vvEPA
United States
Environmental Protection
Agency
Office of Research and
Development
Washington DC 20460
EPA/600/2-91/019
May 1991
On-Site Treatment of
Creosote and
Pentachlorophenal
Sludges and
Contaminated Soil
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EPA/600/2-91/019
May 1991
ON-SITE TREATMENT OF CREOSOTE AND PENTACHLOROPHENOL
SLUDGES AND CONTAMINATED SOIL
by
Gary D. McGinnis
Hamid Borazjani
Daniel F. Pope
David A Strobel
Linda K. McFarland
Mississippi Forest Products Laboratory
Mississippi State University
Mississippi State, Mississippi 39762
PROJECT CR-811498
Project Officer
John Matthews
Extramural Activities and Assistance Division
Robert S. Kerr Environmental Research Laboratory
Ada, Oklahoma 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ADA, OKLAHOMA 74820
Printed on Recycled Paper
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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.
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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 life.
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 transformation 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 demonstrate the
applicability and limitations of using natural processes, indigenous
to the soil and subsurface environment, for the protection of this
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-site 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 field evaluation phase 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. Comprehensive sets of soil core and soil pore liquid
samples were collected during a two-year field evaluation study
period. Data from these samples are discussed and evaluated relative
to transformation and migration of polycyclic aromatic hydrocarbon and
pentachlorophenol components contained in the wood treating wastes
used for this study. Results from the characterization and screening
phases are presented in a previously published EPA report (EPA-600/2-
88-055).
Clinton W. Hall, Director
Robert S. Kerr Environmental
Research Laboratory
iii
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ABSTRACT
Information is presented for quantitative evaluation of
treatment potential for creosote and pentachlorophenol (PCP) wood
treating contaminants in soil systems. The study was conducted in
three phases: (1) characterization, (2) treatability screening and
(3) field evaluation. Data generated in phases 1 and 2 were
discussed in a previous EPA Report (EPA/-600/2-88-055). This
report provides review of data generated during phases 1 and 2 plus
discussion of data generated during the two-year field evaluation
study. Results from this three-phase study indicated that creosote
contaminants, i.e., polycyclic aromatic hydrocarbon (PAH)
compounds, and PCP are subject to degradation in soil systems;
loading rates and previous exposure of site soil to particular
contaminants were identified as important factors in determining
rates of transformation for a particular site. Although
populations of PAH and PCP acclimated organisms increased markedly
when these compounds were applied to test soils, no correlation was
found between microbial population levels and transformation rates
for specific compounds of concern. Migration of compounds of
interest was negligible except in a highly sandy soil from one of
the eight sites for which column leaching studies were conducted.
iv
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CONTENTS
NOTICE ii
FOREWORD iii
ABSTRACT iv
FIGURES x
TABLES xi
1. INTRODUCTION 1
OBJECTIVE 1
EVALUATION REQUIREMENTS 1
EXPERIMENTAL APPROACH 3
Site, Soil, and Sludge Characterization 3
Sludge Treatability/Ijnmobilization 3
Field Evaluation 4
2. CONCLUSIONS 5
3. LITERATURE REVIEW 6
INTRODUCTION 6
WOOD PRESERVING INDUSTRY 7
Introduction (Burdell, 1984) 7
BASIC WOOD-TREATING PROCESS 8
CHARACTERIZATION OF THE ORGANIC WOOD PRESERVATIVES 8
CHARACTERIZATION OF WOOD-PRESERVING WASTES 20
DECOMPOSITION/IMMOBILIZATION OF PCP AND
CREOSOTE COMPONENTS IN SOIL 22
Pentachlorophenol 22
Creosote Components 27
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BIOACCUMULATION/TOXICITY OF PCP AND CREOSOTE 35
Plant/Animal Uptake of PCP 35
Toxic Effects of PCP 36
Plant/Animal Uptake of Creosote 38
4. EXPERIMENTAL METHODOLOGY 44
INTRODUCTION 44
PHASE I - SITE, SOIL, AND SLUDGE CHARACTERIZATION 44
PHASE II - LABORATORY TREATABILtTY STUDIES 45
Transformation/Degradation Using a Standard
Creosote/PCP Mixture: Experiment 1 45
Transformation/Degradation of Site Specific
Sludges: Experiment 2 46
Soil Transport 47
PHASE III - FIELD DEMONSTRATION STUDY 47
5. RESULTS AND DISCUSSION 53
PHASE I - SITE, SOIL, AND SLUDGE CHARACTERIZATION 53
Grenada, MS 53
Gulfport, MS 55
Wiggins, MS 55
Columbus, MS 55
Atlanta, GA 56
Wilmington, NC 56
Meridian, MS 56
Chattanooga, TN 57
Chemical Analysis of Wood-Treating Chemicals
in the Soil 57
Sludge Characterization 64
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PHASE II - LABORATORY TRANSFORMATION/DEGRADATION STUDIES 71
Transformation/Degradation Using a Standard
Creosote/PCP Mixture: Experiment 1 71
Transformation/Degradation of Site Specific
Sludges: Experiment 2 81
Migration Studies 90
PHASE III - FIELD DEMONSTRATION STUDY 91
SOIL CORE SAMPLES 91
Creosote Cells - Background Levels (10/26/87) 91
Creosote Cells - 10/30/87 Loading 105
Creosote Cells - 11/13/87 Sampling 105
Creosote Cells - 2/26/88 Sampling 106
Creosote Cells - 4/20/88 Loading 108
Creosote Cells - 5/10/88 Sampling 108
Creosote Cells - 7/29/88 Sampling
(Incorporation Zone) 108
Creosote Cells - 8/4/88 Loading 109
Creosote Cells - 10/7/88 Sampling
(Incorporation Zone) 109
Creosote Cells - 6/15/89 Sampling 109
Creosote Cells - 7/13/89 Sampling
(Incorporation Zone) 109
Creosote Cells - 8/11/89 Sampling 109
Creosote Cells - 9/8/89 Sampling
(Incorporation Zone) 109
Creosote. Cells - 10/27/89 Sampling
(Incorporation Zone) 110
Pentachlorophenol Cells - Background Levels 110
Pentachlorophenol Cells <- 10/30/87 Loading 110
Pentachlorophenol Cells - 11/13/87 Sampling 110
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Pentachlorophenol Cells - 2/26/88 Sampling 111
Pentachlorophenol Cells - 4/20/88 Loading 112
Pentachlorophenol Cells - 5/10/88 Sampling 112
Pentachlorophenol Cells - 7/29/88 Sampling
(Incorporation Zone) 112
Pentachlorophenol Cells - 8/4/88 Loading 112
Pentachlorophenol Cells - 10/7/88 Sampling
(Incorporation Zone) 112
Pentachlorophenol Cells - 6/15/89 Sampling 113
Pentachlorophenol Cells - 7/13/89 Sampling
(Incorporation Zone) 113
Pentachlorophenol Cells - 8/11/89 Sampling
(Incorporation Zone) 113
Pentachlorophenol Cells - 8/11/89 Sampling 113
Pentachlorophenol Cells - 9/8/89 Sampling
(Incorporation Zone) 114
Pentachlorophenol Cells - 10/27/89 Sampling
(Incorporation Zone) 114
MICROORGANISMS IN CELL SOIL 114
SOIL PORE LIQUID SAMPLES 114
Groundwater 115
GENERAL DISCUSSION 115
6. SUMMARY 120
REFERENCES 121
APPENDIX A ANALYTICAL METHODOLOGY 132
EXTRACTION OF PCP, PAH's AND OCDD FROM SOIL 133
CLEAN-UP AND DETERMINATION OF PAH's AND PCP
IN SOIL EXTRACTS 133
viii
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CLEAN-UP AND DETERMINATION OF
OCTACHLORODIBENZO-P-DIOXIN IN SOIL (MSU 1984) 134
Method Summary 135
Blanks 136
Spike Samples 136
Standard Solution for Gas Chromatography
Calibration ,137
Blind Samples 137
GC/MS Analysis 137
APPENDIX B MICROBIOLOGICAL PROCEDURES 141
APPENDIX C SITE AND SOIL CHARACTERIZATION
EXPERIMENTAL PROCEDURES 143
APPENDIX D RATIONALE FOR THE ADDITION OF CHICKEN
MANURE TO SOIL IN THE DEGRADATION/
TRANSFORMATION STUDIES 145
APPENDIX E STATISTICAL PROCEDURES 148
APPENDIX F RAW DATA FROM EXPERIMENT 1, EXPERIMENT 2,
AND FROM THE OPERATION OF THE WIGGINS
SOIL TREATMENT UNIT 150
IX
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FIGURES
1. Principal Cuts Produced in Coal-Tar Distillation 14
2. Proposed Route for Decomposition of Pentachlorophenol 23
3. Proposed Mechanism for the Microbiological
Degradation of Anthracene (Rogoff 1961) 30
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TABLES
1. Volume of Wood Commodities Treated in 1978 7
2. Comparison of Composition of Commercial Grade
and Purified Grade Pentachlorophenol (U.S. EPA 1978) 9
3. Chlorodioxin Isomer Distributions in Commercial
Grade PCP (Dowicide 7) and PCP-Na Samples
(Buser 1975, 1976) 10
4. Physical Properties of PCP (Crosby 1981;
Bevenue et al. 1967) 11
5. Chemical Composition of a United States and
a German Creosote 13
6. Physical Properties of Creosote and Its Fractions
(USDA 1980) 15
7. American Wood Preservers' Association Specifications
for Creosote-Coal Tar Solutions 16
8. Properties of 16 Priority Pollutant PAH Compounds
(Sims 1987) 17
9. Daily Discharge of Creosote Wastewater Pollutants
by the Wood-Preserving Industry (USDA 1980) 21
10. Degradation of Pentachlorophenol in Soil (USDA 1980) 26
11. Kinetic Parameters Describing Rates of Degradation
of PAH and Phenolic Compounds in Soil Systems
(Sims and Overcash 1983, ERT 1985b) 31
12. Toxicity of Various Dioxin Isomers to Experimental
Animals 40
13. Health Effects of Chemical Constituents of Creosote
(U.S. EPA 1984) 41
14. Loading Rates in Soil Treatment Unit Cells 50
15. Site Location in Major Land Resource Areas 54
16. Overall Field Evaluation Site Soil Composition 54
17. Soil Concentration of PCP at the Proposed Field
Evaluation Sites 59
18. Soil Concentration of PAH's at the Proposed Field
Evaluation Sites 60
xi
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19. Soil Concentration of Octachlorodibenzo-p-dioxin at
the Proposed Land Treatment Sites (0-6 inches) 61
20. Abbreviations and Method Detection Limits of
Compounds Analyzed in this Study 62
21. Microbial Plate Counts at Proposed Field
Evaluation Sites 63
22. Nitrogen and Phosphorous at the Eight Selected Sites 63
23. Characteristics of the Eight Sites Used in this Study 65
24. Composition of the Sludges 66
25. Chemical Composition of the. Sludges 66
26. Concentration of PCP, Total PAH's and OCDD in Each
Sludge Samples 67
27. Concentration of PAH Constituents in Sludges from
the Selected Sites (g/g dry weight) 68
28. Minor Components Present in Sludge 69
29. Concentration of Metals in Each Sludge Sample 70
30. Kinetic Data for PAH Degradation/Transformation
in Atlanta Soils 72
31. Kinetic Data for PAH Degradation/Transformation
in Chattanooga Soils 73
32. Kinetic Data for PAH Degradation/Transformation
in Columbus Soils 74
33. Kinetic Data for PAH Degradation/Transformation
in Grenada Soils 75
34. Kinetic Data for PAH Degradation/Transformation
in Gulfport Soils 76
35. Kinetic Data for PAH Degradation/Transformation
in Meridian Soils 77
36. Kinetic Data for PAH Degradation/Transformation
in Wiggins Soils 78
37. Kinetic Data for PAH Degradation/Transformation
in Wilmington Soils 79
xii
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38. Kinetic Data for PCP Degradation/Transformation
in Site Soils 80
39. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Atlanta Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 82
40. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Chattanooga Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 83
41. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Columbus Soil Loaded with site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 84
42. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Grenada Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 85
43. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Gulfport Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 86
44. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Meridian Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 87
45. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Wiggins Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 88
46. Half-Lives and 95% Confidence Limits of PAH's
and PCP in Wilmington Soil Loaded with Site Sludges at
0.33, 1.0, and 3.0% by Soil Dry Weight 89
47. Polycyclic Aromatic Hydrocarbons in Soil Core
Leachate (ppb) 92
48. Pentachlorophenol in Soil Core Leachate (ppb) 93
49. Polycyclic Aromatic Hydrocarbons in Soil Core
Sections (ppm) 94
50. Pentachlorophenol in Soil Core Sections (ppm) 99
51. Octachlorodibenzo-p-dioxin in Soil Core Sections (ppm) 101
52. Wiggins Soil Treatment Unit - PAH, PCP, and OCDD
in Zone 1 Soil, Creosote Loaded Cells (ppm) 102
xiii
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53. Wiggins Soil Treatment Unit - PAH, PCP, and OCDD
in Zone 1 Soil, Pentachlorophenol Loaded Cells (ppm) 103
54. Wiggins Soil Treatment Unit - PAH, PCP, and OCDD
in Zone 1 Soil, Control Cells (ppm) 104
55. Nutrients and pH of Treatment Unit Soil After
First Loading 107
56. Wiggins Soil Treatment Unit - PAH in Lysimeters (ppb) 116
57. Wiggins Soil Treatment Unit - Pentachlorophenol
in Lysimeters (ppb) * ^^
58. Pentachlorophenol and Total PAH's in Wiggins
LTDU Monitoring Wells (mg/L) 119
i j.! '• • •
59. Analytical Procedures for Soil and Water
(U.S. EPA 1986a) 139
60. Analytical Procedures for Sludges 140
61. Bacteria Levels in Four Soils at 0% Loading
Before and After Addition of Chicken Manure 147
62. Experiment I: PAH in Site Soil (ppm) 151
63. Experiment I: PCP in Site Soil (ppm) 157
64. Experiment I: OCDD in Site Soils (ppm) 158
65. Experiment II - Polycyclic Aromatic Hydrocarbons
in Site Soil (ppm) 159
66. Experiment II - Pentachlorophenol in Site Soil (ppm) 183
67. Experiment II - OctachiorodibeHzo-p-dioxin in
Site Soil (ppm) 191
68. Wiggins Soil Treatment Unit - PAH in Site Soil (ppm) 199
69. Wiggins Soil Treatment Unit - PCP in Soil (ppm) 215
70. Wiggins Soil Treatment Unit - OCDD in Soil (ppm) 218
71. Wiggins Soil Treatment Unit - Polycyclic Aromatic
Hydrocarbons and Pentachlorophenol in Zone of
Incorporation Soil (ppm) 221
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SECTION 1
INTRODUCTION
Soil treatment systems have been used for a variety of
industrial wastes; however, biological treatment of hazardous
industrial waste in a soil system using a controlled engineering
design and a management approach has not been widely practiced.
This is due, in part, to lack of a comprehensive technical
information base detailing behavior of hazardous constituents as
specifically related to current concern regarding the treatability
of such constituents in soil, i.e., degradation, transformation,
and immobilization. Soil treatment systems that are designed and
managed based on a knowledge of soil-waste interactions may provide
a significant technology for the environmentally acceptable
treatment and disposal of selected hazardous wastes.
OBJECTIVE'
The overall objective of this study was to evaluate the
efficacy of biological treatment in a soil system as an on-site
management alternative for contaminated soils and sludges
containing pentachlorophenol and creosote. This goal was pursued
in a three phase study: Phase I - Site, soil and sludge
characterization, Phase II - Sludge treatability/immobilization
screening, and Phase III - Pilot scale evaluation. Phase I was
conducted in order to determine the nature of the contaminated soil
problem at wood treating plant sites - i.e., what kinds of
contaminants are present and where they are located. The soil
characteristics (chemical and pedological) were studied to develop
data for comparison of the effect of soil type and constituents on
soil treatment of wood treating wastes. Phase II was conducted to
determine if soil treatment of wood treating wastes was effective
in controlled laboratory studies, and if the results of such
studies could predict results of soil treatment in the field. The
tendency of the different soils to immobilize the waste components
and retain them in the treatment zone was studied. Phase III was
conducted to apply the results of the earlier phases in the field
and to study the accumulation or transformation of the waste
components in soil under field conditions. Management operations
feasible in a high rainfall hot climate were studied.
EVALUATION REQUIREMENTS
Standards for demonstrating treatment of hazardous wastes in
soils of a land treatment system 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. These same standards should be applicable for any
soil treatment system.
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Complete 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.
Transformation refers to partial degradation 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
biotransformation. The rate of degradation/transformation may be
established by measuring the loss of the parent compound from the
soil/waste matrix over time.
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 partition 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 test units.
Demonstration of soil treatment requires an evaluation of
degradation, transformation, and immobilization processes -.
Quantification of these processes is needed to obtain an integrated
assessment of design and management requirements for successful
assimilation of a waste in a soil system. 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, laboratory analyses and studies, theoretical
parameter estimation methods, field tests, and operating data from
existing soil treatment units. Literature data is discussed in the
Literature Review section of this report.
At this time, the U.S. EPA (1986b) considers the use of only
information from the literature to be insufficient to support
demonstration of treatment of hazardous wastes in soil. Site and
waste specific data must be generated in laboratory and field
studies to demonstrate that the particular waste can be
successfully treated in the particular soil. The regulations
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.
Finally, the ability of the soil to immobilize the waste compounds
must be evaluated.
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EXPERIMENTAL APPROACH
Site. Soil and Sludge Characterization '
Eight wood treating sites located in the southeastern United
States were selected for study. Sites having a variety of soil
types were selected in order to determine how the rates of
degradation/transformation are affected by soil characteristics
such as the organic carbon and clay content. The history and
physiographic characteristics of each site were evaluated and the
physical and chemical characteristics of the soils were determined.
The chemical and physical characteristics of the waste sludges
from each site^w^re^determinedT Some sites had several sludge types
available, but only one from each site was chosen for use in Phase
II.
Sludae Treatabilitv/Immobilization
The potential for degradation/transformation of the organic
hazardous constituents in the sludges was determined by applying
the sludges at three loading rates to the site soils in bench scale
batch tests. Soil concentrations of specific constituents were
measured at thirty-day intervals. The first-order reaction-rate
constant was used to calculate half-lives for each constituent. The
half-lives provided quantitative information for evaluating the
extent and rate of treatment, the effect of different loading rates
and for comparing treatment effectiveness for each waste/soil
combination as a function of design and management factors. First-
order kinetics were used for convenience of comparison only; it
should not be inferred that particular compounds were undergoing
a first-order reaction at a particular site.
Treatment of a hazardous waste refers specifically to
treatment of hazardous constituents contained in the waste.
Standards identified in 40 CFR Part 264.272 (c) (i) refer to Appendix
VIII constituents listed in Part 26. Where waste(s) are from an
identified process, i.e., wood preserving, EPA may accept analyses
performed on a subset of constituents. In this study, the semi-
volatile polycyclic aromatic hydrocarbons (PAH's) including
naphthalene and methyl naphthalenes, larger molecular weight PAH's,
pentachlorophenol (PCP), and octachlorodibenzo-p-dioxin (OCDD), a
total of nineteen compounds, were used as the key parameters.
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.,
1987) . The leaching potentials were characterized for these loading
rates in laboratory soil-column studies using semi-undisturbed soil
cores.
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Field Evaluation
A research and demonstration land treatment unit was
constructed at the Wiggins, MS site to evaluate design and
management scenarios developed from the laboratory studies.
Degradation/transformation/migrajtion-of-^CP and creosote containing
sludges applied at three loading rates)to test plot soils were
studied over a period of tfir&e
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SECTION 2
CONCLUSIONS
The following conclusions are based on transformation and
migration data from laboratory studies and the field evaluation
study:
1) PAH and PCP compounds in wood treating wastes were transformed
in soil treatment systems.
2) Loading rates and previous exposure of the soil to particular
compounds were identified as important factors in determining
transformation rates.
3) Populations of PAH and PCP acclimated microorganisms increased
markedly when these compounds were applied to soil.
4) Migration of the compounds studied was negligible except in
the almost pure sand from one of the eight sites for which
column leaching studies were conducted.
5) Results of the field evaluation study closely approximated
results of the laboratory study both for transformation and
migration data.
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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, textile, 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 which quantify 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 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 tb
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 obtained from several sources including literature
data, field tests, laboratory studies, laboratory analyses,
theoretical parameters, estimation methods, and operating date from
existing land treatment units (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 influence 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.
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In this project, hazardous waste from eight wood-preserving
sites was used to evaluate the soil treatment potential of these
types of waste in various soil types. A comprehensive assessment
of literature available for both waste types, pentachlorophenol
(PCP) and creosote, was conducted as an aid in making these
evaluations.
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) PCP in petroleum
(penta), 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 l: Volume of wood commodities treated in 1978.
Product Volume treated with
Creosote solutions Penta Inorganic salts3
1,000 cu. ft.
Crossties, switch
ties, and land-
scape ties
Pole
Crossarms
Piling
Lumber and
timbers
Fence posts
Other products
103,138
18,237
41
9,993
10,780
4,584
7.815
449
41,905
1,615
1,154
21,209
10,983
2.681
2,498
4,038
29
943
73,317
4,461
7.616
Total 154,587 79,996 92,903
4 The main inorganic salts are copper, chromium, and arsenic.
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8
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 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 is increased until a predetermined
liquid volume is absorbed into1the 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°C to 400°C fractions are creosote. Creosote is
mostly aromatic single to multiple ring compounds (polycyclic
aromatic hydrocarbons). Over 200 different components have been
identified in creosote.
Pentachlorophenol (4-8%) 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.
CHARACTERIZATION OF THE ORGANIC WOOD PRESERVATIVES
The two major organic wood preservatives used in the United
States are PCP and creosote.
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 which is believed to contribute 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 which generate 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).
Table 2: Comparison of composition of commercial grade and
purified grade pentachlorophenol (U. 8. EPA 1978).
Analytical results
Component
Commercial3
(Dowicide 7)
Purified13
(Dowicide EC-7)
Pentachlorophenol
Tetrachlorophenol
Trichlorophenol
Chlorinated phenoxyphenols
Octachlorodioxin
Heptachlorodioxins
Hexachlorodioxins
Octachlorodibenzofuran
Heptachlorodibenzofurans
Hexachlorodibenzofurans
88.4%
4.4%
0.1%
6.2%
2500 ppm
125 ppm
4 ppm
80 ppm
80 ppm
30 ppm
89.8%
10.1%
0.1%
—
15.0 ppm
6 . 5 ppm
1 . 0 ppm
1 . 0 ppm
1.8 ppm
1 . 0 ppm
Sample 9522A.
Technical grade PCP purified by distillation.
-------
10
Table 3: Chlorodioxin isomer distributions in commercial grade
PCP (Dowicide 7) and PCP-Na samples (Buser 1975, 1976).
Chlorodioxin
1,
1,
1,
1,
1,
1,
1,
2,
2,
2,
2,
2,
2,
2,
3
3
3
3
3
3
3
,6
,6
,6
,7
,4
,4
,4
,7,
,8,
,7,
,8,
,6,
,6,
,6,
9-Cl6D
9-Cl6D
8-Cl6D
9-Cl6D
7,9-Cl7D
7,8-Cl7D
7,8,9-Cl8D
PCPa
(ppm)
1
3
5
0
63
171
250
PCP-Nab
(ppm)
0.
1.
1.
0.
16.
22.
110.
5
6
2
1
0
0
0
a
Dowicide 7 (commercial PCP).
Sodium salt of PCP.
^ The physical properties of a compound play an important role
in how the compound behaves under different conditions. These
properties influence the mobility of a compound in air or water,
its ability to adsorb to surfaces, and its susceptibility to
degradation. These factors are important because they relate to
the route and rate of exposure by which a compound might be
received by man or other organism. Some of the selected physical
properties of pentachlorophenol 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 Beckroan, 1967). The chlorinated ring structure tends
to increase stability, but the polar hydroxyl group tends to
facilitate biological degradation (Renberg, 1974).
Pentachlorophenol 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.
x Since pentachlorophenol is moderately volatile, a closed
system should be used when heating environmental samples to prevent
poor recoveries (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).
-------
11
Table 4: Physical properties of POP (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
C6C15OH
255.36
190°C
293°C
1.85 g/CC
4.70-4.80
1760
1.03 X
Vapor pressure, Torr (mm Hg)
20°C
50°C
100°C
200°C
300°C
1.7 x 10
1.7 X 10
3.1 X 10
0.14
25.6
758.4
-5
-4
-3
Solubility in water (g/L)
0°C
20°C
30°C
50°C
70°C
0.005
0.014
0.020
0.035
0.085
Solubility in organic solvents
(g/lOOg solvent)
in methanol
in methanol
in diethylether 20°C
in diethylether 30°C
in ethanol
in ethanol
in acetone
in acetone
in xylene
in xylene
in benzene
in benzene
in carbon tetrachloride 20°C
in carbon tetrachloride 30°C
20°C
30°C
20°C
30°C
20°C
30°C
20°C
30°C
20°C
30°C
57
65
53
60
47
52
21
33
14
17
11
14
2
3
-------
12
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
because of the production process discussed below, it is generally
agreed that creosote contains several thousand different compounds
which could be identified with GC/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 ^polycyclic 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 pyridines, 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 Preservers1 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 terms of their physical properties. The American Wood
Preservers' Association specifications for creosote for various
uses are given in 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.
-------
13
Table 5; Chemical composition of a United states and a German
creosote.
Compound or component
U.S. creosote3
•Percent of
German creosote
Naphthalene
Methyl naphthalene
Diphenyl dimethylnaphthalene
Biphenyl
Acenaphthene
Dimethylnaphthalene
Diphenyloxide
Dibenzofuran
Fluorene-related compounds
Methyl fluorenes
Phenanthrene
Anthracene
Carbazole
Methylphenanthrene
Methyl anthracenes
Fluoranthene
Pyrene
Benzofluorene
Chrysene
TOTAL
2.0
90.4
7.3
4.2
3.2
4.1
3.4
9.6
12.6
5.4
69.0
a Lorenz and Gjovik, 1972.
b Becker, 1977.
-------
Coal
Tar
Distillation
Unit
Pitch
14
Chemical Oil
Top-of-Column Oil
Uncorrected Creosote Oil
Heavy Oil
Figure 1. Principal cuts produced in coal-tar distillation,
-------
15
Table 6: Physical properties of creosote and its fractions (USDA 1980) .
American Wood Preservers' Association Standards
Water % volume
Xylene, insoluble,
% by wt.
Specific gravity 38/15. 5°C
Whole creosote
Fraction 235-315°C
Fraction 315-355°C
Residue above 355°C
Pl-65a
< 1.5
< 0.5
> 1.050
> 1.027
> 1.095
P7-72D
< 1.0
< 0.5
> 1.060
P13-65C
< 1.5
< 0.5
> 1.080
> 1.030
> 1.105
> 1.160
Distillation, % by wt,
Min. Max.
Min.
Max.
a For land and fresh water use.
b For brush or spray application.
c For marine (coastal water) use.
Min. Max.
Up to 210°C
235°C
270°C
315°C
355°C
— -
—
20.0
45.0
65.0
2.0
12.0
40.0
65.0
82.0
1.0
10.0
— —
— — —
65.0
—
— —
20.0
45.0
65.0
2.0
12.0
40.0
65.0
75.0
A comparison of physical properties of creosote and creosote/coal
tar mixtures as shown in Table 7 indicates much higher distillation
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).
-------
Table 7: American Hood Preservers* Association specifications for creosote-coal tar
solutions.9
Composition
Creosote
Coal tar
Water (% by volume)
Xylene, insol.
(% by weight)
Coke residue
(% by weight)
Specific gravity 38/15.
Whole oil
235-315°C
315-355°C
Residue
Distillation
To 210°C
To 235°C
To 270°C
TO 315°C
TO 355°C
Residue
100%
— —
0.99
5°C
1.102
1.054
1.133
1.87
6.89
19.39
49.8
72.58
26.67
A
< 80
—
> 3.0
> 2.0
> 5.0
1.06-1.11
1.025
1.085
—
5
25
— —
36
60
— —
Grade
B
< 70
—
> 3.0
> 3.0
- •
> 7.0
1.07-1.12
1.025
1.085
—
5
25
__
34
56
__
C
< 60
— —
> 3.0
> 3.5
> 9.0
1.08-1.13
1.025
1.085
—
5
25
__
32
52
— —
D
> 50
—
> 3.0
> 4.0
> 11.0
1.09-1.14
1.025
1.085
—
5
25
__
30
48
— —
Lorenz and Gjovik, 1972.
-------
Table 8. Properties of 16 pollutant PAH compounds. (Sims 1987).
Vapor
Aqueous Melting Boiling Pressure Length of
Molecular Solubility* Point * Point * 8 20°C Molecule
Height mg/1 *C -c torr Log K_* A* *„.
1. TWO Rlngg
Naphthalene
2. Thr^e. R^nflS
Acenaphthylene
1 II 1 128 31,700 80 218 4.92xlQ-* 3.37 8.0 1,300*
rrS
I 152 3,470 92 265 2.9xlQ-« 4.07
Acenaphthene
154 3,930
96
279
2.0x10-* 4.33
Fluorene
166 1,900 116 293 1.3x10-*
4.18
Anthracene
Phenanthrene
178 73
178 1,290
216
101
340 1.96xlO-« 4.45
340 6.80x10-" 4.46
10.5 2,600*
9.5 23,000*
-------
Table 8. (continued)
Aqueous Melting Boiling
Molecular Solubility* Point * Point *
Weight mg/1 -C -C
Vapor
Pressure
8 20-C
torr
Log K_*
Length of
Molecule
A*
3. Four Rings
Fluoranthene
202
260
111
6.0xlO-
5.33
9.4
Pyrene
Benz(a)anthracene
Chrysene
4. Five Rings
Benzo(b) fluoranthene
Benzo(k)fluoranthene
202
228
228
252
252
135
14
1.2
0.55
149
158
255
167
217
360
400
400
6.85x10-'
5.0xlO-»
6.3x10-'
5.0x10-'
5.0x10-'
5.32
5.61
5.61
6.57
6.84
9.5
11.8
11.8
62, 700'
84,000*
00
-------
Table 8. (continued)
Molecular
Weight
Aqueous
Solubility*
mg/1
Melting
Point *
•C
Boiling
Point *
•C
Vapor
Pressure
% 20-C
torr
Log K_*
Length of
Molecule
A-
Benzo(a)pyrene
Dibenz (a,h)anthracene
Benz (a,h, Dperylene
Incfeno(l,2,3,cv ctfyzere
252
278
27«
276
3.0
2.49
0.26
62
179
262
222
163
496
5.0x10-'
1.0x10-"
1.0x10-"
6.04
5.97
1.0xlO-» 7-23
7.66
4,510,651
13.5 2,029,000'
* Sims and Overcast) (1983).
+ Karlckhoff et al. (1979).
t Means et al. (1980) (mean value is reported).
-------
20
CHARACTERIZATION OF WOOD-PRESERVING WASTES
There are several sources of contamination at wood-treating
sites. During the treatment cycle, waste water with traces of
preservative is produced from the live steaming of the wood, from
vapor drying or oil seasoning, from cleanup, and from contaminated
rain water. Treatment of this plant process 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 to a stream. A large number of the plants had
sumps or ponds 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 ties and pole plants.
-------
Table 9:
21
Daily discharge of creosote wastewater pollutants by the
wood-preserving industry (USDA 1980).
Creosote
Component
Naphthalene
2-Methylnaphthalene
1-Me thy 1 naphtha 1 ene
Biphenyl
Dimethylnaphthalenes
Acenaphthene
Dibenzofuran
Fluorene
Methyl f luorenes
Phenanthrene
Anthracene
Carbazole
Methylphenanthrenes
Methylanthracenes
Fluoranthene
Pyrene
Benzof luorenes
Chrysene
Composition of
Whole Creosote
Percent
3.0
1.2
.9
.8
2.0
9.0
5.0
10.0
3.0
21.0
2.0
2.0
3.0
4.0
10.0
8.5
2.0
3.0
Allowable Discharae3
1977 1983
Pounds/day
5.0
2.0
1.5
1.3
3.4
15.1
8.4
16.8
5.0
1.4
.6
.4
.4
1.0
4.3
2.4
4.8
1.4
35.3 10.0
3.4
3.4
5.0
6.7
16.8
14.2
3.4
5.0
1.0
1.0
1.4
1.9
4.8
4.0
1.0
1.4
a Discharges are based on a flow rate of 5,000 gal/day per plant, 90
plants, and discharge limitations on oil and grease of 45 mg/liter in
1977 and 13 mg/liter in 1983.
-------
22
DECOMPOSITION/IMMOBILIZATION OF POP AMD CREOSOTE COMPONENTS IN SOIL
Pentachlorophenol
Biodegradation of PCP in soil has been extensively studied.
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 (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 CO2 and inorganic
chloride ions.
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 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 H2O2 to remove organic
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.
-------
OH
OCH
Cl
Cl
co2 + ci
©
dechlorination
COOH
HOOC
Cl
OH
I
OH
Methylation
Reaction
mono-, di-,
and
trichlorophenols
Oxidative
Process
Figure 2. Proposed route for decomposition of pentachlorophenol.
N)
CO
-------
24
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 an anion; whereas, the major
factor influencing PCP adsorption by the fourth soil, showing a
decrease with increasing temperature, is Van der Waal's forces.
Decreasing the concentration of chlorides or sulfate ions also
increases the adsorption of PCP to soil. These results indicate the
pccurrence 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 and
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.
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 Kuwatsuda 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
-------
25
transfer to the laboratory and were most active when placed in an
environment to which they were adapted.
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-tetrachlorophenol; 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, Trichodermaf
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 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 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.
-------
Table 10: Degradation of pentachlorophenol in soil (USDA 1980).
Degradation
parameter
Soil type
Special
conditions
Time
90% degradation
90% degradation
Complete
Effect on growth of
corn and cucumbers
Arable layer
in rice fields
(11 soils)
Forest red-
yellow soil
sublayer
Wooster silt
loam
Dry soil
Fertile sandy
loam
90% degradation Mature paddy soil
Complete degradation Dunkirk silt loam
Complete degradation Paddy soil
Complete degradation Warm, moist soil
98% degradation Permeable soil
60% water
25% water
60% water
25% water
7.5 kg/ha penta,
optimum conditions for
microbial growth
Sealed in air-tight
container
Air-dried
Medium water
Water saturated
Low organic content
Aerated, aqueous soil
suspension
Soil perfusion
Composted with sludge
from wood-treating
plant
Approx. 50 days
Approx. 30 days
No degradation
in 50 days
Approx. 22 days
> 5 years
> 2 months
2 months
1 month
1 month
Approx. 72 days
21 days
> 12 months
205 days
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27
Topp et. al. (1988) found that lag periods before PCP removal
by a Flavobacteriuro sp. were reduced by addition of glutamate,
aspartate, succinate, acetate, glucose, or cellobiose. However, the
rate of PCP removal in micrograms PCP/celI/hour was lower when
these substrates were added.
Lewis et al (1986) found that lag periods in field-collected
periphyton were longer for field sites that were low in dissolved
inorganic nitrogen and phosphorus. Addition of nitrogen and
phosphorus decreased lag periods.
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 with minor amounts of 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.
Clearly, 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. It may be
advantageous in some cases to augment the existing populations with
known degraders to enhance degradation. Edgehill and Finn (1983)
found that an Arthrobacter sp. added at the rate of a million cells
per gram of soil (dry weight) greatly reduced the half-life of PCP
in laboratory and field tests.
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.
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28
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% to 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 mg/kg) of BaP. Shabad et al. also found 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 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 of 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.
The toxicity of intermediate degradation products is of
interest in soil treatment systems. Complete mineralization of
PAH's is slow and some intermediates might be present for
substantial periods of time. Aprill et al (1990) found that no
Ames test mutagenicity was found in soil with incorporated wood
treating wastes after one year of treatment, but some Microtox
toxicity was found in water soluble fractions and leachate samples.
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
-------
29
there is an acclimated bacteria population (Herbes et al., 1980).
These observations had also been made earlier (Sims and Overcash,
1983).
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 Bulman 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% 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% to 6% of the added PAH was lost at a much reduced
rate, and the first-order rate constants tended to be higher with
the 50 mg'kg"1 addition than the 5 mg'kg"1 addition of PAH.
-------
Anthracene
30
HO H
1,2-Dihydro-1,2-
dihydroxy-anthracene
1
COOH
3-Hydroxy-2-
Naphthoic Acid
OH
Salicylic Acid
Catechol
Figure 3. Proposed mechanism for the microbiological degradation
of anthracene (Rogoff 1961).
-------
Table 11: Kinetic parameters describing rates of degradation of PAH and phenolic compounds in soil
systems (Sims and Overcash 1983, ERT 1985b).
Substance
Phenol
Phenol
2 , 4-dimethylphenol
4 , 6-dinitro-o-cresol
2 , 4-dinitrophenol
2 , 4-dinitrophenol
4 -ni trophenol
Pentachlorophenol
Naphthalene
Naphthalene
Naphthalene
Acenaphthylene
Acenaphthylene
Anthracene
Anthracene
Phenanthrene
Phenanthrene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Initial
Concentration
(Mg/g soil)
500
500
500
—
5-50
20-25
—
—
7
7
7
0.57
57
0.041
41
2.1
25,000
0.12
3.5
20.8
25.8
17.2
22.1
42.6
k
(day'1)
0.693
0.315*
0.35-0.69
0.023
0.025
0.099-0.23
0.043
0.018
5.78
0.005*
0.173
0.039
0.035
0.019
0.017
0.027
0.277
0.046*
0.007
0.003
0.005
0.008
0.006
0.003
1/2 Life
(days)
1.0
2.2*
1-2
30
28
3-7
16
28
0.12
125*
4+
18
20
36
42
26
2. SH-
IS. 2*
102
231
133
199
118
252
Reference
Medvedev & Davidov (1972)
Medvedev & Davidov (1972)
Medvedev & Davidov (1972)
Versar, Inc. (1979)
Overcash et al. (1982)
Sudharkar-Barik &
Sethunathan (1978)
Verschuerer (1977)
Murthy et al. (1979)
Herbes & Schwall (1978)
Herbes & Schwall (1978)
Herbes & Schwall (1978)
Sims (1982)
Sims (1982)
Sims (1982)
Sims (1982)
Groenewegen and Stolp (1976)
Sisler and Zobell (1947)
Herbes & Schwall (1978)
Groenewegen & Stolp (1976)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
* Low temperature (<15 C).
+ High temperature (>25°C) .
U)
-------
Table 11 s Kinetic parameters describing rates of degradation of PAH and phenolic compounds in soil
systems (Sims and Overcash 1983, ERT I985b) - continued.
Substance
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Benz (a) anthracene
Fluoranthene
Fluoranthene
Fluoranthene
Fluoranthene
Fluoranthene
Fluoranthene
Fluoranthene
Pyrene
Pyrene
Pyrene
Chrysene
Chrysene
Chrysene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
Benz(a)pyrene
* Low temperature (
+ High temperature
Initial
Concentration
(/ig/g soil)
72.8
0.07
0.10
0.15
7
3.9
18.8
23.0
16.5
20.9
44.5
72.8
3.1
500
5
4.4
500
5
0.048
0.01
3.4
9.5
12.3
7.6
17.0
32.6
;<15°C) .
(>25°C) .
k
(day'1)
0.004
0.005
0.005
0.005
0.016
0.016
0.004
0.007
0.005
0.006
0.004
0.005
0.020
0.067
0.231
0
0.067
0.126
0.014
0.001
0.012
0.002
0.005
0.003
0.002
0.004
1/2 Life
(days)
196
134
142
154
43
44
182
105
143
109
175
133
35
10.5
3
10.5
5.5
50*
694*
57
294
147
264
420
175
Reference
Gardner et al. (1979)
Sims (1982)
Sims (1982)
Sims (1982)
Sims (1982)
Groenewegen and Stolp (1976)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Groenewegen and Stolp (1976)
Medvedev and Davidov (1972)
Medvedev and Davidov (1972)
Groenewegen and Stolp (1976)
Medvedev and Davidov (1972)
Medvedev and Davidov (1972)
Herbes and Schwall (1978)
Herbes and Schwall (1978)
Groenewegen and Stolp (1976)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
Gardner et al. (1979)
i
u>
-------
Table 11: Kinetic parameters describing rates of degradation of PAH and phenolic compounds in soil
systems (Sims and Overcash 1983, ERT 1985b) - continued.
Substance
Benz (a)pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Benz (a) pyrene
Dibenz ( a , h) anthracene
Dibenz ( a, h) anthracene
Initial
Concentration
(Hg/q soil)
1.0
0.515
0.00135
0.0094
0.545
28.5
29.2
9,100
19.5
19.5
19.5
130.6
130.6
9,700
25,000
(day'1)
0.347
0.347
0.139
0.002
0.011
0.019
0
0.018
0.099
0.139
0.231
0.173
0.116
0.033
0.039
1/2 Life
(days)
2 +
2+
5+
406*
66*
37*
—
39+
7+
5+
3+
4+
6+
21+
18+
Reference
Shabad et al. (1971)
Shabad et al. (1971)
Shabad et al. (1971)
Shabad et al. (1971)
Shabad et al. (1971)
Shabad et al. (1971)
Shabad et al. (1971)
Sims et al. (1987)
Sims et al. (1987)
Sims et al. (1987)
Sims et al. (1987)
Sims et al. (1987)
Sims et al. (1987)
Sims et al. (1987)
Sisler and Zobell (1947)
* Low temperature (<15°C).
+ High temperature (>25°C)
GJ
OJ
-------
34
Losses of only 22% to 88% 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 kinetic 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 C
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 CO2
from a 14C-labeled compound may not always be reliable. They
recommend that the rate of transformation of a substance be defined
by direct measurement of its disappearance. Liberation of labeled
CO2 may not be concurrent with transformation because transformed
compounds may not be further degraded to labeled CO2 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
received naphthalene as a growth substrate while a second container
received phenanthrene as a growth substrate. Cometabolism of
pyrene, 1,2-benzanthracene, 3,4-benzpyrene, and 1,2,5,6-
-------
35
dibenzanthracene by the mixed culture was exhibited in the presence
of either naphthalene or phenanthrene.
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 C-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 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 through
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.
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36
Uptake of PCP by animals can occur by inhalation, oral
ingestion (including consumption of PCP-contaminated food and
licking or chewing treated wood), and dermal absorption by direct
contact with treated wood. There is some evidence that PCP may be
a metabolic product of other environmental contaminants, but the
significance of this source is not known. Koss and Koransky (1978)
demonstrated the formation of PCP from hexachlorobenzene in rats,
mice, hens, and trout. Hexachlorobenzene occurs widely in the
environment and low-level residues are frequently 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.
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 14C-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. These
results agreed with Larsen et al. (1972). Quite possibly,
reversible binding of PCP to blood proteins occurred. 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 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
-------
37
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 LD50 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 LD50 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 LD50 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.
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 50 mg/kg were not (Dow 1969). The LD50 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
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 LD50 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 LD50 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 conjunctival and slight iritic congestion. Exposure of
rabbit skin under occlusion caused minimal irritation on intact
skin and slightly more on abraded skin (Dow, 1969).
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38
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.f 1973). Allergic contact dermatitis has not been
a problem in handling the chemical.
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 the 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,
hexachlorodibenzo-p-dioxin and octachlorodibenzo-p-dioxin, present
in technical grade PCP are given in Table 12.
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.
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39
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 catabolized by plants.
The health effects of the major PAH constituents in creosote are
summarized in Table 13.
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40
Table 12: Toxicity of various dioxin isomers to experimental animals.'
Compound
LD-50
Teratogenic Embryo Acnegenic
Effectb Toxicityb Effectb
mg/kg Body wt. mg/kg/day mg/kg/day mg/liter
2,7-Dichlorodi-
benzo-E-dioxin 1,000 None None None
2,3,7,8-Tetrachloro-
dibenzo-E-dioxin 0.0006
0.001 0.00003 0.00004
Hexachlorodibenzo-
E-dioxin 100
0.1 0.0001 0.01
Octachlorodibenzo-
E-dioxin 1,000
None 100 None
a Source: Modified from Alliot, 1975.
b Values denote the lowest dosage or concentration which gives rise to
the corresponding effect.
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41
Table 13. Health effects of chemical constituents of creosote (U.S. EPA 1984).
Compound
Effect
1. Unsubstituted 6-carbon aromatic ring systems
2.
chrysene
pyrene
benzo(a)pyrene
benzo(e)pyrene
benzo(a)anthracene
benzo(a)phenanthrene
naphthalene
phenanthrene
anthracene
dibenzanthracene
acenaphthene
triphenylene
Unsubstituted aromatic ring
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
systems containing 5-carbon rings
fluoranthene
benz(j)fluoranthene
fluorene
co-carcinogenic, initiator, mutagenic
carcinogenic, mutagenic
mutagenic
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42
Table 13. (continued)
Compound
• Effect
Heterocyclic nitrogen bases
quinoline
indole
benzocarbazoles
isoquinoline
1-methyl isoquinoline
3-methyl isoquinoline
5-methyl quinoline
4-methyl quinoline
6-methyl quinoline
5-methyl isoquinoline
7-methyl isoquinoline
6-methyl isoquinoline
1,3-dimethyl isoquinoline
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
Heterocyclic oxygen and sulfur compounds
coumarone
thionaphthene
Alkyl substituted compounds
mutagenic
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
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43
Table 13. (continued)
Compound
Effect
6.
7.
Hydroxy compounds
phenol
p-cresol
o-cresol
m-cresol
Aromatic amines
promoter
promoter
promoter
promoter
8.
2-naphthylamine
p-toluidine
o-toluidine
2,4-xylidine
2,5-xylidine
Paraffins and naphthenes
carcinogenic
carcinogenic
carcinogenic
carcinogenic
carcinogenic
(n is large, e.g., greater than 15)
No effects found in the literature for this structural class.
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44
SECTION 4
EXPERIMENTAL METHODOLOGY
INTRODUCTION
The experimental work, started on February 15, 1985, was
conducted in 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 degradation/transformation
process rates and soil transport properties of creosote and
pentachlorophenol; and Phase III—a field evaluation study at the
Wiggins, MS, site.
Partial results of the first -twophases- were reported in a
progress report entitled "Characterization and Laboratory Soil
Treatability Studies For Creosote and Pentachlorophenol Sludges and
Contaminated Soil (No. PB 89-109 920/AS)11.
The following is a summary of the experimental methods for the
three phases. Additional notes on methodology are presented in
Appendices A-E.
PHASE I - SITE, SOIL AND SLUDGE CHARACTERIZATION
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 \ 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.
3. There must be a method of collecting and
disposing of runoff water from the site.
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.
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45
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 site was
divided with a 10 x 10 grid, with the distance between successive
points in the grid determined by the size of the area. Ten of the
one hundred points indicated by the grid were randomly chosen as
sampling points. Samples at the indicated depths were taken at the
ten chosen points, and the samples at each depth composited for
analysis. See Appendices A and B for details of the chemical and
microbiological methods.
A third visit was made to each site for soil evaluation. Soil
profiles were examined at each site in freshly excavated pits and
described and sampled using standard methods (Soil Survey Staff,
1954} . Soil morphological descriptions included horizonatioiv,
Munsell color, texture, horizon boundaries, consistency, coarse
fragments, root distribution, concretions, and pedological
features. Each horizon was sampled for laboratory analyses.
Detailed procedures used for soil evaluation at each site are
summarized in Appendix C.
PHASE II - LABORATORY TREATABILITY STUDIES
Partial results of the first two phases were reported in a
progress report entitled "Characterization and Laboratory Soil
Treatability Studies For Creosote and Pentachlorophenol Sludges and
Contaminated Soil (No. PB 89-109 920/AS)".
Transformation/Degradation Using a Standard Creosote/PGP Mixture;
Experiment 1
Wet soil from the sites was air-dried until constant weight
was attained. The dried soil was stored in clean glass containers
until used. Each new soil was analyzed for nitrogen, phosphorus,
organic carbon, inorganic metals, pH, and chloride ion. The soil
was sieved just before use to remove coarse plant materials from
the soil and the moisture content was determined. Loaded 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 PCP were added into each
beaker. Technical grade PCP was dissolved in methylene chloride or
methanol before being added to the soil. Then contents of all ten
beakers were combined and mixed for 2 hours in a clean glass jar
using a sample rotator turning at 50 revolutions/minute. This 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 H20 to the soil when mixing was
finished. The same mixing procedure was used for controls.
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46
Two test units were set up for each site. One unit was a
control (0% loading) and one was loaded at 1% by weight with the
standard creosote/PCP mixture. Each unit consisted of a covered
brown glass container containing 500 g of soil (dry weight) . Soil
moisture content was adjusted to 70% of water-holding capacity and
the total weight was determined. The test units were put into a
constant temperature room maintained at 22° + 2°C for the duration
of the study.
The soil in each unit was mixed with a spatula and two
separate 20-g samples of soil (air-dry weight) were taken from each
unit. One sample was used to analyze for PAH's, PCP, and OCDD using
the procedures described in Appendix A. The second sample was used
for microbiological analysis, pH and chloride ion analysis.
Microbiological analyses were conducted according to the procedures
in Appendix B.
The moisture content of each unit was adjusted weekly to 70%
of field capacity by adding deionized water. The soil was
thoroughly mixed every 7 days. Soil samples were taken every 30
days until the experiment was complete.
Soils from sites at Gulfport, Grenada, and Wiggins were loaded
initially and at 30 and 60 days. Soils from sites at Atlanta,
Meridian, and Wilmington were loaded initially 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. Data used for rate
calculations were from analyses made over a 60-120 day period after
the final loading.
Transformation/Degradation of Site Specific Sludges; Experiment 2
Four loading rates in soil were studied—0.0%, 0.3%, 1.0%, and
3.0% sludge solids/soil dry weight. A single loading was used
instead of multiple loading and three replications of each
soil/loading rate combination were prepared. The waste sludge from
each site was used to load the soil from that site. Chicken manure
was added to all soil at 4% by weight. The rationale for addition
of chicken manure is presented in Appendix D. Since sludges from
the Columbus, Wilmington, and Chattanooga sites did not contain
PCP, 128-3000 ppm of PCP were added to these soils in addition to
the site sludges in order to determine the transformation of PCP
in soils with little or no previous exposure to PCP. All other
experimental methods were the same as in Experiment 1.
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47
Soil Transport
Eighteen semi-undisturbed soil cores were taken at each site
for the migration studies. A stainless steel cylinder (22 cm
diameter x 76 cm long) lined with a section (18 cm x 60 cm) of high
density polyethylene pipe (Phillips Driscopipe) was driven into the
soil with a backhoe bucket. This produced an semi-undisturbed soil
core (18 cm x 51 cm) enclosed in the section of pipe.
In the laboratory, soil cores were placed on a rack with the
lower end of each core resting on a fiberglass mat supported by a
stainless steel screen set in a large glass funnel. Each soil core
was subjected to a chloride breakthrough experiment. Five hundred
(500) ml of a solution of 500 ppm NaCl in water was poured on the
top of each core. After this solution entered the soil, distilled
water was added to the top of each core periodically. Water
draining from the bottom of each core was collected in 500-ml
increments and tested for chloride ion concentration. The 12 cores
from each site showing the sharpest, most uniform chloride ion
•peak' were chosen for the migration studies.
Half the soil cores from each site were randomly chosen as
controls to measure background levels of creosote compounds and
PCP. All cores had the top 15 cm of soil removed, pulverized, and
mixed with 4% chicken manure. The soil was replaced in the control
cores without further modification. In the remaining cores, site
sludge was mixed with removed soil at 3% by weight. Removed soil
was replaced in the soil cores ('loaded cores'). For site sludges
with no pentachlorophenol, pentachlorophenol was added to the
removed soil at 200 ppm by weight in order to determine the
mobility of PCP in all soils tested. Distilled water was added to
each core at a rate equivalent to 5-cm rainfall each week (1300
ml/core/week). Water draining from each core was sampled and
analyzed at monthly intervals. After three months, each soil core
was sectioned into six equal portions for analysis to determine how
far sludge components had moved down through the core.
PHASE III - FIELD DEMONSTRATION STUDY
The Wiggins site was chosen for establishment of the field
demonstration and research facility. This facility was permitted
by Region IV and the State of Mississippi for operation as a
Hazardous Waste Land Treatment Facility. The site was cleared,
surface debris (treated poles, scrap metal, tarry materials) was
removed to eliminate any surface contamination, and the site was
graded to a 0.5% slope. Since the site had about a 2% slope
initially, soil was removed from the area at the upper end of the
site (cells 1-6) to bring the site to grade. This removed soil was
used to build the berm. The surface soil in these cells after
grading was the yellowish-red subsoil underlying the site. During
installation of the lysimeters, a sludge pit containing used PCP
treating solution was discovered under Cell 4 and parts of Cells
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48
1, 2, 3 and 5. The solution had apparently been placed in a shallow
bowl shaped pit and covered with soil. This procedure produced a
bowl shaped, thin (approximately 1-5 cm thick) layer of mixed
sludge/soil varying from about 30 cm below the soil surface at the
edges of the "bowl" to about 3 m deep at the center of the bowl.
This material was excavated for proper disposal and replaced with
clean soil. Also during lysimeter installation, part of the area
containing Cells 7-9 was found to have been filled previously with
soil mixed with debris including treated poles, fence posts, fence
wire, and scrap metal. The fill material was found at the subcell
2 end of Cells 7-9. Since the large debris was found below the
treatment zone (1.0 m), this fill material was left in place.
A soil berm (height 0.66 m) was constructed around the site
to control runon and runoff of surface waters. Nine test plots
(cells; each 24 m x 5 m) were laid out in the cleared area within
the berm. Each cell was divided into two 12 m x 5 m subcells.
Three 30-cm square glass brick free drainage lysimeters with
fiberglass covers were buried in random locations in each subcell
- one lysimeter at each of three depths (0.433 m, 0.866 m, and 1.3
m) . A trench was excavated for installing each lysimeter and the
lysimeters were placed in the side wall of the trench under
undisturbed soil. The soil was replaced in the trenches and
compacted after lysimeter installation. A 1.27-cm internal diameter
(ID) Teflon sample line from each lysimeter led to a sampling
station located outside of the cell.
Each cell was sloped (0.5%) to a drainage sump at one end of
the cell. A 20-cm high wooden edging enclosed each cell so that
any water falling on the cell must run into the sump and any water
falling outside the cell could not run onto the cell. The sumps
were designed so that water entering the sump would flow out
through a 7.5-cm ID pipe with an inlet suspended 15 cm above the
bottom of the sump. This arrangement allowed soil carried along by
drainage water to settle out in the bottom of the sump where it
could be returned to the cell. This sump was connected to a 15-cm
ID drainage line that drained into a 20,000-gallon storage tank.
The drainage water was pumped from this tank through an activated
carbon filter and sent to the local POTW.
Three groundwater monitoring wells were installed at the field
demonstration facility. One well was placed about 20 m upgradient
(groundwater hydraulic gradient) from the facility and two wells
were placed about 30 m and 50 m downgradient from the facility.
Each cell was provided with an independently controlled
irrigation system to maintain the soil moisture conditions
necessary for microbial activity and to control wind dispersal of
the soil. Initial plans were to maintain soil moisture at 70% of
field capacity, but abundant rainfall and the long distance between
the university and the soil treatment unit (200 miles) combined to
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49
cause the soil moisture to vary between saturation immediately
after rain and somewhat below 70% at other times between
irrigations. Due to the high rainfall in the area (close to the
Gulf Coast), the soil moisture stayed at high levels most of the
year.
The nine cells were divided into three groups of three cells
each. The groupings corresponded to the amount of soil that had to
be removed for elimination of surface contamination and
establishment of the desired slope during clearing of the site.
Cells 1-3 were on the area that had the greatest amount of soil
removed during construction so the surface soil in these cells were
composed of subsoil that was originally about 30-40 cm below the
soil surface. Cells 4-6 were on an area where about 20-30 cm of
soil was removed and Cells 7-9 were on an area where only the top
5-10 cm of soil was removed during construction. (The soil
characteristics at the different depths are discussed in the Phase
I Results and Discussion.) Each group of cells contained one cell
to be loaded with creosote-containing wastes, one cell to be loaded
with PCP-containing wastes, and one waste-free cell as a control.
Three-fourths of a cubic meter of chicken house bedding (a
mixture of sawdust and chicken manure) was applied and rototilled
into each cell. This corresponds to about 3.3% of the mixture (wet
weight) in the zone of incorporation.
Waste (recycled) treating solution from the creosote and
pentachlorophenol treating cylinders at the Wiggins site was used
to load the cells. (See Table 14 for analyses of the waste treating
solutions used.) The waste treating solution was transported across
the plant site to the demonstration facility in steel tanks and
applied to the appropriate cells by gravity drainage from the tanks
through a hose. The wastes were applied in a criss-cross pattern
to maximize uniformity of application. The wastes were applied to
a 22-m by 4.6-m area in each cell since the first meter at each end
of the cell and the 0.2-m area along each long side of the cell was
difficult to till and used as a buffer zone. After each loading,
the cells were rototilled immediately to mix the waste material
into the soil.
The cells were loaded with waste treating solution three times
(10/30/87, 4/20/88, and 8/4/88). The first loading was at 1666 ppm
total PAH's in the creosote cells and 94 ppm pentachlorophenol in
the PCP cells (PAH or PCP weight/soil weight, based on a 10-cm
depth of incorporation in the soil) . The second loading was at 1768
ppm total PAH's in the creosote cells and 186 ppm PCP in the PCP
cells. The third loading was at 3954 ppm PAH's and 463 ppm
pentachlorophenol. The calculated loading rates for PAH's and PCP
at the three dates are shown in Table 14.
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Table 14. Loading Rates in Soil Treatment Unit Cells
PENTACHLOROPHENOL LOADED CELLS
10/30/87
LOADING DATE
4/20/88
8/4/88
ANALYSIS OF APPLIED SOLUTION (mg/1)
AMOUNT APPLIED PER CELL (kg)
CONCENTRATION IN ZONE
OF INCORPORATION (mg/kg)
TOTAL APPLIED PER CELL (kg)
TOTAL CONCENTRATION EXPECTED (mg/kg)
78317.0
1.6
52150
3.2
52000
7.9
94.0
1.6
94.0
185.5
4.8
279.5
462.5
12.6
742.1
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Table 14. Loading Rates in Soil Treatment Unit Cells
CREOSOTE LOADED CELLS
DAT! WPB 2-MH 1-MIT BIPB JICTBY KTBC DIBM FLOKI PBEB MTBB CUBA FLOOR PTHDIC 1,2-BI CBBYS Bt«-«
171030
ANALYSIS OF APPLIED
SOLUTION (ing/l) 42000 3««40 15721 8820 440 46154 3184« 37892 10121* 1403* 8586 45768 2«5t6 7312 7492 21«2
HHOPin UPPLIED m CILLOcjl 2.73 2.40 1.02 0.57 0.03 3.00 2.07 2.46 6.5» 0.91 0.56 2.9» 1.86 0.48 0.49 0.14
CONCENTRATION IN ZONE
OF INCORPORATION (mq/Xq)l«0.6 140.9 60.2 33.7 1.7 176.5 121. 1 144.9 387.1 53.7 32.1 175.0 109.3 28.0 28.7 t.3
880420
ANALYSIS OF APPLIED
SOLUTION (mg/l> 30400 29100 12500 1070 1590 28900 20600 24800 65500 11800 7020 34300 26600 7460 6480 2180
»omn AMLIID nit cm (k(> 2.87 2.75 1.18 0.76 0.15 2.73 1.95 2.34 6.19 1.12 0.66 3.24 2.51 0.70 0.61 0.21
CONCENTRATION IN ZONE
or INCOKPOKMJOI (.g/k,} 169.0 1(1. t 69.5 44.9 1.8 ISO. 7 114.5 137.9 364.1 65.6 39.0 1»0.7 147.9 41.5 36.0 12.1
880804
ANALYSIS OF APPLIED
SOLUTION (mq/l( 31100 29700 13400 8150 1610 29800 21300 25100 66300 12200 7110 34500 25800 7630 6520 2270
CONCENTRATION IN ZONE
or IHCOHrOKATIOn 380.3 363.2 163.9 99.7 19.7 364.4 260.5 307.0 810.8 149.2 87.0 421.9 315.5 93.3 79.7 27.8
TOTAL APPLIED PER CELL (kg) 12.1 11.3 5.0 3.0 0.5 11.9 8.4 10.0 26.6 4.6 2.7 13.4 9.7 2.8 2.5 0.8
TOTAL CONCENTRATION
EXPECTED (mg/kq) 710.0 665.9 293.5 178.3 30.2 701.6 496.8 589.7 1562.0 268.5 158.8 787.6 572.7 162.7 144.4 48.1
Bghi PC? 2 Bim 3 mm 4 aim t KIM TOTALPU
700 5275 103388 240174 89158 2862 435582
0.05 0.34 6.72 15.62 5.80 0.19 28.32
2.7 20.2 395.4 918.5 341.0 10.9 1665.9
831 U 80070 1(0210 74140 3011 311131
0.08 0.00 7.57 15.14 7.07 0.28 30.06
4.6 0.0 445.1 890.6 416.0 16.7 1768.4
7M HA 823SO.O U3420.0 71450.0 30M.O 323281.0
02 00 17 1 34.0 15.5 0.6 67.2
9.8 0.0 1007.1 1996.5 910.5 37.5 3953.6
0.3 0.3 31.4 64.7 28.3 1.1 125.6
17.1 20.2 1847.6 3807.6 1667.5 65.2 7387.9
CJ1
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52
The cells were tilled approximately every 2-4 weeks during the
study. Initial plans were to till once weekly but high rainfall
during most of the year precluded tilling so often. The high clay
content of the soil caused the soil to form large clumps if the
soil was tilled while wet. When these clumps dried they were
difficult to break up with the tilling equipment available.
Therefore, no tilling was done while the soil was wet enough to
form clumps. The tilling depth (incorporation zone) was about 10
cm.
Compounds applied to the cells were monitored with soil
samples taken at three depths (0.3 m [Zone 1], 0.6 m [Zone 2], and
1.0 m [Zone 3]) in each subcell with water samples from the
lysimeters and from the monitoring wells and with air samples taken
above the cells immediately after loading (note volatilization
study below). Compounds monitored were PCP, OCDD, and 17 PAH's.
Soil samples from Zones 1, 2, and 3 in each subcell were taken
at intervals throughout the study. Each soil sample consisted of
a mixture of six subsamples taken from random locations at the
indicated depth in each subcell. All soil samples were analyzed
for PCP, 17 PAH's, and OCDD. Soil samples from Zone 1 were also
tested for pH and microbial populations in order to determine the
proper operating conditions for the landfarm. Later in the study,
it was decided to take soil samples from the incorporation zone
(about 0-10 cm) as well as Zones 1, 2, and 3. Soil samples from the
incorporation zone were taken once immediately before the third
loading and at five dates after the third loading. These samples
were analyzed similarly to Zone 1 samples.
A group from the University of Utah visited the soil treatment
unit site to conduct a study of volatilization of waste materials
from freshly loaded soil. Two one-meter square plots in Cell 1 were
loaded with waste creosote treating solution and two plots in Cell
2 were loaded with waste pentachlorophenol treating solution. The
plots were not tilled after loading in order to maximize the
potential for volatilization of waste compounds. Each plot was
covered with a plexiglass bubble and a steady stream of oxygen was
passed through the bubble. The oxygen exiting the bubble was passed
through an adsorbent to capture any volatilized materials.
The methodology and results of this volatilization study are
reported in "Final Draft Report, Field Sampling/Training Activities
at a Wood Preserving Land Treatment Facility, Wiggins, Mississippi.
R. Ryan Dupont, Utah Water Research Laboratory, Utah State
Laboratory, Utah State University, Logan, Utah."
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53
SECTION 5
RESULTS AND DISCUSSION
PHASE I - SITE, SOIL, AND SLUDGE CHARACTERIZATION
The eight sites investigated represented very diverse soil,
geologic, climatic, and environmental conditions. The sites ranged
from near sea level in Gulf port, 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 15.
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 16.
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 leachate movement.
The surface horizon was strongly acid and pH levels increased with
depth. Acidity (H) decreased in the deeper horizons as pH
increased. 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 were the dominant metallic
cations with levels increasing with depth. Electrical conductivity
levels were low which indicated 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 the subsoil
contained increasing mica (illite) and decreasing kaolinite.
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54
Table 15: 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
Table 16: Overall field evaluation site soil composition.
Site
Soil
Sand3
Silt3
Claya
Grenada, MS
Gulf port, MS
Wiggins , MS
Columbus , MS
Atlanta, GA
Wilmington, NC
Meridian, MS
Chattanooga , TN
Grenada silt loam
Smithton
McLaurin sandy loam
Latonia loamy sand
Urban land
Urban land
Stough sandy loam
Urban land complex
16.06
57.04
72.55
80.03
—
91.5
60.2
13.01
70.17
28.88
24.16
16.42
—
6.0
31.4
46.77
13.77
14.08
3.29
3.55
—
2.5
8.4
40.22
a These samples were taken from the surface to a depth of 5 inches.
-------
55
Gulfport, MS
The site had 7 to 8 inches of mixed fill-soil overlying a
poorly drained Smithton sandy loam. The site had slow runoff and
moderately slow permeable subsoils. Maximum clay content (24.6%)
occurred in the fill-soil capping but abruptly decreased to 3% in
the subjacent, original surface horizon. Calcareous shells were
common in the fill-soil and were present as deep as the 7- to 12-
inch soil 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
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 mineral in the surface horizon and in the
subsoil. The fill-soil capping contained small amounts of smectite.
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 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 area. The
soil had loamy sand textures to a depth of 40 inches where 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 leachate from treated-wood products.
The surface horizon soil had higher cation exchange capacity
because of elevated organic matter contents from cultural
additions. Electrical conductivity values reflected the low
soluble-salt content with the highest levels in the surface horizon
-------
56
caused by the added leachate. Low contents of Mg, K, and Na were
present throughout the 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. GA
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 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 which reflects the low clay content. Kaolinite was the
dominant clay mineral.
Wilmington, NC
The site was comprised of reclaimed 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. The depth of sampling was limited by a water table at
21 inches and saturated sands below. 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 was less than 1 me/100 g at depths below 10 inches. The
upper analyzed layers had higher electrical conductivities caused
by added materials. The soil material had extremely high
permeability with saturated hydraulic values of 34 inches/hr at
depths below 10 inches. The material had low water-holding capacity
below the surface. The small clay fraction was comprised of a
complex mineral suite containing Kaolinite as the dominant
material.
Meridian, MS
Somewhat poorly drained Stough soils comprised the study area.
These soils were formed in thick beds of fluvial sediments and had
slow runoff and moderately slow permeability. 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
-------
57
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 argillic 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 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 16.
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
octachlorodibenzo-p-dioxin at various depths are summarized in
Tables 17-19. 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 io 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 2.13 ppm (Table 19). The detection
limits for the individual PAH's, OCDD, and for PCP are given in
Table 20.
-------
58
Microbial plate counts for soils at each site are presented
in Table 21. Counts of bacteria were done on potato dextrose agar
(PDA) alone or with various additives. These data provide 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.
The nitrogen and phosphorus contents for the soil at each site
are given in Table 22.
-------
Table 17: Soil concentration of PCP at the proposed field evaluation sites,
Depth
(inches)
0-10
10-20
20-30
30-40
40-50
50-60
Grenada
NDa
ND
ND
ND
ND
ND
Gulf port
0.112
ND
ND
ND
ND
ND
Wiggins Columbus
-Pentachlorophenol
0.389
0.017
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
s Atlanta
concent rat a
20.64b
0.088
0.130
0.147
0.319
—
Wilmington Meridian
1.418 0.129b
0.218 0.090
0.209C 0.096
0.104
0.053
—
Chattanooga
0.288b
0.099
0.090
0.074
0.057
—
a ND - Not detected. Detection limits are given in Table 20.
b This value is the average of 4 values, two samples were taken at 0-6 inches, and two were
taken from 6-10 inches.
c The maximum depth that soil could be collected at this site was 20 to 23 inches due to
the high levels of groundwater.
Ul
-------
Table 18: Soil concentration of PAH's at the proposed field evaluation sites,
Depth
(inches)
0-10
10-20
20-30
30-40
40-50
50-60
Grenada
NDb
ND
ND
ND
ND
ND
Gulf port
1.78
ND
ND
ND
ND
ND
Wiggins
___rPn+-a 1
0.33
ND
ND
ND
ND
ND
Columbus
polycyclic
195. 9C
27.45e
ND
ND
ND
ND
Atlanta
aromatics
110. 81d
ND
ND
ND
ND
ND
Wilmington Meridian
193.3 ND
40.55 ND
43.94f ND
ND
ND
ND
Chattanooga
121. 769
ND
ND
ND
ND
—
a The total concentration of 16 polycyclic aromatic hydrocarbons (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.
b ND = Not detected. Detection limits are given in Table 20.
c Sample taken between 0 to 6 inches.
d Sample taken between 6 to 16 inches.
e Sample taken between 16 to 26 inches.
f Analysis done between 20 to 23 inches (groundwater was at 23 inches and below).
9 Average value of 4 samples (2 samples taken from 0 to 6 inches and 2 samples taken from
6 to 10 inches).
-------
61
Table 19: Soil concentration of octachlorodibenzo-p-dioxin at the
proposed land treatment sites (0 to 6 inches).
Octachlorodibenzo-p-dioxin
(ppm)a
Grenada 0.12 ± 0.22
Gulfport 0.37 ± 0.24
Wiggins 0.077 ±0.19
Columbus 0.034 ± 0.22
Atlanta 2.13 ± 0.34
Wilmington NDb
Meridian ND
Chattanooga 0.36 ± 0.57
a These samples represent soil at 0 to 6 inches and are the average
of a minimum of three replicates ± standard deviation.
b ND = Not detected. Detection limits are given in Table 20.
-------
62
Table 20: Abbreviations and method detection limits of compounds
analyzed in this study.
Compound
Abbreviation
Tricvclics
Acenaphthylene ACTHY
Acenaphthene ACTHE
Dibenzofuran DIBEN
Fluorene FLORE
Phenanthrene PHEN
Anthracene ANTHR
Carbazole CARBA
Tetracyclics
Fluoranthene FLUOR
Pyrene PYREN
1,2-Benzanthracene 12-BZ
Chrysene CHRYS
Pentacyclics
Benzo-a-perylene BEN-A
Benzo-ghi-perylene BGHI
Pentachlorophenol PCP
Octachlorodibenzo- OCDD
p-dioxin
Method Detection Limit
Soil (Aig/g) Water (M9/1)
Bicyclics
Naphthalene
2-Methylnaphthalene
1 -Me thy 1 naphtha 1 ene
Biphenyl
NAPH
2 -MET
1-MET
BIPH
0.2
0.3
0.2
0.2
- 1
- 1
- 1
- 1
2
3
2
2
- 10
- 10
- 10
- 10
0.3 -
0.2 -
0.3 -
0.2 -
0.3 -
0.3 -
0.5 -
0.5
0.5
0.6
0.6
1
1
1
1
1
1
2
1
1
2
3
0.6
0.6
0.03
0.02
- 5
- 10
- 3
-0.14
10
10
1
—
- 12
- 30
- 15
— —
3
2
3
3
3
3
4
3
3
5
6
10
10
1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 12
- 30
- 15
-------
Table 21: Microbial plate counts at proposed field evaluation sites.8
Types of media (counts/gram)
Site
Atlanta
Chattanooga
Columbus
Grenada
Gulf port
Meridian
Wiggins
Wilmington
Soil
Depth
0-6"
0-6*
0-6"
0-6"
0-6"
0-6"
0-6"
0-6"
•
PDAb
900,000
473,000
290,000
1,000,000
1,800,000
1,683,000
1,200,000
763,000
PDAA
60,000
23,OOO
120,000
180,000
100,000
141,000
80,000
40,000
PDA +
creosote
700,000
203,000
220,000
600,000
1,000,000
1,600,000
500,000
523,000
PDA + penta-
chlorophenol
450,000
30,000
20,000
110,000
90,000
466,000
80,000
166,000
PDA + creosote &
pentachlorophenol
450,000
6,000
10,000
125,000
100,000
250,000
80,000
66,000
a Each figure represents an average of three replications. The values were obtained by
adding 0.1 mg of soil diluted with 9.9 mg of sterile soil to each plate.
b Media preparation is described in Appendix B.
Table 22: Nitrogen and phosphorous at the eight selected sites."
Grenada Gulf port Wiggins Columbus Atlanta Wilmington Meridian Chattanooga
ppm
Total
Nitrogen
1709
Total
Phosphorous 310
1999
292
1150
255
1598
338
1501
254
1231
597
2990
315
2000
237
OJ
a Based on dry weight.
-------
64
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 23).
The water content, total organic and inorganic materials, pH,
and total organic carbon are summarized in Table 24. Water contents
of these samples varied from 26.6% to 74.5%. The total organic
material ranged from 8.9% 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 4.0% to 49.7%. 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 and
aromatic fraction found in creosote.
Total phenolics, oil and grease, nitrogen phosphorus, and
chloride content of the sludges are summarized in Table 25.
Concentrations of pentachlorophenol and polycyclic aromatic
hydrocarbons in the sludges are given in Table 26. A more detailed
list of the individual concentration of PAH's in each sludge is
given in Table 27.
The results in Table 26 are obtained by capillary column
gas chromatography, while the results in Table 27 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 28.
The trace metal content of the sludges are summarized in Table
29. The most common metals found at wood-treating plants are
mixtures of copper, chromium, and arsenic salts used for preserva-
tion treatment or ZnCl2 used as a fire retardant chemical for wood.
None of the sludges from the various sites had high levels of
chromium, arsenic or zinc.
-------
Table 23: Characteristics of the eight sites used in this study.
Site
location
Size & age Preservative used
Number & type of
lagoons
Grenada, MS
Gulfport, MS
Wiggins, MS
Columbus, MS
Atlanta, GA
Meridian, MS
100 acres
78 years old
100 acres
80 years old
100 acres
15 years old
15 acres
63 years
Wilmington, NCa —
125 acres
61 years old
Chattanooga, TN 76 acres
62 years old
Both pentachlorophenol
and creosote
Both pentachlorophenol
(65%) and creosote (35%)
Both pentachlorophenol
(60%) and creosote (40%)
Creosote (100%)
Both pentachlorophenol
(80%) and creosote (20%)
Both pentachlorophenol
and creosote
Both pentachlorophenol
(25%) and creosote (75%)
Creosote (100%)
Lagoons are closed; contaminated
soil and sludge are present
Large lagoon of mixed preserva
tives and contaminated soil
Individual lagoons of 1) penta-
chlorophenol, 2) pentachloro-
phenol in heavy oil,, and
3) creosote
Contaminated soil and lagoon
Contaminated soil and lagoon
Lagoons are closed but contami-
nated soil is available
Large lagoon and contaminated
soil available
Enclosed lagoons and contaminated
soil
This site has been an active land farming site for 1 1/2 years.
Ul
-------
66
Table 24: Composition of the sludges.*
Grenada
Gulf port
Wiggins #lb
Wiggins #2^
Wiggins #3d
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
Water
content
74.5
30.6
36.0
31.5
36.5
34.4
69.1
26.6
48.2
67.3
Total
organic
materials
24.3
68.0
40.5
26.0
27.8
61.1
23.7
8.9
50.0
15.7
Inorganic
solids
1.1
1.3
23.3
42.4
35.6
4.4
7,1
64.4
1.7
16.9
PH
6.3
4.0
3.0
3.5
5.7
5.9
5.0
7.2
4.0
7.1
Total
organic
carbon
7.3
22.5
37.8
49.4
36.0
49.7
25.3
4.0
31.9
14.6
Table 25: Chemical composition of the sludges.*
Total Oil and
phenol ics grease
Site
Grenada
Gulf port
Wiggins #lb
Wiggins #2C
Wiggins #3d
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
(ppm)
41
97
45
130
171
224
120
7
114
3
(%)
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
fPP«0
236
506
446
477
261
270
316
435
213
417
Inorganic
chloride
content
(ppm)
267
440
361
753
825
49
278
1138
220
28
J All data reported on the starting weight of sludge.
Lagoon contains mainly pentachlorophenol.
* Lagoon contains mainly pentachlorophenol in a heavy oil
Lagoon contains mainly creosote.
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67
Table 26: Concentration of POP, total PAH's and OCDD in each
sludge sample.'
Octachloro-
Polycyclic aromatic dibenzo-p-
Pentachlorophenol hydrocarbons dioxin
Site (ppm) (ppm) (ppm)
Grenada
Gulfport
Wiggins #1
Wiggins #2
Wiggins #3
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
6,699
5,656
29,022
30,060
1,893
NDC
51,974
ND
13,891
ND
96,078
101,023
20,463
47,075
114,127
475,372
119,546
10,007
119,124
72,346
23
215
114
125
21
ND
160
ND
160
ND
a These values are the means of two replicates and are determined
on a dry basis. All were determined by capillary column gas
chromatography.
b Total of the 17 major polycyclic aromatic hydrocarbons found in
creosote.
c ND * Not detected. Detection levels are given in Table 20.
-------
Table 27: Concentration of PAH constituents in sludges from the selected sites (M9/9 dry weight).
Grenada
Gulf port
Wiggins #1
Wiggins *2
Wiggins #3
Columbus
Atlanta
Wilmington
Meridian
Chattanooga
N
67000
13500
3400
10200
17500
70500
39400
,350
16500
1200
2Mn
24150
14000
2450
7450
120QO
29500
23000
330
5350
815
IMn
13250
7450 ,
1400
4000
6350
16500
11500
185
2700
585
Bi
5850
3000
535
1900
3500
10500
6600
NO
1650
445
Ac
5250
2635
215
1050
2000
7650
2800
ND
- 1800
NO
Ace
IPP")
21500
10150
1550
5550
13000
31000
16500
400
5150
1230
Di
17000
9600
1300
6050
1150
32500
16000
425
6850
1150
Fl
18000
10250
1750
7450
14000
34000
18000
585
7350
1415
Ph
43000
30000
5000
21000
34000
53000
45000
1550,
29500
5400
An
15000
7200
2550
8150
14500
23000
24500
1525
6550
2200
Ca
3450
2100
570
2650
4250
12500
9550
190
2050
870
Flu »
27000 195
17000 12!
2150 15
11500 75
22500 19C
49500 38C
23000 155
840 4
20000 117
3550 21
N = Naphthalene
2Hn = 2-Methylnaphthalene
1Mn = 1-Hethylnaphthalene
Bi = Biphenyl
Ac = Acenaphthylene
Ace = Acenaphthene
Di = Dibenzofuran
Fl = FLuorene
Ph = Phenanthrene
An = Anthracene
Ca = Carbazole
Flu = Fluorathene
Py = Pyrene
1,2B = 1,2-Benzanthracene
Ch = Chrysene
Bz = Benzo(a)pyrene
Bzg = Benzo(ghi)perylene
* These values were obtained by GC/MS.
b ND = Not detected. Detection limits are given in Table 20.
Py
1.2B
Ch
Bz
Bzg
3250 5850
12500 2050 3650
185 495
1300 2400
3850 6000
38000 12500 17000
15500 3400 5800 1100 8050
150 150 ND ND
2200 4800 1350 550
200 200 ND ND
3600
1050
75
355
580
3500
5050
ND6
ND
ND
ND
6850
CTl
00
-------
Table 28: Minor components present in sludge.
Molecular
weight
156
168
170
182
184
192
204
216
218
226
252
230
Possible compounds
diroethylnaphthalene. ethylnaphthalene
methytdiphenyl. methylacenaphthene,
diphenylmethane
trimethylnaphthalene
dimethylbiphenyl, ethylbiphenyl,
ethyldibenzofuran. dimethylacenaphthene
d i benzoth i opene . tetramethyl naphthalene
methyl phenanthr ene . methylanthracene.
phenylindene
phenylnaphthalene. vinylphenanthrene,
vinyl anthracene
methylf luoranthene. methylpyrene.
benzofiuorene
benzonaphthofuran
benzo(ghi )f luoranthene.
cyclopenta(cd) pyrene
benzo(k)f luoranthene. perylene.
benzo(e)pyrene. benzo(abj)
f luoranthene, and others
tetrachlorophenol
Site location and number of isomers
Gr Gp Wi#1 Wi#2 Wi« Co At Wm Mr Ch
232 3 213
1
-.1 y
221
!-.-... .. ! ! .. t -.
33-- 3 2 3 3 -- 3 --
11 -- -- 1
22-- 1 1 2 2 -- 2 --
1 1 - 1 -- 1 1 - 1 --
1 1
11 22
-- -- 1 1 1 -- 1 -- --. --
At = Atlanta, GA
Ch = Chattanooga, TN
Co = Columbus, MS
Gr = Grenada, MS
Gp = Gulfport, MS
Mr = Meridian, MS
Wi = Wiggins, MS
Wm = Wilmington, NC
-------
Table 29: Concentration of Metals in each sludge saople.
Site
Atlanta, GA
Chattanooga, TN
Columbus, MS
Grenada, MS
Gulf port. MS
Meridian. MS
Wilmington, KC
Wiggins, MS #1
Wiggins, MS #2
Wiggins, MS #3
Arsenic
9/9
<.715
<0.500
<0.500
<0.500
0.647
<0.500
2.491
0.562
<0.500
<0.500
Antimony
9/9
<1.50
<1.50
<1.50
<1.50
<1.50
<1.50
<1.560
<1.50
<1.50
<1.50
Barium
9/9
<0.10
3.32
<0.10
<0.10
1.35
<0.10
1.83
4.05
O.H
<0.10
Beryllium
9/9
<0.100
1.792
tO.100
<0.100
0.281
<0.100
0.823
0.521
0.493
0.384
Cadmium
9/9
<0.200
<0.200
0.251
<0.200
0.143
0.160
<0.200
<0.200
<0.200
<0.200
Chromium
9/9
35.14
26.48
13.11
5.85
6.64
1.16
20.60
6.65
8.39
25.34
Cobalt
9/9
0.38
<0.30
<0.30
0.35
<0.30
<0.30
<0.30
5.84
0.85
2.32
Lead
9/9
<2.00
<2.00
12.43
<2.00
<2.00
8.17
<2.00
<2.00
<2.00
<2.00
Mercury
3/3
0.012
0.008
<0.001
<0.001
0.003
0.002
0.003
<0.001
<0.001
<0.001
nickel
9/9
5.82
27.26
14.97
7.19
1.05
0.30
7.66
4.85
10.91
17.00
Selenium
9/9
<0.500
0.612
<0.500
<0.500
<0.500
0.529
<0.500
<0.500
<0.500
<0.500
Vanadium
9/9
1.78
3.64
<0.50
<0.50
4.87
1.51
6.79
1.48
<0.50
2.02
(a) Concentration of metals was determined by digestion method (302E, APHA Standard MTHDS, 16th Edition, pp. 148-149), and Inductively Coupled ergon Plasma
spectroscopy (ICP).
-------
71
PHASE II - LABORATORY TRANSFORMATION/DEGRADATION STUDIES
Transformation/Degradation Psincr a Standard Creosote/PCP Mixtures.
Experiment i
The transformation/degradation rates obtained from Experiment 1
are given in Tables 30-38. The microbiological data was reported
in the earlier report on this project. Complete raw data for
Experiment I are given in Tables 62-64 in Appendix F.
All PAH compounds analyzed were transformed in Gulfport soil
with the exception of pyrene which had a relatively slow breakdown
rate. All PAH compounds but anthracene were transformed in Columbus
soil though at somewhat slower rates than Gulfport for most PAH's.
Higher levels of acclimated organisms developed in the Gulfport and
Columbus soils than in soils from the other sites, possibly
accounting for the better transformation in these soils. Most of
the lower molecular weight PAH compounds were readily transformed
in soil from the other sites. Many of the higher molecular weight
PAH compounds (fluoranthene, pyrene, 1,2-benzanthracene, chrysene,
and benzo-a-pyrene) tended to transform slowly if at all. Pyrene
and fluoranthene appeared to be the most recalcitrant.
PCP transformation occurred in Gulfport, Grenada, Chattanooga,
Wilmington, and Meridian soils. PCP half-life was 64 days in
Gulfport soil, but well over 200 days for the other soils.
Columbus, Atlanta, and Wiggins soil exhibited no transformation of
PCP (Table 38) .
Results of this preliminary experiment indicated that all
compounds studied could be transformed in soils at practically
useful rates under the appropriate conditions. Microorganism counts
of the type used in this experiment did not appear to be extremely
accurate indicators of potential breakdown rates for particular
compounds.
Since some of the soils exhibited no breakdown of particular
PAH's, it would be desirable to test a range of loadings in subse-
quent experiments to see if lower loading rates might allow
enhanced transformation in these soils.
-------
Table 30: Kinetic data for PAH degradation/transformation in Atlanta soils,
Compounds
Naphthalene
2 -Methyl naphtha 1 ene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Initial
Loading
(ppm)
366.1
304.2/1
122. 3 \
89.8 \
21.1 \
510.9 ^/
287.4
321.8
1030.7
61.3
46.8
463.9
415.6
115.2
101.5
51.8
20.9
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
a NT = No transformation observed.
-------
Table 31: Kinetic data for PAH degradation/transformation in Chattanooga soils.
Compounds
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl '
Acenaphthylene
Acenaphthene
Dibenzofurari
Fluor ene
Phenanthrene :
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Initial
Loading
(ppm)
384.9
323.0
139.2
92.5
73.0
520.6
299.5
331.4
964.7
87.1
23.6
671.6
522.9
145.2
187.6
122.3
161.9
K
(day-1)
-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
NT = No transformation observed.
-------
Table 32: Kinetic data for PAH degradation/transformation in Columbus soils.
Compounds
Naphthalene
2 -Me thy 1 naphtha 1 ene
1-Methylnaphthalene
Biphenyl
Acenaphthy 1 ene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1>2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
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
NT = No transformation observed.
-------
Table 33: Kinetic data for PAH degradation/transformation in Grenada 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
K
(day-1)
-O.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
a NT = No transformation observed.
Ul
-------
Table 34: Kinetic data for PAH degradation/transformation in Gulfport soils.
Compounds
Naphthalene
2 -Methyl naphtha 1 ene
1-Methylnaphthalene
Biphenyl
Acenaphthy 1 ene
Acenaphthene
Diberizofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benz anthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Initial
Loading
(ppm)
446.9
291.3
143.8
71.6
46.8
477.2
227.4
260.3
1118.4
NDa
69.9
555.7
479.6
60.1
63.6
ND
ND
K
(day-1)
-0.193
-0.190
-0.183
-0.179
-0.170
-0.200
-0.192
-0.192
-0.203
• — •
-0.184
-0.024
-0.001
-0.194
-0.189
—
—
T 1/2
(days)
4
4
4
4
4
3
4
4
3
—
4
29
1155
4
4
—
—
ND
Not Detected. Detection levels are given in Table 20.
-------
Table 35: Kinetic data for PAH degradation/transformation in Meridian soils,
Compounds
Naphthalene
2 -Methy Inaphthalene
1 -Methy Inaphtha 1 ene
Biphenyl
Acenaph t hy 1 ene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1 , 2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Initial
Loading
(ppm)
481.9
369.2
158.7
131.2
90.4
619.2
442.0
367.4
1202.2
NDa
48.9
647.3
591.0
93.8
121.6
34.4
ND
K
(day-1)
-0.185
-0.186
-0.179
-0.186
-0.174
-0.255
-0.262
-0.258
-0.217
ND
-0.177
NTb
NT
NT
NT
NT
ND
T 1/2
(days)
4
4
4
4
4
3
3
3
3
ND
4
NT
NT
NT
NT
NT
ND
ND = Not detected. Detection limits are given in Table 20.
NT = No transformation observed.
-------
Table 36. Kinetic data for PAH degradation/transformation in Wiggins 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
Initial
Loading
(ppm)
413.8
283.3
141.2
69.9
51.3
495.2
309.3
264.9
1172.4
NDa
47.4
564.0
494.9
21.6
51.7
ND
ND
K
(day-1)
-0.318
-0.313
-0.301
-0.294
-0.299
-0.338
-0.319
-0.329
-0.342
—
-0.305
NT"
NT
-0.006
NT
—
—
T 1/2
(days)
2
2
2
2
2
2
2
2
2
—
2
NT
NT
117
NT
—
—
ND
None detected. Detection limits are given in Table 20.
b NT = No transformation observed.
CD
-------
Table 37: Kinetic data for PAH degradation/trans format ion in Wilmington soils.
Compounds
Naphthalene
2 -Methy Inaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Ben z anthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Initial
Loading
(ppm)
404.7
304.3
140.3
93.9
87.7
488.0
363.7
305.2
1078.2
NDa
55.1
582.1
586.5
110.6
142.2
61.5
49.1
K
(day-1)
-0.193
-0.196
-0.188
-0.185
-0.186
-0.013
-0.137
-0.009
-0.010
NT5
-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
—
4
189
1085
NT
158
4
6
a ND = None detected. Detection limits are given in Table 20.
b NT = No transformation observed.
-------
80
Table 38: Kinetic data for PGP degradation/transformation in site
soils.
Site
Gulf port (GU)
Grenada (GR)
Atlanta (AT)
Wiggins (WG)
Wilmington (WL)
Columbus (CO)
Chattanooga (CH)
Meridian (ME)
Loading
Dry Wt.
(%)
855.2
—
1058.6
944.7
900.8
—
792.9
966.2
K
(day-1)
-0.0107
-0.0024
NTa
NT
-0.0022
NT
-0.0027
-0.0009
T 1/2
(days)
64
289
NT
NT
320
NT
259
815
a NT = No transformation observed.
-------
81
Transformation/Degradation of Site Specific Sludges; Experiment 2
Transformation/degradation kinetic data from this phase of the
study are shown in Tables 39-46. Complete raw data for Experiment
2 are given in Appendix F, Tables 65-67.
The half-lives for total PAH's were similar in soils from all
sites, except for the Chattanooga site. Half-lives in soils from
this site tended to be somewhat higher than the other sites. The
total PAH half-lives varied little for the different loading rates
at each site.
The individual PAH compounds 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 lives of more than
one hundred days. Naphthalene, 2-methylnaphthalene, 1-
methylnaphthalene, biphenyl, acenaphthalene, acenaphthene,
dibenzofuran, and fluorene exhibited half-lives of ten days or less
in most cases; phenanthrene, anthracene, carbazole, and
fluoranthene had half-lives between ten and one hundred days in
most cases and pyrene, 1,2-benzanthracene, chrysene, benzo-a-
pyrene, and benzo-ghi-perylene had half-lives greater than one
hundred days. In several cases these last five showed essentially
no breakdown within the time frame of the experiment.
Breakdown rates of individual PAH compounds 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. 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.
No relationship appeared to exist between microbial
populations found in plate counts (data not shown) and rate of
transformation/degradation. Although the rates at all eight sites
were similar, the number of bacteria varied greatly.
-------
Table 39: Half-lives and 95% confidence limits of PAH's and POP in Atlanta soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2-Methylnaphthalene
1 -Me thy 1 naphtha 1 ene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Ben z anthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
3
3
4
ND
ND
3
3
3
38
57
4
154
114
357
289
ND
ND
536
85
11
Lower
limit
3
3
2
ND
ND
3
3
3
32
38
2
69
70
111
109
ND
ND
151
63
4
Upper
limit
3
3
NT
ND
ND
3
3
3
45
115
NT
NT
296
NT
NT
ND
ND
NT
130
NT
1.
t 1/2
(days)
1
1
1
1
1
1
1
2
12
35
2
35
85
71
31
15
ND
226
20
NT
0% Loading
Lower
limit
1
1
1
1
1
1
1
1
8
15
1
23
34
31
21
9
ND
40
14
NT
Upper
limit
1
1
1
1
1
1
1
NT
22
NT
NT
79
NT
NT
58
43
ND
NT
37
NT
3.0% Loading
t 1/2
(days)
6
3
3
3
8
32
7
22
26
138
8
243
NT
NT
NT
9
ND
62
56
70
Lower
limit
2
2
2
2
2
20
2
17
19
56
2
74
253
520
146
2
ND
33
38
48
Upper
limit
NT
7
7
16
NT
87
NT
31
41
NT
NT
NT
NT
NT
NT
NT
ND
773
113
128
NT = No transformation.
ND = None detected. Detection limits are given in Table 20.
00
-------
Table 40: Half-lives and 95% confidence limits of PAH's and PCP in Chattanooga soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2 -Methyl naphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benz anthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
128
77
70
2
434
24
55
40
72
125
178
190
913
392
450
1371
NT
2418
379
309
Lower
limit
84
33
31
2
116
15
39
26
38
31
35
89
81
89
95
104
242
843
97
109
Upper
limit
274
NT
NT
2
NT
60
93
90
664
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
372
1.
t 1/2
(days)
82
50
144
36
21
161
31
46
19
NT
NT
17
368
NT
NT
NT
NT
652
NT
151
0% Loading
Lower
limit
58
30
42
25
18
32
24
26
16
257
NT
14
127
227
1655
364
1948
310
252
105
Upper
limit
138
152
NT
60
23
NT
45
166
21
NT
NT
25
NT
NT
NT
NT
NT
NT
NT
268
3
t 1/2
(days)
2
ND
ND
ND
3
NT
NT
NT
NT
NT
2
71
50
30
28
2
2
135
372
2921
.0% Loading
Lower
limit
1
ND
ND
ND
1
4372
3
NT
NT
NT
1
43
36
19
20
1
1
92
144
418
Upper
limit
4
ND
ND
ND
NT
NT
NT
NT
NT
NT
4
202
81
71
47
3
3
255
NT
NT
NT - No transformation.
ND - None detected. Detection limits are given in Table 20.
00
-------
Table 41: Half-lives and 95% confidence limits of PAH'a and POP in Columbus soil loaded with
site sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2-Methylnaphthalene
1 -Me thy Inaphtha 1 ene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
F 1 uo r anthene
Pyrene
1 , 2 Ben z anthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
3
3
3
3
3
3
2
2
18
46
NT
52
228
258
98
NT
ND
1094
61
NT
Lower
limit
2
2
2
2
2
2
2
2
11
35
3
29
101
105
60
NT
ND
334
42
NT
Upper
limit
14
14
14
14
15
6
3
3
49
68
NT
247
NT
NT
270
NT
ND
NT
112
NT
1
t 1/2
(days)
17
6
2
3
7
28
22
34
30
NT
101
2837
NT
NT
NT
NT
ND
NT
76
670
. 0% Loading
Lower
limit
11
2
2
2
3
15
15
20
15
91
42
117
124
112
128
97
ND
2188
59
160
Upper
limit
38
NT
3
19
NT
187
43
126
367
NT
NT
NT
NT
NT
NT
NT
ND
NT
110
NT
3.0% Loading
t 1/2
(days)
14
25
39
61
127
128
159
247
185
151
100
106
104
292
105
NT
NT
231
107
1371
Lower
limit
11
19
29
3O
69
100
101
191
116
88
59
66
63
65
50
NT
5
116
80
318
Upper
limit
20
34
60
NT
822
178
373
348
457
554
349
265
299
NT
NT
158
NT
39108
164
NT
NT = No transformation.
ND = None detected. Detection limits are given in Table 20.
00
*>.
-------
Table 42: Half-lives and 95% confidence limits of PAH's and PCP in Grenada soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2 -Methy Inaphthalene
1 -Me thy 1 naphtha 1 ene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pent achl or opheno 1
Total PAH's
OCDD
t 1/2
(days)
2
2
2
3
NT
15
44
21
16
37
2
49
52
NT
NT
NT
96
46
67
1356
Lower
limit
1
1
1
2
2
2
23
2
13
25
1
38
39
117
161
284
55
39
52
132
Upper
limit
4
4
4
NT
NT
NT
555
NT
24
65
4
69
78
NT
NT
NT
379
55
94
NT
1.
t 1/2
(days)
2
2
2
2
2
2
2
2
13
31
2
36
46
96
108
NT
NT
35
44
NT
0% Loading
Lower
limit
2
2
2
2
2
2
2
2
10
19
2
24
26
51
56
98
NT
28
31
351
Upper
limit
2
2
2
2
2
2
2
2
17
76
2
73
183
934
1299
NT
NT
48
76
NT
3
t 1/2
(days)
ND
ND
ND
1
ND
ND
169
ND
2
1
ND
11
19
28
35
525
ND
21
38
NT
.0% Loading
Lower
limit
ND
ND
ND
1
ND
ND
52
ND
1
1
ND
10
16
19
29
24
ND
14
25
317
Upper
limit
ND
ND
ND
NT
. ND
ND
NT
ND
NT
NT
ND
14
23
50
46
NT
ND
38
77
NT
ND = None detected. Detection limits are given in Table 20.
NT = No transformation.
00
Ol
-------
Table 43: Half-lives and 95% confidence limits of PAH*s and PGP in Gulf port soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
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
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
4
3
3
4
3
35
56
38
27
34
3
43
43
18
75
ND
ND
24
37
295
Lower
limit
2
2
2
2
2
27
3
31
21
3
2
26
28
4
34
ND
ND
17
28
107
Upper
limit
NT
7
7
NT
8
53
NT
50
37
NT
6
122
91
NT
NT
ND
ND
38
55
NT
1.
t 1/2
(days)
ND
2
ND
ND
5
31
ND
26
45
90
2
27
64
30
40
NT
ND
49
40
212
0% Loading
Lower
limit
ND
2
ND
ND
2
18
ND
16
34
75
2
19
36
20
23
148
ND
23
31
69
Upper
limit
ND
2
ND
ND
NT
109
ND
70
66
114
2
43
262
62
152
NT
ND
NT
54
NT
3.0% Loading
t 1/2
(days)
2
2
2
3
2
2
2
2
2
3
4
101
NT
5
5
ND
ND
NT
34
169
Lower
limit
1
1
1
1
1
1
1
1
1
1
1
42
109
2
2
ND
ND
776
27
78
Upper
limit
3
3
3
NT
3
3
3
3
12
74
NT
NT
NT
NT
NT
ND
ND
NT
47
NT
NT = No transformation.
ND = None detected. Detection limits are given in Table 20.
CO
a\
-------
Table 44: Half-lives and 95% confidence limits of PAH«s and PCP in Meridian soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2 -Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzantnracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
2
2
2
6
6
2
2
2
14
3
ND
55
56
130
ND
ND
ND
43
31
4
Lower
limit
1
1
1
2
2
1
1
1
2
1
ND
29
32
58
ND
ND
ND
34
23
2
Upper
limit
4
4
4
NT
NT
4
4
4
NT
NT
ND
444
206
NT
ND
ND
ND
60
46
8
1.
t 1/2
(days)
3
3
3
3
3
3
3
3
26
9
3
148
425
7
8
ND
ND
73
54
NT
0% Loading
Lower
limit
2
2
2
2
2
2
2
2
16
2
2
59
73
3
3
ND
ND
39
31
326
Upper
limit
13
14
14
15
15
14
14
13
69
NT
14
NT
NT
NT
NT
ND
ND
468
207
NT
3
t 1/2
(days)
2
2
2
2
2
2
2
2
2
2
2
28
63
2
2
ND
ND
NT
56
NT
.0% Loading
Lower
limit
1
1
1
1
1
1
1
1
1
1
1
22
47
1
1
ND
ND
NT
25
NT
Upper
limit
3
4
4
4
4
3
3
4
3
4
4
41
94
3
4
ND
ND
NT
NT
NT
NT - No transformation.
ND - None detected. Detection limits are given in Table 20,
GO
-J
-------
Table 45: Half-lives and 95% confidence limits of PAH's and POP in Wiggins soil loaded with site
sludges at 0.33, 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2 -Methyl naphtha 1 ene
1 -Me thy 1 naphtha 1 ene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzof uran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
3
3
3
3
10
3
3
3-
3
3
3
29
4
29
2
2
ND
56
23
790
Lower
limit
2
2
2
2
4
2
2
2
2
2
2
20
2
5
2
2
ND
24
18
313
Upper
limit
7
7
8
8
NT
6
5
6
6
6
7
55
26
NT
4
4
ND
NT
31
NT
1.
t 1/2
(days)
3
3
2
2
2
4
21
17
18
57
65
25
51
113
469
NT
2
50
29
434
0% Loading
Lower
limit
1
1
1
1
1
1
13
11
11
32
30
18
31
41
60
NT
1
30
22
220
Upper
limit
NT
NT
4
4
4
NT
61
37
45
245
NT
38
139
NT
NT
NT
4
168
42
14575
3 . 0% Loading
t 1/2
(days)
2
2
3
2
2
17
28
23
20
51
54
48
426
134
2174
3
ND
39
38
179
Lower
limit
1
1
1
2
2
15
24
22
18
38
38
19
115
77
214
1
ND
23
27
86
Upper
limit
NT
NT
NT
2
2
19
34
25
23
76
95
NT
NT
518
NT
NT
ND
122
66
NT
NT = No transformation.
ND = None detected. Detection limits are given in Table 20.
oo
00
-------
Table 46: Half-lives and 95% confidence limits of PAH's and POP in Wilmington soil loaded with
site sludges at 0.33/ 1.0, and 3.0% by soil dry weight.
0.33% Loading
Compounds
Naphthalene
2 -Methyl naphtha 1 ene
1 -Methyl naphtha 1 ene
Biphenyl
Acenaphthylene
Acenaphthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
1,2 Benzanthracene
Chrysene
Benzo-a-pyrene
Benzo-ghi-perylene
Pentachlorophenol
Total PAH's
OCDD
t 1/2
(days)
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
NT
NT
112
3
ND
ND
NT
225
NT
Lower
limit
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
22
40
17
1
ND
ND
NT
21
NT
Upper
limit
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
NT
NT
NT
NT
ND
ND
NT
NT
NT
1.
t 1/2
(days)
ND
ND
ND
ND
ND
ND
ND
1
3
1
ND
378
NT
ND
ND
ND
ND
278
505
NT
0% Loading
Lower
limit
ND
ND
ND
ND
ND
ND
ND
1
1
1
ND
44
33
ND
ND
ND
ND
156
72
NT
Upper
limit
ND
ND
ND
ND
ND
ND
ND
1
NT
NT
ND
NT
NT
ND
ND
ND
ND
1320
NT
NT
3
t 1/2
(days)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1561
NT
NT
.0% Loading
Lower
limit
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
90
165
NT
Upper
limit
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NT
NT
NT
NT = No transformation.
ND = None detected. Detection limits are given in Table 20.
NA = Not analyzed.
00
-------
90
PCP transformation occurred in all the soils but was slow or
non-existent in the Columbus, Atlanta, Wilmington, and Chattanooga
soils. Grenada soil PCP half-lives ranged from one to two months,
a quite practical range for operation of soil treatment systems.
Rapid transformation rates were also exhibited in Meridian soil
except at the highest loading rate. In Wiggins soil, PCP half-lives
of one to two months were exhibited, which is still an appropriate
range for soil treatment operations especially considering the
site's deep south location where soil temperatures are high enough
for good microbiological activity most of the year. PCP was
transformed in Meridian and Gulfport soils fairly well. Although
the Columbus, Chattanooga, and Atlanta soils did exhibit some
transformation of PCP, the low rates would bring into question the
practicality of treating PCP in soil at those locations. Over a
period of time, however, it may be possible to build up populations
of microorganisms suitable for rapid degradation of PCP. The
relatively short time frame of these experiments was apparently
insufficient for these soils. Bioaugmentation may be useful in this
situation. It is likely in most soils with chronic exposure to PCP
that suitable populations could be induced relatively quickly.
Dioxins are widely regarded as being somewhat recalcitrant to
biological transformation. The OCDD results in this study are
inconclusive. Although there was some apparent transformation of
OCDD in some of the soils, the low concentrations of OCDD present
in the experimental soils and the variability of the data preclude
any definitive statement about the amenability of OCDD to treatment
in soil systems.
Migration Studies
i
The migration study results are found in Tables 47-51. PAH's
or PCP were found at levels slightly above background (compared to
control cores) in soil core drainage waters (Tables 49-50) from
four of the sites tested [Wilmington (WL), Columbus (CO), Atlanta
(AT) and Chattanooga (CH)]. For each site, six cores were loaded
with sludge and six were controls. To minimize chemical analyses,
water from two cores were combined for chemical analysis.
Polycyclic aromatic hydrocarbons were migrating from all Wilmington
cores at 60 and 90 days. Lower levels of PAH's were also migrating
from 2/3 of the control cores from Wilmington, albeit at lower
concentrations. This result is not unexpected since Wilmington is
a very sandy soil and would be expected to have a low adsorption
capacity. Low levels of PAH's were in one series of control cores
from Chattanooga at 60 days and two series of loaded cores from
Atlanta at 90 days. No PAH's or PCP was found in soil core drainage
water from cores taken from the other sites. The PCP levels were
in the low parts per billion range except for one sampling date
from the Wilmington cores that was about 349 ppb total PCP. The
Columbus soil, which showed some PCP drainage, has a sandy texture.
The Atlanta soil is a clay soil but exhibited a strong tendency to
fracture into discrete clumps while taking the soil cores. This may
-------
91
have provided channels for movement of the compounds. No PCP was
found in water samples collected from soil cores from the other
sites.
After 90 days, soil cores were sectioned. The results, shown
in Tables 49-51, indicate that movement of the compounds tested was
small or nonexistent except in Wilmington and Atlanta soil cores.
The Grenada soil appeared to allow some movement of PAH's; however,
no movement of PCP was observed. Apparently, movement of these
compounds under the conditions and within the time frame of this
experiment was small. This result was expected since soil organic
matter (from added chicken manure) and clay binds these compounds
relatively tightly.
PHASE III -FIELD DEMONSTRATION STUDY
Results of the field demonstration study indicate that PCP
and creosote compounds are susceptible to rapid transformation in
the demonstration site soil. The following discussion refers to
data from Tables 52-54 in the main text (Zone 1 data only) and
Tables 68-71 in Appendix F (Zones 1,2,3 and incorporation zone
data). Table 14 in the main text gives the loading rates for the
soil treatment unit.
SOIL CORE SAMPLES
Creosote Cells - Background Levels (10/26/87)
Background levels were taken before loading on October 26,
1987. PAH background levels were below detection limits in all
Cells except Cell 9 (Tables 52-54 and Appendix F) . Total PAH levels
in Cell 9 Zone 1 soil were 164 to 167 ppm in Subcells 1 and 2.
Subcell 2 had PAH's in Zone 2 soil at 42 ppm and Zone 3 soil at 81
ppm. Only three and four-ring PAH's were found, with phenanthrene,
fluorene, and pyrene predominating at 40-60 ppm each; and
acenaphthene, dibenzofuran, fluorene, anthracene, fluoranthene,
1,2-benzanthracene, and chrysene in 2-10 ppm concentrations.
PCP background levels were below detection limits in Cell 1.
Cell 4 PCP levels were about 77 ppm in Subcell 1 Zone 1, 779 ppm
in Zone 2, and 18 ppm in Zone 3. Cell 4 Subcell 2 levels were 4059
ppm in Zone 1, 14 ppm in Zone 2, and 1071 ppm in Zone 3. Cell 9
Subcell 1 levels were 29 ppm in Zone 1, 105 ppm in Zone 2, and 5
ppm in Zone 3. Cell 9 Subcell 2 PCP levels were 2372 ppm in Zone
1, 309 ppm in Zone 2, and 37 ppm in Zone 3.
OCDD was found only in Cell 9, Subcell 2. Zone 1 levels were
about 1 ppm, Zone 2 about 0.2 ppm, and Zone 3 levels about 0.1 ppm.
-------
TO* 47. Ftotycycfcarornrtichydrocaibonf IniollcomlMChate(pf)b)
SITE
WILMINGTON
CHATTANOOGA
ATLANTA
CORE
TYPE
LOADED
CONTROL
CONTROL
LOADED
REP
A
8
C
A
B
B
A
B
DATE
K.O
«0.0
90.0
90.0
too
•0.0
W.O
•0.0
NAPH
NO
13.0
4*.o
NO
NO
NO
NO
NO
2-MET
NO
33.0
1(30
NO
NO
NO
ND
NO
1-MET
ND
ND
M.O
NO
ND
NO
ND
NO
81 PH
ND
tl.O
23.0
ND
ND
ND
ND
ND
ACTHY
NO
20.0
13.0
NO
ND
ND
NO
ND
ACTHE
ND
190
(0.0
NO
NO
ND
NO
ND
CHBEN
NO
43.0
K.O
NO
12.0
NO
ND
ND
FLORE
ND
ND
M.O
ND
NO
ND
NO
ND
PHEN
HO
31.0
MO
ND
ND
NO
12.0
23.0
ANTHR
NO
45.0
M.O
M.O
NO
ND
NO
ND
CARBA
ND
ND
4*.0
ND
NO
ND
NO
NO
FLUOR
ND
ND
23.0
ND
NO
ND
NO
ND
PYHENE
ND
ND
13.0
ND
NO
ND
ND
ND
1.2-BZ
NO
NO
1«.0
ND
ND
NO
ND
ND
CHRYS
ND
ND
1>0
ND
ND
NO
NO
ND
BEN-*
NO
NO
NO
ND
ND
13.0
NO
ND
Boh!
ND
ND
ND
ND
ND
ND
NO
ND
2RINQ
ND
M.O
2(1.0
ND
ND
NO
ND
ND
3 RING
19.0
1M.O
4(2.0
M.O
12.0
NO
12.0
23.0
4RINS
NO
NO
70.0
NO
ND
NO
ND
NO
5WNQ
ND
NO
ND
ND
ND
13.0
ND
ND
TOTALPAH
19.0
222.0
M3.0
MO
12.0
13.0
12.0
23.0
Sol eorM *om t» otwr «M h*d no dMcM PAH In *M iMdwM M «y dri> dan ImiU
to
ro
-------
Table 48. Pentachlorophenol in soil core leachate (ppb)
CORE
SITE TYPE
WILMINGTON CONTROL
,
LOADED
ATLANTA CONTROL
LOADED
COLUMBUS CONTROL
LOADED
DAYS
REP
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
0
NO
ND
ND
349
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.7
ND
30
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
60
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.9
8.9
6.4
5.2
ND
90
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
6.7
ND
ND
ND
ND
ND
ND
ND
Soil cores from the other sites had no detected POP in the
leachate at any date and are not shown
ND = Not Detected - See Table 20 for detection limits
CO
-------
Table 49. Pdycycfc aromatic hydrocarbons hi sol core sscSions (ppm)
ATLANTA
SAMPLE CORE
DEPTH TYPE
C-IQen LOADED
OONTROL
10-»cm U»OEO
OONTROL
2D-30CTO UMDED
CONIHUL
REP
A
B
C
A
B
C
A
B
C
A
a
c
A
B
C
A
a
c
NAPH
ND
MD
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
NA
NO
MD
ND
ND
ND
2-KET
ND
ND
NO
ND
NO
NO
ND
NO
ND
ND
ND
ND
NA
ND
NO
ND
ND
ND
WtET
ND
NO
ID
ND
ND
M>
NO
NO
ND
ND
ND
ND
NA
MD
ND
ND
ND
to
ffiPH ACTHY ACTHE DSEN R.ORE
N3
NO
NO
ND
MD
ND
MD
ND
ND
ND
ND
to
NA
ND
MD
ND
MD
ND
m
ND
NO
ND
ND
MD
ND
NO
ND
ND
ND
ND
NA
ND
ND
ND
MD
ND
NO
NO
ND
MD
NO
ND
ND
ND
ND
ND
NO
ND
NA
ND
ND
ND
MD
ND
NO
ND
MD
NO
ND
ND
NO
ND
NO
ND
ND
MO
NA
MD
NO
MD
ND
ND
NO
ND
ND
NO
NO
ND
ND
ND
ND
ND
NO
MD
NA
ND
ND
NO
ND
ND
PAH CONCENTRATIONS
MCORESO8.
PHEN AHTHR CARBA R.UOH PVRENE
ND
tZA
ND
NO
MD
ND
ND
3JU
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
18LO
74
ND
ND
ND
ND
51.0
ao
ND
NO
NO
NA
NO
mo
ND
ND
ND
ND
ND
NO
NO
NO
NO
MD
7jD
NO
NO
Ml
ND
NA
ND
ND
NO
ND
ND
4.0
30JO
7.0
NO
ND
ND
NO
300
&0
3J>
ND
NO
NA
NO
7JO
NO
ND
ND
5.0
22JO
10J3
ND
3J>
NO
ND
32.0
ao
M
NO
ND
NA
NO
&0
ND
ND
ND
12-BZ CHRYS
NO
7JO
NO
NO
MO
NO
ND
10.0
ND
NO
ND
ND
NA
ND
ND
ND
MD
ND
NO
9.0
ND
NO
NO
MO
ND
11JO
ND
NO
ND
ND
NA
ND
ND
ND
MD
ND
BEN*
NO
1 NO
NO
MD
MO
NO
MO
ND
MD
MD
NO
MD
NA
MD
MD
ND
ND
NO
BOM 2RNQ 3RMQ 4RMQ SRMQ TOTALPAK
ND
ND
ND
ND
NO
ND
ND
ND
ND
MD
NO
ND
NA
ND
ND
MD
NO
ND
ND
MO
ND
ND
ND
NO
NO
ND
MD
ND
ND
ND
NA
ND
MD
NO
NO
ND
NO
30.0
7.0
ND
ND
NO
ND
88.0
&0
MD
MD
ND
NA
MD
10.0
ND
NO
ND
8.0
6B.O
174
ND
3.0
MD
NO
«UO
14jO
&0
ND
NO
NA
ND
ISA
NO
ND
MD
MD
MD
ND
MD
ND
MD
NO
ND
MD
ND
ND
MO
NA
NO
ND
ND
ND
MD
9.0
ma
24.0
MD
3JJ
ND
ND
178.0
2Z0
8.0
ND
MD
NA
NO
250
NO
ND
MD
ND-NotDKiiliitf-SMTdbfaaPfaftteHeHoiiiirtu
-------
TabN> 49. Polycydic aromatic hydrocarbons In sol oon aacHom (ppm)
CHATTANOOGA
PAH CONCENTRATIONS
SAMPLE CORE
DEPTH TYPE HEP
0-IOem LOADED A
B
C
CONTROL A
B
C
10-20CIT! LOADED A
'"B
C
CONTROL A
B
C
20.30cm LOADED A
B
C
CONTROL A
B
C
NAPH
NO
NO
NO
NO
NO
ND
5.0
un —
WO
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
2-MET
15.0
NO
NO
ND
NO
NO
68.0
un —
no
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
1-MET
11.0
NO
ND
ND
NO
ND
48.0
Uf\ —
WQ
NO
NO
ND
ND
ND
ND
ND
NO
ND
ND
BIPH t
10.0
ND
4.0
ND
ND
ND
45.0
u>»
NO
ND
ND
ND
ND
NO
ND
NO
NO
NO
ND
CTHY /
NO
NO
3.0
NO
ND
NO
4.0
ua
NO
NO
NO
ND
ND
ND
ND
ND
NO
ND
ND
kCTHE
87.0
14.0
72.0
ND
NO
ND
253.0
*-fl
>W
40.0
ND
ND
NO
NO
ND
NO
NO
NO
ND
DSEN f
37.0
5.0
3.0
NO
NO
NO
178.0
MF) —
no
27.0
NO
ND
ND
ND
ND
ND
ND
ND
ND
T.ORE
61.0
ND
12.0
ND
ND
ND
2*4.0
inn
no
54.0
ND
NO
NO
ND
ND
ND
NO
ND
ND
PHEN 1
1B4.0
4.0
8.0
ND
ND
ND
709.0
wn
no
196.0
NO
ND
ND
ND
ND
ND
ND
ND
ND
WITHR C
41.0
25.0
40.0
ND
NO
NO
115.0
4A-A
1U.U
40.0
ND
ND
ND
ND
ND
ND
NO
ND
ND
JARBA 1
13.0
ND
ND
ND
ND
ND
80.0
wn
no
13.0
NO
ND
NO
NO
NO
ND
ND
ND
ND
FLUOR P
129.0
279.0
200.0
ND
ND
ND
385.0
191 ft
I&I.V
166.0
ND
ND
ND
NO
NO
ND
ND
ND
ND
YRENE
SIX)
188.0
123.0
ND
NO
ND
247X)
77.0
88.0
ND
NO
NO
ND
ND
ND
ND
ND
ND
1.2-BZ (
26.0
70.0
39.0
ND
NO
ND
85.0
200
31.0
ND
ND
NO
ND
ND
NO
ND
NO
ND
5HRY8 1
24.0
68.0
37.0
NO
ND
ND
87.0
26.0
28.0
ND
ND
ND
ND
ND
NO
ND
ND
ND
9EN-*
NO
10.0
NO
ND
ND
ND
20.0
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
BgM i
ND
NO
NO
ND
ND
ND
ND
NO
NO
NO
ND
ND
ND
NO
ND
NO
ND
ND
[RING
38.0
NO
4.0
NO
ND
ND
164.0
ND
NO
ND
NO
ND
ND
ND
NO
NO
ND
ND
3HINQ
403.0
46.0
138.0
ND
ND
ND
14.0
370.0
ND
ND
NO
NO
ND
ND
ND
ND
ND
1
4RINQ I
260.0
616.0
399.0
ND
ND
NO
824.0
262.0
325.0
ND
ND
ND
ND
ND
NO
ND
ND
ND
RING 1C
NO
10.0
NO
NO
NO
ND
~~SJO
ND
NO
NO
ND
ND
ND~~
ND
ND
NO
ND
ND
ITALPAH
608.0
674.0
641.0
ND
NO
NO
2572.0
2660
695.0
ND
NO
ND
ND~
ND
ND
ND
ND
ND
NA- Not Analyzed
NO m Not Detected • SM Tdbto 20 tor detection limits
en
-------
Table 49. Polycydc (vomMlc hydroeaitaam In toll com Mdlora (ppm)
SAMPLE CORE
DEPTH TYPE REP DUPLICATE
0-IOan LOADED A A
I
UUBVb
I A
•
(A»«yj.
C A
B
vusyi.
CONTIKX A A
•
(A
C A
•
lA«By>-
lO-ZOan LOADED A A
•
uuBn.
• A
•
M^Ayi*
C A
•
(ARB»
NO
NO
NO
ND
ND
ND
NO
ND
NO
NO
ND
ND
ND
ND
ND
NO
ND
ND
HD
ND
NO
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
NO
ND
ND
ND
ND
NO
ND
ND
NO
ND
ND
ND
NA
NA
HTRATIONI
OIL
MJOR i
723
30.5
614
221
134
HO
160
17.7
1(4
412
44.1
42.7
32.0
HO
25.0
261
».4
224
• 1
10.3
M
ND
NO
ND
34
24
3.0
NO
NO
NO
ND
NO
NO
NO
NO
NO
5.6
194
126
NO
NO
NO
ND
NA
NA
1
•YflENE
706
34.t
52.7
305
16.1
243
239
273
26.6
476
604
«.1
34.1
21.7
263
30.3
204
254
114
134
12.7
NO
NO
NO
64
41
52
ND
ND
ND
ND
ND
ND
NO
ND
ND
74
20.1
134
ND
NO
ND
NO
NA
NA
12-BZ
314
2(2
»6
2»e
22.9
256
217
244
21.1
3*4
366
36.6
302
16*
244
333
24.1
2*7
2(4
1(4
21.6
(2
(4
64
124
114
1(4
(.7
(4
74
67
•4
»3
11.7
13
10.0
14.1
164
144
ND
ND
3.0
(.1
4.1
NA
NA
CHRY8
464
45.6
47.0
470
36.7
41.*
434
53.6
465
57.0
697
(14
445
22(
336
30*
27.0
264
114
204
272
ND
NO
NO
*j
ND
44
ND
ND
ND
ND
ND
ND
ND
NO
ND
154
192
174
ND
ND
ND
ND
NO
NA
NA
BEN-.
M3
(4.0
45.2
66.7
434
50.1
564
(04
56.7
2(4
274
27.0
2*4
S3
174
(.4
11.1
M
344
104
22.7
13.0
ND
U
114
6.1
(4
NO
NO
NO
NO
NO
ND
ND
NO
NO
146
11.0
124
ND
ND
NO
ND
NA
NA
BgM
1*(
324
2U
46*
26(
366
36*
4*4
434
234
11.1
214
234
ND
11.7
ND
(.7
14
22.1
ND
11.1
NO
ND
NO
74
NO
34
NO
NO
ND
ND
ND
ND
NO
NO
ND
11.7
(4
10.0
ND
ND
ND
ND
NA
NA
2RMO
NO
ND
ND
NO
ND
ND
NO
NO
NO
NO
ND
ND
NO
NO
NO
NO
NO
ND
NO
ND
ND
NO
ND
ND
ND
ND
ND
NO
ND
ND
NO
ND
ND
ND
NO
NO
ND
ND
ND
NO
ND
NO
ND
NA
NA
3 UNO
274
214
2*4
1(0
23.1
1*4
164
176
14.0
103
102
104
74
(4
(4
NO
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
NO
NO
ND
ND
ND
ND
ND
(4
«
ND
NO
ND
ND
NA
NA
4 UNO
223.0
m.i
179.1
1267
(1.1
10*1
1040
1231
113.6
1(0.4
200.7
1*04
1414
(12
1114
1204
(04
1057
(04
(04
704
(2
(4
(4
314
2(4
26.7
6.7
(4
74
6.7
(4
U
11.7
U
10.0
43.1
74.1
5(4
NO
ND
5.1
4.1
IM
NA
(UNO TC
(7(
669
724
1056
721
(6.9
•36
1106
102.1
600
4(4
4*3
632
62
2*2
(4
174
13.1
MS
104
31.7
114
NO
U
1(4
6.1
124
NO
ND
NO
ND
NO
NO
NO
ND
ND
2C2
1*4
224
NO
ND
ND
ND
NA
NA
ITALPAH
306.1
24(4
277.3
2503
1M4
2164
215*
2614
2334
2407
2576
24*.1
202.1
«22
1472
12»
10(7
11(4
1374
714
1044
212
6.6
144
49.4
324
41.0
17
(4
74
(7
(4
94
117
(4
10.0
(04
9*7
645
ND
ND
5.1
4.1
NA
, !*.
en
NA.NOAMlirHd
ND . N«l DltacM - •*• T«Wt 20 tar *Mc*n M>
-------
T«bl» 49. Potycycte «rom»ltc hydrocarbons In soil core •team (ppm)
MOONS
SAMPLE CORE
DEPTH TYPE REP DUPLICATE
HOon LOADED A A
B
a A
B
B
CONTROL A A
B
IA.BVI-
B A
B
B
(A 20 tof (MMOta Ml
-------
98
I
IE
*
Him
So o o o
z z z z
p p p p p
if S 5 0
S2SS5
8 S S S S
SO O O O
z z z z
SO Q O O
Z Z z z
Si 8 - 5 S
§ *? * *
N S rt « •
S S i S S S
s s i s s s
So o o o o
z z z z z
So o o o o
S z z z z
» 3 «i «i «
z z z z z
S S S S 8 8
S S 8 S S
88888
S 8 8 S S
S S 8 8 8
S 8 S 8 S 8
z z £ zz
! !
I
§ S S S £ S
So o o o o
z z z S z
0 g 0 0 p 0
S S S 8 S 8
S 8 S S 5 S
SO O 0 0 0
SO Q Q fi fi
z z z Z z
Z Z Z •) z
888*8
S S S S S S
S S S 8 S 8
So o o o o
z z z z z
So o o o o
z z z z z
go o o p o
z S z S S
So o o o o
z Z S z z
S S S 8 8 8
z z z z z
z z z at z
888888
S I S 3 z
1
SIS JSg
8 S 8 S S |
8 S 8 1 88
S S 8 I 8 8
8 3 S J S 2
S S 8 i 8 3
8 S 8 I 8 8
888188
! 1
1
888188
888188
818188
888188
888188
888188
888188
888188
; i
1
i i i J 5 5
8 8 8 i S S
8881 1 8
izSiii
8 S 8 IS 5
888188
888188
881188
i !
i
n
i 8
-------
Table 50. Pentachtorophenol in soil core sections (ppm)
~ PQP CONCENTRATIONS
, CORE SAMPLE
SOURCE DEPTH
ATLANTA 0-10cm
10-20cm f.
20-30cm
30-40cm
40QOcm
50-60cm
CHATTANOOGA 0-1 Ocm
10-20cm
20-30cm
30-40cm
40-50cm
50-60cm
WILMINGTON 0-1 Ocm
10-20cm
20-30cm
30-40cm
40-50cm
50-60cm
LOADEDCORES
REP A
6.2
1 ?. a .;
5 '
NA
NA
NA
50.2
187
6.4
NA
NA
NA
18.2
15.7
65.7
18.1
1.5
ND
IN CORE
SOIL
CONTROL CORES
REPB REPC
13.1
46.6
2,1
NA
NA
NA
148
58.3
3.5
NA
NA
NA
30.9
44.1
4.8
2.5
ND
ND
4.6
8.1
7.4
1.4
ND
ND
77.2
70.5
3.8
NA
NA
NA
32.4
7.8
8.4
4.8
1
ND
;-
REP A
ND
: 33,
ND
NA
NA
NA
ND
ND
ND
NA
NA
NA
ND
ND
ND
NA
NA
NA
REPB
2.8
8.3
ND
NA
NA
NA
ND
ND
ND
NA
NA
NA
ND
ND
ND
ND
ND
ND
REPC
ND
ND
WO
NA
NA
NA
ND
ND
ND
NA
NA
NA
ND
ND
ND
ND
ND
ND
NA» Not analyzed
ND « Not Detected - See Table 20 for detection limits
-------
TiM* SO. Pentachbrophenol In nil cor* aectbm (ppm)
PCP CONCENTRATIONS IN CORE SON.
LOADED CORES CONTROL CORES
CORE SAMPLE
SOURCE DEPTH
WIGGINS 0-IOcm
10-20cm
20-30cm
30-40cm
40-SOcm
6040cm
„
GRENADA 0-tOcrn
10-20cm
20-30cm
30-40cm
40-60cm
S040cm
DUPLICATE
A
B
(A+B1/2-
A
B
(A+BW2-
A
B
(A+BV2-
A
B
(A+B1/2-
A
B
(A+BW2-
A
B
(A+BI/2-
A
B
(A+BV2-
A
B
{A+BV2-
A
B
(A+B1/2-
A
B
(A+BV2-
A
B
(A+B1/2-
A
B
(A+BW2-
REPA
63
82.9
63
NO
ND
NO
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
19.6
18
18.8
ND
.ND
ND
ND
ND
ND
NA
, NA
NA
NA
NA
NA
NA
NA
NA
REPB
96.4
116.5
106
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
21.2
16.7
18.5
ND
* ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
REPC
65.6
108.7
87.2
ND
ND
ND
ND
ND
ND
NA
NA.
NA
NA
NA
NA
NA
NA
NA
22.8
22.8
22.9
, ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
REP A
22.8
11.8
17.3
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.4
1.1 •
1.3
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
REPB
ND
ND
NO
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.2
1-8
2
ND
ND
ND
NA
NA
NA
.NA
NA
NA
NA
NA
NA
NA
NA
NA
REPC
69.8
768.7
414.8
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
6.1
2JB
4.3
ND
ND
NO
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA. Not Analyzed
ND-Not Detected-See Table 20 for detection limits
CD
O
-------
Table 51. Octachkxodibenzo-p-dioxin in soH core sections (ppm)
OCOO CONCENTRATIONS IN CORE SOIL
LOADED CORES CONTROL CORES
CORE SAMPLE
SOURCE DEPTH DUPLICATE HEP A REPS REPC REPA REPB REPC
CHATTANOOGA
GRENADA
0-10cm
1040cm
2040cm
KMOcm
4040cm
9040cm
0-10cm
0.25
0.4B
ND
NA
NA
NA
A O.A4
B 0.94
0.37
0.2S
ND
NA
NA
NA
0.68
0.71
0.31
ND
ND
NA
NA
NA
0.7S
0.77
ND
ND
ND
NA
NA
NA
ND
ND
ND
ND
ND
NA
NA
NA
0.21
0.24
ND
ND
ND
NA
NA
NA
033
o.aa
oueva.
1040cm A NO ND ND ND NO
B ND NO ND NO NO
(A«eia- ND NO NO ND ND
2040cm A NA NA NO NA NA NA
B NA NA ND NA NA NA
(A4CV2. NA
30 10cm A
B
(A+6I/2.
4040cm A
B
(AtBM-
9040cm A
B
(A46V2*
WIGGINS 0-1 Ocm A
B
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.88
2.7B
NA
NA
NA
NA
NA
NA
NA
NA
3
3.26
NA
NA
NA
NA
NA
NA
NA
NA
2.W
3.29
NA
NA
NA
NA
NA
NA
NA
NA
Z.7B
3.03
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
307
•.3
1040cm
20-aOcm
30-Wcm
40-50cm
9040cm
(A+8V2-
A
B
(A-tfil*.
A
B
(/W81/2-
A
B
(A+8V2-
A
B
UU8V2.
A
B
2.63
NO
NO
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
3.13
NO
ND
ND
NO
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
287
NO
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
514
ND
ND
NO
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA NA
NA.NotAralyzKl
ND . Not DrtMttd - S»» T*l» 20 for dMKfen Into
-------
Table 52. Wiggins Soil Treatment Unit - PAH. PCP. and OCDD In zone 1 soil, creosote loaded cells (ppm)
DATE CELL NAPH 2-MET 1-MET BIPH ACTHV ACTHE DIBEN FLORE PHEN ANTHR CARBA FLUOR PYRENE 1.2-BZ CHRYS
BEN-. BgN 2RINO 3MNQ 4HNO 5MNS TOTALPAH PCP OCDD
10/23/87
11/10/87
2/26166
5/10/BB
6/15/88
8/11/80
5/1 MO
10Y23/8?
11/10/87
2/28/88
5/1 0/88
6/15/89
8/11/89
5/18/90
10/23/87
11/10/87
2/26/86
5/10/88
6/15/89
8/11/69
5/18/90
ND
ND
NO
ND
NO
NO
NO
NO
ND
ND
ND
NO
NO
NO
NO
0.8
ND
ND
ND
ND
ND
NO
2.9
ND
55
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
35
ND
NO
ND
ND
ND
NO
5.6
NO
5
ND
NO
ND
ND
1.5
3.8
0.1
NO
NO
ND
NO
4.5
NO
ND
ND
ND
ND
ND
53
ND
3
ND
ND
ND
ND
1.5
0.2
ND
ND
ND
ND
ND
33
ND
ND
ND
ND
NO
NO
1
NO
05
ND
NO
NO
NO
0.3
1.2
0.4
ND
NO
NO
ND
1.3
ND
NO
NO
NO
ND
ND
74.6
18.5
86
NO
ND
ND
ND
282
544
13
NO
ND
ND
1.5
75.5
178
as
NO
ND
ND
ND
53.9
5.5
54.5
ND
ND
ND
NO
19.3
24.7
3.1
ND
ND
ND
2
44.5
5
ND
ND
ND
NO
ND
105
16.3
77.5
ND
NO
ND
ND
35.9
406
5.5
ND
ND
NO
4.3
936
143
0.5
ND
NO
NO
NO
421.9
35.5
284.3
ND
NO
NO
ND
113.3
87.6
16
NO
NO
NO
414
295.3
34.3
4.3
NO
ND
ND
ND
57.8
19
53.3
ND
ND
ND
ND
202
304
15.1
ND
ND
ND
5.5
523
19.5
4
ND
ND
ND
ND
37
3.3
20.8
ND
ND
ND
ND
10.5
4.8
16
ND
ND
NO
ND
24
0.8
NO
ND
ND
ND
NO
281.4
114
2055
ND
ND
1
NO
76.9
1403
106.4
ND
ND
2
52.9
227.5
1398
42.5
ND
ND
1
ND
1557
96.6
176
NO
NO
3
ND
60
116.9
94.8
NO
ND
4
41.2
160.3
105
33.3
25
NO
6
NO
22.3
19.5
463
ND
ND
3
NO
162
288
27.9
NO
NO
3
8.6
40.5
27.5
166
ND
NO
NO
ND
21.6
23.3
49.8
ND
NO
19
ND
21.5
29.5
41.5
ND
ND
23
7.7
33.5
25.5
15.5
ND
NO
18
ND
3.5
ND
11
ND
ND
to
ND
4.5
8.7
ia3
ND
ND
10
ND
7.8
8.3
4.3
ND
ND
2
NO
ND
ND
1.5
NO
ND
4
ND
NO
ND
3.8
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
NO
13.6
NO
13.5
ND
ND
ND
NO
3
3.9
0.1
ND
NO
ND
ND
12
ND
NO
ND
ND
ND
ND
7512
96
551.8
NO
NO
ND
NO
227.7
243.8
54.6
NO
NO
NO
54.7
588.5
91.5
9.3
ND
ND
NO
NO
255.5
477.5
ND
NO
26
NO
1783
317.2
2725
ND
NO
32
110.4
481 J
2974
108
25
ND
25
NO
3.5
ND
12.5
ND
NO
14
ND
45
8.7
17
ND
ND
10
ND
7.5
6.3
4.3
NO
ND
2
ND
1229.4
353.5
1062.3
ND
ND
40
ND
4136
5733
344.2
ND
ND
42
185.1
1067.8
397.5
121.5
26
NO
27
NO
42.8
17.7
48.6
ND
ND
NO
2088.2
250.4
1402.5
437.1
750
327.5
ND
1200.3
84.8
434
232
NO
0.5
ND
NO
0.5
0.3
1.8
ND
ND
NO
NO
0.2
ND
1.7
0.6
1.9
NO
0.5
0.6
0.9
0.5 •
NO
0.4
NA
NA-NotAfwlyz«l
LMdng D«H» 10/30/87,4/20*8.8/4/88
-------
103
1
j
1
1
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1
0.
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1 1
1 1
1 »
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11
Table 53. W
DATE
S88S8S8 SSSS
SJSJISS'- SSSJj
8888888 8888
latail- 3333
S*;*S8S8 858-
8828888 8388
8888888 8888
8833333 8883
SSS-SSS 8888
833:333 8:83
8t- M *• O O * o *- ^ *
ri w 22 2 M N
855S8S" a-"1*
8=88338 8888
SS3S8SS S-SS
8SS3SSS S3SS
8233883 883S
8-88388 8833
3:33333 8833
833§338 3333
88:8338 8SS3
8833838 3833
8333333 8333
3388838 8333
mm mi
iSi
J-i
238
"i
;ss
288
288
288
288
283
5*8
3"S
£33
"S3
388
183
133
£33
138
£83
£83
£33
£38
m
sss
85S58SS
liii.--
8888888
85888*'
8w388SS
88SS838
8888888
8883888
SS833Sn
383SSSS
SS8SS*"
8;S8388
8888883
8388888
8S8888S
3333383
3338338
S~.33883
8333883
3838383
8833838
S3S3833
3333833
lilssss
!
!
^ t
i
-------
104
i
I
1
I
iiSiiii
si§i§§i
SSiiSSi
iitiiii
SiSiiSS
iiiiiSS
ii§§§ii
iil§i§§
Igissss
S5SSSSS
iSiiiii
SSSiSii
issssss
SiiSSiS
iiiiiii
iiiiisi
SiiSSiS
IIS5555
eissssi
S3SS8S8
etsssss
SJSSSSS
SSSSS8S
8SSSS88
SSSS88S
8SSSS8S
s:8ssss
8S8SSSS
S88SSS8
8SSSSS8
SSSSSiS
SS&SSSS
SSSS88S
SS8SSSS
iiSSSSS
8888888
iil§§§§
sglssss
I!
**t
id
-------
The background levels
105
of PAH's in the three creosote-loaded
cells were low enough tb cause little concern, but the PCP
background levels were vej-y high in Cells 4 and 9. The PCP from
the sludge pit might be the source of these high PCP levels. The
variability of the PCP analysis results (especially the duplicate
analyses) indicate that the PCP was not distributed uniformly
through the soil but was in concentrated deposits. These high
levels and variability were also found in control Cells 3 and 6,
and PCP Cell 5. The lysLmeter results (discussed below) also
suffered from high and variable levels of PCP. Interestingly, the
high PCP background level^ in soil were not associated with high
levels of OCDD.
Creosote Cells - 10/30/87
The three creosote
28 kg per cell total
10/30/87, giving the
PAH's in the incorporation
PAH's in the incorporation
Loading
cetlls (Cells 1, 4, and 9) were loaded with
•s (in waste treating solution) on
concentration of the individual
zone noted in Table 14. Calculated total
was 1666 ppm.
calculated
Creosote Cells - 11/13/8*:
Subcell
Cell 1 sampling resul
total PAH's in Zone 1
1 Subcell 2. These PAH'si
compounds. Three and fou
Subcell 1 at 50 ppm, and a
Zone 3. Three and four-
and 3 (26 ppm) of Subcell
ts indicated a concentration of 1339 ppm
1 and 1120 ppm total PAH's in Zone
were mostly the three and four-ring
-ring PAH's were found in Zone 2 of
trace (0.6 ppm) of pyrene was found in
PAH's were found in Zones 2 (27 ppm)
results
Cell 4 sampling
total PAH's in Zone 1
Subcell 2; again, mostly
Three and four-ring PAH's
ppm. No PAH's were found
of Subcell 2.
riifig
2.
indicated a concentration of 607 ppm
Subdell 1 and 220 ppm total PAH's in Zone 1
three and four-ring compounds were found.
were found in Zone 2 of Subcell 1 at 60
n Zone 3 of Subcell 1 or Zones 2 and 3
Cell 9 sampling results indicated a concentration of 774 ppm
total PAH's in Zone 1 Subtell 1 and 1402 ppm total PAH's in Zone
1 Subcell 2. No PAH's werfe found above detection limits in Zones
2 or 3 in either subcell.
The three and four-ring PAH's apparently moved downward in
small amounts in Cells 1 and 4 during the two weeks between loading
and sampling. The two and
five-ring PAH's apparently did not move
downward. This result riiay be due to rapid transformation,
volatilization or fixation, or just that these components were
applied in such small amounts that the levels moving down were
below detection limits. The lack of detectable levels of PAH's in
Zones 2 and 3 of CelLl 9 is interesting, particularly since Cell 9
had much more of the original topsoil left than Cells 1 and 4 where
-------
106
the priginal topsoil was mostly removed during site preparation.
Cell 9 had high levels of organic matter in Zone 1 soil (Table 55),
and this may have reduced downward movement of PAH's.
Creosote cells - 2/26/88 Sampling
Cell 1 sampling results indicated a concentration of 340 ppm
total PAH's in Zone 1 Subcell 1 and 367 ppm total PAH's in Zone 1
Subcell 2. No PAH's were found in Zones 2 and 3 of Subcell 1, but
four-ring PAH's were found in Zones 2 and 3 of Subcell 2 at 5-7
ppm. No two or five-ring PAH's were found in Zones l, 2 or 3.
Cell 4 sampling results indicated a concentrajtion of 687 pm
total PAH's in Zone 1 Subcell 1 and 460 ppm total PAH's in Zone 1
Subcell 2. Four-ring PAH's were found in Zones 2 and 3 of Subcell
1 at 4-6 ppm, but no PAH's were found in Zones 2 and 3 of Subcell
2.
Cell 9 sampling results indicated a concentration of 216 ppm
total PAH's in Zone 1 Subcell 1 and 579 ppm total PAH's in Zone 1
Subcell 2. No PAH's were found above detection limits in Zones 2
or 3 of Subcell 1 but four-ring PAH's were found in Zone 2 Subcell
2 at 18 ppm and Zone 3 Subcell 2 at 8 ppm.
After loading, three and four-ring PAH's apparently moved
rapidly downward in the soil in Cell 1, but moved more slowly in
Cells 4 and 9. PAH's were found in Cell 1 Zones 2 and 3 in both
subcells at 14 days after loading (11/13/87 sampling), but only in
Subcell 1 Zone 2 in Cell 4; and in Cell 9, PAH's were not found in
either Zone 2 or 3 in either subcell. By the 2/26/88 sampling, no
PAH's were found in Cell 1 Subcell 1 Zones 2 and 3, but PAH's
remained in Cell 1 Subcell 2 Zones 2 and 3. PAH levels in Zone 1
soil of both Cell 1 subcells had been reduced about 75%. PAH's in
Cell 4 Zone 1 soil had apparently increased in both subcells
between the 11/13/87 and 2/26/88 sampling. The apparent increase
was primarily found in the four-ring compounds, especially
fluoranthene and pyrene. The PAH's in Cell 4 Subcell 1 Zone 2 had
decreased by 2/26/88 but PAH's were found in Zone 3 for the first
time. No PAH's were found in Cell 4 Subcell 2 Zones 2 and 3 at the
2/26/88 sampling. PAH's in Zone 1 soil of Cell 9 Subcell 1 had
decreased about 66% by the 2/26/88 sampling and no PAH's were found
in Zones 2 and 3. PAH's in Zone 1 soil of Cell 9 Subcell 2 had
decreased about 60% by the 2/26/88 sampling, but PAH's were again
found in Zones 2 and 3 of Subcell 2. These PAH levels in Cell 9
Subcell 2 Zones 2 and 3 were less than the background levels, but
PAH levels in these zones, measured 14 days after loading, were
below detection limits, so some downward movement may have occurred
between sampling events.
-------
107
Table 55» Nutrient* and pH of treatment unit soil after first
loading.
Cell
Date
1
2
3
4
5
6
1
8
9
Total
Kjeldahl
Nitrogen
(ppm)
li/13/87
408.4
714, 5
561.2
102.0
1173.4
563,1
255.7
251.4
615,3
Total
Organic
Carbon
(ppm)
6748.5
8486.7
8224.9
6997.0
17184.2
7754.9
5973.0
5933.2
11775.9
Total
Phosphorus
(ppm)
611.9
933.0
923.1
301.8
1785.8
782.6
541.7
601.9
822.7
PH
7.05
7.01
6.74
6.52
7.22
6.44
6.81
6.91
7.04
-------
108
It appears that both transformation and migration of PAH's
were taking place during this period in the creosote cells. The
three-ring PAH's were apparently readily transformed, but the four-
ring compounds were more persistent. Cell 4 evidently had no
transformation occurringf but Cells l and 9 showed good
transformation rates. The explanation for the difference in results
between Cell 4 and Cells 1 and 9 is not obvious, but the higher PCP
background levels in Cell 4 may have inhibited transformation of
PAH's. PCP levels in Cells 1 and 9 were below 100 ppm, but PCP
levels in Cell 4 were as high as 2600 ppm. The high PCP background
levels found in Cell 9 were not seen at later sampling dates, but
the high background levels seen in Cell 4 persisted until the end
of the study.
Creosote Cells - 4/20/88 Loading
Two of the three creosote cells (Cells 1 and 4) were loaded
with 30 kg per cell total PAH's (in waste treating solution) on
4/20/88, giving the calculated concentration of the individual
PAH's in the incorporation zone noted in Table 14. Calculated total
PAH concentration was 1768 ppm., Cell 9 was not loaded.
Creosote cells - 5/10/88 Sampling
Cell 1 sampling results indicated 295 ppm, 252 ppm, and 367
ppm total PAH's in Zones 1, 2, and 3, respectively, in Subcell 1.
In Cell 1 Subcell 2 total PAH's were 1830 ppm, 93 ppm, and 79 ppm
in Zones 1, 2, and 3, respectively.
In Cell 4, total PAH's in Subcell 1 Zones 1, 2, and 3 were 306
ppm, 7 ppm, and 5 ppm, respectively. In Cell 4 Subcell 2 total
PAH's were 382 ppm in Zone 1. No PAH's were found in Zones 2 and
3 of Subcell 2.
Cell 9 sampling results indicated total PAH levels of 114 ppm,
5 ppm, and nondetectable in Zones 1, 2, and 3 of Subcell 1. Total
PAH's in Zones 1, 2, and 3 of Subcell 2 were 130 ppm,
nondetectable, and 47 ppm, respectively. The Zone 1 Subcell 1
levels were about 28% of the levels at the 2/26/88 sampling, and
Subcell 2 Zone 1 levels were about 41% of the 2/26/88 sampling,
indicating good transformation rates. The three-ring compounds were
the most readily transformed. The small amounts of PAH's found in
Subcell 2 Zone 2 and 3 were four-ring compounds.
Creosote Cells - 7/29/88 Sampling (Incorporation Zone)
Total PAH's in the incorporation zone soil of Cells 1 and 4
were 123 ppm and 142 ppm, respectively. PAH's in the incorporation
zone of Cell 9 were below detection limits (see Table 71 in
Appendix F).
-------
109
Creosote cells - 8/4/88 Loading
The three creosote cells (Cells 1, 4, and 9) were loaded with
67 kg per cell total PAH's (in waste treating solution) on 8/4/88,
giving the calculated concentration of the individual PAH's in the
incorporation zone noted in Table 14. Calculated total PAH was 3954
ppm.
Creosote Cells - 10/7/88 Sampling (Incorporation Zone)
Total PAH's in the incorporation zone soil of Cells 1, 4, and
9 were 475 ppm, 1017 ppm, and 87 ppm, respectively.
creosote Cells - 6/15/89 Sampling
No PAH's were found in Cells 1 and 4 in Zones 1, 2, or 3 at
this sampling date. PAH's were found in Cell 9 only in Subcell 2
Zones 1 and 2 with total PAH levels of 5ppm and 44 ppm,
respectively.
Creosote Cells - 7/13/89 Sampling (Incorporation Zone)
Total PAH's in the incorporation zone soil of Cell 1 Subcells
1 and 2 were 156 ppm and 376 ppm, respectively. Total PAH's in the
incorporation zone soil of Cell 4 Subcells 1 and 2 were 130 ppm
and 522 ppm, respectively. Total PAH's in the incorporation zone
soil of Cell 9 Subcells 1 and 2 were 67 ppm and 1175 ppm,
respectively.
creosote Cells - 8/11/89 Sampling
The only PAH found in Cell 1 at this sampling date was 6 ppm
pyrene in Subcell 2 Zone 2. No PAH's were found in Zones 1 and 2
of Cells 4 or 9. Cell 9 had total PAH's of 5 ppm in Subcell 2 Zone
1 and 44 ppm in Subcell 2 Zone 2. Zone 3 was not sampled at this
date. The zone of incorporation soil was sampled and total PAH's
in Cell 1 Subcells 1 and 2 were 137 ppm and 400 ppm, respectively.
Total PAH's in the incorporation zone soil of Cell 4 Subcells 1
and 2 were 75 ppm and 153 ppm, respectively. Total PAH's in the
incorporation zone soil of Cell 9 Subcells 1 and 2 were 6 ppm and
7 ppm, respectively.
Creosote Cells - 9/8/89 Sampling (Incorporation Zone)
Total PAH's in the incorporation zone soil of Cell 1 Subcells
1 and 2 were 136 ppm and 122 ppm, respectively. Total PAH's in the
incorporation zone soil of Cell 4 Subcells 1 and 2 were 159 ppm
and 73 ppm, respectively. No PAH's were found in Cell 9 soil.
-------
110
Creosote Cells •• 10/27/89 Samp liner (Incorporation Zone)
Total PAH's in the incorporation zone soil of Cell 1 Subcells
1 and 2 were 78 ppm and 92 ppm, respectively. Total PAH's in the
incorporation zone soil of Cell 4 Subcells 1 and 2 were 51 ppm and
94 ppm, respectively. No PAH's were found in Cell 9 soil.
Pentachlorophenol Cells - Background Levels
PCP background levels in the PCP loaded cells (2, 5, and 7)
were above detection limits only in Cell 5 (Table 53). PCP levels
of 12 ppm were found in Subcell 1 Zone 1 of Cell 5. PCP at 68 ppm
was found in Subcell 2 Zone 1, 21 ppm in Zone 2 and 31 ppm in Zone
3. These background levels were much less than were found in
creosote loaded Cells 4 and 9 and control Cell 6.
No PAH's were found in the penta cells before loading. OCDD
was found only in Cell 5 Subcell 2 Zone 1 soil at 0.1 ppm. See
Tables 68-70 in Appendix F.
Pentachlorophenol Cells - 10/30/87 Loading
The three pentachlorophenol cells (Cells 2, 5, and 7) were
loaded with 1.6 kg per cell PCP (in waste treating solution) on
10/30/87, giving the calculated concentration of PCP in the
incorporation zone of 94 ppm (Table 14).
Pentachlorophenol Cells -
Cell 2 sampling results indicated PCP at 98 ppm in Subcell 1
Zone 1, with no PCP found in Zones 2 and 3 of Subcell 1. PCP in
Subcell 2 Zone 1 was 208 ppm, in Zone 2 was 16 ppm, and Zone 3 was
12 ppm.
Cell 5 sampling results indicated PCP in Subcell 1 Zone 1 at
145 ppm, 7 ppm in Zone 2 and below detection limits in Zone 3. PCP
was found at 585 ppm in Subcell 2 Zone 1, 30 ppm in Zone 2, and 3
ppm in Zone 3.
Cell 7 sampling results indicated PCP in Subcell 1 Zone 1 at
39 ppm, Zone 2 at 37 ppm, and Zone 3 at 2 ppm. PCP was found at 66
ppm in Subcell 2 Zone 1, 6 ppm in Zone 2, and 2 ppm in Zone 3. It
should be noted that the cells which contained background levels
of PCP but which were not loaded with PCP (Cells 4, 6, and 9), were
also remediated during the study. The concentration changes in
Cell 4 were erratic but Cells 6 and 9, in general, showed major
reduction in the levels of PCP.
No OCDD was found in Cell 2. OCDD was found in Cell 5 Subcell
2 Zone 1 at 0.8 ppm. OCDD was also found in Cell 7 Subcells 1 and
2 Zones 1 and 2 at 0.1 ppm.
-------
Ill
Some movement of PCP apparently occurred in the time between
the first loading and the first sampling date after loading, since
PCP was found in Cells 2 and 7 in Zones 2 and 3 where no PCP had
been indicated in the background sampling. OCDD levels would be
expected to increase due to OCDD supplied from the waste treating
solution. The lack of OCDD in Cell 2 indicates some mechanism to
transform or remove OCDD was operating or, more likely, that levels
were below detection limits. Levels of OCDD in Cell 5 remained
constant or decreased slightly after loading, while the levels in
Cell 7 increased after loading. It should be kept in mind that the
OCDD levels are low and close to the detection limit.
Pentachloropl
Cell 2 sampling results indicated PCP at less than 1 ppm in
Subcell 1 Zone 1, and below detection limits in Zones 2 and 3.
PCP in Subcell 2 was 55 ppm in Zone 1 and below detection limits
in Zones 2 and 3.
Cell 5 sampling results indicated PCP at 15 ppm in Subcell 1
Zone 1 and below detection limits in Zones 2 and 3. PCP in Subcell
2 was 524 ppm in Zone 1, 32 ppm in Zone 2, and 93 ppm in Zone 3.
Cell 7 sampling results indicated PCP at 70 ppm in Subcell 1
Zone 1 and below detection limits in Zones 2 and 3. PCP was found
at 15 ppm in Subcell 2 Zone 1 and about 1 ppm in Zones 2 and 3.
OCDD levels of 0.1 ppm were noted in Cell 5 Zone 1, where OCDD
was below detection limits at the previous sampling date. In Cell
5 Subcell 2, OCDD apparently had moved downward in the soil into
Zones 2 and 3. In Cell 7, OCDD was found only in Zone 1. The OCDD
earlier found in Zone 2 of Cell 7 had dropped below detection
limits. The OCDD analysis for Cell 2 at this date is not available.
The variability of the PCP levels make interpretation of the
results difficult. It appears that some transformation and
migration was taking place, but the relative contribution of each
process to the results is difficult to assess. The PCP from the
sludge pit evidently left areas of high PCP concentrations
scattered across the cells of the soil treatment unit. When the
randomly chosen sample locations coincided with an area of high
PCP, the resulting high analyses confounded the results, especially
in Cell 5. This same variability of PCP concentrations was found
in Cells 4, 6, and 9. However, Cell 1 apparently had good
transformation of PCP, with PCP levels in Subcell 1 Zone 1 reduced
to less than 1% of the 11/13/87 measured value, and Subcell 2 Zone
1 levels reduced to 25% of 11/13/87 levels. Cell 5 Subcell l and
Cell 7 Subcell 2 also indicated good transformation, but there was
an apparent increase in PCP levels in Cell 5 Subcell 2 and Cell 7
Subcell 1.
-------
112
Pentachlorophenol Cells - 4/20/88 Loading
Two of the the three pentachlorophenol cells (cells 2 and 5)
were loaded with 3.15 kg per cell PCP (in waste treating solution)
on 4/20/88, giving the calculated concentration of PCP in the
incorporation zone of 186 ppm (Table 14).
Pentachlorophenol Cells - 5/10/88 Si
Cell 2 sampling results indicated 149 ppm, 3 ppm, and
undetectable levels of PCP in Zones 1, 2, and 3, respectively, of
Subcell 1. Cell 2 Subcell 2 results were 376 ppm, 5 ppm, and 1 ppm
PCP in Zones 1, 2, and 3 of Subcell 2.
Cell 5 results were 97 ppm, 3 ppm, and 6 ppm PCP in Zones 1,
2, and 3, respectively, of Subcell 1. Subcell 2 results were 819
ppm, less than 1 ppm, and undetectable levels in Zones 1, 2, and
3.
Cell 7 results were 4 ppm PCP in Subcell 1 Zone 1, and
undetectable levels in Zones 2 and 3 of Subcell 1. Subcell 2
results were 19 ppm in Zone 1 and undetectable levels of PCP in
Zones 2 and 3. PCP levels had decreased from the 10/30/87 loading
except in Subcell 2 Zone 1.
OCDD levels in Cell 2 Zone 1 soil had increased to 0.4 ppm
for Subcell 1 and 0.7 ppm for Subcell 2. No OCDD was found in Zone
2 and 3 soil in Cell 2. OCDD in Cell 5 Zone 1 soil increased to
0.4 ppm for Subcell 1 to 0.9 ppm for Subcell 2. No OCDD was found
in Zones 2 and 3 of Subcell 1 or 2. The OCDD previously found in
Zones 2 and 3 of Subcell 2 had fallen below detection limits. OCDD
in Cell 7 was essentially unchanged from the previous sampling.
Pentachlorophenol Cells - 7/29/88 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 was 19 ppm. Cell
5 PCP was 20 ppm. Cell 7 PCP was below detection limits (Table 71
in Appendix F).
Pentachlorophenol Cells - 8/4/88 Loading
The three pentachlorophenol cells (Cells 2, 5, and 7) were
loaded with 7.9 kg per cell PCP (in waste treating solution) on
8/4/88, giving the calculated concentration of PCP in the
incorporation zone of 463 ppm (Table 14).
Pentachlorophenol Cells - 10/7/88 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 was 273 ppm. Cell
5 PCP was 480 ppm. Cell 7 PCP was 46 ppm.
-------
113
Pentachlorophenol Cells - 6/15/89 Sampling
Cell 2 results indicated less than 1 ppm PCP in Zone 1 of
Subcell 1, and 2 ppm PCP in Zone 1 Subcell 2. No PCP was found in
Zones 2 and 3 of either subcell.
Cell 5 results indicated 24 ppm PCP in Zone 1 of Subcell 2.
No PCP was found in other locations in the cell.
Cell 7 results indicated 2 ppm PCP in Zone 1 and 27 ppm PCP
in Zone 3 of Subcell 2. No PCP was found in other locations in the
cell. These results indicate that PCP transformation was taking
place in all three PCP loaded cells.
OCDD was not found in the penta loaded cells at any depth at
this sampling date. It appears that some mechanism was removing
OCDD from the system. This may be related to the increased
disappearance of PCP noted during this part of the study.
Pentachlorophenol Cells - 7/13/89 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 Subcell 1 was 3
ppm; Subcell 2 PCP was 40 ppm. Cell 5 Subcell 1 PCP was 29 ppm;
Subcell 2 PCP was 4 ppm. Cell 7 Subcell 1 PCP was 72 ppm; Subcell
2 PCP was 8 ppm (Table 71 in Appendix F).
Pentachlorophenol Cells - 8/11/89 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 Subcell 1 was 5
ppm; Subcell 2 PCP was 26 ppm. Cell 5 subcell 1 PCP was 13 .ppm;
Subcell 2 PCP was below detection limits. Cell 7 Subcell 1 PCP was
8 ppm; Subcell 2 PCP was 2 ppm.
Pentachlorophenol Cells - 8/11/89 Sampling
Only Zones 1 and 2 were sampled at this time.
Cell 2 results indicated about 1 ppm PCP in Zone 1 of both
Subcells. No PCP was found in Zone 2 of either subcell.
Cell 5 results indicated 39 ppm and 98 ppm PCP in Zones 1 and
2, respectively, of Subcell 1. PCP levels of 55 ppm and 3 ppm were
found in Zones 1 and 2 of Subcell 2.
Cell 7 results indicated 3 ppm PCP in Zone 1 and 120 ppm PCP
in Zone 2 of Subcell 1. In Subcell 2 Zone 1 PCP levels were 4 ppm
and Zone 2 levels were 3 ppm.
OCDD was noted in all three penta loaded cells at this
loading.
-------
114
The variability of PCP analysis results is indicated by the
apparent increase in PCP levels in Cells 5 and 7.
Pentachlorophenol Cells - 9/8/89 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 Subcell 1 was 2
ppm; Subcell 2 PCP was 7 ppm. Cell 5 Subcell 1 PCP was 55 ppm;
Subcell 2 PCP was 14 ppm. Cell 7 Subcell 1 PCP was 39 ppm; Subcell
2 PCP was 4 ppm.
Pentachlorophenol Cells -10/27/89 Sampling (Incorporation Zone)
PCP in the zone of incorporation in Cell 2 Subcell 1 was 3
ppm; Subcell 2 PCP was 22 ppm. Cell 5 Subcell 1 PCP was 4 ppm;
Subcell 2 PCP was 2 ppm. Cell 7 Subcell 1 PCP was 2 ppm; Subcell
2 PCP was 30 ppm.
Table 14 shows the total expected (calculated) levels of PAH's
and PCP in the cells after all the loadings. It may be noted that
remediation of PAH's was outstandingly successful, with Cells 4 and
9 showing no PAH's above detection limits at the 8/11/89 sampling
date, and Cell 1 showing only 6 ppm pyrene in Subcell 2 Zone 2
soil. There evidently was no accumulation of PAH's in the soil
under the conditions prevailing during this study. The PCP results
could not be said to be as markedly successful as the PAH results,
due primarily to the variability of the PCP data. Nevertheless,
the PCP levels remaining at the 8/11/89 sampling date were well
below the levels found during the course of the study, and it
appears that acceptable transformation was taking place.
MICROORGANISMS IN CELL SOIL
Microorganism counts in the soil core samples from the cells
(data not shown) increased rapidly after addition of the chicken
manure and loading, and the counts stayed between 2 and 10 million
organisms per gram of soil throughout the course of the experiment.
The control cells tended to have slightly lower levels of
microorganisms than the PAH or PCP cells, but all cells maintained
high levels throughout the course of the experiment.
SOIL PORE LIQUID SAMPLES
The background levels of PAH's found in the lysimeters was
minimal (Table 56). Only in Cell 9 were PAH's found in lysimeter
samples before loading. Acenaphthene and fluorene were found in
lysimeter 3 of Subcell 2 at 17 and 29 ppb, respectively. After the
first loading (10/30/87) three and four-ring PAH's were found in
lysimeter 3 of Cell 1 Subcell 1 at the 1/13/88 and 3/23/88 sampling
date. PAH's were not found in any other lysimeter samples
throughout the course of the study.
-------
115
PCP was found in many of the lysimeters before loading the
cells (Table 57). PCP levels as high as 69,000 ppb were found.
The PCP levels showed a generally consistent pattern of decrease
during the course of the study except in Cell 2 Subcell 2 lysimeter
1 and Cell 4 Subcell 2 lysimeter 3, where PCP levels varied
considerably.
There seems to be little correlation between PCP and PAH
levels in lysimeter samples and the cell loading activities. The
difficulty of interpreting the results is compounded by the fact
that most of the lysimeters did not yield enough sample for
analysis (>50ml) during most of the study period. The soil in which
the lysimeters were set seemed to be impermeable enough to greatly
limit water movement down through the soil and into the lysimeters.
It is apparent, however, that movement of PAH's in the soil pore
liquid was negligible. The movement of PCP is more difficult to
determine due to the high background levels.
Groundwater
The data from the three groundwater monitoring wells is shown
in Table 58. Background levels of PCP and PAHs in the groundwater
are not available, but the first sample (8/23/88), taken after all
three loadings, indicated no detectable amounts of PCP or PAHs in
either the upgradient or downgradient wells. At the second sample
(12/2/88), very low levels of PCP and PAH's were found in one
downgradient well, and low levels of PAH's in the other
downgradient well. At the next sampling date (6/19/89), low levels
of PCP were indicated in the upgradient well and one downgradient
well. At the last sampling date (9/1/89), no PCP or PAH's were
found in the wells. Considering the very low levels of
contamination found in the groundwater, the fact that the highest
levels were found in the upgradient well, and the location of the
soil treatment unit on an active wood treating site, it seems
unlikely that the soil treatment unit was the cause of the PAH's
and PCP found in the monitoring wells.
GENERAL DISCUSSION
The results of these experiments indicate that PAH's and PCP
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. Based on treatability data in the soils
tested, soil treatment of creosote and PCP wood treating wastes
appears to provide a viable management alternative. The agreement
of laboratory and field study data on transformation and migration
is very encouraging and certainly indicates that soil treatment of
these compounds can be used in many wood treating site cleanup
-------
Table 56. Wiggins Soil Treatment Unit • PAH In lyslmeters (ppb)
LYSIMETER INDIVIDUAL PAHS MOMOUAl PAHS RMQ GROUPS
DATE CEa SUBCELL DEPTH NAPH 2-MET 1-MET BIPH ACTHY ACTHE DIBEN FLOW PHEN ANTHR CARBA FLUOH PYRENE 1.2-BZ CHRVS BEN* BgM 2WNQ 3MNQ 4WNQ 5WNQ TOTALPAH
t JL3NONONOHONOirNOMNONDNONONONDNONONONO4«NONO «
I/IMS t 1 U NO NO NO NO NO 1427 21.6 J»1 13 21.1 15.1 54.1 U.t NO NO NO NO NO 24M 1174 NO 3US
30WW 1 1 LJ NO NO NO MD ND NO NO 17.3 NO NO MD 213 20 NO NO NO NO NO 17.3 43.3 NO MS
NO - Not DMcM - S<* TlM» 20 lor dMefen Mil
cn
-------
Table 57. Wiggins Soil Treatment Unit - Pentachlorophenol in lysimeters (ppb)
LYSIMETER SAMPLING DATE
CELL SUBCELL DEPTH 9/22/87 10/21/87 1/13/88 3/23/88 5/12/88 7/28/88 11/11/88 5/22/89
8/9/89 5/18/90
1
2
3
4
5
6
7
8
9
1
2
1
2
1
2
1
2
1
2
1
2
1
1
1
2
L1
L3
L1
L3
L1
L3
L1
L1
L2
L1
L2
L3
L2
L1
L2
L3
L2
L3
L3
L1
L1
L2
L1
L2
L3
L1
L3
L1
L2
L3
L2
L3
6261.1
NS
2754.1
2215.3
1008.9
NS
311.9
NS
1385.5
4211.6
15392.8
15912.2
3486.7
NS
NS
69204.1
105.2
96.9
115.7
NS
41.2
71.3
2377.3
103.3
76
98.9
540.3
875.9
3369.2
1057.8
83.1
1243.4
NS
NS
2454.1
1191.3
NS
NS
310.4
NS
NS
5329.3
6303.6
1737.2
4006.8
NS
22371.1
NS
ND
ND
NS
NS
NS
NS
NS
ND
ND
ND
NS
ND
NS
ND
ND
ND
27.6
265
2019.3
469.3
NS
NS
1724.4
NS
NS
1356.5
NS
670.3
496.6
NS
NS
808.8
NS
NS
NS
NS
NS
NS
NS
67.5
NS
NS
NS
NS
NS
NS
NS
NS
NS
320
ND
ND
NS
NS
1850
ND
NS
255
2550
NS
NS
NS
NS
2673.8
89.6
NS
48.9
NS
425
73
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
17.5
112
NS
ND
ND
NS
NS
ND
NS
19.2
1080
NS
NS
NS
NS
4800
NS
NS
ND
NS
4.6
6.3
NS
NS
NS
6.1
NS
NS
NS
NS
NS
NS
NS
ND
NS
ND
NS
2.9
NS
53.2
NS
72.4
362
ND
NS
4220
NS
4440
NS
NS
ND
NS
ND
ND
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
ND
NS
ND
NS
NS
NS
ND
NS
ND
195
NS
NS
NS
NS
1100
NS
NS
NS
NS
ND
66.6
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
ND
NS
ND
ND
NS
NS
NS
NS
NS
ND
ND
NS
NS
NS
NS
ND
NS
NS
NS
NS
ND
ND
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
ND
ND
NS
ND
NS
NS
NS
NS
NS
NS
NS
23.3
NS
NS
NS
5900
NS
NS
NS
125
NS
226
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
ND
ND
ND
ND
NS
ND
NS
NS
NS
ND
NS
ND
NS
NS
NS
ND
NS
NS
ND
NS
ND
NS
NS
NS
NS
ND
NS
NS
NS
ND
NS
NS
ND - Not Detected - See Table 20 for detection limits
NS - No Sample available
LYSIMETER/DATE COMBINATIONS NOT SHOWN HAD NO SAMPLE AVAILABLE
-------
\
scenarios. Those soils with high sand content would need to be
monitored very carefully, but the other soils considered in this
study appear to be well suited for soil treatment. 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 PGP 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 soil treatment as a
practically useful management alternative for these recalcitrant
compounds. Since the environmental problems confronting the wood
treating industry are almost unlimited and since the resources
available to solve these problems are quite limited, soil treatment
is very attractive as a reliable, safe, economical remediation
technique.
-------
119
Table 58: Pentachlorophenol and total PAH's in Wiggins LTDU
monitoring veils (lg/L).
Date
8/23/88
12/02/88
6/19/89
9/01/89
Compounds
POP
PAH
PCP
PAH
PCP
PAH
PCP
PAH
Downgradient
Well
0
0
0
0
0.622
0
0
0
Upgradient
Well A
0
0
0.148
0.085
0.043
0
0
0
Downgradient
Well B
0
0
0
0.539
0
0
NS
NS
NS = No sample available.
-------
\
120
SECTION 6
SUMMARY
Eight wood-treating plant sites were chosen to study the
effectiveness of land treatment toward 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 four
loading rates (0.0%, 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 this study are that PAH's and
PCP are readily degraded in soil systems. PAH's were transformed
readily 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's and PCP
containing wastes to soil greatly increases the population of PAH's
and PCP adapted microorganisms in the soil. The results of this
study indicate that land treatment is an effective alternative for
remediation of PAH's and PCP containing wood treating wastes.
-------
121
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APPENDIX A
ANALYTICAL METHODOLOGY
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EXTRACTION OF PCP, PAH'S AND OCDD 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 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
octachloronaphthalene. 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 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 (10mm 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 (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 of the 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 aliquot 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
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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 GC/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 /ra
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
Air flow: 400 cc/min
Nitrogen makeup: 40 cc/min
Injection: 2 /il splitless, vent after 1.5 min.
Amplifier range: xl
Tracor 540 GC 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 (MSU 1984)
The analysis of OCDD in soil presented two significant
problems which had to be solved in order to obtain reliable
results. First, an extraction procedure had to be used which
would be highly efficient in removing OCDD from the sample
matrix. This was especially important, since the anticipated
concentration of OCDD in the soil was in the parts-per-billion
range. Second, 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.
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Burning n*
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 uses the same extraction procedure, was considered to be
adequate and would save analysis time. For our purposes, the
removal of the majority of chemical interferences could be
accomplished by a modification of two column clean-up techniques
recommended by EPA for 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 wood, 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) .
OCDD for standards, Analabs.
Gas chromatograph equipped with BCD 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.
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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.
A 10-ml volumetric flask was placed under the column.
Before clean-upt 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
Ml sample was injected on the Tracer 540 GC/ECD
using the following conditions:
Oven: 280°C; Injector: 330°C; Detector: 350°C
Five 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.
Diphenymethane, 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
spike sample were used to determine the recovery values for the
individual compounds. Diphenylmethane, 2,4,6-tribromophenol,
octachloronaphthalene were used an internal standards. All
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standards were prepared using a Mettler 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. The solution 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-Cihcinnati, 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. Prior to
GC/MS analysis, a 1.00 ml aliquot of each extract was transferred
to a screw cap test tube and stored at approximately 4°C. The
sample weight range and dilution volume were based on prior
knowledge of concentrations determined by GC/FID analysis.
A Carlo Erba GC fitted with a J. and W. DB-5 capillary
column [0.25 m 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 then programmed to 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 elution 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 /ng/ml and 200 /ig/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:
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100 ml x c Q/ml
Here, C = concentration of each compound in sludge (M9/9)? 100 =
dilution volume, c = concentration of each compound in the sample
extract, and W = dry weight of the sludge sample in grams.
Table 59 and Table 60 list the EPA Method numbers for the
soil and sludge analysis methods and Table 20 gives the detection
limits for the compounds analyzed.
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Table 59: Analytical procedures for soil and water (U. 8. EPA
1986a).
Process
Method
Number Compounds
Comments
Extraction of
soil samples 3540
Extraction of
water samples 3520
Clean up
Analysis
Analysis
Analysis
Anaysis
3630
8100
All
All
All
PAH's
8040 OCDD+PCP
8270
8280
ALL
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
octachlordibenzo-p-dioxin;
using an BCD detector
Check for all compounds
Used for low-level dioxins
(penta, hexa, and hepta
dioxins)
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Table 60: Analytical procedures for sludges,
Process
Procedure
Water content
Organic content
Non-volatile
products
Organic carbon
Total phenolics
Oil and grease
Nitrogen
Phosphorous
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 C02 evolution
Method 222E Standard Methods for
Examination of Water and Wastewater
Method 5030 Standard Methods for
Examination of.Water-and Waterwater
Micro Kjeldahl followed by digestion with
5% hydrogen peroxide and sulfuric acid;
nitrogen was determined colorimetrically
using nessierization
Determined after digestion colprimetrically
using the Fisbe-Subarrow method
Inorganic chloride
Determined using a chloride specific ion
electrode
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APPENDIX B
MICROBIOLOGICAL PROCEDURES
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The media used for this study were potato dextrose agar PDA,
(Difco Laboratories, 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 adjusted to pH 6.9-
7.1, autoclaved for 20 minutes at 15 psi and 121°C, then cooled
to 55°C. Creosote and pentachlorophenol dissolved in methyl
alcohol and the antibiotics were added to the cooled liquid
medium before pouring into petri dishes. 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 screened with a 400 mesh
sieve. Serial dilutions were made with sterilized screened soil.
Three 20-mg soil samples were taken 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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APPENDIX C
SITE AND SOIL CHARACTERIZATION
EXPERIMENTAL PROCEDURES
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Soil profiles were examined at each site in freshly
excavated pits. 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 cores using theconstant 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 N NH4OAc and determined by atomic absorption
spectrophotometry (USDA 1972). Soil pH was measured in water and
1 N 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 Dixon and Weed
(1978). Relative estimates of the amounts of clay minerals
present were based on peak area measurements with corrections for
Lorentz polarization at peaks greater or equal to 14A. The
results of this phase of the study were reported in the earlier
report.
-------
145
APPENDIX D
RATIONALE FOR THE ADDITION OF CHICKEN MANURE TO SOIL
IN THE DEGRADATION/TRANSFORMATION STUDIES
-------
146
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 land treatment 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 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:
Total organic carbon = 8.97%
Total nitrogen = 1.35%
Total phosphorus = 0.12%
Bacteria counts in four of the soils were compared 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 61)
indicate a large increase in both the total bacteria and the
acclimated bacteria in the soil with added chicken manure.
-------
Table 61: Bacteria levels in four soils at 0% loading before and after
addition of chicken manure'.
Total bacteria counts
( mil lion counts/aram of soil)
Site
Gulf port
Wiggins
Columbus
Meridian
Before
1.
0.
1.
1.
addition
13
41
25
10
After addition
4
3
2
3
.50-7
.10-4
.80-3
.10-4
.20
.50
.10
.20
Acclimated bacteria countsb
(million counts/aram of soil)
Before
0.
0.
0.
0.
addition
07
12
25
09
After addition
0.
0.
0.
0.
50-0
64-2
14-0
48-0
.61
.30
.35
.92
aThese soils were 0%-loaded, and counts were taken 30 days after addition
of chicken manure.
bBacteria acclimated to PCP and PAH's.
-------
148
APPENDIX B
STATISTICAL PROCEDURES
-------
149
A linear regression based on first-order kinetics was
used to calculate estimates of transformation/degradation rates
and 95% confidence limits. The half-life of each compound was
calculated from the first-order degradation rate. 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.
-------
150
APPENDIX F
RAW DATA FROM EXPERIMENT 1, EXPERIMENT 2,
AND FROM THE OPERATION OF THE WIGGINS SOIL TREATMENT UNIT
-------
151
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Table 64. Experiment I: OCOO in Site Soils (ppm)
DRYS RFTER INITIRL LORDING
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
SITE OUPLICflTE O 3O SO 9O 12O ISO
XXXXXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
R 1.01 1.30 1.29 2.23
B 1.O4 1.09 1.2S 2.06
GULFPORT
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XXXXXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
WIGGINS R 0.82 0.75 1.05 1.78 2.41 Nfl
B 0.83 0.79 0.93 1.78 2.64 Nfl
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XXXXXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
CHRTTRNOOGfl H 1.88 1.76 2.48 2. OS 2.O6 1.90
B 1.75 1.67 2.35 1.90 1.98 1.85
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XXXXXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
WILMINGTON fl 1.86 1.79 2.50 2.49 3.87 4.79
B 1.76 1.73 2.37 2.52 3.98 4.82
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B 1.19 1.11 2.35 2.14 Nfl NH
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55 5
3515
5593
3595
5515
5593
5515
3315
5515
5515
55
S5
55
55
55
S3
81S
n
f;
53 5
5593
j
<
5595
3585
53
55
35
55
35
53
33!
33
IS f
558?
55!
53
§ f
in 4.
35
35
55
559
SXa
o a M
°
5553
559?
33lf
!N
1
1u
!s
3
I 01
5
5
N
-------
Table 66. Experiment II - Pentachlorophenol in site soil (pprn)
RTLRNTR
DRYS RFTER INITIRL LORDING
xxxxxxx
LORD
xxxx
0.3
KXXK
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxx
1.0
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxx
3.0
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxxxxxx
DUPLICRTE
xxxxxxxx
R
B
/2=
xxxxxxxx
R
B
(R+B>/2=
xxxxxxxx
KKXXXXXX
fl
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
R
B
(fl+B)/'2=
xxxxxxxx
xxxxxxxx
R
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
XMMXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
0
XXXXKKKX
56.4
79.5
68.0
xxxxxxxx
63.9
73.0
66. 5
XKXXXXXX
64.2
72. 1
68.2
XXXXXKXX
179.9
125.6
152.8
xxxxxxxx
178. 1
176.6
177.4
xxxxxxxx
118.2
100.7
109.5
xxxxxxxx
xxxxxxxx
883.2
747.4
815.3
xxxxxxxx
624.9
634. 1
629.5
xxxxxxxx
443.9
477.0
460.5
xxxxxxxx
30
xxxxxxxx
67.4
61.5
64.5
XXXKXXXX
65.5
111.0
88.3
xxxxxxxx
59. O
67.8
63.4
KXXXXXXM
148. O
144.0
146. O
xxxxxxxx
154.0
166. O
160.0
xxxxxxxx
102.0
108.0
105.0
xxxxxxxx
xxxxxxxx
608.0
506.8
557.4
XXXKXXXX
546.5
504.9
525.7
XXXXXXXK
412. 1
426.3
419.2
xxxxxxxx
60
XXXXKXXX
68.9
58. 1
63.5
xxxxxxxx
78.4
118.0
98.2
xxxxxxxx
65.9
50.6
58.3
KXXXXXXX
XXXXXXKX
139.0
162.0
150.0
xxxxxxxx
152.0
167.0
159.5
xxxxxxxx
40. 1
25. 1
32.6
xxxxxxxx
xxxxxxxx
435.3
459.7
447.5
KXXXXXXX
411.0
449.9
430.5
xxxxxxxx
398.3
330.2
364.3
xxxxxxxx
90
XXXKXXXX
66. 1
60.5
63.3
XKXXKXXK
66.2
64. 1
65.2
xxxxxxxx
50.3
53.8
52. 1
KKXXXXXX
XXXXXXXX
153.0
172. O
162.5
xxxxxxxx
78.3
69.2
73.8
KKXXXXXX
30.5
47. 1
38.8
xxxxxxxx
xxxxxxxx
386.6
470.6
428.6
KXXXXXXK
375.5
406.4
391.0
XKXKKKKK
66.7
54.9
60.8
xxxxxxxx
oo
oo
-------
Table 66. Experiment II - Pentach1orophenol in site soil /2=
KXXXXXXX
fl
B
xxxxxxxx
xxxxxxxx
R
8
/2=
XXXXKXKK
H
B
/2=
XXXKKXXK
KKXKKXXX
R
B
/2=
XXXXKXXX
R
B
144. 1
xxxxxxxx
152.2
139.9
146. 1
xxxxxxxx
140.9
139.9
140.4
xxxxxxxx
xxxxxxxx
453.2
458.3
455.8
XXKXXXXX
443.5
405.9
424.7
xxxxxxxx
465.3
463.2
464.3
xxxxxxxx
XXXXXKXX
1342.0
1393.3
1367.7
XXKXXXXX
1503.9
1459.6
1481.8
XXXXXXXK
1507.7
1422. 8
145.7
XXKXKXXX
153.9
151 . 1
152.5
XXXXXXKX
150.3
149.3
149.8
xxxxxxxx
xxxxxxxx
473.6
483.0
478.3
xxxxxxxx
504. 4
479.8
492. 1
XXKKXXXX
512.3
504.2
508.3
XXXXXXKX
XXXXXXKX
1447. 1
1356.5
1401.8
XKXXXXXX
1389.7
1443. 4
1416.6
xxxxxxxx
1522.2
1405.4
139.5
xxxxxxxx
140.0
143.0
141 .5
XXXXKXXX
134.0
147.0
140.5
xxxxxxxx
XXXXXXXK
430.0
435.0
432.5
xxxxxxxx
410. 0
417.0
413.5
XXKXXXKK
441.0
439.0
440.0
XKKKKXXX
XXXXXXXX
1307.2
1367.9
1337.6
xxxxxxxx
1341. 1
1334.5
1337.8
KKXXXKKK
1388.2
1367.4
142.5
xxxxxxxx
152.0
138.0
145.0
XXKXXXXX
140.0
139.0
139.5
xxxxxxxx
XXXKXXXX
430.0
427.0
428.5
XXKXXKXK
416.0
417.0
416.5
XXXXXXXK
423.0
419.0
421.0
XKXXKKKK
KKXXXXXK
867.5
859.6
863.6
KKXXXXXK
888.2
890.2
889.2
KXKKKKKK
878.6
873.4
xxxxxxxx
1465.3 1463.8 1377.8 876.0
KXXXXKXX XXXXXXXX XXXXXXXK KXXXXXXX
oo
-pa
-------
Table 66.
COLUMBUS
xxxxxxx
LORD
xxxx
0.3
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxx
1.0
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxx
3.0
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
KXXXXX
Experiment II - Pentachlorophenol in site soil (ppm)
DRYS RFTER INITIRL LORDING
xxxxxxxx xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
DUPLICATE 0 30 60 90
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
R 130.8 113.0 131.2 119.1
B 135.5 124.1 147.7 116.9
133. 1 118.6 139.4 118.0
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
R 117.8 115.0 138.1 106.4
B 128.7 141.8 136.7 112.1
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
xxxxxxxx
R
B
(R+B>/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
xxxxxxxx
R
B
/2=
XXXXXXKX
R
B
/2=
xxxxxxxx
R
B
(R-t-B)/2=
xxxxxxxx
123.3
xxxxxxxx
125. 1
126.4
125.8
xxxxxxxx
xxxxxxxx
814.4
835.4
824.9
xxxxxxxx
831.5
812.6
822.0
xxxxxxxx
789.2
815. 1
802.2
xxxxxxxx
xxxxxxxx
2915.4
2948.9
2932.2
xxxxxxxx
2887. 1
2935.2
2911.2
xxxxxxxx
2950.4
2895.0
2922.7
XXXXXXXX
128.4
xxxxxxxx
1 17.6
118.4
118.0
xxxxxxxx
xxxxxxxx
654.0
650.5
652.3
xxxxxxxx
1020.0
1146.3
1083.2
xxxxxxxx
643.6
611.4
627.5
xxxxxxxx
xxxxxxxx
2678.6
2237.0
2457.8
xxxxxxxx
2930.4
2951 .9
2941 .2
xxxxxxxx
2848.0
2907.2
2877.6
xxxxxxxx
137.4
xxxxxxxx
131.7
136.5
134. 1
xxxxxxxx
xxxxxxxx
990.7
1O15.2
1002.9
xxxxxxxx
985.5
958.9
972.2
xxxxxxxx
921. 1
916.2
918.7
xxxxxxxx
xxxxxxxx
1640.0
1910.0
1775.0
xxxxxxxx
1620.0
2100.0
1860.0
xxxxxxxx
1860.0
2240.0
2050.0
xxxxxxxx
109.3
xxxxxxxx
121.8
113.2
1 17.5
xxxxxxxx
xxxxxxxx
1044.3
956. O
1000.2
xxxxxxxx
880. 1
888.8
884.4
xxxxxxxx
861.6
939.7
900.6
xxxxxxxx
xxxxxxxx
2427.5
2424.7
2426. 1
xxxxxxxx
2332.7
2522.4
2427.6
xxxxxxxx
2464.6
2541. 1
2502.9
xxxxxxxx
00
01
-------
00
KKKKXXXX
6'6
V6
E'OI
XXKKKKKX
fr'OI
6'01
O'PI
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6'01
I'll
XXXXXXKK
KKXXXXXK
0'2/
^•eej
2'OT
KKKXXXXX
T •&
6'&
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KKKKKXKX
fr'OI
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KKKKKKXX
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6>
0'9
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6'9
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fr "*
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6'6
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KKXXXXXX
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8'8
8'6
xxxxxxxx
9'8
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6'II
XKXXKXKK
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ve
6V
6 "8
KKXXMXXX
E'8
8V
8'8
XKKKXXXK
2'6
6'6
9 "8
KXXXKXXX
09
XXXXXKKX
t'-TII
2"20t
9'02I
XXXXXKXX
t'-SOI
£•£01
S VOI
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8*901
g-VOT
T *60I
KXXXXXXX
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E'^2
6 '22
8
b
XXKKKXXX
=2/
8
b
XXXXXXXK
=2/<8+b>
8
b
XKKXKXXK
KKKKKKXX
=2/
8
b
KKXKXXXK
=2/'
a
b
XXXXXKXK
3iboiidna
XKXXXKKK
XXKXXX
£ d3JJ
KKKXXX
2 dsa
KKXKXX
T d3d
KKKK
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XXXK
KKKKKX
E d3d
KKKKKK
2 d3d
KKKKKK
I d3d
KXKK
O'l
KKKK
KXXKKH
E d3b
xxxxxx
2 d3d
KKKKKK
I d3d
XKKK
E'O
xxxx
ObOl
KKXKKXK
d31Jb SABO
,.
(uidd)
- II quaiujjedx^ -gg a-{qej_
-------
oo
6V9II
Z'0811
O "SEI I
KKKXKKXX
1--68II
6-0211
6V92I
KXXXXXXX
9 '666
9*S20l
9 "E/6
XXXXKXKK
E'&Zfr
Z'69S
6 '86£
KKXKXXXX
9-frEI
2'IEI
0*8EI
XKKKXKXK
9'TII
S'90I
S "91 1
XKKXXKKX
KXKKKKKK
Z'EI
O V
f '02
KKKXKKKK
OVI
E"9I
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o-g
£-9
Z 'V
XXKKKKKX
Z'696
I '296
2 V96
KXXXKXKX
9 V96
E-^96
6-096
KKKKKXXK
Q-9E8
2'68-d
Z'£88
XXKKKKKX
9-ZfrS
6 "9^9
I "SEt'
KXKKKKKX
6-eEt-
i -is*
Z '96E
KKKXXXXX
E't'Ot'
I •92fr
t' "28E
KXKKXXKX
KKXKKXXX
g-t^
2'ZI
0'2£
KKKKKXKX
2'6S
/'OZ
9 '/t'
XKKKKKKK
£-21
Z'll
8 "21
XKKKXXXX
9'9E8
8 "088
E "26Z
KKXXXXKK
E'EIOI
I -1201
*• 'SOOI
XXXKXXXX
6 '928
8-£fre
6 V08
XXXKKKKK
t'-09»'
V28t'
£ *8£t'
XXXKKKKK
2'£Ef
i • vtv
2 '22V
KXKKKKXX
O'SSf
O'EOt'
O'EIS
XKKKKXKX
XKKXKKKK
0-81 I
8VII
I •BIT
XXXKKKKK
9 "26
Z'26
9'26
KKKKKKKK
9'68
Z V8
2 " 16
XKXXXKKX
t-'20U
9-8901
I ^MI
KXXXXKKK
V*36
2'2£OI
9 '968
KKKXXXXX
Q-iza
6 '288
2 '698
XXXKXXXX
SN
SN
SN
XKXXXXXX
SN
SN
SN
xxxxxxxx
SN
SN
SN
XKXXXXXK
KKKKKKKK
E't't'Z
I '86
V "06E
KKKXKKKK
I 'III
I V2I
0'96
KXXXXXXX
I '28
9'E8
9'08
KKKKXKKX
=2/
a
b
XXKKKKKK
=2/CB+b>
a
b
KKKKKKXK
=2/
8
b
KXXXXXXX
=Z/<8+d>
a
b
XKXKXXXX
=2/
a
b
XXXXXXXK
=2/ca+b>
8
b
KMXKXKXX
XXXXKXKX
=2/ca+b>
8
b
KKXKKKXX
=2/ca-t-b>
8
b
KMKXKXKK
=2/.ca+b>
8
b
XKKKXXKK
E daa
KKXXKX
2 daa
KKKKKX
I d3a
XKKK
O'E
KXKK
e d3a
KKKXXX
2 d3a
XXXKXK
I d3d
KKXX
O'l
KXKK
XXXKKX
F _j^w
KKXKKX
z dsa
KKKXHH
I d3d
KHKK
E'O
xxxx
(uidd)
06 09 OE 0
KXXKKXKKKKKKKKKXKXXXXXXXXXXXKXXKXXX
SNIObOl IblllNI a31db SAbO
UT ;ouaqdo-jo ;qoe^ua,-j - I I ^)*.
KXXKKXKX KHKKKHX
-gg
-------
oc
00
xxxxxxxx
0'28£
0'89E
9'T££
0'92E
OVEE
xxxxxxxx
xxxxxxxx
0-B8T
0-9
a
d
xxxxxxxx
=2/
8
d
xxxxxxxx
xxxxxx
xxxxxx
T> _J^3\I
xxxxxx
O'SZE OV^I S'Ot'S £'061
O'lt'i' OV6I 9^92 £'£02
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
E'9 CT8 6'E2 L'lZ
8 xxxx
d O'E
xxxxxxxx xxxx
xxxxxxxx xxxxxx
=2/ £
EV
£-9
xxxxxxxx
2-9
B'E
9'8
xxxxxxxx
9'8
2'01
6'9
xxxxxxxx
6'8
EY
S'OI
xxxxxxxx
0'8I
2"2I
9'9E
xxxxxxxx
8'9I
9'12
I-QI
xxxxxxxx
8'9I
6>2
9'0£
xxxxxxxx
9 '82
K92
S'OE
xxxxxxxx
6-OE
a
d
xxxxxxxx
=2/
a
d
xxxxxxxx
=2/<8+d>
xxxxxx
2 d3d
xxxxxx
I d3d
T'8 L't\ 2'ZI 9"0£ 8 xxxx
Q'6 2'8I 9'9l 2'IE d E'O
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx xxxx
06 09 OE o 3idandno adon
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx xxxxxxxx xxxxxxx
3NICMT1 IdlllNI d3idd SAdQ
'99
-------
Table 66. Experiment II - Pentachlorophenol in site soil (ppm)
WIGGINS
DRYS RFTER INITIRL LORDING
XXXXXKK XKXKKXKX XXXXXXXXXXXXXKXXXXXXXXXXXXXXXXXXXXX
LORD
xxxx
0.3
xxxx
REP 1
KXXXXX
REP 2
xxxxxx
REP 3
XKXXXX
KXXX
1 .0
XXXX
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
XKXX
3.0
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
DUPLICRTE
XXXKXXXX
fl
B
V2=
XXXKKXKX
R
B
/2=
KKXXXXKX
R
B
/2=
XKXXXXXX
R
B
/2=
xxxxxxxx
R
B
/2=
XKXXXMXX
xxxxxxxx
R
B
/2=
Xxxxxxxx
R
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
0
xxxxxxxx
23.3
37. 1
30.2
xxxxxxxx
91.6
25.5
SB. 6
xxxxxxxx
48.7
24.9
36. B
XKXXXXXX
XXXXXXKX
69.3
65.5
67.4
xxxxxxxx
51.7
75.4
63.6
xxxxxxxx
41.2
289.6
165.4
xxxxxxxx
xxxxxxxx
486.6
132. 1
309.3
xxxxxxxx
72.0
166.7
119.4
xxxxxxxx
389.4
154.2
271.8
xxxxxxxx
30
XXXKXXXX
249.3
19.5
134.4
xxxxxxxx
29.7
22.2
25.9
xxxxxxxx
708.7
117.4
413.0
xxxxxxxx
xxxxxxxx
34.4
43.2
38.8
xxxxxxxx
43.3
41.5
42.4
xxxxxxxx
43.3
26.5
34.9
xxxxxxxx
xxxxxxxx
337. O
78.4
207.7
xxxxxxxx
76.6
129.6
103.1
xxxxxxxx
134.5
103.2
118.9
xxxxxxxx
60
XXXKXXXX
15.6
10.8
13.2
xxxxxxxx
2O2.2
36.6
119.4
xxxxxxxx
116.6
9.7
63.2
KXKXXXXX
XXXXXXXX
11.0
10.6
10.8
xxxxxxxx
8.O
106.9
57.4
xxxxxxxx
10.8
10.4
10.6
XXKXXXXX
xxxxxxxx
723.0
35.8
379.4
XXKXXXXX
62.2
47.6
54.9
XXXXKXXX
86.8
190. 3
138.5
xxxxxxxx
90
xxxxxxxx
93. 1
132.6
112.8
xxxxxxxx
91.8
62.4
77. 1
xxxxxxxx
40. O
236.4
138.2
xxxxxxxx
xxxxxxxx
14. 1
17.8
16.0
xxxxxxxx
11.3
14.9
13. 1
xxxxxxxx
11.6
98.8
55.2
xxxxxxxx
xxxxxxxx
37.6
49.8
43.7
xxxxxxxx
26.3
1183.6
605.0
xxxxxxxx
37.8
40.9
39.4
xxxxxxxx
00
to
-------
Table 66. Experiment II - Pentachlorophenol in site soil >2=
KKKKXKKK
B
CR+B>/2=
KXKKXKKK
R
B
/2=
XXKXXXKK
XXKKXXKK
R
B
KKXKXKKX
R
B
/2=
XXKXKXKX
fl
B
/2=
KXKXXKXX
KXXXXXXX
fl
B
/2=
KXXXXXXK
R
B
/2=
XXXXXXKX
fl
B
/2=
KXXXXXXK
148.1
KXXKXKKK
156.6
151.6
154. 1
KKKKKKKK
150.5
146.0
148.3
KXXKXKXX
KXXXXXXK
928.7
1048.6
988.7
KKKXXXXK
950.4
1052.3
1001.4
KXXXXXXX
967.7
922.3
945.0
XXXKXXXX
XXXXXKKK
2279.0
2351.4
2315.2
XKXXXXKK
2486.0
2666. 1
2576. 1
KXXXXXXX
2422.4
2421.8
2422. 1
xxxxxxxx
171.5
KKKKKKKK
123.0
108. 0
115.5
KKKKKKKK
14O.O
165.0
152.5
KXXKKKKK
KXXXKXXX
765.0
778.0
771.5
XKKXKKKK
808.0
688.0
748.0
KXKKXXXX
749.0
734.0
741 .5
XXXKKXXX
XXXKKKKX
937.0
943.0
940.0
xxxxxxxx
973.0
960.0
966.5
KXXXXXXX
967.0
963.0
965.0
XXXXXXXX
286.7
KKKKKKKK
318.9
33O.6
324.8
KKKKKKKK
292.2
297.1
294.7
XKXKXKKH
KXKKKKXX
675.0
697.0
686.0
KKKKKXXK
677.0
688.0
682.5
XXXXKKKK
815.0
691.0
753.0
KXXXXKXX
XXXXKXKK
1622.5
1785.3
1703.9
KXXXXKKK
1638.0
1550.2
1594. 1
XXXXKXXX
1694.6
1632.8
1663.7
XXXXXXXK
107.5
XXKXKKKK
134. O
128.0
131.0
KKKKKKKK
121.0
119.0
120. O
HKKKKKKK
KKKKXXKK
769.0
776.0
772.5
KKKKKKKK
801.0
773. O
787. O
KKKKKXXX
778.0
776.0
777.0
KKXKKKKK
KKXXKXKX
1828. 1
1908.4
1868.3
KKXKXXKX
1930.8
2107.8
2019.3
KXXXXKXK
1884.9
1996.3
1940.6
KKXXXXXX
-------
Table 67. Experiment II - Octachlorodibenzo-p-dioxin in site soil
RTLRNTR
DRYS RFTER INITIRL LORDING
MMMMMMM
LORD
MMMM
0.3
MMMM
REP 1
MMMMMM
REP 2
MMMMMM
REP 3
MMMMMM
MMMM
1.0
MMMM
REP 1
MMMMMM
REP 2
MMMMMM
REP 3
MMMMMM
MMMM
3.0
MMMM
REP 1
MMMMMM
REP 2
MMMMMM
REP 3
MMMMKMMM
DUPLICRTE
MMMMMMMM
R
B
>2=
MMMMKMMM
fl
B
/'2=
MMMMMMMM
R
B
/2=
MMMMKMMM
MMMMKMMM
R
B
/2=
MMMMKMMM
R
B
Cfl+B>/2=
MMMMKMMM
R
B
Cfl+B>/2=
MMMMMMMM
MMMMMMMM
R
B
-------
Table 67. Experiment II - Octachlorodibenzo-p-dioxin in site soil
CHRTTONOOGR
DRYS RFTER INITIRL LORDING
XXMMMXX
LORD
KKKM
,0.3
KKXM
REP 1
MMMMMM
REP 2
MMXXXX
REP 3
XXXM
1.0
XXXM
REP 1
MXKXMX
REP 2
XXXXXK
REP 3
XXXXXM
XX MM
3.0
XXXM
REP 1
MMMMMM
REP 2
MMMMMM
REP 3
XXXXXM
MXXKXXXX
DUPLICRTE
XXXXXXMX
R
B
>2=
xxxxxxxx
R
B
/2=
MXXMXMXM
R
B
/2=
XXXXXXXK
R
B
/2=
xxxxxxxx
R
B
CR+B>/2=
xxxxxxxx
KXXXXXXX
R
B
/2=
xxxxxxxx
R
B
CR+B>/2=
XXXXXXXK
R
B
/2=
xxxxxxxx
KXXXXXXK>
0
XXXXKXXX
0.34
0.29
0.32
XXXXXXKK
0.34
0.33
0.34
xxxxxxxx
0.29
0.31
0.30
XXMXXXXX
0.80
0.83
0.82
xxxxxxxx
0.68
0.81
0.75
xxxxxxxx
0.77
0.81
0.79
XKXXKXXX
XXXXXXXX
1.70
1.99
1.85
XXXXKXXX
2.26
2.03
2. 15
XXXXMXXX
2.57
2. 12
2.35
xxxxxxxx
(XKXXKKKM>
30
XXXXXXXM
0.31
0.23
0.27
XXKKXXXM
0.35
0.29
0.32
XMKXXXMX
0.30
0.29
0.30
xxxxxxxx
0.72
0.71
0.72
XKXXXXXX
0.84
0.70
0.77
XXXXXXKM
0.70
0.79
0.75
MMMMMMMM
XXXXKKXM
2.03
2.21
2. 12
XXXXKXXM
2. 17
2.28
2.23
XXXKXXXX
2.07
2.22
2. 15
xxxxxxxx
CKKXXKKXK>
60
MMMMMMMM
0.29
0.30
0.30
xxxxxxxx
0.29
0.31
0.30
XXXXXXKX
0.61
0.23
0.42
XXXXXXKK
0.51
0.63
0.57
XXXXXXKK
0.44
0.53
0.49
xxxxxxxx
0.52
0.57
0.55
XXKKXXXX
XXXKKKKK
2. 10
2. 19
2. 15
KXKKXXXX
2. 14
2.21
2. 18
XXXXXXXX
2.30
2.29
2.30
XXXXXKKX
(MMMMMMMM
9O
XKMKXXXM
0.66
0.67
0. 67
MMMMMMMM
0.65
0.69
0.67
XXXXXMMK
1. 38
0.51
0.95
XKXXXKXX
0.65
0.58
0.62
xxxxxxxx
0.47
0.52
0.50
XXXKXXXX
0.53
0.56
0.55
MMMMMMMM
XXXXXXXK
1.93
1.83
1.88
XXKKKKKX
2. 16
1.97
2.07
XXXXXKXX
2. 17
2.21
2. 19
KKKXKXKK
ro
-------
Table 67. Experiment II - Octachlorodibenro-p-dioxin ii
COLUMBUS
DRYS RFTER INITIRL LORDING
KXXXXKX
LORD
XKXX
0.3
KXXX
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
XKXXXK
XXXX
1.0
XXXX
REP 1
XKXKXX
REP 2
XXXXXK
REP 3
XXXXKX
XXXX
3.0
XXXX
REP 1
XKXXXX
REP 2
xxxxxx
REP 3
xxxxxx
XXXXXMXX
DUPLICflTE
xxxxxxxx
R
B
V2=
XKKXXXXX
R
B
Cfl+B>/2=
XXKXXXXX
R
B
/2=
xxxxxxxx
XKXXXXXX
R
B
/2=
KKKKKXHK
0
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
XXKXXXXK
R
B
/2=
xxxxxxxx
R
B
/2=
xxxxxxxx
XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXKX
0
xxxxxxxx
0. IB
0.23
0.21
xxxxxxxx
0. 18
0. 18
0. 18
xxxxxxxx
0. 18
0. 19
0. 19
xxxxxxxx
xxxxxxxx
1.25
1.25
1.25
XXXKXKXX
1.29
1.21
1.25
xxxxxxxx
1.20
1.22
1.21
xxxxxxxx
XXXXXXKX
5. 18
5.57
5.38
xxxxxxxx
5.20
5.44
5.32
xxxxxxxx
5.30
5.33
5.31
xxxxxxxx
30
XXKXXKXX
0. 18
O.24
0.21
xxxxxxxx
0. 18
0. 16
0. 17
xxxxxxxx
0. 16
0. 17
0. 17
xxxxxxxx
xxxxxxxx
1.72
1.85
1.79
xxxxxxxx
1.73
1.81
1.77
XXXXXKXX
1.81
1.79
1.80
XXKXXKXX
XXXXXXXX
5. 16
4.37
4. 77
KXXKXXXX
5.43
5.22
5.33
xxxxxxxx
5. 16
5.34
5.25
xxxxxxxx
60
xxxxxxxx
0.22
0.23
0.22
XXXXXXKX
0.24
O.20
0.22
xxxxxxxx
0. 19
0.23
0.21
xxxxxxxx
XXXXXKXX
1.22
1.27
1.24
XXXXKXXX
1.26
1. 15
1.20
XXKXKXXX
1. 16
1. 19
1. 18
xxxxxxxx
XKKXXXXX
3.75
4.51
4. 13
XXXXXXXK
4.26
4.75
4.51
XXXKXXXX
4.60
5. 05
4.83
XXXXXXXK
9D
XXXKXKXX
O. 14
0.29
0.21
KXXKXXKK
0.21
0.22
0.22
KXXXKXKK
0.21
0.34
0.27
XXXXXXKK
KXXXKXKX
1.27
1.31
1.29
xxxxxxxx
1.29
1.26
1.27
xxxxxxxx
1.23
1.25
1.24
xxxxxxxx
xxxxxxxx
5.25
5.20
5.23
XKXKXXXK
5.31
5.48
5.40
KKXXKXXX
5.40
5. 15
5.28
KKXXXXXX
-------
KKKXKXXX KKXXXXXX XKXXXXXX XXXXXXXK
E2-I SS'O E6'0 EO'T
KXXXXXXX
=2/ca+y>
fr2'I 96'0 68'0 SO"I
22'T E^•0 ^6'0 00'I
KKKKXXXX XXXXXXXK XKXXXXXX XXXKXXXX
12'I ±L'Q S&'O iO'\
E2'I ,d
a
y
XXXXXXKX
=2/
SfQ 86'0 89'0 S9'0
68-0 T2M 09'0 69'0
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
XXXXXXXX XXXXXXXX XXXXXXXX XXXXMXXX
IS'O
/IS'O
BS'O
VS'O 9^'0 ZS'O 8S'0
St'-O T8'0 BS'O • 8S-0
XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
eo.- 1
09 '
es-o
a
0
XXXXXXXK
=2/
8
U
KKXXXXXX
/S'O 66'0 29'0 BS'O
6G'0 90'I 8S'0 8S'0
XXKXXXXX XXXXKXXX XKXXXXKX XXXKXXXX
Bfr'O £B'Q 09'0 09'O
Ot'-O T6'0 6S'0 6S'0 8
SS'O E8'0 29'0 29*0 d
KXKKKXXX KXKXXXXK XKXXXXXX XXXKXXKX KXXXXXXX
06 09 oe o 3iuai*idna
KXXXXXXXXKKXXXXXXKXKXXXXXXXXXXKXXXX
SAOQ
KKKXXX
E
KXXXXX
2
I d33
S KXKX
b O'E
XKMXXXXX KXKX
XXXXXKXK KKKKXX
=2/ £
KKKXKK
2 d33
KXXXXX
T d3a
g KKKK
y o't
XXXXXKMK KKXX
XXXXXXXK KKKXXK
E d3a
KXXXXX
t
KKKK
ObOl
KKKKKKKK KKKKXXK
(u«dd) Itos sqts ui UTxoTp-d-ozuaqipo-JOiujoeqoQ _ 11
-/g
-------
Table 67. Experiment II - Octachlorodibenzo-p-dioxin in site soil (ppnO
GULFPORT
DRYS RFTER INITIRL LORDING
MMMMMMM
LORD
XMKX
0.3
MXXM
REP 1
XKXKXK
REP 2
KXXMXM
REP 3
xxxxxx
XKKK
1
XXKX
REP 1
MXXXKX
XXXXXXXX
DUPLICRTE
XXXXKXKX
R
B
>2=
XXXKXXKX
n
B
/2=
XKKXXKKX
fl
B
/2=
XXKKXXXX
KXKKKKKX
R
B
CR+B>/2=
XXKXXXKK
XXXXXXXMXXXXXXXXXXXXXXXXXXXXXXXXXXX
0
XKXXXXXX
0.37
0.37
0.37
KXXKXXXX
0.43
O.SB
0.51
KXXXXXXX
o.eo
O. IS
0.48
XXXXKKXK
XXXXMXXX
1.34
1.40
1.37
XXXXXXMX
30
XXXXXKXK
0.45
0.45
0.45
XXXXXXXK
O.52
0.49
0.51
XKKKXXXK
0.55
0.50
0.53
xxxxxxxx
XXXXKXXX
0.57
0.32
0.45
xxxxxxxx
60
XKXXXXXX
0.25
0.29
0.27
KXKKXKKX
0.32
0.38
0.35
KXXKXXXX
0.40
0.40
0.40
KKKKKKKK
KKKXKKKK
1. 16
1.21
1. 19
XXXKXXXX
90
KKXKKMXH
0.27
0.33
0.30
xxxxxxxx
0.41
0.49
0.45
KKKKKKKK
0.57
0.40
0.49
KKKKKKKK
KKXKKKKK
0.84
1.07
0.96
KXKXXKKK
REP 2
KKXKKX
REP 3
xxxxxx
KKXK
3
KKKK
REP 1
XXKXXK
REP 2
KKKKKK
REP 3
KKKKKK
KKKXKKXK KKKKXXXX XXXKKXXX KKKKKKXK KKKKKKKK
KKKXKXXX XXXXXXXX XXXXXXXX XXXXKXXX KKKXKKKK
R 3.77 7.46 3.20 3.69
B 4.20 6.56 2.47 3.25
/2= 3.99 7.01 2.84 3.47
XKXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX XXKXXXXK
R 4.44 5.75 3.37 3.77
B 4.87 7.74 2.88 3.61
/2= 4.94 4.99 3.89 3.98
KKKKKKKK KKKKKKKK KXXKKKKX KKKKKKKK XXXXXXXX
IO
en
-------
Detach1orodibenzo-p-dioxin in site soil
Table 67. Experiment II
MERIDIRN
DRYS RFTER IN1TIRL LORDING
MXMMKKK XXXXXXXX XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
LORD DUPLICRTE O 3O 6O 90
XMKX XXMMXXKK KMXXXXXX XXXXXXXX XXXXKXXX KXXXXXMK
O.3 fl 0.22 O.23 0.24 NO
XKKX B 0.28 0.22 0.26 NO
REP 1 CR+B>>2= 0.25 0.23 O.2S ND
XXXKKX XXXXXXXK XKXXXXXX XXXKXXXX XXXXKXXX XKMXKXXK
H 0.33 O.23 0.21 NO
B 0.26 0.29 0.21 NO
REP 2 /2=
KKXXXK XXKKKMXX
XXXK XXKXXXXX
l.O fl
xxxx B
REP 1
XXXKXK
REP 2
XXKXXX
REP 3
XXXXKK
XXXK
3.0
XXMK
REP 1
XXKXXK
REP 2
XXXXXK
REP 3 /2=
XKXXKK XXXXXXXX
ND = Not Detected
0.24 0.31 0.23 NO
XKKMXMXK XXXKKXXX XXKXKXXX XXXXXXXK
KXXXXKXX XXXXXXXK XXKXXKXX XKXXKXXK
0.44 0.48 O.40 O.71
0.50 0.57 0.43 0.84
Cfl+B)/2=
XKXKXKKX
fl
B
/2=
MXKXXXXX
R
8
/2=
XXKXXXXX
XXKKKKXK
fl
B
/2=
XXKXXKXX
fl
B
/2=
XXXXKXXX
fl
B
0.47
KXXXXKKX
0.53
0.38
0.46
XKXKXKXX
0.52
0.75
0.64
xxxxxxxx
KKXKXXXX
2.59
2.68
2.64
XKXXXXKK
2.06
2.46
2.26
XKXXXKXK
2.40
2.57
0.53
XXKKKKXK
0.80
0.58
0.69
XXKXXXXX
0.61
0.64
0.63
XXKXXXXX
KKXKKKKK
2.59
2.68
2.64
XXXKKKXK
2.06
2.46
2.26
KXXXKKKK
2.40
2.57
0.42
XKKKHXKK
0.43
0.40
0.42
KXXXKKKK
0.60
0.69
0.65
KXXXKKKK
XXXKKXXX
2.24
2.27
2.26
XXKKKKXX
2.21
2.31
2.26
XXXXXKKK
2.26
2.27
0.78
KXXXXXXX
0.73
0.51
0.62
KXKXKKKX
0.45
O. 79
0.62
xxxxxxxx
XXXXKKKK
6.49
6.97
6.73
XXXKXKKK
5.87
5.78
5.83
KKKXKKKX
3.43
5.70
2.49 2.49 2.27 4.57
XKXXXKXK XXXXXKXX XXXKKXXX KKKKKKXK
- See Table 20 for detection limits
-------
Table 67. Experiment II - Octachlorod ibenzo-p-dioxin in site soil
WIGGINS
DflYS RFTER INITIRL LORDING
XXXXKXX
LORD
XXXM
0.3
xxxx
REP 1
xxxxxx
REP 2
XXXXKX
REP 3
xxxxxx
XXKX
1
xxxx
REP 1
xxxxxx
REP 2
xxxxxx
REP 3
xxxxxx
xxxx
3
XXKX
REP 1
xxxxxx
REP 2
XXXXKX
REP 3
xxxxxx
KXXXXXXX
DUPLICHTE
xxxxxxxx
R
B
V2=
xxxxxxxx
R
B
/2=
KXKXXXXX
R
B
/2t=
XXKXXXXX
xxxxxxxx
R
,B
/2=
xxxxxxxx
R
B
/2=
XKXXXXXX
R
B
/2=
XKXXXXXX
XXXXXXXX
R
B
/2=
XXXXKXXX
R
B
/2=
xxxxxxxx
R
B
CR+B>/2=
XXKXXXXX
XXXXXXXX XXXXXXXX XX XXXXXXXX
0
xxxxxxxx
2. 19
2.08
2. 13
xxxxxxxx
2.41
1.98
2. 19
xxxxxxxx
,1.92
2.01
1.97
xxxxxxxx
xxxxxxxx
2.37
1.87
2. 12
xxxxxxxx
2.30
2.49
2.39
xxxxxxxx
2.06
2.31
2. 19
xxxxxxxx
xxxxxxxx
3.55
3.79
3.67
XXKXXXXX
3.23
3.41
3.32
xxxxxxxx
3. 19
3.23
3.21
xxxxxxxx
60
xxxxxxxx
2.03
1 .88
1 .95
xxxxxxxx
2.43
1.71
2.07
XXXXXXXX
2. 19
1.48
1.84
KXXXXXXX
XXXXXXXX
2.07
2.09
2.O8
XKKKXXXK
2. 16
2.39
2.28
xxxxxxxx
2. 18
1.99
2.09
xxxxxxxx
xxxxxxxx
2.23
1.69
1.96
XXXKXXXX
1.69
2.08
1.89
xxxxxxxx
1.98
2.36
2. 17
XKXXXXXK
90
xxxxxxxx
1.89
1.64
1 .77
xxxxxxxx
2. 13
2.02
2.08
XXXXXKKK
1.95
2.04
2.00
KXXXXXXX
XXXXXXXX
2. 1O
1.85
1.98
KXXXKXXK
1.65
1.79
1.72
XXKXXXXX
1.91
2. 12
2.02
KXXXXXXX
KXXXXXXX
2.55
2.46
2.51
XXXXXXKK
2.47
3.43
2.95
XXXXKKKX
2.29
2.36
2.33
XKXXXXKX
-------
Table 67. Experiment II - Octachlorodibenzo-p-dioxin in site soil (pprrO
WILMINGTON
DRYS RFTER INITIRL LORDING
XXXXXMXXXXXXXXXXXXXXXXKXXXXXXXXXXXK
MXXKMKK XXKXXXXX
LORD DUPLICRTE
XXXX XXXXXXKX
0.3 n
xxxx B
0 30 60 90
xxxxxxxx xxxxxxxx xxxxxxxx xxxxxxxx
0.40 1.01 0.69 1.04
0.40 0.81 0.79 0.79
REP 1
MKXXKK
REP 2
XXKKXM
REP 3
KXXKXM
MKXM
1 .0
KMKM
CR+B)X2=
KKXXXKKX
R
B
/2=
XXKKXXKK
R
B
/2=
XXXKKXXX
XXXXKXXX
R
B
0.40
KKKXXXXX
0.51
0.51
0.51
XKKKXXKX
0.46
0.40
0.43
KXXXKKXX
KKKKKKXX
0.98
0.90
0.91
XXKKKXXK
0.69
0.5O
0.60
XXKKXXKK
0.82
0.65
0.74
KXXKKKXX
XXXXKKXK
1.25
1.44
0.74
XXXKKKKX
1.06
0.84
0.95
XXKKKKKK
0.82
0.73
0.78
XXKXKKKK
KXXKKKKK
1.29
1.46
0.92
XKKXXKXX
0.74
0.65
0.70
XXKKKXXK
0.72
0.81
0.77
KKXXKKXK
KKXXKKXX
1.38
1.57
REP 1
XXKKXM
REP 2
KKXKXX
B
/2=
XXXXKKXK
R
B
/2=
0.90
0.94
KXXKKKXX
0.95
1.05
1.00
XKKXXKKX
0.98
0.94
0.96
1.44
1.35
KKKXXXKX
1.22
1.29
1.26
XXXKKXXX
1.60
1.44
1.52
1.46
1.38
XKKKXXXX
1.32
1.51
1.42
XKXXKKKK
1.29
1.33
1.31
1.57
1.48
KKXXKKKX
1.44
1.70
1.57
XXXKXXXX
2.32
1.20
1.76
REP 3
KXMXXM
XXXX
3.0
KKXX
REP 1
XXXXXM
REP 2
XXKKXM
REP 3
KMMXMM
/'2=
KXXKKKXK
KKXKKXKK
R
B
/2=
XXXKXXKK
R
B
/2=
MKXXKXXX
0.96
XXXKKXXK
XXKKXXKK
2.44
2.55
2.50
XKKKKXXK
2.64
2.66
2.65
XXKKKXXK
2.58
2.71
2.65
KXXXKKXX
1.52
XXXXXKKX
XXXKXXXK
2.53
2.63
2.58
XXXXKKXX
2.55
2.75
2.65
KXXKKXKK
2.60
2.48
2.54
KKXKXXKK
1.31
KKXXXKXK
KXXXKKKK
2.58
2.58
2.58
KKKXXKKK
2.73
2.87
2.80
KXKXKKKK
2.54
2.62
2.58
KKXKKXKK
1.76
MMKKKXXK
KXXXXKXX
2.59
2.73
2.66
MKKKKKXM
2.75
2.90
2.83
MMKMKKKM
2.69
2.84
2.77
xxxxxxxx
00
-------
661
I
I
1
1
k
'i
* §
7
h
•
1 i
i
i
i
5
i
i
5
5
5
5
5
5
i
i
i
i
i
i
S
S
SS
SS
SS
SS
SS
SS
SS
SS
SS
55
55 i
55 <
55 i
55 I
SS I
SS I
SS 2
55 2
55 i
55 I
SS i
ii i
5
i ii
i ii
i ii
S ii
i ii
S ii
5 55
5 55
B 55
5 55
5 55 i
5 SS i
5 55 i
! 55 I
5 55 i
i 55 I
i 55 2
55 2
55 2
ii 2
SS i
55 5
W
W
J
5 55
i 55
i 55
i 55
S 55
3 ii
5 55
5 55
5 ii
S 55
5 55
i 55 <
5 55 <
i 55 i
i 55 i
i 55 I
i 55 i
SS 2
55 2
ii 2
55 I
SS S
H
9
i ii
i ii
i ii
i ii
5 55
5 55
E SS
5 55
5 55
5 55
5 55
5 55 (
5 55 i
5 ii I
5 55 I
5 55 2
i Si 2
55 S
SS S
SS S
SS S
55 5
9
J
5 Si
S ii
i ii
S ii
5 55
§ 55
5 Si
S ii
5 ii
5 ii
5 ii
5 ii
i ii
i 55 I
i 55 I
SS 2
55 2
55 i
55 i
SS S
SS S
SS S
W
5
i ii
i ii
i ii
i ii
i 55
S 55
5 ii
5 ii
S ii
5 ii
5 ii
5 55
5 ii i
i 55 i
i ii i
ii I
SS I
SS 2
Si 2
55 S
ii i
55 5
1
i ii
i ii
i ii
i ii
i ii
5 55
i 55
i Si
3 55
S Si
S ii
S SS i
5 55 I
5 SS I
5 ii 2
> ii 2
i 55 2
55 2
ii i
55 5
ii i
55 i
;
i ii
i Si
S ii
S ii
5 55
5 55
S 55
S 55
5 iS
5 55
5 85
! 55 (
> ii i
' SS 2
ii 2
ii 2
55 i
55 i
ii i
55 i
ii 5
ii i
M
W
3
i ii
i ii
i ii
5 ii
5 55
5 Si
5 55
B 55
5 ii
5 ii
; ii
S ii
> 55
ii I
SS I
SS 2
ii 2
ii 2
ii 2
ii i
55 i
ii 5
J
i ii
i ii
i ii
i ii
i ii
S ii
5 55
5 55
5 55
5 55
5 55
5 55 Z
5 55 i
> ii 2
i ii 2
ii 2
ii i
55 i
Si i
ii i
55 5
ii i
I
i ii
i ii
i ii
5 ii
5 ii
5 ii
5 ii
S ii
5 ii
5 ii
; 55
> 55
SS i
55 i
SS i
SS 2
ii 2
ii 2
ii 2
55 2
ii i
Si i
M
i
9
i ii
i ii
5 ii
i ii
i ii
5 ii
5 ii
5 55
5 55
5 55
S 55
5 55 (
5 55 <
! 55 i
i SS I
SS 2
ii 2
55 2
55 2
55 2
55 2
55 5
9
5 ii
i ii
i ii
i ii
i ii
5 ii
S ii
5 ii
5 55
S ii
5 ii
5 ii i
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