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.
                                    12

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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
-

-------
                                                                 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

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    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

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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

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                     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

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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

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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

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  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

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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

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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

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                               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

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       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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