions with appropriate microbial populations.
Carbazole, a compound containing a nitrogen bridge between two
aromatic rings, varied greatly in persistence in different soils and
loadings. This may be due to the nitrogen atom affecting water
solubility and other properties of carbazole under varying local
oxidation/reduction potentials and pH.
Acenaphthylene and acenaphthene, differing only in the presence or
absence of a double bond (and two hydrogens) show the effect of small
changes in structure. Acenaphthene had much longer average half life
-------
108
than acenaphthylene. Apparently, the double bond is easier to attack,
although the single bond in acenapthene also lowers the vapor pressure,
possibly affecting the half life by vaporization.
The microbial populations found in the plate counts were not
closely related to PAH breakdown, since PAH breakdown was similar at
similar concentrations over the four sites, while microbe counts
varied.
PCP transformation occurred in all the soils, but was slow in
Columbus soil, which was from a site not exposed to PCP treatment
wastes. Grenada soil transformed PCP with half lives ranging from one
to two months, a quite practical range for land treatment operations.
Meridian soil also exhibited rapid transformation rates except at the
highest loading rate. Wiggins soil transformed PCP with half lives of
three to four months, still an appropriate range for land treatment
operations especially considering its deep south location where soil
temperatures are high enough for good microbiological activity most of
the year. Although the Columbus soil did exhibit some transformation of
PCP, the low rates would bring into question the practicality of land
treating PCP at that location. However, it is not known what length of
time is required to build up a population of microorganisms suitable for
rapid degradation of PCP in hitherto unexposed soil. Evidently, the
relatively short time frame of these experiments was insufficient for
the Columbus soil, at least. It is likely in most soils with chronic
exposure to PCP (which is where PCP disposal by landfarming would be
needed) that suitable populations could be induced relatively quickly.
OCDD transformation occurred to some degree in''all the soils, but
only Grenada soil consistently transformed OCDD at all loadings. Since
-------
109
Grenada soil also consistently transformed PCP, a relationship may exist
in the potential for a soil to transform these two compounds. Oioxins
are widely regarded as being somewhat recalcitrant to biological
transformation, but these data indicate the potential for biological
treatment. Concentrated sources of dioxins would probably be
incinerated, but biological treatment in soil could be very useful for
materials such as wood treating wastes that contain low levels of
dioxins.
General Discussion
The results of these experiments indicate that PAH's, PCP, and OCDD
can be transformed at practically useful rates in soil. Although the
variability of the data is relatively large in some cases, the general
trend is clear. Land treatment of creosote and PCP wood treating wastes
appears to provide a viable management alternative based on treatability
data in the soils tested to date. The data variability does support the
need for conducting site-specific treatability studies to discern the
appropriate operation and management scenario for a given site.
Further study of treatment of OCOD, PCP, and the higher molecular
weight PAH's is needed to determine the most advantageous environmental
conditions and management techniques for more rapid transformation of
these compounds. Many of these compounds were readily transformed in
some cases. Therefore, further study may reveal reliable techniques for
enhancing land treatment as a practically useful management alternative
for these recalcitrant compounds. Since the environmental problems that
the wood treating industry has to deal with are almost unlimited, and
the resources available to solve these problems are quite limited, a
reliable, safe, economical remediation technique such as land treatment
is very attractive.
-------
110
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*
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APPENDIX A
METHODOLOGY
TABLE OF CONTENTS
PAGE
Extraction of PCP, PAH's, and OCDD from Soil 121
Clean-up and Determination of PAH's and PCP in Soil Extracts. . . 121
Clean-up and Determination of Octachlorodibenzo-p-dioxin
in Soil (MSU 1984) 123
Quality Assurance Program for Soil Extraction and Analysis. ... 125
Site and Soil Characterization 127
Transformation/Degradation Using a Standard Creosote/PCP
Mixture: Experiment I ..... 129
Transformation/Degradation of Site Specific Sludges:
Experiment II 131
Rationale for the Addition of Chicken Manure to Soil in the
Degradation/Transformation Studies 132
Microbiological Procedures 133
Statistical Procedures 136
List of Tables:
A-l. Analytical procedures for soil and water 120
A-2. Analytical procedures for sludges 120
A-3. Bacteria levels in four soils at 0% loading before and
after addition of chicken manure 134
A-4. Detection limits for PAHs, PCP, and dioxins 137
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120
Table A-l. Analytical procedures for soil and water (U. S. EPA 1986a).
Process
Method
number Compounds
Comments
Extraction of soil samples 3540 All
Extraction of water samples 3520 All
Clean up 3630 All
Analysis 8100 PAH's
Analysis 8040 OCDD+PCP
Analysis 8270 All
Analysis 8280
Use 10 g of soil
Use 1000 ml of water
Done after methylation
of phenols
For polynuclear
aromatic hydrocarbons
For chlorinated
phenols after
methylation and octa-
chlorodibenzo-p-dioxin;
using an ECO detector
Check for all compounds
Used for low-level
dioxins (penta, hexa,
and hepta dioxins)
Table A-2. Analytical procedures for sludges.
Process
Procedure
Water content
Organic content
Non-volatile products
Organic carbon
Total phenolics
Oil and grease
Nitrogen
Phosphorous
Inorganic chloride
ASTM D-95-70
Heating at 600°C for 2 hours in an oxidative
atmosphere
Heating at 600°C for 2 hours in an oxidative
atmosphere
Determined by CO? evolution
Method 222E Standard Methods for Examination
of Water and Wastewater
Method 5030 Standard Methods for Examination
of Water and Wastewater
Micro Kjeldahl followed by digestion with 5%
hydrogen peroxide and sulfuric acid; nitrogen
was determined colorimetrically using
nessierization
Determined after digestion colorimetrically
using the Fisbe-Subarrow method
Determined using a chloride specific ion
electrode
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121
Extraction of PCP. PAH's. and OCOD from Soil
Soil (10 g) was mixed with dry sodium sulfate (10 g). (The sodium
sulfate had been dried at 400°C for four hours and stored in a
V*
desiccator.) The sample was placed in an extraction thimble and 1 ml of
an internal standard in methylene chloride was added. The internal
standard mixture for high levels consisted of 5,000 ppm of
diphenylmethane, 1000 ppm of tribromophenol, and 21 ppm of octachloro-
naphthalene. For low levels, a 1 to 10 dilution of the internal
standard was used. The extraction thimble was placed in the Soxhlet
unit along with 300 ml of pesticide grade methylene chloride and boiling
chips.
The soil in the Soxhlet unit was extracted for 16 hours with a
minimum recycle rate of 5/hour. The extraction units were cooled and
transferred to a Kuderna-Danish unit and condensed to a volume of
approximately 3 ml.
The condensed extract was diluted to exactly 5 ml and aliquots were
taken for OCDD and PCP and PAH analyses. The remaining solution was
stored in a freezer at -27°C in a teflon-lined, screw-cap vial.
Clean-up and Determination of PAH's and PCP in Soil Extracts
Silica gel was activated at 130°C for 16 hours (100-120 mesh
Davison Chemical Grade 923 or equivalent) in a beaker covered with foil.
The silica gel was stored in an air-tight desiccator and redried every
two weeks. The columns (10 mm i.d.) were packed using 9 grams of
activated silica gel. The silica gel was packed into the column with
gentle tapping. The column was pre-eluted with 20 ml of pentane
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122
(pesticide grade or HPLC grade). The pentane was allowed to elute until
the solvent was just above the silica gel. The silica gel was not
allowed to dry before sample addition.
An aliquot ofthe methylene chloride extract was put in a sample
tube. The exact amount depended on the loading amount of creosote or
the analysis of previous sample. Three ml of sample was added if the
loading rate was less than 0.632% (wt/wt) of creosote on soil or if the
previous sample contained less than 6,000 ppm total PAH's.
Diazomethane solution (0.1 ml) was added to the sample tube and
mixed with a vortex mixer. An aliquot was added to the column. If a
1-ml aliquot on column was used, 2 ml of methylene chloride was added to
the column. A 1 to 3 ml aliqot of 40% methylene chloride/60% pentane
was added three times to ensure that all the sample is absorbed on the
column. Columns were eluted with 50 ml of the 40/60 mixture and the
eluant was collected. The eluant was concentrated to 5 ml by
evaporation using a gentle stream of dry air or nitrogen and analyzed
using gas chromatography conditions shown below for PAH's.
A 1-ml sample was removed for PCP analysis and stored in a glass
teflon-lined crimp-top vial. This sample had to be diluted for 6C/ECD
analysis. The exact dilution depended on the anticipated concentration
of PCP.
Tracor 540 Gas Chromatograph Parameters for PAH Analysis
Column: J and W DB-5 fused silica capillary
Length: 30 meters
Film thickness: 1.00 ym
Inside diameter: 0.32 mm
Injector temperature: 325°C
Oven temperature program: 4 minutes to 40°C, then 6°C per minute
for 15 minutes to 325°C
Carrier gas: Helium; Pressure: 12 psi
FID temperature: 325°C
Hydrogen flow: 60 cc/min
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123
Air flow: 400 cc/min
Nitrogen makeup: 40 cc/min
Injection: 2 ul splitless, vent after 1.5 min.
Amplifier range: xl
Tracer 540 G£>Parameter for PCP Analysis
Column: 6 ft x 2 mm i.d. glass packed with 3% SP-2250 on 100/120
mesh supelcoport
Carrier gas: Ar/CH4 at 10 cc/min
Injector: 250°C
Oven: 220°C
Detector: 350°C
ECD detector makeup gas: 95% argon/5% methane at 60 cc/min.
Clean-up and Determination of Octachlorodibenzo-p-dioxin in Soil (HSU
1984)
The analysis of OCDD in soil presented two significant problems
which had to be dealt with in order to obtain reliable results. First,
an extraction procedure had to be used which would be highly efficient
in removing OCDO from the sample matrix. This was especially important,
since the anticipated concentration of OCDD in the soil was in the
parts-per-billion range. Secondly, the majority of the compounds which
co-extracted with OCDD were likely to be several orders of magnitude
higher in concentration than OCDD. A clean-up technique had to be used
which allowed the concentration of OCDD with minimal chemical
interference.
I Method Summary-Methylene chloride Soxhlet extraction was found to
be very efficient in the removal of OCDD from a soil matrix (U. S. EPA
1983). Thus, an aliquot of soil extract from the PAH analysis, which
s
| uses the same extraction procedure, was considered to be adequate and
also would save analysis time. For our purposes, the removal of the
f majority of chemical interferences could be accomplished by a
modification of two column clean-up techniques recommended by EPA for
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124
2,3,7,8-TCDD analysis (U. S. EPA 1983). An elution profile and recovery
were determined for this modified column clean-up and were found to be
quite adequate (Mississippi State 1984).
Materials and Supplies--
Basic alumina, type WB-5, Activity Grade I, Sigma Chemical Co. or
equivalent.
Silica gel, 100/200 mesh, Fisher Scientific Co. or equivalent.
5 ml disposable pipet, Scientific Products Co.
Silane treated glass wool, Supelco, Inc.
9" disposable Pasteur pipets, Scientific Products Co.
10 ml graduated cylinder, Pyrex.
Small funnel with a cut latex bulb attachment.
Disposable 1 ml serological pipet, Scientific Products Co.
Compressed air with regulator and manifold.
Water bath.
Benzene (Burdick and Jackson distilled in glass).
OCOD for standards, Analabs.
Gas chromatograph equipped with ECO and a 6-ft x 2-mm i.d. glass
column packed with 3% SP-2250 on 100/120 mesh supelcoport.
Procedure--
Before use, the silica gel and basic alumina were activated for
16-24 hours at 130°C in a foil-covered glass container.
A small plug of glass wool was placed in the bottom of a 5-ml
pipet.
A funnel with a cut latex bulb attached was placed on the pipet and
2 ml of basic alumina (bottom) and 2 ml of silica gel (top) were
added to the pipet.
The column was pre-rinsed with two 4-ml portions of Benzene which
was then discarded.
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125
A 10-ml volumetric flask was placed under the column. Before
clean-up, the methylene chloride extract was exchanged with
benzene by blowing down the methylene chloride to dryness with
dry air in a 50°C water bath and adding 1 ml of benzene.
The benzene extract was placed on the column.
After the sample extract had flowed into the silica gel layer, 4 ml
of benzene was added to the column.
All of the eluate was collected until the column stopped dripping.
The eluate was diluted to 10 ml with benzene and a 1 yl sample was
injected on the Tracer 540 GC/ECD using the following conditions:
Oven: 280°C; Injector: 330°C; Detector: 350°C
Quality Assurance Program for Soil Extraction and Analysis
Four types of internal checks were used to monitor the accuracy of
the soil extraction and analytical procedures.
Blanks—This control was used to monitor the glassware, solvents,
and the solid supports (silica gel and alumina) background levels. The
blank was processed exactly the same way as the samples except no soil
was used during the Soxhlet extraction. Diphenylmethane, 2,4,6-
tribromophenol, and octachloronaphthalene were added to the extracts as
an internal standard.
Spike Samples—Standard solutions of PAH's, PCP, and OCDD were
prepared using the best standards available (purity * 99% or better) in
methylene chloride. A sample of the standard solution was added to the
soil before Soxhlet extraction. The sample was extracted and cleaned up
using the normal procedures. The values of the spiked sample were used
to determine the recovery values for the individual compounds.
Diphenylmethane, 2,4,6-tribromophenol, octachloronaphthalene were used
as internal standards. All standards were prepared using a Mettler
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5-place analytical balance. Each time a standard was prepared, the
weight, date, and standard number were recorded, and the balance was
checked with standard weights (Class S - National Bureau Standards).
Standard Solutions for Gas Chromatography Calibration—A standard
solution of PAH's containing the 16 compounds of interest was prepared.
It contained an internal standard (diphenylmethane). Standard solutions
were also made for the PCP and octachlorodibenzo-p-dioxin and analysis
with the corresponding internal standards 2,4,6-tribromophenol and
octachloronaphthalene. A minimum of three concentration levels was
used for each compound.
Blind Samples--Blind samples containing EPA standard reference
materials (Quality Assurance Branch EMSL-Cincinnati, U. S. EPA) were
diluted by the Quality Control Officer (Dr. Hamid Borazjani) and
analyzed.
GC/MS Analysis—A part of each sludge sample after homogenizing
(approximately 1 gram) was weighed to three significant figures, mixed
with an equal weight of anhydrous sodium sulfate and extracted for 16
hours with 300 ml of methylene chloride in a Soxhlet extractor. The
volume of methylene chloride from each sample was adjusted to 100 ml
with a volumetric flask. A 1.00 ml aliquot of each extract was
transferred to a screw cap test tube and stored at approximately 4°C
prior to GC/MS analysis. The sample weight range and dilution volume
were based on prior knowledge of concentrations determined by GC/FIO
analysis.
The GC was a Carlo Erba fitted with a J and W DB-5 capillary
column [0.25ym film thickness and 30 m (1) by 0.25 mm (i.d.)].
After sample injection the GC was operated at 70°C for 2 minutes and
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then programed to 280°C at 6 deg/min and from 280° to 320°C at 12
deg/min. The GC oven temperature was kept at 320°C for 20 minutes. The
injector and transfer line temperatures were 320° and 280°C,
*•"
respectively.
The mass spectrometer (Kratos MS80RFA) was operated in the electron
impact mode (70 eV) with a source temperature of 250°C. After a 6.0-
minute delay for elation of the solvent peak, mass spectral data were
acquired with a scan rate of 1 sec/dec for 54.0 minutes. Two standard
solutions (10 yg/ml and 200 yg/ml) containing known concentrations of
selected analytes were used to establish instrument response factors.
The concentration of each compound in solution was reported by the DS-90
data system and the concentration in sludge was calculated as follows:
. 100 ml x c yg/ml
c yg/g = -
Here, C - concentration of each compound in sludge (ng/g); 100 =
dilution volume, c = concentration of each compound in the sample
extract, and W = dry weight of the sludge sample in grams.
Site and Soil Characterization
Soil profiles were examined at each site in freshly excavated pits
and they were described and sampled using standard methods (Soil Survey
Staff, 1951). Soil morphological descriptions included horizonation,
Munsell color, texture, horizon boundaries, consistency, coarse
fragments, root distribution, concretions and pedological features.
Each horizon was sampled for laboratory analyses. Bulk density was
determined on major horizons using the non-disturbed core method (Blake,
1965). Saturated hydraulic conductivity was determined on non-disturbed
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cores using the constant heat method (Klute, 1965). Soil moisture
retention was determined on non-disturbed cores using a pressure
membrane apparatus (Richards, 1949).
Soil samples were air-dried in the laboratory, crushed with a
wooden rolling pin, and sieved through a 10-mesh sieve to remove
fragments larger than 2 mm (USDA, 1972). Particle size distribution was
determined by the hydrometer method and sieving (Day, 1965). Organic
matter was determined by a wet combustion procedure (Allison, 1935).
Extractable acidity was determined by the barium chloride-
triethanolamine method (Peech, 1965). Exchangeable aluminum was
determined in KC1 extractions following the procedure of Yuan (1959).
Exchangeable cations were extracted with neutral 1 j£ Nf^OAc and
determined by atomic absorption spectrophotometry (USDA 1972). Soil pH
was measured in water and 1 ^ KC1 using a 1:1 soil-to-liquid ratio.
Electrical conductivity was determined in saturated paste extracts using
a Wheatstone conductivity cell. Total sulfur was determined on soil
samples ground to pass a 60-mesh sieve in a LECO Sulfur Analyzer using
an induction furnace and I.R. detection.
The clay fraction (<2 mm) was separated by centrifugal
sedimentation using Calgon as a dispersing agent. Clays were
K-saturated, Mg-saturated, and glycerol-solvated for x-ray diffraction
analysis. The clay fraction was analyzed with a Norelco Geiger counter
spectrophotometer using Cu K radiation and a Ni filter. Minerals were
identified based on comparison of diffraction spacings and frequencies
to standard minerals as indicated by Jackson (1956), Carrol (1970), and
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Dixon and Weed (1978). Relative estimates of the amounts of clay
minerals present were based on peak area measurements with corrections
o
for Lorentz polarization at peaks greater or equal to 14 A.
f
Transformation/Degradation Using a Standard Creosote/PCP Mixture:
Experiment I
Wet soil was spread upon a new sheet of plastic and air-dried for
24 hours or longer until the moisture content was reduced. The dried
soil was stored in clean glass containers that had been labeled with the
soil source, the collection day, and a number. A sample of each new
soil was sent to Delta Labs, Inc., for analysis of soil parameters,
nitrogen, phosphorus, organic carbon, and inorganic metals; pH and
chloride ion was determined in-house. The soil was sieved just before
use to remove coarse plant materials from the soil, and the moisture
content was determined. Spiked soil samples were prepared using the
following procedure: Soil samples (50.0 g/beaker) were accurately
weighed into 10 beakers. Known amounts of creosote and/or technical
grade pentachlorophenol were added into each beaker. Technical grade
PCP was dissolved thoroughly in methylene chloride or methanol before
being added to the soil in the beaker. Then contents of all ten beakers
were combined and mixed for 2 hours in a clean glass jar using a sample
rotator with a minimum of 50 revolutions/minute. The dual procedure for
mixing was found to give more uniformly mixed material. Soil moisture
was adjusted to 70% of water-holding capacity by adding deionized f^O
into the soil when mixing was finished. The same mixing procedure was
repeated for controls.
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Two test units were set up for each site. One unit was a control
(0%), and one was loaded at 1% with the standard creosote/PCP mixture.
Each unit consisted of a brown glass container with a lid (baking dish)
containing 500 g*"bf soil (dry weight). Soil moisture content was
adjusted to 70% of water-holding capacity, and the container's weight
was determined. The accurate weight of the unit was important since
this value was used to maintain a proper moisture content during the
study. The test units were put into a constant temperature room
maintained at 22° i 2°C for the duration of the study.
Each test was begun by hand stirring the samples and removing two
separate 20 g samples of soil (air-dry weight) from each of the units.
One sample was used to analyze for PAH's, PCP, and octachlorodibenzo-
p-dioxin using the procedure described in a later section of this
report. The second sample was used for bacterial counts, pH and
chloride ion analysis.
The moisture content of each unit was adjusted weekly to 70% by
adding deionized water. The soil was aerated by thoroughly mixing the
total contents of each unit every 7 days.
The first samples were taken after 30 days (20 g dry weight) and
analyzed for PAH's, PCP, and OCDO. Further samples were taken every 30
days until the experiment was complete.
Soil from sites at Gulfport, Grenada, and Wiggins were loaded
initially and at 30 and 60 days. Soil from sites at Atlanta, Meridian,
and Wilmington were loaded intially and at 30 days, while the soil from
sites at Columbus and Chattanooga were loaded only at day 0. A change
was made in loading frequency because data for several sites indicated
that the bacteria at the sites were readily acclimated with one loading.
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Kinetic data needed to calculate the half lives, assuming first order
kinetics, were taken after the final loading and over a 60-120 day
period. ^
No organic or inorganic additions were made to the soil during the
initial set of experiments. The parameters measured were:
- microbial plate counts
- pentachlorophenol
- major PAH's contained in creosote
The soil microflora were measured using five different media. The
total amounts of bacteria, acclimated bacteria, and fungi were
determined using various media. The same media that were used to count
bacteria (PDA) were amended with creosote (PDA-C), pentachlorophenol
(PDA-P), a combination of creosote and PCP (PDA-PC), and PDA with
antibiotics to count fungi (PDA-AA). Because of the very low counts of
fungi and because their population counts did not change appreciably
during the studies, only the results from the bacteria and acclimated
bacteria are reported.
Transformation/Degradation of Site Specific Sludges: Experiment II
In this phase of the study, three different loading rates in soil
were studied—0.3i, l.Oi, and 3.0%--based on the total dry weight of
solids. A single loading was used instead of multiple loading, and
three replications of each soil and loading rate'combination were used.
Chicken manure was added to all soil at 4% by weight. Sludges from
Columbus did not contain PCP, so in order to get information on the
rates of degradation of PCP with this soil type, 128-3000 ppm of PCP
were added to the Columbus soils. The parameters measured were
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bacteria, fungi, actinomycetes, acclimated bacteria, pentachlorophenol,
major PAH's in creosote, and octachlorodibenzo-p-dioxin. A control
sample of soil from eachsite which contained no added sludges or PCP was
used as a control for the plate counting procedures and to determine the
background levels of PCP, PAH's, and OCDO. Although technical grade PCP
contains traces of two other series of dioxins, their levels are
extremely low (less than 5% of the octachlorodibenzo-p-dioxin levels).
Because of time and resource restraints, it was not possible to monitor
trace level dioxins as part of this study.
All other experimental methods, with the exception of the addition
of chicken manure to the soil (discussed below) were the same as in
Experiment I.
Rationale for the Addition of Chicken Manure to Soil in the
Degradation/Transformation Studies
During the course of this series of experiments, the data generated
reemphasized the importance of soil organic matter in facilitating the
microbial transformation of applied organic wastes. Since the ultimate
goal of these studies was to establish an operating landtreatment test
facility, the decision was made to maximize the operating effectiveness
and efficiency of the facility by amending the experimental soils with
an animal manure. This amendment accomplished several objectives. The
manure furnished: (1) a carbon source for potential cometabolism, which
has been found in at least some instances to be an important component
of the transformation process; (2) both major and minor nutrients; and
(3) a wide variety of microbes that were potentially important
biodegraders. Also, added organic matter should markedly decrease
mobility of hazardous constituents in organic applied wastes, which is
highly desirable in a landtreatment operation. Although other animal
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manures might serve as well, chicken manure was chosen for study because
it is readily available in many parts of the United States. A typical
analysis of the chicken manure used in this study is given below:
v»
Total organic carbon = 8.97%
Total nitrogen = 1.35%
Total phosphorous = 0.12%
A comparison between bacteria counts of four of the soils used in
this study was done before and after manure addition. No PCP or
creosote was added to the soil (0% controls) and the bacteria counts
were determined in soil 30 days after manure loading. The results
(Table A-3) indicate a large increase in both the total bacteria and the
acclimated bacteria in the soil with added chicken manure.
Microbiological Procedures
The media used for this study were potato dextrose agar, PDA (Difco
Labo»atories, Detroit, Michigan), 39 g in one liter of deionized water,
PDA amended with 5 mg/L of technical-grade pentachlorophenol [PDA-P]
(Vulcan Materials Company, Wichita, Kansas), PDA amended with 10 mg/L of
whole creosote [PDA-C], PDA amended with a combination of 5 mg/L of
pentachlorophenol and 10 mg/L of whole creosote [PDA-CP], PDA amended
with antibiotics—120 mg/L of streptomycin sulfate (Nutritional
Biochemical, Cleveland, Ohio) and 30 mg/L of chlorotetracycline
hydrochloride (Nutritional Biochemical, Cleveland, Ohio) [PDAA], and
actinomyces broth (Difco Laboratories, Detroit, Michigan) [ACA], 57 g in
one liter of deionized water amended with 15 g of Difco agar and 30 mg/L
of Pimaricin. The PDA was autoclaved for 20 minutes at 15 psi and 121°C
and then cooled to 55°C. Both creosote and pentachlorophenol were
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Table A-3. Bacteria levels in four soils at 0% loading before and after
addition of chicken manure*.
Total bacteria counts
[million coujjts/gram of soil]
Site
Gulfport
Wiggins
Columbus
Meridian
Before addition
1.13
0.41
1,25
1.10
After addition
4.50-7.20
3.10-4.50
2.80-3.10
3.10-4.20
Acclimated bacteria counts^
(million counts/gram of soil)
Before addition
0.07
0.12
0.25
0.09
After addition
0.50-0.61
0.64-2.30
0.14-0.35
0.48-0.92
aThese soils were OS-loaded, and counts were taken 30 days after addition of
chicken manure.
bBacteria acclimated to PCP and PAH's.
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dissolved thoroughly in methyl alcohol and added to cooled PDA. The
antibiotics were added to the cooled liquid medium before pouring into
petri dishes. The pl+-of the media was adjusted to 6.9 to 7.1 before
autoclaving. Twenty-five ml of PDA, PDA-C, PDA-P, PDA-CP, PDAA, and ACA
were poured into disposable petri plates and were allowed to solidify.
For colony counts, triplicate samples of loaded and non-loaded
soils were air-dried for 24 to 28 hours under a sterilized transfer
hood. The air-dried soil was then screened with a 400 mesh sieve.
Serial dilutions were made by using sterilized screened soil. Three
20-mg soil samples were weighed out from treated and non-treated soil
for each medium at each sampling date. A modified Anderson sampler
(Butterfield et al., 1975, 1977; Warcup, 1950) was used to distribute
the soil on the agar. Three 20-mg samples were distributed over each
medium for each treatment. Colonies were counted after 24 to 48 hours
of incubation at 28°C. A Darkfield Quebec Colony Counter (AO Scientific
Instrument, Keene, New Hampshire) was used to count the number of
colonies on each plate.
The number of counts recovered on PDA plates provided an estimate
of the total number of bacteria per gram of dry soil. On creosote-
containing plates, it represented the approximate number of bacteria per
gram of dry soil that were acclimated to creosote; on PCP-containing
plates, It represented the approximate number of bacteria per gram of
dry soil that was acclimated to pentachlorophenol; on PDA-CP plates, it
represented the approximate number of bacteria per gram of dry soil that
was acclimated to both creosote and pentachlorophenol; on PDAA plates,
it represented the approximate number of fungi per gram of dry soil; and
on ACA plates, it represented the approximate number of actinomycetes
per gram of dry soil.
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Statistical Procedures
Statistical methods were used to help determine estimates of
compound half-lives^,and confidence intervals for individual compounds.
Differences in concentration of PCP, PAH, and OCDD between sampling
times were evaluated by calculating a linear regression based on
first-order kinetics. The slope of the regression line was used to
calculate the first-order degradation rates in the soil/sludge mixtures.
The half-life of each compound was calculated from the first-order
degradation rate. The half-life values for the lower and upper 95
percent confidence intervals were also calculated for PCP, PAH, and OCDD
compounds, when waste was applied to soil, to indicate the range of
values about the half-life.
If the slope of the first-order regression was non-negative,
indicating that no treatment by degradation was observed, or if
degradation could not be quantified due to initial low concentration
(near or below detection limit), no degradation information was reported
in the tables.
The microbiological results for the sludges were analyzed using a
complete random design using days as treatments with three replications
and three samples for each replication. Duncan's multiple range test
was used to compare treatment mean differences at (P = 0.05). Data was
processed using the Statistical Analysis System (SAS) of prepackaged
programs at VIVC (Barr et al., 1979).
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Table A-4. Detection limits for soil and sludge.
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1 ,2-Benzanthracene
Chrysene
Benzo(a)pyrene
Benzo(gni)perylene
Sludge
(ppm)
17
23
17
18
22
18
21
18
27
26
36
35
37
43
46
47
48
Soil
(ppb)
220
290
220
240
280
240
270
230
340
330
460
450
480
560
590
610
620
Pentachlorophenol 0.27 27
Octachlorodibenzo-p-
dioxin 0.54 54
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FOREWORD
EPA is charged by Congress to protect the nation's land, air, and
water systems. Under a mandate of national environmental laws focused
on air and water quality, solid waste management and the control of
toxic substances, pesticides, noise and radiation, the Agency strives to
formulate and implement actions which lead to a compatible balance
between human activities and the ability of natural systems to support
and nurture 1ife.
*
The Robert S. Kerr Environmental Research Laboratory is the
Agency's center of expertise for investigation of the soil and subsurface
environment. Personnel at the laboratory are responsible for management
of research programs to (a) determine the fate, transport, and trans-
formation rates of pollutants in the soil, the unsaturated and saturated
zones of the subsurface environment; (b) define the processes to be used
in characterizing the soil and subsurface environment as a receptor of
pollutants; (c) develop techniques for predicting the effect of pollutants
on ground water, soil, and indigenous organisms; and (d) define and demon-
strate the applicability and limitations of using natural processes,
indigenous to the soil and subsurface environment, for the protection of
is resource.
Environmentally acceptable management of process sludges and
contaminated soils from wood treating facilities presents a widespread
problem that must be addressed under both RCRA and CERCLA regulations
and guidelines. On-sfte management of these wastes may be the most
desirable alternative currently available from both an environmental and
economic viewpoint. Treatment of these wastes in well designed and operated
soil systems is one of the on-site management technologies proposed. There
currently is a lack of readily available information relative to the
treatability potential of wood preservative waste contaminants in complex
waste-soil matrices. This report adds to this information base by presenting
and discussing data from the characterization and treatability screening
phases of a three-phase study directed toward quantitative evaluation of
treatment potential for pentachlorophenol and creosote waste contaminants in
the site soil at wood treating facilities. Characterization data are presented
for soils and sludges from eight wood treating locations in the southeastern
U.S. Degradation kinetic data are presented for four of these locations.
Additional results from the screening phase plus results for the field
evaluation phase will be presented in subsequent reports.
inton W. Hall, Director
Robert S. Kerr Environmental
Research Laboratory
111
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SUMMARY
Eight wood treating plant sites were chosen to study the
effectiveness of land treatment for remediation of wood treating wastes.
*•«
The morphological, chemical, and microbiological parameters of the soil
at each site were characterized. Typical wood treating waste sludges
from each site were chemically analyzed. Soil samples were taken from
each site to study the rate of microbiological breakdown of wood
treating waste components. In a preliminary experiment, a synthetic
waste was mixed with each soil at 1% of the dry weight of the soil in
order to ascertain waste breakdown rates using the same waste for all
soils. In a second experiment, waste sludge from each site was mixed
with soil from each site at three different loading rates (0.33, 1.0,
and 3.0% by weight). Chicken manure was added to the soils at 4%
weight. The soils were tested at thirty day intervals to determine
microbe populations and amounts of waste compounds remaining.
Degradation rates were calculated for PCP, OCDD, and seventeen PAH's.
The general conclusions from tnis study are that PAH's and PCP are
readily degraded in soil systems. PAH's were transformed easily in all
the soils tested, but PCP was transformed much more quickly in soils
with long term exposure to PCP. Lower molecular weight PAH's and PCP
were usually transformed more quickly than higher molecular weight PAH's
and PCP. Application of PAH antf PCP containing wastes to soil greatly
increases the population of PAH and PCP adapted microorganisms in the
soil. The results of this study indicate that land treatment is an
effective alternative for remediation of PAH and PCP containing wood
treating wastes. *
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