United States Robert S. Kerr EPA-600/6-88-001
Environmental Protection Environmental Research Laboratory
Agency Ada, OK 74820 February 1988
Research and Development
SEPA Treatment Potential for 56
EPA Listed Hazardous
Chemicals in Soils
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PB88-174446
EPA/600/6-88/001
February 1988
TREATMENT POTENTIAL FOR 56 EPA LISTED
HAZARDOUS CHEMICALS IN SOIL
by
Ronald C. Sims
William J. Doucette
Joan E. McLean
William J. Grenney
R. Ryan Dupont
Department of Civil and Environmental Engineering
Utah State University
Logan, Utah 84322
Project CR-810979
Project Officer
John E. Matthews
Robert S. Kerr Environmental Research Laboratory
P.O. Box 1198
Ada, Oklahoma 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U;S. ENVIRONMENTAL PROTECTION AGENCY
ADA, OKLAHOMA 74820
OP THE
orncE or SUPERFUND
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DISCLAIMER
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under Cooperative
Agreement CR-810979 to Utah 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.
T** !*"**
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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 the 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
groundwater, 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.
Soil treatment systems that are designed and managed based on
a knowledge of soil-waste interactions may represent a significant
111
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technology for simultaneous treatment and ultimate disposal of
selected hazardous wastes in an environmentally acceptable manner.
Decisions pertaining to which wastes and chemicals are amenable to
this technology must take into account: (1) the long-term
uncertainties associated with the land disposal option; (2) the
*
goal of managing hazardous wastes in an appropriate manner; and (3)
the persistence, toxicity, mobility, and propensity to
bioaccumulate hazardous wastes and their hazardous constituents.
There is currently a lack of scientifically derived fate and
transport information for the wide range of hazardous chemicals for
which such decisions can be made. This report presents information
pertaining to the quantitative evaluation of the treatment
potential in soil for 56 waste constituents identified as hazardous
by the United States Environmental Protection Agency (EPA) .
Clinton W. Hall
Director
Robert S. Kerr Environmental
Research Laboratory
IV
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ABSTRACT
This report presents information pertaining to the quantitative
evaluation of the treatment potential in soil for 56 chemicals identified
as hazardous by the United States Environmental Protection Agency (EPA).
The 56 chemicals evaluated were organized into four categories of
substances: (1) polynuclear aromatic hydrocarbons (PAH), (2) pesticides,
(3) chlorinated hydrocarbons, and (4) miscellaneous chemicals.
Treatability screening studies were conducted to determine: (1)
degradation rates, (2) partition coefficients among air, water, soil, and
oil phases, and (3) transformation characteristics.
The quantitative information developed for a subset of the tested
chemicals was input into two mathematical models (RTTZ and VTP)
specifically designed to describe the soil treatment process. Results of
fate and transport predictions of the models were ccsrpared with laboratory
and literature results in order to evaluate the ability of the models to
predict the behavior of the selected chemicals in a soil system.
The experimental approach used in this study was designed to
characterize degradation, immobilization, and transformation potentials
for the hazardous substances evaluated. Results indicated that the
significance of volatilization and abiotic-loss processes in influencing
"apparent loss rates" of substances from soil depends upon the class of
substance. These processes were insignificant for the majority of PAH
compounds; biodegradation appears to be the major process for the loss of
PAH compounds from soil systems. However, abiotic loss may also be an
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important process for certain pesticide substances. Volatilization was
found to play the major role in influencing loss rates of volatile
chemicals from soil.
Results from transformation experiments using a radiolabelled
chemical indicated that incorporation of the radiolabel into soil organic
material was not a significant process in the behavior and fate of the
chemical in the soil. The formation of biochemical intermediates was
found to be significant. No radiolabelled carbon dioxide was detected in
the short-term incubation studies.
Partition coefficients for substances among oil, air, water, and soil
phases generally indicated a strong affinity for one phase for most
substances. Partitioning into the soil phase was very high for all but
the most volatile substances. Partition coefficients calculated using
SARs were in good agreement with literature values for coefficients.
Very little leaching or air emissions was predicted by either
mathematical model for the subset of pesticides selected, under the
simulated test conditions.
vx
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CONTENTS
Notice ii
Foreword iii
Abstract v
Figures viii
Tables x
Acknowledgements xiii
1. Introduction 1
Objectives 6
Approach 7
2. Conclusions 10
3. Recommendations 12
4 . Methods and Procedures 14
Designated Chemicals and Waste 14
Soil Characterization 21
Determination of Degradation Rates
in Soil 24
Partition Coefficient Determinations ... 35
QA/QC Procedures for Degradation and
Partition Experiments 38
Mathematical Model for Soil-Waste
Processes 40
Transformation Studies 41
5. Results and Discussion 45
Quality Control/Quality Assurance 45
Degradation Rates of Substances in Soil. . 50
Partition Coefficients for Substances
in Soil 79
Land Treatment Model Applications 87
Transformation Studies 90
References 99
vn
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FIGURES
Number Page
1. Laboratory flask apparatus used for mass balance
measurements 29
2. Microbial plate counts for untreated and HgCl2 treated
Kidman soil 46
3. Microbial plate counts for untreated and HgCl2 treated
McLaurin soil 46
4. Intermediate breakdown products for ponamide and famphur
identified from GC/MS results 51
5. First order kinetic plots of the apparent loss of 3-methyl-
cholanthrene from Kidman soil 58
6. First order kinetic plots of the apparent loss of 3-methyl-
cholanthrene from Kidman soil sterilized with HgCl2 .... 58
7. First order kinetic plots of the apparent loss of heptachlor
from Kidman soil 62
8. First order kinetic plots of the apparent loss of heptachlor
from Mclaurin soil 62
9. First order kinetic plots of the apparent loss of dinoseb
from McLaurin soil 68
10. First order kinetic plots of the apparent loss of dinoseb
from McLaurin soil sterilized with HgCl2 68
11. First order kinetic plots of the apparent loss of 1,2,4-tri-
chlorobenzene from Mclaurin soil 71
12. First order kinetic plots of the apparent loss of 1,2,4-tri-
chlorobenzene -from McLaurin soil sterilized with HgCl2 ... 71
13. HPLC chromatogram of soil extract formed from 7,12-dimethyl-
benz (a) anthracene by McLaurin sandy loam soil (low pH) . . . 94
14. Elution profile of metabolites formed from (14C) 7,12-
dimethylbenz (a) anthracene by McLaurin sandy loam soil ... 95
15. Mutagenicity of 7,12-dimethylbenz (a) anthracene metabolites
from McLaurin sandy loam soil (low pH) 96
Vlll
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16. Mutagenicity of 7,12-diraethylbenz (a) anthracene metabolites
from McLaurin sandy loam soil adjusted to neutral pH soil
condition 97
IX
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TABLES
Number Page
1. Characterization information and selected properties
for 16 PAH compounds .............. ^5
2. Characterization information and selected physical
properties for 22 pesticides ........... 17
3. Characterization information and selected physical
properties for 13 chlorinated hydrocarbons ...... 19
4. Characterization information and selected physical properties
for 5 miscellaneous compounds ........... 20
5. Characterization of Kidman sandy loam soil collected from USU
agricultural experiment farm at Kaysville, Utah ..... 22
6. Characterization of Mclaurin sandy loam soil provided by
Mississippi State University, Wiggins, MS ....... 23
7. loading rates for selected compounds on Kidman and Mclaurin
soils for which degradation rates were unconnected for
volatilization ............... 25
8. Loading rates for selected compounds on Kidman and McLaurin
soils for which degradation rates were corrected for
volatilization ............... 26
9. Chemical identification and quantification methods and
conditions ............... 32
10. Extraction efficiencies for PAHs from McLaurin and Kidman soils 47
11. Extraction efficiencies for pesticides from McLaurin and
Kidman soils ................. 48
12. Extraction efficiencies for the chlorinated hydrocarbons and
miscellaneous compounds from McLaurin and Kidman soils ... 49
13. Volatilization of PAH compounds from Kidman and McLaurin soils 52
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14. Volatilization corrected degradation kinetic information
for PAH compounds applied to Kidman sandy loam at -0.33 bar
soil moisture 54
15. Volatilization corrected degradation kinetic information for
PAH compounds applied to Jfclaurin sandy loam at -0.33 bar
soil moisture 55
16. Degradation of PAH coropounds in Kidman and McLaurin
soils poisoned by 2 percent HgCl2 57
17. Apparent loss kinetic information for PAH's from Kidman
and McLaurin soils 59
18. Apparent loss half-life (ti^) of acenaphthylene and
3-methylcholanthrene from Kidman and McLaurin soils with
and without addition of HgCl2 60
19. Apparent loss kinetic information for pesticides from
Kidman soil 65
20. Apparent loss kinetic information for pesticides from
McLaurin soil 66
21. Apparent loss half-life (tj/2) f°r pesticides from Kidman
and McLaurin soils 69
22. Apparent loss kinetics using first order kinetics model for
chlorinated hydrocarbons and aniline in Kidman soil without
addition of HgCl2 73
23. Apparent loss kinetics using first order kinetics model for
chlorinated hydrocarbons and aniline in Mclaurin soil without
addition of HgCl2 74
24. Apparent loss half-life (t^/2) for 1,2,4-trichlorobenzene,
hexachlorocyclopentadiene and analine in Kidman and Ifclaurin
soils with and without addition of HgCl2 hydrocarbons
and aniline in Ifclaurin soil without addition of HgCl2 ... 75
25. Volatilization of chlorinated hydrocarbons from Ifclaurin soil 76
26. Volatilization corrected degradation kinetic information for
chlorinated cocpounds applied to IfcLaurin sandy loam at
-O.33 BAR soil moisture content 77
27. Comparison of volatilization corrected and uncorrected degradation
kinetic data for chlorinated hydrocarbons in McLaurin soil 78
28. Calculated soil/water (RJ), oil/water (Kb), and air/water
(Kh) partition coefficients for 16 PAH compounds 81
XI
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29. Calculated soil/water (Kd), oil/water (Ko), air/water (Kh)
partition coefficients for 22 pesticides 82
30. Calculated soil/water (Kd), oil/water (Kb), and air/water (Kh)
partition coefficients for 13 chlorinated hydrocarbons . . .83
31. Log Kd values estimated using first order MCIs 84
32. Mass balance for tetraalkyl lead in a soil system 86
33. Concentrations of pesticides in soil water, soil air,
and soil solid phases and percent decay at 15 cm depth after
81 days as predicted by the mathematical models 88
34. Transformations of (14C) 7,12-dimethylbenz (a) anthracene by
McLaurin sandy loam soil 92
35. Effect of soil pH on microbial populations in McLaurin
sandy loam soil 98
Xll
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Technical contributions to this research report in the area of
chemical analyses were made by Mr. Michael Walsh (Research Chemist) Mr.
Wayne Aprill (Research Microbiologist), and Mr. James Herrick (Research
Chemist), of the Toxic and Hazardous Waste Management Group at the Utah
Water Research Laboratory.
Technical editing as well as typing of the entire report was done by
Ms. LuAnn Heap.
Xlll
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SECTION 1
INTRODUCTICN
The Solid and Hazardous Waste Amendments of 1984 (PL 98-616) require
the Environmental Protection Agency (EPA) Administrator to promulgate
regulations or make determinations regarding whether or not wastes
specifically identified or listed under 40 CFR Part 261 shall be
prohibited from one or more methods of land disposal, including land
treatment. Determinations must be made based on protection of public
health and the environment for as long as the waste remains hazardous,
taking into account: (1) the long-term uncertainties associated with the
land disposal option, (2) the goal of managing hazardous waste in an
appropriate manner, and (3) the persistence, toxicity, mobility, and
propensity to bioaccumulation of hazardous wastes and their hazardous
constituents.
«
Biodegradation is believed to be the most important degradative
*
mechanism for organic compounds in soil systems and is utilized for
transformation of hazardous organic compounds into innocuous products.
Biodegradation of organic compounds is accomplished in a series of
biochemical reactions through which a parent conpound is gradually changed
or transformed in soil to organic and inorganic end products. Complete
degradation is the term used to describe the process whereby constituents
are mineralized to inorganic end products, including carbon dioxide,
water, and inorganic species of nitrogen, phosphorus, and sulfur. Aerobic
soil bacteria possess the ability to biochemically catalyze the oxidation
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of cxxnpounds using molecular oxygen to initiate reaction sequences,
including the Krebs cycle and the fatty acid spiral, that enter central
pathways of metabolism (Dagley 1975). In the mixed microbial population
of soil systems, one metabolic group of microorganisms may partially
metabolize a compound without deriving carbon or energy for cell synthesis
through the process of cooxidation, but may furnish a suitable growth
substrate for another group. Alternatively, organic compounds may be
partially degraded or transformed from parent compounds to organic
intermediates that may be recalcitrant and/or toxic.
Ihe primary goal of biodegradation testing is to obtain an overall
estimate of the rate at which a compound will biodegrade in a soil
environment. General degradation rate models of organics in soils have
been described by Hamaker (1972), Goring et al. (1975), Rao and Jessup
(1982), U.S. EPA (1984b; 1986a and b), and Hattori and Hattori (1976).
Methods describing the evaluation of biodegradation in natural water
and soil media as a means of assessing the persistence of chemical
substances in the natural environment (Federal Register, Vol. 44, No. 53,
Friday, March 16, 1979, pp. 16272-16280; U.S. EPA 1975), commonly utilize
indirect measures, i.e., oxygen consumption, OC>2 evolution, and dissolved
organic carbon (DOC) loss, to assess the persistence of compounds in test
environments and to predict the relative importance of biodegradation as a
factor affecting compound persistence. While these procedures provide a
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qualitative assessment of biodegradation, results do not provide a means
of determining quantitative rates of degradation for specific constituents
that are essential for the assessment of compound fate and transport as
well as for risk analysis (Federal Register 1979). For quantitative
assessment of the rate of biodegradation of an individual constituent in a
soil system, it is necessary to measure (1) changes in parent compound
concentration with time, (2) loss of chemical due to volatilization, and
(3) chemical loss due to abiotic mechanisms.
In addition to the degradation of hazardous constituents, the
immobilization potential (partitioning into soils, liquid, and gaseous
phases) and the transformation of parent compounds to intermediate
products within a soil system represent additional information
requirements for assessing soil treatment potential for hazardous
constituents.
Ihe information generated in this study concerning degradation,
transformation, and immobilization was entered into a comprehensive soil
fate and transport data base developed as part of a concurrent EPA-funded
study. Specific quantitative information cxjncerning persistence and/or
partitioning (mobility) for 56 specific substances was developed to
provide EPA with treatability information for making decisions concerning
the management of land disposal sites. The 56 substances were organized
into four classes for evaluation: polynuclear aromatic hydrocarbons
(PAHs), pesticides, chlorinated hydrocarbons and miscellaneous compounds.
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The information was also intended for use in mathematical models
developed to evaluate the treatment potential for specific substances in
soil. Use of such models provides an approach for integration of the
simultaneous processes of degradation and partitioning in soil systems so
that an assessment can be made of the presence of hazardous substances in
leachate, soil, and air. Models provide an estimate of the potential for
groundwater and air contamination through a determination of the rate and
extent of contaminant transport and degradation for particular site/
soil/compound characteristics. Description of quantitative organic
chemical decomposition and mobility in soil systems also allows the
identification of chemicals or classes of chemicals that require
management through control of mass transport and/or treatment to reduce or
eliminate their hazard potential (U.S. EPA 1984b, Mahmood and Sims 1986).
The two models used in this study to evaluate fate and transport
behavior in soil systems were: (1) the Regulatory and Investigative
Treatment Zone (RTTZ) Model and (2) the Vadose Zone Interactive Processes
(VIP) Model. The RITZ Model was developed at the Robert S. Kerr
Environmental Research Laboratory (RSKERL), Ma, Oklahoma (Short 1986) ;
the VIP Model which uses RITZ as its base was developed at Utah State
University under a cooperative project with the RSKERL (Grenney et al.
1987).
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Transformation studies were performed with the IfcLaurin sandy loam
soil at low pH and the same soil adjusted to neutral pH for 7,12-
dimethylbenzanthracene (CMBA). Soil pH was adjusted from 4.8 to 7.5 by
adding 70 mg of CaO03 to the Mclaurin soil. CMBA was chosen based on
reported genetic toxicity (Shoza et al. 1974, Walters 1966) and the rate
and extent of degradation measured in laboratory studies (Park 1987).
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OBJECTIVES
Ihe overall objective of this research project was to provide soil
treatability information for 56 specific chemicals identified as hazardous
by EPA. The emphasis was placed on the development of degradation rates
and transport information in the form of partition coefficients that could
be used as input to mathematical models for evaluation of pollutant
behavior in soil systems.
Specific objectives of the research project were to:
(1) Determine biodegradation rates corrected for volatilization.
(2) Determine the extent of soil incorporation into soil organic
material and the biological and chemical characterization of
transformation products.
(3) Determine the contribution of abiotic loss to "apparent loss
rates."
(4) Calculate partition coefficients among oil, water, air, and
soil phases.
(5) Input the degradation rate and partition coefficient data into
the RTTZ and VIP fate and transport Models.
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APPROACH
Degradation kinetic information and/or transport data were developed,
for 56 substances identified by EPA as requiring quantitative evaluation
for soil treatment potential. Laboratory experiments were conducted using
two agricultural soils to generate degradation rates corrected for
volatilization and for abiotic loss for a subset of substances and
apparent loss rates for another subset of substances.
Biodegradation rates were determined experimentally by applying the
chemical of interest to a soil microcosm and monitoring concentration over
time. A plot of the disappearance of a constituent originally present in
the substance/soil mixture versus treatment time can provide the following
information:
1) Ihe reaction order of the process (generally zero or first
order),
2) Ihe reaction rate constant, K (mass constituent/mass soil-time
for zero order reactions or I/time for first order reactions),
and
3) Ihe half-life (t /0, time) of each constituent of concern.
i/^
Methods were employed for the determination of biodegradation rates
corrected for volatilization losses when necessary and for losses in
microbial inactive soil/substance controls that indicate contribution to
degradation of abiotic (e.g., hydrolysis, oxidation, etc.) processes.
Incubation in the absence of light was used for all substances to prevent
compound decomposition due to photodegradation.
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Biodegradation information, which is normally reported as half-life
in soil, can be used to evaluate:
a) Effect of biodegradation on the attenuation of constituent
transport through a soil profile,
b) Effect of soil and constituent characteristics on constituent
biodegradation and constituent transport through the soil
profile, and
c) Effect of environmental parameters, including pH, dissolved
oxygen, nutrients, and amendments on biodegradation of test
substances.
Transformation was evaluated using radiolabelled 7,12-dimethyl-
benz(a)anthracene (CMBA). A mass balance for CMBA among soil, gaseous,
and solvent extractable fractions over incubation time was evaluated to
determine the extent of incorporation of the chemical into the soil
matrix. Chemical and toxicologial properties of biochemical intermediate
products were also characterized. The distribution of radiolabelled
material between parent cccpounds and biochemical intermediates was also
characterized.
Transport data were developed using calculational procedures based
on structure-activity relationships (SARs). Partition coefficients among
soil, air, oil, and water phases were determined for each substance.
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Degradation kinetic information and partition coefficients among
soil, oil, aqueous, and gaseous phases developed in this project were
entered into the comprehensive data base compiled for EPA concerning the
fate and behavior of hazardous substances in soil systems (Soil Transport
and Fate Date Base).
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SECTION 2
CONCLUSIONS
Specific conclusions based on the objectives of this research
project include:
(1) The importance of volatilization and abiotic-loss processes in
influencing "apparent loss rates" of substances from soil
systems depends upon the class of substances. These processes
are insignificant for the majority of PAH compounds.
Biodegradation appears to be the major process for the loss of
PAHs from soil systems. Abiotic loss may be an important
process for certain pesticide substances. Volatilization
appears to be the major process influencing loss rates of
volatile substances from soil systems.
(2) Transformation products of mutagenic parent substances may
exhibit mutagenic characteristics, but may decrease in
mutagenic potential with incubation time in soil. A decrease
in the concentration of parent substance in a soil extract
solution that is not accompanied by an increase in carbon
dioxide evolution may not indicate irreversible soil
incorporation of applied waste. Rather, intermediate
biochemical transformation products may occur that exhibit
changing characteristics with time of incubation in the soil.
10
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(3) Mercuric chloride is effective for reducing soil bacteria and
fungi to levels at least as low as 10 organisms per gram of
soil (dry-weight basis). However, the use of HgCl2 may greatly
affect the recovery of certain compounds from soil. The lose of
HgCl2 sterile controls for biodegradation studies should be
further examined.
(4) It is possible to develop transport information for
mathematical models as partition coefficients based on
structure-activity relationships (SARs) for substances that are
difficult to evaluate experimentally.
(5) In laboratory experiments using the U.S. EPA treatment models,
under environmental and loading rate conditions representative
of well designed and managed land treatment systems, very
little transport of either pesticides or PAH compounds was
predicted, including leaching and air emissions. The same
conclusions were found in the literature citations used in this
study.
11
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SECTION 3
REOCMMENDAITONS
Based on the methodology used; experimental design; data handling;
degradation, transformation, and partitioning information developed; and
mathematical modeling concerning the treatability of hazardous substances
in soil systems, the following reccaranendations are made:
(1) Techniques to manage volatile chemicals to accomplish in situ
treatment should be developed and evaluated for wastes
containing volatile substances.
(2) Transformation products of parent hazardous substances should
be evaluated for potential toxicity and mutagenicity. Also,
the fate and behavior (degradation, detoxification, and
partitioning) of transformation products should be evaluated in
greater detail for all hazardous substances investigated.
(3) Additional research is required for evaluation of the ability
of soil treatment mathematical models to predict the transport
of hazardous substances under field conditions. A subset of
hazardous substances within each class of waste constituents
should be evaluated using the models at full-scale sites.
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(4) Techniques should be evaluated to address the problem of
quantification and characterization of biotic and abiotic
degradation mechanisms in soil systems for chlorinated and
organophosphorus pesticides.
13
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SECTION 4
METHODS AND PROCEDURES
DESIGNATED CHEMICALS AND WASTE
Tables 1 through 4 list 56 substances identified by the EPA Project
Officer for evaluation of degradation and inroobilization information.
Four categories of substances were evaluated including polynuclear
aromatic hydrocarbons (PAHs), pesticides, chlorinated hydrocarbons, and
miscellaneous substances. Tables 1 through 4 also contain
characterization information for each substance including chemical
formula, chemical abstract service (CAS) number, and EPA hazardous waste
number, as well as physical-chemical property information for each
substance including melting point, boiling point, vapor pressure, and
aqueous solubility. The physical-chemical information was used in
calculational procedures, based on structure-activity relationships
(SARs), to calculate partition coefficients among oil, soil, aqueous, and
air phases of a soil system.
All chemicals except toxaphene and tetraalkylead (TAL) were purchased
commercially, analytical grade. The toxaphene sample was collected from a
site where spent toxaphene dipping solution, used in cattle operations,
had been disposed of on soil. The waste sanple consisted of soil, manure,
cattle hair, and partially degraded toxaphene. The TAL sample was
provided by Standard Oil and consisted of tetraalkyllead (61.5%), ethylene
dibromide (17.9%), and ethylene dichloride (18.8%).
14
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TABLE 1. aiARACEERIZATION INFORMATION AND SELECTED PROPERTIES FOR 16 PAH COMPOUNDS.
Compound
Acenaphthylene
Benz(a)anthracene
Benzo(a)pyrene
Chrysene
Dlbenzo(a,h)ant brace ne
Inclcno(l,2,3-cd)pyrcnc
3-MethyIcholanthrcne
Fluoranthene
1-methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
Benzo(b)fluoranthene
7,12-dimethylbenzanthrucenc
anthracene
Benz(c)acrldine
Formula EPA Code CAS No.
C12H10
C18H12
C20H12
C8H12
C22H14
C22H12
C21H16
C16H10
C11H10
C10H8
C14H10
C16H10
C20H12
C20H16
C14H10
C17H11N
X011
U018
U022
U050
U063
U137
U157
U120
-
U165
-
-
-
U094
-
U016
208-96-8
56-55-3
50-32-8
218-01-9
53-70-3
193-39-5
56-49-5
206-44-0
90-12-0
91-20-3
85-01-8
129-00-0
205-99-2
57-97-6
120-12-7
225-51-4
MW
152.2
228
252.3
228.2
278.36
276.34
268.3
202
142.2
128.16
178.22
202.24
252
256.3
178.22
229.3
MP CC) Ref
92
158
179
254
270
163
180
111
-22
80.2
101
149
167
122.5
216
-
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
U.S. EPA, 1983
Sims and Ovcrcnsh, 1983
U.S. EPA, 1983
Sims and Overcash, 1983
Verschueren, 1977
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
U.S. EPA, 1984
Sims and Overcash, 1983
-
BP (C)
279
400
496
448
_
.
280
250
245
217.9
340
360
_
_
340
-
Ref
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
Verschueren, 1977
_
.
U.S. EPA, 1983(70 torr)
Verschueren, 1977
Sims, 1986
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
.
_
Sims and Overcash, 1983
-
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TABLE 1. CONTINUED
Compound
Acenaphthylene
Benz(a)anthracene
Benzo(a)pyrene
Chrysene
Dibenzo(a,h)anthracene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Fluoranthene
1-methylnaphthalene
Naphthalene
Phenimthrcne
Pyrene
IJenzo(b)fluoranthene
7,12-dimethylbenzanthracene
anthracene
Benz(c)acrldlne
V.P.
(mmHg)
2.90E-02
5.00E-09
5.00E-07
6.30E-07
l.OOE-10
l.OOE-10
6.00E-06
1.31E-06
4.92E-02
6.80E-04
6.85E-07
5.00E-07
-
1.96E-04
-
Sims
Sims
Sims
Sims
Ref
and Overcash,
and Overcash,
and Overcash,
and Overcash,
U.S EPA, 1983
Sims
Sims
Sims
Sims
Sims
Sims
Sims
and Overcash,
-
and Overcash,
calculated
and Overcash,
and Overcash,
and Overcash,
and Overcash,
-
and Overcash,
-
1983(20°C)
1983(20°C)
1983(20°C)
1983(20°C)
(20°C)
1983(20°C)
1983(2()°C)
1983(20°C)
1983(20°C)
1983(20°C)
1983(20°C)
1983(20°C)
Aqueous
(mg/L)
3.93
1.40E-02
3.80E-03
2.00E-03
5.00E-04
6.20E-02
1.10E-08
2.60E-01
2.85E+01
3.17E+01
1.30E+00
1.40E-01
5.50E-03
2.40E-02
7.30E-02
-
Aqueous
sol (M)
2.58E-05
6.14E-08
1.51E-08
8.76E-09
1.80E-09
2.24E-07
4.10E-14
1.29E-06
2.00E-04
2.47E-04
7.28E-06
6.92E-07
2.18E-08
9.36E-08
4.10E-07
-
Ref log Kow Ref log Koc*
Sims and
Sims and
Sims and
Sims and
U.S
Sims and
Mackay
Sims and
Mackay
Sims and
Sims and
Sims and
Sims and
U.S.
Sims and
Ovcrcash, 1983
Overcash, 1983
Overcash, 1983
Overcash, 1983
EPA.1983
Ovcrcash, 1983
and Shiu, 1977
Ovcrcush, 1983
and Shiu, 1977
Overcash, 1983
Ovcrcash, 1983
Ovcrcash, 1983
Ovcrcash, 1983
EPA, 1984
Overcash, 1983
-
4.07
5.61
6.04
5.61
5.97
7.66
7.11
5.33
3.87
3.35
4.46
5.32
6.57
5.98
4.45
-
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
Sims and Overcash, 1983
U.S. EPA, 1983
Sims and Overcash, 1983
calculated
Sims and Ovcrcash, 1983
Miller et al., 1985
Miller et al., 1985
Sims and Ovcrcash, 1983
Sims and Ovcrcash, 1983
Sims and Ovcrcash, 1983
U.S. EPA, 1984
Sims and Overcash, 1983
-
3.68
5.20
5.63
5.20
5.56
7.23
6.69
4.93
3.48
2.97
4.06
4.92
6.15
5.57
4.06
-
•"calculated from regression equation developed by Karickhoff et al. (1979).
-------
TABLE 2. CHARACTERIZATION INFORMATION AND SELECTED PHYSICAL PROPERTIES FOR 22 PESTICIDES.
Compound
Aldrin (1)
Cacodyllc Acid
Chlordune, technical ( 1 )
DDT (1)
Dicldrln (1)
Ulnosel)
Disulfoton (2)
Endosulfan (1)
Famphur
Hcptachlor (1)
Llndane (alpha) (1)
Methyl parathion (2)
Parathlon (2)
Phorate (2)
Pronamide
Toxaphene (1)
Warfarin
Aldicarb
pentachloronltrobenzene
Diethyl-p-nitrophenyl phosphate
Floracetic acid
Formaldehyde
Formula EPA Code CAS No.
C12II8CL6
C2H7As02
C10H6CI8
(C1C6H4)2CCC12
C12H8OC16
C10H12N2O5
C8H19O2PS3
C9H6CL603S
C10H16NO5PS2
C10H5CL7
C6H6C16
C6H10O5NPS
C10H14O5NPS
C7H17O2PS3
C12H11C12NO
C10H10C18
C19H16O4
C7H14N202S
C6C15NO2
(2)dOH1406NP
FCH2C02Na
HCHO
PO(M
U136
U036
U061
P037
P020
P039
P050
P097
P059
U129
P071
P089
P094
U192
P123
P001
P070
U185
P041
P028
U122
30900-2
75-60-5
57-74-9
50-29-3
60-57-1
88-85-7
298-04-4
115-29-7
52-85-7
76-44-8
319-84-6
298-00-0
56-38-2
298-02-2
23950-58-5
8001-35-2
81-81-2
116-06-3
82-68-8
311-45-5
62-74-80
50-00-0
MW
364.9
137.99
409.8
354.5
380.93
240.22
274.4
406.95
325
373
290.85
263.2
291.3
260
255.9
413
308
190.25
295.34
275.21
100.02
30.03
MP (°C)
107
195
107
108
175
40
-
106
53
95
157
35-36
6
<-15
155-156
85
161
99-100
141.5
-
33
-118
Ref
U.S EPA, 1983
U.S EPA, 1983
U.S EPA, 1983
Verschuenen, 1977
MSDSf
MSDS
-
MSDS
MSDS
MSDS
Verschuenen, 1977
U.S EPA, 1983
MSDS
U.S EPA, 1983
MSDS
Cohen et al., 1982
MSDS
MSDS
Verschueren, 1977
-
U.S. EPA. 1983
Verschueren, 1977
UP (°C)
175
185
-
-
62
-
-
-
288(decomp)
-
375
118-120 U
-
>120 (Dccomp)
-
-
328 •
169
165
-19.4
Ref
U.S EPA, 1983
U.S EPA, 1983
-
MSDS
-
-
-
Verschuenen, 1977
-
Merck Index, 1968
.S EPA, 1983 (0.8 torr)
Cohen ct al., 1982
-
-
MSDS
Merck Index, 1968
U.S. EPA, 1983
U.S. EPA. 1983
t MSDS = Materials Safety Data Sheet
(1) = Chlorinated Hydrocarbon
(2) = Organophosphate
-------
TABLE 2. CONTINUED
Compound
Aldrin (D
Cacodjlic Acid
Chlordane, technical (D
DDT (1)
Dieldrin ( 1)
Dinoseb
Disulfoton (2)
Endosulfan (1)
Famphur1
Heptachlor (1)
alpha Lindane ( 1 )
Methyl parathion (2)
I';i r:ith ion (2)
1'horate (2)
Pronamide
Toxaphene (1)
Warfarin
A 1 d i c a r b
Pentachloronitrobenzene
V.P.
(mmHg) Ref
6.00E-06 Edwards, 1972 (20-25°C)
l.OOE-05 Edwards, 1972 (20 °C)
1.90E-07 Edwards, 1972 (20-25°C)
l.OOE-07 Edwards, 1972 (20-25°C)
>1.00E-06 Weber, 1972 (20-25 C)
3.00E-04 U.S. EPA, 1984 (20-25 °C)
l.OOE-05 Goebel et al.. 1982
-
3.00E-04 Edwards, 1972 (20 °C)
2.15E-05 U.S. EPA, 1983 (20°C)
9.70E-06 U.S. EPA, 1983
3.78E-05 U.S. EPA, 1983
2.30E-03 U.S EPA, 1984
8.00E-02 U.S. EPA, 1983 (20°C)
l.OOE-06 Cohen el al., 1982
.
l.OOE-04 Holdcn, 1986
1.0 IE- 10 calculated
Aqueous
Aqueous
Sol (mg/L) Sol (M)
0.01
6.67E+01
5.60E-02
l.OOE-03
l.OOE-01
5.20E+01
6.00E+01
6.00E-02
-
5.60E-02
l.OOE+01
5.00E+01
6.54E+00
8.00E+01
1.50E+01
3.00E-hOO
.
4000
0.44
2.74E-08
4.83E-04
1.37E-07
2.82E-09
2.63E-07
Weber, 1972
2.19E-04
1.47E-07
-
1.50E-07
3.44E-05
1.90E-04
2.25E-05
3.08E-04
5.86E-05
7.26E-06
-
2.10E-02
1 .49E-06
Ref log Kow Ref log Koc*
Wauchope, 1978
U.S. EPA, 1983
U.S. EPA, 1983 (20°C)
Edwards, 1972
Wauchope, 1978
U.S. EPA, 1984
U.S. EPA, 1983
-
U.S. EPA, 1983
Verschueren, 1977
U.S. EPA, 1983
Fclsot and Dahm, 1979
Wauchope, 1978
Merck Index, 1968
Edwards, 1972
-
Felsot and Dahm, 1979
U.S EPA. 1983
0.85
0.00
2.78
3.48
2.90
2.30
0.00
3.55
-
3.90
3.81
2.99
3.40
2.92
-
3.30
2.52
0.70
5.57
Felsot and Dahm, 1979
U.S. EPA, 1983
U.S. EPA, 1983
U.S. EPA, 1983
U.S. EPA, 1983
Rao and Davidson, 1980
U.S. EPA, 1983
U.S. EPA, 1983
-
U.S. EPA, 1983
U.S. EPA, 1983
Hansch and Leo,1979
Fclsot and Dahm, 1979
Holden, 1986
-
Cohen ct al., 1982
Hansch and Leo, 1979
Holdcn, 1986
• U. S. EPA, 1983
2.61
-0.35
2.40
3.10
2.52
2.30
3.25
3.16
-
3.51
3.42
2.61
3.02
2.54
2.30
2.92
2.15
0.35
.
Dielliyl-p-nltrophenyl phosphatv '21 . .....
Fluoracetic acid, sodium salt
Formaldehyde
'calculated from regression equation
-
10 Verschueren, 1977 (-88 C)
developed by Karickhoff et al. (1979).
-
-
-
-
-
-
-
-
-
-
-
-
(1) = Chlorinated Hydrocarbon
(2) = Organophosphate
-------
TABLE 3. CHARACTERIZATION INFORMATION AND SELECTED EHYSICAL FHOPERTIES FOR 13 CHLORINATED HYDROCARBONS.
Compound
Bis-(chloromethyl) ether
Chloromethyl methyl ether
l,2-Dibromo-3-chloropropane
Dlchlorodifluorome thane
,1-Dichloroethylene
,1,1-Trichloroethane
,1,2,2-Tetrachloroethane
,1,2-Trichloroethane
,1,2 -Trlchlorotrlfluoroe thane
Trichloromonofluoroe thane
Hexachlorocycopentadlene
4,4-Methylene-bls-(2-chloroanillnc)
1,2,4-trlchlorobenzene
Formula
EPA Code CAS No.
CH2C1OCH2C1 P016 542-88-1
C1CH20CH3 U046 107-30-2
C3H5ClBr2
CC12F2
C2H2C12
CC13CH3
CH2C1CC13
U066 46-12-8
U075 75-71-8
U078 75-35-4
U226 71-55-6
U209 79-34-5
CH2C1CHC12 U227 79-00-5
CFC12CF2C1
C2H2C13F
C5C16
X001 76-13-1
U121 75-69-4
U130 77-47-7
CH2(C6H4C1NH2)2 U158 101-14-4
C6H3C13
XI 05 120-82-1
MW MP (°C) Ref
114.96
80.52 -
236.4
120.91
96.94
133.41
167.9
133.41
187.38
137.38
272.77
267.2
181.46
-41.5 Verschueren, 1977
103.5 Verschueren, 1977
-158 Verschueren, 1977
-122 Verschueren, 1977
-32 Verschueren. 1977
-36 Verschueren, 1977
-35 Aldrich. 1986
-35 Aldrich. 1986
-111 U.S. EPA. 1983
9 U.S. EPA, 1983
-85.9 U.S. EPA, 1983
17 Verschueren. 1977
BP (C)
104
59.5
196
-29.8
31
74-76
146.2
113.7
47
24.1
239
79.6
214
Ref
Verschueren, 1977
Verschueren, 1977
Merck Index, 1968
Verschueren, 1977
Aldrich, 1986
Aldrich, 1986
Verschueren, 1977
Verschueren. 1977
Aldrich, 1986
U.S. EPA. 1983
U.S. EPA, 1983
U.S. EPA. 1983
Aldrich, 1986
Compound
Bis-(chloromethyl) ether
Chloromethyl methyl ether
l,2-Dtbromo-3-chloropropane
Dlchlorodlfluoromethane
, -Dlchloroethylene
, ,1-Trlchloroethane
, ,2,2-Tetrachloroethane
, ,2-Trlchloroethane
, ,2-TrIchlorotrlfluoroethane
Trlchloromononuoroethane
Hexachlorocycopentadlene
4,4-Methylene-bls-(2-chloroanIllne)
1.2,4-trlchlorobenzene
V.P. (mmHg)
3.00E+01
2.04E+00
8.00E+00
4.36E+03
.5.00E+02
l.OOE+02
5.00E+00
1.90E+01
2.70E+02
2.36E+01
8.00E-02
3.69E-01
4.46E-06
Ref
U.S. EPA, 1983 (22 C)
calculated
Merck Index. 1968
U.S. EPA, 1983 (20°C)
Verschueren. 1977 (20°C)
Verschueren, 1977 (20°Q
U.S. EPA, 1983 (20°C)
U.S. EPA. 1983 (20°C)
Verschueren. 1977 (20°C)
calculated
U.S EPA, 1983 (25 Q
calculated
calculated
Aqueous
Aqueous
Sol (mg/L) Sol (M) Ref
2.20E+04
2.80E+02
4.40E+03
2.90E+03
4.40E+03
2.73E+01
2.54E-04
1.91E-01 U.S. EPA, 1983 (20°C)
2.32E-03 U.S. EPA,
1983
log Kow Ref
-0.38 U.S. EPA. 1983
0.91 U.S. EPA, 1983
2.16 U.S. EPA. 1983
3.30E-02 Verschueren. 1977 (20°C) 2.2 U.S. EPA, 1983
1.73E-02 U.S. EPA.
1983
3.30E-02 Merck Index. 1968
l.OOE-04 U.S. EPA,
1.40E-09
1983
4.99 U.S. EPA. 1983
2.17 U.S. EPA, 1983
1.66 calc
5.04 McDuffie. 1981
3.3 Holden. 1986
3.98 Miller et al.,1985
log Ko
-0.72
Of f
.55
1.79
1.83
4.59
1.80
1.30
4.64
2.92
3.59
•calculated from regression equation developed by Karickhoff ct al. (1979).
-------
TABLE 4. CHARACTERIZATION INFORMATION AND SELECTED PHYSICAL PROPERTIES FOR 5 MISCELIANEOUS COMPOUNDS.
Compound
Aniline
Mitomycin C
Pyrldinc
Tetracthyl Lead
Uracil mustard
Formula EPA Code CAS No.
C6H5NH2
C15H18N4O5
'CHCIICIICHCIIN1
PB(C2H5)4
C8H11C12N3O2
U012
U010
U196
P110
U237
62-53-3
50-07-7
110-86-1
78-00-2
66-75-1
MW
93.1
334.34
79.1
323.44
252.1
MI» (°C) Rcf
-6
360
-42
-136
206
Verschueren,
Merck Index,
Verschueren,
Verschueren,
Merck Index,
1977
1968
1977
1977
1968
IIP (C)
184
115.2
110-200(D)
Rcf
Verschueren,
Verschueren,
Verschueren,
1977
1977
1977
to
o
Compound V.P. (rnmllg) Rcf
Aniline (amlno benzene)
Mitomycin C
Pyrldlne
Tetraethyl Lead
Uracil mustard
3.00E-01
1.40E+01
1.50E-01
Verschueren. 1977
U.S. EPA, 1983 (20°C)
Verschueren, 1977 (20°C)
Aqueous Aqueous
Sol (mg/L) sol (M)
3.40E+04
2.91E-01
3.65E-01
9.00E-07
Ref log Row Ref log Koc'
Verschueren, 1977 0.96
-0.038
0.66
-1.07
U.S. EPA, 1983
Hansch.1979
U.S. EPA, 1983
Hansch and Leo, 1979
0.60
-0.38
0.31
-1.40
Calculated from regression equation developed by Kanckhoff et al. (1979).
-------
SOIL CHARACTERIZATION
Two soils used in this study were a Kidman fine sandy loam
(Haplustoll, Utah) and a McLaurin sandy loam soil (Paleudult,
Mississippi). Surface soil to a depth of approximately 6 inches was
sampled for each soil type. The collected soils were air-dried and sieved
to pass a 2-mm sieve. Fhysical and chemical properties of the soils are
shown in Tables 5 and 6. These soils had not received application of any
fertilizer or agricultural chemical in the last five years. Soil
microorganism counts (Tables 5 and 6) are typical for a soil with an
active microbial populations.
DETERMINATION OF DEGRADATION RATES IN SOIL
Degradation describes the chemical and/or biological conversion of a
parent compound to its various intermediates (transformation) and/or to
inorganic end products such as carbon dioxide, water, nitrogen,
phosphorous, sulfur, etc. (corplete degradation). In this study, the rate
of degradation was experimentally determined by measuring the difference
between the amount of compound initially added to a soil and that which
was recovered after specified time intervals. Using sterile soil control
samples rendered microbially inactive using HgCl2 (Fowlie and Bulman
1986), the biological and chemical degradation components were
differentiated. This operational determination of degradation, however,
could not be used to distinguish between complete degradation and
transformation into intermediate products. Transformation was
characterized for one chemical, 7,12-dimethylbenzanthracene (DMBA).
21
-------
TABLE 5. CHARACTERIZATION OF KIDMAN SANDY IDAM SOIL COLLECTED FROM USU
AGRICULTURAL EXPERIMENT FARM AT KAYSVILLE, UTAH
Soil Characteristic
Value
Physical Properties:
Bulk density*
Texture*
Moisture at
1/3 atmosphere
15 atmospheres
Saturation*
Soil Classification:
Chemical Properties:
pH
CEC
Organic carbon*
Total phosphorus
Total nitrogen
Nitrate nitrogen
Sulfate in saturated extract
EC of saturated extract
Iron
Zinc
Phosphorus (bicarbonate extractable)
Potassium
Ammonium acetate-extractable cations
Sodium
Potassium
Calcium
Magnesium
Water soluble cations
Sodium
Potassium
Calcium
Magnesium
Biological Properties:
Soil plate counts
Bacteria
Fungi
1.49 g/cm3
loam
20%
7%
24%
Typic Haplustoll
7.9
10.1 meq/lOOg
0.5%
0.06%
0.07%
3.7 ppm
4.8 ppm
0.2 mmhos/cm
9.0 ppm
1.2 ppm
27 ppm
117 ppm
0.24 meq/lOOg
0.42 meq/lOOg
13.6 meq/lOOg
1.7 meq/lOOg
0.01 meq/lOOg
<0.01 meq/lOOg
0.04 mep/lOOg
0.01 meq/lOOg
6.7 x 106/g
1.9 X 104/9
Soil properties required for use in modeling soil treatment of hazardous
waste (U.S. EPA 1986b).
22
-------
TABLE 6. CHM^ACTERIZATION OF MCLALJRIN SANDY DDAM SOIL PROVIDED BY
MISSISSIPPI STATE UNIVERSITY, WIGGINS, MS
Soil Characteristic
Value
Physical Properties:
Bulk density*
Texture*
Moisture at
1/3 atmosphere
15 atmospheres
Saturation*
Soil Classification:
Chemical Properties:
pH
CEC
Organic carbon*
Total phosphorus
Total nitrogen
Nitrate nitrogen
Sulfate in saturated extract
EC of saturated extract
Iron
Zinc
Phosphorus (bicarbonate extractable)
Potassium
Ammonium acetate-
-------
Two experimental approaches were used to measure degradation rates
for the chemicals evaluated in the study. In the first approach
degradation rates were not corrected for volatilization losses (Table 7).
That is the observed loss of a compound due to volatilization was not
distinguished from losses attributed to degradation. In the second
approach, degradation rates were corrected for volatilization (Table 8).
The later approach provided independent measurement of losses due to
volatilization thus allowing a corrected degradation rate to be
determined.
Determination of Degradation Rates (Uncorrected for Volatilization)
Soil microcosms consisted of 250 mL glass beakers containing 50 g of
either Kidman or McLaurin soil. Each soil sample was initially wetted to
achieve a moisture content of -0.3 bar matric potential. The soils were
then incubated at 20°C for a minimum of five hours.
Chemicals were then applied to the incubated soils in 2 to 5 mL of n-
hexane, methanol, or methylene chloride either as individual constituents
or in mixtures. Loading rates are given in Tables 7 and 8. Samples were
thoroughly mixed and the solvent was allowed to evaporate. The beakers
were then covered with a polyethylene sheet. This material, which is
permeable to air but impermeable to water, was used to minimize water
loss. All soil/chemical mixtures were incubated at 20" C in the dark to
prevent photodegradation of the chemicals tested. Samples were
periodically weighted and deionized water was added to maintain soils at -
0.3 bar matric potential.
Triplicate samples were removed from incubation for extraction and
parent compound quantitation at various time intervals, based on an
estimated half-life of the chemical. The soils were extracted directly in
24
-------
TABLE 7. LOADING PATES FDR SELECTED OCMPOUNDS ON KIDMAN AND MCLAURIN
SOILS FOR WHICH DEGRADATION RATES WERE UNOORRECTED FOR VOLATILIZATION
Compound
Loading Rate
(rag/Kg)
Chemical
Individual
Constituent
Matrix
Synthetic
Mixture
Polynuclear Aromatic Hydrocarbons
Anthracene
Fhenanthrene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7,12 Dimethylbenz (a) -
anthracene
Benzo (b) f luoranthene
Dibenz (a , h) anthracene
Benzo (a) pyrene
Dibenzo(a, i)pyrene
Indeno ( 1 , 2 , 3-cd) pyrene
Acenaphthylene
3Hyfethylcholanthrene
Pesticides
Aldrin
Heptachlor
Endosulfan
Disulfoton
Phorate
Parathion
Methylparathion
Dichlorodiphenyl-
trichloroethane
Pentachloronitrobenzene
Lindane
Aldicarb
Famphur
Warfarin
Dinoseb
Pronamide
Toxaphene
Chlorinated Hydrocarbons
1,2,4 trichlorobenzene
Hexachlorccyclopentadiene
Miscellaneous
Aniline
200
900
900
700
100
100
16
38
12.5
33
10
9.0
96.99
32.25
0.45
0.67
0.69
1.58
1.64
1.83
1.60
0.50
0.34
0.49
99
99
98
102.88
99.33
20
0.732
0.340
100
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
2
«
A
B
B
C
D
D
D
A
A
B
C
D
•"•letters indicate compounds included in given mixture.
2Toxaphene was evaluated as an individual constituent within a complex waste
consisting of soil, manure, cattle hair, and partially degraded dexaphene
used in a cattle dipping solution.
25
-------
TABLE 8. LOADING RATES FOR SELECTED COMPOUNDS ON KIDMAN AND MCLAURIN
SOILS FOR WHICH DEGRADATION RATES WERE CORRECTED FOR VOLATILIZATION.
Ctmpound
Synthetic
Chemical Matrix
Loading Rate
(mg/kg)
Chlorinated Hydrocarbons
1,1-Dichloroethylene
1,1,1-^Trichloroethane
1,1,2 -Tr ichloroethane
1,1,2,2-Tetrachloroethane
Chloromethylethylether
1,3-Dibromo,3,chloropropane
Miscellaneous
Tetraalkyllead
100.
99.
99.
100.
99.
Individual
Constituent
Mixture
Polynuclear Aromatic Hydrocarbons
Naphthalene
1-Methylnaphthlene
Anthracene
Phenantherene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7,12 Dimethylbenz (a) anthracene
Benzo(b) fluoranthene
Dibenz (a , h) anthracene
Benzo (a) pyrene
Dibenzo (a, i) pyrene
Indeno ( 1 , 2 , 3-od) pyrene
100
100
200
900
900
690
100
100
16
38
12.5
33
10
9
X
X
X
X
X
X
X
X
X
X
X
X
X
X
100.5
72.1 (as Pb)
A
A, B
A
B
B
-'-letters indicate corpounds included in given mixture.
2Tetraalkyllead (TAL) was a complex gasoline sanple supplied by Standard Oil
Co. and consisted of 61.5% TAL, 17.9% ethylene dibromide, and 18.8% ethylene
dichloride.
26
-------
the beakers using a homogenization technique (Coover et al. 1987). The
soils were extracted with 150 mL of solvent for 60 seconds using a Tekmar
Tissumizer. A 51 percent/49 percent hexane-acetone mixture was used to
extract the pesticides, while methylene chloride was used in the
extractions for all other compounds. The extract was decanted from the
soil (washed with water to remove acetone, when used), and was dried by
passage through a column of anhydrous sodium sulfate. The extracts were
concentrated, when necessary, in a Kuderna-Danish evaporator or under a
gentle stream of N2-
Abiotic controls were prepared by spiking the soil microcosms with a
HgCl2 solution as described by Fdwlie and Bulman (1986). This method
renders the soil microbially inactive while producing minimal changes in
the physical and chemical properties of the soils. Abiotic control
microcosms were spiked with the test substances, incubated, and extracted
following the same procedures as the nonsterilized microcosms.
In addition to the individual chemicals that were tested, one complex
waste sample containing toxaphene was evaluated. The toxaphene waste was
added to 5 kg of Kidman sandy loam at a 0.1 percent by weight application
rate. The soil/waste mixture was tumbled overnight to ensure uniform
distribution of the toxaphene in the test soil. The mixture was divided
into 100 g aliquots which were placed in 700 mL glass beakers for
incubation. Deionized water was added to the sanples to reach a water
content of -0.3 bar matric potential, mixed thoroughly, incubated, and
sampled as described above.
Determination of Volatilization Corrected Degradation Rates
The procedure for measuring short term (48-100 hours) volatile losses
of a compound from soil was taken from the Permit Guidance Manual on
27
-------
Hazardous Waste land Treatment Demonstrations (USEPA, 1986b). The
chemicals included in this phase of the study are listed in Table 8. The
experimental apparatus used for volatilization measurements consisted of
500 mL Erlenmeyer flask soil reactors (Figure 1) that were used to
simulate the air/soil surface environment.
A representative sample of Kidman or McLaurin soil (250 g air dried)
was placed in the test reactors. The soil was initially wetted to a soil
water content corresponding to a matric potential of approximately -0.33
bar. The reactors were placed in the dark and incubated at room
temperature for approximately one week. Following this initial incubation
period, test compounds were added individually or in a mixture in 30 mL
methanol to the soil in the reactor to achieve the desired initial soil
concentration. The soil was then mixed thoroughly to achieve a uniform
distribution of the chemical in the soil and the flask units were
immediately capped. loading rates are listed in Table 8. All experiments
included soil blank controls (without waste addition), abiotic soil
controls, and duplicate soil-chemical reactors under a given set of
loading and soil environmental conditions.
Once capped, the flask unit was purged with air at a controlled rate
of 250 to 300 mC/niin- High quality breathing air was used as the purge
gas to eliminate the possibility of oxygen limitation and subsequent
impact to microbial processes occurring during the experiment. Emission
measurements were made by drawing a constant volume split stream sample of
flask effluent gas through the sampling/collection system via a constant
volume sample pump and a balanced, capillary flow controlled, four-place
sampling manifold (three samples plus a blank). Use of this procedure
allowed the concurrent sampling of all flask units for the same length of
28
-------
Influent
Purge Gas
Effluent Purge Gas
Kfri
Soil/Waste
Mixture
Capillary Flow
Control p
Constant
Flow
Sample
Pump
Effluent Purge Gas
Figure i. Laboratory flask apparatus used for mass balance measurements.
29
-------
time and during the same time period during a given volatilization
experiment. Ihe sample pump rate and purge gas flow rate were measured
before each sampling event via a bubble tube flow meter. Ihe duration of
sorbent tube sampling was recorded to allow accurate soil loss rate
calculations.
Sorbent tubes were sampled at a rate of 20 to 30 mL/min/trap for a
period of time ranging from 0.5 minutes just after waste application to 5
minutes at the end of the volatilization experiments. Breakthrough traps
were used in all sampling events to allow quantification of breakthrough
which occurred during the experiments. Observed breakthrough values were
reported, and all mass flux values were calculated with the inclusion of
this observed breakthrough mass. Upon completion of the sampling event,
the Tenax sorbent tubes were removed from the sampling system and were
placed in muffled culture tubes with Teflon lined caps and stored at or
below 4°C prior to thermal desorption and GC-FID analysis.
A modification of Method 5030 "Purge-and-Trap Method" (U.S. EPA 1982)
was used for the extraction of soils used in the volatilization study.
The method involves the extraction of 2 to 5 g of soil with approximately
35 mL of distilled-in-glass methanol. The soil/methanol mixture is placed
in screw-top centrifuge tubes without a headspace and is vortexed for two
minutes. The mixture is then centrifuged at 2000 rpm for 20 minutes, and
the centrate is stored in Teflon™ screw-top vials at or below 4°C prior
to analysis by GC-FID.
The sampling and analysis procedure for both gas and soil samples was
repeated at selected time intervals following compound addition
corresponding to the anticipated log decay in compound emission rates.
30
-------
The general sampling schedule used for emission measurements and soil
flask sacrifice and extraction was as follows:
0, 15 min, 1 hr, 2.5 hrs, 10 hrs, 25 hrs, 50 hrs, 100 hrs.
Sorbent tube and soil extraction blanks and spikes were used
throughout the study to provide adequate method QA/QC- Soil drying was
minimized by bubbling the purge gas through distilled deionized water
before entering the microcosm units.
Analytical Methods for Determination of
Substance Concentration in Soil Systems
Analytical methods used for the identification and determination of
the concentration of substances in the test systems, including soil and
air phases, are given in Table 9. Instrumentation and analytical
conditions are presented. All analytical methods were based on EPA
procedures given in Test Method for Evaluating Solid Wastes,
Hiysical/Qiemical Methods (U.S. EPA 1982).
Soil Sterilization - Enumeration of Soil Microbes
Beakers of soil were prepared as described above, with and without
the addition of HgCl2- Plate counts of soil microorganisms including
bacteria, actinomyces and fungi were performed following the procedure of
Wollum (1983). Microorganism counts were performed over a period of 30
days to determine effectiveness of HgCl2 for sterilizing soil.
Data Calculations
Degradation kinetic parameters and half-life (tj/2 in days) values
were calculated from specific constituent soil concentration and vapor
flux data. Mean concentrations for replicate soil flask units were used
in all calculations.
31
-------
TABLE 9. CHEMICAL IDENTTFICATICW AND QUANrnFICATION METHODS AND CONDITIONS
Compound
4,4'-DDT
Aniline
Pentachloronitrobenzene
Trichlorobenzene
3-methylcholanthrene
Acenaphthylene
Aldicarb
Dinoseb
Famphur
Pronamide
Warfarin
Benz[a]anthracene
Benz[a]pyrene
Chrysene
Dibenzo[a,h]anthracene
lndeno(1 ,2,3-cd)pyrene
Flouranthene
Naphthalene
1 -Methylnaphthalene
Phenanthrene
Pyrene
Benzo[b]fluoranthene
Dibenzo[b]pyrene
7,12-Dimethylbenzanthracene
1,1-Dichloroethylene
1,1,1-Trichloroethane
1 ,1 ,2,2-Tetrachloroethane
1,1 ,2-Trichloroethane
1 ,2,4-Trichlorobenzene
Method of
Analysis
GC
GC
GC
GC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
HPLC
GC
GC
HPLC
HPLC
HPLC
HPLC
HPLC
GC
GC
GC
GC
GC
Detector
ECD
NPD
ECD
ECD
UV
UV
UV
UV
UV
UV
UV
UV
UV
UV
UV
UV
UV
FID
FID
UV
UV
UV
UV
UV
FID
FID
FID
FID
ECD
Column GC/HPLC column
conditions
1
2
1
1
3
3
3
3
3
3
3
4
4
4
4
4
4
2
2
4
4
4
4
4
5
5
5
5
1
1
3
1
2
6
6
5
6
5
6
5
7
7
7
7
7
7
2
2
7
7
7
7
7
4
4
4
4
2
Column legend
1= DB-5 15 m x 0.53 mm I.D. capillary column (J&W Scientific), flow rate: 5ml_/min Nitrogen
2= 3% 2250 1.5 m x 2mm I.D. packed glass column (Supelco), flow rate: 30 mL/min Helium
3= C-18 (Sum packing), 250 x 4mm (SGE)
4=ODS (Sum packing), 150 x 4 mm (Supelco, LC-PAH)
5=1% SP 1000 3m x 2 mm I.D. packed glass column (Supelco), flow rate: 30 mL/min Helium
GC column temperature condition legend
1=190°C for 1min, 12°C/min to 220°C, hold tor 5 min
2=120°C isothermal
3= 90°C isothermal
4=100°C for 5 min, 8°C/min to 225°C, hold for 20 min
HPLC column conditions
5= Mobile phase: wateracetonitrile, 49% ACN to 90% ACN, hold 2 min., flow rate: 2ml/min,
6= Mobile phase: watenacetonitrile, 50%ACN to 100%ACN, hold 3 min, flow rate: 2ml_/min,
7= Mobile phase: wateracetonitrile, 40% ACN to 10O% ACN, hold 2 min., flow rate: 2ml/min.
Detector operating conditions
ECD = electron capture detector, Temperature 300 °C, total flow (makeup + column)= 35 mL/min
FID = flame ionization detector. Temperature = 300 °C, Hydrogen flow = 40 ml_/min, air flow = 400 mL/min
NPD = nitrogen-phosphorous detector, temperature = 300 °C, hydrogen flow = 3 mL/min, air flow = 120 ml/min
UV = ultraviolet detector, wavelength = 254 nm
32
-------
Degradation Kinetics—
For each constituent investigated, rate constants and tl/2 values
were calculated assuming first order kinetics. For those compounds for
which degradation rates were not corrected for volatilization, no
modifications to the measured constituent soil mass values were required.
The integrated form of the first order rate expressions was used to
determine the first order rate constant, k1; and tl/2 values. For first
order kinetics, the rate coefficient was determined from a least squares
regression of the natural log transformation of constituent soil
concentration at time t divided by the initial constituent soil
concentration, ln(Ct/Co), versus time. Half-life (ti/2) values are
calculated based on the time to reach a constituent soil concentration
equal to 1/2 the initial concentration, (ln(0.5)/-k^ = -0.693/-ki = t-i^) •
For those compounds for which volatilization losses were monitored,
constituent soil loss data were modified as described below to provide
volatile loss corrected k^ and ti/2 values.
Volatilization Corrected Degradation Rates—
For those constituents for which volatilization rates were measured,
the calculation of a degradation rate corrected for this volatile loss was
carried out using the difference form of the first order degradation rate
equation:
dtVdt = -kM (1)
Use of this equation requires the calculation of the change in
degraded mass over time, along with the mean mass of constituent over a
specific time interval, dt. This procedure is summarized below:
1) An emission rate was determined for each constituent at each
sampling interval taking into account the duration of each sampling event,
33
-------
the fraction of purge flow actually sampled, and the mass collected during
sampling, corrected for breakthrough and method recovery efficiency:
__ . . _ , Mass collected in vapor . Purge air flowrate ,_.
Emission Ratej- = ^t^ of sanple * SagfiL& air flowrate (2)
2) Ihe total emitted mass collected over consecutive sampling times
was calculated from the product of the mean of the emission rates at each
sampling time and the length of time between consecutive sampling events:
Cumulative
Emitted = (Emission Rate^+1 + Emission Ratet)/2*(t£+i-t-^) (3)
3) Ihe soil constituent mass if no degradation had occurred was
calculated as the difference between the constituent mass added to the
soil at time t=0 and the measured cumulative volatilized mass at each
sampling time corrected for method recovery:
Soil Constituent
Mass if Not = Constituent Mass^-^Q - Cumulative Emitted Massf- (4)
Degraded^
4) The mass degraded was calculated as the difference between the
soil mass calculated from Equation 4 and the actual constituent soil
concentration at each sampling time corrected for method recovery:
Soil Constituent _ Soil Constituent _ Actual Constituent
Mass Degradedt- Mass If Not Degradedf- Soil Masst ( '
5) Ihe mean constituent soil mass over each sampling increment was
calculated as the arithmetic mean of constituent soil mass values measured
at each sampling time.
6) Ihe change in degraded mass between consecutive sampling times was
divided by the length of time of each increment to provide calculated
34
-------
values for dty/dt:
Soil Constituent Soil Constituent
Mass Degraded - Mass Degraded
(t+l-t) v '
7) Volatilization corrected degradation rate values, k, were then
calculated from a linear regression of cttVdt versus mean constituent mass
M, over each time interval, as given from Equation 1.
PARTITION COEFFICIENT DETEEMINATIONS
Calculational Approach for Partition Coefficients
Based on Structure~Activitv Relation*^ ipg
Partition coefficients between aqueous and soil (%) / oil (KQ) , and
air (%) phases were estimated for the chemicals listed in Tables 1
through 3. The following methods were used:
Estimation of K^—
The partition coefficient of a chemical between soil and water is
given by:
jr, = Ce/Qj (7)
where K^ is the soil/water partition coefficient (unitless if Cs and C^
are in the same units), Cg is the concentration of chemical in the soil
phase, and C^ is the concentration of chemical in the aqueous phase.
K
-------
correlation equations have been developed which relate K^-. to
octanol/water partition coefficients (K^). The correlation equation used
to calculate KQC for this project was that of Karickhoff et al. (1979) :
log KQC = 1.0 log K^ - 0.21 (9)
Experimental values of log K^ obtained from the literature were used when
available, log K^ values, estimated using the fragment approach of
Hansch and leo (1979), were used when experimental values were not
available.
The second approach employed for the estimation of log KQC was based
on molecular connectivity indexes (MCIs). MCIs are topological parameters
which describe the degree of bonding or connectedness of the nonhydrogen
atoms in a molecule. First order MCIs ^x), calculated from the molecular
structure of a compound, have been shown to be highly correlated with
soil/water partition coefficients (Sabljic, 1984; Sabljic, 1987).
First order Mds were calculated using a computer program written in
Fortran for an Apple Macintosh computer. The KQQ values were calculated
from the first order MCI using the regression equation developed by
Sabljic (1987):
log KQC = (0.53) 1-X + 0.54 (10)
The resultant K^ values were used along with percent organic carbon
values to calculate K-j values of the Kidman and McLaurin soils using
equation 8.
Estimation of K-,—
The partition coefficient of a chemical between water and oil is
given by:
(11)
36
-------
where KQ is the oil/water partition coef f icient (unitless if CQ and C^ are
in the same units), CQ is the oorioentration of chemical in the oil phase,
and Cy is the concentration of chemical in the water phase.
KQ values were estimated using a correlation expression between KQ
and K^ given by Leo and Hansch (Leo et al. 1971). This equation,
developed using olive, cottonseed, and peanut oils, is presented below
after solving for log KQ:
log KQ = 1.12 log K^ - 0.324 (12)
Estimation of K^—
The partition coefficient of a chemical between air and water can be
written as:
% =
-------
values were estimated using the following expression developed by MacKay
et al. (1982).
T T T
In Pv = -(4.4 -f In TB) [1.803 (^ - 1) ] - 0.803 In ^ - 6.8 (^ - 1) (15)
where Pv is in torr and TB, TM and T are the boiling point, melting point
and an environmental temperature (°K), respectively.
QA/QC PROCEDURES FOR DEGRADATION AND PARTITION EXPERIMENTS
Soil spiking and recovery studies were conducted to determine the
effects of soil, test substance, and soil/test substance matrix on
constituent extraction and recovery efficiency. Extracts of the soil and
complex wastes were spiked with test substance (s) of interest to evaluate
the effect of these matrices on constituent identification and
quantification. Interferences due to the extract matrix were identified.
Standard solutions were prepared using primary standards of the test
substance dissolved in a suitable solvent that did not interfere with
constituent identification and quantification. Standard curves were
generated using at least six points ranging from the highest concentration
anticipated to the detection limit for the constituent.
MATHEMATICAL MODEL FOR SOIL-WASTE PROCESSES
A mathematical description of a land treatment system, based upon a
conceptual model of the land treatment process, that incorporates specific
requirements for the land treatment demonstrations specified by the U.S.
Environmental Protection Agency (EPA) in 40 CFR Part 264.272 provides a
framework for integrating and evaluating the relevant information.
Specifically this includes: (1) evaluation of literature and/or
experimental data for the selection of constituents most difficult to
treat, considering the combined effects of degradation and immobilization
(principal hazardous constituents, PHCs), (2) evaluation of the effects of
38
-------
site characteristics on treatment performance (soil type, soil
horizonation, soil permeability), (3) determination of the effects of
design and operating parameters (loading rate, etc.) on treatment
performance, (4) evaluation of the effects of environmental parameters
(season, precipitation), and (5) comparison of the effectiveness of
treatment using different design and management practices in order to
maximize treatment.
The values developed for degradation (or apparent loss) and
immobilization for pesticides in the treatability studies were used as
input for the mathematical models VTP and RITZ. The VIP model (Vadose
Zone Interactive Processes) is an enhanced version of the mathematical
model RTTZ (Regulatory and Investigative Treatment Zone Model), developed
by the U.S. EPA, Robert S. Kerr Environmental Research Laboratory (Short
1986), for quantitatively integrating the processes of degradation and
immobilization in the unsaturated zone of a soil system. The VIP model
was developed at Utah State University for use in evaluation of site-
specific treatment potential for specific waste-soil mixtures, and for
determination of the potential for migration of hazardous constituents
from a site to groundwater and to the atmosphere and is described by
Grenney et al. (1987). The VIP model has been used to rank organic
hazardous constituents with respect to tendencies to leach and to
volatilize, and, therefore, to indicate the relative soil assimilative
capacities (SAC) for a group of hazardous organic constituents (Grenney et
al. 1987, IfcLean et al. 1987).
VIP incorporates the assumptions described by Short (1986). The
major differences between RITZ and VIP are the numerical solution
algorithms used in VIP and the option to use nonequilibrium kinetics in
39
-------
VIP. Use of the numeric solution algorithm is an enhancement allowing the
input of pollutant concentration profiles in any phase as the initial
conditions, monthly variations or recharge, temperature, and pollutant
application at user defined intervals.
The same input parameters and initial conditions were used in both
model simulations, and results of the outputs of the models were evaluated
and compared. Therefore, for the VTP model the following input parameters
were used: (1) initial conditions were set to zero (no initial chemical
concentration in soil), (2) no monthly variation of water flow (or
recharge), (3) temperature in soil remains constant, and (4) chemical
application occurred only once (at time = 0), (5) use of local equilibrium
for partitioning of chemicals among soil, oil, air, and water phases of
the soil system.
Additional information concerning the RTTZ mathematical model is
presented by Short (1986). A detailed description and listing of the VIP
model (formerly R1TZE) can be found in the Permit Guidance Manual on
Hazardous Waste Land Treatment Demonstrations (U.S. EPA, 1986), Grenney
et. al. (1987), and in API (1987).
TRANSTOFMATION STUDIES
Soil Incubation of Dimethylbenzanthracene (CMBA)
Transformation studies were performed with the McLaurin sandy loam
soil at low pH and the same soil adjusted to neutral pH for 7,12-
dimethylbenzanthracene (EMBA). Soil pH was adjusted from 4.8 to 7.5 by
adding 70 mg of CaCC>3 to the McLaurin soil. CUBA was chosen based on
reported genetic toxicity (Shoza et al. 1974, Walters 1966) and the rate
and extent of degradation measured in laboratory studies (Park 1987).
40
-------
One hundred grains (dry weight) of soil at the water potential of -
0.33 bar were placed in a 500 mL glass beaker. Following 14 days of
incubation, 100 mg of CMBA was added to the soil (1000 mg/kg) in a
methylene chloride solution. After the methylene solution evaporated from
the soil (approximately 24 hrs), water was added to adjust the soil
moisture content to -0.33 bar soil-water potential. Soil beakers were
covered with polyethylene film to control soil water content.
Polyethylene film is permeable to oxygen and is effective for reducing the
loss of soil water while maintaining aerobic conditions (Bossert et al.
1984).
Evaporative water losses during incubation were replaced by periodic
(approximately every 14 days) water addition in order to maintain soil-
water potential in the range of -1 to -0.33 bar. Soil beakers were
incubated at 20 "C in the dark to prevent photodegradation of the PAH
compound. Control experiments were performed under identical incubation
conditions. Soil blanks were incubated without CMBA. Poisoned controls
(2% HgCl2) with and without EMEA were also prepared to monitor and account
for possible abiotic transformations of soil humus and the PAH,
respectively, in soil systems.
Analysis of CMBA
Soil beakers were withdrawn from the incubation units at 0, 14, and
28 days after PAH addition. The schedule of sampling times was based
upon preliminary experiments and ensured that a sample would be taken
beyond the chemical half-life in soil. Each beaker was extracted with 200
mL methylene chloride using a homogenization technique (Tekmar Tissue
Homogenizer, lekmar Co. Cincinnati, OH). Methylene chloride extracts were
41
-------
dried over anhydrous sodium sulfate and evaporated to 1 mL under an
aerated hood.
An aliquot of the extract was injected into a Perkin-Elmer HPLC
system fitted with a 4.6 mm I.D. x 250 mm 15-u octadecylsilane column
(Supelco Inc., Bellefonte, PA) and eluted with a water/acetonitrile
gradient (from 35% to 100% of acetonitrile) at a flow rate of 0.9 mL
min~-k The eluate was monitored using a 254 nm UV detector. Seven
reference standards of hydroxylated derivatives of 7,12-dimethylbenz (a)
anthracene were provided by Dr. Melvin S. Newman (Ohio State University,
Columbus, OH) including; 1-hydroxy-, 2-hydroxy-, 3-hydroxy-, 4-hydroxy-,
5-hydroxy, 8-hydroxy-, and 10-hydroxy-7,12-dimethylbenz (a) anthracene.
Ihese cxanpounds were analyzed by HPLC using the same HPLC conditions that
were used for soil extracts.
Experiments with radiolabeled CMBA
Experiments with radiolabeled EMBA were conducted as described above
except 2 uCi (12-14C)CMRA was added to 10 g (dry weight) of the Mclaurin
sandy loam soil (0.2 uCi g"1). (12-14C)EMBA was purchased from Amershaiti
Corp. (Arlington Heights, IL) with a specific radioactivity of 8.3
mCi/mmol, and radiochemical purity of 97%.
The distribution of 14CC>2 between evolved CC^, soil extracts, and
soil residue components was measured to construct a mass balance for CMBA.
Soil samples were extracted at 0, 14, and 28 days after application of
CMBA. Hie extracted soil was air dried and stored in a refrigerator prior
to analysis for soil residue ^4C. The extract was dried over anhydrous
sodium sulfate and concentrated to 1 mL under an aerated hood.
The sample extracts (100 uL) were chromatographed on an HPLC system
using the same conditions and methods as described in the analysis of
42
-------
EMBA. Fractions of the HPLC eluate (0.25 mL) were collected at 1 min
intervals and added to tubes containing 3.5 mL of scintillation liquid.
The radioactivity present in each fraction was determined in a Beckman IS
5801 liquid scintillation counter (Beckman Instruments Inc., Carlsbad,
CA). Corrections were made for machine efficiency and quenching.
A sample of the extracted soil (0.1 g) was combusted at 700 C in a
stream of (>2 in a Biological Material Oxidizer (BMO/R.J. Harvey Instrument
Corp.). After catalytic oxidation of combustion gases, the CC>2 produced
was trapped in a solution of a 2:1 mixture of Carbasorb (Packard Instr-
ument) and Scintiverse II (Fisher Scientific). The trapping solution was
then counted for 14C.
The mineralization of 14C EMBA in the soil was determined using a
flask which has CC>2 trapping liquid. Solutions of KDH (0.1 N) were used
for trapping the evolved CC^. Trapped 14OC>2 was quantified by liquid
scintillation counting. KDH solutions in the CC^ traps were changed once
a week during the 28-day incubation period.
ffotagenicity Evaluation
Soil samples were incubated and extracted as described previously
except 1000 g (dry weight) of EMBA treated soils (1000 mg/kg) were placed
in a 3 L glass beaker. A large amount of soil (1000 g) was used in order
to obtain sufficient amounts of EMBA metabolites (weight of metabolites)
for the Ames mutagenicity assay. Soil extracts were separated into three
metabolite fractions based on HPLC retention time (polarity) (0-15 min,
15-33 min, and 35-45 min) and isolated by preparative scale HPLC on a
21.2 mm I.D. x 250 mm 15-u octadecylsilane column (Supelco Inc.,
Beliefonte,PA) using a water/acetonitrile gradient (35%-100%) at a flow
rate of 8 mL/min. The HPLC fractions were evaporated to dryness under an
aerated hood and reconstituted with dimethylsulfoxide (EMSO).
43
-------
Mutagenicity of CMBA and metabolite fractions were measured with the
Ames assay (Ames et al. 1975; Maron and Ames, 1983; and U.S. EPA, 1983b)
using the Salmonella typhimurium strain TA-100. Salmonella strain TA-100,
which detects mutagens causing base-pair substitutions, was supplied by
Dr. Bruce N. Ames (University of California, Berkeley, CA). Samples were
tested on triplicate plates in the standard plate incorporation assay at
four dose levels with enzyme activation (S9), and 2-Aminofluorene (10
ug/plate) was used as a positive control. Mutagenic potential of each
test sample was expressed as the mutagenic ratio (MR), i.e., ratio of
number of colonies in the presence of a test sample to the number of
colonies on a control growth plate in the absence of the test sample.
44
-------
SECTION 5
RESULTS AND DISCUSSION
QUALITY CCXra»VQUALTIY ASSURANCE
Soil Sterility Controls
Figures 2 and 3 show microbial counts, including bacteria, actinomycetes,
and fungi, for the Kidman and Jfclaurin soils with and without HgCl2 treatment.
HgCl2 treatment was effective in reducing the microbial population in both
soils to less than ten organisms per gram of soil. Generally a five log
reduction in the number of bacteria and a two to four log reduction in the
number of soil fungi was achieved using HgCl2.
Extraction Efficiencies
Initial recovery efficiency data are shown in Tables 10-12. Extraction
efficiencies were in general greater than 80 percent. Exceptions include
volatile constituents and aniline, hexachlorocyclopentadiene and 1,2,4-
trichlorobenzene (McLaurin soil only). The later three compounds are
volatile, making solvent extraction difficult.
The addition of HgCl2 did not effect extraction recoveries for most
compounds evaluated (Tables 10-12). The recoveries of phorate, parathion,
methyl-parathion, disulfoton, famphur, and pronamide in the presence of HgCl2
were, however, less than 10 percent. Recovery studies were repeated with
these compounds to determine whether the mercury reacted directly with the
chemical. When the chemicals were added to distilled water samples with and
45
-------
Figure 2. Microblal plate counts for untreated and HgCl treated Kidman soil.
6 -
4 -
10 20
Time (days)
30
Figure 3. Microbial plate counts for untreated and HgCl treated McLaurin soil.
o
vt
en
o
bacterial and actinomycetes colony form-
ing units (cfu) in non-treated soil.
fungal cfu in non-treated soil.
highest possible number of fungal, bact-
erial and actinomycctes cfu in soil treat-
ed v-ich a 2'/. HgCl solution.
46
-------
TABLE 10. EXTRACTION EFFICIENCIES FOR PAHs FRCM MCIAURIN AND KIEMAN SOILS
Soils
Chemical McLaurin
Kidman
% Recovery
Without HqClo
Average* Std. Dev.
With HoClo
Average Std. Dev.
Without HcjClo
Average Std. Dev.
With HctCl2
Average Std. De
Acenaphthylene 77.1 4.6
3-methylchol-
anthrene 84.8 2.7
Naphthalene 87.9 9.4
1-methylnaphthalene 91.2 12.9
Anthracene 95.8 2.0
Fhenantherene 97.1 6.7
Fluoranthene 89.0 3.5
Pyrene 91.4 5.0
Chrysene 94.1 4.4
Benz(a)anthracene 91.2 3.3
7,12-dimsthylbenz
(a)anthracene 81.7 3.3
Benzo(b)
fluoranthene 89.4 3.9
Dibenz(a,h)
anthracene 90.9 3.7
Benzo(a)pyrene 90.1 2.0
Dibenzo(a,i)
pyrene 92.2 1.9
Indeno(a,2,3-cd)
pyrene 91.2 4.0
74.7
86.1
80.8
82.1
91.7
95.3
88.8
91.3
91.2
88.6
87.2
88.3
89.6
91.2
90.3
90.8
3.8
3.7
5.0
4.4
5.5
2.9
2.6
3.8
2.1
2.3
1.4
2.7
3.0
3.7
58.6
98.4
85.5
85.1
85.7
90.7
88.8
83.2
90.0
82.1
77.3
79.0
79.6
81.2
80.2
90.9
4.9
7.8
3.2
4.5
2.6
4.7
0.90
4.5
3.8
3.4
2.1
2.0
2.6
2.3
2.1
1.8
56.1
92.5
79.6
83.5
90.9
93.6
88.9
87.7
92.3
84.2
79.1
80.7
83.2
81.7
79.1
91.9
3.9
2.9
5.0
3.2
1.4
3.0
2.9
4.0
3.9
3.8
1.9
3.8
3.0
2.4
* n = 3
-------
TABLE 11. EXTRACTION EFFICIENCIES FOR PESTICIDES FROM MCIAUREN AND KIDMAN SOILS
CO
Soils
Chemical
McLaurin
Kidman
% Recovery
Without HoClo
Aldrin
Heptachlor
Endosulfan
Toxaphene
Parathion
Methyl -parathion
Phorate
Disulfoton
Dinoseb
Pronamide
Aldicarb
Fainphur
Warfarin
DDT
Lindane
Pentachloronitro-
benzene
* n = 3
+ n = 2
Average*
94.2
88.9
89.1
84.3
100.2
99.9
124.7
90.1
69.1
81.0
Std. Dev.
3.7
10.3
3.8
4.0
1.5
3.0
4.4
5.3
1.8
3.8
With HqClo
Average
71.4+
0+
87.1
0+
93.4
8.5
88.8
131.0+
78.0+
247+
Without
Average
96.0
88.2
84.5
81.5+
79.2
65.1
87.1
98.4
100.3
86.0
100.2
83.6
120.3
114.0
79.9
88.8
HoClo
Std.
1.8
2.6
1.9
2.5
4.1
1.8
2.0
7.8
6.6
1.0
4.0
4.5
20.1
2.1
25.7
With HqClo
Dev. Average Std. D
89. 4+
95. 7+
61. 3+
0+
0+
0+
0+
90.8
0+
104.3
7.5
93.5
162 . 0+
89. 4+
273+
-------
TABLE 12. EXTRACTION EFFTdENCIES FOR THE CHLDRINATED HYDROCARBONS AND MISCELIANEOUS COMPOUNDS
FROM MCLAURIN AND KIDMAN SOILS
VO
Chemical
Soils
McLaurin
Kidman
% Recovery
1,2, 4-trichloro-
benzene
Aniline
Hexachlorocyclo-
pentadiene
1, 1-cichloroethylene
1,1, 1-tr ichloroethane
1,1, 2-trichloroethane
1,1,2, 2-tetrachloro-
ethane
* n = 3
+ n = 2
Without
Average*
40.0
30.3
11.5
19.7#
32. 4#
58. 2#
53.4*
HdClo
Std. Dev.
8.1
6.5
2.78
6.4
3.9
10.4
24.0
With HoClo Without HoClo With HoClo
Average Average Std. Dev. Average
33.1+ 123.0 23.8 123.0+
50.8 20.7 2.2 40.6
23.4+ 15.0 1.80 41.3+
# n = 6
-------
without HgCl2 (no soil was used), and the samples were immediately extracted
and analyzed, recoveries for samples without HgCl2 were 80-90 percent, while
recoveries for samples with HgCl2 were again less than 10 percent. Inter-
mediate breakdown products, determined by GC/MS, for pronamide and fairphur in
the presence of HgCl2 are shown in Figure 4. As indicated in Figure 4, for
the conpound famphur, organophosphates may undergo oxidation in the presence
of mercury to form the oxygen analog of those compounds. It is speculated
that mercury directly catalyzed the breakdown of the reactive side chains of
these pesticides. Mercuric chloride, while providing excellent and continuous
sterilization of soils used in this investigation, is not recommended for use
with conpounds that are chemically reactive based on results obtained for
pronamide and famphur.
Extraction recoveries for DDT, and pentachloronitrobenzene (PCNB) in the
presence of HgCl2 were greatly enhanced, with recoveries in excess of 150
percent. Soil blanks, with and without HgCl2, were analyzed. There was no
significant difference between the soil blanks. The presence of ODD and DDE
in the Kidman soil blank indicated previous agricultural use of the soil, even
though the soil had been left fallow for the last 10 years. The actual
concentrations of ODD and DDE were, however, insignificant compared with the
DDT added and would not account for enhanced recovery efficiencies. The high
extraction recoveries of DDT and PCNB in the presence of HgCl2 may be due to
analytical error.
Degradation of PAH Constituents
Cumulative volatilized mass for PAH compounds was calculated after 48
hours of incubation. Data are presented in Table 13 for Kidman fine sandy
loam and MsLaurin sandy loam soils. Volatilization loss of naphthalene and 1-
methylnaphthalene was substantial for both soils. No significant volatiliza-
tion was observed for the other PAH compounds investigated.
50
-------
o
CH-
C—NH—C—C=CH
O
C—N.
/
CH-
Pronamide
CH(CH3)2
-CH(CH3)2
CK ^^ "Cl
N,N-bis(l-methylethyl)dichlorobenzainide
Unidentified, M.W. 240?
Cl
O
5,7-dichloro-2-methylbenzofuran
SO2.N-(CH3)2
O—P—(CH3-0)2
S
Famphur
SO2.N-(CH3)2
O—P—(CH3-0)2
O
Famphur Oxygen Analog
Figure 4. Intermediate breakdown products for pronamide and faqphur
identified from GCyMS results.
51
-------
TABLE 13. VOIATILIZATION OF PAH COMPOUNDS FROM
KEEMAN AND MCLALIRIN SOILS
Percent Volatilized
Compound
Naphthalene
1-Methylnaphthalene
Anthracene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7 , 12-Dimethylbenz (a) anthracene
Benzo (b) f luoranthene
Dibenz (a,h) anthracene
Benzo (a) pyrene
Dibenzo (a , i) pyrene
Indeno ( 1 , 2 , 3-cd) pyrene
Kidman
32.3
14.7
<0.1
<0.1
b.d.a
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
McLaurin
29.2
26.9
<0.1
<0.1
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
aCollected mass below detection.
Volatilization corrected PAH degradation information was obtained by
subtracting the total of cumulative volatilized mass and mass of PAH compounds
remaining in the soil from the mass of compounded added. Volatilization
corrected degradation kinetic results for the PAH conpounds in Kidman and
McLaurin soils are summarized in Tables 14 and 15, respectively. Degradation
kinetics are expressed as first-order reaction rates (k^j and as half-lives
(tj/2) for each soil.
The degradation of two-ring PAH compounds, naphthalene and 1 methyl-
naphthalene, was extensive. Half lives for these PAH compounds were
approximately two days. The degradation of three-ring PAHs, anthracene and
phenanthrene, was also extensive. Anthracene, however, was degraded more
52
-------
slowly than phenanthrene. The extensive degradation of these two- and
three-ring EAH conpounds is not unexpected because these compounds can be
utilized as a sole source of carbon and energy for soil microorganisnis
(Davies and Evans 1964, Dean-Raymond and Bartha 1975, Evans et al. 1965).
The four-, five-, and six-ring PAH cotpounds were somewhat recalcitrant.
It has been demonstrated that natural soil microorganisms can degrade
these PAHs by co-metabolic processes (Sims and Overcash 1983). The
relative stability of these PAH compounds in this study suggests that the
resident microbial distribution in the soils used may not have included
organisms capable of degrading these compounds or a suitable substrate was
not present to stimulate co-metabolic decomposition. 7,12-dimethylben-
z (a) anthracene was extensively degraded with average half-lives of 20 days
and 28 days for Kidman and McLaurin soils respectively.
The results (Tables 14 and 15) generally indicated that PAH
persistence increased with increasing molecular weight or compound ring
number. These results are consistent with the results of other studies
using complex wastes (Sims et al. 1986). However, higher molecular weight
PAH compounds were observed to be more resistant to degradation when
present as pure compounds in soil in this study than when present at the
same concentrations in the same soil in complex waste mixtures (Sims et
al. 1986).
The behavior of PAH oonpounds in Kidman and McLaurin soil samples
poisoned by 2 percent HgCl2 are presented in Table 16. Statistical
analysis of the data indicated that the extent of degradation of two-ring
and three-ring compounds was small but significant at a significance level
of 95 percent (p < 0.05). Since 2 percent HgCl2 effectively suppressed
53
-------
TABLE 14. VOLATILIZATION CORRECTED DEGRADATION KINETIC INFORMATION FOR PAH COMPOUNDS
APPLIED TO KIDMAN SANDY LOAM AT -0.33 BAR SOIL MOISTURE
95% Confidence
Lower Limit
Compound
Naphthalene
1-Methylnaphthalene
Anthracene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7 , 12-Dimethylbenz (a)
anthracene
Benzo(b) fluoranthene
Benzo ( a) pyrene
Dibenz (a , h) anthracene
Dibenzo(a, i) pyrene
Indeno ( 1 , 2 , 3-cd) pyrene
n
12
12
15
12
15
15
15
15
12
15
15
15
15
15
Co
(mg/kg)
101
102
210
902
883
686
100
107
18
39
33
12
11
8
k
•*
(day"1)
-0.3370
-0.4150
-0.0052
-0.0447
-0.0018
-0.0027
-0.0019
-0.0026
-0.0339
-0.0024
-0.0022
-0.0019
-0.0019
-0.0024
tl/2
(days)
2.1
1.7
134
16
377
260
371
261
20
294
309
361
371
288
r2
0.883
0.922
0.829
0.952
0.724
0.708
0.804
0.855
0.944
0.830
0.769
0.726
0.746
0.793
k
^
(day-1)
-0.4190
-0.4960
-0.0065
-0.0514
-0.0025
-0.0036
-0.0024
-0.0033
-0.0394
-0.0030
-0.0029
-0.0026
-0.0025
-0.0031
tl/2
(days)
1.7
1.4
106
13
277
193
289
210
18
231
239
267
277
224
Interval
Upper T.imit
k
1
(day'1)
-0.2550
-0.3350
-0.0038
-0.0380
-0.0012
-0.0017
-0.0013
-0.0020
-0.0284
-0.0018
-0.0015
-0.0013
-0.0013
-0.0017
tl/2
(days)
2.7
2.1
182
18
578
408
533
347
24
385
462
533
533
408
-------
TABLE 15. VOIATILIZATION CORRECTED DEGRADATION KINETIC INFORMATION FOR PAH
COMPOUNDS APPLIED TO MCLAURIN SANDY LOAM AT -0.33 BAR SOIL MOISTURE
95% Confidence Interval
Compound
Naphthalene
1-Methylnaphthalene
Anthracene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7 , 12-Dimethylbenz (a)
anthracene
Benzo(b) fluoranthene
Benzo (a) pyrene
Dibenz (a, h) anthracene
Dibenzo (a , i) pyrene
Indeno ( 1 , 2 , 3-cd) pyrene
n
12
12
15
12
15
15
15
15
12
15
15
15
15
15
Co
(mg/kg)
101
106
199
893
913
697
105
99
13
37
33
14
12
9
k
(day"1)
-0.3080
-0.3210
-0.0138
-0.0196
-0.0026
-0.0035
-0.0018
-0.0043
-0.0252
-0.0033
-0.0030
-0.0017
-0.0030
-0.0024
t1/2
(days)
2.2
2.2
50
35
268
199
387
162
28
211
229
420
232
289
r2
0.786
0.809
0.932
0.808
0.575
0.609
0.610
0.878
0.502
0.885
0.857
0.568
0.838
0.841
Lower
k
(day'1)
-0.4150
-0.4240
-0.0164
-0.0259
-0.0040
-0.0053
-0.0027
-0.0053
-0.0335
-0.0041
-0.0039
-0.0026
-0.0039
-0.0031
T.imit
tl/2
(days)
1.7
1.6
42
27
173
131
257
131
21
169
178
267
178
224
Upper T.imit
k
1
(day'1)
-0.2020
-0.2170
-0.0113
-0.0132
-0.0011
-0.0017
-0.0008
-0.0032
-0.0169
-0.0025
-0.0022
-0.0007
-0.0021
-0.0017
t1/2
(days)
3.4
3.2
61
53
630
408
866
217
41
277
315
990
330
408
-------
biological activity in the soil samples, these losses may be attributed to
abiotic degradation. No significant degradation in poisoned soil was
found for the other PAH compounds evaluated.
Generally, the degradation rates of PAH coitpounds in Kidman soils
were not significantly different from those in Mclaurin soils (p < 0.05).
Two PAHs, acenaphthylene and 3-meth.ylcholanthrene, were included in
the long-term degradation study but not in the short-term volatilization
study. Apparent loss kinetics for these two compounds in Kidman and
McLaurin soils are summarized in Table 17. The apparent loss of
acenaphthylene was extensive.
There were no statistically significant differences in half-life
values (Table 18) for acenaphthylene for HgCl2 treated and untreated
McLaurin soil. The similarities in tj/2/ with and without poisoning, may
indicate that the presence of soil microbes did not influence the rate of
loss of acenaphthylene from this unacclimated soil. Although the ti/2
value for the poisoned Kidman soil (Table 18) was significantly different
from the untreated soil, indicating some suppression of biodegradation,
the addition of HgCl2 to this soil did not greatly decrease the loss of
acenaphthylene. At the end of the 65 day study, 96 percent of the
chemical added was lost from the treated Kidman soil. Assuming
acenaphthylene would behave similarly to naphthalene, abiotic loss should
be relatively small. The extensive loss of acenaphthylene, even with the
addition of HgCl2/ is likely due to volatilization. The Henry's law
coefficient for acenaphthylene falls within the range 10<~5
-------
TABLE 16. DEGRADATION OF PAH COMPOUNDS IN KIDMAN AND
McIAUKEN SOUS POISONED BY 2 PERCENT HgCl2
Conpound
Naphthalene
1-Methylnaphthalene
Anthracene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz (a) anthracene
7 , 12-Dimethylbenz (a) anthracene
Benzo(b) fluoranthene
Dibenz (a , h) anthracene
Benzo (a) pyrene
Dibenzo ( a , i ) pyrene
Indeno ( 1 , 2 , 3-cd) pyrene
Percent
Kidman
12.0s
12. 3a
8.7a
17. 4a
0
4.4
5.9
2.5
13.3
8.0
13.8
7.3
10.3
13.5
deoraded
McLaurin
14. la
1.8a
7.9a
14. 2a
3.1
5.5
3.2
1.6
12.0
8.0
6.4
8.3
9.3
11.5
Statistically significant (p < 0.05).
Negligible loss of 3-methylcholanthrene (3-MC) in the poisoned Kidman
soil was observed, as the slope of the regression line was statistically
equivalent to zero, indicated that biodegradation is the primary mechanism
accomplishing destruction of this ccnpound. As with 7,12-DMBA, 3-MC was
less recalcitrant in Kidman soil than would be expected based upon
molecular weight (high) and ring structure (large). However, the loss of
3-MC from McLaurin soil (HgCl2 treated and untreated) was minimal over the
65 day study. The half-lives are extrapolations and serve to demonstrate
the degree to which this oompound tended to persist in soil. As with
other large PAH conpounds, volatile and abiotic loss of 3-MC are
insignificant.
First-order plots of the data for loss of 3-MC from Kidman sandy loam
soil in the absence and presence of HgCl2 in Figures 5 and 6,
57
-------
First order kinetic plots of the apparent loss of 3-methyl-
cholanthrene from Kidman soil.
o
O
O -
.05^
0'
-.05^
-.15-
-.2-
-.*:;>•
-.3-
-.4.
-.45.
-.5.
-.55.
- 6.
-1
1
— — ^— ^—
0 (
•-..._
| . S^.».m<..» - . .. —~.~.jf.*.J*
1
1 .......
) 10 20 30 40 50 60 7
Days
Figure 6. First order kinetic plots of the apparent loss of 3-methyl-
cholanthrene from Kidman soil sterilized with
58
-------
TABLE 17. APPARENT LOSS KINETIC DEFORMATION FOR PAH'S FROM KIDMAN AND MCLAURIN SOILS
95% Confidence Interval
lower limit Upper limit
Chemical
Kidman Soil
.Acenaphthylene
3-methyldiolanthrene
McLauren Soil
Acenaphthylene
3-roethvlcholanthrne
n Co
(mg/Rj)
17 56.8
17 31.7
17 74.7
17 27.3
(day-1)
-0.134
-0.0078
-0.039
-0.0044
(d*M (day'1) (days)
5 0.876 -0.185 4
89 0.960 -0.0087 80
18 0.708 -0.053 13
158 0.660 -0.0061 114
k
(day'1)
-0.084
-0.0069
-0.025
-0.0027
(days)
8
100
28
257
VO
-------
TABLE 18. APPARENT LOSS HALF-LIFE (t1//2) OF ACENAPHTHYLENE AND 3-MEmiYLCHOIANTHRENE FROM KIDMAN
AND MCLAURIN SOILS WITH AND WITHOUT ADDITION OF HgCl2
Compound Average
Acenaphthylene
3-methylchol-
anthrene
Kidman (^2/2)
(days)
Without HoClo
95%
Confidence Average
Interval
5 4-8 17
89 80-100 b
With HdClo
95%
Confidence
Interval
12-32
Without HctClo
95%
Average Confidence
Interval
18a 13-28
158a 114-257
McLaurin (ti/2)
(days)
With HdCl->
95%
Average Confidence
Interval
22a 15-41
238a 133-1216
aSlopes of the two lines for the same chemical (i.e., with and without HgCl2) are not statistically different at
95% confidence level.
not statistically different from zero (p<0.05).
-------
respectively. Standard deviations of triplicate samples for each point
are indicated on each figure by brackets. Also, the dotted lines indicate
the 95 percent confidence intervals about the slope of the line. First
order plots of results similar to those shown in Figures 5 and 6 were
generated for each chemical evaluated in this study.
Degradation of Pesticides
Toxaphene waste residue exhibited no measurable degradation after 150
days of incubation at an initial soil concentration of 20 mg/kg. The
major mechanism for the degradation of toxaphene in soils occurs by
reductive dechlorination (Parr and Smith 1976, Short 1986, Smith and
Willis 1978). Fresh manure was applied to the soil waste mixture (2
percent manure, dry weight basis) to lower the redox potential of the
soil. Application of manure was not effective in stimulating degradation
of the toxaphene residue after the same period of incubation. Toxaphene
would be classified as persistent in soil (Rao and Davidson 1981).
Degradation information for pesticides obtained in laboratory treat-
ability studies using the Kidman and MzLaurin soils is presented in Tables
19 and 20, respectively. Information obtained in the study included the
initial soil concentration, degradation rate constant and constituent
half-life based on a first-order kinetic rate model, and the coefficient
of determination (r-squared value) for each constituent. The 95 percent
confidence limits for the degradation rate constant and half-life value
were also determined.
First order plots for heptachlor in Kidman sandy loam and MiLaurin
sandy loam soils are shown in Figures 7 and 8, respectively. Standard
deviations of triplicate samples for each point are indicated in each
61
-------
80 100 120 140 160
-2
-20
Figure 7. First order kinetic plots of the apparent loss of heptachlor from
Kidman soil.
o
O
O
"c"
-20 0 20 40 60 80 100 120 140 160
-2.5
Figure 8. First order kinetic plots of the apparent loss of heptachlor from
McLaurin soi 1 .
62
-------
figure by brackets. Hie dotted lines indicate the 95 percent confidence
intervals about the slope of the line.
Very little information was available in the literature on
degradation kinetics for warfarin, fairphur, pronamide and dinoseb.
Results of the degradation study for the other pesticides presented in
Tables 19 and 20, are in agreement with published half-life values (t±/2)
for laboratory degradation studies conducted by other investigators (Rao
and Davidson 1981). The tj/2 values generated in the present study for
lindane and DDT on the Kidman soil, however, were much shorter. Rao and
Davidson (1981) reported values of 266 days for lindane and 1657 days for
DDT, however, confidence intervals were not given. The pesticides
investigated in this study exhibited half-life values between 17 and 385
days, and therefore would be classified as moderately persistent to
persistent in soil (Rao and Davidson 1981).
The microbiological degradation of chlorinated pesticides has been
reported to follow first-order kinetics (Hiltbold 1974, Nash and Wbolson
1968). The first-order fit of the data generated in this study for many
of the chlorinated pesticides was not as good as would be expected if the
apparent loss truly followed first order kinetics. In many cases the plot
of In C/Co vs t displayed a curvelinear relationship. Other kinetic
models should be investigated. Because multiple reactions, including
volatilization, biodegradation, and abiotic degradation, are occurring
simultaneously, the application of simple zero, first and second order
kinetic equations may not adequately describe this system.
The degradation of organophosphorus pesticides could not be clearly
characterized using a first-order reaction kinetic model. Use of first
63
-------
order kinetics overestimated half-lives for these pesticides. Saltzman et
al. (1974) described the surface-catalyzed chemical degradation kinetics
of parathion as two first-order reactions. Various mathematical
expressions have been used to describe the degradation kinetics of the
organophosphorus insecticides (Edwards 1972), including the approach of
Saltzman et al. (1974) using multiple first order kinetic equations.
No loss of warfarin was observed in the Kidman soil. Negligible loss of
warfarin and DDT in the McLaurin soil was indicated since the slope of the
curves were statistically equivalent to zero. There was, however, an initial
decrease in warfarin concentration in the Mclaurin soil over the first five
days of the study, after which no degradation occurred. Doss of aldicarb from
Kidman soil was minimal over the 85 day study. The estimated half-live for
aldicarb was obtained using an extrapolation method and serves only to
indicate the persistence of this compound in Kidman soil.
The addition of HgCl2 caused complete and immediate breakdown of the
organophosphate pesticides including famphur and pronamide, as was evident
from the extraction efficiency study, where less than 10 percent of the added
pesticide was recovered at time zero. It appears that the presence of mercury
catalyzed the breakdown of reactive side chains of these chemicals as
discussed previously. Mercuric chloride, while providing excellent and
continuous sterilization of soils, is not a useful soil sterilent for these
chemically reactive compounds.
64
-------
TABLE 19. APPARENT LOSS KINETIC INFORMATION FOR PESTICIDES FROM KIDMAN SOIL
95% Confidence Interval
Lower limit Upper limit
Pesticide
Pentachloronitrobenzene
Disulfoton
Methylparathion
Phorate
Parathion
Endosulfan
Aldrin
Famphur
Heptachlor
EOT
Lindane
Pronamide
Dinoseb
Aldicarb
Warfarin
n
18
18
18
17
18
18
18
22
18
18
15
17
17
22
22
Co
(rag/Kg)
0.300
1.56
1.04
1.42
1.45
0.580
0.429
82.7
0.588
0.574
0.394
85.3
103.1
99.1
117.8
k
(day'1)
-0.0398
-0.036
-0.025
-0.022
-0.017
-0.016
-0.013
-0.013
-0.012
-0.015
-0.0113
-0.0072
-0.0067
-0.0018
0.0024a
tl/2
(days)
17
19
28
32
41
43
53
53
58
60
61
96
103
385
r2
0.925
0.589
0.472
0.435
0.690
0.854
0.889
0.860
0.908
0.524
0.384
0.876
0.890
0.435
0.520
k
(day-1)
-0.046
-0.052
-0.039
-0.036
-0.023
-0.02
-0.016
-0.015
-0.014
-0.0173
-0.0199
-0.0086
-0.008
-0.0027
tl/2
(days)
15
13
18
19
30
35
43
46
50
40
35
81
87
257
k
(day-1)
-0.034
-0.02
-0.011
-0.0082
-0.011
-0.013
-0.011
-0.01
-0.010
-0.0057
-0.0027
-0.0057
-0.0054
-0.0008
tl/2
(days)
21
35
63
85
63
53
63
69
70
122
257
122
128
845
aSlope (k) of first order regression line is not significantly different from zero, no degradation observed.
-------
TABLE 20. APPARENT LOSS KINETIC INPORMATICK FOR PESTICIDES ERCM MdAURIN SOIL
95% Confidence Interval
Lower limit
Pesticide
Phorate
35
Aldicarb
Pentachloronitrobenzene
Liindane
Heptachlor
Fainphur
Dinoseb
Pronamide
COT
Warfarin
n
15
24
18
15
18
24
17
17
18
24
Co
(rag/Kg)
1.47
99.1
0.274
0.340
0.628
98.9
91.5
83.6
0.452
122.1
k
(day-1)
-0.029
-0.023
-0.0137
-0.0106
-0.011
-0.010
-0.0075
-0.0074
-0.0025
-0.0007
(days)
24
30
51
65
G3
69
92
94
a
a
0.812
0.921
0.737
0.436
0.933
0.736
0.827
0.678
0.184
0.012
k
(day'1)
-0.037
-0.026
-0.0181
-0.0178
-0.012
-0.012
-0.0094
-0.01
(days)
19
27
38
39
50
58
74
69
Upper limit
k
(day'1)
-0.02
-0.02
-0.0094
-0.0034
-0.0091
-0.0071
-0.0056
-0.0046
tl/2
(days)
35
74
204
76
98
124
151
aSlope (k) not statistically different from zero (p<0.05), no degradation observed.
-------
In Table 21 the t-i/2 values for aldicarb, warfarin, lindane, and
dinoseb in Kidman and Mclaurin soils with and without the addition of8
HgCl2 are presented. Figures 9 and 10 show first order plots for the loss
of dinoseb from McLauren soil in the absence and presence of HgCl2,
respectively. Unlike PAH compound behavior, loss of these pesticides
occurred in the presence of the sterilent.
Ihere was no significant difference in t]/2 values with and without
the addition of HgCl2 for the pesticide dinoseb in McTaurin soil and the
pesticide lindane in both soils. This may indicate that the loss
mechanisms for these compounds in the treated and untreated soil were the
same, including abiotic degradation and/or volatilization.
The major mechanism for breakdown of chlorinated pesticides and
dinoseb reported in the literature is microbial degradation (Kaufman
1974). In the unacclimated soils used in this study, however, microbial
degradation may be limited. Mechanisms for abiotic loss of these
compounds have not been extensively studied. Volatilization of
chlorinated pesticides, however, has been observed in field and laboratory
studies (Glotfelty et al. 1984; Harris and Lichtenstein 1961; Geobel et
al. 1982), and may be the major loss mechanism of these pesticides in this
study. The addition of HgCl2 to dinoseb in the Kidman soil did affect the
reaction kinetics significantly (Table 21) indicating that microbial
degradation may have been a loss mechanism in this soil.
The loss of aldicarb in both soils and warfarin in Mclaurin soil was
accelerated by the addition of HgCl2 (Table 21). Warfarin did not degrade
(slope not statistically different from zero) in the McLaurin soil over
the 88 day study. With the addition of HgCl2, 72 percent of the warfarin
was lost in this time period from McTaurin soil. The effect of HgCl2 on
67
-------
o
O
O
-1
-10
Figure 9. First order kinetic plots of the apparent loss of dinoseb from
McLauren soil.
o
O
O
-1
-10
Figure 10.
First order kinetic plots of the apparent loss of dinoseb from
McLaurin soil sterilized with HgCl2.
68
-------
TABLE 21. APPARENT LOSS HALF-ULFE (t^) P01* PESTICIDES FROM KIDMAN ANDMC1AURIN SOILS
WITH AND WITHOUT ADDITION OF HgCl2
Kidman soil (t^/2)
(days)
Without HqCl
With HoCl
Without HqClo
MsLaurin soil
(days)
With HqCl"
Compound
Aldicarb
Warfarin
Londane
Dinoseb
Average
385
c
61a
103
95%
Confidence
Interval
257-845
35-257
87-128
Average
58
b
37a
248
95%
Confidence
Interval
36-141
27-60
154-630
Average
30
65a
92a
95%
Confidence
Interval
27-35
39-204
74-124
Average
21
43
42a
122a
95%
Confidence
Interval
17-29
32-69
27-91
80-257
of the two lines are not statistically different at 95% confidence level.
not statistically different from zero (p<0.05), indicating that treatment was not observed.
of first order regression line is positive, indicating that treatment was not observed.
-------
aldicarb was significant but not as dramatic in the McLaurin soil. In the
Kidman soil the half-life decreased from 385 days to 58 days with the
addition of HgCl2- Similar to the organophosphate pesticides, aldicarb
and warfarin contain reactive side chains. Mercury in HgCl2 may be acting
as a catalyst, accelerating the chemical breakdown of these compounds.
The slope of the line for warfarin in the treated Kidman soil was not
statistically significant (p<0.05).
Chlorinated Hydrocarbons and Aniline
Table 22 and 23 list the apparent loss rate constants and constituent
half-lives based on a first order kinetic model for chlorinated
hydrocarbons and aniline. Apparent compound loss rates for the highly
volatile chlorinated hydrocarbons in the McLaurin soil were determined
from methanol extracts of soils from the volatilization flasks obtained at
various time intervals during the volatilization studeis, accounting for
compound recovery efficiency from soil. Recovery efficiencies for 1,2,4-
trichlorobenzene from McLaurin soil and hexachlorocyclopentidiene from
both soils were poor (Table 23). All three compounds showed rapid
disappearance from Kidman soil, and slower disappearance from the McLaurin
soil.
First-order plots of the disappearance of 1,2,4-trichlorobenzene from
McLaurin sandy loam soil in the absence and presence of HgCl2 are shown in
Figures 11 and 12 respectively.
The addition of HgCl2 to either soil had no significant effect on the
reaction kinetics of 1,2,4-trichlorobenzene, hexachlorocyclopentadiene, or
1,1,2-trichloroethane (Table 24). Similar t^/2 values indicate
nonbiologicalloss of these compounds primarily through volatilization.
70
-------
First order kinetic plots of the apparent loss of 1,2,4 tri-
chlorobenzene from McLaurin soil.
First order kinetic plots of the apparent loss of 1,2,4 tri-
chlorobenzene from McLaurin soil sterilized with HgCl2.
71
-------
Ihe slopes of the curves for aniline in the HgCl2 treated Kidman and
McLaurin soils were not statistically different from zero (p=0.05).
Volatilization corrected degradation rates were determined for the
six most volatile chlorinated hydrocarbons in the McLaurin soil over a 50
hour incubation period. Volatilization corrected degradation rates were
determined from the loss of mass of parent compound attributed to
degradation, as described in the Methods and Procedures, by subtracting
the mass of compound collected on the Tenax sorbent tubes from the
observed loss of compound in the soil between sampling intervals.
Volatilization, as measured by cumulative mass of compound collected on
Tenax over the course of the experiments, was a significant loss mechanism
for all compounds studied, ranging from 17 percent for 1,1,2,2-
Tetrachloroethane, to over 76 percent for 1,1,2-Trichloroethane (Table
25). Volatilization corrected degradation results are presented in Table
26 and a comparison of corrected and uncorrected data are summarized in
Table 27 for the McLaurin soil.
A rapid reduction in soil concentration was observed for all
compounds investigated in both the poisoned and unpoisoned soil
experiments. All first order apparent loss rate relationships were
significant at an p=0.05, with apparent loss mean half life values ranging
from 0.07 to 0.6 days for the volatile chlorinated hydrocarbons tested.
The magnitude of the observed apparent loss rates followed the order of
compound vapor pressure. This result would be predicted if volatilization
was the primary loss mechanism from soil systems. Apparent loss rate
values from low to high followed the order: Aniline = 1,2,4-
Trichlorobenzene < Hexachlorocyclopentadiene < Chloromethylmethyl ether =
72
-------
Aniline
1,2,4-trichloro-
benzene
TABLE 22. APPARENT LOSS KINETICS USING FIRST ORDER KINETICS MODEL FOR CHLORINATED
HYDROCARBONS AND ANILINE IN KIDMAN SOIL WITHOUT ADDITION OF HgCl2
95% Confidence Interval
lower limit Uooer limit
Compound
Co k
n (mg/Kg) (day"1)
ti/2 r
(days)
2 k
(day-1)
ti/2
(days)
k
(day"1)
(days)
22
18
Hexachlorocyclopenta-
diene 15
20.7 -0.072
0.904 -0.093
0.051 -0.256
10 0.882 -0.086
7 0.692 -0.126
3 0.709 -0.355
-0.057
-0.060
-0.158
12
12
-------
TABLE 23. APPARENT LOSS KINETICS USING FIRST ORDER KINETICS MODEL FOR CHLORINATED
HYDROCARBONS AND ANILINE LN MCLAURIN SOIL WITHOUT ADDITION OF HgCl2
Compound
Aniline
1,2,4 -tr ichloro-
benzene
Hexachlorocyclopenta-
diene
1, 1-Dichloroethylene
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
1,1,2, 2-Tetrchloroetnane
n
24
18
15
5
6
7
7
Co
(ing/Kg)
23.0
0.292
0.038
156.6
155.2
155
157
k
(day"1)
-0.025
-0.040
-0.173
-10.49
-4.56
-1.70
-1.82
tl/2
(days)
28
17
4
0.07
0.15
0.41
0.38
r2
0.521
0.623
0.725
0.994
0.928
0.875
0.943
95% Confidence Interval
Lower limit Upoer limit
k
(day'1)
-0.036
-0.057
-0.237
-11.98
-6.34
-2.45
-2.33
fcl/2
(days)
19
12
3
0.06
0.11
0.28
0.30
k
(day'1)
-0.015
-0.024
-0.109
-9
-2.78
-0.96
-1.30
tl/2
(days)
46
29
6
0.08
0.25
0.72
0.53
-------
TABLE 24. APPARENT IDSS HALF-LIFE (t^) F0**- 1,2,4-TRECHLDRDGENZENE, HEXACHIDRCEYC^PENTADIENE
AND ANAUNE IN KIDMAN AND MCLAURIN SOILS WITH AND WITHOUT ADDITION OF HgCl2
Kidman
(days)
Without HqCU With HoCl-
Compound
Interval
95%
Average Confidence
Interval
95%
Average Conf dence
Interval
Without HaCl2
95%
Average Confidence
Interval
McLaurin (ti/2)
(days)
With HoCl2
95%
Average Confidence
Aniline
10
1,2,4-trichloro-
benzene 7
Hexachlorocyclo-
pentadiene 3
1,1-Dichloroethylene
1,1,1-Tr ichloroethane
1,1,2,2-Tetra-
chloroethane
Chlororoethyl-
methyl ether
1,1,2 -Tr ichloroethane
l,2-Dibroino-3-
chloropropane
8-12
6-12
2-4
6-15
2-18
28
17
4
0.07
0.15
0.38
0.41
19-46 a
12-29 16 10-39
3-6 4 3-8
0.06-0.08
0.11-0.25
0.30-0.53
0.25 0.17-0.54
0.28-0.72 0.32 0.23-0.53
0.60- 0.40-1.26
ano statistical significance of slope (p<0.05).
-------
TABLE 25. VOLATILIZATION OF CHLORINATED HYDROCARBONS FROM MCLAURIN SOIL
Percent Volatilized
Coirpound No HgCl2 With HgCl2
1,1,Dichloroethylene 16.9
1,1,1-Trichloroethane 64.6
l,l,2-JTrichloroethane 60.8 76.4
1,1,2,2-Tetrachloroethane 36.8
Chloronethylmethyl ether - 60.1
l,2,DibromO-3-chloropropane - 63.5
-------
TABLE 26. VOLATILIZATION CORRECTED DEGRADATION KINETIC INFORMATION FOR CHLORINATED
COMPOUNDS APPLIED TO MCIAURIN SANDY LOAM AT -0.33 BAR COIL MOISTURE CONTENT.
Compound n
Degradation Data Corrected
1,1, Dichloroethylene 4
1,1, 1-Trichloroethane 4
1,1, 2-Trichloroethane 6
1,1,2,2-Tetrchloroethane 6
Degradation Data Corrected
Chloromethyltnethyl ether 5
1,1, 2-Trichloroethane 5
1 , 2-Dibromo-3-chloro-
propane 6
Co
(ng/Kg)
k
(day'1)
tl/2
(days)
95% Confidence Interval
Lower limit Upper limit
r* k t1/2 k tV2
(day'1) (days) (day-1) (days)
for Volatilization, Unpoisoned Soil
156.0
155.2
155
147
-16.34
-9.60
-30.55
-53.42
for Volatilization, HqCl
123.6
155
144.9
-55.68
-63.48
-70.34
0.04
0.07
0.02
0.01
Poisoned
0.01
0.02
0.01
0.788 -42.14 0.02
0.936 -17.21 0.04 1.97 0.35
0.599 -65.28 0.01
0.588 -115.54 0.01
Soil
0.558 -146.69 0.00
0.536 -172.10 0.00
0.516 -164.05 0.00
Degradation rate not statistically different from zero
-------
TABLE 27. COMPARISON OF VOLATILIZATION CORRECTED AND UNCORRECTED DEGRADATION KINETIC DATA
FOR CHLORINATED HYDROCARBONS IN MCLAURIN SOIL.
Compound
1 , 1-Dichloroethylene
1,1, l-Trichloroethane
1,1,2, 2-Tetrachloroethane
Chloromethylmethyl ether
1,1, 2-Trichloroethane
1 , 2-Dibromo-3-chloropropane
McLaurin (t]/2>
Volatilization Corrected
Average
0.04
0.07
0.01
0.01
0.02
0.01
95% Confidence
NED3
0.04-0.35
NSD3
NSD3
NSD3
NSD3
Volatilization
Average
0.07
0.15
0.38
0.25
0.32
0.60
Uncorrected
95% Confidence
0.06-0.08
0.11-0.25
0.30-0.53
0.17-0.54
0.23-0.53
0.40-1.26
ano statistical difference in degradation
-------
1,1,2,2-Tetrachloroethane = 1,1,2-Trichloroethane = l,2-Dibromo-3-
chloropropane = 1,1,1-^Irichloroethane < 1,1/Dichloroethylene. Based on
results shown in Tables 26 and 27 for the unpoisoned Mclaurin soil,
observed loss of all constituents except 1,1,1-Trichloroethane could not
be attributed statistically to biodegradation. Only 1,1,1-
Trichloroethane exhibited a volatilization corrected degradation rate that
was significantly greater than zero at p=0.05. The corrected degradation
rate constant in McLaurin soil of 9.60 + 7.63 d"1, corresponding to a mean
corrected half life of 0.07 days for 1,1,1-Trichloroethane (range 0.04 to
0.35 days), was not significantly different (p=0.05) from the uncorrected
rate value.
Abiotic degradation studies conducted for the volatile chlorinated
hydrocarbons confirmed the significance of volatilization as a loss
mechanism for this class of compounds. All abiotic, uncorrected loss
rates were significantly greater than zero, while all volatilization
corrected rates were not different from zero at p=0.05. There was no
significant difference (p=0.05) between sterilized and unsterilized
apparent loss rates for 1,1,2-Trichloroethane. In addition, total 1,1,2-
Trichloroethane mass emitted (Table 25) indicated only a 20 percent
increase in volatilization in sterilized soil suggesting that loss from
McLaurin soil is not significantly affected by soil biological activity.
PARTITION COEFFICIENTS FOR SUBSTANCES IN SOIL
SAR-derived partition coefficients for both experimental soils for
the chemicals in the four classes evaluated are summarized in Tables 28-
31. Values for aqueous-soil (%), aqueous-oil (KQ) , and aqueous-air (%)
partition coefficients are presented in Tables 28-30. As expected, PAH
and pesticide compound exhibited high KQ and K^ values, while
the volatile class compounds showed high K^ values. Partition
79
-------
coefficients estimated using SARs were in good agreement with literature
values for coefficients for the conpounds addressed. Values for aqueous-
soil (Kd) partition coefficients based on first order molecular
connectivity index (MCI) calcuations are presented in Table 31.
Apparent Loss of Tetraalkyllead (TAL)
Tetraalkyllead (TAL) mixture typically consists of tetraethyllead
(TEL), tetramethyllead (TML), triethylmethyllead (TEML), and
trimethylethyllead (TMEL). GC/MS analysis indicated that the sample used
contained TEL, TEML, and a triethyllead alcohol.
The degradation of TAL is thought to follow the reaction sequence
shown below:
F^Pb— >R3pb+—>RaFb24"—>Eb2+ (1)
where R - Me, Et or Me-Et combination. Tetraalkyllead degrades into
alkyllead salts and inorganic lead.
All species of lead likely to be present in this study are adsorbed
by organic matter, silica, road dust, sediments, and/or soils (Harrison
and Laxan 1978, Jarvie et al. 1981, van Cleavenberger 1986, Blais and
Marshall 1986). Sorption of TAL by road dust and atmospheric particles is
usually followed by rapid decomposition to trialkyllead salts (Harrison
and Laxan 1978, Jarvie et al. 1981).
Lead in soil extracts and in air samples (volatilized lead) for this
study were determined using an atomic adsorption spectrophotometer (AAS).
AAS analysis for total lead in solution cannot be used to distinguish lead
species present in soil or air fractions. Volatilization of lead was
80
-------
TABIE 28. CAIOJIAIED SOU/WATER (Fd) , OII/WMER (Kb), AND AHyWAIER (Kh)
PARTITION COEFFICIENTS
Compound
Acenaphthylene
Benz (a) anthracene
Benzo (a) pyrene
Chrysene
Dibenzo ( a , h) anthracene
Ideno ( 1 , 2 , 3 -cd) pyrene
3-Methylcholanthrene
Fluoranthene
1-Methylnapthalene
Naphthalene
Phenanthrene
Pyrene
Benzo (b) fluoranthene
7 , 12-Dimethylbenz (a) anthracene
Anthracene
leg Kd
(McLaurin)
1.72
3.24
3.67
3.24
3.6O
5.27
4.73
2.97
1.52
1.01
2.11
2.96
4.19
3.61
2.10
FOR 16 PAH
log Kd
(Kidman)
1.38
2.90
3.33
2.90
3.26
4.93
4.38
2.62
1.18
0.67
1.76
2.61
3.86
3.27
1.75
COMPOUNDS.
log Kb
4.23
5.95
6.43
5.95
6.35
8.24
7.63
5.64
4.00
3.42
4.66
5.63
7.02
6.36
4.65
log Kh
-1.22
-5.36
-2.75
-2.41
-5.52
-7.62
-
-3.60
-
-1.97
-2.30
-4.27
-2.91
-
-1.59
Benz (c) acridine
81
-------
TABLE 29. CALCULATED SOLI/WATER (Kd) , OIL/WATER (Ko) , AIR/WATER (Kh)
PARTITION COEFFICIENTS FOR 22
Qarpound
Aldrin
Cacodylic Acid
Chlordane, technical
DDT
Dieldrin
Dinoseb
Disulfoton
Endosulfan
Famphur
Heptachlor
Alpha Ldndane
Methyl parathion
Parathion
Phorate
log Kd
(McLaurin)
0.65
-2.31
0.44
1.14
0.56
-
-2.31
1.21
-
1.55
1.46
0.65
1.06
0.58
log Kd
(Kidman)
0.31
-2.65
0.10
0.79
0.22
-
-2.65
0.86
-
1.21
1.12
0.31
0.72
0.24
PESTICIDES.
log Ko
0.62
-0.32
2.79
3.57
2.92
2.25
-0.32
3.65
-
4.04
3.94
3.02
3.48
2.94
Log Kh
-1.93
-
-2.40
-2.44
-4.69
-
-4.13
-2.44
-
-0.97
-4.47
-5.56
-4.04
-3.40
Pronamide
Toxaphene 0.96
Warfarin 0.19
Aldicarb -1.61
Pentachloronitrobenzene
Diethyl-p-nitrophenyl phosphate -
Floracetic acid
Formaldehyde
0.62
-0.15
-1.95
3.37
2.49
0.46
-5.13
-6.59
82
-------
TABLE 30. CALCUIATED SOII/WATER (Kd), OII/WATER (Kb), AND AnyWATER (Kh)
PARTITION OOEFFTCG05NIS FOR 13 CHLORINATED Hm»CARBONS.
Compound log Kd log Kd
(Mzlaurin) (Kidman) log Kb log Kh
Bis-(chloranethyl) ether -2.68 -3.02 -0.75
Chloromethyl methyl ether -1.41 -1.75 0.69
1,2-Dibromo-3-chloropropane
DichlorodifliiorcBnethane -0.17 -0.51 2.09 2.01
1,1-Dichloroethylene
1,1,1-Trichloroethane 0.13 0.47 2.14 -0.79
1,1,2,2-Tetrachloroethane 2.63 2.29 5.26 -1.81
1,1,2-Trichloroethane -0.16 -0.50 2.10 -1.51
1,2,2-Trichlorotrifltioroethane -0.66 -1.01 1.53
TricMorortonofluoroethane - -
Hexachlorocycopentadiene 2.68 2.34 5.31 -1.37
4,4-Methylene-bis-
(2-chloroaniline) 0.96 0.62 3.37
1,2,4-Trichlorobenzene 1.63 1.29 4.13 -0.77
83
-------
TABLE 31. IDG Kd VALUES ESTIMATED USING FIRST ORDER MCIS.
Compound
I'NAs
Acenaphthylene
Bcnz(a)anthraccnc
Ben/.o(a)pyrcne
Ctirysene
Dihen/.o(a,li)anlhracenc
Indeno(l,2,3-cd)pyrcnc
3-Metliylcholantlirune
Fluoraiuhene
1-methylnaplithalenc
Naphthalene
Phenanthrenc
Pyre nc
Ben/.o(b)fluoranthenc
7,12-dimethylbenzanthracene
anthracene
Benz(c)acndmc
Pesticides
Aldrin
Cacodylic Acid
Chlordane
ror
Dicldrm
Dmoseb (2,4 dmitro-6-scc-butylphenol)
Disulfoton
Endosulfan
Famphur
Heptachlor
Lindane (hexachlorocyclohexane) tech
alpha
Methyl parathion
Parathion
Phorale
Pronamide
Toxaphene
Warfarin
Aldicarb
pentachloronitrobenzcne
Diethyl-p-mtrophcnyl phosphate
Floracetic acid
Formaldehyde
Chlorinated Hydrocarbons
Bis-(chloromethyl) ether
Chloromethyl methyl ether
1 ,2-Dibromo-3-chloropropane
Dichlorodifluoromethane
1 , 1 -Dichloroethylene
1,1,1 -Trichloroethane
1 , 1 ,2,2-Tetrachloroethane
1 , 1 ,2-Trichloroethane
1 , 1 ,2-Trichlorotrifluoroe thane
Trichloromonofluoroethane
Hexachlorocycopentadiene
4,4-Methylene-bis-(2-chloroaniline)
1 ,2,4-trichloroben/.enc
Misc. Compounds
Aniline
Mitomycin C
Pyridme
Tctraelhyl Lead
Uracil mustard
MCI*
5.949
8.916
9.916
8.933
10.865
10.916
10.327
7.949
5.377
4.966
6.949
7.933
9.933
9.771
6.933
8.899
9.254
2.000
8.114
8.876
9.714
7.879
6.682
7.942
8.987
7.703
5.464
5.464
7.504
8.504
6.182
6.777
8.225
11.075
5.621
6.375
8.504
2.808
1.000
2.414
1.914
2.808
2.000
1.732
2.000
2.643
2.270
3.250
2.561
4.887
8.059
4.198
3.394
10.913
3.000
4.243
6.774
log Koc* log Kd
(McLaurin)
3.69
5.27
5.80
5.27
6.30
6.33
6.01
4.75
3.39
3.17
4.22
4.74
5.80
5.72
4.21
5.26
5.44
1.60
4.84
5.24
5.69
4.72
4.08
4.75
5.30
4.62
3.44
3.44
4.52
5.05
3.82
4.13
4.90
6.41
3.52
3.92
5.05
2.03
1.07
1.82
1.55
2.03
1.60
1.46
1.60
1.94
1.74
2.26
1.90
3.13
4.81
2.76
2.34
6.32
2.13
2.79
4.13
3.99
6.96
7.96
6.97
8.91
8.96
8.37
5.99
3.42
3.01
4.99
5.97
7.97
7.81
4.97
6.94
7.30
0.04
6.16
6.92
7.76
5.92
4.72
5.98
7.03
5.74
3.51
3.51
5.55
6.55
4.22
4.82
6.27
9.12
3.66
4.42
6.55
0.85
-0.96
0.46
-0.05
0.85
0.04
-0.23
0.04
0.68
0.31
1.29
0.60
2.93
6.10
2.24
1.44
8.95
1.04
2.28
4.82
log Kd
(Kidman)
3.65
6.62
7.62
6.63
8.56
8.62
8.03
5.65
3.08
2.67
4.65
5.63
7.63
7.47
4.63
6.60
6.95
-0.30
5.81
6.58
7.41
5.58
4.38
5.64
6.69
5.40
3.16
3.16
5.20
6.20
3.88
4.48
5.92
8.77
3.32
4.07
6.20
0.51
-1.30
0.11
-0.39
0.51
-0.30
-0.57
-0.30
0.34
-0.03
0.95
0.26
2.59
5.76
1.90
1.09
8.61
0.70
1.94
4.47
tl-irst order molecular connectivity index
"Calculated from first order MCI using regression equation (11) developed by Sagljic (1987).
84
-------
evaluated, however, degradation could not be determined for TAL since the
AAS method cannot distinguish between TAL and lead in breakdown products.
Two extraction procedures were used to remove lead species including
TAL, TAL salts, and Ft*24" from the soil. At each sampling interval a
subsample of soil was either (1) extracted with methylisobutal-ketone
(MIBK) or (2) digested with hot nitric acid-hydrogen peroxide (Method 3050
U.S. EPA 1982). Volatilized TAL (sorbed by Tenax traps) was extracted
with MIBK. Since specific organic lead species extracted with MTRK is
unknown, the use of MIBK as a solvent did not facilitate isolation of
various organic and inorganic forms of lead. Nonextractable lead, defined
as the difference between lead in the hot nitric acid digestion and the
MTBK extraction, may be inorganic and organic lead species sorbed to soil
or various lead spoecies not as readily extracted with MIBK.
Table 32 shows the distribution of lead as volatile, organic (MIBK)
extractable and nonextractable with time. Less than 10 percent of the
total lead added to Kidman soil volatilzed over the first four hours of
the study. After 24 hours, 49.4 percent of the total lead had
volatilized. The ratio of MIBK extractable and nonextractable lead over
this time period was relatively constant, indicating a loss of lead from
both fractions. Either volatilization of lead was from both fractions, or
volatilization was occurring from one fraction with the desorption and/or
decomposition of lead in the other fraction replacing that lost through
volatilization.
The TAL parent compounds and trialkyllead salts are volatile and are
soluble in MIBK, whereas the dialkyllead salts and inorganic lead are less
volatile and are more polar in nature. No conclusion, however, can be
85
-------
TABLE 32. MASS BALANCE FOR TETRAALKYL LEAD IN A SOIL SYSTEM
CD
01
Time (hr)
0
1
2
4
8
24
70
n
2
2
2
2
2
2
2
Hot1
Nitric Acid
Soluble Lead
% Total
99.6
98.3
96.7
92.7
83.5
50.5
25.9
Organic2
Extractable
(MIBK) Lead
% Total
57.2
56.4
59.8
52.5
50.6
33.2
5.0
Nonextractable3
Lead
% Total
42.4
41.9
36.9
40.2
32.8
17.3
21.0
Volatile4
Loss
% Total
0.4
1.8
3.4
7.2
16.5
49.4
74.0
Mass Balance Total Lead5
Acid Extract + Volatile
rag/Kg
71.7
71.8
72.1
71.4
70.3
64.8
68.6
•'•hot nitric acid soluble lead was measured experimentally.
2organic extractable lead was measured experimentally.
3nonextractable lead was calculated as the difference between hot nitric acid soluble lead and organic extractabl*
lead.
Volatile loss of lead was measured independently of other measurements.
5the mass balance was calculated as mg/kg as follows:
hot nitric acid lead(l) + volatile loss(4) = total lead.
-------
made concerning specific mechanisms of reactions in this system. After 70
hours, 74 percent of the added lead was volatilized. The majority of the
lead remaining in the soil (81 percent) was in the nonextractable form.
LAND TREATMENT MODEL APPLICATIONS
The mathematical models (RTTZ and VIP) were used to simulate the
behavior of eight pesticides in Kidman soil at a time period beyond the
laboratory determined half-life. Input parameters for the models
included: pesticide concentration in soil (g/m3), soil water content
corresponding to 90 percent saturation (9 = 22 percent), calculated
partition coefficients (Kh and Kd), Kidman soil parameters, and laboratory
determined kinetic (k) values. Table 33 lists the predicted concentration
of each pesticide in soil water, soil air, and soil solid phase after 91
days at the bottom of the zone of pesticide incorporation (15 cm), in an
HWLT unit. The concentration of the pesticides in soil water, soil air,
and soil solid phases at the next depth increment, 18 cm, were at least
six orders of magnitude less than at 15 cm and were below analytical
detection limits. The organophosphorus pesticides were predicted to
degrade significantly in 91 days (96.2 percent for disulfotcn to 78.8
percent for parathion). Approximately 70 percent of the applied
chlorinated pesticides were predicted to degrade in this time period.
When apparent loss was eliminated in the models (by setting k=0),
treatment was limited to the sorptive capacity (inmobilization) of the
soil for each pesticide. No movement through volatilization or leaching
was predicted by the models except for toxaphene where detectable
concentrations were predicted to be volatilized and to leach frcm the zone
of incorporation in 91 days. Therefore, from the time of application to
87
-------
TABLE 33. CONCENTRATIONS OF PESTICIDES IN SOIL WATER, SOIL AIR,
AND SOIL SOLID PHASES AND PERCENT DECAY AT 15 cm DEPTH AFTER 81 DAYS
AS PREDICTED BY THE MATHEMATICAL MDDELS.
Disulfoton
Fhorate
Methylparathion
Parathion
Aldrin
Endosulfan
Heptachlor
Toxaphene
Concentration
in soil water
(g/m3)
2 X 10~5
5 X 10~6
5 X 10~7
2 X 10~8
1 x 10~10
2 x 10~8
1 X 10~8
1 x 10"5
Concentration
in soil air
(g/m3)
2 x 10~9
1 x 1(T9
1 x 1CT12
5 x 1CT13
2 x 10~12
7 x 1CT11
1 X 10~9
2 x 10~4
Concentration in
soil solid phase
(g/m3)
6 X 10~8
2 X 10~7
1 x 10~7
3 x 10~7
1 X 10~7
2 X 10~7
2 X 10~7
2 X 10~5
%
decay
96
87
90
79
69
72
66
0
91 days, significant treatment was observed in the modeled systems (with and
without degradation as an input parameter), with no migration of the
pesticides out of the zone of incorporation (15 cm) at the soil concentrations
and soil water content of 22 percent.
The prediction of no leaching observed by both models under conditions
used in the laboratory study is supported by both laboratory and field studies
of other investigators. Only trace amounts of chlorinated pesticides have
been found below the zone of incorporation in field studies after long time
periods (Freeman et al., 1975, Lichtenstein et al., 1971, Nash and Wbolson,
1967, Rao and Murty, 1980). Although organophosphorus pesticides are
88
-------
relatively soluble compared with chlorinated pesticides, they also do not
readily migrate in soil systems (Singh and Singh, 1984, Voerman and Besemer,
1970, Weber, 1972).
For losses due to volatilization, the VIP model employs a partition
coefficient between water and air and a diffusion gradient through the soil-
pore air space. The model predicted no significant diffusion of any of the
pesticides with the exception of toxapnene, into the atmosphere under
conditions used in this study. Volatilization of chlorinated and
organophosphorus pesticides, however, has been observed in field studies (Burt
et al., 1965, Glotfelty et al., 1984, Grenney et al., 1987, Harris & Chapman,
1980, Harris and Lichtenstein, 1961, Nash, 1983). Maximum loss due to
volatilization generally occurred within the first few days after application.
Field studies are often performed without making efforts to minimize potential
volatile losses. Factors influencing volatilization include the concentration
of the pesticide used, soil/pesticide sorption reactions, soil temperature,
soil water content, application method, relative humidity of the air and rate
of movement of air over the soil surface (Farmer et al., 1972, Harris and
Lichtenstein, 1961, Igue et al., 1972, Spencer and Cliath, 1977). In the
laboratory study reported here, methods were used to minimize volatilization
as described previously. Methods for minimizing volatile losses with field
application of pesticides are given by the U.S. EPA (U.S. EPA, 1984a and b).
Since the VIP and KETZ models do not presently address non-steady state
flow or macropore flow, fracture flow or immiscible flow, the intended
application, at present, is primarily to aid in environmental pathways
analysis, i.e., to indicate the results of the interactions of
89
-------
natural processes (degradation and immobilization) on the relative
distribution of multiple chemicals in soil/waste systems.
The use of the VIP model for evaluating the mobility of polynuclear
aromatic hydrocarbons (PAH compounds) under steady state conditions in
laboratory column reactors, conducted as part of this research project, is
discussed in detail by Grenney et al. (1987).
TRANSPOFMATTOI STUDIES
The distribution of 14C from the incubation of (12-14C)CMBA with McLaurin
sandy loam soil is summarized in Table 34. Total 14C recoveries varied from
78 to 90% over the 28-day incubation period for both nonpoisoned and poisoned
(2% HgCl2) samples. The recovery efficiencies range is typical for a -*-4C
tracer study (Bulman et al. 1985).
Parent 14C CMBA was extensively biodegraded with a half life of 17 days.
Microbial transformation half-life was determined from the decrease of the
CMBA 14C fraction over time, which was corrected for abiotic loss and volatil-
ization. These results are consistent with the results obtained for the non-
radiolabeled CMBA degradation study, which showed bicdegradation half lives
of 20 to 28 days (Park 1987). Abiotic loss of 14C CMBA from soil samples
poisoned by 2% HgCl2 was statistically not
significant (p=0.05). ^4C CMBA volatilization was not detected during the 28-
day soil incubation period.
Table 34 also shows that the decrease in the parent PAH 14C is
accompanied by an increase in metabolite ^4C fraction. Incorporation of ^-4C
CMBA into a nonextractable soil residue 14C increased from 12 to 17%, however,
the increase was not statistically significant (p=0.05). Evolution of ^-4OC>2
was not detected during the 28 days of incubation.
90
-------
These results do not demonstrate that the parent compound was not metabolized
to OC>2 since 14C EMBA used was radiolabeled only at the 12 position carbon.
In order to detect 14OC>2 the benzene ring which contained the carbon-12 was
required to be mineralized to (X^.
The HPLC chromatogram of EMBA metabolites is presented in Figure 13. The
chromatogram revealed several metabolic products. Peaks 7, 8, and 9 were
tentatively characterized as 10-hydroxy-, 4-hydroxy-, and S-hydroxy-EMBA,
respectively. HPLC retention time of these metabolites were identical with
those given by reference standards. The mass spectrum of peak 3 displayed
ions at m/e values of 272 (molecular ion), 257 (loss of CH3), and 226 (loss of
CH3, OH, and CH2) and indicated that the metabolite is 7,12-dihydro-12-methyl-
7-roethylene-benz(a)anthracene-12-ol. HPLC elution profile (Figure 14) from
the incubation of 14C EMBA revealed a complex mixture of metabolic products
which was similar to the HPLC chromatogram (Figure 13) for nonradiolabeled PAH
metabolites. The elution profile further shows the formation of highly polar
metabolic products eluting prior to HPLC retention time of 15 min.
Results for Ames assay testing with strain TA-100 for EMBA metabolites at
low and neutral pH soil are presented in Figures 15 and 16, respectively. The
highly polar metabolic: fraction (HPLC retention time 0-15 min) was
mutagenically inactive towards TA-100 for both soil pH conditions, suggesting
that these metabolites may be the detoxified conjugation products of soil
microbial enzymes. Cerniglia and Gibson (1979), who studied the oxidation of
14C benzo(a)pyrene by Cunnincfoamella elegans. demonstrated that the
metabolites eluting in the very polar HPLC region were mostly sulfate
conjugates of dihydroxy benzo(a)pyrene metabolites and benzo(a)pyrene phenols.
91
-------
TABLE 34. TRANSroKMATIONS OF (14C) 7,12-DIMETHYIEENZ(A)ANTHRACENE BY MCLAURIN SANDY LDAM SOIlA
•^c appearing in each fraction (%)
Time
(days)
0
14
28
Soil Extract
7 , 12-dimethylbenz (a) - Metabolites
anthracene
(parent compound)
62 (69) 4 (6)
26 43
20 (60) 53 (11)
Soil
Residue
12 (13)
16
17 (16)
CCh Total
0 (0) 78 (88)
0 85
0 (0) 90 (87)
aPoisoned (control) data in parentheses.
-------
Moderate and nonpolar (HPI£ retention time 15-33 min and 35-45 min,
respectively) metabolite fractions induced a positive response (mutagenic
ratio greater than 2.5 (U.S. EPA 1983b)) for both soils. Ihe inutagenic
potential of these metabolite fractions, however, decreased during the 28
day soil incubation time. This detoxication potential of EMEA may be
important for engineering management and control of hazardous wastes
containing this PAH compound since toxicity reduction as a function of
incubation time in the soil can be used to assess the success of
treatment. Ihe phenomenon of detoxification was reported by other
investigators (Sims 1982, Sims et al. 1986) who found that the
mutagenicity of polar transformation products of benzo(a)-pyrene increased
and then decreased with incubation time, or treatment time, in the soil.
Mutagenic responses for the metabolites formed from low and neutral
pH soil were not different. Soil pH adjustment changed the microbial
populations by one order of magnitude, but significant and equivalent
amounts of both bacteria and fungi still existed in both soils after 30
days incubation (Table 35). Thus, differences in the metabolic products
between low and neutral pH soil are not likely, and similar mutagenic
responses between two soil treatments may have resulted.
Parent 14C EMBA biodegraded extensively with a half life of 17 days.
The decrease in the parent 14C PAH (62% to 20%) was acccnpanied by an
increase in metabolite 14C fraction (4% to 53%). Soil residue 14C,
however, did not increase significantly (p=0.05) during the 28 days of
soil incubation. CMBA was transformed into several metabolic products in
the McLaurin soil.
93
-------
III
<• «•
I
I
10
20
-------
23 J "A
j
~
'°
9 „
7 8 _
o
••* 7 _
CL,
0 6 „
<;
z .
2.
\ .
0
:
,.
. 8
- ;
\
1
. ' .1
mi. .ilium
i
i
j
]
1!
! !
! i
< j
1 1
I :
j!
$
! i
t!
2>
i
111,,.
20
<0 0
TIME (rn'm)
20
Figune 14. Elution profile of uetabolites formed from
7,12-diiret^lbenz(a)anthraoene by Mciaurin sandy loam
soil. (A) 14 days, (B) 28 days incubation time.
95
-------
o
I—
-------
o
3 -^
CJ
2:
UJ
CJ3
2 ~
HM£ - 14 DAYS
I1ME = 28 DAYS
o to
50
100 0 10
so
I
100
DOSE (ug/ploie)
-= PARENT COMPOUND
o = METASOUTE FRACTION 1 (High Priority)
A= META80UTE FRACTION 2 (Uodcrole Polarity)
0= META30UTE FRACTION I (Low Polorily)
Figure 16. Mutagenicity of 7,12-
-------
Compounds that were tentatively identified included 4-hydroxy-, 5-
hydroxy-, and 10-hydroxy-CMBA and 7,12-dihydro-12-methyl-7-methylene-
benz(a)anthracene-12-ol. High polarity transformation products of CMBA
were not rautagenic for both low and neutral pH soil treatments. Moderate
and low polarity metabolites, however, induced a positive response for
both soil treatments. The rautagenic potential of these fractions
decreased with increasing incubation time. Soil pH adjustment did not
achieve a significant change in the microbial population and thus
contributed to the similar mutagenic responses between the two pH soil
treatments.
TABLE 35. EFFECT OF SOIL pH ON MICROBIAL POPULATIONS IN
MdAURIN SANDY LOAM SOIL
Soil pH
cfu/g soil
Bacteria
Fungi
4.8
7.5
l.lxlO5
2.5X106
5.3X104
4.0X103
98
-------
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